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）.     

Synthesis and Crystal Structure of 1-（4-Bromobenzoyl）-3- [5-（E）-styryl-1,3,4-thiadiazol-2-yl]urea

1 INTRODUCTION 1,3,4-Thiadiazole derivatives represent an interes- ting class of compounds possessing broad spectrum biological activities[1~4]. Aroyl ureas are known to exhibit diverse biological effects, such as insecticidal, fungicidal, herbicidal and plant growth regulating activities[5~8]. Therefore, it is worthwhile to investi- gate the compounds incorporating both 1,3,4-thiadia- zole nucleus and aroyl urea group. In the previous paper[9], a series of aroyl ureas containing 1,3,4-t…     

1,3,4,6—四硫代戊搭烯—2,5—二酮制备含硫取代基的四硫富瓦…

以１，３，４，６－四硫代戊搭烯－２，５－二酮为原料，经偶联，醇解，烃化或醇解，烃化，偶联等步骤，制得四甲硫基四硫富瓦烯，四乙硫基四硫富瓦烃，二喹喔啉硫醚，４－甲硫基－５－甲氧甲酰硫基－１，３－二硫环戊烯－２－酮。四甲基乙烯和４，４＇－二甲硫基－５，５＇－二甲氧甲酰硫基四硫富瓦烯及它的异构体混合物，提出了１，３，４，６－四硫代戊搭烯－２，５－二酮醇解机理。讨论了未得到某些预期产物的原因，报道了３种四     

Synthesis and Crystal Structure of 2-Benzylsulefnyl-3-cyano-5,7-dimethyl-pyrazolo[1,5-a]pyrimidine

1 INTRODUCTION The pyrazolo[1,5-a]pyrimidines are the active compositions in many pesticides and medicines. A new class of KDR (tyrosine kinase VEGFR-2) ki- nase inhibitors is discovered and found to have affi- nity for the human CRF-1 (Corticotrophin re…     

甲苯类化合物的选择性氧化

综述了以O2为清洁氧源甲苯类化合物的气相和液相选择性氧化.甲苯类化合物的气相选择性氧化中主要介绍了金属氧化物、分子筛和负载型催化剂并对影响催化剂活性和选择性的因素进行了分析;甲苯类化合物的液相选择性氧化中重点介绍了MC (mid-century)催化体系及其反应机理方面的研究进展,并特别介绍了仿生催化在甲苯类化合物催化氧化中的应用.对各催化氧化体系的应用前景进行了展望.     

纳米Cu(OH)2分解温度对CuO粒度的影响

以CuSO4.5H2O和NaOH为原料,采用沉淀法制备得到Cu(OH)2纤维,再进行Cu(OH)2的分解反应.考察了在不同实验条件下温度对Cu(OH)2热分解过程的影响.结果表明:在反应温度20℃,反应终点pH值为12,搅拌速度为1 200 r.min-1,NaOH溶液的滴加速度为50 mL.min-1的反应条件下,得到的样品为纳米Cu(OH)2纤维,其直径为10~30 nm、长度为1~6μm;在固相纳米Cu(OH)2热分解制备CuO过程中CuO粒径随温度的升高而增大,在温度不超过200℃时CuO的粒径约为20 nm左右;在液相中先沉淀后升温时,产物的形貌为球形,CuO粒径随温度的升高而增大,低于80℃可得到纳米级的CuO.     

Synthesis of New Ligand 1,2-Bis{di[（R,R）-1,3,2-oxzaphosphlidine]phosphino}ethane with C_2-symmetric Axis and Application in Rh-catalyzed Asymmetric Hydrogenation

New ligand 1,2-bis{di[（R,R）-1,3,2-oxzaphosphlidine]phosphino}ethane [（R,R）-BDOPPEs 1,2,3 and 4] with C2-symmetric axis and bearing nitrogen and oxygen were synthesized from readily available optically active amino alcohols.Rh complexes with these ligands were highly enantioselective catalysts for asymmetric hydrogenation of N-benzoyldehydroamino acid derivatives and α-functionalized ketones in 99%e.e.and 98%e.e.,respectively.This new class of（R,R）-BDOPPEs 1,2,3 and 4 gave much more effectivity and enantionselectivity than their corresponding non-C2-asymmetric aminophosphine phosphinite.     

Pb2＋在液/液界面迁移的电化学研究及其应用

用循环伏安法研究了双硫腙络合推动Pb^2＋在水/乙酰丙酮界面迁移的伏安过程. 实验证明, 该过程是受扩散控制的不可逆过程, Pb^2＋由水相转移到有机相中, 与双硫腙形成络合物Pb(DzH)₂. Pb^2＋的峰电位在－0.3 V处, 并且在5× 10^－6～0.1 mol•L^－1范围内与峰电流成正比. 这一方法为工业废水中铅的在线、现场测定提供了可靠、灵敏的检测方法.     

N-TiO2/ZnO复合纳米管阵列的掺杂机理及其光催化活性

以ZnO纳米柱阵列为模板, 采用溶胶-凝胶法制备出TiO2/ZnO和N掺杂TiO2/ZnO的复合纳米管阵列. 扫描电镜(SEM)、X射线光电子能谱(XPS)和紫外-可见漫反射吸收光谱(UV-Vis)的结果表明: 两种阵列的纳米管均为六角形结构, 直径约为100 nm, 壁厚约为20 nm; 在N-TiO2/ZnO复合纳米管阵列中, 掺入的N离子主要是以N-Ox、N-C和N-N的形式化学吸附在纳米管表面, 仅有少量的N离子以取代式掺杂的方式占据TiO2晶格O的位置; 表面N物种形成的表面态能级和取代式掺杂导致带隙的窄化, 增强了纳米管阵列的光吸收效率, 促进了光生载流子的分离. 光催化实验结果表明, N离子的掺杂有利于N-TiO2/ZnO复合纳米管阵列光催化活性的提高.     

MoO3/SiO2催化剂的异丁烷选择氧化反应性能

分别采用浸渍法和溶胶－凝胶法制备了MoO3/SiO2催化剂，用XRD，TPR，IR，TPD和活性评价等手段对催化剂的影响，晶格氧活泼性，化学吸附性能和异丁烷选择氧化反应性能进行了研究。结果表明，催化剂表面由Lewis碱位Mo=M,Mo-O-Mo中的晶格氧和Lewis酸位Mo^6 构成，在MoO3/SiO2催化剂上，异丁烷主要通过甲基的H双位吸附在表面的Lewis碱位Mo=O上；在常压条件下，异丁烷选择氧化产物主要为异丁烷，甲基丙烯醛和甲基丙烯酸，其中深度氧化产物CO2主要由吸附的异丁烯继续反应生成；采用溶胶－凝胶法制备的MoO3/SiO2催化剂，可得到较高的异丁烷转化率和含氧有机物选择性。