Mechanical and thermal properties of dragline silk from the spider Nephila clavipes

Dragline silk from the spider, Nephila clavipes, was characterized by thermal analysis (TGA, DSC, DMA), computational modeling, scanning electron microscopy and by quasi-static as well as high rates of strain. Thermal stability to about 230°C was observed by TGA, two transitions by DMA, ?75°C, representative of localized motion in the amorphous domain, and a main chain motion associated with partial melt at 210°C. Tensile tests indicated average initial modulus, ultimate tensile strength and ultimate tensile strain of 22 GPa, 1.1 GPa and 9%, respectively. The corresponding properties of the best fibers tested were 60 GPa, 2.9 GPa and 11%, respectively. High strain rates (>50,000%/sec) indicated similar mechanical properties to the average values indicated above. Microscopy showed compressive and tensile strains to failure of 34%. Computational modeling yielded a crystal modulus of 200 GPa.     

Effect of Silk Protein Processing on Drug Delivery from Silk Films

Sericin removal from the core fibroin protein of silkworm silk is a critical first step in the use of silk for biomaterial‐related applications, but degumming can affect silk biomaterial properties, including molecular weight, viscosity, diffusivity and degradation behavior. Increasing the degumming time (10, 30, 60, and 90 min) decreases the average molecular weight of silk protein in solution, silk solution viscosity, and silk film glass‐transition temperature, and increases the rate of degradation of a silk film by protease. Model compounds spanning a range of physical‐chemical properties generally show an inverse relationship between degumming time and release rate through a varied degumming time silk coating. Degumming provides a useful control point to manipulate silk's material properties.

     

Self‐(Un)rolling Biopolymer Microstructures: Rings,Tubules, and Helical Tubules from the Same Material

We have demonstrated the facile formation of reversible and fast self‐rolling biopolymer microstructures from sandwiched active–passive, silk‐on‐silk materials. Both experimental and modeling results confirmed that the shape of individual sheets effectively controls biaxial stresses within these sheets, which can self‐roll into distinct 3D structures including microscopic rings, tubules, and helical tubules. This is a unique example of tailoring self‐rolled 3D geometries through shape design without changing the inner morphology of active bimorph biomaterials. In contrast to traditional organic‐soluble synthetic materials, we utilized a biocompatible and biodegradable biopolymer that underwent a facile aqueous layer‐by‐layer (LbL) assembly process for the fabrication of 2D films. The resulting films can undergo reversible pH‐triggered rolling/unrolling, with a variety of 3D structures forming from biopolymer structures that have identical morphology and composition.     

3D Printing of Silk Protein Structures by Aqueous Solvent‐Directed Molecular Assembly

Hierarchical molecular assembly is a fundamental strategy for manufacturing protein structures in nature. However, to translate this natural strategy into advanced digital manufacturing like three‐dimensional (3D) printing remains a technical challenge. This work presents a 3D printing technique with silk fibroin to address this challenge, by rationally designing an aqueous salt bath capable of directing the hierarchical assembly of the protein molecules. This technique, conducted under aqueous and ambient conditions, results in 3D proteinaceous architectures characterized by intrinsic biocompatibility/biodegradability and robust mechanical features. The versatility of this method is shown in a diversity of 3D shapes and a range of functional components integrated into the 3D prints. The manufacturing capability is exemplified by the single‐step construction of perfusable microfluidic chips which eliminates the use of supporting or sacrificial materials. The 3D shaping capability of the protein material can benefit a multitude of biomedical devices, from drug delivery to surgical implants to tissue scaffolds. This work also provides insights into the recapitulation of solvent‐directed hierarchical molecular assembly for artificial manufacturing.     

吡咯亚胺配体与过渡金属的反应性及其催化烯烃聚合

在经典的Brookhart吡啶双亚胺后过渡金属烯烃聚合催化剂基础上,用吡咯五元环代替吡啶六元环骨架可得到具有不同电子效应的新型吡咯亚胺配体.通过吡咯环特殊的电子效应和位阻效应可设计出种类繁多的有别于吡啶亚胺配体的配合物.综述了吡咯亚胺配体与前过渡金属(Ti,Zr等)、后过渡金属(Fe,Co,Ni,Pd等)、稀土金属(Y...     

A Cationic Stearamide-based Solid Lipid Nanoparticle for Delivering Yamanaka Factors: Evaluation of the Transfection Efficiency

Induced pluripotent stem cells (IPSC) are preferred as an alternative source for regenerative medicine, disease modeling, and drug screening due to their unique properties. As seen from the previous studies in the literature, most of the vector systems to transfer reprogramming factors are viral-based and have some well-known limitations. This study aims to develop a non-viral vector system for the transfection of reprogramming factors. Cationic stearamide lipid nanoparticles (CSLN) were prepared via the solvent diffusion method. The obtained CSLNs were used for the delivery of plasmid DNA (pDNA) encoding Oct3/4, Sox2, Klf4, and GFP to fibroblast cell lines. The optimization studies, for zeta potential and particle size of the conjugate, was performed to achieve high cell viability. CSLN63 with 36.5±0.06 mV zeta potential and 173.6±13.91 nm size was used for the transfection of Fibroblast cells. The transfection efficiency was observed by following GFP expression and was found as 70 %±0.11. The expression of the Oct4, Sox2, Klf4 was determined by RT-qPCR; an increase was observed after the 12th cycle in Klf4 (Ct averages: 13,41), Sox2 (Ct averages; 12,4), Oct4 (Ct average; 13,77). The tendency of colonization was observed. The upregulation efficiency of Oct4 and SSEA-1 with CSLN and another non-viral vector designed for the transportation of Yamanaka factors developed in our lab previously were compared with flow cytometer analysis.     

Characterization of a lipid-rich fraction synthesized by Streptomyces avermitilis

Isolation of the macrocyclic lactone parasiticide avermectin and other closely related natural products produced by Streptomyces avermitilis also yields a lipid-rich fraction. The latter has been characterized by techniques based on gas-liquid chromatography (GLC) and mass spectrometry (MS). Initial examination of the lipid-rich fraction by direct probe electron-impact (EI) MS and packed-column GLC showed that it consists primarily of a mixture of triglycerides possessing C14-C17 acyl groups. Further examination of this fraction by capillary column GLC-MS demonstrated that it contains low levels of C15-C17 free fatty acids, squalene and diglycerides and, as the major components, at least ten mixed acyl triglycerides (total number of acyl carbon atoms ranging from 43 to 50). Prominent among the triglycerides were a C15-C15-C16 species, a C15-C16-C16 species and a C15-C16-C17 species. Capillary-column GLC and GLC-MS of the fatty acid methyl esters resulting from transesterification demonstrated that the major triglyceride acyl groups are anteiso-C15 (12-methyltetradecanoyl), iso-C16 (14-methylpentadecanoyl), n-C16 (hexa-decanoyl) and anteiso-C17 (14-methylhexadecanoyl). Lower levels of the methyl esters of the following fatty acids were observed: iso-C14 (12-methyltridecanoic), n-C14 (tetradecanoic), iso-C15 (13-methyltetradecanoic), n-C15 (pentadecanoic), iso-C17 (15-methylhexadecanoic) and n-C17 (heptadecanoic). Little evidence was seen for either unsaturated acyl groups or acyl groups of less than 13 or more than 18 carbon atoms. Desorption chemical ionization MS (ammonia reagent gas) analysis confirmed the nature of the lipid-rich fraction, and is an attractive one-step approach for determining the molecular weights and distribution of triglycerides in a mixture.     

时频方法分析长骨中的超声导波及皮质骨厚度

超声导波在长骨中传播时,接收信号中含有相互叠加的多个导波模式。本文提出将希尔伯特-黄变换(HHT)用于分析叠加的多模式导波信号,将其分解成许多单个独立的模式,然后对分解出的模式求得其对应频率下的群速度,并与短时傅里叶变换所得的结果进行比较。通过与理论计算结果比较,可得到长骨皮质骨的厚度。研究结果表明,实验得到的厚度与实际厚度一致。说明通过测量导波模式的速度可以评价皮质骨的厚度,也说明HHT方法是一种识别叠加多模式导波信号的有效方法。