Ruthenium-Containing Block Copolymer Assemblies: Red-Light-Responsive Metallopolymers with Tunable Nanostructures for Enhanced Cellular Uptake and Anticancer Phototherapy.
The use of self-assembled nanostructures consisting of red-light-responsive Ru(II)-containing block copolymers (BCPs) for anticancer phototherapy is demonstrated. Three Ru-containing BCPs with different molecular weights are synthesized. Each BCP contains a hydrophilic poly(ethylene glycol) block and an Ru-containing block. In the Ru-containing block, more than half of the side chains are coordinated with [Ru(2,2':6',2''-terpyridine)(2,2'-biquinoline)](2+) , resulting in more than 40 wt% Ru complex in the BCPs. The Ru complex acts as both a red-light-cleavable moiety and a photoactivated prodrug. Depending on their molecular weights, the BCPs assemble into micelles, vesicles, and large comp…
Anisotropic carrier diffusion in single MAPbI(3) grains correlates to their twin domains
Polycrystalline thin films and single crystals of hybrid perovskites – a material group successfully used for photovoltaic and optoelectronic applications – reportedly display heterogeneous charge carrier dynamics often attributed to grain boundaries or crystalline strain. Here, we locally resolved the carrier diffusion in large, isolated methylammonium lead iodide (MAPbI3) grains via spatial- and time-resolved photoluminescence microscopy. We found that the anisotropic carrier dynamics directly correlate with the arrangement of ferroelastic twin domains. Comparing diffusion constants parallel and perpendicular to the domains showed carriers diffuse around 50–60% faster along the parallel d…
Engineering von Proteinen an Oberflächen: Von komplementärer Charakterisierung zu Materialoberflächen mit maßgeschneiderten Funktionen
Removal of Surface Oxygen Vacancies Increases Conductance Through TiO(2) Thin Films for Perovskite Solar Cells
[Image: see text] We report that UV–ozone treatment of TiO(2) anatase thin films is an efficient method to increase the conductance through the film by more than 2 orders of magnitude. The increase in conductance is quantified via conductive scanning force microscopy on freshly annealed and UV–ozone-treated TiO(2) anatase thin films on fluorine-doped tin oxide substrates. The increased conductance of TiO(2) anatase thin films results in a 2% increase of the average power conversion efficiency (PCE) of methylammonium lead iodide-based perovskite solar cells. PCE values up to 19.5% for mesoporous solar cells are realized. The additional UV–ozone treatment results in a reduced number of oxygen…
Anisotropic Charge Carrier Diffusion Correlated to Ferroelastic Twin Domains in MAPbI3 Perovskite
Measuring the Contact Angle of Individual Colloidal Particles.
The aim of this study was to measure the contact angles of individual colloidal spheres ( solidus in circle 4.4 µm) and compare it to contact angles obtained on similarly prepared planar surfaces. For this purpose the particles were attached to atomic force microscope cantilevers. Then the force between the particle in aqueous medium and an air bubble was measured versus the distance. From the resulting force curves we obtained contact angles and detachment forces of single particles. Contact angles of gold coated silica particles were adjusted between 20 degrees and 100 degrees by self-assembling monolayers from different mixtures of undecanethiols and omega-hydroxy undecanethiols from sol…
One-Dimensional Hypersonic Phononic Crystals
We report experimental observation of a normal incidence phononic band gap in one-dimensional periodic (SiO(2)/poly(methyl methacrylate)) multilayer film at gigahertz frequencies using Brillouin spectroscopy. The band gap to midgap ratio of 0.30 occurs for elastic wave propagation along the periodicity direction, whereas for inplane propagation the system displays an effective medium behavior. The phononic properties are well captured by numerical simulations. The porosity in the silica layers presents a structural scaffold for the introduction of secondary active media for potential coupling between phonons and other excitations, such as photons and electrons.
Dynamic studies on living cells with an atomic force fluorescence microscope
Analysis of the reaction of bone structure to mechanical stimulation is a key issue in understanding the origins of osteoporosis and mechanical adaptation of living bone to external forces. This is thought to be regulated on a cellular level. We have investigated quantitative mechanical stimulation of single bone cells and their immediate intracellular calcium responses using a combination of an atomic force microscope (AFM) and a fluorescence microscope, developed in our laboratory. The force stimulation system can apply quantified forces in the pico- and nano-newton regime on exactly defined positions of a cell. We present here the first measurements using this system on the mechanically …
Tapered copolymers of styrene and 4‐vinylbenzocyclobutene via carbanionic polymerization for crosslinkable polymer films
Slide electrification: charging of surfaces by moving water drops.
We investigate the charge separation caused by the motion of a water drop across a hydrophobic, insulating solid surface. Although the phenomenon of liquid charging has been consistently reported, these reports are primarily observational, results are difficult to reproduce, and no quantitative theory has been developed. In this work, we address both the experimental and theoretical sides of this problem. We reproducibly measure the charge gained by water drops sliding down a substrate, and we outline an analytical theory to describe this charging process. As an experimental system, we choose water drops moving down an inclined plane of glass hydrophobized with perfluoro octadecyltrichloros…
Defect-controlled hypersound propagation in hybrid superlattices
We employ spontaneous Brillouin light scattering spectroscopy and detailed theoretical calculations to reveal and identify elastic excitations inside the band gap of hypersonic hybrid superlattices. Surface and cavity modes, their strength and anticrossing are unambiguously documented and fully controlled by layer thickness, elasticity, and sequence design. This new soft matter based superlattice platform allows facile engineering of the density of states and opens new pathways to tunable phoxonic crystals.
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…
Modulation of mitochondriotropic properties of cyanine dyes by in organello copper-free click reaction
Cyanine (Cy) dyes show a general propensity to localize in polarized mitochondria. This mitochondriotropism was used to perform a copper-free click reaction in the mitochondria of living cells. The in organello reaction of dyes Cy3 and Cy5 led to a product that was easily traceable by Forster resonance energy transfer (FRET). As determined by confocal laser scanning microscopy, the Cy3-Cy5 conjugate showed enhanced retention in mitochondria, relative to that of the starting compounds. This enhancement of a favorable property can be achieved by synthesis in organello, but not outside mitochondria.
Force Measurements on Myelin Basic Protein Adsorbed to Mica and Lipid Bilayer Surfaces Done with the Atomic Force Microscope
The mechanical and adhesion properties of myelin basic protein (MBP) are important for its function, namely the compaction of the myelin sheath. To get more information about these properties we used atomic force microscopy to study tip-sample interaction of mica and mixed dioleoylphosphatidylserine (DOPS) (20%)/egg phosphatidylcholine (EPC) (80%) lipid bilayer surfaces in the absence and presence of bovine MBP. On mica or DOPS/EPC bilayers a short-range repulsive force (decay length 1.0-1.3 nm) was observed during the approach. The presence of MBP always led to an attractive force between tip and sample. When retracting the tip again, force curves on mica and on lipid layers were different…
Nanowear on Polymer Films of Different Architecture
In this paper, we describe atomic force microscope (AFM) friction experiments on different polymers. The aim was to analyze the influence of the physical architecture of the polymer on the degree and mode of wear and on the wear mode. Experiments were carried out with (1) linear polystyrene (PS) and cycloolefinic copolymers of ethylene and norbornene, which are stabilized by entanglements, (2) mechanically stretched PS, (3) polyisoprene-b-polystyrene diblock copolymers, with varying composition, (4) brush polymers consisting of a poly(methyl methacrylate) (PMMA) backbone and PS side chains, (5) PMMA and PS brushes grafted from a silicon wafer, (6) plasma-polymerized PS, and (7) chemically c…
End-Group-Dominated Molecular Order in Self-Assembled Monolayers
Engineering Proteins at Interfaces: From Complementary Characterization to Material Surfaces with Designed Functions
Abstract Once materials come into contact with a biological fluid containing proteins, proteins are generally—whether desired or not—attracted by the material's surface and adsorb onto it. The aim of this Review is to give an overview of the most commonly used characterization methods employed to gain a better understanding of the adsorption processes on either planar or curved surfaces. We continue to illustrate the benefit of combining different methods to different surface geometries of the material. The thus obtained insight ideally paves the way for engineering functional materials that interact with proteins in a predetermined manner.
Rupture Force of Single Small Drug Molecule Binding a Split Aptamer
Aptamers are specific oligonucleotides (DNA or RNA) which bind small inorganic or organic molecules, large proteins or cells. In particular, the high affinity of aptamers is expected to lead to a new class of therapeutic reagents. Thus the detection and characterization of binding strength of small molecules is important for drug and medical research. Atomic force spectroscopy (AFS) with a force resolution in the piconewton range is a valuable tool for studying interactions on a single molecular level. The detection of very small target molecules less than 500 Dalton is characterized by only a few hydrogen interactions between the aptamer and the target molecules. Thus tiny rupture forces w…
Flexible minerals: self-assembled calcite spicules with extreme bending strength.
Flexi-Fibers Glass or metal fibers can show incredible flexibility. Natalio et al. (p. 1298 ; see the Perspective by Sethmann ) used the protein silicatein-α, which is responsible for the biomineralization of silicates in sponges, to guide the formation of spicules made of calcite. These synthetic spicules could be bent to a high degree because of their inherent elasticity, whilst retaining the ability to guide light.
Rough Surfaces by Design: Gold Colloids Tethered to Gold Surfaces as Substrates for CaCO3 Crystallization
Influence of Binding-Site Density in Wet Bioadhesion
Detaching Microparticles from a Liquid Surface.
The work required to detach microparticles from fluid interfaces depends on the shape of the liquid meniscus. However, measuring the capillary force on a single microparticle and simultaneously imaging the shape of the liquid meniscus has not yet been accomplished. To correlate force and shape, we combined a laser scanning confocal microscope with a colloidal probe setup. While moving a hydrophobic microsphere (radius 5-10 μm) in and out of a 2-5 μm thick glycerol film, we simultaneously measured the force and imaged the shape of the liquid meniscus. In this way we verified the fundamental equations [D. F. James, J. Fluid Mech. 63, 657 (1974)JFLSA70022-112010.1017/S0022112074002126; A. D.…
Adaptive Wetting-Adaptation in Wetting
Many surfaces reversibly change their structure and interfacial energy upon being in contact with a liquid. Such surfaces adapt to a specific liquid. We propose the first order kinetic model to describe dynamic contact angles of such adaptive surfaces. The model is general and does not refer to a particular adaptation process. The aim of the proposed model is to provide a quantitative description of adaptive wetting and to link changes in contact angles to microscopic adaptation processes. By introducing exponentially relaxing interfacial energies and applying Young's equation locally, we predict a change of advancing and receding contact angles depending on the velocity of the contact line…
Exciton diffusion controlled quantum efficiency in hybrid dye sensitized solar cells.
Well-ordered and uniform titania nanoparticle arrays were synthesized using diblock copolymers as structure directing agents. High molecular weight copolymers of polystyrene-b-polyethylene oxide and poly(methylmethacrylate)-b-polyethylene oxide were used to control the distance between titania nanoparticles in the range of 20-60 nm. Using these titania nanoparticle arrays and regioregular poly(3-hexylthiophene), models for a dye sensitized photovoltaic cell were assembled, in which the interparticle spacing was systematically varied. In these simplified solar cells, the titania nanocrystals were surrounded by a continuous regioregular poly(3-hexylthiophene) phase. The spacing between the ti…
Stimuli-Responsive Y-Shaped Polymer Brushes Based on Junction-Point-Reactive Block Copolymers
Reversibly responsive, thin or ultrathin polymer fi lms, often referred to as “smart surfaces”, can alter their properties upon application of external stimuli. [ 1 , 2 ] One particular application fi eld represents the engineering of nanostructured fi lms mimicking cell membranes. [ 3 , 4 ] Such materials offer application potential for sensors, textiles, construction materials, and smart coatings due to a rapid change in surface energy and morphology. [ 5–7 ] The surface response can be triggered by various external stimuli such as light, temperature, electrical potential, mechanical force, magnetic fi eld, pH change, or selective solvent treatment. [ 1 , 8–12 ] A variety of different thi…
Microsphere tensiometry to measure advancing and receding contact angles on individual particles
In this paper, a method to measure the advancing and receding contact angles on individual colloidal spheres is described. For this purpose, the microspheres were attached to atomic force microscope cantilevers. Then the distance to which the microsphere jumps into its equilibrium position at the air-liquid interface of a drop or an air bubble was measured. From these distances the contact angles were calculated. To test the method, experiments were done with silanized silica spheres (4.1 μm in diameter). From the experiments with drops, an advancing contact angle of 101 ± 4° was determined. A receding contact angle of 101 ± 2° was calculated from the jump-in distance into a bubble. Both ex…
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.
Forces Between Solid Surfaces Across Polymer Melts as Revealed by Atomic Force Microscopy
Forces between solid surfaces across polymer melts are poorly understood despite their fundamental importance and their relevance for making composite materials. Such force measurements reveal information on the structure of polymers at surfaces and of confined polymers. Experiments with the atomic force microscope and polyisoprene (PI) confirmed theoretical predictions that no long‐range force should be present in thermodynamic equilibrium. In poly(dimethyl siloxane) (PDMS) repulsive forces are observed at high molar mass. We attribute this to the formation of an immobilized layer caused by a slow release of adsorbed segments enhanced by entanglement. In low molar mass PDMS attractive forc…
Redox-Responsive and Thermoresponsive Supramolecular Nanosheet Gels with High Young's Moduli
Supramolecular gels made from 2D building blocks are emerging as one of the novel multifunctional soft materials for various applications. This study reports on a class of supramolecular nanosheet gels formed through a reversible self-assembly process involving both intramolecular folding and intermolecular self-assembly of poly[oligo(ethylene glycol)-co-(phenyl-capped bithiophenes)]. Such hierarchical self-assembled structure allows the gels to switch between sol and gel states under either redox or thermostimulus. Moreover, the gels illustrate high Young's moduli, compared to their controls that are made from the same oligo(ethylene glycol) and phenyl-capped bithiophenes blocks but have h…
Measuring single small molecule binding via rupture forces of a split aptamer.
The rupture force of a split (bipartite) aptamer that forms binding pockets for adenosine monophosphate (AMP) was measured by atomic force spectroscopy. Changes in the rupture force were observed in the presence of AMP, while this effect was absent when mutant aptamers or inosine were used. Thus, changes in the rupture force were a direct consequence of specific binding of AMP to the split aptamer. The split aptamer concept allowed the detection of nonlabeled AMP and enabled us to determine the dissociation constant on a single-molecule level.
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.
Formation of nanorods by self-assembly of alkyl-substituted polyphenylene dendrimers on graphite
Alkyl-substituted polyphenylene dendrimers with a tetrahedral or disk-like shape form self-assembled monolayers on graphite (HOPG) which show complex supramolecular structures, such as parallel rods of 6 nm diameter or two-dimensional crystals.
Submicrometer-Sized Roughness Suppresses Bacteria Adhesion.
Biofilm formation is most commonly combatted with antibiotics or biocides. However, proven toxicity and increasing resistance of bacteria increase the need for alternative strategies to prevent adhesion of bacteria to surfaces. Chemical modification of the surfaces by tethering of functional polymer brushes or films provides a route toward antifouling coatings. Furthermore, nanorough or superhydrophobic surfaces can delay biofilm formation. Here we show that submicrometer-sized roughness can outweigh surface chemistry by testing the adhesion of E. coli to surfaces of different topography and wettability over long exposure times (>7 days). Gram-negative and positive bacterial strains are tes…
Fluorescence Correlation Spectroscopy in Dilute Polymer Solutions: Effects of Molar Mass Dispersity and the Type of Fluorescent Labeling
Fluorescence correlation spectroscopy (FCS) has become an important tool in polymer science. Among various other applications the method is often applied to measure the hydrodynamic radius and the degree of fluorescent labeling of polymers in dilute solutions. Here we show that such measurements can be strongly affected by the molar mass dispersity of the studied polymers and the way of labeling. As model systems we used polystyrene and poly(methyl methacrylate) synthesized by atom transfer radical polymerization or free-radical polymerization. Thus, the polymers were either end-labeled bearing one fluorophore per chain or side-labeled with a number of fluorophores per chain proportional to…
Grafting Silicone at Room Temperature—a Transparent, Scratch-resistant Nonstick Molecular Coating
Silicones are usually considered to be inert and, thus, not reactive with surfaces. Here we show that the most common silicone, methyl-terminated polydimethylsiloxane, spontaneously and stably bonds on glass-and any other material with silicon oxide surface chemistry-even at room temperature. As a result, a 2-5 nm thick and transparent coating, which shows extraordinary nonstick properties toward polar and nonpolar liquids, ice, and even super glue, is formed. Ten microliter drops of various liquids slide off a coated glass when the sample is inclined by less than 10°. Ice adhesion strength on a coated glass is only 2.7 ± 0.6 kPa, that is, more than 98% less than ice adhesion on an uncoated…
ChemInform Abstract: Mercaptophenol-Protected Gold Colloides as Nuclei for the Crystallization of Inorganic Minerals: Templated Crystallization on Curved Surfaces.
Stability of a Split Streptomycin Binding Aptamer
Here we investigated the stability of an aptamer, which is formed by two RNA strands and binds the antibiotic streptomycin. Molecular dynamics simulations in aqueous solution confirmed the geometry and the pattern of hydrogen bond interactions that was derived from the crystal structure (1NTB). The result of umbrella sampling simulations indicated a favored streptomycin binding with a free energy of ΔGbind° = −101.7 kJ mol–1. Experimentally, the increase in oligonucleotide stability upon binding of streptomycin was probed by single-molecule force spectroscopy. Rate dependent force spectroscopy measurements revealed a decrease in the natural off-rate (koff-COMPLEX = 0.22 ± 0.16 s–1) for the …
Adhesion and Friction Forces between Spherical Micrometer-Sized Particles
An experimental setup, based on the principles of atomic force microscopy (AFM), was used to measure directly the adhesion and rolling-friction forces between individual silica microspheres of radii between 0.5 and 2.5 \ensuremath{\mu}m. It showed that the linear dependence of the pull-off force on the particle radius is still valid for micron-sized particles. Rolling-friction forces between silica microspheres were measured for the first time by combining AFM methods and optical microscopy: They are $\ensuremath{\sim}100$ times lower than the corresponding adhesion forces.
Direct measurement of forces between particles and bubbles
One of the elementary stages of the flotation process is the formation of an aggregate between the particle and a bubble. This aggregate formation is governed by hydrodynamic, capillary and interparticle forces. During the last four years, techniques have been developed to measure directly the force between a colloidal particle and a bubble. These techniques are closely related to the development of atomic force microscopy. Advantages and possibilities, as well as limits and drawbacks are described.
Measuring electrostatic double-layer forces on HOPG at high surface potentials
Abstract The aim of this study was to investigate surface forces in aqueous electrolyte solutions between surfaces with high electric potentials. Therefore the force between a surface of highly oriented pyrolytic graphite (HOPG) and a silicon nitride tip of an atomic force microscope was measured. Various electric potentials by a counter electrode were applied to the HOPG, which served as working electrode. As predicted by the Poisson–Boltzmann theory the electrostatic double-layer force changed only in a narrow potential range of ≈300 mV. At high negative sample potentials, where the negatively charged tip was repelled from the sample, the force saturated. At positive potentials an attract…
Synthesis of Mesoporous Supraparticles on Superamphiphobic Surfaces
A method for mesoporous supraparticle synthesis on superamphiphobic surfaces is designed. Therefore, supraparticles assembled with nanoparticles are synthesized by the evaporation of nanoparticle dispersion drops on the superamphiphobic surface. For synthesis, no further purification is required and no organic solvents are wasted. Moreover, by changing the conditions such as drop size and concentration, supraparticles of different sizes, compositions, and architectures are fabricated.
Ultralow-intensity near-infrared light induces drug delivery by upconverting nanoparticles
Mesoporous silica coated upconverting nanoparticles are loaded with the anticancer drug doxorubicin and grafted with ruthenium complexes as photoactive molecular valves. Drug release was triggered by 974 nm light with 0.35 W cm(-2). Such low light intensity minimized overheating problems and prevented photodamage to biological samples.
Templated Crystallisation of Calcium and Strontium Carbonates on Centred Rectangular Self-Assembled Monolayer Substrates
SrCO3crystals display patterns of templating when grown on tailored self-assembled monolayers (right). As SrCO3 is isostructural with aragonite, comparison of the crystallisation of SrCO3 in the aragonite/strontianite modification with the crystallisation of CaCO3 in all three modifications might yield some insights into which factors are important for crystal growth.
Monolayers of asymmetrical diethylalkanoat disulfides on gold(111):.the influence of chain length difference on atomic force microscope images
Several symmetrical and asymmetrical long-chain diethylalkanoat disulfides were synthesized and character- ized. The differences in the chain lengths of the disul- fides ranged between zero and five methylene units. Self- assembled monolayers of these disulfides formed on Au(111) surfaces were studied by atomic force microscopy (AFM) in order to obtain information about the origin of the image contrast. Domains with hexagonal lattices (lattice constants 5:2- 5:3 A) were detected for all derivatives, independent of the chain length differences. This indicates that the contrast arises roughly at a depth of 4- 8 A in the monolayers at imag- ing forces between 0: 2a nd 3n N. For SAMs of diethyl…
Redox active polymers with phenothiazine moieties for nanoscale patterning via conductive scanning force microscopy
Redox active polymers with phenothiazine moieties have been synthesized by Atomic Transfer Radical Polymerization (ATRP). These novel polymers reveal bistable behaviour upon application of a bias potential above the oxidation threshold value. Using conductive Scanning Force Microscopy, two distinguishable conductivity levels were induced on a nanoscale level. These levels were related to a high conducting “On” and a low conducting “Off” state. The “On” state is generated by the oxidation of the phenothiazine side chains to form stable phenothiazine radical cations. The formation and stability of the radical sites was examined by cyclic voltammetry, electron spin resonance and optical spectr…
Phoxonic Hybrid Superlattice
We studied experimentally and theoretically the direction-dependent elastic and electromagnetic wave propagation in a supported film of hybrid PMMA (poly[methyl-methacrylate])-TiO2 superlattice (SL). In the direction normal to the layers, this one-dimensional periodic structure opens propagation band gaps for both hypersonic (GHz) phonons and near-UV photons. The high mismatch of elastic and optical impedance results in a large dual phoxonic band gap. The presence of defects inherent to the spin-coating fabrication technique is sensitively manifested in the band gap region. Utilizing Brillouin light scattering, phonon propagation along the layers was observed to be distinctly different from…
Siliceous spicules enhance fracture-resistance and stiffness of pre-colonial Amazonian ceramics
AbstractPottery was a traditional art and technology form in pre-colonial Amazonian civilizations, widely used for cultural expression objects, utensils and as cooking vessels. Abundance and workability of clay made it an excellent choice. However, inferior mechanical properties constrained their functionality and durability. The inclusion of reinforcement particles is a possible route to improve its resistance to mechanical and thermal damage. The Amazonian civilizations incorporated freshwater tree sponge spicules (cauixí) into the clay presumably to prevent shrinkage and crack propagation during drying, firing and cooking. Here we show that isolated siliceous spicules are almost defect-f…
Preliminary results on the electrostatic double-layer force between two surfaces with high surface potentials
Abstract The aim of this study is to measure interaction forces between surfaces with high electric potentials in aqueous electrolyte solutions. Therefore the force between a gold sample and a gold sphere attached to the end of an atomic force microscope cantilever was measured. Gold sample and sphere were electrically connected and served as the working electrode. A potential was applied via a platinized platinum electrode. Experimental results are compared to forces approximated with the Poisson-Boltzmann theory.
Segregation in Drying Binary Colloidal Droplets
When a colloidal suspension droplet evaporates from a solid surface, it leaves a characteristic deposit in the contact region. These deposits are common and important for many applications in printing, coating, or washing. By the use of superamphiphobic surfaces as a substrate, the contact area can be reduced so that evaporation is almost radially symmetric. While drying, the droplets maintain a nearly perfect spherical shape. Here, we exploit this phenomenon to fabricate supraparticles from bidisperse colloidal aqueous suspensions. The supraparticles have a core-shell morphology. The outer region is predominantly occupied by small colloids, forming a close-packed crystalline structure. Tow…
Ultrastrong composites from dopamine modified-polymer-infiltrated colloidal crystals
Although strong and stiff synthetic composites have long been developed, the microstructure of today's most advanced composites has yet to achieve the sophisticated hierarchy of hybrid materials built up by living organisms. We have assembled hard and tough multilayered nanocomposites, which contain alternating layers of Fe3O4 nanoparticles and a 3-hydroxy-tyramine (dopamine) substituted polymer (dopamine modified polymer), strongly cemented together by chelation through infiltration of the polymer into the Fe3O4 mesocrystal. With a Young's modulus of 17 ± 3 GPa and a hardness of 1.3 ± 0.4 GPa the nanocomposite exhibits high resistance against elastic as well as plastic deformation. Key fea…
Humidity-Induced Grain Boundaries in MAPbI3 Perovskite Films
Methylammonium lead halide perovskites (MAPbI3) are very sensitive to humid environments. We performed in situ scanning force microscopy and in situ X-ray diffraction measurements on MAPbI3 films to track changes in the film morphology and crystal structure upon repeated exposure to a high relative humidity environment (80%). We found that the appearance of monohydrate (MAPbI3·H2O) Bragg reflections coincided with the appearance of additional grain boundaries. Prolonging the exposure time to humidity induced more grain boundaries and steps in the MAPbI3 films, and the peak intensities of the monohydrate MAPbI3·H2O increased. The monohydrate was not stable under dry atmosphere and could be r…
Capillary Imbibition, Crystallization, and Local Dynamics of Hyperbranched Poly(ethylene oxide) Confined to Nanoporous Alumina
The crystallization and dynamics of hyperbranched poly(ethylene oxide) (hbPEO), obtained from the direct random copolymerization of EO and glycidol (PEO-co-PG), are studied both in bulk and within nanoporous alumina (AAO). Copolymerization decreases the degree of crystallinity and lowers the crystallization and melting temperatures as compared to linear PEO. The dynamics of capillary imbibition within AAO followed the t1/2 prediction but is slower than predicted by the classical Lucas–Washburn equation. The most prominent effect of confinement is the change in nucleation mechanism—from heterogeneous nucleation in bulk to homogeneous nucleation inside AAO. The homogeneous nucleation temperat…
Engineering the hypersonic phononic band gap of hybrid Bragg stacks.
We report on the full control of phononic band diagrams for periodic stacks of alternating layers of poly(methyl methacrylate) and porous silica combining Brillouin light scattering spectroscopy and theoretical calculations. These structures exhibit large and robust on-axis band gaps determined by the longitudinal sound velocities, densities, and spacing ratio. A facile tuning of the gap width is realized at oblique incidence utilizing the vector nature of the elastic wave propagation. Off-axis propagation involves sagittal waves in the individual layers, allowing access to shear moduli at nanoscale. The full theoretical description discerns the most important features of the hypersonic one…
Structure Formation of Polymeric Building Blocks: Complex Polymer Architectures
This chapter describes macromolecules with a complex structure, their defined aggregation in solution, their adsorption to surfaces, and their possible aggregation on surfaces. The term “complex structure” implies that the macromolecules show different, distinct structural elements or building blocks on a supra-atomic length scale. Key to understanding the complex structure of macromolecules, their aggregation, and adsorption to surfaces are intra- and intermolecular interactions such as van der Waals, electrostatic, π–π interactions, and hydrogen bonds.
Elastic Superhydrophobic and Photocatalytic Active Films Used as Blood Repellent Dressing.
Durable and biocompatible superhydrophobic surfaces are of significant potential use in biomedical applications. Here, a nonfluorinated, elastic, superhydrophobic film that can be used for medical wound dressings to enhance their hemostasis function is introduced. The film is formed by titanium dioxide nanoparticles, which are chemically crosslinked in a poly(dimethylsiloxane) (PDMS) matrix. The PDMS crosslinks result in large strain elasticity of the film, so that it conforms to deformations of the substrate. The photocatalytic activity of the titanium dioxide provides surfaces with both self-cleaning and antibacterial properties. Facile coating of conventional wound dressings is demonstra…
ChemInform Abstract: Rough Surfaces by Design: Gold Colloids Tethered to Gold Surfaces as Substrates for CaCO3 Crystallization.
Mercaptophenol-Protected Gold Colloids as Nuclei for the Crystallization of Inorganic Minerals: Templated Crystallization on Curved Surfaces
The self-assembly of monolayers of thiols on gold(111) surfaces yields substrates that are able to template in a controlled manner, the nucleation and growth of crystals of calcium carbonate from solution. In the absence of additives, various factors such as the nature of the thiol, the temperature, and the pH are now established as influencing the nature and relative amounts of the different CaCO3 phases (calcite, vaterite, and aragonite). Recently, we have been able to extend the use of thiol/gold self-assembled monolayers as templates for the growth of inorganic crystals by utilizing protected gold colloids instead of flat gold surfaces. The thiol monolayers that protect the colloids pro…
Ferroelastic Fingerprints in Methylammonium Lead Iodide Perovskite
Methylammonium lead iodide (MAPbI3) perovskite shows an outstanding performance in photovoltaic devices. However, certain material properties, especially the possible ferroic behavior, remain unclear. We observed distinct nanoscale periodic domains in the piezoresponse of MAPbI3(Cl) grains. The structure and the orientation of these striped domains indicate ferroelasticity as their origin. By correlating vertical and lateral piezoresponse force microscopy experiments performed at different sample orientations with X-ray diffraction, the preferred domain orientation is suggested to be the a1–a2-phase. The observation of these ferroelastic fingerprints appears to strongly depend on the film t…
Red-Light-Controlled Release of Drug-Ru Complex Conjugates from Metallopolymer Micelles for Phototherapy in Hypoxic Tumor Environments
Traditional photodynamic phototherapy is not efficient for anticancer treatment because solid tumors have a hypoxic microenvironment. The development of photoactivated chemotherapy based on photoresponsive polymers that can be activated by light in the “therapeutic window” would enable new approaches for basic research and allow for anticancer phototherapy in hypoxic conditions. This work synthesizes a novel Ru‐containing block copolymer for photoactivated chemotherapy in hypoxic tumor environment. The polymer has a hydrophilic poly(ethylene glycol) block and a hydrophobic Ru‐containing block, which contains red‐light‐cleavable (650–680 nm) drug–Ru complex conjugates. The block copolymer se…
Changes in surface stress at the liquid/solid interface measured with a microcantilever
Abstract The bending of microfabricated silicon nitride cantilevers was used to determine surface stress changes at solid–liquid interfaces. The radius of curvature of the bent cantilever is directly proportional to changes in the differential surface stress between its opposite sides. To demonstrate the possibilities and limitations of the technique, cantilevers coated on both sides with gold and densely packed monolayers of different thiols were put in a constant flow of aqueous electrolyte solution and the deflection was measured using a optical lever technique. Changes in the surface stress for the different thiol monolayers due to specific proton adsorption are presented. Possible appl…
Direct Measurement of Particle−Bubble Interactions in Aqueous Electrolyte: Dependence on Surfactant
The aim of this study was to determine the influence of surfactant on the particle−bubble interaction. Therefore we constructed an experimental setup with which the interaction between colloidal pa...
Crystallization of Vaterite Nanowires by the Cooperative Interaction of Tailor-Made Nucleation Surfaces and Polyelectrolytes
The concepts of template-induced crystallization on self-assembled monolayers (SAMs) and the use of polymer additives are combined into a new strategy, where, through the cooperative interaction of a SAM matrix involved in the nucleation process, poly(acrylic acid), a dissolved polyelectrolyte, and the dissolved ions, hierarchically ordered mineral structures are formed. The adsorption of poly(acrylic acid) to the SAM is monitored using a quartz microbalance. Transmission electron microscopy measurements on samples that are taken from polyacrylate solution in short intervals after the start of the reaction reveals that nanometer-sized particles pre-formed in solution are being attached to t…
Morphosynthesis of Strontianite Nanowires Using Polyacrylate Templates Tethered onto Self-Assembled Monolayers
Strontianite nanowires have been synthesized on self-assembled monolayers (SAM) in the presence of polyacrylate templates. The morphology of this product exhibits characteristic differences from that of products obtained in the absence of polyacrylate. It is demonstrated that the template-induced crystallization process involves the interaction between the SAM surface, polyacrylate (a dissolved polyelectrolyte), and the cations/anions in solution. By the combination of these components, hierarchically ordered mineral hybrid structures are formed.