Formation of surface relief grating in polymers with pendant azobenzene chromophores as studied by AFM/UFM.

We studied peculiarities of the structural reconstruction within holographically recorded gratings on the surface of several different amorphous azobenzene-containing polymers. Under illumination with a light interference pattern, two processes take place in this type of polymer. The first process is the light-induced orientation of azobenzene units perpendicular to the polarization plane of the incident light.

New photorotor for the induction of anisotropy.

A new class of photosensitive compounds generates optical anisotropy comparable to azobenzene systems upon irradiation with linearly polarized light, but, in contrast to these systems, the new photorotor system does not absorb in the visible range. High values of dichroism and birefringence are induced and in the case of LC polymers the light induced order can be amplified by self-organization.

Optical oxygen micro- and nanosensors for plant applications.

Pioneered by Clark's microelectrode more than half a century ago, there has been substantial interest in developing new, miniaturized optical methods to detect molecular oxygen inside cells. While extensively used for animal tissue measurements, applications of intracellular optical oxygen biosensors are still scarce in plant science. A critical aspect is the strong autofluorescence of the green plant tissue that interferes with optical signals of commonly used oxygen probes.

Acrylate functionalized tetraalkylammonium salts with ionic liquid properties.

Acrylate functionalized ionic liquids based on tetraalkylammonium salts with terminal acrylates- and methylacrylates were synthesized. Melting points and ionic conductivity of twenty compounds in six groups were determined. Within one group the effect of three different counterions was investigated and discussed.

Note: Piezoelectric polymers as transducers for the ultrasonic-reflection method and the application in mechanical property-screening of coatings.

In the last years, non-destructive ultrasonic testing methods are more and more frequently employed in order to investigate the drying and curing processes of different coatings. Among them an ultrasonic reflection method was developed allowing the simultaneous measurement with longitudinal and transversal waves. In order to generate the ultrasonic pulse, piezoelectric ceramics or oxides are usually used as transducer materials which are connected to a delay line.

Controlled folding of synthetic polymer chains through the formation of positionable covalent bridges.

Covalent bridges play a crucial role in the folding process of sequence-defined biopolymers. This feature, however, has not been recreated in synthetic polymers because, apart from some simple regular arrangements (such as block co-polymers), these macromolecules generally do not exhibit a controlled primary structure--that is, it is difficult to predetermine precisely the sequence of their monomers. Herein, we introduce a versatile strategy for preparing foldable linear polymer chains.

Thermotropic and Thermochromic Polymer Based Materials for Adaptive Solar Control.

The aim of this review is to present the actual status of development in adaptive solar control by use of thermotropic and organic thermochromic materials. Such materials are suitable for application in smart windows. In detail polymer blends, hydrogels, resins, and thermoplastic films with a reversible temperature-dependent switching behavior are described.

Smart PEGylation of trypsin.

Thermoresponsive oligo(ethylene glycol)-based copolymers were investigated for trypsin conjugation. These copolymers have been synthesized by atom transfer radical polymerization of 2-(2-methoxyethoxy)ethyl methacrylate (MEO(2)MA) with oligo(ethylene glycol) methyl ether methacrylate (OEGMA(475), M(n) = 475 g.mol(-1)) at 60 degrees C in the presence of copper(I) chloride and 2,2'-bipyridyl.

Mesomorphic hydrogen-bonded complexes of complementary semiperfluorinated components.

2,4-Diamino-6-phenyl-1,3,5-triazines carrying one or two semiperfluorinated chains at the phenyl substituent have been investigated in binary mixtures with partially fluorinated benzoic acids by polarizing microscopy, differential scanning calorimetry, and X-ray diffraction. The number and positions of the fluorinated tails of the acid component were systematically modified. Equimolar mixtures of the triazines with the aromatic acids form discrete hydrogen-bonded heterodimers with an elongated central core.

Well-defined synthetic polymers with a protein-like gelation behavior in water.

Homopolymers of N-acryloyl glycinamide were prepared by reversible addition-fragmentation chain transfer polymerization in water. The formed macromolecules exhibit strong polymer-polymer interactions in aqueous milieu and therefore form thermoreversible physical hydrogels in pure water, physiological buffer or cell medium.

Sequence control in polymer synthesis.

The control over comonomer sequences is barely studied in macromolecular science nowadays. This is an astonishing situation, taking into account that sequence-defined polymers such as nucleic acids and proteins are key components of the living world. In fact, fascinating biological machines such as enzymes, transport proteins, cytochromes or sensory receptors would certainly not exist if evolution had not favored chemical pathways for controlling chirality and sequences.

Phenomenology of photoinduced processes in the ionic sol-gel-based azobenzene materials.

Very recently, supramolecular azobenzene-containing materials have been demonstrated to be effective for holographic inscription of surface relief gratings. High efficiency of grating formation in these materials is advantageously combined with easy material preparation because of the supramolecular principle of building blocs combination, availability of chemical components, and good film-forming properties. The materials show great promise for wide optical applications.

Fabrication and spectroscopic studies on highly luminescent CdSe/CdS nanorod polymer composites.

Highly luminescent nanocomposites were prepared by incorporating CdSe/CdS core/shell nanorods into different polymer matrices. The resulting nanocomposites show high transparency of up to 93%. A photoluminescence quantum efficiency of 70% was obtained, with an optimum combination of nanorod (0.

Liquid-phase synthesis of block copolymers containing sequence-ordered segments.

Monodisperse sequence-defined oligomers have been synthesized in solution in the absence of protecting groups. These structures have been prepared stepwise using two consecutive chemoselective reactions: 1,3-dipolar cycloaddition of terminal alkynes and azides and amidification of carboxylic acids with primary amines. These oligomers were efficiently constructed on either a conventional solid support (commercial Wang resin) or tailor-made soluble polystyrene supports synthesized by atom-transfer radical polymerization.

PEG-based thermogels: applicability in physiological media.

Novel biocompatible thermogels have been synthesized and characterized. The hydrogelators were synthesized by atom transfer radical copolymerization of 2-(2-methoxyethoxy)ethyl methacrylate (MEO(2)MA) and oligo(ethylene glycol) methyl ether methacrylate (OEGMA(475), M(n)=475 g mol(-1) or OEGMA(300), M(n)=300 g mol(-1)) in the presence of a 4-arm star poly(ethylene glycol) (PEG) macroinitiator. The formed macromolecules possess a permanently hydrophilic PEG core and thermoresponsive P(MEO(2)MA-co-OEGMA) outer-blocks.

Tuning the thickness of polymer brushes grafted from nonlinearly growing multilayer assemblies.

A new versatile method for tuning the thickness of surface-tethered polymer brushes is introduced. It is based on the combination of polyelectrolyte multilayer deposition and surface-initiated atom transfer radical polymerization. To control the thickness of the brushes, the nonlinear growth of certain polyelectrolyte multilayer systems is exploited.

Polarization-electric field hysteresis of ferroelectric PVDF films: comparison of different measurement regimes.

Polarization-electric field hysteresis is an important property of ferroelectric materials. Different experimental procedures and measurement regimes are demonstrated and frequently used in order to determine this hysteresis behavior. For the characterization of the poling behavior of ferroelectric polymers it is common to analyze the poling current and separate current contributions, which are based on charging the sample capacitance as well as on conductivity.

Development of a library of N-substituted maleimides for the local functionalization of linear polymer chains.

A novel kinetic process was investigated for functionalizing "on-demand" local regions of well-defined linear polystyrene chains. This concept relies on the atom transfer radical copolymerization (ATRP) of functional N-substituted maleimides with styrene. This copolymerization is a controlled radical process, which combines two unique kinetic features: i) all the polymers chains are growing simultaneously and ii) the cross-propagation of the comonomers is highly-favored as compared to homopolymerization.

Efficient construction of therapeutics, bioconjugates, biomaterials and bioactive surfaces using azide-alkyne "click" chemistry.

The concept of "click" chemistry, introduced by Sharpless and coworkers a couple of years ago, promotes the use of efficient, selective and versatile chemical reactions in synthetic chemistry. For instance, the copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) is regarded as a prime example of "click" chemistry. This reaction is regioselective, chemoselective and moreover can be performed in aqueous medium at room or physiological temperature.

Investigation of a dual set of driving forces (hydrophobic + electrostatic) for the two-step fabrication of defined block copolymer micelles.

The aqueous complexation of an amphiphilic block copolymer AB containing a hydrophobic segment A and a polyanionic segment B, with a double hydrophilic block copolymer CD containing a polycationic block C and a non-ionic block D was studied. Defined A(BC)D aggregates ( spherical micelles and vesicles) were obtained by this novel sequential pathway superposing both hydrophobic and electrostatic forces. This proof of concept indicates that this straightforward strategy could be further applied for preparing compartmented polymer-based nanostructures.

Photoinduction of optical anisotropy in an azobenzene-containing ionic self-assembly liquid-crystalline material.

Liquid-crystalline (LC) phase behavior and photoinduction of optical anisotropy in the ionic self-assembly complex 4-(4-diethylaminophenylazo) benzenesulfonate-dimethyldidodecylammonium (EO-C12D) has been investigated by polarized light microscopy, differential scanning calorimetry (DSC), x-ray scattering, null-ellipsometry, and UV-visible absorbance techniques. The complex exists in a bilayer smectic- A (smA{2}) LC phase at elevated temperatures (65-160 degrees C) and in a rectangular columnar (Col{r}) LC phase in the temperature range of -5-65 degrees C . Hysteresis in the transition from the smectic to the columnar LC phase was observed.