Preparation and antibacterial activity of polyvinyl alcohol/regenerated silk fibroin composite fibers containing Ag nanoparticles

Polyvinyl alcohol (PVA)/regenerated silk fibroin (SF)/AgNO₃ composite nanofibers were prepared by electrospinning. A large number of nanoparticles containing silver were generated in situ and well‐dispersed nanoparticles were confirmed by transmission electron microscopy (TEM) intuitionally. Ultraviolet (UV)‐visible spectroscopy and X‐ray diffraction (XRD) patterns indicated that nanoparticles containing Ag were present both in blend solution and in composite nanofibers after heat treatment and after subsequent UV irradiation. By annealing the nanofibers, Ag⁺ therein was reduced so as to produce nanoparticles containing silver. By combining heat treatment with UV irradiation, Ag⁺ was transformed into Ag clusters and further oxidized into Ag₃O₄ and Ag₂O₂. Especially size of the nanoparticles increased with heat treatment and subsequent UV irradiation. This indicated that the nanoparticles containing silver could be regulated by heat treatment and UV irradiation. The antimicrobial activity of heat‐treated composite nanofibers was evaluated by Halo test method and the resultant nanofibers showed very strong antimicrobial activity. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Phase separation structure in poly(vinyl alcohol)/silk fibroin blend films

Blend films of a commercial poly(vinyl alcohol) (a-PVA) derived from vinyl acetate and silk fibroin (SF) obtained from degummed silk were prepared by mixing the aqueous solutions of both samples. A plain weave structure was recognized only in the blend films, whereas no structure was found for the superimposed films of both samples. The phase separation structure of the blend films was examined by microscopic observations elongation, tensile tests, and IR measurements. The microphase separation region increased with increase in the degree of polymerization of the PVA. In the IR spectra of the blend films with high PVA contents cast under certain conditions, the absorption peak attributed to the cross-β-form conformation of SF appeared strongly. Gelatin, a water-soluble and natural polymer, was also used for comparison with SF. The ternary phase diagram in an a-PVA/gelatin/H₂O system was obtained experimentally and the critical point was used to estimate the interaction parameter between PVA and gelatin molecules. The phase separation structure and the interaction between PVA and SF molecules were also discussed taking into consideration the results of the a-PVA/gelatin system. © 1998 SCI.     

Immobilization of glucose oxidase in the regenerated silk fibroin membrane: Characterization of the membrane structure and its application to an amperometric glucose sensor employing ferrocene as electron shuttle

The structural changes of the regenerated silk fibroin membranes for immobilizing glucose oxidase were characterized with FT-IR spectra. The results of electronic absorption spectra and scanning electron microscopy illustrated that the glucose oxidase in the membranes existed in aggregates. The blend membranes exhibited an island-like structure, attributable to the incompatible and weak intermolecular interactions between regenerated silk fibroin and glucose oxidase. The glucose sensor was constructed by combining glucose oxidase immobilized in regenerated silk fibroin membrane with an Eastman-AQ-ferrocene modified electrode. The advantages of the mediator include high stability and the ability to use a less positive potential for increased selectivity.     

Blend membrane of regenerated silk fibroin,poly(vinyl alcohol), and peroxidase and its application to a ferrocene-mediating hydrogen peroxide sensor

Before or after the blend membrane of regenerated silk fibroin (RSF), poly(vinyl alcohol) (PVA), and peroxidase is treated with ethanol, RSF, PVA, and peroxidase maintain their own structures. The conformational transition of RSF in the blend membrane is accomplished from the silk I structure to the silk II structure by ethanol treatment, which is used to immobilize peroxidase. A ferrocene-mediating sensor for H₂O₂ is made, which is based on the immobilization of peroxidase in the blend membrane of RSF and PVA. Performance and characteristics of the sensor were evaluated with respect to response time, detection limit, selectivity, and dependencies on temperature and pH as well as on operating and storage stability. © 1996 John Wiley & Sons, Inc.     

Green fabrication route of robust,biodegradable silk sericin and poly(vinyl alcohol) nanofibrous scaffolds

Silk sericin (SS) has been extensively used to fabricate scaffolds for tissue engineering. However, due to its inferior mechanical properties, it has been found to be a poor choice of material when being electrospun into nanofibrous scaffolds. Here, SS has been combined with poly(vinyl alcohol) (PVA) and electrospun to create scaffolds with enhanced physical properties. Crucially, these SS/PVA nanofibrous scaffolds were created using only distilled water as a solvent with no added crosslinker in an environmentally friendly process. Temperature has been shown to have a marked effect on the formation of the SS sol–gel transition and thus influence the final formation of fibers. Heating the spinning solutions to 70 °C delivered nanofibers with enhanced morphology, water stability and mechanical properties. This is due to the transition of SS from β‐sheets into random coils that enables enhanced molecular interactions between SS and PVA. The most applicable SS/PVA weight ratios for the formation of nanofibers with the desired properties were found to be 7.5/1.5 and 10.0/1.5. The fibers had diameters ranging from 60 to 500 nm, where higher PVA and SS concentrations promoted larger diameters. The crystallinity within the fibers could be controlled by manipulation of the balance between PVA and SS loadings. In vitro degradation (in phosphate buffer solution, pH 7.4 at 37 °C) was 30–50% within 42 days and fibers were shown to be nontoxic to skin fibroblast cells. This work demonstrates a new green route for incorporating SS into nanofibrous fabrics, with potential use in biomedical applications. © 2019 Society of Chemical Industry     

Thermal characteristics of poly(vinyl alcohol) and poly(vinylpyrrolidone) IPNs

Interpenetrating polymer network (IPN) hydrogels based on poly(vinyl alcohol) (PVA) and 1‐vinyl‐2‐pyrrolidone (VP) were prepared by radical polymerization using 2,2‐dimethyl‐2‐phenylacetophenone (DMPAP) and methylene bisacrylicamide (MBAAm) as initiator and crosslinker, respectively. The thermal characterization of the IPNs was investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and dielectric analysis (DEA). Depressions of the melting temperatures of PVA segments in IPNs were observed with increasing VP content via the DSC. The DEA was employed to ascertain the glass transition temperature (T_g) of IPNs. From the result of DEA, IPNs exhibited two T_gs indicating the presence of phase separation in the IPN. The thermal decomposition of IPNs was investigated using TGA and appeared at near 270°C. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1844–1847, 2002     

The influence of poly(vinyl alcohol) suspending agents on suspension poly(vinyl chloride) morphology

The requirements for PVC suspension resin have changed considerably in the last few years, so much so that few companies have products on their ranges that are more than 4 or 5 years old. The suspending agent has a crucial influence on the morphology of the resin, so the changes in resin characteristics have largely been achieved by changes in the suspending agent systems. After a brief review of the mechanism of PVC suspension polymerisation, the properties of polymers made using PVOH suspending agents are related to changes in the latter. The effect of variations in PVAc degree of hydrolysis and viscosity are related to changes in surface tension. Methods of achieving higher porosity by using low hydrolysis co-suspending agents are described. It is shown that higher bulk densities can be achieved by delayed addition of the PVOH. Levels of conjugated unsaturation and copolymer distributions are also shown to have important influences.     

Morphology of regenerated silk fibroin: Effects of freezing temperature,alcohol addition,and molecular weight

Regenerated silk fibroin (RSF) was prepared by dissolving in a CaCl₂/ethanol/H₂O solvent system, freezing, and lyophilization. The effect of freezing temperature, alcohol addition, and molecular weight on the morphological and conformational changes were investigated through scanning electron microscopy, X‐ray diffraction, Fourier transform infrared spectroscopy, circular dichroism spectroscopy, and differential scanning calorimetry analysis. However, the addition of a small amount of methanol induced the morphological change of RSF to a fine‐particle aggregate, which resulted from the formation of a β‐sheet crystalline structure. The lower the freezing temperature was, the more the formation of aggregates was favored, and the finer powder aggregates were formed. As the amount of added hydrophilic alcohol such as methanol and ethanol increased in the silk fibroin solution, a spherical powder form was changed to fine aggregates with the enhancement of thermal stability and crystallinity. On the other hand, RSFs prepared with a hydrophobic alcohol such as 1‐butanol or 1‐octanol showed a lump‐like or sheet‐like shape of morphology without any changes in conformational transition. It is concluded that the molecular weight of the silk fibroin and the type and amount of alcohol were determining factors in the morphological features of RSF, especially the size and shape of fibroin particles. A uniform ultrafine powder of RSF with a spherical form (～ 1 μm) can be obtained when the molecular weight and the alcohol addition to the silk fibroin solution are controlled. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3008–3021, 2001     

聚乙烯醇膜的改性及应用研究进展

聚乙烯醇（PVA）的改性处理是其应用于膜分离过程必不可少的环节。本文对PVA膜常用的交联、接枝、共混、杂化和取代等改性方法进行了综述,比较了这几种改性方法的优缺点,针对这些改性方法存在的问题,提出了一些改进思路。论文也详细介绍了PVA改性膜在渗透汽化、超滤、纳滤及燃料电池等方面的应用,最后分别对保持良好亲水性PVA膜在渗透汽化脱水领域和高导电率、低甲醇渗透率PVA膜在燃料电池中的应用前景作了展望。     

Poly(vinyl alcohol) and poly(vinyl amine) blend membranes for isopropanol dehydration

Blended membranes of hydrophilic polymers poly(vinyl alcohol) (PVA) and poly(vinyl amine) (PVAm) were prepared and crosslinked with glutaraldehyde. The prepared membranes were characterized using infrared (attenuated total reflection mode) spectroscopy, differential scanning calorimetry, X‐ray diffractometry, and scanning electron microscopy measurements. Pervaporation performances of the membranes were evaluated for the separation of water‐isopropanol (IPA) mixtures. As the PVAm content increased from PVAm0 to PVAm1.5, the flux through a 70 μm film increased from 0.023 to 0.10 kg/m² h at an IPA/water feed ratio of 85/15 at 30 °C. The driving force for permeation of water increased due to the temperature but it has no effect on IPA permeation. Activation energies for the permeation of IPA and water were calculated to be 17.11 and 12.46 kJ/mol, respectively. Controlling the thickness of the blend membrane could improve the permeation flux with only a marginal reduction in the separation factor. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45572.     

Effects of the tacticities of poly(vinyl alcohol) on the structure and morphology of poly(vinyl alcohol) nanowebs prepared by electrospinning

The effects of tacticities on the characteristics of poly(vinyl alcohol) (PVA) nanowebs prepared by an electrospinning technique were investigated. PVA webs composed of uniform nanofibers with syndiotactic dyad (s‐dyad) contents of 53.5 and 57.3% were successfully obtained with electrospinning. By changing processing parameters such as the initial polymer concentration, applied voltage, and tip‐to‐collector distance, we found suitable conditions for forming PVA webs with uniform nanofibers. PVAs of higher s‐dyad contents were prepared at a lower solution concentration and at a higher applied voltage because of the easy formation of syndiotactic PVA chain entanglements at a very low polymer concentration. The average diameter of the nanofibers in a PVA web with the higher s‐dyad content of 57.3% (ca. 240 nm) was thinner than that of the nanofibers in a PVA web with the lowers‐dyad content of 53.5% (ca. 270 nm). In addition, the crystallinity and thermal stability were greatly increased with an increase in the s‐dyad content. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Properties of branched and network poly(vinyl alcohols) prepared with poly(vinyl alcohol) having aldehyde groups at the chain ends

Branched and network poly(vinyl alcohols) (PVAs) were prepared with inter-acetalization of the PVA with aldehyde groups at the chain ends which was prepared by the cleavage of 1,2 glycol bonds in commercial PVA. The numbers of branches estimated from molecular weights were compared with those estimated by theory. Huggins' constant and crystallinity decreased with increasing branch number. Dissolution of branched PVAs into dimethylsulphoxide was not so easy compared with commercial PVA. The colour of branched PVA–iodine complex decreased rapidly with standing while that of commercial PVA decreased gradually. Network PVAs with Young's modulus of 1–8 MPa were prepared.     

Synthesis and characterization of an interpenetrating polymer network composed of poly(methacrylic acid) and poly(vinyl alcohol)

Temperature and pH‐responsive interpenetrating polymer network (IPN) hydrogels, constructed with poly(methacrylic acid) (PMAA) and poly(vinyl alcohol) (PVA), by a sequential IPN method, were studied. The characterization of IPN hydrogels was investigated by Fourier‐transform infrared spectroscopy, differential scanning calorimetry (DSC) and swelling under various conditions. The IPN hydrogels exhibited relatively high swelling ratios, in the range 230–380 %, at 25 °C. The swelling ratios of the PMAA/PVA IPN hydrogels were pH and temperature dependent. DSC was used for the quantitative determination of the amounts of freezing and non‐freezing water. The amount of free water increased with increasing PMAA content in the IPN hydrogels. Copyright © 2004 Society of Chemical Industry     

Studies on aluminum-isopropoxide doped poly(ethylene oxide), poly(vinyl alcohol), and poly(ethylene oxide)-poly(vinyl alcohol) blends

Poly(ethylene oxide), poly(vinyl alcohol), and their blend in a 40 : 60 mole ratio were doped with aluminum isopropoxide. Their structural, thermal, and electrical properties were studied. Aluminum isopropoxide acts as a Lewis acid and thus significantly influences the electrical properties of the polymers and the blend. It also acts as a scavanger for the trace quantities of water present in them, thereby reducing the magnitude of proton transport. It also affects the structure of polymers that manifests in the thermal transformation and decomposition characteristics. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2147–2157, 1998     

Influences of individual and composed poly(vinyl alcohol) suspending agents on particle morphology of suspension poly(vinyl chloride) resin

Effects of individual and composed poly(vinyl alcohol) (PVA) suspending agents on the particle morphology of poly(vinyl chloride) (PVC) resins were investigated and discussed in the view of PVA absorption at the oil/water interface and interfacial behavior. It was shown that the percentage and surface coverage of PVA at the oil/water interface decreased with the increase of the degree of hydrolysis (DH) of PVA in the DH range of 70–98 mol %, while the interfacial tension of VC/PVA aqueous solution increased linearly with the increase of DH of PVA. PVC resin with more regular particle shape, increased agglomeration and fusion of primary particles, lower porosity and higher bulk density, was prepared by using PVA with a higher DH as a suspending agent. This was caused by the occurrence of drop coalescence at the very early stage of VC polymerization, the increase of particle shrinkage, and the lower colloidal protection to primary particles. It was also shown that the interfacial tension of VC/water in the presence of composed PVA suspending agents varied linearly with the weight composition of the composed PVA suspending agents. The particle properties of PVC resin prepared by using the composed PVC suspending agents were usually situated in between the properties of PVC resins prepared by using the corresponding individual PVA suspending agent. The particle morphology and properties of PVC resin could be controlled by the suitable choice of the composed PVA suspending agents. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3848–3855, 2003     

Surface grafting of a poly(organophosphazene) onto poly(vinyl alcohol) and poly(ethylene-co-vinyl alcohol) using triethoxysilane as a coupling agent

Triethoxysilane HSi(OEt)₃ was used as coupling agent to graft a poly(organophosphazene) (POPZ) containing allylic functions to the surface of poly(vinyl alcohol) or poly(ethylene-co-vinyl alcohol) films. Hydrolyzed HSi(OEt)₃, which contained both inorganic (Si–OH) and organic (Si–H) reactivities, acted at the interface between the hydroxylated substrates (via a condensation reaction) and the allylic functions in POPZ (via a hydrosilylation reaction). Starting materials and grafting surfaces were studied by ATR-IR and XPS spectroscopies and contact angle measurements. Data obtained indicated that different POPZ layers were produced, depending on whether the functionalization of materials with silane, and the grafting reaction were separately or simultaneously made. The POPZ layer thickness was higher when the grafting reaction was preceded by the POPZ functionalization. In each cases, the modified surfaces showed marked increases in hydrophobicity character. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1965–1974, 1998     

Separation characteristics of pervaporation membrane separation processes using modified poly(vinyl alcohol) membranes

Modified poly(vinyl alcohol) (PVA) membranes prepared by the ‘solution technique’ were tested for ethanol-water mixtures by varying the reaction density (X_cr = 0.05, 0.1) at various temperatures. The results are compared with those of PVA membranes (X_cr = 0.05) prepared by the technique of the GFT Company, Germany.     

部分醇解的聚乙烯醇纤维结构性能初探

对较低聚合度的聚醋酸乙烯进行醇解,得到一系列不同醇解度的聚乙烯醇,经纺丝拉伸后,得到不同醇解度、不同拉伸倍数的聚乙烯醇纤维。用FT-IR、DSC和强力仪等研究了醇解度和拉伸倍数对纤维结构性能的影响。结果表明,部分醇解的聚乙烯醇有利于降低拉伸中的氢键作用,提高易拉伸性。     

聚乳酸/聚乙烯醇纳米纤维的制备及结构

以二甲基亚砜为溶剂,制备不同配比的聚乳酸(PLLA)和聚乙烯醇(PVA)的混合溶液,静电纺丝制得PLLA/PVA纳米纤维。采用红外光谱仪、原子力显微镜等对PLLA/PVA纳米纤维结构与性能进行了表征。结果表明:PLLA/PVA纳米纤维中PVA上的羟基与PLLA上的羰基形成了氢键,PLLA与PVA之间存在一定的相互作用,但PLLA/PVA纳米纤维存在相分离现象;混合溶液的PLLA质量分数为11%,PVA质量分数为8%时可以得到较好的PLLA/PVA纳米纤维,但PVA质量分数为6%时出现液滴及珠丝,PVA质量分数为4%时,不能制得纳米纤维。