Oligo(ethylene oxide) side‐chain steric screening effects on conductimetric properties of grafted poly(4‐vinylpyridinium) salts in aqueous solutions

A set of poly[N‐oligo(ethylene oxide)yl 4‐vinylpyridinium tosylate] (P4VOEOOTs) has been prepared by spontaneous polymerization of 4‐vinylpyridine. This method gives a grafted polyelectrolyte having a positive charge on every backbone pyridinic moiety. The P4VP15Ts, P4VP164Ts, P4VP350Ts and P4VP750Ts aqueous solution conductivities were determined in the concentration range from 6 × 10^?4 to 10^?2 M at 25 °C. The variation of the conductivity versus concentration of the investigated system exhibits typical polyelectrolyte behaviour. The polyelectrolyte mobility was found to be dependent on the oligo(ethylene oxide) (OEO) side‐chain length. Manning's rod‐like model fails to describe these results. A simple steric effect is proposed to explain the influence of the OEO length. Copyright © 2003 Society of Chemical Industry     

Synthesis and characterization of chitosan/poly(acrylic acid) polyelectrolyte complex

Polyelectrolyte complex based on chitosan and acrylic acid monomer by photoinitiated free‐radical polymerization in the absence of crosslinker showed a large transition in swelling in response to changes in pH of surrounding medium. Their ability to swell arises from polyelectrolyte interactions and molecular structure of the complex. The main properties of interest that related to the molecular structure, swelling volumes, glass transition temperature, and elastic modulus of the complex were investigated. The effect of water content, the only variable in the sample component, played an important role in molecular structure of the complex and as a consequence, the extent of intermolecular linkage, especially amide bonds which in turn governed the degree of swelling of the polyelectrolyte complex in this study. The decreased degree of swelling and higher temperature shift of glass transition temperature was found with increased water content, whereas increased modulus of elasticity of dry complex was found in lower water content of synthesis component. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1025–1035, 2002     

Encapsulated yeast cells inside Paramecium primaurelia: a model system for protection capability of polyelectrolyte shells

One of the most promising applications of encapsulated living cells is their use as protected transplanted tissue into the human body. A suitable system for the protection of living cells is the use of nano‐ or microcapsules of polyelectrolytes. These shells can be deposited easily on top of the cells by means of a layer‐by‐layer technique. An interesting feature of the capsules is the possibility to control their properties on a nanometre level, tuning their wall texture via the preparation conditions. Here we introduce a model system to test the protection ability of polyelectrolyte capsules. Common bakery yeast cells were encapsulated. They were coated with a fluorescently labelled shell at conditions known to guarantee cell survival, and the cell interior was stained with DAPI. The protozoan Paramecium primaurelia was incubated with this double‐stained living yeast and visualized by means of two‐photon excitation fluorescence microscopy. Cross‐sections of the dye‐stained material as well as autofluorescence of the fixed protozoan allowed us to follow the digestion of the coated yeast with time. Our investigation reveals that capsules prepared under these deposition conditions are permeable to lysosomal enzymes, leading to degradation of the yeast inside the intact capsules. Our preliminary results indicate the suitability of the introduced model as a test system of this permeability.     

细胞固定化催化生产精细化学品的研究进展Q

摘要：细胞固定化技术具有流程简单、生物相容、操作稳定等优点，可有效保证细胞活性，实现高效的细胞催化生产精细化学品。本文介绍了表面附着、凝胶包埋、聚电解质层层自组装膜等多细胞固定化方法，及其在二元醇、生物乙醇、乳酸、酯、多糖等精细化学品生产中的研究现状和进展，并分析讨论了各种方法存在的问题。同时，总结了近年来新发展的单细胞纳米涂层固定化方法的机理、趋势及应用于精细化学品生产的可能性。最后对细胞固定化催化生产精细化学品面临的技术挑战及研究方向做出展望，以期为精细化学品生产提供一定的技术支持。     

Volume phase transition of polyelectrolyte gels in dimethyl sulfoxide/ tetrahydrofuran mixtures

Copolymer gels were prepared from 2-(acrylamido)-2-methylpropanesulfonic acid (AMPS), N,N-dimethylacrylamide (DMAA, comonomer) and N,N′-methylenebis(acrylamide) (BIS). The mole fraction of AMPS were 0.2674 and 0.4318, respectively, with the same BIS mole fraction of 0.013. These gels with counterions H⁺, Na⁺, and K⁺ were swollen at 25°C in mixtures of dimethyl sulfoxide (DMSO) and tetrahydrofuran (THF). A volume phase transition was observed at the THF volume fraction of about 0.58, indicating that the volume phase transition in a polyelectrolyte gel occurs when the medium polarity decreases sufficiently for ion-pair formation. On changing the counterion, the fraction of DMSO in the solvent mixture which is required to initiate swelling decreases in the order Na⁺, H⁺, and K⁺, the same as for counterion condensation in identical gels.     

Effect of crosslinkers on the preparation and properties of ETFE‐based radiation‐grafted polymer electrolyte membranes

This study concerns a comparative study of three crosslinkers, divinylbenzene (DVB), 1,2‐bis(p,p‐vinylphenyl)ethane (BVPE), and triallyl cyanurate (TAC) crosslinked poly(ethylene‐co‐tetrafluoroethylene) (ETFE)‐based radiation‐grafted membranes, which were prepared by radiation grafting of p‐methylstyrene onto ETFE films and subsequent sulfonation. The effect of the different types and contents of the crosslinkers on the grafting and sulfonation, and the properties such as water uptake, proton conductivity, and thermal/chemical stability of the resulting polymer electrolyte membranes were investigated in detail. Introducing crosslink structure into the radiation‐grafted membranes leads to a decrease in proton conductivity due to the decrease in water uptake. The thermal stability of the crosslinked radiation‐grafted membranes is also somewhat lower than that of the noncrosslinked one. However, the crosslinked radiation‐grafted membranes show significantly higher chemical stability characterized in the 3% H₂O₂ at 50°C. Among the three crosslinkers, the DVB shows a most pronounced efficiency on the crosslinking of the radiation‐grafted membranes, while the TAC has no significant influence; the BVPE is a mild and effective crosslinker, showing the moderate influence between the DVB and TAC crosslinkers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4565–4574, 2006     

聚电解质复合物研究现状及应用前景

介绍了聚电解质复全物的制务及研究方法，对影响聚电解质复合物形成及其结构的结果进行了阐述，简要介绍了其性能并对应用前景作了展望。     

Sulfonated polyimide and poly (ethylene glycol) diacrylate based semi‐interpenetrating polymer network membranes for fuel cells

Semi‐interpenetrating polymer network (semi‐IPN) membranes based on novel sulfonated polyimide (SPI) and poly (ethylene glycol) diacrylate (PEGDA) have been prepared for the fuel cell applications. SPI was synthesized from 1,4,5,8‐naphthalenetetracarboxylic dianhydride, 4,4′‐diaminobiphenyl 2,2′‐disulfonic acid, and 2‐bis [4‐(4‐aminophenoxy) phenyl] hexafluoropropane. PEGDA was polymerized in the presence of SPI to synthesize semi‐IPN membranes of different ionic contents. These membranes were characterized by determining, ion exchange capacity, water uptake, water stability, proton conductivity, and thermal stability. The proton conductivity of the membranes increased with increasing PEGDA content in the order of 10^?1 S cm^?1 at 90°C. These interpenetrating network membranes showed higher water stability than the pure acid polyimide membrane. This study shows that semi‐IPN SPI membranes based on PEGDA which gives hydrophilic group and structural stability can be available candidates comparable to Nafion® 117 over 70°C. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Strategies for electrosynthesis of poly(vinylbenzyltrimethylammonium chloride) and composite films

Poly(vinylbenzyl trimethyl ammonium chloride) (PVT) exhibits functional properties, which have generated interest in the fabrication of PVT and composite films. New electrochemical strategies have been utilized for the deposition of PVT-zirconia composites. The problems, related to the electrodeposition of strong polyelectrolytes, such as PVT, were addressed by the development of charge compensation mechanisms. The deposition strategies involved electrophoretic cathodic deposition (EPD) of PVT and EPD or electrochemical synthesis of zirconia. The proof of concept investigations involved deposition yield studies under different conditions, Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), differential thermal analysis (DTA), and electron microscopy studies. The electrochemical strategies can be used for electrodeposition of various composites, utilizing the properties of functional polymers and inorganic materials.     

Synthesis of Janus polyaniline–polyelectrolyte complex membrane via in situ confined polymerization

Polyelectrolyte complex (PEC) membranes prepared from poly(styrene sulfonate) (PSS) and poly(diallyldimethylammonium chloride) (PDADMAC) were modified by crossflow polymerization of aniline (ANI). The PEC membranes were used as separators in a two-compartment setup where ANI monomer and ammonium persulfate (APS) oxidant diffused through the membranes to form polyaniline (PANI). APS and ANI having different distributions throughout the membranes, the reaction led to the asymmetric polymerization of PANI on one face of each PEC membrane thus producing Janus membranes. Due to the excess PANI content, the membrane displayed distinct asymmetric electrical conductivities on each face. Interestingly, very different ANI polymerizations were obtained when nonstoichiometric PEC membranes having different molar ratio of cationic and anionic polyelectrolytes (P⁺:P^? represents PDADMAC:PSS) were used and transport of APS was fastest through the 2:1 PEC when compared to the 1:2 PEC. In all experiments, the polymerization was most intense on the ANI side of the membranes. Also, the influence of NaCl both during PEC fabrication and during polymerization was studied and found to have some effect on the solute permeability. Results showed that a higher content of PANI was formed on PEC membranes having excess P⁺ and with no NaCl added during PEC fabrication. Although X-ray diffraction confirmed the presence of PANI on both sides of each membrane, scanning electron microscopy images demonstrated that both sides of each membrane had different PANI content deposited. Electrical conductivity measurements using a four-point probe setup also showed that the PEC–PANI exhibits asymmetric electrical property on different sides. © 2021 Society of Industrial Chemistry.