Sixteen parallel polymerization reactions of 2‐ethyl‐2‐oxazoline have been performed at different temperatures in an automated synthesizer that allowed individual heating of each reactor. During the reactions samples were taken automatically, which were characterized by means of both online GPC and offline GC, in order to optimize the reaction temperature and to determine the activation energy of the polymerization.
This paper highlights the powerful combination of reversible addition–fragmentation chain transfer (RAFT) radical polymerization and various click/coupling chemistries. This is not an exhaustive review but rather an overview demonstrating the impressive possibilities that the “marriage” of these two synthetic approaches offers in modern macromolecular design and synthesis.
The catalytic properties of bis(phenoxy‐imine) Zr and Hf complexes incorporating perfluorophenyl groups with methylaluminoxane were investigated. The fluorinated complexes produced far higher‐molecular‐weight polyethylenes and ethylene/propylene copolymers with increased activities compared with the non‐fluorinated congeners. Moreover, the fluorinated complexes displayed a higher incorporation ability for propylene.
The straightforward synthesis of a series of poly(thioether)s by photoinduced thiol‐ene click polyaddition of α,ω‐alkylene thiols is reported. It is found that linear and telechelic poly(thioether)s can be directly obtained from α,ω‐alkylene thiols with, for example, alkyl chain length of m = 1,2,3, and 9. The reaction proceeds without additives such as (radical) initiators or metal compounds and can simply be carried out by UV‐irradiation of the bulk monomer or monomer solution. Ex situ kinetic studies reveal that the reaction proceeds by a typical a step‐growth polyaddition mechanism. As the homologue series of poly(thioether)s are now synthetically accessible, new direct pathways to tailored poly(alkyl sulphoxide)s and poly(alkyl sulfone)s are now possible.
Grafted conjugated polyelectrolytes were synthesized for the first time and characterized. The polymers demonstrated properties of a convenient and efficient protocol for creating Hg2+ sensors. The unique character of the new material comes from an anionic counterion nature with no external cofactors, and imparts high selectivity and fast detection for mercury ion in a fluorescence probe. The concept may be potentially applied to create new sensors for monitoring other ions.
A dielectric elastomer derived from a polystyrene‐block‐poly(ethylene‐co‐butylene)‐block‐polystyrene triblock copolymer swollen with a midblock‐selective solvent is reported to show promise as a nanostructured organic actuator requiring no pre‐strain. This might provide an attractive alternative to conventional acrylic, siloxane, and polyurethane elastomers since the electromechanical properties are composition‐tunable.
We have created a new functional biosensor coating composed of polyelectrolyte multilayers containing gold nanoparticles. This gold‐hybridized polyelectrolyte multilayer film possesses a stable nanoporous structure under physiological conditions. Antibody molecules were successfully conjugated onto the gold nanoparticles within the film. This functional coating successfully extinguished false signals from non‐specific binding of proteins and cells and also provided highly enhanced detection sensitivity. Furthermore, the drastic differences in protein and cellular adhesion properties between a chip coated with the nanoporous PEM film and a bare chip demonstrate that morphological control of biological interactions on chip surfaces is possible.
We report here a facile synthesis of high performance electro‐active polymer actuator based on a sulfonated polyimide with well‐defined silver electrodes via self‐metallization. The proposed method greatly reduces fabrication time and cost, and obviates a cation exchange process required in the fabrication of ionic polymer‐metal composite actuators. Also, the self‐metallized silver electrodes exhibit outstanding metal‐polymer adhesion with high conductivity, resulting in substantially larger tip displacements compared with Nafion‐based actuators.
Summary: We report a new method for the preparation of polyaniline nanoballs by using HAuCl4 as an oxidizing agent. During the reaction, aniline is oxidized and forms polyaniline whilst the hydrogen tetrachloroaurate is reduced and forms gold nanoparticles. These gold nanoparticles are found to decorate the nanoballs.
The resultant precipitate and corresponding TEM image of the gold‐nanoparticle covered polyaniline nanoball. 相似文献
Poly(ethersulfone) membranes were surface modified in a one‐step procedure. For this purpose, the membranes were soaked with aqueous solutions of different low‐molecular weight molecules bearing diverse hydrophilic functionalities and subject to electron beam treatment. No catalysts, photoinitiators, organic solvents or other toxic reagents were used, and no additional synthetic or purification steps were required.
An organosilane with an alkyne group at the non‐condensable end, [(2‐propynylcarbamate)propyl]triethoxysilane, has been synthesized. Condensation of this organosilane with tetraethoxysilane can be achieved by a co‐condensation strategy to produce silica nanoparticles with surface alkyne functionality. The size and uniformity of size distribution of the silica nanoparticles are influenced by varying the concentration of the added organosilane. The alkyne‐functionalized silica nanoparticles are coupled directly with azide‐modified polymers by ‘click chemistry’ to yield organic–inorganic hybrid nanomaterials.
Model high density DNA arrays have been realized by direct deposition with Dip‐Pen Nanolithography of acrylamido‐functionalized oligonucleotides (23‐mer) on spin‐coated, flat polystyrene surfaces. A highly specific interaction between the acrylamide end functionality and polystyrene was found. The surface morphology of the model array was studied by atomic force microscopy (AFM). Spots are clearly seen both in topography and demodulation modes. The array withstands the hybridization process with label free, complementary oligonucleotides and the following cleaning procedures. The final AFM characterization showed significant changes especially in demodulation images which may be an indication that molecular recognition between complementary oligos has occurred.
Films of polyaniline (PANI) featuring about 80% crystallinity and characterised with strong π‐π stacking alignment parallel to the film surface have been obtained directly after the original synthesis upon simple drying of the aqueous PANI suspension. A strong anisotropy in the growth of the nano‐sized crystals produced during the synthesis results in the formation of micrometer‐length fibrils perpendicular to the film surface in the course of water evaporation. The regular intercalation of water molecules between the PANI chains seems to be crucial for their ordering throughout the synthesis and film formation.
A new method to control the morphology and functionality of micelles is reported. Triblock copolymer micelles with atom transfer radical polymerization initiators at the interface are prepared in aqueous solution. After in‐situ polymerization at the interface, the structures of the interface and corona change, and micelles with PDMAEMA‐PEG comb–coil coronal chains are obtained. In aqueous solution, the pH exerts an influence on the morphology of the micelles. The coronal chains adopt different conformations at different pH values. Upon drying, the two coronal chains phase separate and form nanometer‐sized domains.
A direct access to photochromic polymeric vesicles was demonstrated via polymerization‐induced self‐assembly and reorganization (PISR). The resulting vesicles displayed interesting photochromic behaviors different from that of their free polymer chains in DMF, and the vesicles exhibited stronger fluorescence and excellent photostability due to confinement of conformational flexibility of the polymer chains in aggregates.
Shining a light on click chemistry: The use of UV‐radiation as trigger signal provides a facile means to obtain spatial and temporal control over polymer conjugation reactions in addition to providing a further means of achieving orthogonality in click transformations. In the current contribution, UV‐radiation was employed to induce a highly efficient Diels–Alder conjugation of polymeric building blocks via the photo‐induced in situ formation of highly reactive cis‐dienes from a 2‐methylbenzophenone precursor.
