The Role of Emission Layer Morphology on the Enhanced Performance of Light-Emitting Diodes Based on Quantum Dot-Semiconducting Polymer Hybrids

The influence of the morphology of quantum dot (QD)-semiconducting polymer hybrid emission layers on the performance of quantum dot-based light emitting diodes (QLEDs) is systematically investigated. Chemically grafted QD-semiconducting polymer hybrids are fabricated by the ligand exchange procedure between CdSe/CdxZn1−xS QDs and a new block copolymer consisting of a carbazole-based electroactive block with a low highest occupied molecular orbital level and a disulfide-based anchor block. The performance of QLEDs with hybrid emission layers is compared with QLEDs utilizing QD-only and physically mixed QD/polymer emission layers. It is shown that only in the emission layers formed by chemica…

CdSe/ZnS Nanocrystals with Dye-Functionalized Polymer Ligands Containing Many Anchor Groups

Polymers with Side-chain Mesogenic Units

Liquid crystalline (LC) polymers are usually prepared by combining formanisotropic structural units (so-called mesogenic groups) and polymer chains (Figure 1). The mesogenic groups used for this purpose are rigid rod-like or disc-like units, which are known to favour LC phases in the case of low molar mass substances. There are two main ways of combining the mesogenic groups and polymer chains. The mesogenic groups can either be incorporated actually into the polymer chains (LC main-chain polymers, see Volume 5, Chapter 38) or they can be attached to flexible polymer chains as side groups (LC side-chain polymers).

Well-defined carbohydrate-based polymers in calcium carbonate crystallization: Influence of stereochemistry in the polymer side chain on polymorphism and morphology

Abstract In this work we demonstrate the remarkable phase control on the crystallization of calcium carbonate by the stereochemistry of carbohydrate-based polymers. The polymers (poly(2-(2,3,4,6-tetra-O-acetyl-β- d -glucosyloxy)ethyl methacrylate) and poly(2-(2,3,4,6-tetra-O-acetyl-β- d -galactosyloxy)ethyl methacrylate)) have been synthesized from the respective glucose or galactose containing monomers (3 step synthesis) by RAFT polymerization leading to well-defined carbohydrate-based polymers with number averages of the molecular weights (Mw) of 10,000–18,000 g/mol and a dispersities (Đ) from 1.1 to 1.2. For the deprotected polymers we found differences in the phase selection of calcium …

3D photonic crystal intermediate reflectors for enhanced light-trapping in tandem solar cells

The concept of 3D photonic crystals embedded in tandem solar cells as intermediate reflective layers is investigated. Numerical as well as experimental results will be presented.

Influence of End Groups on the Stimulus-Responsive Behavior of Poly[oligo(ethylene glycol) methacrylate] in Water

The influence of the chemical structure of both end groups onto the lower critical solution temperature (LCST) of poly[oligo(ethylene glycol) monomethyl ether methacrylate] (POEGMA) in water was systematically investigated. POEGMA of Mn = 3550 g/mol and Mw/Mn = 1.14 prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization was equipped with two different functional end groups in a one-step postpolymerization reaction combining activated esters, functional amines, and functional methane thiosulfonates. As end groups, n-propyl, n-hexadecyl, di(n-octadecyl), poly(ethylene glycol)-550 (PEG), 1H,1H-perfluorononyl, azobenzene, and trimethylethylammonium groups were system…

Block copolymers from ionic liquids for the preparation of thin carbonaceous shells

This paper describes the controlled radical polymerization of an ionic-liquid monomer by RAFT polymerization. This allows the control over the molecular weight of ionic liquid blocks in the range of 8000 and 22000 and of the block-copolymer synthesis. In this work we focus on block copolymers with an anchor block. They can be used to control the formation of TiO2 nanoparticles, which are functionalized thereafter with a block of ionic-liquid polymer. Pyrolysis of these polymer functionalized inorganic nanoparticles leads to TiO2 nanoparticles coated with a thin carbonaceous shell. Such materials may, e.g., be interesting as battery materials.

Polyacrylonitrile block copolymers for the preparation of a thin carbon coating around TiO2 nanorods for advanced lithium-ion batteries.

Herein, a new method for the realization of a thin and homogenous carbonaceous particle coating, made by carbonizing RAFT polymerization derived block copolymers anchored on anatase TiO2 nanorods, is presented. These block copolymers consist of a short anchor block (based on dopamine) and a long, easily graphitizable block of polyacrylonitrile. The grafting of such block copolymers to TiO2 nanorods creates a polymer shell, which can be visualized by atomic force microscopy (AFM). Thermal treatment at 700 °C converts the polyacrylonitrile block to partially graphitic structures (as determined by Raman spectroscopy), establishing a thin carbon coating (as determined by transmission electron m…

Novel Amphiphilic Styrene-Based Block Copolymers for Induced Surface Reconstruction

This paper describes the synthesis of amphiphilic block copolymers by living radical polymerization (NMP) of new styrene-like monomers. The polar monomers (ethylene oxide side chains and free hydroxyl- or amino-groups after deprotection) were polymerized in a “protected form” to adjust the solubility of the monomers. In this way high molar mass polymers with a narrow polydispersity (around or below 1.2) were accessible. In the bulk state hydrophobic and hydrophilic domains demix. By exposing thin films of these polymers to vacuum (air) or alternatively to water or a hydrophilic surface it becomes possible to switch the surface polarity reversibly between contact angles of about 105° and 83°…

Cover Picture: Macromol. Rapid Commun. 20/2006

Functional Liquid Crystalline Polymers: Ferroelectric Polymers and Liquid Crystalline Elastomers and Ionomers

Abstract The incorporation of different functional groups in liquid crystalline polymers opens the way to a variety of interesting new materials, which may be used for non-linear optics, as piezo-elements or as two-phasic composite materials.

Tuning the defect configurations in nematic and smectic liquid crystalline shells

Thin liquid crystalline shells surrounding and surrounded by aqueous phases can be conveniently produced using a nested capillary microfluidic system, as was first demonstrated by Fernandez-Nieves et al. in 2007. By choosing particular combinations of stabilizers in the internal and external phases, different types of alignment, uniform or hybrid, can be ensured within the shell. Here, we investigate shells in the nematic and smectic phases under varying boundary conditions, focusing in particular on textural transformations during phase transitions, on the interaction between topological defects in the director field and inclusions in the liquid crystal (LC), and on the possibility to rel…

ChemInform Abstract: Tuning the Defect Configurations in Nematic and Smectic Liquid Crystalline Shells

Thin liquid crystalline shells surrounding and surrounded by aqueous phases can be conveniently produced using a nested capillary microfluidic system, as was first demonstrated by Fernandez-Nieves et al. in 2007. By choosing particular combinations of stabilizers in the internal and external phases, different types of alignment, uniform or hybrid, can be ensured within the shell. Here, we investigate shells in the nematic and smectic phases under varying boundary conditions, focusing in particular on textural transformations during phase transitions, on the interaction between topological defects in the director field and inclusions in the liquid crystal (LC), and on the possibility to relo…

Fabrication of Single Cylindrical Au-Coated Nanopores with Non-Homogeneous Fixed Charge Distribution Exhibiting High Current Rectifications

We have designed and characterized a cylindrical nanopore that exhibits high electrochemical current rectification ratios at low and intermediate electrolyte concentrations. For this purpose, the track-etched single cylindrical nanopore in polymer membrane is coated with a gold (Au) layer via electroless plating technique. Then, a non-homogeneous fixed charge distribution inside the Au-coated nanopore is obtained by incorporating thiol-terminated uncharged poly(N-isopropylacrylamide) (PNIPAM) chains in series to poly(4-vinyl pyridine) (PVP) chains, which are positively charged at acidic pH values. The functionalization reaction is checked by measuring the current–voltage (I–V) curves prior …

Photoswitchable Smectic Liquid-Crystalline Elastomers

We succeeded in the synthesis of azo side chain containing polysioxanes with broad smectic C* and A phases. In these polymers the phase transition temperatures can be shifted reversibly by up to 17°C by irradiation with UV (cis) or VIS (trans) light. Thin films of these polymers in the smectie phase (both on substrates and as free-standing films) orient perfectly in a homeotropic manner. As a consequence, the aze chromophores do no longer absorb during a perpendicular illumination with light (dichroism). It is thus possible to crosslink these films photochemically to prepare photoswitchable smectic LC elastomers.

Pentafluorophenyl Ester-based Polymersomes as Nanosized Drug-Delivery Vehicles

In this work, activated ester chemistry is employed to synthesize biocompatible and readily functionalizable polymersomes. Via aminolysis of pentafluorophenyl methacrylate-based precursor polymers, an N-(2-hydroxypropyl) methacrylamide (HPMA)-analog hydrophilic block is obtained. The precursor polymers can be versatile functionalized by simple addition of suitable primary amines during aminolysis as demonstrated using a fluorescent dye. Vesicle formation is proven by cryoTEM and light scattering. High encapsulation efficiencies for hydrophilic cargo like siRNA are achieved using dual centrifugation and safe encapsulation is demonstrated by gel electrophoresis. In vitro studies reveal low cy…

Two-dimensional self-assembly of disulfide functionalized bis-acylurea: a nanosheet template for gold nanoparticle arrays.

A new functional bis-acylurea molecule allows a two-stage self-organization process. It self-organizes--at first--into 2D nanosheets with disulfide groups at the surface, which act--in the second stage--as a template for gold nanoparticle arrays.

Nanoimprint lithography for organic electronics

Thin films made of organic semiconductors (α-sexithiophene, PDAS and PBAS) have been printed and the impact on morphology studied by optical, atomic force and electron microscopy. Surfaces in contact with the stamp during printing undergo a change towards smoother and more ordered material at the macromolecular scale. Interdigitated nanoelectrodes to be used as source and drain in TFTs have been made and printed down to 100 nm. PDAS and PBAS can be printed at room temperature and preserve their printed feature provided they are cross-linked afterwards.

Preparation of 3D photonic crystals from opals

Molecular dynamics in low-molar and polymeric ferroelectric liquid crystals

Broadband dielectric spectroscopy covering the frequency range from 10−1 Hz to 109 Hz was employed to study the molecular dynamics in low-molar and polymeric ferrroelectric liquid crystals. At frequencies below 106 Hz the ferroelectric modes, soft and Goldstone mode are observed. In the frequency regime from 106 Hz to 109 Hz a fast relaxation process is found, which is assigned to the hindered rotation of the mesogens around their long molecular axis. It turns out that the molecular dynamics is not principally different between low-molar and polymeric systems.

Strain‐induced compression of smectic layers in free‐standing liquid crystalline elastomer films

The deformation of oriented smectic liquid crystal elastomer films with smectic layers parallel to the film surface was studied using optical reflectometry and small angle X‐ray diffraction. Reflectometry data show that in the chosen material, in‐plane strain causes a change in the optical thickness of the free‐standing films. Small angle X‐ray scattering was used to explore the molecular origin of this effect. The X‐ray scattering data confirm that the change in optical thickness originates from the compression of the individual smectic layers. The measured Poisson ratio in the smectic A and C* phases is close to ½, in contrast to the smectic elastomers investigated earlier by Nishikawa et…

Polymeric Nanoparticles: Polymeric Nanoparticles with Neglectable Protein Corona (Small 18/2020)

Electrochemically Induced Reversible and Irreversible Coupling of Triarylamines

The electrochemical coupling and dimerization behavior of the low molecular compounds triphenylamine (TPA) and 9-phenylcarbazole (PHC) in comparison to tri-p-tolylamine (p-TTA) with para-blocked methyl groups has been investigated in detail. In contrast to the unsubstituted radical cations of TPA and PHC, the radical cations of p-TTA are stable in the radical cation state and do not undergo any further coupling reactions. However, we found that the dicationic state of p-TTA does undergo two different competitive reaction pathways: (1) an irreversible intramolecular coupling reaction which leads to phenylcarbazole moieties and (2) a reversible intermolecular dimerization leading to charged σ…

Micro- and nanostructuring of oligo- and polythiophenes in two and three dimensions

Abstract Oligothiophenes bearing methacrylic functionalities were two-dimensional-structured by stamping techniques. The localised monomer was hardened by radical polymerisation in UV light. The structures in micrometre- and nanometre-scale were characterised electrochemically by SECM. An inverse polymer opal with extremely high inner surface and periodicity was obtained by localising the photosensitive oligothiophene within an opal template of SiO 2 beads. Cyclic voltammetry of the oligothiophenes in aprotic solvents was carried out to examine possible electrochemical conversions. A self-assembling technique for lateral and vertical structuring of polythiophenes with pendant sulfonate and …

Cationic Nanohydrogel Particles as Potential siRNA Carriers for Cellular Delivery

Oligonucleotides such as short, double-stranded RNA (siRNA) or plasmid DNA (pDNA) promise high potential in gene therapy. For pharmaceutical application, however, adequate drug carriers are required. Among various concepts progressing in the market or final development, nanosized hydrogel particles may serve as novel transport media especially for siRNA. In this work, a new concept of synthesizing polymeric cationic nanohydrogels was developed, which offers a promising strategy to complex and transport siRNA into cells. For this purpose, amphiphilic reactive ester block copolymers were synthesized by RAFT polymerization of pentafluorophenyl methacrylate as reactive ester monomer together wi…

Structure and elastic properties of smectic liquid crystalline elastomer films

Mechanical measurements, x-ray investigations, and optical microscopy are employed to characterize the interplay of chemical composition, network topology, and elastic response of smectic liquid crystalline elastomers (LCEs) in various mesophases. Macroscopically ordered elastomer films of submicrometer thicknesses were prepared by cross linking freely suspended smectic polymer films. The cross-linked material preserves the mesomorphism and phase transitions of the precursor polymer. The elastic response of the smectic LCE is entropic, and the corresponding elastic moduli are of the order of MPa. In the tilted ferroelectric smectic-C* phase, the network structure plays an important role. Du…

Smectic Liquid-Crystalline Colloids by Miniemulsion Techniques

Poly(N-isopropylacrylamide)-Modified Styrene-Butadiene Rubber as Thermoresponsive Material

Not just for tumor targeting: unmet medical needs and opportunities for nanomedicine.

During the last 3 decades, nanomedicines have provided novel opportunities to improve the delivery of chemotherapeutics in cancer therapy effectively. However, many principles learnt from there have the potential to be transferred to other diseases. This perspective article, on the one hand, critically reflects the limitations of nanomedicines in tumor therapy and, on the other hand, provides alternative examples of nanomedicinal applications in immunotherapy, noninvasive drug deliveries across epithelial barriers and strategies to combat intra- and extra-cellular bacterial infections. Looking ahead, access to highly complex nanoparticular delivery vehicles given nowadays may allow further…

Block Copolymers Build-up of Electron and Hole Transport Materials

In this article we describe the synthesis of various monomers modified with triphenyl-1,3,5-triazine side groups as electron transport moieties. By nitroxide-mediated polymerization with a TEMPO unimer it was possible to obtain polymers with a narrow polydispersity. Furthermore, by living radical polymerization block copolymers were obtained from these monomers. Therefore, microphase separated structures are accessible which possess hole conducting moieties in one phase and electron conducting moieties in the other phase.

Physicochemical characterization of octakis(alkyloxy)-substituted Zn(ii)-phthalocyanines non-covalently incorporated into an organogel and their remarkable morphological effect on the nanoscale-fibers

A series of octakis(alkyloxy)-substituted Zn(II)-phthalocyanines were efficiently incorporated into an organogel made of (1R,2R)-trans-1,2-bis(dodecanoylamino)cyclohexane by means of multiple cooperative non-covalent interactions, and SEM revealed the formation of unique brush-like nanostructures.

New Perspectives of HPMA-based Copolymers Derived by Post-Polymerization Modification

Poly[N-(2-hydroxypropyl) methacrylamide] (HPMA) was one of the first polymers applied as polymer drug conjugate in the clinics. Since then many attempts have been made to expand the functionality of HPMA-based copolymers from advanced synthetic pathways to multiple biomedical applications. This Feature Article highlights multifunctional HPMA based copolymers prepared by controlled radical polymerization and subsequent post-polymerization modification of activated ester precursor polymers via aminolysis. This approach combines precise control of the polymer's microstructure (molecular weight, dispersity, block copolymer formation, end group functionalization) with an easy introduction of var…

Multilayer Thin Films by Layer-by-Layer Assembly of Hole- and Electron-Transport Polyelectrolytes: Optical and Electrochemical Properties

In this paper, we pressent the synthesis of a series of p-type and n-type semicondnctring polyelectrolytes with triarylamine, oxadiazole, thiarliazole and triazine moictes. The synthesized polymeric hole and electrom iransport materials were examined optically and electrochemically using UV/Vis spectroscopy. PL spectroscopy and CV. Based on the optical and electrochemical data, each of the energy levels were calculated and all values suggested that the were promising hole-(p-type) or alectron=transprot (n-type) materials for devices. Moreover, the synthesized ionie polymers were suitable for LBL thin film deposition from ditute polymer solutions and the multilayers were fully characterized …

Liquid Crystalline Elastomers—Characterization as Networks

Abstract This paper summarises the properties of archiral and chiral liquid crystalline (LC) elastomers, the latter of which have found interest due to their piezoelectric properties. In addition the formation of new LC elastomers by a radical polymerization of acrylate groups covalently linked to LC polymers was investigated. This was done concerning the progress of the crosslinking reaction, concerning the influence of the crosslinking on the LC phases and concerning the network properties (swelling ratio and elastic modulus) of the resulting elastomers. It turns out that the networks prepared in this way are very soft and their crosslinking density is low. This can be explained assuming …

Free-standing smectic LC elastomer films

ABSTRACTWe probe the mesophase transitions and layer structures in thin ordered smectic liquid crystalline elastomer films by means of x-ray diffraction and optical microscopy. Oriented elastomer films of submicrometer thickness are produced by crosslinking freely suspended smectic polymer films. After crosslinking, the mesomorphism is similar to that of the precursor polymer. Smectic layers align parallel to the film plane. The layer spacing increases with temperature in the SmC* phase while it decays above the SmC*-SmA transition.

Infrared spectroscopic study of a phenyl benzoate side group—methacrylate main chain polymeric liquid crystal

Abstract The temperature dependence of the infrared dichroism of a side chain polymeric liquid crystal was investigated for two homogeneously oriented samples, one aligned with a PVA coating and the other aligned by a magnetic field. From the apparent order parameters, it was found that the rotation of the mesogenic side group was restricted. Not only the rigid part of the side group, but also the alkyl chains were found to be partly ordered. Realignment of the side groups was observed in the case of the magnetically aligned sample at the smectic-nematic transition temperature. Unlike the other absorption bands, the C˭O bond vibration band shifted to higher wavenumbers with increasing tempe…

Ferroelectric LC-elastomers

Ferroelectric liquid crystalline elastomers combine the rubber elasticity of polymer networks with liquid crystalline phases and ferroelectric ordering. Ferroelectric switching leads therefore to a deformation of the polymer network and an elastic stress. The coupling between both effccts can be varied by changing the topology of the netpoints.

Fluorescent Concentrators for Photovoltaic Applications

One-piece micropumps from liquid crystalline core-shell particles

Responsive polymers are low-cost, light weight and flexible, and thus an attractive class of materials for the integration into micromechanical and lab-on-chip systems. Triggered by external stimuli, liquid crystalline elastomers are able to perform mechanical motion and can be utilized as microactuators. Here we present the fabrication of one-piece micropumps from liquid crystalline core-shell elastomer particles via a microfluidic double-emulsion process, the continuous nature of which enables a low-cost and rapid production. The liquid crystalline elastomer shell contains a liquid core, which is reversibly pumped into and out of the particle by actuation of the liquid crystalline shell i…

Gelling and the collective dynamics in ferroelectric liquid crystals

Dielectric spectroscopy has been applied to investigate the dynamic behaviour of a ferroelectric liquid crystal in the smectic C* and smectic A phases confined in gel matrices of a fibre like (1D) or platelet like (2D) structure. These gel matrices were obtained from semicarbazide or bis-acylurea derivatives, which self assemble because of their H-bonding motif. The confinement strongly influences the magnitude of the spontaneous polarization and the collective fluctuations of the director detected as the Goldstone-mode. It is thus possible to detect gelation by dielectric spectroscopy. By this method it was possible to follow the destruction and restoration of the gel structure induced by …

Directionality of light emission in three-dimensional opal-based photonic crystals (Invited Paper)

Experimental and theoretical studies of the emission directionality diagrams of a perylene dye covering the inner surface of three-dimensional opal-based photonic crystals with incomplete photonic bandgap are reported. Directionality diagram of emission intensity is interpreted in terms of the spontaneous emission suppression by photonic band gap and the emission enhancement due to photon focusing phenomenon. A theoretical model is based on the classical analysis of an angular distribution of the radiated power of a point dipole.

Facile hybridization of Ni@Fe2O3 superparticles with functionalized reduced graphene oxide and its application as anode material in lithium-ion batteries

Abstract In our present work we developed a novel graphene wrapping approach of Ni@Fe2O3 superparticles, which can be extended as a concept approach for other nanomaterials as well. It uses sulfonated reduced graphene oxide, but avoids thermal treatments and use of toxic agents like hydrazine for its reduction. The modification of graphene oxide is achieved by the introduction of sulfate groups accompanied with reduction and elimination reactions, due to the treatment with oleum. The successful wrapping of nanoparticles is proven by energy dispersive X-ray spectroscopy, high-resolution transmission electron microscopy and Raman spectroscopy. The developed composite material shows strongly i…

The synthesis and phase behaviour of a series of polymers having liquid crystalline sidechains and a poly(acrylic acid) backbone are described. These polymers show a dependence of the phase transition temperatures on molecular weight. In copolymers of two liquid crystalline acrylic esters, induced smectic phases occur. A comparison of the phase transitions of the different polyacrylates, with those of liquid crystalline polymethacrylates and polysiloxanes, published elsewhere, establishes that the spacer group achieves partial “decoupling” of liquid crystalline and polymer properties.

High-Performance TiO2 Nanoparticle/DOPA-Polymer Composites

Many natural materials are complex composites whose mechanical properties are often outstanding considering the weak constituents from which they are assembled. Nacre, made of inorganic (CaCO 3 ) and organic constituents, is a textbook example because of its strength and toughness, which are related to its hierarchical structure and its well-defi ned organic–inorganic interface. Emulating the construction principles of nacre using simple inorganic materials and polymers is essential for understanding how chemical composition and structure determine biomaterial functions. A hard multilayered nanocomposite is assembled based on alternating layers of TiO 2 nanoparticles and a 3-hydroxytyramine…

Applications of Liquid Crystalline Elastomers

This chapter focuses on recent developments in the field of liquid crystalline elastomers (LCEs) that bring these materials closer to the world of real applications, concentrating on their actuation properties. First, we briefly introduce different LCE materials that show actuation behavior and explain how they can be synthesized. In the second part, we focus on materials in which a shape change is triggered by a phase transition. In particular, we discuss how the chemistry of the polymeric material influences the strength and direction of the shape change. We review the efforts made to trigger the actuation event by stimuli other than temperature variation. Subsequently, we summarize prepa…

Polymer based tuneable photonic crystals

We report on the fabrication and characterization of photonic crystal slab waveguide resonators which contain a nanostructured second-order nonlinear optical polymer. The combination of a photonic crystal resonator realized in a second-order nonlinear optical polymer allowed the detection of electro-optical modulation of light with a sub-1-V sensitivity. Furthermore we report on the synthesis of novel nonlinear optical polymers with large second-order hyperpolarizability and improved glass transition temperature. The polymer slab waveguide is micro patterned by means of electron-beam lithography and reactive ion etching. The photonic crystal slab-based resonator consisted of a square lattic…

Light scattering in opal heterojunctions

Light propagation in photonic hetero-crystals, consisting of two opal films with different lattice constants, has been investigated in the realistic regime of weak scattering, when the main light flux is transported by ballistic photons. The light scattering at the photonic bandgap interface is studied in combination with transmission data. The spectra and directionality diagrams of scattered light of single- and hetero-opal films are compared. The rate of decrease of the scattering intensity as a function of the scattering angle has been used to quantify the scattering strength. The anisotropy of the interface scattering is identified by deducing the trajectories of single scattered photon…

Microfluidic Preparation of Liquid Crystalline Elastomer Actuators

This paper focuses on the microfluidic process (and its parameters) to prepare actuating particles from liquid crystalline elastomers. The preparation usually consists in the formation of droplets containing low molar mass liquid crystals at elevated temperatures. Subsequently, these particle precursors are oriented in the flow field of the capillary and solidified by a crosslinking polymerization, which produces the final actuating particles. The optimization of the process is necessary to obtain the actuating particles and the proper variation of the process parameters (temperature and flow rate) and allows variations of size and shape (from oblate to strongly prolate morphologies) as wel…

Creating Defined 3-D Defects Inside an Opaline Ormocer® Matrix with Two-Photon Lithography

The creation of defined structures inside a synthetic opal is a key step toward applications in optics, where control of the propagation of light inside a photonic crystal is necessary. In a previous paper, we described the nanostructuring of Ormocer® to form inverse opals (Lange et al., Macromol. Rapid Commun. 2006, 27, 1746). Here, we report an application for this robust replica process in which defects can be directly produced within the PC by two-photon lithography. The holes of an inverse opal structure are first filled with a resin of similar refractive index. In this transparent material, polymerization can be initiated at defined places via two-photon lithography. After removal of …

Nanoparticles in the Biological Context: Surface Morphology and Protein Corona Formation

Small 16(39), 2002162 (2020). doi:10.1002/smll.202002162

Langmuir-Blodgett films of biocompatible poly(HPMA)-block-poly(lauryl methacrylate) and poly(HPMA)-random-poly(lauryl methacrylate): influence of polymer structure on membrane formation and stability.

Membranes based on functional biocompatible polymers can be regarded as a useful model system to study biological interactions, e.g. antibody-antigen interactions or protein polymer interactions. These model systems may give a better insight into these processes and may help to find suitable polymeric structures offering biocompatibility as well as reduced polymer protein interaction. In this respect, Langmuir-Blodgett (LB) layer formation at the air/water (A/W) interface is studied in respect to polymer architecture in this article. For this purpose, narrowly distributed N-(2-hydroxypropyl)-methacrylamide (HPMA) random and block copolymers have been prepared by the RAFT polymerization meth…

PAA-PAMPS Copolymers as an Efficient Tool to Control CaCO3 Scale Formation

Scale formation, the deposition of certain minerals such as CaCO3, MgCO3, and CaSO4 center dot 2H(2)O in industrial facilities and household devices, leads to reduced efficiency or severe damage. Therefore, incrustation is a major problem in everyday life. In recent years, double hydrophilic block copolymers (DHBCs) have been the focus of interest in academia with regard to their antiscaling potential. In this work, we synthesized well-defined blocklike PAA-PAMPS copolymers consisting of acrylic acid (AA) and 2-acrylamido-2-methyl-propane sulfonate (AMPS) units in a one-step reaction by RAFT polymerization. The derived copolymers had dispersities of 1.3 and below. The copolymers have then b…

Two-Dimensional Aggregation of Organogelators Induced by Biaxial Hydrogen-Bonding Gives Supramolecular Nanosheets

Functionalized magnetic nanoparticles for selective targeting of cells

AbstractInitiation of pathways that lead to proliferation and chemoresistance by Toll-like receptors (TLRs) is an important factor in cancer progression. Here, we show the response of human cancer cells to TLR signaling inevitably linked to tumor biology. The approach is based on tailored multifunctional magnetic nanoparticles equipped with pathogen-derived ligands (CpG) functioning as TLR agonists (molecular component) to investigate the impact of transcription factor immune activation on human cancer cells. Magnetic nanoparticles (MnO and bifunctional Au-MnO) particles were covalently coated with a multifunctional polymer, displaying no cytotoxicity, to being able to enter cells while car…

Preparation of actuating fibres of oriented main-chain liquid crystalline elastomers by a wetspinning process

We present a versatile method to prepare oriented fibres with a defined thickness from main-chain liquid crystalline elastomers. A microfluidic setup is utilized to inject a solution of a photocrosslinkable smectic A main-chain polymer into a co-flowing stream of silicone oil. Diffusion of the solvent into the oil yields solid polymer filaments that are crosslinked in a continuous way by UV-irradiation. The obtained fibres are highly oriented and show a reversible and significant contraction during the liquid crystal's phase transition.

Functional Polymer-Opals from Core-Shell Colloids

Colloidal photonic crystals were prepared from monodisperse core-shell particles. The shell is hereby formed from a functional monomer, such as glycidylmethacrylate or different reactive ester monomers, which can perform chemical reactions and the core from a standard monomer, which yields highly monodisperse colloids. It was possible to crystallize the core-shell particles into artificial opals with excellent optical properties. Reactions on the functional surface of the colloids were carried out, which lead to a dramatic rise in the mechanical stability or to a functionalization of His-tagged silicatein, which acts as nanoreactor to synthesize and immobilize gold nanoparticles from auric …

Combined LC-polymers possess the structural properties of both LC main chain and LC side chain polymers. Beneath this structural speciality, their broad LC-phases and their polymorphism (different smectic phases and one nematic phase as a function of temperature) make them interesting. Crucial to an understanding of them is the fact that main chain and side chain mesogens orient parallel to each other and interact cooperatively to form the LC-phase. Due to this synergism the temperature range of the LC-phase is much broader than that of the corresponding LC main chain and LC side chain polymers. This interplay of main chain and side chain mesogens allows structures to be designed with prefe…

Liquid Crystalline Orientation of Semiconducting Nanorods in a Semiconducting Matrix

This paper describes the synthesis of narrowly distributed block copolymers consisting of a hole conducting triarylamine block and an anchor block via RAFT polymerization. The anchor block is thereby introduced via a reactive ester approach. Block copolymers with dopamine anchor groups bind to oxidic semiconductors like TiO 2 , SnO 2 , and ZnO. Thus, it becomes possible to cover inorganic electron conducting (acceptor) nanomaterials with a corona of an organic hole conducting (donor) polymer like poly(triphenylamine), giving new hybrid materials. The poly(triphenylamine) grafted to inorganic nanorods allows the preparation of stable nanorod dispersions in appropriate solvents. At higher con…

Exploring integration prospects of opal-based photonic crystals

Different methods of functionalisation of thin opal films are discussed, including synthesis of opals on pre-patterned substrates, post-synthesis electron beam lithography, preparation of opals with heterogeneous photonic band gap structure and integrating opals with light sources. These approaches have been tested experimentally and key technological problems have been identified.

Light-induced charge separation in a donor–chromophore–acceptor nanocomposite poly[TPA-Ru(tpy)2]@ZnO

The synthesis and characterisation of a new donor–chromophore–acceptor system based on poly(vinyltriphenylamine) as the electron donor and a glycine-functionalised bis(2,2′;6′,2′′-terpyridine)ruthenium(II) complex acting both as a chromophore and as an anchor group attached to ZnO nanorods as the electron acceptor are described. The TPA-containing block copolymer was synthesised by Reversible Addition Fragmentation Chain Transfer (RAFT) polymerisation and the ruthenium complex glycine conjugates prepared by Solid Phase Peptide Synthesis (SPPS) were attached via post-polymerisation esterification. GPC, NMR, IR and UV-Visible spectroscopy were used to characterise the multifunctional chromoph…

Liquid-crystalline ordering as a concept in materials science: from semiconductors to stimuli-responsive devices.

While the unique optical properties of liquid crystals (LCs) are already well exploited for flat-panel displays, their intrinsic ability to self-organize into ordered mesophases, which are intermediate states between crystal and liquid, gives rise to a broad variety of additional applications. The high degree of molecular order, the possibility for large scale orientation, and the structural motif of the aromatic subunits recommend liquid-crystalline materials as organic semiconductors, which are solvent-processable and can easily be deposited on a substrate. The anisotropy of liquid crystals can further cause a stimuli-responsive macroscopic shape change of cross-linked polymer networks, w…

Cationic Nanohydrogel Particles for Therapeutic Oligonucleotide Delivery.

Short pharmaceutical active oligonucleotides such as small interfering RNA (siRNA) or cytidine-phosphate-guanosine (CpG) are considered as powerful therapeutic alternatives, especially to medicate hard-to-treat diseases (e.g., liver fibrosis or cancer). Unfortunately, these molecules are equipped with poor pharmacokinetic properties that prevent them from translation. Well-defined nanosized carriers can provide opportunities to optimize their delivery and guide them to their site of action. Among several concepts, this Feature Article focuses on cationic nanohydrogel particles as a universal delivery system for small anionic molecules including siRNA and CpG. Cationic nanohydrogels are deri…

SiRNA-mediated in vivo gene knockdown by acid-degradable cationic nanohydrogel particles

Cationic nanohydrogel particles have become an attractive tool for systemic siRNA delivery, but improvement of their in vivo tolerance is desirable, especially to prevent potential long term side effects by tissue and cellular accumulation. Here, we designed novel ketal cross-linked cationic nanohydrogel particles that were assessed for reduced tissue accumulation and robust siRNA delivery in vitro and in vivo. An oligo-amine cross-linker equipped with a ketal moiety in its core was synthesized and applied to nanohydrogel cross-linking of self-assembled reactive ester block copolymers in DMSO. The resulting acid-sensitive cationic nanoparticles spontaneously disassembled over time in acidic…

Gelation of smectic liquid crystal phases with photosensitive gel forming agents.

This paper studies the potential of 3 newly synthesized low molecular weight gelling agents (2 of them with azo groups) with the semicarbazide group as a H-bonding motif to gel the smectic phase of a commercial chiral smectic C material. To detect gelation two methods were used: the stabilization of the director pattern, which measures the interaction of the physical gel network with the LC-director, and the suppression of the onset of electrohydrodynamic instabilities, which measures the increase of viscosity. Special emphasis was put on the influence of the photochemical - isomerization of the gelling agents on gelation.From the stabilization of the director pattern an elastic component c…

Photoimaging through in-Situ Photopolymerization of Heterobifunctional Mesogenic Compounds in Liquid Crystalline State

A series of heterobifunctional mesogenic biphenyl esters having two different polymerizable groups, i.e., acryl and diacetylene groups, were synthesized and their thermal behaviors and polymerization investigated. All compounds showed enantiotropic transitions. Under POM, highly birefringent focal-conic fan textures appeared on heating and cooling from the isotropic melt. Compounds 6−8 having a butyl spacer between a biphenyl and a diacetylene group exhibited LC phases even at room temperature. The X-ray diffractograms of compounds 6−8 showed a set of reflections in the small-angle region. They consisted of more than three sharp diffraction peaks with d spacings in the ratio of 1:1/2:1/3, s…

Ordering and mobility of ferroelectric liquid crystal dimer as studied by FT-IR spectroscopy with 2D-IR correlation analysis

Both a conservative rapid-scan FT-IR technique and a novel step-scan FT-IR technique with 2D correlation analysis were used to study the orientation and the mobility ofa ferroelectric liquid crystal dimer during switching under an electric field. The detailed mutual arrangements of different molecular segments (mesogen, poly(methylene) chain, polysiloxane chain) in a smectic C* phase were derived from the static spectra. It was shown that the long mesogen axis, the average poly(methylene) and the average polysiloxane chain axes do not coincide with each other. The hindered rotation of the carbonyl group is confirmed. Time-resolved FT-IR technique was used to follow the segmental motion with…

Second harmonic generation in ferroelectric liquid crystalline thiadiazole derivatives

Photoresponsive Ferroelectric Liquid-Crystalline Polymers

The photoresponse of ferroelectric smectic side-chain liquid-crystalline (LC) polymers containing a photoisomerizable azobenzene derivative as a covalently linked photochromic side group is investigated. By static measurements in different photostationary states, the effect of trans-cis isomerization on the material's phase-transition temperatures and its ferroelectric properties (spontaneous electric polarization Ps and director tilt angle 0) are analyzed. It turns out that the Curie temperature (transition S C * to S A ) can be reversibly shifted by up to 17 °C. The molecular mechanism of this "photoferroelectric effect" is studied in detail using time-resolved measurements of the dye's o…

Aggregation behavior of amphiphilic p(HPMA)-co-p(LMA) copolymers studied by FCS and EPR spectroscopy.

A combined study of fluorescence correlation spectroscopy and electron paramagnetic resonance spectroscopy gave a unique picture of p(HPMA)-co-p(LMA) copolymers in aqueous solutions, ranging from the size of micelles and aggregates to the composition of the interior of these self-assembled systems. P(HPMA)-co-p(LMA) copolymers have shown high potential as brain drug delivery systems, and a detailed study of their physicochemical properties can help to elucidate their mechanism of action. Applying two complementary techniques, we found that the self-assembly behavior as well as the strength of hydrophobic attraction of the amphiphilic copolymers can be tuned by the hydrophobic LMA content or…

Strategy for good dispersion of well-defined tetrapods in semiconducting polymer matrices.

The morphology or dispersion control in inorganic/organic hybrid systems is studied, which consist of monodisperse CdSe tetrapods (TPs) with grafted semiconducting block copolymers with excess polymers of the same type. Tetrapod arm-length and amount of polymer loading are varied in order to find the ideal morphology for hybrid solar cells. Additionally, polymers without anchor groups are mixed with the TPs to study the effect of such anchor groups on the hybrid morphology. A numerical model is developed and Monte Carlo simulations to study the basis of compatibility or dispersibility of TPs in polymer matrices are performed. The simulations show that bare TPs tend to form clusters in the m…

UV-Free Microfluidic Particle Fabrication at Low Temperature Using ARGET-ATRP as the Initiator System

Radioactive labeling of defined HPMA-based polymeric structures using [18F]FETos for in vivo imaging by positron emission tomography.

During the last decades polymer-based nanomedicine has turned out to be a promising tool in modern pharmaceutics. The following article describes the synthesis of well-defined random and block copolymers by RAFT polymerization with potential medical application. The polymers have been labeled with the positron-emitting nuclide fluorine-18. The polymeric structures are based on the biocompatible N-(2-hydroxypropyl)-methacrylamide (HPMA). To achieve these structures, functional reactive ester polymers with a molecular weight within the range of 25,000-110,000 g/mol were aminolyzed by 2-hydroxypropylamine and tyramine (3%) to form (18)F-labelable HPMA-polymer precursors. The labeling procedure…

Labeling of DOTA-conjugated HPMA-based polymers with trivalent metallic radionuclides for molecular imaging.

Background In this work, the in vitro and in vivo stabilities and the pharmacology of HPMA-made homopolymers were studied by means of radiometal-labeled derivatives. Aiming to identify the fewer amount and the optimal DOTA-linker structure that provides quantitative labeling yields, diverse DOTA-linker systems were conjugated in different amounts to HPMA homopolymers to coordinate trivalent radiometals Me(III)* = gallium-68, scandium-44, and lutetium-177. Results Short linkers and as low as 1.6% DOTA were enough to obtain labeling yields > 90%. Alkoxy linkers generally exhibited lower labeling yields than alkane analogues despite of similar chain length and DOTA incorporation rate. High sta…

Synthesis, characterization, and hierarchical organization of tungsten oxide nanorods: spreading driven by Marangoni flow.

Tungsten oxide nanorods were synthesized by a soft chemistry approach using tungsten alkoxide and trioctyl amine and oleic acid as the surfactants. The optical properties of the nanorods were studied. The nanorods were found to be soluble in a wide range of solvents like chloroform, cyclohexane, and so on. Upon solvent evaporation, the nanorods formed hierarchically organized solid state structures. Depending on the solvent used, the nanorods organized in different mesostructures. Moreover, the organization of the nanorods from mixtures of polar and nonpolar solvents was studied. Here, the Marangoni effect resulting from differences in the surface tensions of the two solvents was found to p…

A Deeper Insight into the Postpolymerization Modification of Polypenta Fluorophenyl Methacrylates to Poly(N -(2-Hydroxypropyl) Methacrylamide)

This work provides a detailed insight into the synthesis of N-(2-hydroxypropyl)methacrylamide (HPMA) polymers employing the activated ester approach. In this approach, polypenta fluorophenyl methacrylate (PFPMA)-activated ester polymers are synthesized by the reversible addition-fragmentation chain transfer (RAFT) polymerization and transferred into HPMA-based systems by the use of 2-hydroxypropylamine. To prove quantitative conversion in the absence of side reactions, special attention is devoted to investigate different reaction conditions by different analytical methods ((1) H, (19) F, inverse-gated (13) C NMR, and zeta potential measurements). Furthermore the influence of common solvent…

Surfactant-Free Emulsion Polymerization of Various Methacrylates: Towards Monodisperse Colloids for Polymer Opals

A systematic investigation of the surfactant-free emulsion polymerization (SFEP) on three different methacrylates (MMA, tert-butyl methacrylate and 2,2,2-trifluoro ethyl methacrylate) is described to obtain monodisperse colloids for the preparation of artificial polymer opals. The experimental results are in agreement with a model, in which seed particles are formed very early during the polymerization process. The particles are formed very early during the polymerization process. The particles grow afterwards into the colloids until all monomer is consumed. This gives rise to a linear relationship between the volume of the colloids and the ratio of monomer to water in the reaction batch. T…

Suppression of electron trapping by quantum dot emitters using a grafted polystyrene shell

A fundamental problem of adding chromophores to an organic host is that their smaller band gap leads to severe trapping of either electrons or holes, resulting in strongly unbalanced transport. We demonstrate that electron trapping by an inorganic quantum dot (QD) in a conjugated polymer host can be suppressed by functionalizing its shell with a thin insulating polystyrene layer. The polystyrene shell not only reduces trapping, but also suppresses detrapping of captured electrons, resulting in increased charging of the QDs with subsequent voltage scans, after initial charging, a red-emitting hybrid polymer:QD light-emitting diode is obtained with voltage independent electroluminescence spec…

Reversible Physical Network Stabilized Ferroelectric Liquid Crystals

Liquid Crystalline Elastomers

Today, material science is directed towards the development of multifunctional and oriented structures. One example of such supramolecular systems are liquid crystalline (LC) elastomers which combine the properties of LC phases (the combination of order and mobility) with rubber elasticity, one of the most typical polymer properties. Their most outstanding characteristic is their mechanical orientability; strains as small as 20% are enough to obtain a perfectly oriented LC monodomain. This orientability, if LC elastomers with chiral phases are used, leads, for example, to elastomers with chiral smectic C* phases which are likely to show piezo-electric behavior.

Synthesis of Heterotelechelic α,ω Dye-Functionalized Polymer by the RAFT Process and Energy Transfer between the End Groups

The synthesis of a vinyl polymer with two different fluorescent dye end groups using reversible addition-fragmentation chain transfer (RAFT) polymerization is described. Use of a pentafluorophenyl (PFP) activated ester chain transfer agent (CTA) provided a polymer with an R end group that was reactive toward amines and a dithioester ω end group. The R PFP ester was amidated with Oregon Green Cadaverin. This did not harm the ω dithioester, which was subsequently aminolyzed with an excess of n-propylamine in the presence of Texas Red-2-sulfonamidoethyl methanethiosulfonate, resulting in a disulfide bond connecting the second dye to the polymer chain. Excess dyes and side products were removed…

RAFT-polymerized poly(hexafluoroisopropyl methacrylate)s as precursors for functional water-soluble polymers

Post-polymerization modification of well-defined precursor polymers is a versatile tool to obtain multifunctional water-soluble polymers that cannot be synthesized by common polymerization techniques. For the first time, 1,1,1,3,3,3-hexafluoroisopropyl methacrylate (HFIPMA) based homo and block copolymers were synthesized via RAFT polymerization to provide precise precursors for the post-polymerization modification of the 1,1,1,3,3,3-hexafluoroisopropyl ester side chains with water-soluble amines (methoxy tri(ethylene glycol) amine, 2-hydroxypropyl amine and 3-(dimethylamino)-1-propylamine). Sequential aminolysis using Oregon Green cadaverine first followed by 2-hydroxypropyl amine enables …

HPMA-Based Nanoparticles for Fast, Bioorthogonal iEDDA Ligation

Contains fulltext : 216143.pdf (Publisher’s version ) (Open Access) Fast and bioorthogonally reacting nanoparticles are attractive tools for biomedical applications such as tumor pretargeting. In this study, we designed an amphiphilic block copolymer system based on HPMA using different strategies to introduce the highly reactive click units 1,2,4,5-tetrazines (Tz) either at the chain end (Tz-CTA) or statistical into the hydrophobic block. This reactive group undergoes a rapid, bioorthogonal inverse electron-demand Diels-Alder reaction (iEDDA) with trans-cyclooctenes (TCO). Subsequently, this polymer platform was used for the preparation of different Tz-covered nanoparticles, such as micell…

Quantum dot-block copolymer hybrids with improved properties and their application to quantum dot light-emitting devices.

To combine the optical properties of CdSe@ZnS quantum dots (QDs) with the electrical properties of semiconducting polymers, we prepared QD/polymer hybrids by grafting a block copolymer (BCP) containing thiol-anchoring moieties (poly(para-methyl triphenylamine-b-cysteamine acrylamide)) onto the surfaces of QDs through the ligand exchange procedure. The prepared QD/polymer hybrids possess improved processability such as enhanced solubility in various organic solvents as well as the film formation properties along with the improved colloidal stability derived from the grafted polymer shells. We also demonstrated light-emitting diodes based on QD/polymer hybrids, exhibiting the improved device …

Precursor Polymers for the Carbon Coating of Au@ZnO Multipods for Application as Active Material in Lithium-Ion Batteries

The synthesis of statistical and block copolymers based on polyacrylonitrile, as a source for carbonaceous materials, and thiol-containing repeating units as inorganic nanoparticle anchoring groups is reported. These polymers are used to coat Au@ZnO multipod heteroparticles with polymer brushes. IR spectroscopy and transmission electron microscopy prove the successful binding of the polymer onto the inorganic nanostructures. Thermogravimetric analysis is applied to compare the binding ability of the block and statistical copolymers. Subsequently, the polymer coating is transformed into a carbonaceous (partially graphitic) coating by pyrolysis. The obtained carbon coating is characterized by…

72/74As-labeling of HPMA based polymers for long-term in vivo PET imaging

Abstract In the context of molecular imaging, various polymers based on the clinically approved N-(2-hydroxypropyl)-methacrylamide (HPMA) have been radio-labeled using longer-living positron emitters 72As t1/2 = 26 h or 74As t1/2 = 17.8 d. This approach may lead to non-invasive determination of the long-term in vivo fate of polymers by PET (positron emission tomography). Presumably, the radio label itself will not strongly influence the polymer structure due to the fact that the used nuclide binds to already existing thiol moieties within the polymer structure. Thus, the use of additional charges or bulky groups can be avoided.

Self-assembled three-dimensional inverted photonic crystals on a photonic chip

Three dimensional photonic crystals (PhCs) exhibiting a full photonic band gap have high potential in optical signal processing and detector applications. However, the challenges in the integration of the 3D PhCs into photonic circuits have so far hindered their exploitation in real devices. This article demonstrates the fabrication of 3D PhCs exploiting the capillary directed self-assembly (CDSA) of monodisperse colloidal silica spheres, their inversion to silicon shells, and integration with silicon waveguides. The measured transmission characteristics agree with numerical predictions and provide strong indication of a full photonic band gap in the inverted 3D photonic crystals at wavelen…

Micromoulding of three-dimensional photonic crystals on silicon substrates

International audience; The growth of three-dimensional photonic crystals (PhCs) on patterned silicon substrates is reported. It is shown that deep trenches can be uniformly filled by a self-assembly of polymer microspheres, in a close-packed face-centred cubic lattice. The crystalline quality is compared for different channel widths. These observations are confirmed by optical reflectance measurements in the visible range, showing a bandwidth of enhanced reflection. The possibility to detach the PhC, i.e. to use the substrate as a mould, is also demonstrated. The potential of this approach for building PhC-based complex architectures is discussed.

Ferroelectric liquid-crystalline elastomers

Emission of Rhodamine B in PMMA opals for luminescent solar concentrators

In conventional luminescent solar concentrators (LSC) incident light is absorbed by luminophores and emitted isotropically. Most of the emitted light is trapped inside the LSC by total internal reflection and guided to solar cells at the edges. Light emitted towards the surfaces, however, is lost in the escape cone. Furthermore, when the luminophore emits light in its absorption range, light is lost due to reabsorption. To overcome these losses, we embed the luminescent material in photonic structures to influence the emission characteristics. Directional and spectral redistribution of emission is supposed to enhance the light guiding in LSCs and reduce reabsorption losses. For this purpose…

Directing the self-assembly of semiconducting copolymers: the consequences of grafting linear or hyperbranched polyether side chains.

The synthesis and self-assembly of novel semiconducting rod-coil type graft block copolymers based on poly(para-phenylene vinylene) (PPV) copolymers is presented, focusing on the ordering effect of linear versus hyperbranched side chains. Using an additional reactive ester block, highly polar, linear poly(ethylene glycol), and hyperbranched polyglycerol side chains are attached in a grafting-to approach. Remarkably, the resulting novel semiconducting graft copolymers with polyether side chains show different solubility and side-chain directed self-assembly behavior in various solvents, e.g., cylindrical or spherical superstructures in the size range of 10 to 120 nm, as shown by TEM. By adju…

Degradable cationic nanohydrogel particles for stimuli-responsive release of siRNA.

Well-defined nanogels have become quite attractive as safe and stable carriers for siRNA delivery. However, to avoid nanoparticle accumulation, they need to provide a stimuli-responsive degradation mechanism that can be activated at the payload's site of action. In this work, the synthetic concept for generating well-defined nanohydrogel particles is extended to incorporate disulfide cross-linkers into a cationic nanonetwork for redox-triggered release of oligonucleotide payload as well as nanoparticle degradation under reductive conditions of the cytoplasm. Therefore, a novel disulfide-modified spermine cross-linker is designed that both allows disassembly of the nanogel as well as removal…

P(HPMA)-block-P(LA) copolymers in paclitaxel formulations: Polylactide stereochemistry controls micellization, cellular uptake kinetics, intracellular localization and drug efficiency

In order to explore the influence of polymer microstructure and stereochemistry in biological settings, the synthesis, micellization, cellular fate and the use in paclitaxel formulations of poly(N-(2-hydroxypropyl)-methacrylamide)-block-poly(L-lactide) (P(HPMA)-block-P(LLA)) and poly(N-(2-hydroxypropyl)-methacrylamide)-block-poly(DL-lactide) block copolymers (P(HPMA)-block-P(DLLA)) were studied. To this end, P(HPMA)-block-P(lactide) block copolymers and their fluorescently labeled analogues were synthesized. The polymers exhibited molecular weights M-n around 20,000 g/mol with dispersities (D=M-w/M-n) below 1.3. In addition, the solution conformation of this new type of partially degradable…

Giant lateral electrostriction in ferroelectric liquid-crystalline elastomers

Mechanisms for converting electrical energy into mechanical energy are essential for the design of nanoscale transducers, sensors, actuators, motors, pumps, artificial muscles, and medical microrobots. Nanometre-scale actuation has to date been mainly achieved by using the (linear) piezoelectric effect in certain classes of crystals (for example, quartz), and 'smart' ceramics such as lead zirconate titanate. But the strains achievable in these materials are small--less than 0.1 per cent--so several alternative materials and approaches have been considered. These include grafted polyglutamates (which have a performance comparable to quartz), silicone elastomers (passive material--the constri…

Photonic Crystals from Core-Shell Colloids with Incorporated Highly Fluorescent Quantum Dots

We report the preparation of nanoscaled PS/PMMA core-shell spheres with highly fluorescent CdS/ZnS coated CdSe quantum dots (QDs) integrated in the core. Core-shell spheres of different diameters have been self-assembled to colloidal photonic crystals (PCs) with photonic stop bands located in the visible range of the electromagnetic spectrum. For the synthesis of the core, a modified miniemulsion polymerization has been used; the shell was prepared by a newly developed core-shell polymerization. The CdSe QDs embedded in the core were coated with the higher band gap semiconductor materials CdS and ZnS in a successive ion layer adsorption reaction (SILAR) keeping up the light-emitting propert…

Orientation and Dynamics of ZnO Nanorod Liquid Crystals in Electric Fields.

ZnO nanorod polymer hybrids (i.e., ZnO nanorods coated with a block copolymer with a short anchor block (dopamine) and a longer solubilizing block of polystyrene (PS)) form liquid crystalline (LC) phases if they are dispersed at high concentration e.g., in a PS oligomer matrix. Due to the high mobility of the low T(g)-matrix the nanorod polymer hybrids show a switching behavior under an applied AC electric field. Hence, the orientation of the nanorod mesogens can be changed from planar (parallel to the substrate) to homeotropic (perpendicular) in full analogy to the switching of low molecular liquid crystals in an electric field. Dielectric measurements show that such a switching is mainly …

Modifying the body distribution of HPMA-based copolymers by molecular weight and aggregate formation.

There is a recognized need to create well-defined polymer probes for in vivo and clinical positron emission tomography (PET) imaging to guide the development of new generation polymer therapeutics. Using the RAFT polymerization technique in combination with the reactive ester approach, here we have synthesized well-defined and narrowly distributed N-(2-hydroxypropyl)methacrylamide homopolymers (pHPMA) (P1* and P2*) and random HPMA copolymers consisting of hydrophilic HPMA and hydrophobic lauryl methacrylate comonomers (P3* and P4*). The polymers had molecular weights below (P1* and P3*) and above the renal threshold (P2* and P4*). Whereas the homopolymers dissolve in isotonic solution as in…

Design, Synthesis, and Use of Y-Shaped ATRP/NMP Surface Tethered Initiator.

Heterogeneous polymer brushes on surfaces can be easily formed from a binary initiator on a silicon oxide substrate where two different types of polymers can be grown side-by-side. Herein, we designed a new Y-shaped binary initiator using straightforward chemistry for “grafting from” polymer brushes. This initiator synthesis takes advantage of the Passerini reaction, a multicomponent reaction combining two initiator sites and one surface linking site. This Y-shaped binary initiator can be synthesized in three steps with a higher yield than other similar initiators reported in the literature, and can be performed on a multigram scale. We were able to attach the initiator to a silicon oxide s…

Photo-crosslinking in freely-suspended films of ferroelectric lc-polymers

Polymeric Nanoparticles with Neglectable Protein Corona

Small : nano micro 16(18), 1907574 (2020). doi:10.1002/smll.201907574

Liquid crystalline phases from polymer functionalized ferri-magnetic Fe3O4nanorods

Here, we present the surface functionalization of anisotropic in form ferri-magnetic Fe3O4-nanorods (NRs) with a diblock copolymer, having a PMMA- or PDEGMEMA-block, for solubilization, and a dopamine anchor block. These polymers were synthesized through RAFT polymerization via a macro-initiator approach. The successful surface functionalization, performed via a grafting-to method, was monitored using TGA, IR and TEM measurements. The NRs were very soluble in organic solvents after functionalization. Afterwards, the liquid crystalline (LC) behavior was investigated. During solvent evaporation, birefringent domains were formed. The self-assembly into lyotropic LC structures could be observed…

Functionalization of TiO2Nanoparticles with Semiconducting Polymers Containing a Photocleavable Anchor Group and Separation via Irradiation Afterward

The controlled radical polymerization (RAFT polymerization) of semiconducting polymers based on poly(4,4′-dimethyl-triphenylamine) is described. These polymers are afterward end-functionalized with a photocleavable group and an anchor unit (catechol) for oxidic nanoparticles (NPs). Serving as a reference, polystyrene oligomers with the same end groups are also synthesized. Using these polymers allows functionalization of the TiO2-NPs, leading to an improved solubility and miscibility in organic solvents or polymer matrices. Irradiation in the UV region is used to split the photocleavable group and remove the polymer chains from the NPs, which leads to their aggregation.

Overcoming the PEG-addiction: well-defined alternatives to PEG from structure-property relationships to better defined therapeutics

Synthetic methods in polymer chemistry have evolved tremendously during the last decade. Nowadays more and more attention is devoted to the application of those tools in the development of the next generation of nanomedicines. Nevertheless, poly(ethylene glycol) (PEG) remains the most frequently used polymer for biomedical applications. In this review, we try to summarize recent efforts and developments in controlled polymerisation techniques that may allow alternatives to PEG based systems and can be used to improve the properties of future polymer therapeutics.

Liquid Crystals from Polymer-Functionalized TiO2 Nanorod Mesogens

In this work, we functionalized TiO2 nanorods with dopamine-functionalized diblock copolymers. After functionalization, they are well dispersible in organic solvents. Light scattering proves that t...

Non-ionic photo-acid generators for applications in two-photon lithography

Non-ionic photoacid generators (PAGs) have been designed and synthesized for use in two-photon lithography (TPL). The chromophores in these new PAGs are covalently linked to the photocleavable group by a flexible joint. Their thermal stability, solubility and efficiency to produce acid under both one- and two-photon excitation were characterized. The potential of these PAGs for TPL was tested in two negative-tone resist systems relying on different mechanisms: free-radical/cationic polymerization or a cationically initiated cross-linking reaction. These PAGs needed lower threshold power for polymerization compared to a commercially available photoinitiator, isopropylthioxanthone, and a phot…

Liquid Crystalline Phases from Polymer-Functionalized TiO2 Nanorods

LC-Polymers with Axial Chirality

Abstract Liquid crystalline polymers with axial chirality are prepared. These polymers are chiral, not due to a single asymmetric carbon atom, but due to a larger molecular fragment, which is chiral as a whole. They exhibit cholesteric and chiral smectic C* phases. Dielectric spectroscopy proves strong ferroelectric properties in the chiral smectic C* phases of these polymers.

Influence of a Crosslinker Containing an Azo Group on the Actuation Properties of a Photoactuating LCE System

Photoactuating liquid crystalline elastomers (LCE) are promising candidates for an application as artificial muscles in microdevices. In this work, we demonstrate that by optimizing (1) the illumination conditions and (2) the mixture of azo monomer and azo crosslinker, thick films of an all-azo LCE can be prepared, which show a strong length change without bending during photoactuation. This becomes possible by working with white light (about 440 nm), whose absorption is low, leading to a large penetration depth. By adding an azo crosslinker to a previously prepared system, several improvements of the actuation properties—like a stronger photoactuation at lower operational temperatures—coul…

Noise-Assisted Crystallization of Opal Films

International audience; An improvement of the crystal quality of opal fi lms self-assembled from polymer spheres in a moving meniscus using the agitation by white noise acoustic vibrations is demonstrated. A tenfold higher ordering of a hexagonal sphere packing in the (111) plane is achieved. This crystallization method, the mechanism of which is described in terms of the stochastic resonance, is a contrast to the widely used approach based on maintaining equilibrium conditions during the crystallization process. The precise quantifi cation of the incremental lattice order improvement as a function of acoustic noise intensity is achieved by calculating the probability of finding an opposite…

Tuning the Properties of Photonic Films from Polymer Beads by Chemistry

This paper describes the preparation of monodisperse colloids from various methacrylates. These colloids sediment well on glass slides and formin the dried statelarge three-dimensional face-centered cubic photonic crystal films with Bragg reflection in the visible region. Depending on crystallization conditions, the domain sizes vary between 50 and 300 μm. By cross-linking the polymer within the colloids, it is possible to increase the thermal stability of the polymeric photonic structure tremendously (up to 1 h at 200 °C). These photonic structures soften above Tg (rubbery photonic structure), but they cannot fuse. Cross-linked colloids from poly(tert-butyl methacrylate) can either thermal…

Poly-l-Lysine-Poly[HPMA] Block Copolymers Obtained by RAFT Polymerization as Polyplex-Transfection Reagents with Minimal Toxicity

Herein we describe the synthesis of poly-L-lysine-b-poly[N-(2-hydroxypropyl)-metha-crylamide)] (poly[HPMA]) block copolymers by combination of solid phase peptide synthesis or polymerization of α-amino acid-N-carboxy-anhydrides (NCA-polymerization) with the reversible addition-fragmentation chain transfer polymerization (RAFT). In the presence of p-DNA, these polymers form polyplex micelles with a size of 100-200 nm in diameter (monitored by SDS-PAGE and FCS). Primary in vitro studies with HEK-293T cells reveal their cellular uptake (FACS studies and CLSM) and proof successful transfection with efficiencies depending on the length of polylysine. Moreover, these polyplexes display minimal to…

From LC‐polymers to Nanomedicines: Different Aspects of Polymer Science from a Materials Viewpoint

Inverted-opal photonic crystals for ultra light-trapping in solar cells

We investigated a three dimensional inverted opal having the potential to notably increase light-trapping in solar cells. The 3D photonic crystal top layer is an angle- and direction-selective filter, which decreases the acceptance cone of the solar cell. Numerical optimisation methods are used to verify the optical and electrical properties for a large angluar and energy spectrum for a system consisting of an inverted opal on top of a thin crystalline silicon solar cell. It is numerically shown that an inverted opal grown in the Τ - Xdirection might fulfill the requirement for such a filter. An estimate for the theoretically achievable efficiency for nonconcentrated light is presented that…

MEMS analogous micro-patterning of thermotropic nematic liquid crystalline elastomer films using a fluorinated photoresist and a hard mask process

In this work, we present a method to pattern liquid crystal elastomers (LCEs) in the micrometer range without using any mechanical processing steps to prepare micron sized LCE actuators compatible with microelectromechanical system (MEMS) technology. Multi-layer spin-coating processes are developed to synthesise and structure 300–3500 nm thick LCE films. A water soluble sacrificial layer, a photoalignment layer and a LCE formulation, which is polymerised and crosslinked in its liquid crystal phase, are spin-coated successively onto a substrate. A fluorinated photoresist layer is used to structure LCE films with thicknesses up to 700 nm in a photolithographic and etching process. For thicker…

Der Einfluß von Trichlormethan auf die δ-Relaxation eines kristallin-flüssigen Seitenkettenpolymers

Dielektrische Untersuchungen an flussig-kristallinen Polymeren, in denen die Flussigkristalleinheit in der Seitenkette angeordnet ist, wurden von 10 Hz bis 100 kHz bei unterschiedlichen Temperaturen durchgefuhrt. Es konnte gezeigt werden, das sowohl die Relaxationsfrequenz als auch die Geometrie der Absorptionskurven der δ-Relaxation (Reorientierung der Seitenkette infolge der segmentalen Beweglichkeit der Hauptkette) durch Zugabe von Trichlormethan verandert werden. Trichlormethan wirkt als Weichmacher. Bei langerer Lagerung verdunstet das Trichlormethan und die molekulare Beweglichkeit vermindert sich. Dielectric investigations on liquid-crystalline polymers with the liquid crystal unit p…

De Vries smectic A phase formed by a liquid crystal side chain copolymer? A13C NMR study

We study the orientation and order parameter of a liquid crystalline random side chain copolymer by 13C NMR. Evidence has previously been presented that this material forms a de Vries smectic A phase. The NMR data show that the molecular tilt angle in the smectic A phase is very small or zero and the smectic A–smectic C* transition is attributed predominantly to a change of the molecular tilt rather than azimuthal ordering. We discuss the NMR results in the context of earlier X‐ray and elastic characterizations of structurally similar materials.

Solubilisation of multi walled carbon nanotubes by alpha-pyrene functionalised PMMA and their liquid crystalline self-organisation.

alpha-Pyrene functionalised poly(methyl methacrylate) (PMMA) chains were synthesised by RAFT polymerisation and found to be highly efficient to solubilise and disentangle multi walled carbon nanotubes that can now self-organise as liquid crystalline phases in PMMA and PEG 400 matrices.

Light Propagation in Heterogeneous Opal-Based Photonic Crystals

Ballistic light propagation in the heterogeneous photonic crystals based on the thin triple-film opal have been studied in the wavelength range of low order photonic bandgaps. Since the scattered light experiences the diffraction attenuation, the spectra and the angle diagrams of the transmitted and forward scattered light have been used to identify the effect of heterostructuring.

Linear-Hyperbranched Graft-Copolymers via Grafting-to Strategy Based on Hyperbranched Dendron Analogues and Reactive Ester Polymers

The synthesis of hyperbranched polyglycerol dendron analogues with precisely one focal amino functionality (H2N-hbPG) and their use for the synthesis of linear-hyperbranched graft-copolymers in a grafting-to approach is reported. By use of N,N-dibenzyl tris(hydroxylmethyl) aminomethane as a novel initiator for the ring-opening multibranching polymerization of glycidol, dendron analogues with one focal amino functionality of molecular weights ranging from 500 to 15000 g mol–1 and narrow to moderate polydispersities (Mw/Mn = 1.2–1.9) were synthesized, as confirmed by NMR and SEC. After removal of the benzyl protective groups, the accessibility and selective transformation of the focal amino g…

Cover Picture: Macromol. Mater. Eng. 2/2004

Microactuators: Control of the Properties of Micrometer Sized Actuators from Liquid Crystalline Elastomers Prepared in a Microfluidic Setup (Adv. Funct. Mater. 24/2010)

In this article new results on the preparation of monodisperse particles from a liquid crystalline elastomer in a microfluidic setup are presnted. For this, droplets from a liquid crystalline monomer are prepared in a microfluidic device and polymerized while they are flowing inside a microtube. The parti­cles obtained by this method possess an internal orientation, which gives them actuating properties. When they are heated into the isotropic phase of the liquid crystalline material they show a reversible change in shape whereby they change their length in one direction by almost 100%. It is shown how the variation of experimental parameters during their synthesis impacts the properties of…

A minimal hydrophobicity is needed to employ amphiphilic p(HPMA)-co-p(LMA) random copolymers in membrane research.

Because a polymer environment might be milder than a detergent micelle, amphiphilic polymers have attracted attention as alternatives to detergents in membrane biochemistry. The polymer poly[N-(2-hydroxypropyl)-methacrylamid] [p(HPMA)] has recently been modified with hydrophobic lauryl methacrylate (LMA) moieties, resulting in the synthesis of amphiphilic p(HPMA)-co-p(LMA) polymers. p(HPMA)-co-p(LMA) polymers with a LMA content of 5 or 15% have unstable hydrophobic cores. This, on one hand, promotes interactions of the hydrophobic LMA moieties with membranes, resulting in membrane rupture, but at the same time prevents formation of a hydrophobic, membrane mimetic environment that is suffici…

Living Light-Induced Crystallization-Driven Self-Assembly for Rapid Preparation of Semiconducting Nanofibers.

Well-defined nanostructures composed of conjugated polymers have attracted significant attention due to their intriguing electronic and optical properties. However, precise control of the size and uniformity of these semiconducting nanostructures is still rare and challenging, despite recent advances in strategies to obtain self-assembled nanostructures with narrow dispersions. Herein, we demonstrate the preparation of fluorescent conjugated block copolymers by one-shot polymerization and rapid formation of nanofibers in a few minutes via light-induced crystallization-driven self-assembly, driven by facile cis-to- trans photoisomerization of its poly( p-phenylenevinylene) blocks. Furthermor…

Transparent conductive oxide photonic crystals on textured substrates

Three-dimensional ZnO:Al photonic crystals were fabricated by atomic layer deposition on highly textured substrates. It turns out that these inverted opals consist of a thin intermediate disordered layer close to the textured substrate followed by a highly-ordered photonic crystal layer. The photonic crystals themselves exhibit comparable optical properties to those on planar substrates.

Cover Picture: Macromol. Chem. Phys. 17/2004

Aggregation behavior of cationic nanohydrogel particles in human blood serum.

For systemic siRNA delivery applications, well-defined drug carriers are required that guarantee stability for both carrier and cargo. Among various concepts progressing in market or final development, cationic nanohydrogel particles may serve as novel transport media especially designed for siRNA-in vivo experiments. In this work, the interaction of nanohydrogel particles with proteins and serum components was studied via dynamic light scattering in human blood serum as novel screening method prior to applications in vivo. The formation of larger aggregates mostly caused by charge interaction with albumin could be suppressed by nanogel loading with siRNA affording a neutral zeta potential …

Polymeric Selectin Ligands Mimicking Complex Carbohydrates: From Selectin Binders to Modifiers of Macrophage Migration

Novel polymeric cell adhesion inhibitors were developed in which the selectin tetrasaccharide sialyl-LewisX (SLeX ) is multivalently presented on a biocompatible poly(2-hydroxypropyl)methacrylamide (PHPMA) backbone either alone (P1) or in combination with O-sulfated tyramine side chains (P2). For comparison, corresponding polymeric glycomimetics were prepared in which the crucial "single carbohydrate" substructures fucose, galactose, and sialic acid side chains were randomly linked to the PHPMA backbone (P3 or P4 (O-sulfated tyramine)). All polymers have an identical degree of polymerization, as they are derived from the same precursor polymer. Binding assays to selectins, to activated endo…

Tunable defects in colloidal photonic crystals

We present a bottom-up approach for the construction of tunable functional defects in colloidal photonic crystals (CPCs). These structures incorporate polyelectrolyte multilayer (PEM) planar defects embedded in silica CPCs through a combination of evaporation induced self-assembly and microcontact transfer printing. We show how the enormous chemical diversity inherent to PEMs can be harnessed to create chemically active defect structures responsive to solvent vapor pressures, light, temperature as well as redox cycling. A sharp transmission state within the photonic stopband, induced by the PEM defect, can be precisely, reproducibly and in some cases reversibly tuned by these external stimu…

Back Cover: Macromol. Biosci. 10/2014

Size-dependent knockdown potential of siRNA-loaded cationic nanohydrogel particles.

To overcome the poor pharmacokinetic conditions of short double-stranded RNA molecules in RNA interference therapies, cationic nanohydrogel particles can be considered as alternative safe and stable carriers for oligonucleotide delivery. For understanding key parameters during this process, two different types of well-defined cationic nanohydrogel particles were synthesized, which provided nearly identical physicochemical properties with regards to their material composition and resulting siRNA loading characteristics. Yet, according to the manufacturing process using amphiphilic reactive ester block copolymers of pentafluorophenyl methacrylate (PFPMA) and tri(ethylene glycol)methyl ether m…

The effect of band gap alignment on the hole transport from semiconducting block copolymers to quantum dots

Semiconducting hole transporting block copolymers were chemically modified to adjust their energy levels to that of CdSe/CdS/CdZnS red quantum dots. Hybrids with optimized energy levels could be used to build strongly improved quantum dot based LEDs (QLEDs).

Engineering Polymer Microparticles by Droplet Microfluidics

Capillary-based flow-focusing and co-flow microsystems were developed to produce sphere-like polymer microparticles of adjustable sizes in the range of 50 to 600 μm with a narrow size distribution (CV < 5%) and different morphologies (core-shell, janus, and capsules). Rod-like particles whose length was conveniently adjusted between 400 μm and few millimeters were also produced using the same microsystems. Influence of operating conditions (flow rate of the different fluid, microsystem characteristic dimensions, and design) as well as material parameters (viscosity of the different fluids and surface tension) was investigated. Empirical relationships were thus derived from experimental data…

Reductive Decationizable Block Copolymers for Stimuli-Responsive mRNA Delivery

Messenger ribonucleic acids (mRNAs) are considered as promising alternatives for transient gene therapy, but to overcome their poor pharmacokinetic properties, smart carriers are required for cellular uptake and stimuli-responsive release. In this work, a synthetic concept toward reductive decationizable cationic block copolymers for mRNA complexation is introduced. By combination of RAFT block copolymerization with postpolymerization modification, cationic block copolymers are generated with disulfide-linked primary amines. They allow effective polyplex formation with negatively charged mRNA and subsequent release under reductive conditions of the cytoplasm. In first in vitro experiments w…

LC Ionomers with Phosphonate Groups and Their Multilayer Build-Up

This paper describes the synthesis of new liquid-crystalline (LC) ionomers (semiflexible LC mainchain polymers with ionic groups as side groups) by polycondensation of substituted malonates with mesogenic diols. Phosphonic acids were used as negative groups, and phosphonium and ammonium ions as positive groups. The presence of these ionic groups leads to gelation (physical crosslinking) of the polymers, which display a rubbery consistency. As expected from the reference polymers without an ionic group, all polymers show smectic phases. These phases are destabilized by bulky side groups (e.g., phosphonium ions or phosphonic acid esters). They are, however, stabilized by phosphonic acid group…

CpG-DNA loaded multifunctional MnO nanoshuttles for TLR9-specific cellular cargo delivery, selective immune-activation and MRI

Initiation of pathways that lead to a proliferation and chemoresistance by Toll-like receptors (TLRs) are an important factor in cancer progression. Multifunctional magnetic nanoparticles equipped with a pathogen-derived ligand (CpG) functioning as TLR agonists were used to show the impact of immune activation on human HNSCC (head and neck squamous cell carcinoma) cells. The response of human cancer cells to TLR signaling is linked to tumor biology. The magnetic MnO nanoparticles were coated with a multifunctional polymer, displaying no cytotoxicity and being able to enter cells while carrying foreign DNA (unmethylated CpG) to recognize intracellular TLR9. Both the particle and the nucleic …

Light induced charging of polymer functionalized nanorods.

ZnO nanorods were functionalized with new block copolymers containing a hole transporting moiety in one block and a dye and an anchor system in the second block. After functionalization, the ZnO nanorods are well dispersible in organic media and the fluorescence of the dye is quenched. Kelvin probe force microscopy was used to measure changes in electrical potential between the ZnO nanorod and the polymeric corona. Upon light irradiation, potential changes on the order of some tens of millivolts were observed on individual structures. This effect is attributed to light-induced charge separation between the ZnO nanorod and its hole transporting polymeric corona.

Microfluidic Synthesis of Highly Shape-Anisotropic Particles from Liquid Crystalline Elastomers with Defined Director Field Configurations

In this article, we present the synthesis of highly shape-anisotropic, micrometer-sized particles from liquid crystalline elastomers, which have the ability to reversibly change their shape in response to a certain external stimulus. For their preparation, we utilized a microfluidic setup. We succeeded in preparing sets of particles with differing degrees of shape anisotropy in their ground state including highly anisotropic fiber-like objects. All samples produced movement during the phase transition from the nematic to the isotropic phase of the liquid crystal. Depending on the direction of this shape change, we classified the samples in two groups. One type showed a contraction, while th…

Optical suppression of ferroelectricity in polysiloxane copolymers with chiral and photochromic side groups

The ferroelectricity of surface-stabilized aligned films of polysiloxane copolymers containing chiral esters and photochromic azobenzene moieties within the side groups is suppressed on UV irradiation and is rebuilt on visible irradiation. The liquid crystalline polymer (Sc* 64 SA 80 i) shows ferroelectric behavior below 64°C. The photoinduced modification of supramolecular order and the corresponding changes in its dynamics are studied by polarized UV/vis spectroscopy and broad band dielectric spectroscopy (10−2–105 Hz). The dielectric measurements show that UV irradiation causes a loss of ferroelectricity within an interval of 10 K below the phase transition temperature. The photochemical…

Transmission anisotropy in triple-film opal photonic crystals

Summary form only given: For photonic crystals (PhCs) to have successful impact on advancement of optical circuits and realisation of various functionalities, the incorporation of artificial defects into 3D PhCs is necessary. Opal films represent a convenient approach to the realisation of 3D PhCs. Taking into account the limited flexibility of the self-assembly, the first steps can be studies of planar defects in opals and hetero-opals. Characterisation of heteroPhCs should include the investigation of the dispersion of photonic bandgaps (PBG). While the dispersion of low-order PBGs in opal films is well known, the high order PBGs were hardly studied so far owing to high requirements to th…

Functionalization of P3HT with Various Mono- and Multidentate Anchor Groups

Due to its favorable optoelectronic properties and the accessibility via Grignard metathesis (GRIM) polymerization, poly(3-hexylthiophene) (P3HT) is one of the most applied conjugated polymers. The ‘living' nature of GRIM polymerization enables the modification of the polymer and the installation of desired properties. In the present study, two versatile approaches for the synthesis of anchor group-modified P3HT have been developed, which enable the functionalization of various inorganic nanoparticles. Depending on the polymerization conditions, mono- and bifunctional ethynyl-terminated P3HT or solely monofunctionalized aldehyde-terminated P3HT was synthesized. Afterwards, the quantitative …

Ferroelectric block copolymers

A block copolymer consisting of polystyrene and a side chain ferroelectric liquid crystalline polymer was synthesized using polymer analogous chemistry on a monodisperse poly(styrene-b-isoprene). Composition was adjusted to give lamellar microstructure after addition of the mesogenic side groups. If placed in an LC cell without orientation of domains, no ferroelectric response was observed. After shearing the thin film, presumably due to alignment of lamellae, a bistable ferroelectric switching could be detected.

Photosensitive functionalized surface-modified quantum dots for polymeric structures via two-photon-initiated polymerization technique.

In this paper, the surface modification of CdSe- and CdZnS-based quantum dots (QDs) with a functional silica shell is reported. Functionalized silica shells are prepared by two routes: either by ligand exchange and a modified Stober process or by a miniemulsion process with amphiphilic poly(oxyethylene) nonylphenylether also know as Igepal CO-520 (IG) as oligomeric amphiphile and modified silica precursors. The polymerizable groups on the functionalized silica shell allow covalent bonding to a polymer matrix and prevent demixing during polymerization and crosslinking. This allows the homogeneous incorporation of QDs in a crosslinked polymer matrix. This paper furthermore demonstrates that t…

Fourier-transform infrared study of the switching process in a ferroelectric liquid crystalline polymer

The implementation of the step-scan technique on our spectrometer enabled us to follow the electric field induced reorientation dynamics of different molecular segments of the ferroelectric liquid crystalline polymer [Si(Me)(R)O/Si(Me)(R')O/Si(Me) 2 O] n (R= (CH 2 ) 11 OPhCOOPhOCO * CHCl * CH(Me)(Et); R'= (CH 2 ) 11 OPhN=NPhO * CH(Me)(Hex)) on a sub-millisecond time scale. It was detected that not only the mesogen but also the spacer and at least part of the backbone take part in the reorientation process

Morphology control in biphasic hybrid systems of semiconducting materials.

Simple blends of inorganic nanocrystals and organic (semiconducting) polymers usually lead to macroscopic segregation. Thus, such blends typically exhibit inferior properties than expected. To overcome the problem of segregation, polymer coated nanocrystals (nanocomposites) have been developed. Such nanocomposites are highly miscible within the polymer matrix. In this Review, a summary of synthetic approaches to achieve stable nanocomposites in a semiconducting polymer matrix is presented. Furthermore, a theoretical background as well as an overview concerning morphology control of inorganic NCs in polymer matrices are provided. In addition, the morphologic behavior of highly anisotropic na…

Functional Diblock Copolymers for the Integration of Triboluminescent Materials into Polymer Matrices

This work describes the synthesis and use of new diblock copolymers to integrate functional inorganic particles into a polymer matrix. These diblock copolymers were synthesized by nitroxide-mediated polymerization (NMP) from styrene and two styrene-like monomers with protected functional groups for the later connection to the functional inorganic material. It was possible to keep the polydispersity of the block copolymers around or below 1.2 and to preset the length of the functional block to about 20 monomers or 10 mol-% of monomers. The groups for the surface functionalization (amino groups or chelating ligands) were obtained in their free form by polymer analogous reactions. As an exampl…

P0493 : Selectin-targeting nanoparticles for immunomodulatory therapy of liver diseases

Fast electroclinic switching in a ferroelectric LC-polysiloxane

Ferroelectric polysiloxane liquid crystals with ‘de Vries’-type smectic A*–smectic C* transitions

We report preliminary results of optical and small angle X-ray scattering (SAXS) experiments on the smectic A*−smectic C* transition in two ferroelectric liquid crystalline polysiloxanes. Although the optical tilt angle in the SmC* phases reaches values up to 30°, temperature-dependent SAXS measurements clearly reveal that the smectic layer spacing is basically conserved during the A*–C* transition as well as in the subsequent C* phase. Connected with the A*–C* transition we further observed a significant increase in birefringence, hence reflecting an increase of orientational order. The practical absence of layer shrinkage and the enhanced orientational ordering are consistent with the de …

Liquid-Crystalline Colloidal Particles

Here we report about the synthesis of colloidal particles of nematic and smectic liquid-crystalline polymers. For this purpose mesogen-containing acrylate monomers were synthesized and polymerized in a special modification of a precipitation polymerization called dispection polymerization. By variation of the polymerization conditions colloidal particles of different size and polydispersity could be obtained including very narrowly distributed samples in optimized batches. On azobenzene-containing colloidal particles switching experiments with polarized light were performed. It could be observed that the nematic director of the mesogens within the colloidal particles can be rotated due to t…

Copolymerization of Polythiophene and Sulfur To Improve the Electrochemical Performance in Lithium–Sulfur Batteries

We first report on the copolymerization of sulfur and allyl-terminated poly(3-hexylthiophene-2,5-diyl) (P3HT) derived by Grignard metathesis polymerization. This copolymerization is enabled by the conversion of sulfur radicals formed by thermolytic cleavage of S8 rings with allyl end-group. The formation of a C–S bond in the copolymer is characterized by a variety of methods, including NMR spectroscopy, size exclusion chromatography, and near-edge X-ray absorption fine spectroscopy. The S-P3HT copolymer is applied as an additive to sulfur as cathode material in lithium–sulfur batteries and compared to the use of a simple mixture of sulfur and P3HT, in which sulfur and P3HT were not covalent…

HPMA-Based Nanocarriers for Effective Immune System Stimulation.

The selective activation of the immune system using nanoparticles as a drug delivery system is a promising field in cancer therapy. Block copolymers from HPMA and laurylmethacrylate-co-hymecromone-methacrylate allow the preparation of multifunctionalized core-crosslinked micelles of variable size. To activate dendritic cells (DCs) as antigen presenting cells, the carbohydrates mannose and trimannose are introduced into the hydrophilic corona as DC targeting units. To activate DCs, a lipophilic adjuvant (L18-MDP) is incorporated into the core of the micelles. To elicit an immune response, a model antigen peptide (SIINFEKL) is attached to the polymeric nanoparticle-in addition-via a click rea…

3D defect engineering in polymer opals

The possibility to create defined structures inside a synthetic opal is a key step towards applications in optics, where control of the propagation of light inside a photonic crystal is necessary. Here we report different methods for realizing defined embedded defects in opaline structures. Monodisperse colloids are synthesized by surfactant free emulsion polymerization of the acid labile monomer t-butyl-methacrylate (tBMA). The PtBMA colloids can be filled with sensitizer and photo acid generator and it is possible to crystallize them into photosensitive polymer opals. One method for the introduction of defects is a multilayer build-up of photo-labile (filled with photo acid generator) and…

Dye-containing S∗cside-on/end-on copolymers

Abstract Mesomorphic copolysiloxanes, which combine ‘normal’ end-on linked chiral mesogenic units inducing S∗c phases and side-on fixed chromophores were prepared. The interplay of the different orientational tendencies of these moieties, which are perpendicular (end-on linked mesogenic groups) or parallel (side-on fixed chromophores) to the polymer chain, lead to a strong destabilization of the S∗c phase. However, copolymers with up to about 10 mol % of chromophores still show a smectic C∗ phase. FTIR measurements show that both moieties orient parallel to each other and perpendicular to the polymer chains. These copolymers are interesting to consider as coloured guest-host S∗c materials f…

Mechanical manipulation of molecular lattice parameters in smectic elastomers.

Smectic liquid crystalline elastomers (SLCE) represent unique materials that combine a 1-D molecular lattice arrangement and orientational order with rubber-elasticity mediated by a polymer network. Such materials may exhibit large thermo-mechanical, opto-mechanical and electro-mechanical effects, due to the coupling of macroscopic sample geometry and microscopic structural features. It is shown that the molecular layer dimensions in the smectic phases can be influenced reversibly by macroscopic strain of the material. We present a microscopic model on the basis of experimental results obtained by mechanical dilatation measurements, optical interferometry, X-ray scattering, (13)C NMR, FTIR …

Characterization of quantum dot/conducting polymer hybrid films and their application to light-emitting diodes.

Quantum dot/conducting polymer hybrid films are used to prepare light-emitting diodes (LEDs). The hybrid films (CdSe@ZnS quantum dots excellently dispersed in a conducting polymer matrix, see figure) are readily prepared by various solution-based processes and are also easily micropatterned. The LEDs exhibit a turn-on voltage of 4 V, an external quantum efficiency greater than 1.5%, and almost pure-green quantum-dot electroluminescence.

Site-specific DBCO modification of DEC205 antibody for polymer conjugation

The design of multifunctional polymer-based vectors, forming pDNA vaccines, offers great potential in cancer immune therapy. The transfection of dendritic immune cells (DCs) with tumour antigen-encoding pDNA leads to an activation of the immune system to combat tumour cells. In this work, we investigated the chemical attachment of DEC205 antibodies (aDEC205) as DC-targeting structures to polyplexes of P(Lys)-b-P(HPMA). The conjugation of a synthetic block copolymer and a biomacromolecule with various functionalities (aDEC205) requires bioorthogonal techniques to avoid side reactions. Click chemistry and in particular the strain-promoted alkyne-azide cycloaddition (SPAAC) can provide the req…

Co-flow microfluidic synthesis of liquid crystalline actuating Janus particles

A microfluidic synthesis of stimuli-responsive actuating Janus particles composed of a liquid crystalline elastomer (LCE) and a polymeric hydrogel is reported. , In this article the microfluidic synthesis and characterization of micrometer sized actuating Janus particles containing a liquid crystalline elastomer (LCE) is presented. On one side these Janus particles consist of a hydrophobic liquid crystalline part, featuring strong shape changes during the thermotropic phase transition, whereas the other side contains a hydrophilic polyacrylamide network. The synthesis is based upon the dispersion of two immiscible monomer mixtures in a continuously flowing silicone oil, using two glass capi…

Ferroelectric liquid-crystalline elastomers

Oriented liquid-crystalline (LC) elastomers (polar monodomains, concerning the direction of polarisation) have been prepared from polar monodomains of ferroelectric LC-polysiloxanes by a radical photocrosslinking process. Attempts to perform ferroelectric switching lead in these soft elastomers to an elastic stress which prohibits—for low voltages—a complete reorientation of the polar axis (ferroelectric switching). A ferroelectric switching can, however, be observed for high voltages. The loop of hysteresis of this switching is asymmetric concerning the zero point of the driving voltage. Piezoelectric measurements show that these elastomers combine an elastic memory for one polar state wit…

Microfluidic synthesis of micrometer-sized photoresponsive actuators based on liquid crystalline elastomers

The fabrication of photoresponsive micrometer-sized liquid crystalline elastomer (LCE) particles has been described in this article for the first time. The preparation of the LCE particles using a microfluidic device by a continuous “on the fly” technique allows their fast processing with an irradiation time of less than 2 seconds. In order to accelerate the polymerization and to make the preparation of samples with thicknesses of several hundred microns possible, we modified a NIR-photoinitiation system by adding a bleaching agent. In addition to the photoinitiator, a side-chain liquid crystalline monomer containing an azo-group and a LC-crosslinker were used in the polymerization mixture.…

2D photonic defect layers in 3D inverted opals on Si platforms

Dielectric spheres synthesised for the fabrication of self-organized photonic crystals such as opals offer large opportunities for the design of novel nanophotonic devices. In this paper, we show a hexagonal superlattice monolayer of dielectric spheres inscribed on a 3D colloidal photonic crystal by e-beam lithography. The crystal is produced by a variation of the vertical drawing deposition method assisted by an acoustic field. The structures were chosen after simulations showed that a hexagonal super-lattice monolayer in air exhibits an even photonic band gap below the light cone if the refractive index of the spheres is higher than 1.93.

Orientation of Polymer Functionalized Nanorods in Thin Films

A directed self assembly of anisotropic nanostructures offers a possibility to provide unique functional materials, which are e.g., important in optoelectronic devices. We use the liquid crystalline behavior of polymer functionalized TiO2 and ZnO nanorods to apply methods well known for low molecular liquid crystals to achieve oriented thin films. Convective forces in the meniscus on a structured substrate obtain thin layers of oriented nanoparticles with a ordering parameter of S = 0.7. As another method we present the orientation of polystyrene covered ZnO nanorods under an applied electric field. The method offers a perpendicular alignment of the rods to the surface.

Multidentate Polysarcosine-Based Ligands for Water-Soluble Quantum Dots

We describe the synthesis of heterotelechelic polysarcosine polymers and their use as multidentate ligands in the preparation of stable water-soluble quantum dots (QDs). Orthogonally functionalized polysarcosine with amine and dibenzocyclooctyl (DBCO) end groups is obtained by ring-opening polymerization of N-methylglycine N-carboxyanhydride with DBCO amine as initiator. In a first postpolymerization modification step, the future biological activity of the polymeric ligands is adjusted by modification of the amine terminus. Then, in a second postpolymerization modification step, azide functionalized di- and tridentate anchor compounds are introduced to the DBCO terminus of the polysarcosine…

Colloidal Nanoplatelet/Conducting Polymer Hybrids: Excitonic And Material Properties

WOS:000370678700053 Here we present the first account of conductive polymer/colloidal nanoplatelet hybrids. For this, we developed DEH-PPV-based polymers with two different anchor groups (sulfide and amine) acting as surfactants for CdSe nanoplatelets, which are atomically flat semiconductor nanocrystals. Hybridization of the polymers with the nanoplatelets in the solution phase was observed to cause strong photoluminescence quenching in both materials. Through steady-state photoluminescence and excitation spectrum measurements, photoluminescence quenching was shown to result from dominant exciton dissociation through charge transfer at the polymer/nanoplatelet interfaces that possess a sta…

Synthesis, Characterization and Preliminary Biological Evaluation of P(HPMA)-b-P(LLA) Copolymers: A New Type of Functional Biocompatible Block Copolymer

We describe a synthetic pathway to functional P(HPMA)-b-P(LLA) block copolymers. The synthesis relies on a combination of ring-opening polymerization of L-lactide, conversion into a chain transfer agent (CTA) for the RAFT polymerization of pentafluorophenyl methacrylate. A series of block copolymers was prepared that exhibited molecular weights $\overline M _{\rm n}$ ranging from 7 600 to 34 300 g · mol(-1) , with moderate PDI between 1.3 and 1.45. These reactive precursor polymers have been transformed into biocompatible P(HPMA)-b-P(LLA) copolymers and their fluorescently labeled derivatives by facile replacement of the pentafluorophenyl groups. The fluorescence label attached to this new …

(Photo)crosslinkable Smectic LC Main-Chain Polymers

This paper presents the synthetic route to SmA LC main-chain polymers, that can be (photo)-crosslinked without solvent in the bulk phase. They are based on soluble polymalonates, in which higher ordered phases can be suppressed by copolymerization with a laterally brominated biphenyl. Two routes were developed to incorporate the crosslinkable groups into the polyester backbone. The first consists in the incorporation of phenols into the polyester. These phenols are not reactive enough to participate in the transesterification reaction used to build up the polymer, but they can be esterified afterwards with acrylates. Thermally or photochemically created radicals then start the crosslinking.…

Opaline effect pigments by spray induced self‐assembly on porous substrates

Self‐assembling of opaline materials on porous substrates like paper requires a very fast crystallization, which can be realized with highly monodisperse colloids. This opens the possibility of applying effect pigments to such substrates not by spraying the rather large effect pigments themselves, but by spraying their building blocks, which self‐assemble later on. The feasibility of this approach is presented here for monodisperse polymethyl methacrylate (PMMA) spheres. This process tolerates additives used for ink‐jet printing.

Pyrene Containing Polymers for the Non-Covalent Functionalization of Carbon Nanotubes

Pyrene containing diblock copolymers based on poly(methyl methacrylate) were synthesized and investigated regarding their adsorption on carbon nanotubes (CNT). The pyrene units were introduced using a reactive ester monomer for the build up of the second block which later on was reacted polymer-analogously with amine functionalized pyrene derivatives. As we started from the same reactive ester intermediate, full block length identity is given. We varied the length of the anchor block to find an optimal block length and used pyren-1-yl-methylamine as well as 4-pyren-1-yl-butylamine as anchor units. For both anchor units a maximal adsorption was found for 13 and 20 anchor units, respectively.…

High-Performance Electron-Transporting Polymers Derived from a Heteroaryl Bis(trifluoroborate)

In this communication, we report that dipotassium aryl bis(trifluoroborate)s make stable and easy-to-purify yet reactive monomers under Suzuki polycondensation reactions. A bis(trifluoroborate) of 2-alkylbenzotriazole was prepared successfully and copolymerized with dibromobenzothiadiazole in the presence of a Pd catalyst and LiOH, yielding high molecular weight conjugated polymers. This polymer (P1) composed of all electron-accepting units shows excellent electron-transport properties (μ(e) = 0.02 cm(2) V(-1) s(-1)), which proves the value of the aryl bis(trifluoroborate) monomers and suggests that many other types of semiconducting polymers that could not be accessed previously can be syn…

Langmuir−Blodgett Films of Fluorinated Glycolipids and Polymerizable Lipids and Their Phase Separating Behavior

This paper describes the phase separating behavior of Langmuir monolayers from mixtures of different lipids that (i) either carry already a glycopeptide recognition site or can be easily modified to carry one and (ii) polymerizable lipids. To ensure demixing during compression, we used fluorinated lipids for the biological headgroups and hydrocarbon based lipids as polymerizable lipids. As a representative for a lipid monomer, which can be polymerized in the hydrophilic headgroup, a methacrylic monomer was used. As a monomer, which can be polymerized in the hydrophobic tail, a lipid with a diacetylene unit was used (pentacosadiynoic acid, PDA). The fluorinated lipids were on the one hand a …

Stabilizing nanostructured lithium insertion materials via organic hybridization: A step forward towards high-power batteries

Abstract Herein, we present the electrochemical characterization of carbon-coated TiO 2 nanorods, obtained by carbonizing RAFT (reversible addition fragmentation chain transfer) polymerization derived block copolymers anchored on anatase TiO 2 nanorods. These carbon-coated TiO 2 nanorods show an improved electrochemical performance in terms of first cycle reversibility, specific capacity, cycling stability, and high rate capability. More importantly, however, the structural disordering observed in the uncoated TiO 2 nanorods by means of galvanostatic and potentiodynamic cycling as well as ex situ XRD analysis, does not occur for the carbon-coated material. Preventing this structural disorde…

Distributed feedback lasing in cellulose films

Cellulose derivatives, because of their molecular structure and chirality, can self-assemble to form spatially periodic cholesteric liquid crystal phases. We have synthesized and produced solid cross-linked cholesteric cellulose based films optimized to provide high reflectivity. Since these films are self-assembled photonic bandgap materials, they may be expected to show distributed feedback lasing. By doping samples with fluorescent dyes and optically pumping thin films of these materials, we were able to demonstrate, to the best of our knowledge, for the first time, mirrorless band-edge lasing in cellulose derivatives.

Light-induced demixing of hole or electron transporting moieties

This paper describes the synthesis of two tri-phenylamine monomers (hole conducting) and one triazine monomer (electron conducting) which differ in their copolymerization parameters because of their styrene and vinyl ester nature. A blend of triphenylamine monomer and poly-(ethylene glycol) and mixtures of both types of monomers (triphepylamine and triazine) were illuminated through a line mask, creating laterally modulated radicals, thus leading to lateral demixing. The experiments with mixtures of triphenylamine and triazine monomers show that the concentration of p- or n-type polymers can be modulated laterally in a controlled way.

Macromol. Rapid Commun. 24/2014

Comparaison de deux polyarylates nitrile ayant des groupes d'espace differents [(CH 2 ) 2 ou (CH 2 ) 6 ]

Template-Based Fabrication of Nanometer-Scaled Actuators from Liquid-Crystalline Elastomers

Targeting cells of the immune system: mannosylated HPMA–LMA block-copolymer micelles for targeting of dendritic cells

Background: Successful tumor immunotherapy depends on the induction of strong and sustained tumor antigen-specific immune responses by activated antigen-presenting cells (APCs) such as dendritic cells (DCs). Since nanoparticles have the potential to codeliver tumor-specific antigen and DC-stimulating adjuvant in a DC-targeting manner, we wanted to assess the suitability of mannosylated HPMA-LMA block polymers for immunotherapy. Materials &amp; methods: Fluorescence-labeled block copolymer micelles derived from P(HPMA)-block-P(LMA) copolymers and according statistical copolymers were synthesized via RAFT polymerization, and loaded with the APC activator L18-MDP. Both types of copolymers wer…

Tunable Phosphorescent Emission through Energy Transfer within Multilayer Thin Films Based on a Carbazole-Based Host and Ir(III)-Complex Guest System

A new method to tune both phosphorescence emission intensity and spectroscopic colors based on the alternatively structured host/guest multilayer thin films prepared by the spin-assisted LbL deposition is presented. Their emission characteristics are demonstrated with pairs of positively charged Ir-PEI complexes as guests and negatively charged CBZ-PAA as hosts. The phosphorescent emission of Ir-PEI complexes is enhanced by the energy transfer from the host to the guest and, additionally, this energy transfer can be finely tuned by the insertion of spacer layers between the phosphorescent donor and acceptor layers to vary the emission intensity as well as to render different emission colors.

Bioinspired actuated adhesive patterns of liquid crystalline elastomers.

Gecko-inspired arrays of micropillars made of a liquid crystalline elastomer display thermoswitchable adhesive behavior as a consequence of elongation changes caused by reorientation of the mesogens at the nematic-isotropic (N-I) phase transition.

Supramolecular Linear-g-Hyperbranched Graft Polymers: Topology and Binding Strength of Hyperbranched Side Chains

Complex, reversible hyperbranched graft polymer topologies have been obtained by spontaneous self-assembly. Well-defined adamantyl- and β-cyclodextrin-functionalized polymers were employed to generate linear-g-(linear–hyperbranched) supramolecular graft terpolymers. For this purpose the synthesis of monoadamantyl-functionalized linear polyglycerols (Ada-linPG) and hyperbranched polyglycerols (Ada-hbPG) as well as poly(ethylene glycol)-block-linear polyglycerol (Ada-PEG-b-linPG) and poly(ethylene glycol)-block-hyperbranched poly(glycerol) (Ada-PEG-b-hbPG) block copolymers was established. Isothermal titration calorimetry (ITC) with β-cyclodextrin revealed a shielding effect of hyperbranched …

Functionalization of Active Ester-Based Polymersomes for Enhanced Cell Uptake and Stimuli-Responsive Cargo Release

Poly(2,3-dihydroxypropyl methacrylamide) (P(DHPMA))-based amphiphilic block copolymers have recently proven to form polymer vesicles (polymersomes). In this work, we further expand their potential by incorporating (i) units for pH-dependent disintegration into the hydrophobic membrane and (ii) mannose as targeting unit into the hydrophilic block. This last step relies on the use of an active ester prepolymer. We confirm the stability of the polymersomes against detergents like Triton X-100 and their low cytotoxicity. The incorporation of 2-(2,2-dimethyl-1,3-dioxolane-4-yl)ethyl methacrylate into the hydrophobic block (lauryl methacrylate) allows a pH-responsive disintegration for cargo rele…

Nanomedicine: In Vivo Gene-Silencing in Fibrotic Liver by siRNA-Loaded Cationic Nanohydrogel Particles (Adv. Healthcare Mater. 18/2015)

Functional 3D Photonic Films from Polymer Beads

This paper describes synthesis and properties of polymer opals with a special emphasis on functional opals. Polymer opals are formed from monodisperse polymer colloids by self-assembly. Their potential applications range from coloring pigments, 3D bicontinuous supports for catalysis to photonic materials. This latter application requires especially the controlled creation of defects and the incorporation of fluorescent materials. (© 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

Hetero-Telechelic Dye-Labeled Polymer for Nanoparticle Decoration

The synthesis of poly(methyl methacrylate) (PMMA) exhibiting one fluorescent dye (Texas Red) and one methyl disulfide end group is described. It is shown that the latter end group enabled the exchange of both oleic amine on gold nanoparticles (AuNP) and of oleic acid on CdSe/ZnS quantum dots (QD), allowing for a phase transfer of both types of nanoparticles (NP) from hexane into dimethylformamide due to the solubility provided by the PMMA chains. For AuNP, a fluorescence quenching of the dye was found due to fluorescence resonance energy transfer (FRET) from the dye to the AuNP, while QDs caused a fluorescence enhancement by FRET from the QD to the attached dyes. Due to the hetero-telecheli…

"Smart" defects in colloidal photonic crystals

AbstractWe present a bottom-up approach for the construction of "Smart" active defects in colloidal photonic crystals (CPCs). These structures incorporate polyelectrolyte multilayer (PEM) planar defects embedded in silica CPCs through a combination of evaporation induced self-assembly and microcontact transfer printing. We show how the enormous chemical diversity inherent to PEMs can be harnessed to create chemically active defect structures responsive to solvent vapor pressures, light, temperature as well as redox cycling. A sharp transmission state within the photonic stopband, induced by the PEM defect, can be precisely, reproducibly and in some cases reversibly tuned by these external s…

Liquid crystalline polymers and elastomers

The results of experiments and theory correlate increasingly well in the investigation of liquid crystalline polymers. Current work focuses on rheology and the behavior of blends of thermotropic LC polymers, due to reemerging economic interest in these materials. Research on liquid crystalline elastomers concentrates on potential applications such as artificial muscles and lasing.

Muscular MEMS—the engineering of liquid crystal elastomer actuators

A new class of soft-matter actuator, the liquid crystal elastomer (LCE), shows promise for application in a wide variety of mechanical microsystems. Frequently referred to as an 'artificial muscle', this family of materials exhibits large actuation stroke and generates considerable force, in a compact form which may easily be combined with the structures and devices commonly used in microsystems and MEMS. We show here how standard microfabrication techniques may be used to integrate LCEs into mechanical microsystems and present an in-depth analysis of their mechanical and actuation properties. Using an example from micro-optics and optical MEMS, we demonstrate that their performance and fle…

Targeting distinct myeloid cell populations in vivo using polymers, liposomes and microbubbles

Identifying intended or accidental cellular targets for drug delivery systems is highly relevant for evaluating therapeutic and toxic effects. However, limited knowledge exists on the distribution of nano- and micrometer-sized carrier systems at the cellular level in different organs. We hypothesized that clinically relevant carrier materials, differing in composition and size, are able to target distinct myeloid cell subsets that control inflammatory processes, such as macrophages, neutrophils, monocytes and dendritic cells. Therefore, we analyzed the biodistribution and in vivo cellular uptake of intravenously injected poly(N-(2-hydroxypropyl) methacrylamide) polymers, PEGylated liposomes…

Trend report macromolecular chemistry 2001

Liquid-Crystalline Elastomer Fibers Prepared in a Microfluidic Device

The electro-optical properties of liquid crystalline polymers with polar mesogenic units in the side chain were investigated. It could be shown, that in an electric field, they show all effects known from low molecular weight liquid crystals, e.g. the Freedericksz-transition, the DAP-effect, the formation of William's domain, and the dynamic scattering. The optical response times are slightly longer than for low molecular weight liquid crystals, but in some cases at higher temperatures as short as 200 ms. By comparison of different polymers and some corresponding liquid crystalline monomers, it is found that: (1) the difference between the measuring temperature and the glass transition temp…

Synthesis of Functional Block Copolymers Carrying One Poly(p-phenylenevinylene) and One Nonconjugated Block in a Facile One-Pot Procedure

Block copolymers composed of a MEH–PPV block and a nonconjugated functional block (molecular weights between 5 and 90 kg/mol) were synthesized in a facile one-pot procedure via ROMP. This one-pot procedure permits the synthesis of numerous block copolymers with little effort. Amphiphilic block copolymers were obtained via incorporation of oxanorbornene carrying a PEG side chain as well as via postpolymerization modification of a reactive ester carrying norbornene derivative with methoxypoly(ethylene glycol)amine. These amphiphilic block copolymers can be self-assembled into micelles exhibiting different sizes (60–95 nm), morphologies (micelles or fused, caterpillar-like micelles), and optic…

Optical Properties of Assemblies of Molecules and Nanoparticles

Organic dye molecules, colloidal semiconductor quantum dots, and light-harvesting complexes have been employed as optically active building blocks to create complex molecular assemblies via covalent and non-covalent interactions. Taking advantage of the chemical flexibility of the dye and quantum dot components, as well as recombinant protein expression and the ordering capability of cholesteric phases, specific optical function could be implemented. Photophysical phenomena that have been addressed include light-harvesting, electronic excitation energy transfer (EET), and lasing. Optical single-molecule experiments allow control of energy transfer processes in individual molecular dyads and…

Preferential CO oxidation over catalysts with well-defined inverse opal structure in microchannels

Catalyst supports of CeO 2 /SiO 2 and Al 2 O 3 with three-dimensionally ordered macroporous structure were fabricated in microchannels by application of PMMA opals as templates. Pt-Rh supported on CeO 2 /SiO 2 showed high efficiency for CO removal in preferential CO oxidation in the presence of excess hydrogen. Pt-Rh supported on Al 2 O 3 with an inverse opal structure showed higher reactivity than that supported on wash-coated Al 2 O 3 layers in microchannel reactor.

Polymers, Ferroelectric Liquid Crystalline Elastomers

Ferroelectric materials are a subclass of pyro- and piezoelectric materials. They are very rarely found in crystalline organic or polymeric materials because ferroelectric hysteresis requires enough molecular mobility to reorient molecular dipoles in space. So semicrystalline polyvinylidene fluoride (PVDF) is nearly the only known compound. On the contrary, ferroelectric behavior is very often observed in chiral liquid crystalline materials, both low molar mass and polymeric. Ferroelectric LC-elastomers represent an interesting class of material because they combine the ordering of liquid crystalline ferroelectric phases and the rubber elasticity of polymer networks. Switching of the electr…

Photoinduced Charge Separation of Self-Organized Semiconducting Superstructures Composed of a Functional Polymer-TiO2 Hybrid

Functional Opals from Reactive Polymers: Complex Structures, Sensors, and Modified Photoluminescence

This paper describes the synthesis and properties of functional opal structures, so-called colloidal photonic crystals (CPCs), from a variety of reactive polymers. Photoprocessable opals are presented as well as opals with incorporated smart defect layers that can be actively addressed by external stimuli. In addition, opals with functional bio-macromolecular defects have been developed. They present a new class of materials for optical biomonitoring through shifts of the induced photonic defect mode. Strong modification of photoluminescence according to the photonic bandstructure is observed from opals with embedded exclusively luminescent defect layer.

Interfacial Self-Assembly of Amphiphilic Dual Temperature Responsive Actuating Janus Particles

Manipulation of the ferroelectricity in LC polymers via photomechanical isomerization of azobenzene moieties

We report the synthesis and characterization of a new ferroelectric liquid crystalline side chain copolymer containing photoisomerizable chromophores and non-photoisomerizable mesogenic units. On illumination with UV-light a suppression of the polar order is obtained as indicated by a substantial drop of the spontaneous polarization (Ps) compared to the dark state. We interpret this as the phase order being disrupted by the cis-isomer of the chromophore. After illumination with VIS-light only the major part of Ps is restored. The photochemical cis-trans back-isomerization (restoration of the phase) leads to a different stationary state than the dark state of the material. The thermal reisom…

A Method for Obtaining Defined End Groups of Polymethacrylates Prepared by the RAFT Process during Aminolysis

Macromolecules is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Communication to the Editor A Method for Obtaining Defined End Groups of Polymethacrylates Prepared by the RAFT Process during Aminolysis Peter J. Roth, Daniel Kessler, Rudolf Zentel, and Patrick Theato Macromolecules, 2008, 41 (22), 8316-8319 • Publication Date (Web): 01 November 2008 Downloaded from http://pubs.acs.org on November 19, 2008

Effect of Core-Crosslinking on Protein Corona Formation on Polymeric Micelles.

Most nanomaterials acquire a protein corona upon contact with biological fluids. The magnitude of this effect is strongly dependent both on surface and structure of the nanoparticle. To define the contribution of the internal nanoparticle structure, protein corona formation of block copolymer micelles with poly(N-2-hydroxypropylmethacrylamide) (pHPMA) as hydrophilic shell, which are crosslinked-or not-in the hydrophobic core is comparatively analyzed. Both types of micelles are incubated with human blood plasma and separated by asymmetrical flow field-flow fractionation (AF4). Their size is determined by dynamic light scattering and proteins within the micellar fraction are characterized by…

Density of conjugated antibody determines the extent of Fc receptor dependent capture of nanoparticles by liver sinusoidal endothelial cells

Despite considerable progress in the design of multifunctionalized nanoparticles (NPs) that selectively target specific cell types, their systemic application often results in unwanted liver accumulation. The exact mechanisms for this general observation are still unclear. Here we asked whether the number of cell-targeting antibodies per NP determines the extent of NP liver accumulation and also addressed the mechanisms by which antibody-coated NPs are retained in the liver. We used polysarcosine-based peptobrushes (PBs), which in an unmodified form remain in the circulation for >24 h due to the absence of a protein corona formation and low unspecific cell binding, and conjugated them with …

Influences of Ortho‐Fluoroazobenzenes on Liquid Crystalline Phase Stability and 2D (Planar) Actuation Properties of Liquid Crystalline Elastomers

The fiber patterns of a series of liquid crystalline polymers were analysed. For polymers with smectic phases and for polymers with long spacers and nematic phases, the mesogenic groups orient perpendicularly to the polymer main chains which are parallel to the fiber axis. The fiber pattern indicate a short range order of the mesogenic groups analogous to that in low-molecular weight liquid crystals. For polymers with short spacer groups and nematic phases qualitatively different fiber patterns are found. These fiber patterns are indicative for a special nematic phase formed by ribbon-like molecules.

Microfluidic Synthesis of Liquid Crystalline Elastomer Particle Transport Systems which Can Be Remote‐Controlled Magnetically

Synthesis of Liquid-Crystalline Colloids in Nonpolar Media and their Manipulation in Electric Fields

The first synthesis of anisotropic liquid-crystalline colloids in silicone oil by a direct (radical) polymerization of a monomer in THF/silicone oil mixtures with the help of siloxane containing stabilizers is described. The size of the colloids is in the lower μm range and can be adjusted by varying the mixture. The resulting colloids show a bipolar director configuration if they are small (<1.5 μm) and a radial configuration if they are larger. The colloids are sterically stabilized, and, due to the nonpolarity of the solvent, the disturbing effects of migrating ions are excluded and experiments in the electric field can be conducted. Both line formation in DC fields and a periodic switch…

Bioreducible Poly-l-Lysine-Poly[HPMA] Block Copolymers Obtained by RAFT-Polymerization as Efficient Polyplex-Transfection Reagents

Polylysine-b-p[HPMA] block copolymers containing a redox-responsive disulfide bond between both blocks are synthesized by RAFT polymerization of pentafluorphenyl-methacrylate with a macro-CTA from Nϵ-benzyloxycarbonyl (Cbz) protected polylysine (synthesized by NCA polymerization). This polylysine-b-p[PFMA] precursor block copolymer is converted to polylysine(Cbz)-b-p[HPMA] by postpolymerization modification with 2-hydroxypropylamine. After removal of the Cbz protecting group, cationic polylysine-b-p[HPMA] copolymers with a biosplittable disulfide moiety became available, which can be used as polymeric transfection vectors. These disulfide linked polylysine-S-S-b-p[HPMA] block copolymers sho…

Amphiphilic Copolymers Shuttle Drugs Across the Blood-Brain Barrier.

Medical treatment of diseases of the central nervous system requires transport of drugs across the blood-brain barrier (BBB). Here, it is extended previously in vitro experiments with a model compound to show that the non-water-soluble and brain-impermeable drug domperidone (DOM) itself can be enriched in the brain by use of an amphiphilic copolymer as a carrier. This carrier consists of poly(N-(2-hydroxypropyl)-methacrylamide), statistically copolymerized with 10 mol% hydrophobic lauryl methacrylate, into whose micellar aggregates DOM is noncovalently absorbed. As tested in a BBB model efficient transport of DOM across, the BBB is achievable over a wide range of formulations, containing 0.…

Synthesis of Maleimide-Functionalyzed HPMA-Copolymers and in vitro Characterization of the aRAGE- and Human Immunoglobulin (huIgG)-Polymer Conjugates

Herein the synthesis of antibody–polymer conjugates, with a quite narrow dispersity based on the polymer HPMA, are reported. These conjugates are synthesized by coupling antibodies to maleimide-functionalized poly(N-(2-hydroxypropyl)-methacrylamide) (poly-HPMA) copolymers derived through reversible addition-fragmentation chain transfer (RAFT) polymerization of pentafluorophenyl methacrylate via the intermediate step of an activated ester polymer. We develop a protocol that allows the attachment of two different model antibodies, monoclonal anti-RAGE (receptor for advanced glycation end-products) antibody, and polyclonal human immunoglobulin (huIgG). Modification of the antibody and conjugat…

Controlled Synthesis of CdSe Tetrapods with High Morphological Uniformity by the Persistent Kinetic Growth and the Halide-Mediated Phase Transformation

We report scalable controlled synthesis of CdSe tetrapods with high morphological uniformity based on the continuous precursor injection (CPI) approach with halide ligands. The CPI approach involves the successive injection of precursors into the seed solution at a controlled rate so that the reaction condition remains in the kinetic growth regime. To initiate the successful development of tetrapod structure, the controlled amount of halide ligands are added during the reaction, which triggered the formation of wurtzite arms on {111}-facets of the zincblende seeds. The formation of the wurtzite phase is responsible for the halide-mediated displacement of oleate ligands, destabilizing the em…

Rear Side Diffractive Gratings for Silicon Wafer Solar Cells

Solid opalescent films originating from urethanes of cellulose

Simple chiral urea gelators, (R)- and (S)-2-heptylurea: their gelling ability enhanced by chirality.

Abstract We present the first report on the synthesis of chiral ureas, ( R )- and ( S )-2-heptylurea, and their gelling behaviors. The ureas were prepared by the reactions of chiral amines and phenyl carbamate in the presence of triethylamine. On cooling from homogeneous solutions, the chiral ureas form gels in water and various nonpolar organic solvents, such as cyclohexane, toluene, and tetrachloromethane, while the racemate gelatinize only toluene and tetrachloromethane among the solvents we examined. The gelling ability of the enantiomeric urea is higher than the racemate, as the critical gelling concentrations in toluene, for example, were 0.2% and 0.7% (wt/wt), respectively. The enhan…

HPMA-LMA copolymer drug carriers in oncology: an in vivo PET study to assess the tumor line-specific polymer uptake and body distribution.

Polymeric drug carriers aim to selectively target tumors in combination with protecting normal tissue. In this regard polymer structure and molecular weight are key factors considering organ distribution and tumor accumulation of the polymeric drug delivery system. Four different HPMA based copolymer structures (random as well as block copolymers with lauryl methacrylate as hydrophobic block) varying in molecular weight, size and resulting architecture were analyzed in two different tumor models (AT1 prostate carcinoma and Walker-256 mammary carcinoma) in vivo. Polymers were labeled with (18)F and organ/tumor uptake was followed by μPET imaging and ex vivo biodistribution. Vascular permeabi…

Electrodeposition of ZnO nanorods on opaline replica as hierarchically structured systems

We present a new method to prepare hierarchical structures by using ZnO replica and ZnO-coated PMMA opals as electrodes in an electrodeposition process of ZnO nanorods. Depending on the approach the nanorods can be either grown exclusively on top of the replica or inside the replica structures. Therefore two types of systems are accessible: 3D photonic crystals with a hierarchically structured surface consisting of nanorods and macroporous ZnO structures with an increased surface area.

Photonic crystals based on two-layer opaline heterostructures

AbstractOptical properties of several heterostructures representing two-layer opaline photonic crystals have been examined. Two separate stop-bands have been observed both in transmission and emission spectra. The effect of the interface disorder on the optical spectra was not observed, probably, due to the insufficient degree of order of the opaline layers.

P0419 : In vivo cell specific gene silencing in the liver using novel siRNA-loaded nanohydrogel particles

Origin of enhanced efficiency and stability in diblock copolymer-grafted Cd-free quantum dot-based light-emitting diodes

The efficiency and operational lifetime of quantum dot (QD) based light-emitting diodes (QLEDs) are essentially affected by the electron–hole charge balance. Although various methods have been reported to improve the charge balance, these methods cause issues at the same time, such as increasing a driving voltage and complicating a device structure. In this work, we introduce hybrid InP/ZnSeS/ZnS QDs, in which the oleic acid ligands are substituted with semiconducting diblock copolymer units possessing hole-transporting carbazole groups, to facilitate hole injection and to reduce electron leakage. As a result, the efficiency and the operational lifetime were improved by 1.4-fold and 4-fold,…

Inside Front Cover: Redox-Tunable Defects in Colloidal Photonic Crystals (Adv. Mater. 20/2005)

The inside front cover illustrates reversible tuning of an intragap transmitting state induced by redox cycling, accomplished using a redox-active polyferrocenylsilane polyelectrolyte multilayer planar defect embedded in a colloidal photonic crystal (CPC) synthesized by a bottom–up method combining colloidal self-assembly and microcontact printing. In work reported on p. 2455 by Manners, Ozin, and co-workers, the wavelength position of the defect state can be changed by changing the oxidation state of the ferrocene moieties in the polymer backbone. This could find applications in electrochemically tunable microcavities, and—if light emitters are incorporated—electrochemically tunable CPC-ba…

Overcoming the barrier of CD8+ T cells: Two types of nano-sized carriers for siRNA transport

Abstract Bioengineering immune cells via gene therapy offers treatment opportunities for currently fatal viral infections. Also cell therapeutics offer most recently a breakthrough technology to combat cancer. These primary human cells, however, are sensitive to toxic influences, which make the utilization of optimized physical transfection techniques necessary. The otherwise commonly applied delivery agents such as LipofectamineⓇ or strongly cationic polymer structures are not only unsuitable for in vivo experiments, but are also highly toxic to immune cells. This study aimed to improve the design of polymeric carrier systems for small interfering RNA, which would allow efficient internali…

Time-Resolved Fourier-Transform Infrared Spectroscopy on the Inter- and Intramolecular Orientational Dynamics in Ferroelectric Liquid Crystalline Dimers

On a base of time-resolved step-scan IR-spectroscopy data, we present a detailed model of the segmental reorientation during the ferroelectric and electroclinic switching of a chiral liquid crystalline dimer. We detected that the magnitude of the motion of the molecular segments differ from each other: The tilt angle is maximal for the mesogens and minimal for the ``virtual polysiloxane backbone.'' In contrast to a recently published conjecture, we prove that in the \ensuremath{\mu}s scale the responses of different molecular segments are unambiguously synchronous with each other.

Makromolekulare Chemie 2001

In der Grundlagenforschung der Makromolekularen Chemie liegen die Schwerpunkte auf gezielten Verfahren zur Polymerisation bekannter Monomerer und auf neuen Polymerarchitekturen. Anwendungsaspekte rucken dabei immer mehr in den Vordergrund – bis zur direkten Entwicklung von Funktionsmaterialien. Die Industrie erweitert mit neuen Katalysatoren, Blends, Additiven und Copolymerstrukturen ihr Repertoire.

PEGylation of HPMA-based block copolymers enhances tumor accumulation in vivo: a quantitative study using radiolabeling and positron emission tomography.

Abstract This paper reports the body distribution of block copolymers (made by controlled radical polymerization) with N-(2-hydroxypropyl)methacrylamide (HPMA) as hydrophilic block and lauryl methacrylate (LMA) as hydrophobic block. They form micellar aggregates in aqueous solution. For this study the hydrophilic/hydrophobic balance was varied by incorporation of differing amounts of poly(ethylene glycol) (PEG) side chains into the hydrophilic block, while keeping the degree of polymerization of both blocks constant. PEGylation reduced the size of the micellar aggregates (Rh = 113 to 38 nm) and led to a minimum size of 7% PEG side chains. Polymers were labeled with the positron emitter 18F,…

RAFT Synthesis of Reactive Multifunctional Triblock‐Copolymers for Polyplex Formation

New ferrocene-containing copolyesters

We have synthesized four new ferrocene monomers (three diols and one diester). The redox potential of these ferrocene derivatives varies between 0 mV and 230 mV due to different degrees of ring alkylation. Amorphous and liquid crystalline copolyesters were prepared with these monomers in the polymer main chain. Cyclovoltammetric measurements show that the redox potential of the ferrocene units is increased by about 40 mV upon polymer formation (esterification). Since the ester group is 4 to 6 σ-bonds away from the ferrocene unit this increase is probably caused by some charge-transfer interaction through space. First rheological measurements show an unusual rubber-like behaviour of the ferr…

Three-dimensional photonic crystal intermediate reflectors for enhanced light-trapping in tandem solar cells

A three-dimensional photonic crystal intermediate reflector for enhanced light trapping in tandem solar cells is presented. The intermediate reflector consists of a transparent and conductive ZnO:Al inverted opal sandwiched in between the top amorphous silicon and bottom microcrystalline silicon cell.

A thermotropic liquid crystal elastomer micro-actuator with integrated deformable micro-heater

We present a liquid crystal elastomer (LCE) actuator with large stroke and fast reaction time. LCEs show a large macroscopic shape change when heated above the phase transition (≈120°C). Buried wafer-level fabricated micro-heaters offer optimal thermal reaction times and compact design of the actuators. A relative length change of λ = 1.28 was obtained with 320 mW power consumption. Heating the device from room temperature takes τrise = 19.7 s, cooling below the phase transition temperature from the fully contracted state needs τfall - 5.6s. We verify that the displacement may be accurately controlled by varying electrical input power.

Second-order NLO main-chain polymers by polymerization of poled monomers

A new method of preparing oriented NLO main chain polymers is presented. We synthesized NLO-monomers that consist of donor acceptor substituted tolane molecules that can be poled in the low molar mass state. In the oriented polar state these monomers can be chemically linked using a thermally activated polyaddition reaction. This reaction links the donor head of one monomer to the acceptor tail of the next hibiting bulk noncentrosymmetry with the average direction of the molecular dipoles parallel to the aligning field.

Facile Synthesis of Fluorescent Polymer Nanoparticles by Covalent Modification-Nanoprecipitation of Amine-Reactive Ester Polymers

Emission wavelength control in fluorescent nanoparticles (NPs) is crucial for their applications. In the case of inorganic quantum dots or dye-impregnated silica NPs, such a control is readily achieved by changing the size of the particles or choosing appropriate fluorescent dyes, respectively. A similar modular approach for controlling the emission wavelength of fluo-rescent polymer NPs, however, is difficult. This article reports on fluorescent polymer NPs, the synthesis of which provides a platform for a modular approach towards the preparation of fluorescent NPs of desired emission wavelength. Atom-transfer radical polymerization (ATRP) is employed to synthesize reactive ester polymers,…

CdSe/ZnS-Nanokristalle mit farbstoffmarkierten Polymerliganden mit mehrfachen Ankergruppen

Photonic crystal intermediate reflector in micromorph tandem solar cells

Experimental and numerical evidences are presented which show that the efficiency of silicon based tandem solar-cells can be increased by incorporating a three-dimensional photonic crystal as an intermediate reflector.

Dimesogenic ferroelectric polysiloxanes

Dimesogenic polysiloxane [Si(Me) 2 O] m [Si(Me)(R)O] n (R= (CH 2 ) 3 CH(COO[CH 2 ] 11 OPhPhOCOPh(NO 2 )OC * H(Me)C 6 H 13 ) 2 are synthesized by hydrosilylation. The phase transition temperaturs are determined and the ferroelectric properties are investigated

Functional liquid crystalline particles and beyond

ABSTRACTRecently the preparation and handling of liquid crystalline (LC) particles, which cover the size from some 100 nano-meters to micro- and millimetres found more interest. This review describ...

Crystallization of silica opals onto patterned silicon wafer

We report on fabrication of high quality opaline photonic crystals from large silica spheres, self-assembled in hydrophilic trenches of silicon wafers by using a drawing apparatus with a combination of stirring. The achievements here reported comprise a spatial selectivity of opal crystallization without special treatment of the wafer surface, a filling of the trenches up to the top, leading to a spatially uniform film thickness, particularly an absence of cracks within the size of the trenches, and finally a good three-dimensional order of the opal lattice even in trenches with a complex confined geometry, verified using optical measurements. The opal lattice was found to match the pattern…

Mechanical and optical properties of continuously spun fibres of a main-chain smectic A elastomer

Oriented smectic liquid crystal elastomer fibres are prepared with a special wet-spinning technique. The continuous spinning process in principle allows the preparation of fibres with arbitrary length. In comparison to ordinary rubbers, they have unique mechanical properties that qualify them as potential candidates for mechanical actuator applications. We demonstrate that these fibres show a remarkable contraction and extension at the transition from the ordered smectic to the disordered isotropic phase. We characterise their most relevant physical properties, viz. the thermally driven shape changes, stress–strain relations and optical birefringence, by optical and mechanical measurements.

Tailored Semiconducting Polymers: Living Radical Polymerization and NLO-Functionalization of Triphenylamines

This paper describes the preparation of various polymers with triarylamine side groups. High molecular weight materials were obtained by free radical polymerization utilizing the gel effect. Polymers with a marrow polydispersity and a predetermined molecular weight could be prepared by living radical polymerization. The T g could, thereby, be controlled between 50 and 140°C either by using different monomers or by varying the molecular weight. Living radical polymerization allowed in addition the preparation of block copolymers. The triarylamine side groups could be transformed into NLO-chromophores by reaction with tetracyanoethylene. This leads to the incorporation of tricyanoethylene. Th…

Nanomedicine for immunotherapy

High Optical Quality Films of Liquid Crystalline Cellulose Derivatives in Acrylates

Freestanding ferroelectric elastomer films

3D photonic crystal intermediate reflector for micromorph thin-film tandem solar cell

The concept of 3D photonic intermediate reflectors for micromorph silicon tandem solar cells has been investigated. In thin-film silicon tandem solar cells consisting of amorphous and microcrystalline silicon with two junctions of a-Si/μc-Si, efficiency enhancements can be achieved by increasing the current density in the a-Si top cell. It is one goal to provide an optimized current matching at high current densities. For an ideal photon-management between top and bottom cell, a spectrally selective intermediate reflective layer (IRL) is necessary, which is less dependent of the angle of incidence than state-of-the-art thickness dependent massive interlayers. The design, preparation and cha…

HPMA copolymers as surfactants in the preparation of biocompatible nanoparticles for biomedical application.

In this work we describe the application of amphiphilic N-(2-hydroxypropyl)methacrylamide (HPMA)-based copolymers as polymeric surfactants in miniemulsion techniques. HPMA-based copolymers with different ratios of HPMA (hydrophilic) to laurylmethacrylate (LMA; hydrophobic) units were synthesized by RAFT polymerization and postpolymerization modification. The amphiphilic polymers can act as detergents in both the miniemulsion polymerization of styrene and the miniemulsion process in combination with solvent evaporation, which was applied to polystyrene and polylactide. Under optimized conditions, monodisperse colloids can be prepared. The most promising results could be obtained by using the…

Amphiphilic HPMA-LMA copolymers increase the transport of Rhodamine 123 across a BBB model without harming its barrier integrity.

Abstract The successful non-invasive treatment of diseases associated with the central nervous system (CNS) is generally limited by poor brain permeability of various developed drugs. The blood–brain barrier (BBB) prevents the passage of therapeutics to their site of action. Polymeric drug delivery systems are promising solutions to effectively transport drugs into the brain. We recently showed that amphiphilic random copolymers based on the hydrophilic p(N-(2-hydroxypropyl)-methacrylamide), pHPMA, possessing randomly distributed hydrophobic p(laurylmethacrylate), pLMA, are able to mediate delivery of domperidone into the brain of mice in vivo. To gain further insight into structure–propert…

Macromol. Rapid Commun. 17/2010

Iris-Like Tunable Aperture Employing Liquid-Crystal Elastomers

A liquid-crystal elastomer (LCE) iris inspired by the human eye is demonstrated. With integrated polyimide-based platinum heaters, the LCE material is thermally actuated. The radial contraction direction, similar to a mammalian iris, is imprinted to the LCE by a custom-designed magnetic field. Actuation of the device is reproducible over multiple cycles and controllable at intermediate contraction states.

LC‐Polymers and Smectic Phases with Special Substructures/Nanophase Segregation

Artificial Opals as Effect Pigments in Clear-Coatings

In this paper, we describe the use of artificial opals from polymer beads as effect pigments in transparent industial and automotive coatings. For this purpose, we synthesized monodisperse colloids from fluorinated methacrylates by surfactant-free emulsion polymerization. The fluorinated monomers, in combination with crosslinking, lead to a refractive index contrast, thermal stability, and solvent resistivity necessary for use as effect pigments. After crystallization of the monodisperse polymer beads, crystal flakes with iridescent colors can be obtained. The crystal flakes can act as effect pigments in various transpartent industrial and automotive coatings. due to photonic crystal behavi…

Flüssigkristalline Ordnung als Konzept in den Materialwissenschaften: von Halbleitern zu funktionalen Bauteilen

Die einzigartigen optischen Eigenschaften von flussigkristallinen Phasen (LCs) werden schon seit langem in Flachbildschirmen genutzt. Durch die Besonderheiten dieser Mesophase im Zwischenbereich zwischen dem Kristall (Ordnung) und der isotropen Schmelze (Beweglichkeit) eignen sich flussigkristalline Materialien aber auch zu einer Vielzahl von weiteren Anwendungen. Der hohe Grad an molekularer Ordnung, die Moglichkeit zur grosflachigen Orientierung und das Strukturmotiv aromatischer Einheiten machen Flussigkristalle zu interessanten Materialien fur organische Halbleiter, die in Losungsmitteln verarbeitet und leicht auf Substraten abgeschieden werden konnen. Die Anisotropie der Flussigkristal…

Low temperature catalytic combustion of propane over Pt-based catalyst with inverse opal microstructure in microchannel reactor

A novel Pt-based catalyst with highly regular, periodic inverse opal microstructure was fabricated in a microchannel reactor, and catalytic testing revealed excellent conversion and stable activity for propane combustion at low temperatures.

Liquid-crystalline ionomers

Liquid-crystalline (LC) ionomers combine the properties of ionomers (cluster formation of the ionic groups) with LC phases. They can be prepared with LC main-chain and LC side-chain polymers.

Back Cover: Macromol. Biosci. 5/2014

Nanosized shape-changing colloids from liquid crystalline elastomers.

A method to prepare shape-changing nanospheres from liquid crystalline elastomers is reported. The nanosized colloids are prepared by a miniemulsion process. During this process, colloids are prepared from a liquid crystalline (LC) main-chain polyester and subsequently crosslinked into a nanometer-sized LC elastomer. The ability of these LC elastomers to change their shape at the phase transition temperature from the smectic A to the isotropic phase was detected by temperature-dependent transmission electron microscopy. The phase transition-induced shape change leads to strongly shape anisotropic nanosized elastomer particles.

Chiral Polyisocyanates from an Azomonomer with a Very High Chiral Induction

The synthesis of new chiral polyisocyanates is described. For this purpose a new chiral azobenzene containing monomer with the chiral center in α-position to the isocyanate group was synthesized. The anionic copolymerization was carried out in THF as solvent with potassium cyanide that was complexed by 18-crown-6 as initiator. This allowed a better control of the reaction and thereby the synthesis of polyisocyanates with a fairly low polydispersity. The copolymers show an extremely high transfer of chirality from the chiral side groups to the helical backbone in dilute solution. Copolymers with only 1.6 mol % of chiral side groups show nearly the full optical rotation and exist predominantl…

Hydrogen bonded ferroelectric liquid crystal gels in freely suspended film geometry

We study freely suspended films of smectic C* liquid crystalline gels by means of polarizing microscopy. The gel point of the system is determined from the suppression of flow in the films. The network of hydrogen bonds is mechanically fragile but stabilizes orientation patterns of the sample, in particular it stores the texture present during gelation. Electro-optical experiments are performed to study the dynamics of the sample reorientation under the influence of in-plane electric fields. Mesogen orientation and optical properties can be switched in electric fields of a few kV m−1. After removal of electric fields, the network restores the ‘frozen-in’ texture. This texture can be erased …

From Defined Reactive Diblock Copolymers to Functional HPMA-Based Self-Assembled Nanoaggregates

This paper describes the synthesis of functional amphiphilic poly( N-(2-hydroxypropyl) methacrylamide)-block-poly(lauryl methacrylate) copolymers by RAFT polymerization via the intermediate step of activated ester block copolymers (pentafluoro-phenyl methacrylate). Block copolymers with molecular weights from 12000-28000 g/mol and PDIs of about 1.2 have been obtained. The amphiphilic diblock copolymers form stable super structures (nanoaggregates) by self-organization in aqueous solution. The diameters of these particles are between 100 and 200 nm and depend directly on the molecular weight of the block copolymer. Furthermore, we investigated the impact of these nanoaggregates on cell viabi…

Blends from redox active liquid crystal ionomers and amorphous ionomers

Abstract Biphasic blends (mixtures) of liquid crystal ionomers (prepared from ferrocene containing liquid crystal polymers by a redox reaction) and partially sulfonated polystyrene combine the constituent properties in a way, which is dependent on the measuring method. Polarizing microscopy shows homogenous textures similar to the pure liquid crystal polymer. Mechanical measurements show however the elastomeric behaviour of sulfonated polystyrene. The phase separated structure of these blends is proved by differential scanning calorimetry measurements.

X-ray measurements of stretched crosslinked liquid-crystalline side group polymers show that two types of orientation of the mesogenic groups relative to the polymer chains (parallel or perpendicular) are possible, depending on the structure of the polymer chain. For two liquid-crystalline polymethacrylates with long spacer groups (6 methylene units) the mesogenic groups orient preferably perpendicularly to the polymer chains (axis of strain). For three liquid-crystalline polyacrylates with long or short spacer groups (6 or 2 methylene units), the mesogenic groups orient preferably parallel to the polymer chains (axis of strain). The reason for this difference is not yet clear. These result…

Fabrication of Robust High-Quality ORMOCER® Inverse Opals

The nanostructuring of ORMOCER® to form inverse opals is described. For this purpose a polymer opal is used as a template and infiltrated with liquid ORMOCER®. After photopolymerization of the resin the host opal is dissolved in tetrahydrofuran and an ORMOCER® inverse opal is obtained. It shows excellent periodicity (by SEM) and optical properties to reveal a high degree of face centered cubic order. This replication process leads to a nanostructured photonic crystal with the outstanding mechanical properties of ORMOCER® and high temperature stability up to 350 °C.

X-ray scattering experiments on oriented polysiloxanes with paired mesogens and different distances between these swallow-tailed side groups show a remarkable dependence of the smectic monolayer thickness on the degree of dilution, whereas the interplanar distance of the side groups remain nearly constant. Due to the dominating interaction of the mesogenic moieties, the flexible main chain is forced to take part in the layer formation. A packing model is proposed to explain the results of the X-ray studies. For polymers with five or more dimethylsiloxane copolymer segments, a diffuse scattering appears in the smectic as well as in the isotropic phase. This scattering is independent of the o…

Dielectric Relaxation Measurements and X-Ray Investigations of Liquid Crystalline Side-Chain Polymers

In the last few years several liquid crystalline side-chain polymers have been synthesized,1 – 4 which combine the properties of low molecular weight liquid crystals with those of polymers.5 – 9

Thin Films by Multilayer Build-Up of Electron Transport Materials

We present the synthesis and the electrochemical characterization of polymeric electron transport materials, synthesized by polycondensation of substituted triazines and α,ω-dihaloalkanes. They can be reversibly reduced with the least negative potential at −0.39 V, which is below the reduction potential of oxygen. In addition, the formation of polyelectrolyte multilayers is possible by the electrostatic self-assembly method. This multilayer formation takes place in a very defined way up to thirty double layers. An example of one of the polymeric triazine electron transport materials synthesized and a schematic diagram of a self-assembled multilayer film.

Immunomodulatory Therapy of Inflammatory Liver Disease Using Selectin-Binding Glycopolymers

Immunotherapies have the potential to significantly advance treatment of inflammatory disease and cancer, which are in large part driven by immune cells. Selectins control the first step in immune cell adhesion and extravasation, thereby guiding leukocyte trafficking to tissue lesions. We analyzed four different highly specific selectin-binding glycopolymers, based on linear poly(2-hydroxypropyl)-methacrylamide (PHPMA) polymers. These glycopolymers contain either the tetrasaccharide sialyl-LewisX (SLeX) or the individual carbohydrates fucose, galactose, and sialic acids mimicking the complex SLeX binding motive. The glycopolymers strongly bind to primary human macrophages, without activatin…

Dielectric spectroscopy of an aligned liquid crystalline side chain polymer using high pressures

Abstract The complex permittivity of a liquid crystalline side group polymer has been measured at pressure from ambient up to 300 MPa. The samples were initially not aligned, then planar and finally homeotropically aligned by the field of a 7.2 Tesla magnet. Temperatures ranged up to 130°C, and measurement frequencies from 5 Hz to 5 MHz. The equilibrium permittivity es has been interpreted in terms of an effective dipole moment μ. The frequency of maximum loss has been analysed in terms of enthalpy of activation and volume of activation for α and β relaxation processes.

Combining Ring-Opening Multibranching and RAFT Polymerization: Multifunctional Linear–Hyperbranched Block Copolymers via Hyperbranched Macro-Chain-Transfer Agents

The synthesis of a hyperbranched macro-chain-transfer agent for RAFT polymerization of functional methacrylate or methacrylamide monomers was achieved by selectively attaching one single CTA onto hyperbranched polyglycerol dendron analogues. The combination of ring-opening multibranching polymerization of glycidol and subsequent RAFT polymerization of the hyperbranched macro-chain-transfer agents created a new route to a variety of multifunctional linear–hyperbranched block topologies. All linear–hyperbranched block copolymers could be synthesized with controlled molecular weight (Mn = 3.2–43.7 kg/mol) and low polydispersity (PDI = 1.15–1.34). As first examples for this universal approach, …

α,ω-Functionalized poly-N-isopropylacrylamides: controlling the surface activity for vesicle adsorption by temperature

The synthesis of alpha,omega-end-functionalized copolymers of N-isopropylacrylamide and N-(3-dimethylaminopropyl)acrylamide was performed. Monomer ratios of 100:0, 96:4, and 81:19 were investigated. The lower critical solution temperature (LCST) of these polymers was determined by cloud-point measurements and by microcalorimetric measurements. The LCST increased from 32 over 37 to 47 degrees C as the hydrophobicity increased with increasing amount of comonomer N-(3-dimethylaminopropyl)acrylamide. The polymers could successfully be adsorbed onto gold surfaces. Finally, vesicle adsorption onto these self-assembled polymer films on flat gold surfaces was investigated as the vesicle solution te…

FTIR spectroscopy of smectic elastomer films under lateral strain

Polarized Fourier transform infrared (FTIR) spectroscopy is used to study the strain‐induced compression of molecular layers in oriented smectic liquid crystal elastomer films. A reversible change of the smectic layer thickness in SmA and SmC* films in response to external strain was revealed earlier by optical reflectometry and X‐ray measurements. However, these methods cannot probe the mechanism of layer compression on a molecular level. Polarized FTIR spectra show that the induced mesogenic tilt, one of the possible mechanisms, is too small to provide the dominating contribution to the layer shrinkage. The FTIR absorbance spectra of stretched samples are also evidence that there are no s…

Semiconductor Nanocrystals with Multifunctional Polymer Ligands

In this letter, we describe the preparation of a versatile polymer ligand, which can be attached to CdSe/ZnS semiconductor nanocrystals via a phase transfer reaction. The ligand is based on a chain of reactive esters, which can, in principle, be substituted by any compound containing amino-functionalities. The polymer/nanocrystal complexes are characterized in terms of structure and photostability.

Versatile ω-end group functionalization of RAFT polymers using functional methane thiosulfonates

Five different polymers, poly[methyl methacrylate] (PMMA), poly[lauryl methacrylate] (PLMA), poly[diethylene glycol methacrylate] (PDEGMA), poly[N-iso-propylacrylamide] (PNIPA), and poly[styrene] (PS) prepared by the RAFT process and thus terminated with dithioesters were aminolyzed in the presence of S-3-butynyl methane thiosulfonate (MTS), which was synthesized in two steps. Analysis of the polymers by 2D NMR, UV–vis absorbance, and gel permeation chromatogra-phy revealed them to quantitatively carry acetylene end groups connected with disul-fide bridges, indicating that functional MTS reagents can be employed for end group functionalization of RAFT polymers. This versatile method is of ad…

Pathogen-Mimicking MnO Nanoparticles for Selective Activation of the TLR9 Pathway and Imaging of Cancer Cells

Here, design of the first pathogen-mimicking metal oxide nanoparticles with the ability to enter cancer cells and to selectively target and activate the TLR9 pathway, and with optical and MR imaging capabilities, is reported. The immobilization of ssDNA (CpG ODN 2006) on MnO nanoparticles is performed via the phosphoramidite route using a multifunctional polymer. The multifunctional polymer used for the nanoparticle surface modification not only affords a protective organic biocompatible shell but also provides an efficient and convenient means for loading immunostimulatory oligonucleotides. Since fluorescent molecules are amenable to photodetection, a chromophore (Rhodamine) is introduced …

Two-photon absorption dye based on 2,5-bis(phenylacrylonitrile)thiophene with aggregration enhanced fluorescence

This paper reports the synthesis and characterization of a 2,5-bis(phenylacrylonitrile) thiophene based two-photon dye, designed to show enhancement in fluorescence quantum yield in nanoaggregated form. Strong solvatochromism has been observed and explained by the favoritism of locally excited (LE) or internal charge transfer (ICT) state depending on the solvent polarity. Aqueous dispersions of nanoparticles have been prepared and investigated regarding their optical properties which were correlated to the LE and ICT state and the molecular structure of the aggregates. (C) 2016 Optical Society of America

Water-Soluble Polymers Coupled with Glycopeptide Antigens and T-Cell Epitopes as Potential Antitumor Vaccines

Highly decorated: Tumor-associated MUC1 glycopeptide and tetanus toxoid T-cell epitope P2 can be attached to water-soluble poly(N-(2-hydroxypropyl)methacrylamide) carriers by orthogonal ligation techniques. Fully synthetic vaccine A with additional nanostructure-promoting domains induced antibodies that exhibit high affinity to tumor cells.

Propagation and scattering of light in opal heterojunctions

The directionality of the polarised light transmission has been studied in heterogeneous photonic crystals based on double-film opal in comparison to homogeneous crystals on single-film opals. In spite of additional scattering at the photonic bandgap interface, ballistic propagation has been preserved. Changes of the polarisation anisotropy in hetero-opal compared to homogeneous opal have been assigned to specific mode matching conditions at the photonic bandgap interface.

Opalescent Cholesteric Networks from Chiral Polyisocyanates in Polystyrene

Multilayer build-up of a reactive polymer with α,ω-functionalized chromophores

Alternating multilayers with up to ten layers have been prepared by sequential reaction of a reactive polymer (poly[(1-methylvinyl isocyanate)-alt-(maleic anhydride)]) with α,ω-functionalized chromophores. For this purpose new chromophores were synthesized varying the length of the hydrophobic spacer. The analysis of the multilayer build-up shows that physisorption is more important than chemisorption for fixation of new polymer layers. Thus, a multilayer build-up is only possible with the shorter, more hydrophilic chromophore and not with the long hydrophobic spacer.

Micromorph silicon tandem solar cells with fully integrated 3D photonic crystal intermediate reflectors

A 3D photonic intermediate reflector for textured micromorph silicon tandem solar cells has been investigated. In thin-film silicon tandem solar cells consisting of amorphous and microcrystalline silicon with two junctions of a-Si/c-Si, efficiency enhancements can be achieved by increasing the current density in the a-Si top cell providing an optimized current matching at high current densities. For an ideal photon-management between top and bottom cell, a spectrally-selective intermediate reflective layer (IRL) is necessary. We present the first fully-integrated 3D photonic thin-film IRL device incorporated on a planar substrate. Using a ZnO inverted opal structure the external quantum eff…

Differences between smectic homo‐ and co‐polysiloxanes as a consequence of microphase separation

This paper compares smectic phases formed from LC‐homo‐ and LC‐co‐polysiloxanes. In the homopolysiloxane, each repeating unit of the polymer chain is substituted with a mesogen, whereas in the copolysiloxanes mesogenic repeating units are separated by dimethylsiloxane units. Despite a rather similiar phase sequence of the homo‐ and co‐polysiloxanes—higher ordered smectic, smectic C* (SmC*), smectic A (SmA) and isotropic—the nature of their phases differs strongly. For the copolymers the phase transition SmC* to SmA is second order and of the ‘de Vries’ type with a very small thickness change of the smectic layers. Inside the SmA phase, however, the smectic thickness decreases strongly on ap…

Organic nanosheets with charged surface: two dimensional self-assembly of a non-symmetric bis-acylurea with pyridyl end group

We present a novel non-symmetric bis-acylurea that self-assembles into two dimensional nanosheet superstructures. The bis-acylurea (PyrC8Bn) has a pyridyl and a benzyl end group divided by a spacer group [–NHCONHCO–(CH2)8–CONHCONH–, C8] with two hydrogen bonding sites. Upon cooling a hot solution in ethanol, the molecule self-assembles into multilayered nanosheet structures due to the intermolecular biaxial hydrogen bonding. The surface charge of the nanosheets could be switched between positive and neutral by adjusting the pH. The charged character of the nanosheets was utilized in immobilizing negatively charged gold nanoparticles. An attempt to regulate the self-assembly allowed us to fi…

Long-term biodistribution study of HPMA- ran -LMA copolymers in vivo by means of 131 I-labeling

Abstract Background For the evaluation of macromolecular drug delivery systems suitable pre-clinical monitoring of potential nanocarrier systems is needed. In this regard, both short-term as well as long-term in vivo tracking is crucial to understand structure-property relationships of polymer carrier systems and their resulting pharmacokinetic profile. Based on former studies revealing favorable in vivo characteristics for 18 F–labeled random (ran) copolymers consisting of N-(2-hydroxypropyl)methacrylamide (HPMA) and lauryl methacrylate (LMA) – including prolonged plasma half-life as well as enhanced tumor accumulation – the presented work focuses on their long-term investigation in the li…

Monodomain Liquid Crystal Main Chain Elastomers by Photocrosslinking

A new synthetic strategy for the preparation of macroscopically oriented smectic main chain liquid crystal elastomers (MC-LCE) by the photocrosslinking of laterally functionalized polyesters is presented. X-ray measurements proved the formation of the monodomain and allowed a quantitative determination of the order parameter. The thermo-actuation of our material at the phase transition from the liquid-crystalline to the isotropic phase was demonstrated by temperature dependent measurements of the sample length, showing a fully reversible shape change of � 40%. Mechanical measurements showed that the sample can be stretched by up to 60% along the smectic layer normal without any reorientatio…

Control of CaCO3 Crystallization by Demixing of Monolayers

In this paper we describe how to template a demixed monolayer into a spatially patterned inorganic replica. For this purpose a new amphiphilic monomer was synthesized which can be polymerized both in solution and in the monolayer of a Langmuir-Blodgett (LB) trough. Since it inhibits the crystallization of CaCO3, it can be used--in combination with stearic acid (nucleation-promotor)--to control CaCO3 crystals formed under the monolayer. Investigations of the two-component monolayer (Langmuir isotherms and AFM measurements of transferred films) show--in the biphasic region--demixing in solid analogue stearic acid domains and the liquid analogue phase of the monomer. Crystallization of CaCO3 s…

Interplay of Chiral Side Chains and Helical Main Chains in Polyisocyanates

Here we describe the synthesis of seven new copolymer series prepared by copolymerization of hexyl isocyanate with seven new chiral azo chromophores with an isocyano functionality. The resulting copolyisocyanates (Nylon 1) possess a helical polymer conformation. In the cases in which the chiral group and polymer chain are linked to the same phenyl ring (copolymer series VI-IX) a transfer of chirality to the polymer chain is possible. I.e. one helical twist sense is preferred in this case. By variation of the chiral center, polymers with preferable right- or left-handed helical conformation are accessible. The photochemical isomerization of the azo chromophore (trans → cis) is possible in hi…

Study of smectic elastomer films under uniaxial stress

We study the mechanical properties of free-standing films of smectic liquid crystalline elastomers. Macroscopically ordered elastomer films of submicrometer thickness are prepared from freely suspended smectic A polymer films by photo crosslinking. The deformation characteristics depend criticically on the sample composition, in particular on the density of mesogenic side chains at the siloxane backbone. In materials where the siloxane backbone is only partially substituted (dilute systems), a uniaxial stretching of the films in the layer plane is accompanied by a shrinkage of the smectic layers. This layer shrinkage is to only a minor extent achieved by the induction of a molecular tilt. W…

Induced roughness in thin films of smectic-C* elastomers

The surface topography of a thin homeotropically oriented film of ferroelectric smectic-C* elastomer is studied by atomic force microscopy. We find that when the film is mechanically stretched, its surface becomes increasingly rough, in proportion to the applied strain. The effect depends strongly on the nature of crosslinks forming the elastomer network. The r.m.s. roughness correlations show a consistent trend [h(x) − h(0)]21/2 ~ (x/ξ)0.5. We introduce a theoretical model assuming that random disorder in the smectic tilt angle is induced by deformations via the coupling of mesogens to the elastic network. The model describes the observed power law and gives a prediction for the correlatio…

Liquid Crystalline Ordering and Charge Transport in Semiconducting Materials

Organic semiconducting materials offer the advantage of solution processability into flexible films. In most cases, their drawback is based on their low charge carrier mobility, which is directly related to the packing of the molecules both on local (amorphous versus crystalline) and on macroscopic (grain boundaries) length scales. Liquid crystalline ordering offers the possibility of circumventing this problem. An advanced concept comprises: i) the application of materials with different liquid crystalline phases, ii) the orientation of a low viscosity high temperature phase, and, iii) the transfer of the macroscopic orientation during cooling to a highly ordered (at best, crystalline-like…

In Vivo siRNA Delivery to Immunosuppressive Liver Macrophages by alpha-Mannosyl-Functionalized Cationic Nanohydrogel Particles

Macrophages are the front soldiers of the innate immune system and are vital for immune defense, tumor surveillance, and tissue homeostasis. In chronic diseases, including cancer and liver fibrosis, macrophages can be forced into an immunosuppressive and profibrotic M2 phenotype. M2-type macrophages overexpress the mannose receptor CD206. Targeting these cells via CD206 and macrophage repolarization towards an immune stimulating and antifibrotic M1 phenotype through RNA interference represents an appealing therapeutic approach. We designed nanohydrogel particles equipped with mannose residues on the surface (ManNP) that delivered siRNA more efficiently to M2 polarized macrophages compared t…

Towards micrometer sized core-shell actuators from liquid crystalline elastomers by a continuous flow synthesis

We present here the successful preparation of liquid crystalline core-shell elastomers via a microfluidic double-emulsion process. The customized set-up allows for a temperature-controlled fabrication of the core-shell particles from a thermoresponsive mesogenic monomer. The nematic liquid crystalline shell is filled with a non-mesogenic core of silicone oil. To verify the core-shell structure with optical microscopy, we prepared particles with a colored core using a red dye. We were also able to micro-manipulate the particles and penetrate them with a small glass capillary to extract the liquid core.

Two dimensional self-assembly of bis-acylureas having various functional end groups.

We present the synthesis and morphology study of thirteen bis-acylurea molecules with various functional end groups. The bis-acylureas have two acylurea groups, -NH-CO-NH-CO-, divided by a pentamethylene spacer, -(CH(2))(5)-, and two symmetric functional end groups, such as, aliphatic, benzyl, mono- and bi-thiophenyl, sulfur-containing, and propargyl (HC[triple bond]CCH(2)-) moieties. The bis-acylureas were synthesized by the coupling reactions of ureas with pimeloyl chloride or pimelic acid. Upon cooling from hot isotropic solutions, the bis-acylureas spontaneously form supermolecules. In the cases of aliphatic, benzyl, mono- and bi-thiophenyl functional groups, two dimensional supramolecu…

Endocytotic uptake of HPMA-based polymers by different cancer cells: impact of extracellular acidosis and hypoxia.

Daniel G&amp;uuml;ndel,1 Mareli Allmeroth,2 Sarah Reime,1 Rudolf Zentel,2 Oliver Thews1 1Institute of Physiology, Martin Luther University Halle-Wittenberg, Halle (Saale), 2Institute of Organic Chemistry, Johannes Gutenberg-University, Mainz, Germany Background: Polymeric nanoparticles allow to selectively transport chemotherapeutic drugs to the tumor tissue. These nanocarriers have to be taken up into the cells to release the drug. In addition, tumors often show pathological metabolic characteristics (hypoxia and acidosis) which might affect the polymer endocytosis.Materials and methods: Six different N-(2-hydroxypropyl)methacrylamide (HPMA)-based polymer structures (homopolymer as well as…

The uptake of N-(2-hydroxypropyl)-methacrylamide based homo, random and block copolymers by human multi-drug resistant breast adenocarcinoma cells

A series of well-defined, fluorescently labelled homopolymers, random and block copolymers based on N-(2-hydroxypropyl)-methacrylamide were prepared by reversible addition–fragmentation chain transfer polymerization (RAFT polymerization). The polydispersity indexes for all polymers were in the range of 1.2–1.3 and the number average of the molar mass (Mn) for each polymer was set to be in the range of 15–30 kDa. The cellular uptake of these polymers was investigated in the human multi-drug resistant breast adenocarcinoma cell line MCF7/ADR. The uptake greatly depended on the polymer molecular mass and structure. Specifically, smaller polymers (approx. 15 kDa) were taken up by the cells at m…

Extraordinary Performance of Carbon‐Coated Anatase TiO 2 as Sodium‐Ion Anode

The synthesis of in situ polymer‐functionalized anatase TiO2 particles using an anchoring block copolymer with hydroxamate as coordinating species is reported, which yields nanoparticles (≈11 nm) in multigram scale. Thermal annealing converts the polymer brushes into a uniform and homogeneous carbon coating as proven by high resolution transmission electron microscopy and Raman spectroscopy. The strong impact of particle size as well as carbon coating on the electrochemical performance of anatase TiO2 is demonstrated. Downsizing the particles leads to higher reversible uptake/release of sodium cations per formula unit TiO2 (e.g., 0.72 eq. Na+ (11 nm) vs only 0.56 eq. Na+ (40 nm)) while the …

Molecular dynamics in ferroelectric liquid crystals: From low molar to polymeric and elastomeric systems

Macromol. Rapid Commun. 9-10/2011

Synthesis and characterization of carbon coated sponge-like tin oxide (SnOx) films and their application as electrode materials in lithium-ion batteries

Nanoporous metal oxides are widely used for the development of various functional nanostructures. We report on the synthesis of sponge-like tin oxide films on copper foil by anodization of electrochemically deposited tin films. The thin films are functionalized using a surface-anchoring carbon precursor-polymer (poly(acrylonitrile-b-dopamine acrylamide)) followed by annealing at elevated temperature to convert the polymer coating into a carbonaceous coating. The as prepared and the carbon coated films are characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and Raman spectroscopy. Subsequently, both SnOx films are employed as a…

Ferroelectric Liquid Crystalline Elastomers

Ferroelectric LC-elastomers represent an interesting class of material because they combine the ordering of liquid crystalline ferroelectric phases and the rubber elasticity of polymer networks. Switching of the electric polarization leads to deformation of the polymer network, equivalent to stretching a spring, and creates a stress in the network of polymer chains. The interaction of mesogens and the network can be varied by using different topologies of net points: Crosslinking is carried out either within the siloxane sublayers (leading to fast switching elastomers) or between the siloxane sublayers (resulting in an elastomer that favors the ferroelectric switching state in which the cro…

A New Opto-dielectric Effect Based on the Photoisomerization of Azo Compounds in Ferroelectric Liquid Crystals

Smart artificial muscle actuators: Liquid crystal elastomers with integrated temperature feedback

Abstract We present a smart, thermally stimulated liquid crystal elastomer actuator with an integrated heater and temperature sensor based on deformable polyimide wiring technology. Due to optimal thermal contact to the active material, heating from room temperature to the point of maximum contraction takes only 19.6 s; cooling requires only 5.6 s. The integrated temperature sensor allows closed-loop operation and characterize the thermomechanical properties of the material: open-loop positioning precision was found to be better than 45 μm and no inherent drift or hysteresis were observed. The maximum force generated by the actuator was 133 mN, corresponding to 76 kPa of stress. This ultra-…

Chemical Approach to Functional Artificial Opals

Artificial opals are self-assembled colloidal crystals, which consist of a cubic dense packing (fcc) of hard (not film-forming) colloids with diameters ranging from 200 to 900 nm. Because of their periodic nanostructure the assemblies are able to reflect light that matches their periodicity, i.e., UV- to IR-radiation depending on the size of the colloids. Thus, they present a subgroup of 'photonic crystals'. While, originally, the chemistry inside the colloids and the resulting opals was of minor significance, nowadays the chemical variation of opals is becoming more and more important for the preparation of functional and patterned opals. The search for functional opals is, therefore, espe…

Photoresponsive anisotropic and isotropic gels of semicarbazide-azobenzene organogelators: the use of magnetic polymer colloids to detect gel-sol transformation.

Photoinduced gel-sol transformation of semicarbazide-azobenzene-based organogels containing entrapped organic solvents (isotropic gel) and liquid-crystalline material (anisotropic gel) has been studied. Thin films (4 µm) of gel materials were used to study the gel-sol transformation, as thicker films possess high absorbance due to the relatively high concentration of the gelator molecules. Photoinduced trans-cis isomerization of the azobenzene units causes destruction of the gel structure, and the consequent change in viscosity has been investigated employing magnetic polymer colloids. In the gel state the movement of the colloids is restricted due to their entrapment within the gel fibers …

Conducting Polymer with Orthogonal Catechol and Disulfide Anchor Groups for the Assembly of Inorganic Nanostructures

To combine several inorganic components with organic material in a controlled special and permanent manner still remains a difficult issue. Two specifically functionalized block copolymers were synthesized separately and combined in a second step. A heterofunctional poly(ethylene glycol) (PEG) block copolymer bearing a single amino unit, a short PEG spacer, and multiple catechol functionalities was obtained via anionic ring-opening polymerization (AROP). Using the reversible addition–fragmentation chain transfer (RAFT) radical polymerization technique, a semiconducting block copolymer with carbazole side groups was obtained. The second polyacrylate block contained reactive ester groups and …

ChemInform Abstract: Liquid-Crystalline Ordering as a Concept in Materials Science: From Semiconductors to Stimuli-Responsive Devices

While the unique optical properties of liquid crystals (LCs) are already well exploited for flat-panel displays, their intrinsic ability to self-organize into ordered mesophases, which are intermediate states between crystal and liquid, gives rise to a broad variety of additional applications. The high degree of molecular order, the possibility for large scale orientation, and the structural motif of the aromatic subunits recommend liquid-crystalline materials as organic semiconductors, which are solvent-processable and can easily be deposited on a substrate. The anisotropy of liquid crystals can further cause a stimuli-responsive macroscopic shape change of cross-linked polymer networks, w…

Improved SiRNA Loading of Cationic Nanohydrogel Particles by Variation of Crosslinking Density

In Vivo Gene-Silencing in Fibrotic Liver by siRNA-Loaded Cationic Nanohydrogel Particles

Cationic nanohydrogel particles loaded with anti-Col1α1 siRNA suppress collagen synthesis and deposition in fibrotic mice: Systemically administered 40 nm sized nanogel particles accumulate in collagen-expressing cells in the liver. Their siRNA payload induces a sequence specific in vivo gene knockdown affording an efficient antifibrotic effect in mice with liver fibrosis.

Towards tunable defect arrangements in smectic liquid crystal shells utilizing the nematic–smectic transition in hybrid-aligned geometries

We produce and investigate liquid crystal shells with hybrid alignment—planar at one boundary, homeotropic at the other—undergoing a transition between the nematic (N) and smectic-A (SmA) phases. The shells display a dynamic sequence of patterns, the details depending on the alignment agents and on the diameter and thickness of the shell. In shells of sufficient diameter we typically find a transient striped texture near the N–SmA transition, stabilising into a pattern of tiled, more or less regularly spaced focal conic domains in the SmA phase. The domain size and spacing decrease with reduced shell thickness. In case of strong homeotropic anchoring at one boundary and small shell size, ho…

In vivo gene silencing in the liver: Comparison of siRNA-loaded non biodegradable vs. biodegradable nanohydrogel particles for antifibrotic therapy

Theoretical and experimental analysis of photonic structures for fluorescent concentrators with increased efficiencies

In this study we present a theoretical and experimental analy- sis of the application of photonic band stop filters on top of photovoltaic fluorescent concentrators in order to increase the photon collection efficiency. The light guiding effect of the fluorescent concentrator relies on total internal reflection. The escape cone of total internal reflection is their major loss mechanism. Our ray tracing simulation allows to calculate the beneficial effect of photonic band stop reflection filters, which reduce these losses, and to simulate the angular distribu- tion of the light trapped in the concentrator. We present simula- tions of the optical properties of 1D and 3D photonic structures an…

Opale: Photonische Kristalle

Opale sind selbstorganisierte, kubisch dichtest gepackte Kolloidkristalle mit Kolloid-Durchmessern im Nanometer- und Submikrometerbereich. Aufgrund der periodisch modulierten Dielektrizitatskonstante bilden sich photonische Bandlucken aus, so dass die Ausbreitung von Licht mit Wellenlangen in der Grosenordnung der Gitterkonstanten unterdruckt wird. Dies erklart u.a. den brillianten Farbeindruck. Opale konnen synthetisch aus Polymer- oder Metalloxidkolloiden in einem Bottom-up-Prozess hergestellt und auf vielfaltige Weise chemisch funktionalisiert, strukturiert oder als Template fur ihre invertierten Strukturen verwendet werden. Anwendungsgebiete reichen von optischen Chips, Farbdisplays und…

Ferroelectric liquid crystalline polysiloxanes designed for high second-order nonlinear susceptibilities

Ferroelectric liquid crystalline (FLC) copolysiloxanes containing suitable comonomers («NLO-chromophores») for second harmonic generation (SHG) have been prepared. Their important feature is a donor-acceptor x-system sited perpendicular to the long axis of the side-group moieties in order to adopt the polar ordering of the ferroelectric LC phase. The influcences of the mesogen structure and of the content of NLO-chromophores on the liquid crystalline and ferroelectric properties are studied. The desired chiral smectic C * phase is retained up to 30 mol-% of chromophore. Also, first measurements of second harmonic generation have been performed

Synthesis of pentafluorophenyl(meth)acrylate polymers: New precursor polymers for the synthesis of multifunctional materials

Pentafluorophenyl acrylate and -methacrylate were polymerized using AIBN as a thermal initiator. The obtained polymers were soluble polymeric active esters that could be used for the preparation of multifunctional polymers. The reactivity of poly(pentafluorophenylacrylate) and poly(pentafluorophenylmethacrylate) towards primary and secondary amines, as well as alcohols was investigated in a quantitative way. Both poly(active esters) reacted satisfactorily with aliphatic primary and secondary amines but only low conversion was found in the case of aromatic amines. Conversions of only 30% were reached when poly(pentafluorophenylacrylate) was treated with one equivalent of alcohol under base c…

Nanoparticles and the immune system: challenges and opportunities

Synthesis of Reactive Telechelic Polymers Based on Pentafluorophenyl Esters

A diazo initiator and a chain transfer agent (CTA), both containing a pentafluorophenyl (PFP) activated ester, were synthesized. In a RAFT polymerization using the functionalized chain transfer agent (PFPCTA), methyl methacrylate (MMA), diethylene glycol monomethyl ether methacrylate (DEGMA), poly(ethylene glycol) monomethyl ether methacrylate (PEGMA), and lauryl methacrylate (LMA) could successfully be polymerized into homopolymers and diblock copolymers with good control over molecular weight, very high conversions, and narrow molecular weight distributions. Polymers derived from the PFP-CTA possessed an activated ester at the R-end of the polymer chain, which could be reacted with amines…

Interaction of pHPMA–pLMA Copolymers with Human Blood Serum and Its Components

Immediately after administration, polymer therapeutics are exposed to complex biological media like blood which may influence and alter their physicochemical properties due to interactions with proteins or serum components. Among such interactions those leading to larger sized aggregates can be sensitively detected by dynamic light scattering (DLS) as a pre in vivo screening method. Random copolymers from N-(2-hydroxypropyl)methacrylamide and lauryl methacrylate p(HPMA-co-LMA) and copolymers loaded with the model drug domperidone were characterized by DLS in isotonic salt solution and in blood serum. The bare amphiphilic copolymer micelles (Rh=30 nm in isotonic salt solution) formed large a…

Redoxactive liquid crystalline (LC) side group polymers were prepared by copolymerization of liquid crystalline acrylates and ferrocene-containing acrylates. The corresponding liquid crystalline ionomers were synthesized by a reversible redox reaction. The incorporation of tetra-alkylated ferrocene derivatives leads to LC polymers with reduced redox potential. These polymers can be oxidized under mild conditions to the corresponding ionomers, which are much more stable in solution than LC ionomers containing monoalkylated ferrocenium ions. Dynamic mechanical measurements and small angle X-ray scattering (SAXS) perfomed on LC ionomers prove the existence of ionic superstructures (clusters) w…

Ferroelectric liquid crystalline polysiloxanes with high spontaneous polarization and possible applications in nonlinear optics

Elastic Properties of Liquid Crystal Elastomer Balloons

We introduce a method to measure elastic properties of smectic liquid crystalline elastomers. Freely suspended smectic polymer films containing photoreactive groups are inflated to spherical bubbles and crosslinked by UV light irradiation. After crosslinking, the balloon volume is varied and elastic properties of the material are determined from the relation between radius and inner excess pressure. The influence of the network topology on the elastic behaviour is discussed.

Microactuators from a main-chain liquid crystalline elastomer via thiol–ene “click” chemistry

Recently it has been described that liquid crystalline elastomer (LCE) particles of the side-chain type can be prepared in microfluidic devices. Here we present the preparation of micrometer-sized LCE particles of the main-chain type by thiol–ene chemistry. The LCE particles are UV-crosslinked via thiol–ene click chemistry of the nematic monomer, carrying terminal thiol and ene groups, and non-mesogenic tetrathiol and tetraene crosslinkers. The preparation of the LCE particles with a microfluidic device by a continuous “on the fly” technique allows their fast processing with an irradiation time of less than 2 seconds. The resulting particles undergo a temperature-driven volume change up to …

Control of the Properties of Micrometer-Sized Actuators from Liquid Crystalline Elastomers Prepared in a Microfluidic Setup

In this article new results on the preparation of monodisperse particles from a liquid crystalline elastomer in a microfluidic setup are presnted. For this, droplets from a liquid crystalline monomer are prepared in a microfluidic device and polymerized while they are flowing inside a microtube. The parti­cles obtained by this method possess an internal orientation, which gives them actuating properties. When they are heated into the isotropic phase of the liquid crystalline material they show a reversible change in shape whereby they change their length in one direction by almost 100%. It is shown how the variation of experimental parameters during their synthesis impacts the properties of…

Influence de la structure de chaine sur le type de phase et relation entre la masse moleculaire et les temperatures de transition

Side-chain conjugated polymers for use in the active layers of hybrid semiconducting polymer/quantum dot light emitting diodes

Three monomers, M1–M3, with modified carbazole cores and styrene functionality were prepared for use in the active layers of hybrid polymer/quantum dot light emitting diodes. Utilizing reversible addition fragmentation chain transfer polymerization, side-chain conjugated polymers, P1–P3, with narrow polydispersities and disulfide end groups were obtained. The thermal, optical, and electrochemical properties of the polymers varied depending on the substituents of the carbazole cores. Through the disulfide end groups the polymers were chemically blended with quantum dots to obtain QD/polymer hybrids, which were further used as active layers in light emitting diodes. The fabricated devices ret…

Covalently crosslinked liquid crystalline networks with elastic properties were prepared in isotropic solution from linear liquid crystalline polymers. As linear precursors for the networks were used: (i) polymers with the mesogenic groups in the side groups (polyacrylates and polymethacrylates), (ii) polymers with the mesogenic groups in the main chain (polymalonates) and (iii) polymers with the mesogenic groups in main chain and side groups (“combined liquid crystalline polymers”). In all crosslinked polymers the liquid crystalline phases of the linear polymers are retained. For low degrees of crosslinking (≤2 mol-%) the phase transition temperatures remain nearly unchanged. These elastom…

Polymere Selectinliganden als komplexe Glykomimetika: von Selectinbindung bis zur Modifizierung der Makrophagenmigration

Bei neuartigen polymeren Inhibitoren der Zelladhasion wird das Selectin-bindende Tetrasaccharid Sialyl-LewisX (SLeX) multivalent auf einem biokompatiblen Poly(2-hydroxypropyl)methacrylamid (PHPMA) entweder alleine (P1) oder in Kombination mit O-sulfatierten Tyramin-Seitenketten (P2) prasentiert. Zum Vergleich wurden entsprechende polymere Glykomimetika hergestellt, in denen die entscheidenden Fucose-, Galactose und Sialinsaure-Seitenketten statistisch verteilt im PHPMA-Ruckgrat (P3 oder P4 (O-sulfatiertes Tyramin) vorliegen. Alle Polymere haben den gleichen Polymerisationsgrad, da sie vom selben Ausgangspolymer abstammen. Assays fur die Bindung an Selectine, aktivierte Endothelzellen und Ma…

Characterization of opal photonic hetero-crystals by light scattering

Spectra of the light scattered in the heterogeneous photonic crystal based on the thin triple-film opal, which was prepared by successive, convective force-assisted crystallisation of colloidal suspensions containing spheres of 374, 474 and again 374 nm in diameter, have been studied in the wavelength range of low order photonic bandgaps. If the ballistic regime of light propagation is preserved, the forward scattered light becomes the subject of the diffraction attenuation, whereas the backscattered light experiences both the diffraction enhancement and attenuation. A variety of possible configurations of scattered light measurements have been examined and corresponding spectra of scattere…

Light transport in hetero-opal photonic crystals

The effect of photonic bandgap interface upon the light scattering was studied in hetero-opals consisting of two opal thin films with different lattice constant. It is shown that the weak scattering regime is preserved in thin hetero-opal films. By comparing scattering spectra of single and hetero-opal films recorded under reversing angles of light incidence and detection it was demonstrated that the interface scatters stronger the light at oblique incident angles. Squeezing of the scattering diagram of hetero-opals compared to single opal films is also assigned to the interface scattering.

Versatile, Multifunctional Block Copolymers for the Self-Assembly of Well-Defined, Nontoxic pDNA Polyplexes

In the field of systemically applied, nucleic acid-based drugs, polyplexes are interesting candidates for therapeutic systems. In this study, we synthesized a multifunctional triblock copolymer via...

Liquid crystalline phases from polymer functionalised semiconducting nanorods

The orientation of semiconducting nanomaterials is a hot topic in optoelectronic applications. Liquid crystallinity offers the potential to orient inorganic anisotropic nanorods, if they can be solubilised sufficiently as realised by polymer functionalisation. In this work we functionalised TiO2, SnO2, ZnO and CdTe nanorods with PMMA, PS and PDEGMEMA (poly(diethylene glycol monomethyl ether) methacrylate) diblock copolymers containing anchor groupsvia grafting-to. The block copolymers were synthesised by RAFT polymerisation (PDI ≈ 1.2) via reactive ester diblock copolymers, which were functionalised later with anchor units polymer-analogously. The surface coverage of the nanorods (determine…

Better Actuation Through Chemistry: Using Surface Coatings to Create Uniform Director Fields in Nematic Liquid Crystal Elastomers.

Controlling the molecular alignment of liquid crystal monomers (LCMs) within nano- and microstructures is essential in manipulating the actuation behavior of nematic liquid crystal elastomers (NLCEs). Here, we study how to induce uniformly vertical alignment of nematic LCMs within a micropillar array to maximize the macroscopic shape change using surface chemistry. Landau-de Gennes numerical modeling suggests that it is difficult to perfectly align LCMs vertically in every pore within a poly(dimethylsiloxane) (PDMS) mold with porous channels during soft lithography. In an untreated PDMS mold that provides homeotropic anchoring of LCMs, a radially escaped configuration of LCMs is observed. V…

Dielectric and electro-optical studies of a ferroelectric copolysiloxane.

This paper reports an extensive study of the static (spontaneous polarization, ${\mathit{P}}_{\mathit{s}}$, tilt angle \ensuremath{\theta}, and pitch) and dynamic properties of a ferroelectric liquid-crystalline polymer. It is shown that a ferroelectric liquid-crystalline polymer (diluted polysiloxane) exhibits physical behavior similar to that of a low-molar-mass liquid crystal in terms of contrast ratio, pitch of the helix, and relationship between ${\mathit{P}}_{\mathit{s}}$ and \ensuremath{\theta}. The degenerated collective modes for the director rotation are shown to split into two modes at the Sm-A--Sm-${\mathit{C}}^{\mathrm{*}}$ phase transition temperature using dielectric spectros…

CpG-Loaded Multifunctional Cationic Nanohydrogel Particles as Self-Adjuvanting Glycopeptide Antitumor Vaccines

Self-adjuvanting antitumor vaccines by multifunctional cationic nanohydrogels loaded with CpG. A conjugate consisting of tumor-associated MUC1-glycopeptide B-cell epitope and tetanus toxin T-cell epitope P2 is linked to cationic nanogels. Oligonucleotide CpG complexation enhances toll-like receptor (TLR) stimulated T-cell proliferation and rapid immune activation. This co-delivery promotes induction of specific MUC1-antibodies binding to human breast tumor cells without external adjuvant.

Redox-Tunable Defects in Colloidal Photonic Crystals

Microfluidic Synthesis of Actuating Microparticles from a Thiol-Ene Based Main-Chain Liquid Crystalline Elastomer.

In this article the microfluidic synthesis of strongly actuating particles on the basis of a liquid crystalline main-chain elastomer is presented. The synthesis is carried out in a capillary-based co-flow microreactor by photo-initiated thiol-ene click chemistry of a liquid crystalline monomer mixture. These microparticles exhibit a deformation from a spherical to a rod-like shape during the thermal-initiated phase transition of the liquid crystalline elastomer (LCE) at which the particles’ aspect ratio is almost doubled. Repeated contraction cycles confirm the complete reversibility of the particles’ actuation properties. The transition temperature of the LCE, the temperature range of the …

Mit Glycopeptid-Antigenen und T-Zell-Epitopen verknüpfte wasserlösliche Polymere als potenzielle Antitumor-Vakzine

In Vivo Myofibroblast Specific Gene Silencing in the Liver Using Novel Sirna-Loaded Biodegradable Nanohydrogel Particles

Preparation of Soft Microactuators in a Continuous Flow Synthesis Using a Liquid-Crystalline Polymer Crosslinker

We present the synthesis of a polymeric liquid crystalline (LC) crosslinker and its usage in the preparation of soft microactuators. The microactuators, composed of thermoresponsive liquid crystalline elastomers (LCE), are fabricated in a microfl uidic device in a continuous “on the fl y” process. The LC polymer crosslinker is miscible with the LC monomer and provides for a rapid polymerization and crosslinking. Most importantly, it promotes an enantiotropic mesophase of the mobile monomer phase, which is not provided by conventional nonmesogenic crosslinkers. This allows an isothermal handling inside the microfl uidic setup. Temperature-driven shape changes up to 65% could be achieved by j…

Large Photonic Films by Crystallization on Fluid Substrates

Cracks, which appear due to shrinkage during drying of artificial opaline films, strongly limit the use of these materials. Crystallization on fluid substrates (liquid metals) is a way to circumvent this problem. By this method it is possible to prepare crack-free three-dimensional “monocrystals” with a very low defect density and the size in millimeters.

α-Mannosyl-Functionalized Cationic Nanohydrogel Particles for Targeted Gene Knockdown in Immunosuppressive Macrophages

Immunosuppressive M2 macrophages govern the immunophathogenic micromilieu in many severe diseases including cancer or fibrosis, thus, their re-polarization through RNA interference is a promising concept to support combinatorial therapies. For targeted siRNA delivery, however, safe and stable carriers are required that manage cell specific transport to M2 macrophages. Here, siRNA-loaded cationic nanogels are reported with α-mannosyl decorated surfaces that target and modify M2 macrophages selectively. Via amphiphilic precursor block copolymers bearing one single α-mannosyl moiety at their chain end mannosylated cationic nanohydrogel particles (ManNP) were obtained of 20 nm diameter determin…

Chiral polyisocyanates, a special class of helical polymers

Abstract Polyisocyanates (nylon 1) offer a lot of fascinating properties due to their dynamic helical conformation, which gives rise to orientational phenomena (large persistence length) or chiral amplification. This paper summarizes new results on polyisocyanates that appeared after the review by Bur and Fetters [Chem Rev 76 (1976) 727]. It starts with an overview of new synthetic methods, and then describes chiral polyisocyanates, their properties and the theoretical concepts developed to understand the experimental findings. Thereafter concentrated solutions (gels and LC phases) as well as photochromic polyisocyanates are discussed in detail. Finally, solid phase composite materials from…

Preparation of cholesteric particles from cellulose derivatives in a microfluidic setup

A microfluidic setup was used to process lyotropic cholesteric liquid crystalline mixtures of cellulose derivatives into spherical particles in the micrometre scale. By the method of co-flowing injection, monodisperse droplets of the liquid crystal, dispersed in an aqueous carrier fluid, were prepared. Polymerization of the acrylic solvent with UV-light fixed the orientation obtained by the flowing motion. The resulting particles were characterized by polarizing optical microscopy.

Size Tunable Core Crosslinked Micelles from HPMA-Based Amphiphilic Block Copolymers

A variety of core crosslinkable hydroxypropylmethacrylamide-based block copolymers are synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization, which are composed of hydroxypropyl-methacrylate as hydrophilic block combined with a statistical hydrophobic block from laurylmethacrylate and the photo crosslinkable monomer. It is discovered that the self-assembled micellar aggregates from these systems vary strongly in size depending not only on the velocity of the polarity switch (nanoprecipitation or slow dialysis) but also on the solvent from which they were dialyzed. In this way micellar aggregates with an Rh varying between 15 and 80 nm can be prepared from the…

Towards Si-based photonic circuits: Integrating photonic crystals in silicon-on-insulator platforms

In the context of Si-based photonics, we report on a strategy to integrate two optical components, a 3D photonic crystal light emitter and a waveguide, in a silicon-on-insulator patterned substrate. Self-assembled colloidal photonic crystals are produced with high crystalline quality and spatial selectivity. Plane wave expansion and finite-difference time-domain have been used to find suitable configurations for positioning emitters and waveguides. The first steps toward the realisation of these configurations are presented.

Dual Functionalization of Nanostructures of Block Copolymers with Quantum Dots and Organic Fluorophores

HPMA-based block copolymers promote differential drug delivery kinetics for hydrophobic and amphiphilic molecules.

Abstract We describe a method how polymeric nanoparticles stabilized with (2-hydroxypropyl)methacrylamide (HPMA)-based block copolymers are used as drug delivery systems for a fast release of hydrophobic and a controlled release of an amphiphilic molecule. The versatile method of the miniemulsion solvent-evaporation technique was used to prepare polystyrene (PS) as well as poly-d/l-lactide (PDLLA) nanoparticles. Covalently bound or physically adsorbed fluorescent dyes labeled the particles’ core and their block copolymer corona. Confocal laser scanning microscopy (CLSM) in combination with flow cytometry measurements were applied to demonstrate the burst release of a fluorescent hydrophobic…

Semicarbazides as gel forming agents for common solvents and liquid crystals

This paper describes the synthesis of 14 new gelling agents with semicarbazide groups as H-bonding motifs and alkyl- and/or azobenzene side groups. They gel solvents like decaline, 1,2-dichlorobenzene and toluene and liquid crystalline mixtures. X-Ray structure analysis shows that the semicarbazides are connected by H-bonds, each molecule to four neighbours. As a result a ribbon is formed with a core of H-bonded semicarbazide groups and alkyl chains sticking to the side. IR measurements show an unchanged H-bonding motif in large crystals and in the gel fibres, even in LC-mixture. During heating the gel melts (rheology), while the H-bonding motif of the crystal disappears (IR and DSC measure…

Carbon-Coated Anatase TiO2Nanotubes for Li- and Na-Ion Anodes

aInstitute of Physical Chemistry and MEET Battery Research Centre, University of Muenster, 48149 Muenster, Germany bHelmholtz-Institute Ulm (HIU), Electrochemistry I, 89081 Ulm, Germany cKarlsruher Institute of Technology (KIT), 76021 Karlsruhe, Germany dInstitute for Organic Chemistry, University of Mainz, 55128 Mainz, Germany eGraduate School Materials Science in Mainz, 55128 Mainz, Germany fInstitute for Inorganic and Analytical Chemistry, University of Mainz, 55128 Mainz, Germany gMax Planck Institute for Polymer Research, 55128 Mainz, Germany

DNA Designer Defects in Photonic Crystals: Optically Monitored Biochemistry

NLO-polymers containingtert-butyloxycarbonyl protecting groups: Modification after processing leading to thermally stable nonlinear optical materials

Artificially inscribed defects in opal photonic crystals

Opals are three-dimensional photonic crystals, self-assembled from dielectric spherical beads into a face-centered cubic lattice. By introducing intentional defects in the crystal lattice, one modifies features such as spontaneous emission and the directionality of diffracted light. We here present a method for the artificial introduction of a lattice of such intentional defects in self-assembled poly(methyl methacrylate) (PMMA) photonic crystals by means of electron beam lithography. The inscribed defects are of the size of an individual bead, providing a broad spectral range between adjacent resonance peaks. This opens for devices with single line transmission in the photonic band gap, as…

18F-Radiolabeling, Preliminary Evaluation of Folate-pHPMA Conjugates via PET

The synthesis of a 10.5 kDa and a 52.5 kDa polymer, based on pHPMA functionalized with tyramine for (18) F-labeling and a folate derivative as targeting moiety, is reported. FCS studies are conducted using Oregon Green-labeled conjugates. No aggregation is observed for the 10.5 kDa conjugate, but strong aggregation for the 52.5 kDa conjugate. In vivo studies are conducted using Walker-256 mammary carcinoma model to determine body distribution as function of size and especially targeting unit. These in vivo studies show a higher short time (2 h) accumulation for both conjugates in the tumor than for untargeted pHPMA, confirmed by blockade studies. The 10.5 kDa polymer accumulates with 0.46% …

Light propagation in triple-film hetero-opals

Spectra of transmitted and forward scattered light of single opal films and triple-film hetero-opals have been compared. The presence of an intermediate film in hetero-opal results in an anomalous increase of the scattered light intensity and in the change of the mainly ballistic light propagation regime to the mainly diffusive one in the frequency range of the photonic bandgap defect state.

Dimesogenic liquid crystalline oligosiloxanes

Abstract In this paper, the syntheses, phase properties and ferroelectric properties of new liquid crystalline oligosiloxane dimesogens are described. Smectic phases are dominant in this class of materials. Spontaneous polarizations are in the range of 10 to approximately 100 nCcm−2. The materials show interesting properties for display applications. Although offering higher mechanical stability than low molar mass materials, their switching is significantly faster (switching times in the range of some 10−5s) than is the case for similar side group polymers (typically some 10−3s). Therefore these new oligosiloxane derivatives may be ideal for building flexible displays. In addition, mixture…

Reduced efficiency roll-off in light-emitting diodes enabled by quantum dot–conducting polymer nanohybrids

We demonstrate QLEDs implementing wider active layers (50 nm) based on QD–conducting polymer nanohybrids, which exhibit a stable operational device performance across a wide range of current densities and brightness. A comparative study reveals that the significant suppression of efficiency roll-off in the high current density regime is primarily attributed to a sufficient charge carrier distribution over the wider active layer and improved charge carrier balance within QDs enabled by the hybridization of QDs with conducting polymers. Utilization of this finding in future studies should greatly facilitate the development of high performance, stable QLEDs at high current density or luminance…

Toward Anticancer Immunotherapeutics: Well-Defined Polymer-Antibody Conjugates for Selective Dendritic Cell Targeting

This paper describes the synthesis of semitelechelic maleimide-modified N-(2-hydroxypropyl)methacrylamid) (HPMA) based polymers of narrow dispersity that can be conjugated e.g. to anti-DEC-205 antibodies affording "star-like" topologies (one antibody decorated with several polymer chains). FCS revealed a hydrodynamic diameter of R(h)  = 7.9 nm and SEC narrow dispersity (1.45). Primary in vitro studies with bone marrow derived dendritic cells (DC) show higher cellular binding and uptake rates compared to control samples. Moreover, incubating these conjugates to primary splenocytes demonstrates a much higher affinity to the primary DCs than to any other immune cell population within the splee…

HPMA Based Amphiphilic Copolymers Mediate Central Nervous Effects of Domperidone

In this study we give evidence that domperidone encapsulated into amphiphilic p(HPMA)-co-p(laurylmethacrylate) (LMA) copolymer aggregates is able to cross the blood-brain barrier, since it affected motor behaviour in animals, which is a sensitive measure for CNS actions. Carefully designed copolymers based on the clinically approved p(HPMA) were selected and synthesized by a combination of controlled radical polymerization and post-polymerization modification. The hydrodynamic radii (R(h) ) of amphiphilic p(HPMA)-co-p(LMA) alone and loaded with domperidone were determined by fluorescence correlation spectroscopy.

Macromol. Chem. Phys. 21/2013

Amphotropic Ionomers by Attachment of Secondary Amines to a Reactive Ester Polymer

We report on the synthesis of polyacrylamides that were prepared by the reaction of a reactive ester polymer with a mesogen-containing secondary amine and N-methyl-piperazine. As the polymers do not form hydrogen bonds near the amide groups, their mobility is significantly higher than that of poly(N-monoalkylacrylamides). The initially nonionic polymer shows no liquid-crystalline behavior in bulk and in mixture with ethylene glycol. This is due to the low polarity difference between the different side chains. The polarity difference can be increased by protonation or quarter-nization of the tertiary amino groups, and liquid-crystalline behavior is observed. The self-assembly multilayer buil…

Freely-Suspended and Transferred Freely-Suspended Films of Polymeric Liquid Crystals

Freely-suspended (FS) liquid-crystal (LC) films of a polymethylsiloxane homo- and a copolymer with different mesogenic side groups have been prepared and investigated. For both substances the preparation of the films succeeded only in the isotropic phase but the higher ordered phases were reached after cooling. The films of the homopolymer have only been obtained with thicknesses estimated to be in the pm-range and with an unusual “Book-Shelf” orientation of the smectic layers. In contrast, the films of the copolymer were thinner and showed a homeotropic orientation of the mesogens in the smectic A phase. Interestingly, this material exhibited a different layer spacing in film and bulk, alt…

Synthesis and In Vitro Evaluation of Defined HPMA Folate Conjugates: Influence of Aggregation on Folate Receptor (FR) Mediated Cellular Uptake

In this article we report the synthesis and in vitro evaluation of well-defined, folate functionalized and fluorescently labeled polymers based on the clinically approved N-(2-hydroxypropyl)-methacrylamide (HPMA). The polymers were prepared applying the RAFT polymerization method as well as the reactive ester approach. The molecular weights of the polymers synthesized were around 15 and 30 kDa. The total content of conjugated folate varied from 0, 5, and 10 mol %. The cellular uptake of these polymers was investigated in the folate receptor (FR)-positive human nasopharyngeal epidermal carcinoma (KB-3-1) and FR-negative human lung epithelial carcinoma (A549) cancer cell lines. In FR-positive…

Phase behavior and elastic properties of a slightly crosslinked liquid crystalline main-chain polymer

A liquid crystalline main-chain polymer was slightly crosslinked by a reaction withα, ω-difunctionalized oligo-siloxanes. Crosslinking does not disturb the liquid crystalline phases, which are identified by x-ray measurements as smecticB and smecticA phases. Measurements of the elastic properties of the crosslinked sample show rubber-like elasticity, even in the liquid crystalline phases. A difference of 7 K was found between cooling and heating for the smecticA/isotropic transition from DSC and mechanical measurements.

Oligothiophenes for Pattern Formation by Stamping

Oligothiophene monomers with a fixed length varying from 3 to 5 thiophene rings were prepared by Stille coupling. They were functionalised with one or two methacrylate groups to allow polymerization and cross-linking. These monomers can be patterned with the help of soft silicon stamps (e.g., with the micro-injection moulding in capillaries process) on substrates like glass or flexible polymer foils. If a photoinitiator has been added, they can then be hardened by exposure to UV-light through the transparent stamp. Afterwards the stamp can be removed. This allows the preparation of several centimeters long oligothiophene lines of a width varying between 50 and 0.5 μm. These lines of semicon…

Ordering and dewetting in spin-coated films of a liquid crystalline main chain polymer

Abstract The ordering of spin-coated films of a main-chain smectic liquid crystalline polymer with an azobenzene group connected by flexible spacers to a phenyl malonate unit has been studied as a function of film thickness using scanning force microscopy and UV/Vis spectroscopy. Already the as-prepared films are characterized by a significant out-of-plane orientation of the azobenzene groups. Annealing of films thicker than 7 nm results in aggregation and homeotropical alignment of azobenzene groups forming smectic layers parallel to the substrate. An optically isotropic mesophase was found upon annealing in the temperature range of smectic mesophase. Films thinner than the bilayer thickne…

Functionalization of P3HT with Various Mono- and Multidentate Anchor Groups

Due to its favorable optoelectronic properties and the accessibility via Grignard metathesis (GRIM) polymerization, poly(3-hexylthiophene) (P3HT) is one of the most applied conjugated polymers. The ‘living' nature of GRIM polymerization enables the modification of the polymer and the installation of desired properties. In the present study, two versatile approaches for the synthesis of anchor group-modified P3HT have been developed, which enable the functionalization of various inorganic nanoparticles. Depending on the polymerization conditions, mono- and bifunctional ethynyl-terminated P3HT or solely monofunctionalized aldehyde-terminated P3HT was synthesized. Afterwards, the quantitative …