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.     

桑蚕丝素蛋白初始结构对其矿化作用的影响

以碱金属离子诱导桑蚕丝素蛋白溶液发生构象转变, 研究了蛋白质初始结构对其矿化作用的影响. FT-IR, XRD和SEM等测试结果显示, 未经任何处理的桑蚕丝素蛋白溶液矿化后形成片状复合物, 其无机相以二水磷酸氢钙(DCPD)为主; 而经过K^＋和Na^＋金属离子处理后, 桑蚕丝素溶液的结构由无规线团/螺旋构象向β-折叠发生转变, 矿化后成纤维状, 并相互结合呈现纳米级的三维多孔结构, 其无机相以热力学稳定的羟基磷灰石(HA)为主. 可以认为, 丝素蛋白结构转化为较伸展的β-折叠后, 使得更多的亲水基团暴露在外面, 在丝素蛋白分子不断凝聚成纤过程中, HA结晶快速生长并附着在这些微纤上, 最终形成纤维状的丝素蛋白/HA复合物. 该结果为阐明蛋白质的生物矿化过程及其调控机理提供了理论依据, 同时可以从矿化复合物的形成来反映这些微量元素可能对骨组织形成的影响, 为临床骨组织的修复提供一定的参考.     

Immobilization of glucose oxidase with the blend of regenerated silk fibroin and poly(vinyl alcohol) and its application to a 1,1′- dimethylferrocene-mediating glucose sensor

The structure and properties of the blend of regenerated silk fibroin (RSF) and poly(vinyl alcohol) (PVA) were investigated. The two polymers in the blend are in the state of phase segregation. Infrared (IR) spectra indicate that the RSF in the blend maintains its intrinsic properties, thus, ethanol treatment can transfer silk I structure of RSF to silk II structure. The water absorption property and mechanical property of the blend are improved in comparison with those of RSF. The blend maintains the major merit of RSF, that is, it can immobilize glucose oxidase on the basis of the conformational transition from silk I structure to silk II structure. The properties of the immobilized enzyme are examined. Moreover, the second generation of glucose sensor based on the immobilized enzyme is fabricated and it has a variety of advantages including easy maintenance of enzyme, simplicity of construction, fast response time and high stability.     

Conformational Transformation Exhibited by the Peptide Extracted from Crystalline Region of Bombyx mori Silk Fibroin in Solid and Solution States

The conformational transformation of a 30-residue peptide H（Ala-Gly-Ser-Gly-AIa-Gly）5OH, i.e., （AGSGAG）5, extracted from highly crystalline region of Bombyx mori （B. mori） silk fibroin was described by using the high resolution solid state 13^C NMR, and CD spectroscopies. Based on the conformation-dependent 13^C NMR chemical shifts of the Ala, Gly and Ser residues and the line-shape analysis of the conformation sensitive Ala Cβ resonance, the peptide revealed a strong preference for silk Ⅱ structural form, i,e,, an antiparallel fl-sheet structure （φ= - 140±20°and ψ= 135±20°） in solid state. On the contrary, the CD spectra of this peptide in the two non-native hexafluorinated fibre spinning solvents, hexafluoroisopropanol （HFIP） and hexafluoroacetone （HFA）, exhibited the existence of an unusual tightly-folded conformation resembling 310-helix （φ=- 60±20° and ψ=-30±20°）, as judged from the R ratio of [θ]222/[θ]203 in HFIP solution, whereas a dynamically averaged unordered structure in HFA, Taken together, the information inclined to hypothesis that the primary structure of the highly crystalline regions of B. mori silk fibroin may be easily accessible to the large conformational changes, which in turn may be critical for facilitating the structural transformation from unprocessed silk fibroin （silk I form） to processed silk fiber （silk Ⅱform）.     

桑蚕丝素蛋白的结构、形态及其化学改性

通过对桑蚕吐丝机构的描述,着重从高分子科学的角度介绍桑蚕丝和蚕丝素蛋白大分子的组成、形态及各种化学、物理性质,讨论了蚕丝素蛋白的纤维化机理,并简述了丝索蛋白纤维的化学接枝改性及其应用。     

Manganese(II) tetrasulfophthalocyanine covalently supported on natural silk: A new highly active catalyst for synthesis of benzoxazepine derivatives in water

Natural silk as a biodegradable, biocompatible, renewable, green and abundant biomaterial was used as a support for chemical immobilization of a water‐soluble manganese(II) complex with a phthalocyanine ligand possessing covalent binding ability. The prepared manganese(II) tetrasulfophthalocyanine complex supported on natural silk revealed efficient catalytic activity and reusability for the synthesis of benzoxazepine derivatives in water at room temperature.     

Novel Methods for Obtaining High Modulus Aliphatic Polyamide Fibers

Super high modulus polyethylene fibers can be created by converting high molecular weight flexible PE chains into highly oriented and extended chain conformations. However, unlike polyethylene, aliphatic polyamides have very high cohesive energy and therefore cannot be easily drawn and highly oriented. This review addresses this fundamental problem by analyzing various novel approaches that can be used to suppress hydrogen bonding in these types of polyamides. Plasticization of such polymers with ammonia, iodine, salts, and Lewis acids, as well as dry spinning, wet spinning, and gel spinning, are discussed. Specialized techniques that involve vibrational zone drawing and annealing as well as laser heating zone drawing and annealing are also reviewed. Some of these methods definitely lead to remarkable improvements in initial modulus and other mechanical properties. The development of recombinant spider silk proteins as well progress in spinning these materials is also reported. The advantages and disadvantages of all of these processes are then summarized.     

Silk‐Pectin Hydrogel with Superior Mechanical Properties,Biodegradability, and Biocompatibility

A new method is developed to prepare silk hydrogels and silk‐pectin hydrogels via dialysis against methanol to obtain hydrogels with high concentrations of silk fibroin. The relationship between the mechanical and biological properties and the structure of the silk‐pectin hydrogels is subsequently evaluated. The present results suggest that pectin associates with silk molecules when the silk concentration exceeds 15 wt%, suggesting that a silk concentration of over 15 wt% is critical to construct interacting silk‐pectin networks. The silk‐pectin hydrogel reported here is composed of a heterogeneous network, which is different from fiber‐reinforced, interpenetrated networks and double‐network hydrogels, as well as high‐stiffness hydrogels (elastic modulus of 4.7 ± 0.9 MPa, elastic stress limit of 3.9 ± 0.1 MPa, and elastic strain limit of 48.4 ± 0.5%) with regard to biocompatibility and biodegradability.