Summary: Amphiphilic hyperbranched polyester (H20‐AM) with methacrylate end groups was synthesized based on hyperbranched aliphatic polyester (Boltorn™ H20). Narrow‐dispersed crosslinkable vesicles were obtained by dissolving H20‐AM in water, and characterized by laser light scattering and TEM. The hollow structural vesicle is composed of around 350 H20‐AM molecules, having a radius of around 40 nm and of 1.9 × 106 g · mL−1. The vesicles were fixed by crosslinking of methacrylate groups to form shape‐persistent structures.
TEM images of the crosslinked vesicles at lower magnification. 相似文献
Summary: In the present communication we describe a photolithographic method to produce polyaniline (PANI) patterns using PANI modified with a traceless removable functional group (nitrosated polyaniline, PANI‐NO) and external inexpensive polymeric photoacid generators (poly(vinyl chloride), PVC). Therefore, residual sub‐products created by irradiation of the plate do not remain occluded in the polymeric films. The borders of the patterns are better defined than in the case of chemical lithography using inorganic acids as the hydrolyzing agent.
Summary: Reversible pH‐induced swelling of (PAH/PSS) polyelectrolyte microcapsules is accompanied by increased porosity, making them permeable to poly(acrylic acid) (PAA) at pH values higher than 11.2. This pH‐switchable permeability was used to encapsulate the polyanion in alkaline conditions. Relationship between starting PAA concentration in solution and amount finally being encapsulated has been established and can be used further as calibration curve. A desired amount of encapsulated polymer in the picogram range per capsule can be achieved. The loaded capsules were then used as microreactors by forming a complex between the PAA and Ca2+ ions.
General scheme for pH‐induced encapsulation of (PAA) in alkali condition by switching their permeability. 相似文献
This review deals with nanoporous materials made from the self‐assembly of block copolymers with a special interest in the chemical functions covering the surface of their nanopores. A detailed overview of the existing methods and strategies to generate well‐defined organic functional groups covering the surface of the pore walls is provided. This further enables to finely tune the affinity of the pore walls and to perform well‐defined chemical reactions onto them, which is essential for further dedicated applications.
Self‐assembled hollow nanosphere composites of polyaniline and Au nanoparticles (PANI‐p‐TSA/Au) were chemically synthesized from solutions containing p‐toluenesulfonic acid (p‐TSA) with the addition of gold chloride trihydrate as the oxidant. The composite materials were characterized by SEM, TEM, and a range of spectroscopic methods. Spectroscopic characterizations confirmed that the polymeric product is a form of doped PANI, while electron diffraction and X‐ray diffraction showed that elemental Au was present in the PANI‐p‐TSA/Au nanocomposites. The room temperature electrical conductivity of the PANI‐p‐TSA/Au nanocomposites was two orders of magnitude greater than a PANI‐p‐TSA obtained in the presence of ammonium persulfate as the oxidant under the same conditions.
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.
Polyaniline nanodisks have been synthesized successfully by the chemical oxidation polymerization of aniline by a self‐assembly process without the use of any acid. The thickness and lateral dimensions of the polyaniline nanodisks are in the range of 20–30 nm and 1–2 µm, respectively. The influence of synthetic parameters, such as the concentration of ammonium peroxydisulfate and pH, on the morphologies of polyaniline nanostructures have been investigated.
A novel approach has been explored to prepare brain‐like polyaniline (PANI) nanostructures with many convolutions (140–170 nm in average diameter) using aniline/citric acid (CA) salt as the template and chlorine gas as the oxidant by a gas/solid reaction for the first time. The method provided here differs significantly from the traditional one in which the polymerization of PANI is usually carried out in acidic solution.
Summary: A series of helix‐coil diblock copolymers based on poly(ethylene oxide) and optically active helical poly{(+)‐2,5‐bis[4′‐((S)‐2‐methylbutoxy)phenyl]styrene} (PMBPS) were synthesized via atom transfer radical polymerization (ATRP). The synthetic methodology permitted straightforward preparation of the diblock copolymers with relatively low polydispersities and a broad range of compositions and molecular weights. Depending on the composing block length and the initial concentration, the copolymers self‐assembled into different supramolecular structures in aqueous solution, including spherical micelles, vesicles, multilamellar vesicles, large compound vesicles, and tubules.
Schematic representation of the synthesis of PEO‐b‐PMBPS block copolymers and their aggregation in aqueous solution. 相似文献
A superhydrophobic polyaniline (PANI)‐coated fabric was prepared by in‐situ doping polymerization in the presence of perfluorosebacic acid (PFSEA) as the dopant. It is found that the PANI‐coated fabric undergoes a change in wettability from superhydrophobic (doped state) to superhydrophilic (de‐doped state) when it is exposed to ammonia gas. In particular, a reversible wettability of the PANI‐fabric is observed when it is doped with PFSEA and de‐doped with ammonium gas. It is proposed that the coordination effect of the pore structure of the polyester fabric, low surface energy of the PFSEA dopant, and reversible doping/dedoping characteristics of PANI results in the reversible wettability of the PANI‐coated fabric from superhydrophobicity to superhydrophilicity. Moreover, the tactic used here may provide a new method to monitor the toxic gas.
The interaction of surface‐attached weak polyelectrolyte brushes, grown directly from the surface of a solid substrate by surface‐initiated polymerization, with weak polyelectrolyte molecules in solution is studied. In addition, the formation of PEL multilayers onto such brush substrates is investigated. A strong template effect is observed and the thickness of each adsorbed layer is closely related to the thickness of the initial brush. Thus monolayers of more than 100 nm can be adsorbed in one single dipping cycle.
Layer thickness of PEI layers adsorbed to PMAA brushes as a function of the thickness of the surface‐attached monolayer. The solid line represents a case in which the PEI layer has exactly the same thickness as the brush monolayer. 相似文献
A novel pH‐responsive polymer vesicle obtained by the aqueous self‐assembly of carboxy‐terminated hyperbranched polyesters is reported. The synthesis is very simple, just a one‐step esterification of the commercially available hydroxy‐terminated hyperbranched polyester of Boltorn Hx (x = 20, 30, 40) with succinic anhydride. The vesicle size can be controlled from 200 nm to 10 µm by simply adjusting the solution pH as well as the degrees of branching (or generation).
Summary: The synthesis, morphology, and photophysical properties of PF‐b‐PAA with different coil lengths in dilute solutions of dichloromethane/methanol are reported. A tape‐like lamellar morphology is observed at a short coil length of PF‐b‐PAA. As the coil length increases, a large compound micelle, sphere, or vesicle is observed with different methanol contents because of the enhancement of the PAA swelling with methanol and the interfacial tension between the PF core and the PAA corona. Upon further increase of the coil length, an inverted morphology of a sphere or rod with a PF corona and PAA core is first observed but the core/corona is then reversed at a high methanol content as a result of the enhanced solubility of PAA. The morphological transformation leads to a significant variation in optical absorption or fluorescence characteristics because of the possible H‐aggregate formation.
Some of the various morphologies observed upon varying the coil length and the selective solvent content. 相似文献
Superhydrophobic conducting polyaniline (PAni) films were electrochemically deposited in acetonitrile‐H2O electrolyte containing aniline monomer and perfluorooctanesulfonic (PFOS) acid. The films exhibited an extended network structure composed of helical PAni sub‐micron fibers. The helical fibrous structure is thought to form through a supermolecular templating process. The surface of the PFOS‐doped PAni films showed a water contact angle of 153°. Reducing the PFOS‐doped PAni (in emeraldine salt form) by negative potential led to de‐doped PAni films (in leucoemeraldine base form) which were superhydrophilic (water contact angle close to 0°). By controlling the electrical potential, PAni films were changed between the doped state and de‐doped state, resulting in reversibly switchable superhydrophobic and superhydrophilic surfaces.
A series of novel temperature and pH responsive block copolymers composed of poly(N‐isopropylacrylamide) (PNIPAM) and poly(L ‐lysine) (PLL) were synthesized. The effect of pH and the length of PLL on the lower critical solution temperature (LCST) of PNIPAM, and the self‐assembly of these PLL‐based copolymers induced by temperature and pH changes were investigated by the cloud point method, dynamic light scattering (DLS) and environmental scanning electron microscopy (ESEM). These PNIPAM‐b‐PLL copolymers can self‐assemble into micelle‐like aggregates with PNIPAM as the hydrophobic block at acidic pH and high temperatures; and at alkaline pH and low temperatures, they can self‐assemble into particles with PLL as the hydrophobic block. The copolymers may have potential applications in biotechnological and biomedical areas as drug release carriers.
Porous surface patterns are used in a wide variety of practical applications. Honeycomb‐patterned porous polymer films are good templates for preparing porous surfaces due to their simple fabrication and the arrangement of pores on the surface. Catechol groups include in adhesive protein of mussels have attracted much attention due to their highly and substrate‐independent adhesive properties. In this paper, highly and substrate‐independent adhesive honeycomb‐patterned porous polymer films are prepared by using amphiphilic copolymer having catechol moieties. Furthermore, porous surface patterns are transferred on various organic or inorganic substrates by wet etching with using adhesive honeycomb films as templates.
Summary: Rough polydimethylsiloxane (PDMS) surface containing micro‐, submicro‐ and nano‐composite structures was fabricated using a facile one‐step laser etching method. Such surface shows a super‐hydrophobic character with contact angle higher than 160° and sliding angle lower than 5°, i.e. self‐cleaning effect like lotus leaf. The wettabilities of the rough PDMS surfaces can be tunable by simply controlling the size of etched microstructures. The adhesive force between etched PDMS surface and water droplet is evaluated, and the structure effect is deduced by comparing it with those own a single nano‐ or micro‐scale structures. This super‐hydrophobic PDMS surface can be widely applied to many areas such as liquid transportation without loss, and micro‐pump (creating pushing‐force) needless micro‐fluidic devices.
Etched PDMS surface containing micro‐, submicro‐, and nano‐composite structures shows a self‐cleaning effect with water CA as high as 162° and SA lower than 5°. 相似文献
This work reports on thermally tunable surface wettability of electrospun fiber mats of: polystyrene (PS)/poly(N‐isopropylacrylamide) (PNIPA) blended (bl‐PS/PNIPA) and crosslinked poly[(N‐isopropylacrylamide)‐co‐[methacrylic acid)] (PNIPAMAA) (xl‐NIPAMAA). Both the bl‐PS/PNIPA and xl‐PNIPAMAA fiber mats demonstrate reversibly switchable surface wettability, with the bl‐PS/PNIPA fiber mats approaching superhydrophobic ≥150° and superhydrophilic contact angle (CA) values at extreme temperatures. Weight loss studies carried out at 10 °C indicate that the crosslinked PNIPAMAA fiber mats had better structural integrity than the bl‐PS/PNIPA fiber mats. PNIPA surface chemistry and the Cassie–Baxter model were used to explain the mechanism behind the observed extreme wettability.
A novel crosslinked conductive polyaniline (PANI) was prepared by chemically copolymerizing aniline (An) and p‐phenylenediamine (PPDA) with triphenylamine (TPA) as crosslinker, using ammonium peroxydisulfate (APS) as an oxidant. The effects of different preparation conditions on the electrical conductivity of polymers were systematically investigated by adjusting acid kinds, concentration, the ratio of APS/An, the mounts of TPA and PPDA. The crosslinked PANI displayed a conductivity increase of up to 25% compared with the linear one. Their structures were characterized by Fourier‐transformed infrared spectroscopy and X‐ray photoelectron spectroscopy, and the electrical conductivity was also tested by a typical four‐point probe (RTS‐8) technique.
Copolymerization of aniline with octa(aminophenyl) silsesquioxane (OAPS) was performed, which resulted in polyaniline‐tethered, polyhedral oligomeric silsesquioxane (POSS‐PANI), with star‐like molecular geometry. The spectro‐electrochemical studies show that the electrochromic contrast of POSS‐PANI is much higher than that of polyaniline (PANI). The great improvement can be attributed to the more accessible doping sites and the facile ion movement during the redox switching, brought by the loose packing of the PANI chains. This was evidenced by a drastic increase in ionic conductivity, a decrease in the electrical conductivity, and a decrease in the crystallinity and crystal size, with the increase of the OAPS concentration in the POSS‐PANI.
