Adsorption of neutral polymers on negatively charged liposomes. A novel quantitative method to measure the rate of polymer adsorption on the liposomal surface

We studied the adsorption of two neutral polymers [poly(vinyl pyrrolidone) and poly(vinyl alcohol) (PVA)] on negatively charged liposomes composed of 25:2:3 (molar ratio) soy lecithin/dicetyl phosphate/cholesterol.The liposomes were prepared in buffered solution at pH 7.4 and were mixed with the solution of the polymers in the desired polymer/lipid ratios. Adsorption was measured by determination of the equilibrium bulk concentration of the polymer. Protamine hydrochloride was used to aggregate the liposomes with polymers adsorbed on their surface and to facilitate their separation from the equilibrium bulk solution. In the case of PVA, quantitative adsorption measurements with a specific reagent were possible. Adsorption isotherms were recorded at 25 ± 0.2 °C. It was concluded that adsorbed and nonadsorbed PVA molecules are in equilibrium even at low polymer/lipide ratios. The results were confirmed by dynamic laser light scattering, X-ray diffraction and thermal activity monitoring experiments. Received: 13 October 2000 Accepted: 8 March 2001     

燃料电池用聚乙烯醇基碱性聚合物电解质膜的制备及其性能

通过在不同浓度KOH溶液中进行掺杂,制备出了聚乙烯醇(PVA)、聚乙烯醇/聚乙烯吡咯烷酮(PVA/PVP)和聚乙烯醇/聚乙二醇二甲醚(PVA/PEGDE)碱性聚合物电解质膜详细考察了膜的外观形貌、微观结构、热稳定性、离子电导率和化学稳定性等.结果表明,PVA与PVP以及PEGDE具有很好的相容性,所制备的复合膜断面致密...     

Stabilization of small unilamellar DMPC-liposomes by uncharged polymers

 Polymer-free and polymer-bearing small unilamellar (SUV) liposomes from dimyristoyl-phosphatidylcholine (DMPC) were prepared under standardized conditions. Polymer-bearing liposomes were formed by incorporating an uncharged polymer [hydrolyzed poly(vinyl alcohol) (PVA), poly(vinyl alcohol-co-vinylacetal) (PVA-Al), poly(vinyl alcohol-co-vinyl propional) (PVA-Prol) poly(vinyl alcohol-co-vinyl butiral) (PVA-Bul) copolymer or poly(vinyl pyrrolidone) (PVP)] into the membrane bilayer of vesicles. The kinetic (long-term) stability of the liposome dispersions stored in distilled water, in physiological NaCl solution and at various pH values, respectively, were studied. The physical stability of vesicles was tested by measuring the size and the zeta potential of liposomes by means of a Malvern Zetasizer 4 apparatus. It was shown that most of these polymers are effective steric stabilizers for the DMPC-liposomes. Among the polymers, the PVA-Bul and PVA-Prol copolymers and the PVP of high molecular mass exhibited the most efficient stabilizing effect at each pH studied, indicating that the formation of a relatively thick polymer layer around the lipid bilayers ensures an enhanced and prolonged physical stability of liposomes. Also, the butiral or propional side chain in the PVA-based copolymers presumably promotes the anchoring of macromolecules to the vesicles. Using these macromolecules, the colloidal interactions between vesicles can be modified and so the physical stability of liposomes and the kinetic stability of liposome dispersions can also be controlled. Received: 20 May 1997 Accepted: 03 September 1997     

Preparation of poly(vinyl pivalate) microspheres by dispersion polymerization in an ionic liquid and saponification for the preparation of poly(vinyl alcohol) with high syndiotacticity

We report here a successful free-radical dispersion polymerization of vinyl pivalate (VPi) in an ionic liquid, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([bmim][TFSI]) using poly(vinyl pyrrolidone) (PVP) as a stabilizer. Morphological analysis by FE-SEM revealed that poly(vinyl pivalate) (PVPi) obtained from dispersion polymerizations were in the form of spherical particles. Micron-sized, PVPi particles with a number-average molecular weight (M_n) of 166,400 g/mol could be obtained using 5% stabilizer (w/w to monomer) at 65 °C for 20 h. The effects of varying concentration of stabilizer, initiator and monomer upon polymer yield, molecular weight, and morphology of PVPi were also investigated. Analogous polymerizations in dimethyl sulfoxide (DMSO) and bulk served as references. In addition, the preparation of poly(vinyl alcohol) (PVA) by saponification of the resultant PVPi was described.     

Electrospinning and characterization of medium-molecular-weight poly(vinyl alcohol)/high-molecular-weight poly(vinyl alcohol)/montmorillonite nanofibers

Submicron fibers of medium-molecular-weight poly(vinyl alcohol) (MMW-PVA), high-molecular-weight poly(vinyl alcohol) (HMW-PVA), and montmorillonite clay (MMT) in aqueous solutions were prepared by electrospinning technique. The effect of HMW-PVA and MMT on the morphology and mechanical properties of the MMW-PVA/HMW-PVA/MMT nanofibers were investigated for the first time. Scanning electron microscopy, viscometer, tensile strength testing machine, thermal gravimetric analyzer (TGA), and transmission electron microscopy (TEM) were utilized to characterize the PVA/MMT nanofibers morphology and properties. The MMW-PVA/HMW-PVA ratios and MMT concentration played important roles in nanofiber's properties. TEM data demonstrated that exfoliated MMT layers were well distributed within nanofibers. It was also found that the mechanical property and thermal stability were increased with HMW-PVA and MMT contents.     

壳聚糖/聚乙烯醇共混超细纤维的制备及紫外光交联研究

用静电纺丝法制备壳聚糖/聚乙烯醇的共混超细纤维,采用扫描电镜考察了纺丝液浓度、共混物配比、喷丝口内径对纤维形貌的影响.此外,为减少壳聚糖/聚乙烯醇纤维膜的溶胀变形,在上述体系中加入可光交联的单体二缩三乙二醇双甲基丙烯酸酯(TEGDMA)、引发剂2-羟基-2-甲基-1苯基丙酮(1173),对电纺纤维进行紫外光交联.结果表明,当壳聚糖与聚乙烯醇质量比为8:2的共混体系中加入占混合溶液质量分数4%的TEGDMA、0.12%的1173作为交联剂时,所得的无纺布纤维直径比较均一,平均约为200 nm,经光交联处理后其耐水性能得到提高.     

Facile preparation of methylcellulose/poly(vinyl alcohol)physical complex hydrogels with tunable thermosensitivity

Novel complex hydrogels of methylcellulose(MC)and poly(vinyl alcohol)(PVA)with wide-spectrum thermoresponsivity were prepared via physical and mild process.Thermal phase transition of MC/PVA hydrogels exhibited two forms including sol/sol to gel/sol and sol/gel to gel/gel.The phase transition temperature of MC/PVA solution ranged from 38.7 to 60.6℃and was able to be adjusted by simply changing the feeding ratios of two components.The interior morphology of MC/PVA gels was examined with fluorescence analy...     

高稳定性化学交联聚乙烯醇/聚乙烯吡咯烷酮碱性固体电解质膜

碱性固体电解质膜的稳定性是影响其在电化学领域应用的一个重要因素.本文在前期研究工作的基础上,通过直接共混和化学交联修饰制备出了聚乙烯醇/聚乙烯吡咯烷酮(PVA/PVP)碱性聚合物电解质膜.采用傅里叶变换红外(FTIR)光谱、热重分析(TGA)、扫描电镜(SEM)和交流阻抗等方法详细考察了复合膜的分子结构、热稳定性、化学稳定性、氧化稳定性和尺寸稳定性.红外光谱结果表明,PVP成功地混入聚合物基体中,在1672cm-1处表现出来自于PVP第I带C襒O的强吸收峰.TGA结果表明,提高掺杂的KOH溶液浓度对PVA/PVP碱性膜的热稳定性没有明显影响.SEM分析结果表明,复合膜经高温、高浓度碱(80℃,10mol·L-1)处理后,其断面结构仍致密均匀,未出现类似小孔等膜降解情况,此时膜电导率(1.58×10-3S·cm-1)相比室温相同碱液时提高91.5%,表明PVA/PVP膜具有很好的耐碱化学稳定性.同时,PVA/PVP碱性膜表现出良好的抗氧化性,在60℃的3%和10%H2O2溶液中处理均没有观察到明显的质量损失,150h后仍能保持原膜质量的89%和85%.此外,由于膜内形成致密的内互交联网络结构,复合膜在水中800h之后也表现出很好的同向性和电导率稳定性.     

Poly(vinyl alcohol) Chains Grafted onto the Surface of Copper Oxide Nanoparticles: Application in Synthesis and Characterization of Novel Optically Active and Thermally Stable Nanocomposites Based on Poly(amide-imide) Containing N-trimellitylimido-L-valine Linkage

Green polymer nanocomposites (NCs) show unique properties of combining the advantages of nanofillers and organic polymers. In this study, in order to control the dispersion of nanoparticles (NPs) in a polymer matrix, first, poly(vinyl alcohol) (PVA) as a green modifier was grafted on the surface of the CuO NPs to obtain CuO-PVA nanohybrid. Then poly(amide-imide) (PAI) was synthesized by the direct step growth polymerization of N-trimellitylimido-L-valine and 4,4′-methylenebis(3-chloro-2,6-diethylaniline) in ionic liquid medium. Finally, CuO-PVA hybrids were incorporated into the PAI matrix using ultrasonic technique for the preparation of PAI/CuO-PVA NCs. The obtained PAI/CuO-PVA NCs were characterized by different methods. The results of thermogravimetric analysis showed that thermal stability of the NCs was enhanced by incorporation of CuO-PVA nanohybrid compared to the pure PAI.     

Modification and characterization of semi-crystalline poly(vinyl alcohol) with interpenetrating poly(acrylic acid) by UV radiation method for alkaline solid polymer electrolytes membrane

Semi-crystalline poly(vinyl alcohol) was modified by UV radiation with acrylic acid monomer to get interpenetrating poly(acrylic acid) modified poly(vinyl alcohol), PVAAA, membrane. The stability of various PVAAA membranes in water, 2 M CH₃OH, 2 M H₂SO₄, and 40 wt% KOH aqueous media were evaluated. It was found that the stability of PVAAA membrane is stable in 40 wt% KOH solution. The PVAAA membranes were characterized by differential scanning calorimetry, X-ray diffraction, and thermogravimetry analysis. These results show that (1) the crystallinity in PVAAA decreased with increasing the content of poly(acrylic acid) in the PVAAA membranes. (2) The melting point of the PVAAA membrane is reduced with increasing the content of poly(acrylic acid) in the membrane. (3) Three stages of thermal degradation were found for pure PVA. Compared to pure PVA, the temperature of thermal degradation increased for the PVAAA membrane. The various PVAAA membranes were immersed in KOH solution to form polymer electrolyte membranes, PVAAA-KOH, and their performances for alkaline solid polymer electrolyte were conducted. At room temperature, the ionic conductivity increased from 0.044 to 0.312 S/cm. The result was due to the formation of interpenetrating polymer chain of poly(acrylic acid) in the PVAAA membrane and resulting in the increase of charge carriers in the PVA polymer matrix. Compared to the data reported for different membranes by other studies, our PVAAA membrane are highly ionic conducting alkaline solid polymer electrolytes membranes.     

Gel spinning of poly(vinyl alcohol) from dimethyl sulfoxide/water mixture

Gel spinning of poly(vinyl alcohol) (PVA) was attempted from the PVA dope prepared from the mixture of dimethyl sulfoxide (DMSO) and water. The DMSO/H₂O = 80/20 (w/w) mixture and methanol were found to be the best solvent for the spinning dope and the coagulant, respectively, to give PVA fiber with the highest drawability. PVA fiber with the highest strength and Young's modulus were obtained from the undrawn gel fibers when subjected to hot two-stage drawing under conditions such as to produce maximum drawability. Furthermore, higher draw ratios of PVA fiber were attained at 6 wt % dope by lowering the coagulating temperature of methanol. In the present work, the highest tensile strength (2.8 GPa) and the highest Young's modulus (64 GPa) were realized, when the spinning dope was prepared from PVA with DP of 5,000 and the DMSO/H₂O (80/20) mixed solvent to have the PVA concentration of 6 wt %, the coagulating temperature of methanol was ?20°C, and the two-stage drawing was carried out at 160 (first) and 200°C (second). The PVA fiber prepared under this gel spinning condition could be elongated to 45 times draw ratio. The very high drawability of PVA fibers obtained from the DMSO/H₂O (80/20) mixture dope was ascribed to the ability of the DMSO/H₂O mixture to promote gelation. © 1994 John Wiley & Sons, Inc.     

Alkaline Zn-air and Al-air cells based on novel solid PVA/PAA polymer electrolyte membranes

High ionic conducting solid polymer electrolyte membranes (SPEM) had been successfully prepared from poly(vinyl alcohol) (PVA) and poly(acrylic acid) (PAA). The solution casting method yielded highly hydrophilic membranes with uniform structure that were suitable for electrochemical applications. The room temperature ionic conductivity of the alkaline PVA/PAA polymer electrolyte membranes was in the range of 0.142–0.301 S cm⁻¹ depending on the composition. The cyclic voltammetry analysis was carried out using Zn|SPEM|Zn and Al|SPEM|Al cells. The analysis results revealed the excellent electrochemical stability of these newly developed alkaline solid PVA/PAA polymer electrolyte membranes. Metal-air fuel cells were also prepared from the alkaline solid PVA/PAA polymer electrolyte membranes. The electrochemical cell performance was evaluated based on Zn-air and Al-air cells at C/10 and C/5 discharge rates. The experimental results exhibited high percent of utilization for metal powders at room temperature. It was up to 90% for Zn-air cell when assembled with PVA:PAA = 10:7.5 polymer electrolyte membrane and discharged at C/10 rate. The power density could be as high as 50 mW cm⁻² at room temperature. However, the cell percent utilization was reduced to 73% with the same composition electrolyte membrane when C/5 discharge rate was tested.     

Synthesis and biocidal activity of modified poly(vinyl alcohol)

Functionalized polymers and their polymer nature give them more advantages than the corresponding small molecules. In this respect, polymeric ammonium and phosphonium salts were prepared by chemical modifications of poly(vinyl alcohol) (PVA) aiming to explore their antimicrobial activities against pathogenic bacteria and fungi. The modifications were performed by chloroacetylation with chloroacetyl chloride. Incorporation of the ammonium and phosphonium salts was conducted by the reaction of chloroacetylated poly(vinyl alcohol) (CPVA) with triethylamine (TEA), triphenylphosphine (TPP), and tributylphosphine (TBP). The antimicrobial activity of the polymers against variety of test microorganisms was examined by the cut plug and viable cell counting methods of shake cultures of 10 times dilute nutrient broth and Sabouraud^’s media, seeded with the test microorganisms. It was found that the immobilized polymers exhibited antimicrobial activity against the Gram negative bacteria (Escherichia coli, Pseudomonas aeruginosa, Shigella sp. and Salmonella typhi) and Gram positive bacteria (Bacillus subtilis and B. cereus) and the dermatophyte fungus (Trichophyton rubrum). The growth inhibition of the test microorganisms (ratio of surviving cell number, M/C) varied according to the composition of the active group in the polymer and the test organism. It increased by increasing the concentration of the polymer. Triphenyl phosphonium salt of the modified poly(vinyl alcohol) exhibited the most biocidal activity against both Gram-negative and Gram-positive bacteria after 24 h.     

聚乙烯醇/聚乙烯吡咯烷酮碱性复合膜的制备及其性能

通过在不同浓度KOH溶液中进行掺杂,制备出了聚乙烯醇/聚乙烯吡咯烷酮(PVA/PVP)碱性聚合物电解质膜.详尽考察了膜的组成、微观结构、热稳定性、离子电导率和甲醇吸收率.结果表明,PVA与PVP两者具有较好的相容性,当m(PVA)∶m(PVP)=1∶0.5时,膜断面致密、均匀,未发生大尺度相分离.PVP的混入可以极大提高复合膜的电导率和热稳定性.当m(PVA)∶m(PVP)=1∶1时,复合膜的电导率可达2.01×10-3 S.cm-1.PVA/PVP/KOH膜的甲醇吸收率随温度的升高没有明显变化,100℃时其甲醇吸收率仅为同条件下Nafion 115膜的1/4.这表明该复合膜有望作为一种新型的碱性直接甲醇燃料电池用固体电解质膜且可提高膜的使用温度.     

聚乙烯醇水凝胶溶胀特性研究

在前文对聚乙烯醇水溶液冰冻凝胶化浓度依赖性研究基础上，对接触浓度（Ｃ）以上聚乙烯醇水溶液通过冰冻－融化处理，制得了一种含水率高达９５～９８％的水凝胶．系统研究了该水凝胶在蒸馏水中的溶胀及溶解特性．得到了一个与实验结果相吻合的溶胀动力学方程：Ｑ１＝Ｑｅ－（Ｑｅ－ＱＯ）／ｅｋｔ，及平衡溶胀比Ｑｅ与浓度之间的定量关系：Ｑｅ＝６０．３－４．４５×１０２Ｃ．发现当冰冻－融化次数Ｎ≤５时，平衡溶胀比Ｑｅ及溶解量Ｗ与冰冻－融化次数（Ｎ）间满足幂函数关系：Ｑｅ。Ｗ通过对聚乙烯醇水凝胶平衡溶胀比与经冰冻处理的聚乙烯醇水溶液特性粘数进行比较，发现反映链间氢键凝聚缠结效应与反映链内氢键凝聚缠结效应的定量指标具有等效性．     

海藻糖改性聚乙烯醇及其防雾/防霜涂层

以聚乙烯醇和羧基化海藻糖为原料合成了聚乙烯醇-g-海藻糖(PVA-g-Tre), 将接枝物与少量乙二醇二甲基丙烯酸酯混合, 通过光引发聚合制备了亲水性半互穿网络防雾/防霜涂层. 通过核磁共振氢谱和傅里叶变换红外光谱对PVA-g-Tre的化学结构进行了表征, 利用原子力显微镜、 水接触角测试仪、 拉曼光谱等分析了涂层表面的粗糙度、 润湿性及水与大分子之间的氢键作用, 并考察了涂层的透光性和防雾及防霜性能. 结果表明, 含有不同海藻糖接枝率PVA-g-Tre的涂层表面粗糙度较低且透光率好, 与含有PVA的涂层相比, 引入海藻糖提高了PVA-g-Tre涂层的亲水性和润湿性, 使其同时具有良好的防雾和防霜性能.     

Preparation of electrospun chitosan/poly(vinyl alcohol) membranes

Electrospinning of chitosan from its solutions in 2% aqueous acetic acid was studied by adding poly(vinyl alcohol) (PVA) as a “guest” polymer. Properties of the chitosan/PVA solutions including viscosity, conductivity, and surface tension were measured, and effects of the polymer concentration, chitosan/PVA mass ratio and processing parameters (applied voltage, flow rate, capillary-to-collector distance) on the electrospinnability of chitosan/PVA were investigated. Analyses of scanning electron micrographs and transmission electron micrographs suggested that the chitosan/PVA ultrafine fibers were often obtained along with beads, and chitosan was located in the elctrospun fibers as well as in the beads. Uniform chitosan/PVA fibers with an average diameter of 99 ± 21 nm could be prepared from a 7% chitosan/PVA solution in 40:60 mass ratio. Results of Fourier transform infrared spectroscopy and X-ray diffraction demonstrated that there were possible hydrogen bonds between chitosan and PVA molecules, which could weaken the strong interaction in chitosan itself and facilitate chitosan/PVA electrospinnability. The electrospun chitosan/PVA membranes showed higher water uptake and would have potential applications in wound dressings.     

用于燃料电池的季铵基团的PVA/PAADDA碱性聚合物电解质膜的制备及稳定性

通过聚合物共混法成功地制备出了具有化学交联结构的聚乙烯醇/二甲基二烯丙基氯化铵和丙烯酰胺共聚物(PVA/PAADDA)碱性聚合物电解质膜。采用傅里叶红外分析（FTIR）、扫描电镜（SEM）、热重分析（TGA）和交流阻抗等方法详细考察了PVA/PAADDA膜的分子结构、微观形貌、热稳定性、耐碱稳定性、尺寸稳定性和电导率。红外分析结果表明,PAADDA成功地混入聚合物基体中。SEM分析结果表明,当m(PVA):m(PAADDA)=1:1时,膜可观察到明显的微相分离。TGA结果表明,混入PAADDA后膜的热稳定性没有明显降低,并且在210 oC之前能保持很好的热稳定性。PVA/PAADDA膜在经过高温、高浓度碱溶液（80 oC, 6 mol?L-1）处理后,仍表现出很好的耐碱稳定性。同时,由于膜内形成致密的内互交联网络结构,PVA/PAADDA膜在60 oC水中处理300 h后也能表现出优良的尺寸稳定性和电导率稳定性。此外,膜的甲醇吸收率随着温度的升高没有明显变化,90 oC时甲醇吸收率仅为同条件下Nafion115膜的1/5。     

PVA/PVP共混物的SAXS研究

聚乙烯醇(PVA)/聚吡咯烷酮(PVP)共混物的小角X-射线散射(SAXS)研究表明,PVA/PVP共混物的结构参数与共混物组分比及热历史密切相关。按Vonk一维电子密度相关函数法,得到PVA/PVP共混物的长周期,过渡层厚随PVP组分含量增加而增加;结晶片层厚和比内表面积却随PVP含量增加而降低。热处理可提高共混物的结晶性。     

Preparation,surface morphology,and optical properties of indium(III) oxide nanoparticles by thermolysis of indium–poly(vinyl alcohol) coordination polymer

First report on the preparation of well-dispersed, indium(III) oxide (In₂O₃) nanoparticles with 22–35?nm size by polymer thermolysis is presented. Indium–poly(vinyl alcohol) (PVA) coordination polymer films were prepared by ‘solution casting technique’ from the homogeneous aqueous solution of coordination polymer prepared using PVA and indium(III) nitrate as starting materials; subsequently the films were calcined at 550?°C to yield In₂O₃ nanoparticles. Both indium–PVA coordination polymer that served as the precursor and the titled nanoparticles were characterized by Fourier transform-infrared spectroscopy, photoluminescence (PL), powder X-ray diffraction (XRD), transmission electron microscopy, and thermal analysis. Room temperature PL spectra of the prepared indium oxide nanoparticles showed intense blue emissions around 360, 410 and 430?nm, characteristic of indium oxide nanoparticles due to oxygen vacancies. The lower energy PL emission decreases with an increase of indium(III) content in the precursor. The size of the nanoparticles calculated from line broadening of XRD pattern (cubic; JCPDS: 06-0416) was found to be around 24?nm. The average particle size of the synthesized nanoparticles increased with metal ion content in the precursor coordination polymer.