Influence of the draw ratio on the tensile and fracture behavior of NMMO regenerated silk fibers

The tensile properties and fracture surfaces of N‐methylmorpholine‐N‐oxide (NMMO) regenerated silk fibroin fibers produced with a range of draw ratios has been characterized and related to their microstructure with data obtained from Raman spectroscopy and birefringence measurements. The spinning process allows control of two different draw ratios, coagulation, and postspinning, and it has been found that the microstructure and the properties of the fibers can be modified by the proper combination of both draw ratios. NMMO regenerated silk fibroin fibers subjected to postspinning drawing yield tensile properties comparable to other regenerated fibers and strain at breaking comparable to natural Bombyx mori silk fibers. Tensile strength; however, is still significantly lower than that of natural fibers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2568–2579, 2007     

Correlation between processing conditions,microstructure and mechanical behavior in regenerated silkworm silk fibers

Regenerated silkworm fibers spun through a wet‐spinning process followed by an immersion postspinning drawing step show a work to fracture comparable with that of natural silkworm silk fibers in a wide range of spinning conditions. The mechanical behavior and microstructure of these high performance fibers have been characterized, and compared with those fibers produced through conventional spinning conditions. The comparison reveals that both sets of fibers share a common semicrystalline microstructure, but significant differences are apparent in the amorphous region. Besides, high performance fibers show a ground state and the possibility of tuning their tensile behavior. These properties are characteristic of spider silk and not of natural silkworm silk, despite both regenerated and natural silkworm silk share a common composition different from that of spider silk. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

丝素蛋白纤维及功能化材料的设计与构筑

随着环境污染、资源枯竭和医疗健康等问题的加剧,研发同时满足特定使用性能、安全性及可再生性的新型材料成为当前的发展趋势.而丝素蛋白材料正是以天然蚕丝为基本原材料,经一定的加工和功能化而形成的具有特殊结构、独特性能和广泛应用的生物质材料,近年来在生物医药、生物电子、智能传感等领域展现出巨大的应用潜力.本专论总结了丝素蛋白纤维及功能化材料的最新成果,结合本课题组相关工作,重点阐述了再生丝素蛋白纤维的仿生制备、生物医用支架的构筑与功能化、智能电子材料的设计以及天然多功能蚕丝及其构筑基元制备的研究进展,以期为高性能丝素蛋白材料的设计与构筑提供指导和借鉴.     

Structural changes of silk fibroin membranes induced by immersion in methanol aqueous solutions

Structural changes of native and regenerated silk fibroin membranes were induced by immersion in water-methanol solutions and examined as a function of immersion time and methanol concentration. X-ray diffractometry and infrared spectroscopy data showed that transition from random coil to β-sheet structure occurred favorably when both native and regenerated silk fibroin membranes were immersed in water-methanol solutions, regardless of the different immersion time. Only native silk membrane, treated for 2 min with pure methanol, maintained its original amorphous structure, as demonstrated by differential scanning calorimetric (DSC) curves. The degree of displacement, measured by thermomechanical analysis (TMA), was much greater for regenerated than for native silk fibroin membranes. SDS-PAGE pattern showed that native silk fibroin has a molecular weight of 350, while the regenerated sample is formed by a large number of polypeptides in the range of 200-50 KD. The amount of acidic and basic amino acids decreased slightly in regenerated silk fibroin. Physical properties of silk membranes treated with water-methanol solutions are discussed in terms of membrane structure, treatment conditions, and chemical structure of starting material. © 1994 John Wiley & Sons, Inc.     

蚕丝基智能纤维及织物：潜力、现状与未来展望

纤维及织物因具有良好的柔性、透气性以及适宜的力学性能而成为人们日常生活必不可少的材料。随着柔性电子器件的快速发展,纤维及织物在其自身优势的基础上,开始被人们赋予智能化特征,使得智能纤维和织物逐渐在可穿戴领域占据一席之地。天然蚕丝具有产量大、机械性能优异和生物可降解的优势。近年来,面向智能应用的蚕丝基纤维与织物逐渐发展,被用于传感、致动、光学器件、能量收集和储能等领域。本文将首先介绍天然蚕丝的层级结构和性能,并介绍各种形貌结构的再生蚕丝材料;然后根据其在智能纤维及织物中应用领域的不同,详细阐述蚕丝基智能纤维及织物的制备方法、性能及工作机制;最后讨论进一步发展所面临的挑战与机会,并对未来前景进行展望。     

再生蚕丝的制备及其结构和性能初探

在制备高浓度高分子量蚕丝素蛋白水溶液的基础上, 采用湿法纺丝技术, 在一定条件下纺制出力学性能优于天然蚕(茧)丝的再生蚕丝纤维, 其断裂强度及断裂伸长率分别达到0.5 GPa和20%. 扫描电镜观察结果显示: 初生纤维具有典型的“皮芯”结构, 而纤维内部则为疏松多孔的网状或蜂窝状结构; 经过一定的后拉伸处理后, 纤维的表面变得光滑, 且内部结构也趋于致密. 固体 13C核磁共振及拉曼光谱分析结果表明, 后拉伸及热湿处理均有利于提高纤维内部β-折叠结构的含量, 分子链的规整度和取向性也随之改善, 从而使再生蚕丝纤维的力学性能得到进一步提高.     

Porous 3‐D scaffolds from regenerated Antheraea pernyi silk fibroin

In this study, porous three‐dimensional (3‐D) materials were prepared with the regenerated Antheraea pernyi (A. pernyi) silk fibroin by freeze‐drying from a lithium thiocyanate solution of its fibers. The relationship between preparation conditions and morphological structures of 3‐D materials was also studied. We concluded that with the decrease in A. pernyi silk fibroin solution concentration and the increase in the freezing temperature, the porosity and the average pore diameter of the 3‐D materials were increased while the pore density was decreased. By adjusting the freezing temperature and the silk fibroin solution concentration, the 3‐D materials having the average pore diameter of 75–260 µm and the porosity of 70–90% can efficiently be produced. As a kind of new material with excellent biocompatibility and bioactivity, the material is expected to be applied to tissue regeneration scaffolds. Copyright © 2007 John Wiley & Sons, Ltd.     

POSITRON LIFETIME STUDY OF THERMALLY INDUCED MICROSTRUCTURAL CHANGES IN NISTARI SILK FIBER

Positron lifetime measurements have been made in natural polymer-Nistari silk fibers as a function of isochronalannealing temperature in the range of 27℃ to 280℃. The variations in the positron results indicate the structural changesoccurring in the Nistari silk fibers and determine the glass transition temperature as 170℃. Activation energies weremeasured separately for the crystalline and amorphous regions indicating the versatility of the technique. These values areclose to the N--H bond dissociation energy, suggesting N--H bond dissociation as the most probable process occurringduring thermal treatment As an extension of the positron results, the molecular weight of the Nistari silk fibers wasdetermined to be 10.7×10~5 based on free volume, which lies within the range suggested for the silk fibers. There seems to bean indication that cross-linking changes the spiral structure of cotton fibers to network type. However, this needs to be validated by other techniques.     

从天然动物丝到丝蛋白基材料的研究

作为具有优异综合力学性能的天然蛋白质纤维,丰产的动物丝特别是蚕丝长期伴随着人们的日常生活,近十余年来,各种具有特色的功能性丝蛋白基材料更是层出不穷.但在探索动物丝和丝蛋白基材料的过程中,动物丝纤维是经由蚕或蜘蛛等动物的纺器而纺制得到的简单事实往往被忽视;换言之,动物丝实际上是动物对丝蛋白进行体内“加工”后的产物,也是丝蛋白基材料中的一种.因此,天然动物丝中独特的各等级间构效关系与丝蛋白基材料的构效关系之间并不存在着必然的传承效应.本文着重介绍了我们在对动物丝和丝蛋白基材料探索中的经验和体会,即在强调以丝蛋白分子链结构与性能及其之间的关系为研究重点的基础上,从比较和发掘各种天然动物丝的特性入手,进而了解丝蛋白分子链在本体和溶液中的行为,并通过对动物丝蛋白分子链聚集态结构的调控,以达到设计制备一系列多形貌和多功能的动物丝蛋白基材料的目的.     

Wet-spinning of Regenerated Silk Fiber fromAqueous Silk Fibroin Solutions: Influence ofCalcium Ion Addition in Spinning Dope on thePerformance of Regenerated Silk Fiber简

Ca（II） ions are added in the spinning dope to adjust the solidification rate of regenerated silk fibroin （RSF） solution during the wet-spinning process since Ca（II） ions are proved to be favorable to maintain the stable silk fibroin network in our previous work. The results show that when Ca（II）/RSF ratios are 1/50 and 1/20, the resulted RSF fibers exhibit good performance with the breaking energy more than 70 kJ/kg. However, higher Ca（II）/RSF ratio （for example, 1/10） hinders the solidification of spinning dope and results in poor RSF fibers. These observations together with earlier papers from this laboratory confirm that to produce tough silk fibers the spinning conditions must allow sufficient time for the adjustment of silk fibroin molecular chains.     

蚕腺体内和再生丝素蛋白水溶液的性能研究

用偏光显微镜观察了蚕腺体内和再生丝素蛋白水溶液的流动状态和各向异性现象,用乌氏粘度计测试了其流出时间,并用HAKKE流变仪测试了其粘度。结果发现蚕腺体内和再生丝素蛋白水溶液的性质差别非常大,认为丝素蛋白水溶液在蚕腺体内存在一个逐步熟成的过程。随着丝素蛋白水溶液在腺体内的前移,丝素蛋白分子逐渐沿移动方向取向而呈有序态,最终成为粘度非常大的各向异性的凝胶体,而再生丝素蛋白水溶液是粘度非常低的各向同性溶液。这些差异表明,丝素蛋白水溶液在蚕腺体内的熟成过程是蚕能够吐出优良蚕丝的关键步骤,要想制备出高性能的纤维,在“仿生纺丝”之前,首先要“仿生制备纺丝液”。     

Water-annealing regulated protein-based magnetic nanofiber materials: tuning silk structure and properties to enhance cell response under magnetic fields

In this study, flexible silk fibroin protein and biocompatible barium hexaferrite (BaM) nanoparticles were combined and electrospun into nanofibers, and their physical properties could be tuned through the mixing ratios and a water annealing process. Structural analysis indicates that the protein structure of the materials is fully controllable by the annealing process. The mechanical properties of the electrospun composites can be significantly improved by annealing, while the magnetic properties of barium hexaferrite are maintained in the composite. Notably, in the absence of a magnetic field, cell growth increased slightly with increasing BaM content. Application of an external magnetic field during in vitro cell biocompatibility study of the materials demonstrated significantly larger cell growth. We propose a mechanism to explain the effects of water annealing and magnetic field on cell growth. This study indicates that these composite electrospun fibers may be widely used in the biomedical field for controllable cell response through applying different external magnetic fields.     

甲基丙烯酸双酯改性真丝的热性质

众所周知 ,真丝绸因具有柔和的光泽、细腻的手感、良好的舒适性和保健性而素有“纤维皇后”的美称 .但其极易起毛起皱 ,尤其是湿态下更为严重 ,这大大影响了它的实用价值 .70年代以来 ,人们就开始用化学整理的方法提高和改善真丝绸的各种性能 ,但所用整理剂含有游离甲醛 ,或经其整理后织物会释放对人体有害的甲醛 .随着人们生活水平的提高 ,人们对“绿色纺织品”的需求越来越迫切 ,要求整理向低甲醛、无甲醛方向发展 .近年来 ,人们对用单烯类和环氧化合物对真丝进行改性的研究作了大量的工作[1～ 4] ,这些改性在某种程度上能够改善真丝的性…     

Carbonized silk fibers for in‐tube solid‐phase microextraction to detect polycyclic aromatic hydrocarbons in water samples

Silk fibers were carbonized to develop a biomass carbon material as an adsorbent for solid‐phase microextraction. The surface structure of the carbonized silk fibers was characterized by scanning electron microscopy, and the graphitization degree was determined by Raman spectrometry. After carbonization under high temperature, the orderliness and structural regularity of carbon atoms on silk fibers were promoted. Extraction tube packed with carbonized silk fibers was prepared for in‐tube solid‐phase microextraction. Coupled with high performance liquid chromatography, it exhibited good extraction performance for hydrophobic polycyclic aromatic hydrocarbons. Main parameters including sampling volume, sampling rate, methanol content in sample, and desorption time were systematically investigated. Under the optimum conditions, the analysis method was established and it exhibited wide linear range (0.016–20 μg/L) with good linearity (correlation coefficient ≥ 0.9947), low limits of detection (0.005–0.050 μg/L), and high enrichment factors (1189–2775). Relative standard deviations (n = 3) for intraday (≤3.3%) and interday (≤9.6%) tests indicated that the extraction material had satisfactory repeatability. Finally, the analytical method was successfully applied to detect trace polycyclic aromatic hydrocarbons in real water samples, demonstrating its satisfactory practicability.     

Polylactic acid/silk fibroin composite hollow fibers as excellent controlled drug release systems

Polylactic acid (PLA) and silk fibroin (SF) have been widely used in biomedical applications because of their excellent biocompatibility and degradability. In this study, PLA and SF were used as raw materials to prepare hollow fibers with a skin-core structure by wet spinning technology. Scanning electron microscopy observations revealed that the structure of hollow fibers became increasingly uniform with increasing silk fibroin mass fraction. Tensile test results showed that with the increase of silk fibroin content, the elastic modulus of hollow fibers decreased and their tensile properties improved. The results of hollow fibers degradation experiments revealed that increasing the content of silk fibroin can effectively shorten the degradation time of hollow fibers. Ultraviolet spectrophotometry was used to measure the absorbance of tetracycline hydrochloride in phosphate buffer saline and calculate its release rate in hollow fibers with different silk fibroin contents, the result is HFs-9 > HFs-7 > HFs-0 > HFs-5 > HFs-3. The PLA/SF controlled drug release system has precise controlled release of the drug, realizes the separation of the drug from the controlled release system, and solves the problem of sudden drug release. In addition, the controlled release system is non-toxic, degradable, and has excellent mechanical properties.     

Comparative thermal analysis of Eri,Mori, Muga,and Tussar silk cocoons and fibroin fibers

Wild silks are often extremely durable and have many advantages over the domesticated silk. In this study, three kinds of wild silks—Indian Antheraea mylitta (Tussar), Antheraea assama (Muga), and Philosamia ricini (Eri) silkworm cocoons were successfully degummed and their thermal properties were studied comparatively with domesticated Chinese mulberry (Bombyx mori) silkworm cocoons and fibers. Advanced thermal analysis methods, such as differential scanning calorimetry (DSC) and temperature-modulated DSC were utilized to identify glass transition temperatures (T _g), heat capacity increments at T _g, and degradation temperatures of these silk materials. In addition, the bound water contents and the thermal degradation mechanisms of different silk systems were also quantified using thermogravimetric analysis. Compared with the mulberry silk materials, wild silk materials showed higher thermal stabilities, and variable degradation profiles. These comparative methods would offer a new pathway to understand the physical properties of silk-based biomaterials, such as their tunable thermal, mechanical, optical, and electrical properties. And it could provide useful insights for the development of new silk-based medical devices and sutures with controllable biological functions in the future.     

Implantation of multiscale silk fibers on poly (lactic acid) fibrous membrane for biomedical applications

Despite that poly (lactic acid) (PLA) has satisfactory biodegradation in vivo, its application in biomedicine is restricted due to its unsatisfactory cytocompatibility. Silk fiber (SF) has outstanding biocompatibility and silk fibroin protein obtained from silk by degumming has good hydrophilicity. Therefore, combining the PLA and silk can improve hydrophilicity of PLA to apply as biomedical materials. In this study, different concentrations of sodium hypochlorite (NaClO) were used to separate the silk to obtain multiscale silk fibers (MSFs), which were implanted into the PLA electrospun fibrous membranes (EFMs). The morphology and structure of silk fibers separated by different concentrations of NaClO were studied by Zetasizer Nano ZS, UV spectroscopy, Fourier transform infrared spectroscopy, X-ray diffraction, and scanning electron microscopy. Moreover, the biocompatibility of the surface-modified PLA composite membranes by MSFs was investigated by cell cultivation and proliferation. The results showed that the surface-modified PLA EFMs through MSF bundles obtained from NaClO split silk exhibited a certain improvement on PLA hydrophilicity and enhancement on cellular compatibility, which could have a broad prospect in the practical application of biomedical materials.     

具有定向形貌的丝蛋白支架的制备

利用冰晶为模板并结合冷冻干燥技术, 成功地获得了具有一定力学强度的定向多孔丝蛋白支架. 采用扫描电镜、流变、拉曼光谱和压缩测试等方法, 考察了丝蛋白原液在不同pH值和初始浓度的情况下对定向支架的成因、内部形貌及力学性能的影响. 结果表明, 当溶液的pH值为4.4, 浓度由低到高时, 所制备的丝蛋白支架内部将分别出现纤维状结构、轴向片层状和梭状多孔结构. 特别是由初始浓度为15% (及以上)的丝蛋白溶液定向冷冻得到的支架, 在压缩试验中表现出较好的力学性能, 其轴向压缩模量和屈服应力分别达122.6和6.9 MPa, 满足了进一步应用的基本需求.     

The effect of water on the conformation transition of Bombyx mori silk fibroin

Near-infrared spectroscopy (NIR) and differential scanning calorimetry (DSC) were used to investigate temperature-induced changes in the secondary structure and hydration of reconstituted Bombyx mori silk fibroin, with and without freezing water, by looking at regenerated silk fibroin films with a range of water content. We suggest that freezing water facilitates the movement of peptide chains and thus contributes to the conformational transition at 60 °C. The structural changes during heat treatment were analyzed by the two-dimensional correlation method. It was found that the band at 4600 cm⁻¹ consists of complex overlapping components due to different secondary structure elements which compose the protein architecture. Thus, this band could be used as a sensitive probe to estimate the conformations of silk fibroin. By monitoring the variations of the spectral components dynamically, an NIR procedure for tracking the conformational transition of silk fibroin was established.     

Thermal characterization of social vespid silk

In this paper we try to establish a link between the microclimate in the wasp nest and the structure and thermal stability of vespid silk. We suggest that there are at least two types of water that is absorbed by the silk of Oriental hornets, namely, surface water and intrinsic structural water. The release of both types of water was found to be reversible. The enthalpy values of the endothermic peaks associated with the release of water from different silk samples do not differ substantially and are in the range of 106 to 130 J g^-1 for the Vespa orientalis male larvae silk (sample #1), Paravespula germanica (yellowjacket) worker larvae silk (#3) and Vespa orientalis nest envelope(#4). For the Vespa orientalis worker larvae silk (sample #2), however, it is twice as large (228 J g^-1). This is in agreement with the increased total amount of absorbed water. The silk studied has a fibrilar structure with interconnecting surfaces overlying entire regions. It is assumed that the initial water loss stems from water evaporation from the coat of the fibers - a daily occurrence in the hornets' nest. Heating to above 70°C may result in structural changes in the silk core. This revised version was published online in July 2006 with corrections to the Cover Date.