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     

Fabrication and characterization of electrospun Plantago major seed mucilage/PVA nanofibers

Electrospinning is a well-known technique for producing nanofibers using synthetic and natural polymers like mucilage. In this study, Plantago major Mucilage (PMM) was blended with polyvinyl alcohol (PVA) as a nontoxic adding agent, in order to produce electrospun nanofiber. Electrospinning parameters (voltage, tip-to-collector distance, feed rate, and PMM/PVA ratio) were optimized and solution properties were analyzed. The morphology of nanofibers was investigated using scanning electron microscopy (SEM), Fourier transform infrared (FTIR), X-ray diffraction (XRD), and Brunauer–Emmett–Teller (BET). Mechanical strength of nanofibers was determined, and cell viability on nanofibers was discussed by MTT assay. The results of SEM indicated that the PMM/PVA (50/50) nanofibers obtained with average diameter of 250 nm. Viscosity, electrical conductivity, and surface tension of PMM/PVA solution were 550 Cp, 575 μS/cm, and 47.044 mN/m, respectively. FTIR and XRD results verified the exiting PMM in produced nanofibers and no chemical reaction between PMM and PVA. Improvement in mechanical strength and cell viability of nanofibers by adding PMM to PVA nanofibers indicated the potential application of PMM-based nanofibers for medical and food industries. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47852.     

Thermal and structural characterization of nanofibers of poly(vinyl alcohol) produced by electrospinning

Poly(vinyl alcohol) (PVOH) was obtained from the alkaline hydrolysis of poly(vinyl acetate) (PVAc). Nonwoven membranes (mats) of PVOH nanofibers were produced by electrospinning of solutions of PVOH in water with and without aluminum chloride. The concentration of the PVOH/water solution was 12.4% w/v. The morphology of the mats was analyzed by scanning electron microscopy (SEM). The thermal properties and the degree of crystallinity of the nanofibers were measured by differential scanning calorimetry (DSC); the crystal structure of the mats was evaluated by wide‐angle X‐ray diffraction. The best nanofibers were obtained by electrospinning the PVOH/water solution with aluminum chloride (45% w/v) in which an electrical field of 3.0 kV/cm was applied. It was observed that the addition of the aluminum chloride and the increase in the applied electrical field decreased the number‐average nanofibers diameters. The mats without aluminum chloride had higher melting temperatures and higher degrees of crystallinity than the mats with the salt. The crystal structure of the mats was found to be monoclinic; however, the mats were neither highly oriented nor have a high degree of crystallinity. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

钒掺杂TiO2纳米纤维的制备及其光催化性能

以体积比为1∶2的N,N-二甲基甲酰胺和丙酮为溶剂、钛酸四丁酯[Ti(OiPr)4]和氯化钒[VC13]为前驱体、醋酸纤维素(CA)为模板,采用静电纺丝法制备了V-TiO2/醋酸纤维素纳米纤维.将V-TiO2/醋酸纤维素纳米纤维用0.1 mol/L NaOH/乙醇溶液水解得到V-TiO2/纤维素纳米纤维.在500℃煅烧V-TiO2/纤维素纳米纤维5h,得到直径为(200±53)nm的V-TiO2纳米纤维.利用扫描电子显微镜、X射线粉末衍射仪和紫外-可见漫反射光谱对纤维形貌、物相和结构进行了表征.以染料罗丹明B为目标降解物考察了纤维的光催化活性.结果表明:掺杂少量V后,TiO2对紫外光的最大吸收峰和吸收带边发生了红移,说明V-TiO2对光响应更宽、光利用率更高.TiO2和V-TiO2纳米纤维在20min内对罗丹明B的降解率分别为67％和77％.     

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     

Study of electrospinning of sodium alginate,blended solutions of sodium alginate/poly(vinyl alcohol) and sodium alginate/poly(ethylene oxide)

Alginate is an interesting natural biopolymer for many of its merits and good biological properties. This paper investigates the electrospinning of sodium alginate (NaAlg), NaAlg/PVA‐ and NaAlg/PEO‐ blended systems. It was found in this research that although NaAlg can easily be dissolved in water, the aqueous NaAlg solution could not be electrospun into ultrafine nanofibers. To overcome the poor electrospinnability of NaAlg solution, synthetic polymers such as PEO and PVA solutions were blended with NaAlg solution to improve its spinnability. The SEM images of electrospun nanofibers showed that the alginate (2%, w/v)–PVA (8%, w/v) blended system in the volume ratio of 70 : 30 and the alginate (2%, w/v)–PEO (8% w/v) blended system in the volume ratio of 50 : 50 could be electrospun into finest and uniform nanofibers with average diameters of 118.3 nm (diameter distribution, 75.8–204 nm) and 99.1 nm (diameter distribution, 71–122 nm), respectively. Rheological studies showed a strong dependence of spinnability and fiber morphology on solution viscosity and thus on the alginate‐to‐synthetic polymer (PVA or PEO) blend ratios. FTIR studies indicate that there are the hydrogen bonding interactions due to the ether oxygen of PEO (or the hydroxyl groups of PVA) and the hydroxyl groups of NaAlg. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

On the electrospinning of poly(vinyl alcohol) nanofiber mats: A revisit

Electrospinning was used to fabricate mats of poly(vinyl alcohol) (PVA; M_w = 72,000 Da, degree of hydrolysis ≈ 97.5–99.5) nanofibers from PVA solutions in reverse osmotic water. The effects of solution concentration, applied electrical potential, sonication, and collection distance on morphological appearance and diameters of the as‐spun fiber mats as well as those of the individual fibers were carefully investigated mainly by scanning electron microscopy. The effect of the distance from the center of the as‐spun fiber mat on morphological appearance and diameters of the as‐spun fibers was also investigated. The mechanical integrity of some as‐spun PVA fiber mats was also investigated. At all concentrations and applied electrical potentials investigated, the average diameters of the as‐spun PVA fibers ranged between 85 and 647 nm. The use of sonication to prepare a PVA solution caused the viscosity of the solution to decrease; hence, the observed decrease in the average diameters of the as‐spun fibers and the average diameters of the as‐spun fibers were practically the same throughout the as‐spun fiber mat. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

PLLA/PVA/PLCA三元共混体系分子间相互作用

聚L-乳酸(PLLA)及聚乙烯醇(PVA)由于其良好的生物相容性,在生物医学领域得到了广泛的关注。但聚乳酸由于其疏水性及缺乏反应位点而使其应用受到一定的限制。将聚乙烯醇与聚乳酸共混,不仅可以降低聚乳酸的成本,同时可以改善其亲水性,但由于其结构差异,存在严重的相分离现象。本研究将含有反应活性位点的乳酸-柠檬酸共聚物(PLCA)引入PLLA/PVA体系中,以期改善二者的相容性。通过红外光谱分析手段,研究了PLLA/PVA/PLCA体系中分子间的相互作用,并对不同组成体系的力学性能进行了分析及表征。结果表明,PLCA的加入使PLLA/PVA复合体系的相容性及力学性能得到了明显的改善。     

聚乙烯-乙烯醇/TiO2共混非织造布的制备及其表征

通过高压静电纺丝技术,以异丙醇/水为混合溶剂,通过TiO2共混改性,制备了不同二氧化钛含量的聚乙烯-乙烯醇(EVOH)/二氧化钛(TiO2)非织造布,通过扫描电子显微镜、X-射线衍射(XRD)对其微观形貌、结晶性能进行了研究,并分析了相对面电阻和吸碱率与TiO2共混量的关系。结果表明:经TiO2共混改性后,纤维中有白色团状突起出现,有实心纤维和空心纤维两种形貌;XRD分析表明,随着TiO2含量的增加,EVOH/TiO2非织造布的结晶度越来越低;非织造隔膜的吸碱率最大可达到950%。     

聚乙烯醇/二氧化硅互穿网络膜的研究

采用溶胶凝胶法制备了聚乙烯醇/二氧化硅有机/无机互穿网络结构。扫描电子显微镜(SEM)观察到样品表面光滑,均匀;原子力显微镜(AFM)观察到样品中无机相与有机相呈互穿网络结构,且随无机物的增多两相分布更均匀;元素分析结果为纯PVA中w(O)为38%,随着无机物的增多w(O)逐渐降低为24.9%,是硅羟基与醇羟基之间脱去水,两相之间进行交联的结果;29SiNMR表明随无机物的增多,化学位移Q3的强度有所降低而化学位移Q4值却略有上升,说明硅羟基含量逐渐减少,两相交联程度逐渐增大,与元素分析结果相印证;热重曲线(TG)表明,无机物的加入使PVA的热降解温度由400℃提高到420℃,进一步证明两相之间已形成网状结构。     

Cellular PVA hydrogels produced by freeze/thawing

Cellular poly(vinyl alcohol) (PVA) hydrogels that exhibit enhanced swelling kinetics from an initial dry state were prepared by freezing and thawing techniques in the presence of NaCl. Gels that were dried immediately after preparation demonstrated a dual‐sorption effect upon swelling. Gels that were exposed to a 10‐day washing period to remove NaCl and excess PVA chains before drying showed an increased initial rate of swelling and overall water content. Freeze/thawed, cellular PVA gels showed overall enhanced swelling with increased mechanical strength over traditional gels prepared by chemical or irradiative crosslinking techniques. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 2075–2079, 2000     

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     

The effect of UV irradiation on the electrospun PCL/TiO2 composites fibers

The effect of UV irradiation and micro‐ and nano‐TiO₂ as well as titanate nanotubes (TiNT) on the phase morphology and thermal properties of the electrospun PCL composite fibers was investigated. Polycaprolactone (PCL)/TiO₂ (micro‐ and nano‐TiO₂ as well as titanate nanotubes) composite fibers were prepared by electrospinning a polymer solution. The PCL and PCL/TiO₂ composite fibers were exposed to UV light at irradiation times of 5 and 10 days. After UV irradiation the crystallinity of the electrospun PCL/TiNTcomposite fibers increased because of the large specific surface area of TiNT. The thermal stability of the PCL/TiNT electrospun composite fibers increased due to the formation of crosslinking structure after UV irradiation. The SEM analysis suggests that after UV radiation the fibers showed high degree of degradation due to the high number of fibers breakages and fibers surface voids. The results of FTIR spectroscopy confirmed that the TiO₂ particles enhance the degradation process because of their photocatalytic activity. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43539.     

Preparation and characterization of poly(vinyl alcohol) nanofiber mats crosslinked with blocked isocyanate prepolymer

Poly(vinyl alcohol) (PVA) nanofibers crosslinked with blocked isocyanate prepolymer (BIP) were successfully prepared using the electrospinning process and subsequent thermal treatment. Fourier transform infrared spectroscopy and solid‐state ¹³C NMR spectroscopy demonstrated that chemical crosslinks between the hydroxyl group of PVA and the isocyanate group of BIP were formed. Thermogravimetric analysis and differential scanning calorimetry results indicated that when the BIP content was increased, the thermal stability of PVA/BIP nanofibers increased, and the crystallinity of PVA decreased. Field emission scanning electron microscopy was used to measure the average diameter (200–300 nm) of the electrospun PVA/BIP nanofibers. The water contact angles were 10.2° and 113° for the pristine PVA nanofibers and PVA nanofibers crosslinked with 8 wt% BIP, respectively. The tensile strength of the crosslinked PVA nanofibers was 53.7 MPa, which was seven times higher than that of pristine PVA. The improved tensile strength and water resistance of the crosslinked PVA/BIP nanofibers were due to a combination of increased crosslinking density and decrease in the number of hydroxyl groups on the surface of the PVA/BIP nanofibers. Copyright © 2010 Society of Chemical Industry     

聚乙烯醇改性及吹膜技术研究

研究了聚乙烯醇（PVA）改性及吹膜技术。经改性剂改性前后的IR分析结果表明，改性剂与PVA分子间发生了强烈的相互作用，并形成了较强的分子复合键。改性PVA塑化温度的研究表明，醇解度为88％的PVA，随相对分子质量的增加塑化温度升高。醇解度升高时，PVA塑化性能下降；改性剂用量增加，塑化温度下降。吹膜工艺研究表明，成膜助剂的加入能明显改善改性PVA的加工流动性，PVA膜对冷却效果要求较高，吹膜后的热定型处理能降低其吸湿性，延长水溶时间。     

Dehydration of water–alcohol mixtures by vapor permeation through PVA/clay nanocomposite membrane

An organic/inorganic hybrid nanocomposite membrane, poly(vinyl alcohol)/clay (PVAC), was prepared. The morphology of PVAC nanocomposite membranes were characterized using transmission electron microscopy (TEM), X‐ray diffraction (XRD), and atomic force microscopy (AFM). The crystallinity and surface roughness increases with an increasing clay content in the PVAC nanocomposite membrane. Compared with the pure poly(vinyl alcohol) (PVA) membrane, the hybrid nanocomposite membrane (PVAC) shows an improvement in the thermal stability and the prevention of the water‐soluble property. The oxygen permeability and the water‐vapor permeation rate decreases with an increasing clay content (1–3 wt %) in the PVAC nanocomposite membranes. In addition, the effects of the clay content on the vapor‐permeation performance of an aqueous ethanol solution through the PVAC nanocomposite membranes was also investigated. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3632–3638, 2003     

One-step fabrication of branched poly(vinyl alcohol) nanofibers by magnetic coaxial electrospinning

Branching has been emerging in 3-D interconnecting building blocks. Branched and hyperbranched poly(vinyl alcohol) (PVA) nanofibers were fabricated by coaxially electrospinning two-liquids under an alternating magnetic field in a facile manner. Both the PVA nanofiber trunks with diameter of 100–200 nm and the PVA nanofiber branches with diameter of 10–30 nm were formed in a single step. The length and the morphology of the branched PVA nanofibers could be controlled through a rational design of the magnetic field. The facile technique may readily be extended to prepare 3-D branched nanofibers from other materials such as various polymers and polymer–ceramic materials. Moreover, the multifunctional and multicomponent materials with branched nanostructure could be expected by using the magnetic coaxial electrospinning technique. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

聚乙烯醇／水滑石共混纤维的制备及其性能研究

采用凝胶纺丝法制备聚乙烯醇／水滑石（PVA／HT）共混纤维。通过扫描电镜（SEM）观察水滑石在PVA／HT共混纤维中的分散状况和共混纤维的表面形态。从傅里叶变换红外光谱（FT-IR）可以看出HT和PVA之间存在明显的氢键作用;热重分析（TG）测试表明水滑石的加入可以有效提高PVA的热性能;加入适量的HT可以提高PVA纤维的断裂强度;随着HT含量的增加,PVA／HT共混纤维的最大拉伸倍数下降且表面易产生缺陷。     

Electrochemical investigations on the effect of dispersoid in PVA based solid polymer electrolytes

Various compositions of TiO₂ dispersed PVA‐PMMA‐LiBF₄‐EC based electrolytes were prepared using solution casting technique. The prepared electrolytes were characterized using AC impedance, XRD, SEM, FTIR, etc. The ionic conductivity value is increased with the increase in filler content (up to 8 wt %) and then decreased with the increase in filler content. The results are described using Vogel–Tamman–Fulcher theory. The thermal and transport properties of the electrolyte exhibiting maximum conductivity have also been studied. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3950–3956, 2007