Surface sulfonation of silk fibroin film by plasma treatment and in vitro antithrombogenicity study

To improve the blood compatibility of Bombyx mori silk fibroin (SF) film, the film was modified by SO₂ gas plasma treatment, or by a two-step process including NH₃ gas plasma treatment and reaction with 1,3-propane sultone. XPS and ATR-FTIR were used to analyze the surface chemical elements. In vitro antithrombogenicity was determined by the method of the activated partial thromboplastin time (APTT), prothrombin time (PT) and thrombin time (TT) tests. Percents of sulfur element on the surfaces of both modified SF films were 4.03% and 3.30%, respectively, while that of the control film was only 0.32%. Moreover, the antithrombogencity of treated films was increased remarkably due to surface sulfonation. The results implied a potential use of sulfonated SF for blood-contacting biomaterials.     

Fabrication of a novel micro-nano fibrous nonwoven scaffold with Antheraea assama silk fibroin for use in tissue engineering

The success of developing artificial organs by tissue engineering depends on scaffold properties and architecture. Here, we describe the fabrication of an Antheraea assama fibroin based novel micro-nano fibrous nonwoven scaffold. The morphological and chemical characterization was done by scanning electron microscope (SEM) and Fourier transform infrared spectroscopy (FTIR) respectively, which demonstrated the formation of scaffold with micro-nano architecture. The biocompatibility was assessed in vitro by haemolysis and cytotoxicity assays, whereby the scaffold was found to be nontoxic and efficient in supporting cell adhesion and growth.     

Controlled release of heparin from blended polyurethane and silk fibroin film

Polyurethane was blended with silk fibroin and heparin to prepare a heparin-releasing system. The release rate and the percentage of the cumulative amount of the released heparin can be controlled by the loading amount of heparin in the film, the composition ratio of silk fibroin to polyurethane, and the thickness of the film. The slower and more sustained release of heparin can be obtained by increasing the film thickness, the loading amount of heparin and the content of silk fibroin in the film. Thus the high bioactivity and long lasting antithrombogenicity of the raw heparin can be maintained for the blended film. The coagulation time tests showed that the composite film had good blood compatibility.     

Micropattern of nano-hydroxyapatite/silk fibroin composite onto Ti alloy surface via template-assisted electrostatic spray deposition

The surface topography plays an important role in bone formation, which may present specific physical cues to cells and tissues and further improve the bioactivity or osteoconduction of the implants. In this report, nano-hydroxyapatite/silk fibroin (n-HA/SF) composite were prepared via a simplified coprecipitation method. Then these nanocrystals were deposited onto Ti alloy substrates via a template-assisted electrostatic spraying deposition (ESD) technique. The output voltage and flow rate were investigated to produce a cone-jet spraying of n-HA/SF suspensions. By using different types of precisely-designed templates (stripe, grid, and ring), the Ti alloy substrates with different micropatterns (stripe, square, and ring) composed of n-HA/SF composite were created. Our results demonstrated that the precisely-designed micropatterns of n-HA/SF composite onto Ti and its alloy substrates could be easily achieved by using template-assisted ESD.     

Preparation and characterization of regenerated fiber from the aqueous solution of Bombyx mori cocoon silk fibroin

The regenerated silk fibers with high strength and high biodegradability were prepared from the aqueous solution of Bombyx mori silk fibroin from cocoons with wet spinning method. Although the tensile strength of the regenerated silk fibroin fiber, 210 MPa is still half of the strength of native silk fiber, the diameter of the fiber is about 100 μm which is suitable for monofilament of suture together with high biodegradability. The high concentration (30%, w/v) of the aqueous solution of the silk fibroin which corresponds to the high concentration in the middle silkgland of silkworm was obtained. This was performed by adjusting the pH of the aqueous solution to 10.4 which corresponds to pK_a value of the OH group of Tyr residues in the silk fibroin. The mixed solvent, methanol/acetic acid (7:3 in volume ratio) was used as coagulant solvent for preparing the regenerated fiber. The structural change of silk fibroin fiber by stretching was monitored with both ¹³C solid state NMR and X-ray diffraction methods, indicating that the high strength of the fiber is related with the long-range orientation of the silk fibroin chain with β-sheet structure.     

Optical and photocatalytic properties of sulfide semiconductor quantum dots (QDs) synthesized by silk fibroin template

Bio-template method is a simple, controllable and environmental friendly strategy to synthesize nanomaterials. It also avails the formation of bioactive and biocompatible nanoparticle–biomolecule hybrid for biotechnical applications. In this paper, silk fibroin was first successfully used as biomolecule template for the biomimic synthesis of CdS and ZnS quantum dots (QDs). The QDs showed promising applications as fluorescence probes and nanocatalysts. The effect of preparation situation to their optical and photocatalytic properties was well researched and CdS QDs with satisfying catalytic activities could be achieved by adjusting the protein matrix. It offers us a low-cost and effective way to synthesize series of sulfide semiconductor nanomaterials using silk fibroin.     

Preparation and cytocompatibility of silk fibroin/chitosan scaffolds

One challenge in soft tissue engineering is to find an applicable scaffold, not only having suitable mechanical properties, porous structures, and biodegradable properties, but also being abundant in active groups and having good biocompatibility. In this study, a three-dimensional silk fibroin/chitosan (SFCS) scaffold was successfully prepared with interconnected porous structure, excellent hydrophilicity, and proper mechanical properties. Compared with polylactic glycolic acid (PLGA) scaffold, the SFCS scaffold further facilitated the growth of HepG2 cells (human hepatoma cell line). Keeping the good cytocompatibility and combining the advantages of both fibroin and chitosan, the SFCS scaffold should be a prominent candidate for soft tissue engineering, for example, liver.     

Preparation and characterization of silk fibroin hydrogel as injectable implants for sustained release of Risperidone

The principal objective of the present study is to achieve a depot formulation of Risperidone by gelation of silk fibroin (SF). For this purpose, hydrochloric acid (HCl)/acetone-based and methanol-based hydrogels were prepared with different drug/polymer ratios (1:3, 1:6, and 1:15). For all the drug-loaded methanol-based hydrogels, gel transition of SF solutions occurred immediately and the gelation time was 1?min, while the gelation time of HCL/acetone-based hydrogels was around 360?min. According to the results obtined from Fourier transform infrared spectroscopy (FT-IR) and X-ray diffraction (XRD) spectra, solvent systems and Risperidone could induce β-sheet structure, but HCL/acetone system had the lowest effect on induction of β-sheets. The crystallinity was increased by increasing the amount of Risperidone, and drug to polymer ratio of 1:3 possessed the highest crystallinity. Thermogravimetric analysis (TGA) indicated that increasing the amount of drug in formulation increased the stability of hydrogels, and methanol-based hydrogel with a ratio of 1:3 had the most stable structure. The release rate of Risperidone from methanol-based hydrogel at ratio of 1:3 was lower than that for HCl/acetone-based one, and it decreased by increasing the amount of Risperidone. The release of Risperidone from methanol hydrogel at ratios 1:3 and 1:6 continued up to 25?d which is acceptable for depot form of Risperidone and shows that the extended release of Risperidone was achieved successfully. In conclusion, SF hydrogel with the ability to respond to the environmental stimuli is an excellent candidate for injectable implants for extended release of Risperidone.     

Preparation and cytocompatibility of silk fibroin / chitosan scaffolds

One challenge in soft tissue engineering is to find an applicable scaffold, not only having suitable mechanical properties, porous structures, and biodegradable properties, but also being abundant in active groups and having good biocompatibility. In this study, a three-dimensional silk fibroin/chitosan (SFCS) scaffold was successfully prepared with interconnected porous structure, excellent hydrophilicity, and proper mechanical properties. Compared with polylactic glycolic acid (PLGA) scaffold, the SFCS scaffold further facilitated the growth of HepG2 cells (human hepatoma cell line). Keeping the good cytocompatibility and combining the advantages of both fibroin and chitosan, the SFCS scaffold should be a prominent candidate for soft tissue engineering, for example, liver.     

Morphology and conductivity of polyaniline sub-micron fibers prepared by electrospinning

Sub-micron fibers of pure polyaniline (PANI) doped with sulfuric acid or hydrochloric acid were prepared by electrospinning PANI with suitable molecular weight dissolved in hot sulfuric acid. A modified electrospinning setup was employed with a coagulation bath as a collector, where dilute sulfuric acid was used as coagulation bath. The factors influencing the morphology and conductivity of the synthesized PANI fibers were investigated, including the concentration of dilute H₂SO₄ solution in the coagulation bath, the doped PANI concentration in H₂SO₄ solution, the type of doping acid and the voltage applied to the solution. The morphologies of doped PANI fibers were characterized by scanning electron microscope (SEM). The structure of the resulting fibers was analyzed by Fourier transform infrared spectroscopy and UV–vis spectrometer. The conductivity of PANI fibers were characterized by I–V characteristics. Homogeneous PANI fibers with a diameter of 370 nm and a high conductivity of 52.9 S/cm were prepared. The possible mechanisms of different morphology formation and conductivity of PANI fibers were also discussed.     

Mechanical properties of nylon-6/SiO2 nanofibers prepared by electrospinning

SiO₂ nanoparticles reinforced nylon-6 nanofibers were prepared by electrospinning of nylon-6/SiO₂ solution in formic acid. The effect of concentration and applied voltage on the diameter of the fibers was investigated. A nanoscale three-point bending test was used to evaluate the mechanical property of a single nylon-6/SiO₂ nanofiber. It was found that the elastic modulus of the nanofibers decreased with the increase in fiber diameter. This elastic modulus was in the range of 3.1-6.9GPa as the diameter ranged from 600 to 100nm.     

化学交联改性丝素蛋白/海藻酸钠纤维的制备与性能

利用聚乙二醇二缩水甘油醚(PEGDE)化学交联丝素蛋白(SF)、以CaCl_2交联海藻酸钠(SA),采用分步交联的方法制备了SF/SA双网络型复合纤维,通过DV-C型数显黏度计、FTIR、XRD、电子单纤维强力仪、核磁共振变温弛豫分析仪、SEM等对纺丝溶液表观黏度和交联改性SF/SA复合纤维的结构性能进行了表征,研究了交联剂PEGDE添加量对纺丝溶液的表观黏度和交联改性SF/SA复合纤维的力学性能、交联度、微观形貌、吸湿性能和保湿性能等的影响。结果表明,随着PEGDE含量的增加,纺丝溶液的表观黏度呈先下降后增加的趋势,加入适量的交联剂可以降低纺丝溶液的表观黏度,增加纤维的可纺性;纤维的断裂强度、断裂伸长率和交联度呈先增加后减少的趋势,PEGDE与SF的质量比为3∶1时,交联改性SF/SA复合纤维的断裂强度和交联度达到最大值,分别为2.34cN/dTex和55.38%;交联改性SF/SA复合纤维的交联度越大,纤维表面沟槽结构越密集,纤维内部结构越紧密均匀,SF与SA的相容性越好;交联改性后,SF/SA复合纤维吸湿性能和保湿性能得到提高,吸湿平衡时间提前。     

同轴静电纺再生丝素/丝胶蛋白纤维的制备及其形态结构表征

模仿蚕丝的组成和结构,利用同轴静电纺丝法制备了以再生丝素蛋白（RSF）为＂芯＂、丝胶蛋白（SS）为＂皮＂的双组分静电纺纤维。通过扫描电镜和透射电镜研究了内层纺丝液流速（Qc）、电压（U）、接收距离（D）以及场强（E）等参数对同轴静电纺RSF/SS纤维形态结构的影响。研究结果表明纤维的平均直径在1400～2100nm左右,皮-芯层结构清晰;Qc对纤维皮-芯层结构的影响较大,过大的内层纺丝液流速会因外层丝胶对内层丝素的包裹不均匀而导致偏芯现象;随E的增加（U增加或D减小）,纤维的直径及其分布显著减小,皮-芯层结构清晰;相同E下,高电压、长距离利于纤维的细化,使直径变细且分布均匀,皮-芯层结构明显。     

甲醇、戊二醛交联剂对丝素蛋白/明胶多孔支架的性能影响

为了对比甲醇、戊二醛两种交联剂对丝素蛋白/明胶复合多孔支架的性能影响,采用冷冻干燥法等比例制备该支架,分两组分别用甲醇和戊二醛进行交联。通过观察支架的微观形貌,测量支架的孔隙率、吸水率、溶胀率,测试热稳定性及力学性能,比较经两种交联剂处理后支架结构和性能的变化。结果表明,经戊二醛交联后的支架孔隙分布更加规则、均匀,孔隙率、吸水率、溶胀率更高,力学性能更强。采用戊二醛交联丝素蛋白/明胶复合多孔支架,能够使支架性能更加优良。     

丝朊上接枝聚丙烯腈和聚丙烯酰胺复合过滤膜的性能

以高浓度ZnCl₂水溶液为溶剂,采用氧化-还原引发体系,在丝朊（SF）上接枝丙烯腈（AN）和丙烯酰胺（AM）得到铸膜液,以水为凝固浴制备SF上接枝聚丙烯腈-聚丙烯酰胺（SF-g-P（AN-co-AM））复合过滤膜。通过SEM、TG和水接触角对SF-g-P（AN-co-AM）复合过滤膜进行表征,研究了其力学性能、分离性能和抗污染性能。结果表明,随着AM添加量的增加,SF-g-P（AN-co-AM）过滤膜的断裂强度逐渐增加,通量逐渐减少。当AM用量为0.5 g时,SF-g-P（AN-co-AM）复合过滤膜的断裂强度达到1.4 MPa,在0.1 MPa压力下,水通量为35 L/（m2h）。该过滤膜具有良好的分离性能,对0.03 g/L刚果红（M_w=696.68）溶液的截留率达到99%。SF-g-P（AN-co-AM）复合过滤膜具有良好的抗污染性能,未经清洗条件下,三次纯水和牛血清白蛋白溶液循环过滤后,通量恢复率还能达到94.4%。      

纳米羟基磷灰石/丝素蛋白/聚己内酯复合超细纤维的制备及表征

通过静电纺丝法制备出纳米羟基磷灰石/丝素蛋白/聚己内酯复合超细纤维,利用扫描电镜、红外光谱仪、X射线衍射仪对纳米羟基磷灰石/丝素蛋白/聚己内酯复合超细纤维形貌和结构进行表征,并进行了拉伸测试。结果表明,随着超细纤维中羟基磷灰石含量的增加,纤维的直径逐渐降低,纤维中聚己内酯的结晶逐渐变差。相比于丝素蛋白/聚己内酯超细纤维,含有质量比为30%羟基磷灰石的复合超细纤维仍具有较好的力学性能。体外小鼠成纤维细胞(L929)培养表明,纳米羟基磷灰石/丝素蛋白/聚己内酯复合超细纤维对细胞没有毒性。     

丝素改性胶原膜的肝素化及其体外抗凝血性能评价

以1-(3-二甲氨基丙基)-3-乙基碳二亚胺(简称EDCI)为缩合剂对丝素改性胶原膜进行了肝素固定化,测定并研究了固定化肝素的稳定性,应用X光电子能谱分析了材料的表面性质。以凝血酶原时间(PT)、部分凝血活酶时间(APTT)、凝血酶时间(TT)等3个体外凝血时间为评价标准,考察了材料的抗凝血性能。结果表明,肝素化后的丝素改性胶原膜具有良好的抗凝血性。     

静电纺丝制备壳聚糖/聚己内酯血管支架及表征

结合壳聚糖(CS)和聚己内酯(PCL)二者的优点, 以静电纺丝的方法制备了CS/PCL血管支架。采用SEM和电子万能试验机检测了该支架的结构和力学性能, 将内皮祖细胞(EPCs)与该支架膜复合培养, 评估了该血管支架维持细胞黏附、 繁殖和分化的能力。SEM结果显示: 通过静电纺丝可以得到多孔、 类似于天然细胞外基质的直径约400nm的纤维微结构; 当CS与PCL质量比为0.5时, 静电纺丝所制备的CS/PCL血管支架弹性最大形变达到31.64%, 应力-应变曲线显示其弹性变形能力较强; EPCs在CS/PCL血管支架黏附率可达95.1%, 荧光显微镜观察结果也显示了CS/PCL血管支架利于细胞黏附、 生长。      

丝素改性胶原膜的低温等离子体改性及体外抗凝血性研究

选用SO2、NH3、CO2三种工作气体，采用低温等离子体技术对丝素改性胶原膜进行了表面改性。运用X光电子能谱分析了材料的表面性质。材料的体外抗凝血性能由体外凝血时间——凝血酶原时间(PT)、部分凝血活酶时间(APTT)、凝血酶时间(TT)作为评价标准。结果表明，SO2、CO2等离子体处理可分别在材料表面引入磺酸和酸酸基团，材料的体外抗凝血性得到很大的改善。NH3等离子体处理可以增加材料表面的氨基的数目，它对材料的抗凝血性没有贡献。