壳聚糖修饰纳米纤维膜表面对氧化还原酶行为的影响

采用静电纺丝法制备了丙烯腈/丙烯酸共聚物(PANCAA)纳米纤维膜, 研究了纺丝液浓度对纤维形态的影响, 以扫描电子显微镜观察纤维形貌, 遴选得到最佳纺丝条件. 以1-乙基-3-(N,N-二甲基氨基丙基)碳二亚胺/N-羟基丁二酰亚胺(EDC/NHS)为偶联剂, 在纤维膜表面引入壳聚糖修饰层, 采用衰减全反射傅里叶变换红外光谱(ATR/FTTIR)、水接触角和称重法考察了修饰前后膜的变化. 通过戊二醛将过氧化氢酶固定到壳聚糖修饰的PANCAA纳米纤维膜上, 研究了壳聚糖及戊二醛浓度对固定化过氧化氢酶的影响, 结果表明, 在壳聚糖浓度为25 mg/mL及戊二醛质量分数为5%条件下, 壳聚糖修饰膜的固定化酶活性比空白膜提高了41.7%, 稳定性也得到了不同程度的提高.     

海藻酸盐/壳聚糖衍生物复合抗菌纤维

通过溶液纺丝法制备海藻酸盐/羧甲基壳聚糖（CMC）共混纤维,并用红外光谱,X射线衍射和扫描电镜对共混纤维进行了表征.结果表明：共混体系中的两种组分之间存在着较强的相互作用,有良好的相容性.当ωCMC=0.30时,共混纤维的干态抗张强度达到最大值,13.8cN/tex.当ωCMC=0.10时,纤维的干态断裂伸长率可达23.1%.纤维的湿态抗张强度和断裂伸长率随着CMC含量的增加而降低.CMC的引入,可显著提高纤维的吸水率.用壳聚糖季铵盐对纤维进行处理,可赋予纤维抗菌性.     

PVA微晶交联和SA/PAA双网络协效增强增韧SA纤维

为了提高海藻酸钠(SA)纤维的断裂强度和断裂伸长率, 以丙烯酸(AA)为化学交联组分, SA为离子交联组分, 聚乙烯醇(PVA)为微晶交联组分, 采用湿法纺丝和冻融循环方法制备含有PVA微晶交联点和海藻酸钠/聚丙烯酸(SA/PAA)双网络结构的海藻酸钠/聚丙烯酸/聚乙烯醇(SA/PAA/PVA)复合纤维. 通过流变性能、 力学性能、 红外光谱、 X射线衍射仪(XRD)和扫描电子显微镜(SEM)测试研究了交联剂N,N-亚甲基双丙烯酰胺(MBA)含量和PVA微晶交联对SA/PAA/PVA纺丝原液和复合纤维的结构与性能的影响. 结果表明, 当MBA质量分数为0.5%时, 纺丝原液的损耗模量(G″)最小, 可纺性最好, 复合纤维的断裂强度达到2.83 cN/dtex, 断裂伸长率达到9.38%, 比再生SA纤维分别提高了15.98%和38.96%; PVA冷冻之后形成微晶交联点并且PAA和PVA已经复合到体系中; PAA和PVA的加入提高了复合纤维的结晶度; 复合纤维的表面形貌趋于光滑和规整, 纤维断面更加致密.     

PLMA/PU共混纤维的制备与吸附性能

以聚乙烯醇(PVA)为分散剂,过氧化苯甲酰(BPO)为引发剂,采用水相悬浮聚合法合成了聚甲基丙烯酸十二酯(PLMA),将其与聚氨酯(PU)共混、造粒、熔融纺丝制得PLMA/PU共混纤维.通过傅里叶变换红外光谱仪(FTIR)、扫描电子显微镜(SEM)、单纤维强力仪及光学接触角测量仪等分析了纤维的结构与性能,同时研究了纤维对有机液体的吸附性能及循环使用性能等.研究结果表明,纤维具有良好的疏水亲油性,吸附后,纤维形态明显胀大;纤维对油性低分子有机物具有良好的吸附性能,其中对甲苯、三氯乙烯、柴油、煤油和含有原油(质量分数为10%)的甲苯溶液最大吸附率分别为4.86,8.1,2.42,2.04和3 g/g,吸附油品后的纤维经脱附可多次循环使用;PLMA对纤维吸附有机液体起决定作用,而PU的存在对纤维吸油时保持形态和纺丝成形起到重要作用.     

核-壳结构壳聚糖/聚乙烯醇-聚碳酸亚丙酯超细纤维的制备

利用同轴电纺丝技术制备出具有核-壳结构的壳聚糖/聚乙烯醇-聚碳酸亚丙酯电纺丝纤维,考察了溶剂复配对成纤的影响,采用扫描电镜和透射电镜对纤维的形貌、结构、直径分布等进行了探索,并在优化的工艺条件下,将羟基磷灰石负载在内层结构中.研究表明,采用氯仿/N,N-二甲基甲酰胺(1/1)复配溶剂可有效避免聚合物溶液在喷丝口处的凝结现象.同单纺纤维相比,核壳结构的纤维直径分布较宽,纤维壳层和核层界限清晰;红外谱图分析证明羟基磷灰石可负载在纤维的核结构中.     

离子液体中纤维素/纳米层状ZnO复合抗菌纤维的制备及性能

以表面活性剂十二烷基磺酸钠(SDS)为模板,Zn(NO_3)_2·6H_2O和NaOH为锌源和沉淀剂,通过改进的模板法在温和条件下制得纳米层状ZnO.以离子液体1-烯丙基-3-甲基咪唑氯盐([Amim]Cl)为溶剂,木浆纤维素和纳米层状ZnO为原料,采用溶液共混方法,通过干湿法纺丝制备了ZnO质量分数分别为3%,5%,7%及9%的纤维素/ZnO纳米复合纤维.采用X射线衍射(XRD)、X射线光电子能谱(XPS)、透射电子显微镜(TEM)、场发射扫描电子显微镜(SEM)及热重分析(TG)等方法对纳米层状ZnO及纤维素/ZnO复合纤维进行了表征,并探讨了ZnO的加入对复合体系流变性的影响,同时对复合纤维进行了力学和抗菌性能测试.研究结果表明,所制备氧化锌纯度高,且呈现出重复周期为3.58 nm的层状结构,抗菌性能优异.纳米层状ZnO的加入提高了纤维素纤维的热稳定性和机械强度,同时赋予纤维对金黄色葡萄球菌和大肠杆菌的抑菌性.ZnO片层被纤维素链剥离,并均匀分散于纤维素/ZnO复合物中.ZnO的加入增大了纤维素溶液的黏度,当ZnO含量达到5%以上时,在整个频率范围内,弹性模量大于损耗模量,纳米粒子可稳定悬浮.     

聚(3-羟基丁酸酯-co-3-羟基戊酸酯)改性及纤维成形北大核心CSCD

聚(3-羟基丁酸酯-co-3-羟基戊酸酯)(PHBV)是一种微生物发酵生产的热塑性聚合物。从物理、化学改性及其纤维成形两个方面综述了PHBV的研究进展。PHBV的物理改性主要有无机纳米粒子共混体系(PHBV/iNPs)、有机纳米晶共混体系(PHBV/oNPs)、高聚物共混体系(PHBV/Polymer)和绿色全降解共混体系;化学结构构筑主要包括接枝共聚改性、嵌段共聚改性、端基扩链改性等。从改性的手段及介质,分析了改性方法的优缺点。PHBV纤维的成形方法主要有熔融纺丝法、干法纺丝法及静电纺丝法。从PHBV纤维应用领域看,熔融纺纤维应用目标在于替代现有石油基相关产品,而静电纺纤维主要应用于开拓组织工程再生医学领域。最后,对PHBV今后的研究及发展提出了展望。     

Armos/聚砜共混中空纤维基膜及其纳滤复合膜的制备与性能研究

中空纤维膜因其体积装填密度高、占地面积小、成本相对低等优点备受关注。本文通过将Armos聚合液与聚砜(PSf)共混，经干-湿法纺丝制备了Armos/PSf共混中空纤维超滤膜，研究表明：Armos均匀分散在中空纤维膜中，中空纤维膜断面呈现疏松的多孔结构，随着Armos共混含量的增加，膜的亲水性和纯水通量均提高，但对PEG-20000截留率下降明显。以Armos/PSf共混中空纤维膜为基膜，通过界面聚合制备了中空纤维复合纳滤膜，优化的制备条件为：基膜中Armos的共混含量为4%、水相单体浓度为3%、油相单体浓度为0.15%时，制得的中空纤维复合纳滤膜性能最佳，其通量为8.40L/(m²·h)，对MgSO₄的截留率为88%。     

ZnO纳米纤维的静电纺丝及其光催化性能的研究

以聚乙烯醇溶液为络合剂与醋酸锌反应制得前驱体溶液,采用静电纺丝法制备PVA/Zn(Ac)2复合纳米纤维,经过高温煅烧得到直径为100 nm的ZnO纳米纤维,采用差热-热重分析、红外光谱分析、X射线粉末衍射分析及扫描电镜等手段对其进行了表征.光催化降解酸性品红溶液的实验结果表明,太阳光照65 min使质量浓度为45 mg/L酸性品红水溶液的脱色率达93%;另外,重复使用ZnO纳米纤维4次之后,其光催化降解率仍能达到70%以上.这充分说明ZnO纳米纤维具有良好的光催化性能.     

魔芋葡甘聚糖/聚乙烯醇纳米纤维膜及其释药行为研究

为了研制药物缓释效果优良的薄膜材料,利用静电纺丝设备研制不同比重的魔芋葡甘露聚糖/聚乙烯醇纳米纤维膜,并通过扫描电镜、傅里叶变换红外光谱和示差扫描量热法表征纳米纤维膜的结构和性能,结合体外实验和数学模型研究其缓释行为.结果显示当魔芋葡甘露聚糖含量占纳米纤维膜总质量约76%时,纳米纤维膜中微纤丝粗细最均匀且结点较少,纳米纤维膜中魔芋葡甘聚糖和聚乙烯醇之间存在明显的相互作用,含有5-氨基水杨酸的纳米纤维膜在pH=7.4 PBS磷酸盐缓冲液中25 h的累积释放量大约为45%,显示出良好的药物缓释效果,其缓释行为与Higuchi模型具有较高的拟合度.研究表明利用静电纺丝设备研制的魔芋葡甘聚糖/聚乙烯醇纳米纤维膜可以为药物缓释载体的开发提供理论依据.     

Stabilization of electrospun poly(vinyl alcohol) nanofibrous mats in aqueous solutions

<正>The stability ofpoly(vinyl alcohol)(PVA) nanofibrous mats in water media was improved by post-electrospinning treatments.Bifunctional glutaraldehyde(GA) in methanol was used as a crosslinking agent to stabilize PVA nanofiber,but fiber twinning was observed frequently,and the highly porous structure of PVA nanofibrous mats was destroyed when the crosslinked fiber was soaked in water.To overcome this shortcoming,chitosan(CS) was introduced into the PVA spinning solution to prepare PVA/CS composite nanofibers.Their treatment in GA/methanol solution could retain the fiber morphology of PVA/CS nanofibers and porous structure of PVA/CS nanofibrous mats even if they were soaked in aqueous solutions for 1 month.Scanning electron microscopy(SEM),X-ray diffraction(XRD),thermal gravimetric analysis(TGA) and differential scanning calorimetry(DSC) were applied to characterize the physicochemical structure and thermal properties of PVA nanofibers.It was found that the water resistance of PVA nanofibrous mats was enhanced because of the improvement of the degree of crosslinking and crystallinity in the electrospun PVA fibers after soaking in GA/methanol solution.     

Thermal,mechanical and water barrier properties of graphene oxide/polyvinyl alcohol/polyol composite films

The novel polymer composite of polyvinyl alcohol (PVA), polyol(PO) and graphene oxide (GO) was used to prepare the PVA/PO and GO/PVA/PO with different weight percents of GO (0.5 and 1% denoted as (0.5 wt%)GO/PVA/PO and (1 wt%)GO/PVA/PO, respectively) through solution casting blend technique. The structure–properties of all used films were confirmed by scanning electron microscope (SEM), Transmission Electron Microscope (TEM), X-ray powder diffraction (XRD), thermogravimetric analysis (TGA) and mechanical properties. The SEM results exhibited the uniform and homogeneous dispersion of GO in the PVA/PO blend matrix. The TEM and XRD analysis confirmed the structure and exfoliation of GO nanosheets, respectively. Thermal stability suggested that (0.5 wt%)GO/PVA/PO and (1 wt%) GO/PVA/PO films are more stable than PVA/PO. The tensile strength of (0.5 wt%)GO/PVA/PO and (1 wt%)GO/PVA/PO films reached 270.5% and 1349.6%, respectively, which are higher than that of the PVA/PO film. The decrease in the water absorption (WA) of GO/PVA/PO was found from 110.5 to 38.4%. The physico-mechanical properties of used films suggested that the prepared GO/PVA/PO blend composite films can be applied in food packaging areas.     

Influence of finishing oil on structure and properties of multi-filament fibers from cellulose dope in NaOH/urea aqueous solution

Cellulose multi-filament fibers have been spun successfully on a pilot plant scale, from a cellulose dope in 7 wt% NaOH/12 wt% urea aqueous solution pre-cooled to −12 °C. Coagulation was accomplished in a bath with 10 wt% H₂SO₄/12 wt% Na₂SO₄ and then 5 wt% H₂SO₄ aqueous solution. By using different finishing oil, including H₂O, 4% glycerol aqueous solution, 2% polyvinyl alcohol (PVA) aqueous solution, 2% polyethylene glycol octyl phenylether (OP) aqueous solution, mobol and 2%glycerol/1%PVA/1%OP aqueous solution (PGO), we prepared six kinds of the cellulose multi-filaments, with tensile strength of 1.7–2.1 cN/dtex. Their structure and properties were investigated with scanning electron microscope (SEM), ¹³C NMR solid state, wide-angle X-ray diffraction (WAXD) and tensile testing. The cellulose fibers treated with PGO possessed higher mechanical properties and better surface structure than others. Interestingly, although the orientation of the cellulose multi-filaments is relatively low, the tensile strength of the single-fiber was similar to that of Lyocell. It was worth noting that the dyeability of the multi-filament fibers was superior to viscose rayon.     

Study on morphology of electrospun poly(vinyl alcohol) mats

Submicron poly(vinyl alcohol) (PVA) fiber mats were prepared by electrospinning of aqueous PVA solutions in 6-8% concentration. Fiber morphology was observed under a scanning electron microscope and effects of instrument parameters including electric voltage, tip-target distance, flow rate and solution parameters such as concentration on the morphology of electrospun PVA fibers were evaluated. Results showed that, when PVA with higher degree of hydrolysis (DH) of 98% was used, tip-target distance exhibited no significant effect on the fiber morphology, however the morphological structure can be slightly changed by changing the solution flow rate. At high voltages above 10 kV, electrospun PVA fibers exhibited a broad diameter distribution. With increasing solution concentration, the morphology was changed from beaded fiber to uniform fiber and the average fiber diameter could be increased from 87 ± 14 nm to 246 ± 50 nm. It was also found that additions of sodium chloride and ethanol had significant effects on the fiber diameter and the morphology of electrospun PVA fibers because of the different solution conductivity, surface tension and viscosity. When the DH value of PVA was increased from 80% to 99%, the morphology electrospun PVA fibers was changed from ribbon-like fibers to uniform fibers and then to beaded fibers. The addition of aspirin and bovine serum albumin also resulted in the appearance of beads.     

改性海藻酸钠聚集行为对电纺纳米纤维形貌的影响

以过硫酸钾(KPS)为引发剂, 采用双丙酮丙烯酰胺(DAA)对海藻酸钠(SA)进行改性, 制备了海藻酸钠-聚双丙酮丙烯酰胺两亲性共聚物(SA-PDAA). 将SA-PDAA与聚乙烯醇(PVA)复配, 并进行静电纺丝, 制得SA-PDAA/PVA电纺纳米纤维. 通过红外光谱、 差示扫描量热和荧光光谱表征了SA-PDAA的结构和性能, 通过黏度仪、 表面张力仪和电导率仪测试了SA-PDAA纺丝液的物理性能, 用扫描电子显微镜表征了SA-PDAA/PVA电纺纳米纤维的形貌, 考察了SA-PDAA/PVA电纺纳米纤维的释药性能. 结果表明, DAA接枝到SA分子链上, SA-PDAA的临界聚集浓度为0.072 g/L, SA-PDAA具有良好的两亲性, SA-PDAA/PVA电纺纳米纤维具有均一的形貌. 改性后的SA可以有效地减缓药物释放速度, 提高SA-PDAA/PVA电纺纳米纤维的缓释性能.     

Electrospinning of cyclodextrin functionalized chitosan/PVA nanofibers as a drug delivery system

A new type of nanofibrous structure from chitosan bearing carboxymethyl-β-cyclodextrin (CS-g-β-CD) as a novel drug delivery system was synthesized by grafting carboxymethyl-β-cyclodextrin (CM β-CD) onto chitosan (CS) in the presence of water soluble 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC) as the condensing agent and N-hydroxysuccinimide (NHS). Defect free mats containing CS-g-β-CD have been fabricated using electrospinning of an aqueous solution of poly(vinyl alcohol) (PVA)/CS-g-β-CD blends. The morphology and diameter of the electrospun nanofibers were examined by scanning electron microscopy (SEM). The average fiber diameter was in the range of 130–210 nm. SEM images showed that the morphology and diameter of the nanofibers were mainly affected by weight ratio of the blend at constant applied voltage. The results revealed that increasing CS-g-β-CD content in the blends decreases the average fiber diameter. It was observed that the PVA/CS-g-β-CD nanofibrous mat provided a slower release of the entrapped drug in compare to PVA/CS nanofibrous mat.     

The synthesis of translucent polymer nanolatexes via microemulsion polymerization

Surface-enhanced Raman scattering (SERS)-active substrates of polyvinyl alcohol/gold-silver (PVA/Au-Ag) nanofibers were prepared using a simple approach involving electrospinning. The tunable surface plasmon resonance (SPR) of gold-silver alloy (Au-Ag alloy) nanoparticles (NPs) was achieved by controlling the feed ratio between gold and silver precursors. A higher concentration of Au-Ag alloy NPs could be obtained than the conventional methods, using 1wt% of PVA as the stabilizer. The Au-Ag alloy structure was demonstrated by HRTEM and STEM-EDX. After the electrospinning, the Au-Ag alloy NPs were successfully embedded in PVA nanofibers, as shown in the SEM and TEM images. Raman spectra displayed an apparent enhancement in the signal of 4-mercaptobenzoic acid (4-MBA), pyridine, and thiophenol molecules pre-absorbed from their ethanol solution onto the PVA/Au-Ag nanofibers. Different SERS effects were achieved by varying the Au content or excitation wavelength.     

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.     

Preparation of Fluorine-Containing Polyacrylate Emulsion by a UV-initiated Polymerization

A fluorine-containing polyacrylate emulsion was synthesized by a UV-initiated emulsion polymerization from methyl methacrylate (MMA) and hexafluorobutly methacrylate (HFMA) in the presence of 2-hydroxy-4-(2-hydroxyethoxy)-2-methyl-propiophenone (Irgacure 2959) as a hydrophilic photoinitiator at room temperature. The latex and films were characterized by Fourier transformed infrared (FT-IR) spectrometry, nuclear magnetic resonance (¹H-NMR, ¹⁹F-NMR) spectrometry, transmission electron microscopy (TEM), recycling gel permeation chromatography (GPC), dynamic light scattering (DLS), and contact angle (CA) analysis, respectively. The effects of photoinitiator and emulsifier concentration on the polymerization were discussed. Compared to the corresponding thermal polymerization, UV-initiated polymerization of the MMA/HFMA emulsion could be accomplished at a much higher speed. The polymerization conversion in UV-initiated polymerization reached 95% within 10 min at an emulsifier concentration of 0.6 wt%, photoinitiator concentration of 0.4 wt%, and monomer concentration of 10 wt%.