丝纤维的结构、性能及仿生丝纤维的合成研究进展

综述了丝纤维蛋白的组成、结构、形成和机械性能,以及仿生丝纤维蛋白的合成研究及主要应用前景.各种天然的丝纤维蛋白如家蚕丝蛋白和蜘蛛丝蛋白可作为仿生模型,对它们的结构和功能的不断研究可能设计制造出在性能上接近或超过天然丝纤维蛋白的性能优异的新材料.蜘蛛丝具有其它纤维无法比拟的性能特征,如它同时具有强度、可延伸性、生物可降解性和自修补能力,这些特点使得像蜘蛛丝一样的纤维在许多领域具有广阔的应用前景.     

含金属酞菁的再生蚕丝蛋白肽粉末的制备及其抗菌消臭性

将蚕丝蛋白用有机无机混合溶液溶解并透析制成蚕丝蛋白肽水溶液,将此水溶液与用固相法合成的锌金属酞菁的醇溶液进行物理共混制备含金属酞菁的再生蚕丝蛋白肽粉末.对相关化合物进行了紫外光谱、红外光谱表征,显示出再生蚕丝蛋白肽与锌金属酞菁能在大分子层面上进行结合.试验了相关化合物对金黄葡萄球菌、大肠杆菌的抗菌作用以及对氨气的消除作用,结果表明,混合金属酞菁的再生蚕丝蛋白肽具备抗菌作用,并能在约6h内将氨气浓度降解为0.     

光学功能化蚕丝纤维材料

家蚕蚕丝是一种天然的蛋白质纤维,蚕丝及其衍生物(凝胶、蚕丝薄膜和海绵等)具有独特的力学性能、良好的生物相容性和生物降解性,已经被应用在纺织、生物医学等领域。最近,利用蚕丝独特的性质制备光学功能化蚕丝吸引了研究者的兴趣。基于对蚕丝的丝胶和丝素结构组成的总结,介绍了目前蚕丝结构的相关研究进展,综述了近年来对光学功能化蚕丝的研究,具体包括光学功能化蚕丝的重要种类、制备和应用。重点介绍了荧光性功能蚕丝基因工程、喂食法和复合等制备方法,该种材料用于生物支架成像、药物缓释载体和光学器件等领域。总结了利用生物仿生技术制备具有光子晶体结构色的蚕丝材料,这为化妆品,变色服饰和生物光控器件开辟了新方向;此外,蚕丝材料还可以应用于非线性光学领域,如光限幅和激光防护。     

蚕丝在生物医用材料领域的应用研究

蚕丝既是优质的天然蛋白纤维,也是优质的高分子蛋白质材料,具有良好的力学性能、生物相容性和可控的生物降解性等。随着生物医用材料领域的不断发展和各学科的交叉融合,蚕丝作为生物医用材料已展示出很强的竞争力,其在该领域的应用潜力已逐渐展现。介绍了蚕丝的构成和特点,总结了蚕丝丝素及丝胶提取的方法,综述了近年来蚕丝及蚕丝蛋白在组织工程、载药、敷料等方面的应用,并客观分析了蚕丝及蚕丝蛋白在这些具体应用过程中所发挥的重要作用及各种蚕丝材料的优缺点,最后就蚕丝在生物医用材料领域的应用前景进行了展望。     

蚕丝在功能化离子液体中的溶解与再生

功能化离子液体氯化1-(2-羟乙基)-3-甲基咪唑是蚕丝的优良溶剂,在70℃时对脱胶蚕丝的溶解能力达到5.2%左右。向离子体液蚕丝溶液中加入甲醇可获得再生蚕丝。用数码相片、傅里叶变换红外光谱、扫描电镜和热重分析对再生蚕丝进行了表征。数码相片显示,经研磨后的再生蚕丝外观与脱胶蚕丝一样;扫描电镜表明再生蚕丝和脱胶蚕丝的微观结构基本一致,主要为5μm～10μm蚕丝纤维缠绕组成;再生蚕丝和脱胶蚕丝的傅里叶变换红外光谱谱图相同。实验表明,功能化离子液体是蚕丝的直接溶剂;热重分析数据表明再生蚕丝的分解温度略低于天然脱胶蚕丝,分解残留略高于天然脱胶蚕丝。对溶解机理进行了初步探讨。     

丝质包装纸的特性研究

研究了蚕丝纤维的最佳脱胶工艺、打浆方法以及丝质包装纸的各项物理性能.结果表明,蚕丝纤维的最佳脱胶工艺为:温度100℃、时间90(30 60)min、化学药品为Na2CO3,药品质量分数为0.5%,脱胶后蚕丝经打浆处理具有明显分丝帚化的性质;不同打浆度的丝质包装纸的耐破指数呈上升趋势;抗张指数、撕裂指数和耐折度呈现先增加后下降的趋势;丝质包装纸具有极优良的柔软性和透气性.     

新材料产业的人才困境与对策

新材料产业是战略性基础性产业,是高技术的必争领域,也是高度知识密集型产业,新材料技术的创新突破和新材料产业的发展离不开人才的支撑.与快速发展的新材料产业对新材料需求相比,我国新材料人才供给还存在总量、结构、区域3大不均衡现象,削弱了新材料产业创新发展动力.鉴于此,本文剖析了造成新材料产业人才发展不均衡的原因,并从加强顶...     

蚕丝基柔性导电复合材料在传感器中的应用进展

蚕丝作为传统的纺织纤维，较大的纤维长径比使其具有优异的力学性能，其强度优于钢铁，弹性优于尼龙，同时兼具轻盈透气等优点。将蚕丝织物作为柔性导电材料基材对可穿戴电子产品在医疗检测、运动康复、食品检测等方面的应用具有重要意义。介绍了蚕丝的结构及柔性传感器的传感机理，综述了国内外以蚕丝织物作为基底的柔性导电复合材料在传感器件中的应用进展，并对蚕丝基柔性导电复合材料的发展前景进行了展望。     

淄博:新材料产业高地——访淄博市科技局局长王纯国

2010年,中国材料研究学会授予淄博市全国首个"新材料名都"称号,成功实现了2002年提出打造"新材料名都"的设想.淄博市作为首个荣获"新材料产业名都"称号的城市,是国家级新材料成果转化及产业化基地,在国家科技部举行的首次综合评价中,淄博市在全国43个新材料基地中排名第6位,目前已成为在国内具有较大影响力的综合型新材料产业化基地之一. 十年来,淄博市倾力打造新材料产业,组建的省级以上工程技术研究中心和企业技术中心、院士工作站等科技创新服务平台为淄博市经济快速发展发挥了巨大的支撑作用,现已形成了以新材料产业为核心、上下游齐全、其他产业快速发展的格局.近日,围绕如何建设"新材料名都"地域品牌形象,本刊记者对淄博市科技局局长王纯国进行了专访.     

饲喂法制备碳纳米材料改性蚕丝的导热性能

将纳米石墨烯、单壁碳纳米管和纳米石墨粒子这三种碳纳米材料均匀涂覆在桑叶上饲喂四龄蚕,采用简易且绿色经济的饲喂法制备改性蚕丝。利用瞬态电热技术(TET)对蚕丝的导热性能进行研究结果表明:饲喂添加碳纳米材料的桑叶所得到的改性蚕丝的导热性能均有所降低,并且碳纳米材料的添加量越大,改性蚕丝的导热性能越低。导致改性蚕丝导热性能下降的主要原因有蚕丝蛋白质结构受损、结晶度减小、纤维内部结构存在较大的接触电阻。     

Engineering the Future of Silk Materials through Advanced Manufacturing

Silk is a natural fiber renowned for its outstanding mechanical properties that have enabled the manufacturing of ultralight and ultrastrong textiles. Recent advances in silk processing and manufacturing have underpinned a re‐interpretation of silk from textiles to technological materials. Here, it is argued that silk materials—optimized by selective pressure to work in the environment at the biotic–abiotic interface—can be harnessed by human micro‐ and nanomanufacturing technology to impart new functionalities and opportunities. A critical overview of recent progress in silk technology is presented with emphasis on high‐tech applications enabled by recent innovations in multilevel modifications, multiscale manufacturing, and multimodal characterization of silk materials. These advances have enabled successful demonstrations of silk materials across several disciplines, including tissue engineering, drug delivery, implantable medical devices, and biodissolvable/degradable devices.     

Scalable Spider‐Silk‐Like Supertough Fibers using a Pseudoprotein Polymer

Spider silks are tougher than almost all other materials in the world and thus are considered ideal materials by scientists and the industry. Although there have been tremendous attempts to prepare fibers from genetically engineered spider‐silk proteins, it is still a very large challenge to artificially produce materials with a very high fracture energy, not to mention the high scaling‐up requirements because of the extremely low productivity and high cost levels. Here, a facile spider‐silk‐mimicking strategy is first reported for preparing scalable supertough fibers using the chemical synthesis route. Supertoughness (≈387 MJ m^?3), more than twice the reported value of common spider dragline silk and comparable to the value of the toughest spider silk, the aciniform silk of Argiope trifasciata, is achieved by introducing β‐sheet crystals and α‐helical peptides simultaneously in a pseudoprotein polymer. The process opens up a very promising avenue for obtaining excellent spider fibers.     

在大肠杆菌中表达蜘蛛拖丝融合蛋白

蜘蛛丝凭借其优良的理化性质倍受人们青睐,但是蜘蛛本身难以高密度养殖给应用造成巨大的障碍。由此利用基因工程的手段来开发利用蜘蛛拖丝蛋白目前成为各国研究的热点。以往的研究表明,不同的编码蛛丝蛋白的cDNA片段在表达中的稳定性各不相同。在应用中存在适宜片段的筛选问题。本文从该角度出发,首次建立了Araneus diadematu克隆的拖丝蛋白基因ADF3与GSF融合产物的稳定原核表达系统。为今后进一步开发利用蜘蛛拖丝蛋白的研究奠定了基础。     

甲醇、乙醇凝固剂对再生丝素纤维性能的影响

本文以六氟异丙醇(HFIP)溶解无定形丝素膜,湿法纺丝获得再生丝素纤维,并通过X射线衍射法、红外光谱法、热重分析法比较了分别以甲醇、乙醇为凝固剂纺丝对再生丝素纤维的结构及力学性能的影响.结果表明甲醇、乙醇凝固剂对再生丝素纤维结构性能影响不大.     

Physical characterization of functionalized spider silk: electronic and sensing properties

Abstract

This work explores functional, fundamental and applied aspects of naturally harvested spider silk fibers. Natural silk is a protein polymer where different amino acids control the physical properties of fibroin bundles, producing, for example, combinations of β-sheet (crystalline) and amorphous (helical) structural regions. This complexity presents opportunities for functional modification to obtain new types of material properties. Electrical conductivity is the starting point of this investigation, where the insulating nature of neat silk under ambient conditions is described first. Modification of the conductivity by humidity, exposure to polar solvents, iodine doping, pyrolization and deposition of a thin metallic film are explored next. The conductivity increases exponentially with relative humidity and/or solvent, whereas only an incremental increase occurs after iodine doping. In contrast, iodine doping, optimal at 70 °C, has a strong effect on the morphology of silk bundles (increasing their size), on the process of pyrolization (suppressing mass loss rates) and on the resulting carbonized fiber structure (that becomes more robust against bending and strain). The effects of iodine doping and other functional parameters (vacuum and thin film coating) motivated an investigation with magic angle spinning nuclear magnetic resonance (MAS-NMR) to monitor doping-induced changes in the amino acid-protein backbone signature. MAS-NMR revealed a moderate effect of iodine on the helical and β-sheet structures, and a lesser effect of gold sputtering. The effects of iodine doping were further probed by Fourier transform infrared (FTIR) spectroscopy, revealing a partial transformation of β-sheet-to-amorphous constituency. A model is proposed, based on the findings from the MAS-NMR and FTIR, which involves iodine-induced changes in the silk fibroin bundle environment that can account for the altered physical properties. Finally, proof-of-concept applications of functionalized spider silk are presented for thermoelectric (Seebeck) effects and incandescence in iodine-doped pyrolized silk fibers, and metallic conductivity and flexibility of micron-sized gold-sputtered silk fibers. In the latter case, we demonstrate the application of gold-sputtered neat spider silk to make four-terminal, flexible, ohmic contacts to organic superconductor samples.     

三种不同功能蛛丝的超微结构与拉伸力学行为

蜘蛛丝是一种具有优良机械性能的天然动物蛋白纤维,是自然界极具应用潜力的生物材料,但它特有的结构和机械性能与其生物学功能密切相关。为此,本文采用扫描电镜和单纤强力仪对两种结圆网蜘蛛的卵袋框丝和内层丝与圆网铆钉丝三种不同功能蛛丝的超微结构、拉伸力学性能以及断裂能在应力应变曲线的弹性区、屈服区和加强区的分配进行了研究,结果表明不同生物学功能的蛛丝表现出不同的力学行为,并呈现一定的机械性能策略,主要表现为：断裂能在应力应变曲线的弹性区、屈服区和加强区的权衡;不同力学性能参数之间的权衡,如伸长和荷载、断裂强度和延展性等参数之间的权衡,以适应不同的功能要求。这对人们进行新型防护材料的仿生设计具有重要指导意义。     

Structuring of Functional Spider Silk Wires,Coatings, and Sheets by Self‐Assembly on Superhydrophobic Pillar Surfaces

Spider silk has recently become a material of high interest for a large number of biomedical applications. Previous work on structuring of silk has resulted in particles (0D), fibers (1D), films (2D), and foams, gels, capsules, or microspheres (3D). However, the manufacturing process of these structures is complex and involves posttreatment of chemicals unsuitable for biological applications. In this work, the self‐assembly of recombinant spider silk on micropatterned superhydrophobic surfaces is studied. For the first time, structuring of recombinant spider silk is achieved using superhydrophobic surfaces under conditions that retain the bioactivity of the functionalized silk. By tuning the superhydrophobic surface geometry and the silk solution handling parameters, this approach allows controlled generation of silk coatings, nanowires, and sheets. The underlying mechanisms and governing parameters are discussed. It is believed that the results of this work pave the way for fabrication of silk formations for applications including vehicles for drug delivery, optical sensing, antimicrobial coatings, and cell culture scaffolds.     

傅里叶红外光谱研究重组蛛丝蛋白分子构象的影响因素

利用FT-IR研究重组蛛丝蛋白pNSR16在各种影响因素中构象的变化,结果表明,溶剂对pNSR16构象的影响取决于溶剂的种类,甲酸使其构象进一步向无规卷曲方向转变,而饱和溴化锂溶液则使其构象向β-折叠方向转变;加热和变性能促使pNSR16构象向β-折叠方向转变;PVA、CS的加入使pNSR16构象从无规卷曲向β-折叠转化。这些结论可从分子水平上指导重组蛛丝蛋白组织工程复合材料的制备。     

Physical characterization of functionalized spider silk: electronic and sensing properties

This work explores functional, fundamental and applied aspects of naturally harvested spider silk fibers. Natural silk is a protein polymer where different amino acids control the physical properties of fibroin bundles, producing, for example, combinations of β-sheet (crystalline) and amorphous (helical) structural regions. This complexity presents opportunities for functional modification to obtain new types of material properties. Electrical conductivity is the starting point of this investigation, where the insulating nature of neat silk under ambient conditions is described first. Modification of the conductivity by humidity, exposure to polar solvents, iodine doping, pyrolization and deposition of a thin metallic film are explored next. The conductivity increases exponentially with relative humidity and/or solvent, whereas only an incremental increase occurs after iodine doping. In contrast, iodine doping, optimal at 70 °C, has a strong effect on the morphology of silk bundles (increasing their size), on the process of pyrolization (suppressing mass loss rates) and on the resulting carbonized fiber structure (that becomes more robust against bending and strain). The effects of iodine doping and other functional parameters (vacuum and thin film coating) motivated an investigation with magic angle spinning nuclear magnetic resonance (MAS-NMR) to monitor doping-induced changes in the amino acid-protein backbone signature. MAS-NMR revealed a moderate effect of iodine on the helical and β-sheet structures, and a lesser effect of gold sputtering. The effects of iodine doping were further probed by Fourier transform infrared (FTIR) spectroscopy, revealing a partial transformation of β-sheet-to-amorphous constituency. A model is proposed, based on the findings from the MAS-NMR and FTIR, which involves iodine-induced changes in the silk fibroin bundle environment that can account for the altered physical properties. Finally, proof-of-concept applications of functionalized spider silk are presented for thermoelectric (Seebeck) effects and incandescence in iodine-doped pyrolized silk fibers, and metallic conductivity and flexibility of micron-sized gold-sputtered silk fibers. In the latter case, we demonstrate the application of gold-sputtered neat spider silk to make four-terminal, flexible, ohmic contacts to organic superconductor samples.