Cu（Ⅱ） effect on the conformation of regenerated silk fibroin in dilute aqueous solution

Much attention has been paid to the natural mechanism of silkworm spinning due to the impressive mechanical properties of the natural fibers. In this work, we studied the effect of Cu（Ⅱ） ions on the secondary structure of Bombyx mori regenerated silk fibroin （SF） in dilute solution by circular dichroism （CD）. The results indicate that a given amount of Cu（Ⅱ） induces the SF conformational transition from random coil to β-sheet, however, further addition of Cu（Ⅱ） is unfavorable for this conversion. Meanwhile, the conformational changes induced by Cu（Ⅱ） follow a nucleation-dependent aggregation mechanism, which is similar to that found in Prion protein （PrP） denaturation and Aβ-peptide aggregations, leading to the neurodegenerative disease. This work would help one understand further the natural spinning process of silkworm. Additionally, it would be significant for the study of the nervous system diseases, because silk fibroin, extracted in large amounts from Bombyx mori silkworm gland, could be a proper model to study PrP denaturation and Aβ-peptide aggregations.     

抗有机杂质镀镍添加剂对阴极极化性能的影响

研究了有机杂质以及抗有机杂质添加剂对镀镍过程中阴极极化性能的影响．实验结果表明，有机杂质增大了阴极极化，而抗有机杂质添加剂却能减小阴极极化．实验结果还显示，添加剂消除有机杂质污染的效果同其降低阴极极化的能力密切相关     

苯基重氮盐-冠醚分子嵌合物的FAB-MS及其准分子离子生成机理的研究

Fast atom bombardment mass spectra of a series of arenediazonium salts with various substituents complexed with 18-crown-6 and dibenzo-24-crown-8 ethers were examined. The correlation between quasi-molecular ion abundance of various complexes and the properties, coordination ability of donor-acceptor linkages in the complexes were studied. By using molecular orbital calculation we have successfully demonstrated that the correlation cited is related to the electron cloud densities on the heteroatoms α-N and β-N of arenediazonium salts.     

掺铒a-SixC1-x-H薄膜的发光特性

用等离子体增强化学气相沉积（PECVD）的方法，以固定的氢气（H2）流量和不同的硅烷（SiH4）和甲烷（CH4）流量比沉积了一系列的氢化非晶SiC（a-Si，C1-x-H）膜。用这种宽带隙的a-SixC1-x-H材料作为掺铒的基体材料，通过离子注入的方法得到掺铒的a-SixC1-x-H（a-SixC1-x-H：Er）膜。注入以后的样品经过不同温度的退火。用X射线光电子能谱（XPS）、红外吸收光谱（IR）、拉曼散射谱（Raman）等技术研究不同的SiH4／CH4流量比和退火温度对a-SixC1-x-H：Er发光强度的影响。结果表明，高温退火引起了膜中C的分凝，对饵的发光是不利的。通过低温和室温下铒发光强度的比较，表明这种材料具有较弱的温度猝灭效应。     

钇对Ti-1100高温钛合金热稳定性和蠕变行为的影响

量了Ｔｉ１１００和Ｔｉ１１００／０１％Ｙ（质量分数）高温钛合金在６００℃／１００ｈ空气中暴露后的拉伸性能及在６００℃／１５０ＭＰａ／１００ｈ条件下的蠕变性能，利用透射电镜观察了合金室温及蠕变后的组织。结果表明，Ｔｉ１１００合金加入０１％的Ｙ后，由于原始β晶粒得到细化，明显改善了其热稳定性；固溶在基体中的硅原子阻碍位错滑移和攀移，使蠕变中的回复过程难于实现；稀土还抑制α２相的长大，所形成的氧化物也阻碍位错的运动。这些均有利于提高Ｔｉ１１００合金的抗蠕变性能。     

环氧丙烯酸酯的紫外光固化

制备了适于配制紫外光固化涂料的环氧丙烯酸酯，研究了反应温度、阻聚剂、催化剂等因素对环氧树脂与丙烯酸反应的影响；讨论了反应机理和动力学；并利用红外光谱观察了产物的紫外光固化行为。季铵盐能有效地催化环氧树脂和丙烯酸的反应，当其用量为０．６％～１．２％时，在９０～１１０℃反应４．５～８小时后，环氧基转化率大于９７％。由此配制的光固化涂料经紫外光辐照能快速固化。     

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.     

Solid state synthesis of copper(I) thiotungstate cluster compounds at low heating temperatures. Crystal structures of [(n-Bu)4N]3-[WS4Cu3Cl3Br] and [Et4N]4[WS4Cu4I6]

Summary Reaction of [NH₄]₂[WS₄] with CuX (X = Cl or I) and R₄NX (R = Et or n-Bu) in the solid state gave two new bimetallic compounds with W:Cu compositions from 1:3 to 1:4. Compound (1), [(n-Bu)₄N]₃[WS₄Cu₃Cl₃Br], crystallizes in the hexagonal space group R3c with a = 17.051(5), c = 38.372(5) Å, V = 9661.8 ų, Z = 6. The cluster anion of (1) comprises a cubane-like cluster core [WS₃Cu₃Br] of C₃ symmetry with a Cl atom attached to each of the three Cu atoms and one terminal sulphido ligand attached to the W atom. Compound (2), [Et₄N]₄[WS₄Cu₄I₆], crystallizes in the monoclinic space group C2/m with a = 29.702(6), b = 12.7887(5), c = 15.327(3)Å, = 99.69(2), V = 5738.1 ų, Z = 4. In the cluster anion of (2), four edges of the WS₄ core are coordinated by four Cu atoms, giving a WS₄Cu₄ aggregate of approximate C_2V symmetry.     

2-(苯并噻唑-2-基)-5-(N,N-二乙基氨基)苯酚衍生物的合成及其对H2S的识别

以4-N,N-二乙基氨基水杨醛为原料,制备了2-(苯并噻唑-2-基)-5-(N,N-二乙基氨基)苯酚衍生物(探针L),并对其结构进行了表征。在DMSO/PBS(体积比3∶7,pH=7.4)溶液中,探针L具有高选择性并可荧光"关-开"识别H_2S,在365nm紫外灯照射下,由无荧光变成蓝色荧光。实验表明,探针L识别H_2S的检测限为2.05×10~(-6)mol/L,pH适用范围为6～9,可用于检测实际水样中的H_2S。     

An efficient method for constructing nonorthogonal localized molecular orbitals

A new method for constructing nonorthogonal localized molecular orbitals (NOLMOs) is presented. The set of highly localized NOLMOs is obtained by minimization of the spread functional starting from an initial set of canonical orthogonal molecular orbitals. To enhance the stability and efficiency, the centroids of the NOLMOs are constrained to be those of the corresponding orthogonal localized molecular orbitals (OLMOs), which are obtained with the Boys criterion in advance. In particular, these centroid constraints make the optimization for each NOLMO independent of the others, which is an attractive feature for application to large systems. The minimization with the constraints incorporated through the multiplier-penalty function method is stable and efficient in convergence. While exhibiting the classical bonding pattern in chemistry and sharing a spatial distribution similar to that of the corresponding OLMOs, the obtained NOLMOs are more compact than the corresponding OLMOs with about 10%-28% reduction in the value of the spread functional and devoid of the troublesome "orthogonalization tails."