丝素在NMMO·H2O中的溶解及溶液流变性能的研究

探讨了丝素在N-甲基吗啉-N-氧化物一水合物(NMMO.H2O)中的溶解行为,结果发现:天然蚕丝纤维脱胶后得到的丝纤维可以直接溶解在NMMO.H2O中,但是很难得到高于10%浓度的溶液,因而无法用于纺丝.而由再生丝素水溶液制得的再生丝素膜则易于溶解在NMMO.H2O中,并可以得到浓度高达25%的再生丝素/NMMO.H2O溶液,在上述研究的基础上,本文还对再生丝素/NMMO.H2O的流变行为进行了初步研究.     

支链淀粉稀溶液和半稀溶液的流变性质

利用激光光散射仪表征了蜡状谷物支链淀粉和土豆支链淀粉在浓度为0.5 mol/L的NaOH水溶液中的重均相对分子质量(Mw)、根均方旋转半径()和第二维利系数(A2),通过这些分子参数计算了蜡状谷物支链淀粉和土豆支链淀粉的临界交叠浓度.系统地研究了支链淀粉在稀溶液和半稀溶液中的流动行为,讨论了剪切速率、浓度、温度等对溶液表观黏度(aη)、流动指数(n)、零切黏度(0η)等的影响.结果表明,蜡状谷物支链淀粉在NaOH水溶液中表现为非牛顿型流体,且随着浓度增加,非牛顿性增强;而土豆支链淀粉即使在临界交叠浓度以上也表现为牛顿型流体.     

碱脱胶法优化提取蚕丝素蛋白及其构象光谱

采取碱脱胶法对广西产桑蚕茧脱胶条件进行优化,利用苦味酸胭脂红法和扫描电镜对蚕丝脱胶程度进行检测,结果表明,蚕丝在脱胶浴比为1:200,脱胶30 min的条件下,其表面丝胶可脱除效果最好。将蚕丝脱胶所得丝素蛋白分别溶解在CaCl2-EtOH-H2O、LiBr-H_2O和LiBr-EtOH-H_2O3种溶剂中获再生蚕丝素蛋白溶液。在相同条件下,采用红外光谱、拉曼光谱对比研究蚕丝索蛋白的构象,结果表明碱脱胶法得到的天然丝素蛋白以β-折叠构象为主,再生丝素蛋白溶液构象以无规卷曲为主。对比3种溶剂对蛋白构象的影响,结果表明:溶剂中Li~(+)比Ca~(2+)对丝素蛋白的二级结构扰动更显著,倾向破坏蚕丝素蛋白的β-折叠构象,且溶剂中加入适量乙醇会进一步促进金属离子对丝素蛋白构象的影响。     

多孔柞蚕丝素支架的制备及其在药物缓释中的应用

采用冷冻干燥法制备了多孔柞蚕丝素支架,分析了丝素溶液浓度与支架孔径、孔隙率之间的关系,并研究了多孔柞蚕丝素支架负载5-氟尿嘧啶的缓释性能.研究表明,当丝素浓度较低时,支架中的孔洞分布较为均匀,孔径和孔隙率也较大,而随着丝素溶液浓度增大,支架的孔径和孔隙率逐渐减小;支架的药物释放过程可分为快速释放和缓慢释放两个阶段.     

剪切速率对高浓度再生丝素水溶液构象的影响

对高浓度的再生丝素水溶液（15％～37％）在不同剪切速率下（1000s-1和2000s-1）的构象变化进行了研究，对剪切前后的溶液进行了DSC和Raman对比测试。发现经过剪切，丝素溶液更客易发生从无规线团或α-螺旋向β-折叠构象的转变，且转变的程度随所受剪切速率的增加而提高。而且当丝素浓度低于27％时对剪切不敏感；超过30％时则对剪切敏感。     

多孔丝素材料的结构与性能研究

用CaCl2.CH3CH2OH.H2O三元溶剂溶解蚕丝丝素,通过对丝素溶液冷冻之后的状态,以及冷冻干燥后丝素结构和性质的测试和分析,指出采用冷冻干燥制备再生蚕丝丝素多孔材料时,若冷冻温度低于－20℃,则丝素的结构以无定型为主,含少量的SilkII,若冷冻温度高于－20℃,则又增加了较多的SilkI,采用冷冻干燥法可以制得平均孔径为10－300um,孔密度为1－2000个／mm^2,孔隙率为35％－70％的多孔丝素材料,通过调节冷冻温度和丝素溶液质量分数,达到控制多孔丝素材料的上述表态结构,聚集态结构和透湿性,压缩性,强度,伸长率等物理性能的目的是可能的,将快速冷冻的丝素水溶液真空干燥之前,进行反复解冻－冷冻－则所制得的多孔丝素材料的孔径增大,孔密度减小,同时其压缩率和透湿性有所提高,拉伸断裂强度和在热水中的溶失率下降。     

微晶纤维素/1-丁基-3-甲基咪唑氯体系流变性能研究

离子液体1-丁基-3-甲基咪唑氯(BmimCl)可用作溶解微晶纤维素(MCC)的优良溶剂。通过稳态剪切和动态扫描测试考察了微晶纤维素离子液体溶液的流变性能。结果表明,所有浓度的MCC/BmimCl溶液在高剪切速率和低剪切速率表现出剪切变稀行为。温度和浓度对MCC/BmimCl溶液的黏弹性质产生重要影响。将复合黏度数据用于Cross模型,并利用Arrhenius公式计算了不同浓度MCC/BmimCl溶液的流动活化能。     

低浓度部分水解聚丙烯酰胺与柠檬酸铝交联体系流变性研究

用HAAKERS150流变仪对低浓度部分水解聚丙烯酰胺与柠檬酸铝交联反应所形成的交联聚合物溶液流变性及其时间效应进行了分析。结果表明,聚合物质量浓度为0.1g/L及NaCl质量浓度为2.0g/L的交联聚合物溶液与同条件的低浓度部分水解聚丙烯酰胺溶液的流变性不同,交联聚合物溶液在中等剪切速率范围内(400～1000s-1)表现为胀流性,低剪切速率(43～400s-1)时为假塑性,高剪切速率(1000～1500s-1)时表现为牛顿性;而相应的低浓度部分水解聚丙烯酰胺溶液只表现轻微的假塑性(5～900s-1)。交联聚合物溶液具有时间效应,表现为负触变性(震凝性),而低浓度部分水解聚丙烯酰胺溶液流变性不产生时间效应。     

葡萄糖氧化酶在丝素膜中的固定化及其性能和应用于生物传感器(英文)

应用二种中性盐溴化红和氯化钙作为溶解蚕丝丝素的试剂,制成了二种固定化葡萄糖氧化酶丝素膜。经酶比色法和红外分光光度法分析,结果表明这二种丝素膜都是良好的固定化酶的生物材料。葡萄糖氧化酶经这些丝素膜固定以后对热和pH稳定性得到明显改良。这些酶膜性能稳定,具有高的活性得率,能长期存放。以这些固定化葡萄糖氧化酶丝素膜和氧电极为基础,研制的流动注射分析式电流型葡萄糖生物传感器性能较稳定,具有较宽的葡萄糖线性响应范围(0.5～15.0mmol/L),相关系数为0.999,可以反复测定葡萄糖一千次以上。     

蚕丝深度加工开发潜力大

丝素膜类产品１．可利用其良好的透氧性，用于制造隐形眼镜；２.日本东京大学用其研制成生物传感器，用于检测血糖值；３.日本钟纺公司开发的由丝素膜构建的癌症自动诊断系统，已进入临床试用阶段；４.我国近来也开发出固定葡萄糖氧化的专用丝素膜；５.其它如硅胶丝膜，用于丰乳术，加入抗血凝成分可制造人工血管、人工皮肤和人工肺等。丝素经低温冷冻粉碎后的蚕丝，如７～８ｕｍ的丝素，具有良好的抗血栓作用，日本已应用于临床。丝素肽由蚕丝经酶解而成，具有显著的护肤、护发、美容功能。日本每年用于化妆品上的蚕丝达５～６ｔ。人工骨胳…     

Fine Structure of Regenerated Silk Fibroin Solids

ＩｎｔｒｏｄｕｃｔｉｏｎＳｉｌｋｆｉｂｒｏｉｎ (Ｂｏｍｂｙｘｍｏｒｉ)ｉｓｔｈｅｐｏｌｙｍｅｒｗｉｔｈｔｗｏｋｉｎｄｓｏｆｃｒｙｓｔａｌｓｔｒｕｃｔｕｒｅ,ｓｉｌｋⅠａｎｄｓｉｌｋⅡ[1,2 ] .ＴｈｅｓｐａｃｅｃｏｎｆｏｒｍａｔｉｏｎｏｆｓｉｌｋⅠｔａｋｅｓｏｎｔｈｅｓｈａｐｅｏｆｃｒｏｏｋｅｄｈａｎｄｌｅ ,ｔｈｅｉｎｔｅｒｍｅｄｉａｔｅｆｏｒｍｂｅｔｗｅｅｎα ｓｐｉｒａｌｓｔｒｕｃｔｕｒｅａｎｄβ ｆｏｌｄｅｄｓｔｒｕｃｔｕｒｅ ,ａｎｄｔｈａｔｏｆｓｉｌｋⅡｉｓａｎｔｉ ｐａｒａｌｌｅｌβ ｆｏｌｄｅ…     

Examination of Subunit Composition of Bombyx Mori Silk Fibroin

Main subunits of the silk fibroin were separated by GFC(gel filtration chromatography)technigue.The nativesilk fibroin and α,c subunits were measured by gel elec-trophoresis.The aminoacid compositions of the nativesilk fibroin and α,c subunits were analyzed by means ofaminoacid measurement.Some properties of silk was inter-preted in view of subunit composition of silk fibroin.     

天然丝素制备三维多孔支架

研究盐沥滤法制备三维多孔丝素支架,在丝素多孔支架上培养人成骨肉瘤细胞、成纤维细胞及肝细胞.研究材料的细胞相容性,发现多种动物细胞在盐沥滤法所制备的丝素多孔支架材料上能够很好地黏附和增殖.通过调整丝素水溶液的浓度、溶解丝素溶剂体系、NaCl添加量和NaCl粒径,制备出结构和性质可以调控的三维支架.该结果为丝素多孔支架材料的制备提供了新的研究思路和方法.     

IMPROVEMENT OF WET-CREASE RECOVERY PROPERTIES OF SILK FABRICS TREATED WITH EPOXIDES

Silk fabrics is finished with epoxide TDEA or TDEB. By the determination of washing fastness, DSC, IR spectrum and amino acid contents tests, TDEA or TDEB is confirmed to react with silk fibroin. By means of tests of silk fibroin swelling and solubility in some solvents, crosslinking reactions between TDEA or TDEB and silk fibroin arc further proved, which is obviously responsible to the increase of wet-crease recovery of silk fabrics finished with epoxide TDEA or TDEB.     

Preparation and Characterization of Silk Fibroin Aerogel

Silk protein fibroin,as a biomedical material,has good biocompatibility,biodegradability,regulation and excellent physical and chemical properties. In this work,a low density porous silk fibroin material is prepared from fibroin solution by high-speed shearing with impeller. By adjusting shear rate of the stirrer,silk fibroin aerogel with different sizes of the aperture is prepared. In general, this aerogel has small porosity, uniform pores, good mechanical properties and slow rate of degradation. It is observed that increasing the shear rate results in higher porosity of aerogel,while the diameter of the aerogel becomes smaller. This silk aerogel may offer a new option as biomaterial for the tissue engineering application based on the information on the structural behaviors.     

Physico-Chemical Properties of a Water-Insoluble Silk Fibroin Film

The conventional silk fibroin(SF)films obtained by casting from SF aqueous solution are amorphous,and easily dissolved in water.This defect limits the practical use of SF films in biomedical field.A new water-insoluble silk fibroin film(an SF-FA film)could be simply prepared by casting from SF formic acid solution.The physical properties and moisture permeability of SF-FA films were examined.The results show that the SF-FA film swollen in water exhibits outstanding pliability.The weight loss of SF-FA films ...     

切变速度和Ca~(2+)对再生丝素蛋白溶液构象转变的影响

采用偏光显微镜和拉曼光谱研究了切变速度和Ca2+对再生丝素蛋白水溶液构象转变的影响.结果表明:切变速度和Ca2+是影响再生丝素蛋白溶液性质的两个主要因素,对于同一再生溶液,切变速度增大,溶液中丝素蛋白分子沿切变方向的有序排列也随之增加,丝素溶液更容易从无规线团或α-螺旋向β-折叠转变,并且转变的程度随着剪切速度的增加而加强;透析溶液中Ca2+含量增加,则样品出现偏光现象的临界切变速度有所降低.拉曼光谱显示丝素蛋白分子构象由SilkⅠ向SilkⅡ转变.     

Nanoscale control of silks for regular hydroxyapatite formation

The control of nanoparticle shape is still a challenge for different hydroxyapatite (HA) preparation ways.In the present study,silk fibroin with regular nanostructures was firstly prepared and then emp...     

Cu（Ⅱ） effect on the conformation of regenerated silk fibroin in dilute aqueous solution

Much attention has been paid to the natural mechanism of silkworm spinning due to the impressive mechanical properties of the natural fibers. In this work, we studied the effect of Cu（Ⅱ） ions on the secondary structure of Bombyx mori regenerated silk fibroin （SF） in dilute solution by circular dichroism （CD）. The results indicate that a given amount of Cu（Ⅱ） induces the SF conformational transition from random coil to β-sheet, however, further addition of Cu（Ⅱ） is unfavorable for this conversion. Meanwhile, the conformational changes induced by Cu（Ⅱ） follow a nucleation-dependent aggregation mechanism, which is similar to that found in Prion protein （PrP） denaturation and Aβ-peptide aggregations, leading to the neurodegenerative disease. This work would help one understand further the natural spinning process of silkworm. Additionally, it would be significant for the study of the nervous system diseases, because silk fibroin, extracted in large amounts from Bombyx mori silkworm gland, could be a proper model to study PrP denaturation and Aβ-peptide aggregations.