Interaction of diazoresins and sulfonate containing polyelectrolytes

The interaction of the photosensitive strong polycations diphenylamine‐4‐diazonium‐formaldehyde resin (DR) or 2‐nitro‐N‐methyl‐4‐diazonium‐formadehyde resin (NDR) with the sulfonate‐containing polyelectrolytes (SPE) poly(sodium vinylsulfonate) (PSV), poly(sodium‐p‐styrenesulfonate) (PSS), poly(potassium salt, 3‐sulfopropyl acrylate) (PPSA) or poly(potassium salt, 3‐sulfopropyl methacrylate) (PPSMA) has been studied. It was found that water‐insoluble DR‐based polyelectrolyte complex (i‐DR‐PEC) was formed at molar ratios (chain units) of polyanions to diazoresins of less than 1:1, but the added excessive polyanion would dissolve the i‐DR‐PEC to form water‐soluble DR‐based polyelectrolyte complex (s‐DR‐PEC). This dissolution process of PECs is related to the structure of their components: the polyanion with flexible longer side‐chain or the DR with stronger hydrophobic group exhibits high ability to dissolve the PEC. It is believed that the hydrophobic interaction between the excessive polyanion molecules and DR‐PEC chains plays a key role in the dissolution of i‐DR‐PEC. The influences of molecular weight of polyanion and concentration of NaCl on the dissolution of i‐DR‐PEC and the thermal stability of s‐DR‐PEC in excessive polyanion aqueous solution have also been investigated. © 2000 Society of Chemical Industry     

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。     

Water-soluble polyelectrolyte complexes formed by poly(diallyldimethylammonium chloride) and poly(sodium acrylate-co-sodium 2-acrylamido-2-methyl-1-propanesulphonate)-graft-poly(N,N-dimethylacrylamide) copolymers

The formation of polyelectrolyte complexes (PECs) between the cationic homopolymer poly(diallyldimethylammonium chloride) (PDADMAC) and the anionic graft copolymers poly(sodium acrylate-co-sodium 2-acrylamido-2-methyl-1-propanesulphonate)-graft-poly(N,N-dimethylacrylamide) (P(NaA-co-NaAMPS)-g-PDMAM) was studied in aqueous solution in comparison with the PECs formed between PDADMAC and the graft copolymer backbone poly(sodium acrylate-co-sodium 2-acrylamido-2-methyl-1-propanesulphonate). The turbidimetric study of the PECs formed revealed that associative phase separation is prevented when the anionic polyelectrolyte is grafted with the nonionic hydrophilic poly(N,N-dimethylacrylamide) side chains. The PECs are formed through a charge neutralisation process and they adopt a compact structure, as shown by conductivity and viscometry measurements respectively. The water-insoluble PEC core seems to be stabilised by a hydrophilic PDMAM corona, leading to the formation of nanoparticles with a hydrodynamic radius of some decades of nanometers as determined by quasi-elastic light scattering measurements.     

有机相中壳聚糖-海藻酸固定化脂酶的特性

研究了壳聚糖 海藻酸固定化脂酶在有机相反应中的稳定性与活性。考察了凝胶时间、壳聚糖浓度及壳聚糖分子质量对固定化脂酶包埋率与活性的影响 ,确定了适宜 pH值与批反应时间。同时讨论了溶剂极性和操作时间对固定化酶稳定性的影响。测定了固定化脂酶水解橄榄油反应的动力学参数。结果表明 ,壳聚糖 海藻酸聚电解质膜可提高固定化酶的包埋率与稳定性     

Quaternized microgels as soft templates for polyelectrolyte layer-by-layer assemblies

A cationic microgel with quaternized amine groups was prepared and used as a soft template for layer-by-layer (LbL) assemblies. The presence of quaternized amine groups inside the microgels was necessary to prevent rearrangements and subsequent bridging between the coated microgels, which were observed for the precursor microgels containing protonated primary amino groups. Sequentially, negatively charged polyelectrolyte poly(sodium styrene sulfonate) (PSS) and positively charged polyelectrolyte poly(diallyldimethylammonium chloride) (PDADMAC) were added to a suspension of quaternized microgels. This leads to an odd-even effect with respect to particle size and surface charge of the formed microgel–polyelectrolyte complexes (MPECs). MPECs with an even number of layers exhibit positive surface charge due to PDADMAC as the outermost layer and are larger compared to complexes with an odd number of layers, which are negatively charged having PSS in the outermost layer. Taking into account previous results (Macromolecules,2009,42, 1229), these observations show that electrostatic interactions are the major force for the odd-even effect in polyelectrolyte multilayers on microgels: the cationic groups of PDADMAC compete with the cationic moieties of the microgel for binding with the sulfonate groups of PSS. Concomitantly, a fluctuating size of the MPECs is induced by an osmotic pressure modulation within the microgel. In contrast, surface tension effects invoked by a possible varying hydrophilicity of the different terminal layers are negligible.     

用聚电解质微胶囊固定化Monascus purpureus多次培养生产天然色素(英文)

In general, productions of natural pigment in submerged microorganism culture were much less than that in solid-state fermentation, because the solid-state culture can provide a support carrier for the mycelium. To improve natural pigment production, the cultivation of Monascus purpureus in submerged encapsulated cell was investigated. Monascus purpureus immobilized in polyelectrolyte complex (PEC) microcapsules, which were prepared by sodium cellulose sulphate (NaCS) and poly-dimethyl-diallyl-ammonium chloride (PDMDAAC), was a good substitute for submerged cell culture because it mimicked the solid-state environment. The repeated-batch process with encapsulated cells was studied in flasks and a bubble column. The results indicated that the bubble column was more suitable for the encapsulation culture than the shaking flasks because of its good mass transfer performance and minor shear stress on cells. Owing to the protection of the microcapsule’s membrane, Monascus purpureus in microcapsules increased approximately three times over that in free cell culture with negligible cell leakage to the medium. The pigment production in the bubble column finally reached 3.82 (OD500), which was two times higher than in free cell culture. In addition, the duration of each batch was shortened to 15% of that in free cell culture.     

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。     

Mechanisms of molecular interactions in polybase–polyacid complex formed by copolymers of N,N‐dimethylaminoethylmethacrylate with alkylmethacrylates and methacrylic acid with ethylacrylate

Mechanisms of molecular interaction in the blends of a polybase, a copolymer of N,N‐dimethylaminoethylmethacrylate with methylmethacrylate and butylmethacrylate (PDMAEMA–MMA/BMA), with a polyacid, a copolymer of methacrylic acid with ethylacrylate (PMAA‐co‐EA), and plasticizer, triethylcitrate (TEC), have been investigated with FTIR Spectroscopy and potentiometry. To evaluate the strengths of hydrogen and ionic bonds in the polyelectrolyte complexes, quantum‐chemical calculations were performed. According to this analysis, the energy of ionic and hydrogen bonding diminishes in the order: multi‐component complexes involving protonated aminogroup of DMAEMA (ammonium cation) in the presence of chlorine counterion with ionized or unchanged carboxyl groups and water molecules (690–520 kJ/mol) > ternary H‐bonded acid‐base complexes associated with molecule of water (520–420 kJ/mol) > binary ionic complex of carboxylate anion and ammonium cation (404 kJ/mol) > H‐bonded complex of carboxylate and ammonium ions (257 kJ/mol) > binary H‐bonded complex of uncharged carboxyl group with ammonium cation (114 kJ/mol) > ternary H‐bonded complex of uncharged carboxyl group, aminogroup and water molecule (43 kJ/mol) > binary H‐bonded complex between nonionized carboxyl and amino groups (26 kJ/mol). Proton‐donating capability of functional groups in the studied polyelectrolyte blends diminishes in the order: HN⁺(CH₃)₂ ? > HOOC? > HO? . The proton‐donating capacity can be significantly improved in the presence of Cl^? ions, the effect of which may be appreciably inhibited if Na⁺ cations are available in the blend or solution. Proton‐accepting capability weakens in the order: uncharged aminogroup > carboxylate anion > uncharged carboxyl group > hydroxyl group. The results of quantum chemical calculations facilitate interpretation of FTIR spectra. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Efficient liquid phase oxidation of olefins and aromatic alcohol catalyzed by reusable polymer anchored Schiff base complexes

BACKGROUND: Heterogenization of homogeneous catalyst has become an interesting process for the catalytic oxidation of olefins and aromatic alcohol. This may provide a new kind of catalyst that is not only friendly to the environment but also exhibits higher thermal and chemical stabilities. RESULTS: Polymer anchored Schiff‐base complexes of iron(III), copper(II) and cobalt(II) have been synthesized and characterized. The catalytic potential of these complexes has been tested for the oxidation of cyclohexene. The effect of varying solvent, oxidant, substrate oxidant molar ratio, temperature and catalyst amount has been studied. Under optimized reaction conditions 91, 88 and 81% conversion of cyclohexene was obtained with Fe(III), Cu(II) and Co(II) catalysts, respectively. Moreover, the oxidation of other substrates, such as styrene, benzylalcohol, toluene and 1‐hexene were also efficiently carried out by these catalysts. CONCLUSION: The immobilized complexes showed excellent catalytic activity along with high selectivity for the oxidation of olefins and alcohols. The catalysts can be recycled more than five times without any noticeable loss of catalytic activity. Copyright © 2009 Society of Chemical Industry     

Polyelectrolyte Complex that Minimizes Bacterial Adhesion to Polyester

Bacterial adhesion is a major concern in the medical field, where bacterial fouling can lead to diminished device efficacy and failure. To combat this, polyelectrolyte complexes (PECs) can be used to modify surfaces to reduce bacterial attachment. In the present study, a water-based PEC of poly(diallyldimethylammonium chloride) [PDDA] and poly(acrylic acid) are deposited in a simple two-step process to the surface of polyester fabric. This process includes the deposition of a dissolved mixture of the two polyelectrolytes, followed by the formation of the ionic network through exposure to citric acid buffer. These coatings facilitate the removal of >95% of deposited Staphylococcus aureus after simple rinsing with deionized water. The high degree of surface ionization monitored by FTIR suggests that electrostatic repulsion is responsible for the observed antifouling activity. The morphology of these coatings which is monitored by scanning electron microscope (SEM) and atomic force microscope (AFM) is shown to depend on curing the curing conditions, which suggests that this simple process can be tailored to many applications.     

Surface modification by polyelectrolyte complexes: Influence of modification procedure,polyelectrolyte components,and substrates

The complex formation between oppositely charged polyelectrolytes (PEL) and their interaction with negatively charged silicate powders have been investigated. The PEL studied were poly(ethyleneimine)s, poly(diallyldimethylammonium chloride), and copolymers of maleic acid and propylene or styrene. PEL complexes (PEC) are formed by a combination of aqueous PEL solutions containing definite amounts of charges (n₋, polyanion; n₊, polycation). The point of zero charge of the PEC depended on the selection of different PEL. Changing the molar ratio n₋/n₊ permitted the preparation of nonstoichiometric PEC (nPEC). Preformed cationic nPEC were used to modify the silicate powders (variation A). The nPEC were able to generate a strongly cationic surface charge in most cases. It is concluded that the preformed PEC adsorbs roughly with the same stoichiometry on the surface as in solution. Changes of the mechanism and a strong enhancement of the attainable cationic surface charge density could be observed by a two-step modification procedure (variation B). The influence of the surface charge density of the untreated substrates on the extent of surface modification for both variations is also described. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 41–50, 1997     

A comparative study of two polyelectrolyte complexes

Interpenetrating polymeric networks (IPNs) based on natural sodium alginate (NaAlg) biopolymer matrix and synthetic hydrophilic polymer were synthesized using sequential method. Poly(acryloxyethyl‐trimethylammonium chloride‐co‐2‐hydroxyethyl methacrylate) (poly(Q‐co‐H)) with high content of quaternary ammonium groups (Q units) was used as a synthetic polymer for the purpose. Since NaAlg has anionic nature and poly(Q‐co‐H) is a polycation polyelectrolyte complex (PEC) was also prepared via ion interaction between these natural and synthetic components by mixing their water solutions. The all prepared materials were characterized by thermogravimetric analysis (TGA) and Fourier transform infrared spectroscopy (ATR‐FTIR). The comparative analysis of IPNs of different compositions was carried out. Behavior of IPNs was also compared to PEC, material obtained via simple ionic interaction between oppositely charged polymers. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Destabilization of model silica dispersions by polyelectrolyte complex particles with different charge excess,hydrophobicity, and particle size

Nonstoichiometric polyelectrolyte complex dispersions (PECs) with different charge excess and hydrophobicity as well as different average hydrodynamic particle size were used to induce flocculation of oppositely charged silica dispersions. PECs were formed with poly(diallyldimethylammonium chloride) (PD) as polycation and poly(styrene‐p‐sodium sulfonate) (NaPSS) and poly(acrylamide‐co‐sodium acrylate) (PR2540) as polyanions. PD was used as single polymer flocculant too. Flocculation process was characterized by optical densities of supernatants OD₅₀₀, by UV/VIS spectrometry, and determination of average floc sizes D(v; 0.5) as well as volume distribution of floc sizes by laser diffraction and determination of sedimentation velocity s by means of LUMiFuge? 114. It was found that the reaction process between silica and the used flocculants could be divided into three intervals (destabilization, flocculation optimum, and restabilization) as it is known for all other polymer flocculants. For an effective flocculation of a charged substrate, both electrostatic as well as hydrophobic interactions play an important role. The interval up to the beginning of the flocculation optimum is mainly ascertained by electrostatic interactions (the charge density of the flocculant) but the broadness of flocculation optimum depends largely on hydrophobic interactions. Hydrophobic interactions also play an important role for shear stability of the formed flocs. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3776–3784, 2007     

高聚物离子导电体的研究

本文合成了一种新型网状结构聚合物电解质－聚磷酸多缩乙二醇酯高氯酸锂复合物，该复合体系在Ｔ＝２９８Ｋ时电导率达１．５×１０－５Ｓ·Ｃｍ－１，讨论了聚合物结构与电导率的关系     

PEC生物微胶囊研究进展

聚电解质复合物(PEC)生物微胶囊由聚合物阴阳离子络合反应形成,因其反应温和、生物相容性好,近年来已成为热门的研究领域,在人工器官、医疗诊断、细胞固定化等方面有着广泛的用途。本文系统介绍了PEC生物微胶囊的制备、特性研究和应用研究,并综述了这3个方面的最新研究进展,最后对PEC生物微胶囊的发展前景进行了展望。     

Immobilization of β‐amylase using polyacrylamide polymer derivatives

Barley β‐amlyase was immobilized on two polymeric materials; poly(acrylamide–acrylic acid) resin [P(AM‐AAc)] and poly(acrylamide–acrylic acid–diallylamine–HCl) resin [P(P(AM‐AAc‐DAA‐HCl) using two different methods: covalent and cross‐linking immobilization. Thionyl chloride, used to activate the polymers for covalent immobilization, has the advantage that it is able to react with a number of surface groups of protein under very mild conditions. Cross‐linking with glutaraldehyde gave a higher coupling yield (approximately 70%) than covalent immobilization (approximately 20%). The activity and stability of the resulting biopolymers have been compared with those of free β‐amylase. The specific activity of the immobilized enzyme was significantly influenced by the amount of enzyme loaded onto the polymers, the optimal level being 3.5 mg g^?1 polymer. It was found that the immobilized β‐amylase stored at 4°C retained approximately 90% of its original activity after 30 days, whereas free β‐amylase stored in solution at 4°C retained only 47% of its activity after same period. The difference in long term stability was more significant when the enzyme was stored at room temperature; the immobilized enzyme maintained 40% of its activity after 30 days, whereas the residual activity of free enzyme was only 10%. Copyright © 2003 Society of Chemical Industry     

Hyaluronan/Diethylaminoethyl Chitosan Polyelectrolyte Complexes as Carriers for Improved Colistin Delivery

Improving the therapeutic characteristics of antibiotics is an effective strategy for controlling the growth of multidrug-resistant Gram-negative microorganisms. The purpose of this study was to develop a colistin (CT) delivery system based on hyaluronic acid (HA) and the water-soluble cationic chitosan derivative, diethylaminoethyl chitosan (DEAECS). The CT delivery system was a polyelectrolyte complex (PEC) obtained by interpolymeric interactions between the HA polyanion and the DEAECS polycation, with simultaneous inclusion of positively charged CT molecules into the resulting complex. The developed PEC had a hydrodynamic diameter of 210–250 nm and a negative surface charge (ζ-potential = −19 mV); the encapsulation and loading efficiencies were 100 and 16.7%, respectively. The developed CT delivery systems were characterized by modified release (30–40% and 85–90% of CT released in 15 and 60 min, respectively) compared to pure CT (100% CT released in 15 min). In vitro experiments showed that the encapsulation of CT in polysaccharide carriers did not reduce its antimicrobial activity, as the minimum inhibitory concentrations against Pseudomonas aeruginosa of both encapsulated CT and pure CT were 1 μg/mL.