静电纺丝工艺参数对丝素/壳聚糖纳米纤维的形貌及直径的影响

以98%的甲酸为溶剂,不同质量分数的再生丝素溶液和3.5%的壳聚糖溶液以质量比70:30共混静电纺丝。用扫描电子显微镜(SEM)观察了丝素质量分数、电压和极距(喷丝口到收集装置的距离)对丝素/壳聚糖纳米纤维的形貌及直径的影响。正交试验结果表明:在丝素/壳聚糖溶液静电纺丝的工艺参数中,对纤维平均直径的影响因素由大到小依次为丝素质量分数、电压、极距。单因素试验表明:丝素/壳聚糖纳米纤维的平均直径及其分布范围随丝素质量分数的增加而增大;在15￣30kV范围内纤维的平均直径随电压增大而减小;当极距大于12cm时,对纤维直径影响不大。最佳工艺条件为:丝素质量分数13%,电压30kV,极距为12cm,制得的纳米纤维平均直径104nm。     

丝素/羧甲基壳聚糖共混膜的结构性能探讨

将含有甘油和戊二醛的丝素与羧甲基壳聚糖按一定比例混合,制得丝素/羧甲基壳聚糖共混膜,对共混膜的结构与性能进行了探讨。结果表明:随着羧甲基壳聚糖含量的增加,共混膜的透气率增大,加入交联剂戊二醛有效地改善了共混膜的力学性能,但其透气率有所降低;当丝素与羧甲基壳聚糖的质量比为4/1时,共混膜的断裂强度最大,力学性能较好,共混膜相容性较好,其断面光滑、致密。制备丝素/羧甲基壳聚糖共混膜的较佳条件为:丝素中的甘油质量分数为15%,戊二醛质量分数为0.075%,丝素与羧甲基壳聚糖质量比为4/1。     

丝素-聚乙烯醇共混溶液静电纺丝及其含银纳米纤维形态研究

研究了不同丝素-聚乙烯醇（SF-PVA）配比的共混溶液和加入硝酸银的丝素-聚乙烯醇（SF-PVA）共混溶液的静电纺丝,利用扫描电镜观察纤维的形态变化。结果表明：在丝素（SF）或聚乙烯醇（PVA）占绝大部分时,整个体系溶解性保持相对稳定,容易形成比较均一的溶液,且纺丝后纤维形态比较均匀、规则;而在两组分含量接近时整个体系的溶解性能较差,不易形成比较均一的溶液,表现为溶液粘度的显著增大,纺丝后纤维不均匀、不规则。笔者选用SF/PVA=1：9（质量比）的共混纺丝液加入硝酸银,随着硝酸银在溶液中含量的增加,溶液电导率会明显增加,纤维的直径明显下降;但随着电导率的增大,纤维中珠状物会增多,纤维均一性也变差。     

壳聚糖/玉米醇溶蛋白膜液的流变与膜热性能

将壳聚糖与玉米醇溶蛋白按不同质量比共混得到了系列共混膜液(C/Z-0、C/Z-1、C/Z-3、C/Z-5)并通过溶液浇铸制得相应共混膜。通过旋转流变仪、SEM及DSC分析了不同质量比对共混膜液体系的流变特性、共混膜的微观结构及共混膜热特性的影响。结果表明:不同质量比的共混膜液均具有假塑性,且随着玉米醇溶蛋白质量分数的增加,膜液的稠度系数减小,流动指数增大(从0.849增加到0.882),共混膜液的活化能均逐渐升高。动态频率扫描流变学分析表明,储能模量和损耗模量均表现出对频率的依赖性,且随着玉米醇溶蛋白质量分数的增加,两者数值均上升,此外,交叉点向低频方向移动,表明分子间氢键作用力增强。C/Z-1共混膜中壳聚糖与玉米醇溶蛋白分子结合紧密,相容性好,这也导致了共混膜热稳定性的提高。     

壳聚糖/玉米醇溶蛋白共混膜液体系的流变特性与共混膜的热特性分析

摘 要：将壳聚糖与玉米醇溶蛋白按不同质量比共混得到系列共混膜液 (C/Z-0、C/Z-1、C/Z-3、C/Z-5)并通过溶液浇铸制得相应共混膜。通过旋转流变仪、SEM及DSC分析不同质量比对共混膜液体系的流变特性、共混膜的微观结构及共混膜热特性的影响。结果表明：不同质量比的共混膜液均具有假塑性，且随着玉米醇溶蛋白质量分数的增加，膜液的稠度系数减小，流动指数增大，流动指数从0.849增加到0.882，共混膜液的活化能均逐渐升高。动态频率扫描流变学分析表明，储能模量和损耗模量均表现出对频率的依赖性，且随着玉米醇溶蛋白质量分数的增加，两者数值均上升，此外交叉点向低频方向移动，表明分子间氢键作用力增强。C/Z-1共混膜中壳聚糖与玉米醇溶蛋白的分子结合紧密，相容性好，这也导致了共混膜热稳定性的提高。     

静电纺丝PLA/丝素复合纤维膜的结构和性能

以氯仿、丙酮为混合溶剂,制得质量分数为5%的聚乳酸(PLA)纺丝液,经静电纺丝制备PLA纤维膜;以98%的甲酸为溶剂,制得丝素纺丝液,在PLA纤维膜上喷射丝素纺丝液制成PLA/丝素复合纤维膜.采用扫描电镜观察其形貌结构,并测定其微细结构、力学性能、溶失率及生物性能.结果表明:PLA/丝素复合纤维膜呈规整排列的多孔网状结构.与丝素膜相比,PLA/丝素复合纤维膜的丝素蛋白转向β折叠结构,断裂比功提高18倍,水中溶失率降低3倍,更有利于人脐静脉内皮细胞在纤维膜上的生长.     

丝素/羧甲基壳聚糖共混膜的结构与性能

利用丝素(SF)与羧甲基壳聚糖(CMCS)共混制取不同比例的SF/CMCS共混膜。研究了CMCS诱导的丝素构象转变行为,测试了共混膜的吸湿性、透湿性和保水性。当CMCS的质量分数为5%时,共混膜中丝素的构象以β-折叠为主;当CMCS的质量分数为10%时,共混膜中丝素的构象由β-折叠向α-螺旋发生转变;当CMCS的质量分数达到15%时,共混膜中丝素的构象向无规卷曲发生转变。当CMCS质量分数小于15%时,共混膜中SF与CMCS具有良好的相容性,溶胀度较小,吸湿性随CMCS含量的增加而迅速降低。     

羧甲基壳聚糖与明胶共混膜的制备及其性能的研究

制备出羧甲基壳聚糖(CM-ch)/明胶共混膜,研究了CM-ch、交联剂等对共混膜的断裂强度、断裂伸长率、溶出率、吸水率等的影响,并通过DSC、扫描电镜等测试手段对共混膜进行了表征。结果表明:CM-ch的加入降低了明胶膜的结晶度,断裂伸长率增大明显,由38%增至76%,且随着CM-ch含量的增加,膜的吸水率和溶出率均有所增大;交联剂的加入能有效地改善共混膜的机械性能,而随交联剂浓度的提高,膜的吸水率和溶出率均有所降低。截面的电镜照片表明这两种生物材料有很好的相容性。     

柞蚕丝丝素/壳聚糖共混体系的静电纺丝研究

利用六氟异丙醇和三氟乙酸为溶剂,通过静电纺丝制备了不同共混比的柞蚕丝丝素(TSF)/壳聚糖(CS)纳米纤维。研究了TSF/CS共混比对纺丝液黏度、电导率和纤维形貌的影响。结果表明,TSF/CS共混液的电导率随CS含量的增加而增加;随着CS含量的增加(≤15%),共混液的黏度增加缓慢,纤维由转曲的扁平带状逐渐变为圆柱形且直径逐渐降低;当CS含量超过15%时,共混液的黏度随CS含量的增加而显著增大,纤维出现粗细两极分化现象。     

油酸对壳聚糖/玉米醇溶蛋白膜性能的影响

为了提高壳聚糖/玉米醇溶蛋白膜的机械性能,将壳聚糖液与玉米醇溶蛋白液共混,向其中加入含量为0、15%、30%、45%(以复合膜液中壳聚糖和玉米醇溶蛋白的总质量为基准,下同)的油酸进行改性,制得复合膜液。考察了膜液的粒径、Zeta电位、静态和动态流变特性;分析了油酸添加量对膜阻隔性能、机械性能和相容性的影响。结果表明:添加油酸后,膜液体系粒径增大、分散均匀,添加30%油酸的膜液分散性更好,PDI为0.34,粒径为1307.5 nm。随着油酸含量增大,膜液黏度减小,流动指数增大,弹性模量和黏性模量增加。含30%油酸的膜机械性能较好,抗拉强度为36.37 MPa,断裂伸长率为22.32%。与不含油酸的膜相比,添加45%油酸膜的阻隔性增强,水蒸气、氧气透过率分别降低了44.21%和67.52%。复合膜中壳聚糖与玉米醇溶蛋白分子相容性较好,表面光滑平整。     

Metal ion permeation properties of silk fibroin/chitosan blend membranes

Silk fibroin/chitosan (SF/CS) blend membranes were prepared and characterized by infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and scanning electron microscopy. It was found that SF and CS were compatible in the blend membranes and that the membranes were dense without microscopic phase separation. Swelling experiments showed that the swelling ratio of the blend membranes increased with CS content and reached the highest value when CS content was 70 wt%. Experiments indicated that the permeability coefficient of K⁺ through the blend membrane was 2–4 times higher than that of pure CS membrane, and 10 times higher than that of pure SF membrane. The permeation rate of K⁺ increased linearly with CS content in the blend membrane for the lower concentration feeding solution. For different metal ions, the permeability through SF/CS blend membranes was in the sequence K⁺ > Ca²⁺ > Cd²⁺ > Pb²⁺ > Cu²⁺ > Ni²⁺. Copyright © 2006 Society of Chemical Industry     

Effect of chitosan on morphology and conformation of electrospun silk fibroin nanofibers

The electrospinning of silk fibroin(SF)/chitosan(CS) blends with different composition ratios was performed with formic acid as a spinning solvent. The SF/CS blends containing up to the CS content of 30% could be electrospun into the continuous fibrous structure, although pure CS was not able to be electrospun into the fibrous structure. As-spun SF/CS blend nanofibers showed smaller diameter and narrower diameter distribution than pure SF nanofibers, and the diameter gradually decreased from 450 to 130 nm with the addition of CS in blends. However, at the blend compositions with above 40 wt% chitosan, the continuous SF nanofibers containing CS beads were produced. We also investigated the influence of the methanol treatment on the secondary structure of as-spun SF or SF/CS blend nanofibers by means of ATR-IR and solid-state CP-MAS ¹³C-NMR. Comparing with the pure SF nanofibers, the conformational change of the as-spun SF/CS blend nanofibers into β-sheet was faster because the CS with rigid backbone synergistically might promote the conformational transition of SF by an intermolecular interaction.     

Ultraviolet-light-filtering behavior of fullerene-amine derivative/chitosan blended membranes

The aminated fullerene/chitosan blended membranes with novel ultraviolet-light-filtering properties have been prepared by mixing chitosan with fullerene ethylenediamine or ethanolamine derivative in a solution containing 2% acetic acid, then casting the mixture on a glass plate. The effects of fullerene-amine derivative and chitosan structures on light transmission properties of the blended membranes are investigated systematically. The fullerene derivative kind, aminated fullerene content and crosslinking degree of chitosan greatly affect their light-filtering properties, while deacetylation degree, molecular weight and carboxymethylation of chitosan only have slight influence. Further, a possible mechanism for the UV filtering property was discussed. The strong interactions, especially electron donor-acceptor occur in condensed state may play a significant role in the unique optical property.     

邻苯二酰化壳聚糖与聚乳酸接枝共聚物的研究

选用三种不同相对分子质量的壳聚糖进行实验,对接枝共聚物的制备的工艺及条件进行较为详细的研究。采用＂保护氨基-接枝反应-脱保护＂的接枝路线,将聚左旋乳酸接枝在不同相对分子质量的壳聚糖主链上,制得壳聚糖接枝聚乳酸共聚物。结果表明：（1）通过改变投料比、温度、时间等条件确定最佳的工艺条件制备邻苯二甲酰化壳聚糖（PHCS）。在投料比（CS/PH）为1∶4,反应温度为125℃,反应时间7 h时,壳聚糖的氨基保护反应基本反应完全;（2）增加投料比（PHCS/PLLA）中的PLLA含量时,PHCS-g-PLLA的接枝率随之升高,在投料比（PHCS/PLLA）为1∶3时,PHCS-g-PLLA接枝率可达到接近100%。     

醋酸纤维素/壳聚糖复合膜制备与性能优化

为拓展醋酸纤维素(CA)在可降解包装材料中的应用,采用溶液共混法制备了醋酸纤维素(CA)和壳聚糖(CS)复合膜,研究了CS含量对CA/CS二元复合膜性能的影响。通过观察并分析复合膜的形貌、断面结构、化学键发现,CS能够充分结合膜内外的孔隙结构,两者之间强烈的相互作用增强了复合膜的各项性能。性能测试结果表明,当CS含量为10%时,复合膜的力学性能达到最大,断裂伸长率及抗拉强度分别增加12.37%和38.62 MPa,降解损失率提高了50.14%。同时,抑制了大肠杆菌及金黄色葡萄球菌的生长,抗菌率最高能够达到73.9%和54.6%。因此,CS在提高CA膜的力学性能和降解性能的同时,还赋予了复合膜优异的抗菌性。     

交联剂的用量对淀粉-壳聚糖-聚乙烯醇-明胶共混膜的性能影响

本文研究了交联剂对淀粉/壳聚糖/聚乙烯醇/明胶共混膜的透光性、透气性、吸水性及保水性和力学性能的影响。结果表明：共混膜的性能与交联剂有较大关系。在交联剂用量在0%~5%的范围内,随着交联剂用量的增加,共混膜的扯断伸长率、吸水性和保水性随之降低,共混膜的拉伸强度、撕裂强度、透水气性和透光性先增加后减小。     

Chitosan/CaCO3 solvent‐free nanofluid composite membranes for direct methanol fuel cells

Natural polyelectrolyte chitosan (CS) has been considered to be a promising proton‐exchange membrane material for direct methanol fuel cells due to its low cost and excellent methanol barrier ability. To further improve the ionic conductivity and mechanical property of CS, calcium‐carbonate solvent‐free nanofluids (CaCO₃‐SF) with unique flow behavior were prepared by an ion‐exchange method, and then used a novel nanofiller to modify CS to fabricate composite membranes. The surface‐grafted organic long chains on the surface of CaCO₃ nanoparticles could promote the homogeneous dispersion of CaCO₃ in the CS matrix, and thus improve the interfacial bonding and facilitate the load transfer from the matrix to stiff CaCO₃. When the content of CaCO₃‐SF was 6 wt%, the tensile strength and fracture elongation of the composite membrane were 28.25 MPa and 17.17%, respectively, which increased by 25% and 36% when compared with those of pure membrane. Moreover, the ? SO₃H groups in the structure of organic long chains could form new proton transport sites, and thus enhance the proton conductivity of the membranes. Consequently, when compared with pure CS membrane (0.0131 S cm^?1), incorporation of 6 wt% CaCO₃‐SF (0.0250 S cm^?1) exhibited about onefold increase of proton conductivity. POLYM. ENG. SCI., 59:2128–2135, 2019. © 2019 Society of Plastics Engineers     

聚乳酸–壳聚糖–茶多酚复合膜的制备及其性能

为研究壳聚糖(CS)、茶多酚(TP)和聚乳酸(PLA)3种物质所得复合膜的性能效果,采用流延成膜法,制备不同CS与TP质量比的PLA–CS–TP复合膜。通过测试纯PLA膜及各复合膜的密度、力学性能、热封性能、水蒸气透过率和溶解度等指标,对比分析了复合膜的综合性能,研究其实用价值。结果表明,相比纯PLA膜,CS与TP的加入使复合膜的密度和拉伸性能明显降低,但显著提高了复合膜的热封强度、水蒸气透过率和溶解度。当CS与TP质量比为3/7时,热封强度最高,比纯PLA膜提高了245.72%;当CS与TP质量比为5/5时,水蒸气透过率最高,比纯PLA膜提高了28.59%;当CS与TP质量比为1/9时,溶解度最高,比纯PLA膜提高了758.04%。复合膜具有较好的热封性、透湿率和溶解度,在食品包装领域有较好的应用潜力,可使无花果在5℃下的保存期由2 d延长至13 d以上。