Combining Orthogonal Reactive Groups in Block Copolymers for Functional Nanoparticle Synthesis in a Single Step.

We report on the synthesis of polysarcosine-block-poly(S-alkylsulfonyl)-l-cysteine block copolymers, which combine three orthogonal addressable groups enabling site-specific conversion of all reactive entities in a single step. The polymers are readily obtained by ring-opening polymerization (ROP) of corresponding α-amino acid N-carboxyanhydrides (NCAs) combining azide and amine chain ends, with a thiol-reactive S-alkylsulfonyl cysteine. Functional group interconversion of chain ends using strain-promoted azide–alkyne cycloaddition (SPAAC) and activated ester chemistry with NHS- and DBCO-containing fluorescent dyes could be readily performed without affecting the cross-linking reaction betw…

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.

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…

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…

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.

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

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…

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 …

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…

(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.…

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.…

Macromol. Rapid Commun. 24/2014

Tetrazine- and trans -cyclooctene-functionalised polypept(o)ides for fast bioorthogonal tetrazine ligation

The inverse electron demand Diets-Alder (IEDDA) reaction-initiated ligation between 1,2,4,5-tetra-zines (Tz) and trans-cyclooctenes (TCO) is one of the fastest bioorthogonal reactions known today and is therefore increasingly used for in vivo click chemistry. Described herein is the synthesis of Tz- and TCO-functionalised polypeptides, polypeptoids and polypeptide-block-polypeptoids (polypept(o) ides) by ring-opening polymerisation of the corresponding N-carboxyanhydrides using Tz- or TCO-functional amine initiators. Despite the reactivity of tetrazines, polymers with low dispersity and high end group integrity can be obtained as observed by gel permeation chromatography (GPC), nuclear magn…

Sekundärstrukturbildung als Triebkraft für die Selbstorganisation reaktiver Polypept(o)ide: Steuerung von Größe, Form und Funktion kernvernetzter Nanostrukturen

Prazise Kontrolle uber Morphologie und Funktion polymerer Nanostrukturen im Rahmen der Selbstorganisation stellt nach wie vor eine Herausforderung im Feld der Material- und biomedizinischen Wissenschaften dar, insbesondere wenn unabhangige Kontrolle uber einzelne Partikeleigenschaften erwunscht ist. Hier wird uber Sekundarstruktur-gesteuerte Selbstorganisation von Nanostrukturen basierend auf amphiphilen Blockcopolypept(o)iden berichtet und eine Strategie zur bio-reversiblen Einstellung der Kernpolaritat und –funktion unabhangig von der Partikelpraparation vorgestellt. Der Peptiden eigene Prozess der Sekundarstrukturbildung erlaubt so die Herstellung spharischer und wurmartiger kernvernetzt…

Exploring new activating groups for reactive cysteine NCAs

Abstract Due to its ability to reversibly crosslink proteins, cysteine has a unique role as an amino acid in nature. For controlled, asymmetric formation of disulfides from two thiols, one thiol needs to be activated. While few activating groups for cysteine have been proposed, they are usually not stable against amines making them unsuitable for solid phase peptide synthesis or amine initiated polymerization of α-amino acid-N-carboxy-anhydrides (NCAs). In this Letter we describe a series of new thiol activated cysteines, as well as their NCAs and explore the link between electron deficiency of the leaving group and control over NCA polymerization.

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…

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…

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…

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…

Secondary-Structure-Driven Self-Assembly of Reactive Polypept(o)ides: Controlling Size, Shape, and Function of Core Cross-Linked Nanostructures.

Achieving precise control over the morphology and function of polymeric nanostructures during self-assembly remains a challenge in materials as well as biomedical science, especially when independent control over particle properties is desired. Herein, we report on nanostructures derived from amphiphilic block copolypept(o)ides by secondary-structure-directed self-assembly, presenting a strategy to adjust core polarity and function separately from particle preparation in a bioreversible manner. The peptide-inherent process of secondary-structure formation allows for the synthesis of spherical and worm-like core-cross-linked architectures from the same block copolymer, introducing a simple y…

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…

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 …