Insertion reactions of the p-complex structure of silylenoid into C–X bonds (X = F,Cl, Br,O, and N)

The insertion reactions of the p-complex structure (A) of silylenoid H₂SiLiF into C–X bonds of CH₃XH _n−1 (X = F, Cl, Br, O, N; n = 1, 1, 1, 2, 3) have been studied using ab initio and DFT methods. The results indicate that the insertions proceed in a concerted manner, forming H₂SiXH _n−1CH₃ and LiF. The order of reactivity by A insertion indicates the reaction barriers increase for the same-row element X from right to left in the periodic table, whereas change very little for the same-family element X. The insertions of A and the three-membered-ring structure of H₂SiLiF are similar. Both structures may participate in insertion reactions.     

新型手性氨基醇的合成及其用于不对称催化醛类烷基化反应

制备了一种由糖类化合物衍生的新型手性氨基醇（Ⅰ），并将其作为手性源用于醛类的不对称烷基化反应．考察了在手性氨基醇的存在下，各种醛和二乙基锌作用生成相应的手性仲醇的光学收率及化学收率．结果表明，该催化剂对于芳香醛的烷基化更为有效．并考察了几种反应条件对于苯甲醛的不对称催化烷基化反应的影响，其中最佳结果为１－苯基－１－丙醇的光学收率达８２．７％，而化学收率达５８．８％．     

Theoretical studies on the pentacoordinate silylenoid PhCH<Subscript>2</Subscript>(NH<Subscript>2</Subscript>)CH<Subscript>3</Subscript>SiLiF

The structures of pentacoordinate silylenoid PhCH₂(NH₂)CH₃SiLiF were studied by density functional theory at the B3LYP/6-31G(d) level. Three equilibrium structures, the three-membered ring (1), the p-complex (2), and the σ-complex (3) structures, were located. Their energies are in the order of 2 > 1 > 3 both in vacuum and in THF. To exploit the stability of PhCH₂(NH₂)CH₃SiLiF, the insertion reactions of 1 and PhCH₂(NH₂)CH₃Si into C–F have been investigated, respectively. The results show that the insertion of PhCH₂(NH₂)CH₃Si is more favorable. To probe the influence of amine-coordination to the stability of PhCH₂(NH₂)CH₃SiLiF, the insertion reaction of PhCH₃CH₃SiLiF was also investigated. The calculations indicate that the insertion of PhCH₃CH₃SiLiF is more favorable than that of 1. So the N atom plays an important role on the stability of silylenoid PhCH₂(NH₂)CH₃SiLiF.     

Enhanced amperometric immunoassay for the prostate specific antigen using Pt-Cu hierarchical trigonal bipyramid nanoframes as a label

A dual enhancing strategy has been employed to develop a sandwich type of electrochemical immunoassay for the prostate specific antigen (PSA). The signal is enhanced by using Pt-Cu hierarchical trigonal bipyramid nanoframes (HTBNFs) and a composite consisting of Fe₃O₄ nanoparticles and reduced graphene oxide in polydopamine that serve to capture the primary antibody (Ab1). This nanocomposite shows better electrical conductivity than Fe₃O₄ and reduced graphene oxide (RGO), respectively, alone. The Pt-Cu HTBNFs were used to label the secondary antibody (Ab2) and act as tags for signal amplification by virtue of their outstanding electrochemical reduction activity towards H₂O₂. At a working potential of +0.1 V (vs. SCE), the interference by dissolved oxygen can be avoided. This immunoassay is highly sensitive, with a linear range that extends from 0.1 pg?mL^?1 to 5 ng?mL^?1 and an ultralow detection limit of 0.03 pg?mL^?1.

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Graphical abstract Schematic of the dual amplification strategy in the immunosensor for the prostate specific antigen (PSA) that is based on the use of a first antibody (Ab₁) conjugated to a Fe₃O₄-reduced graphene oxide nanocomposite (Fe₃O₄-RGO), and of Pt-Cu trigonal bipyramid nanoframes as a label for the second antibody (Ab₂).

     

铸铁表面化学沉积Ni—P镀层和Ni—P—SiC复合镀层的耐磨性研究

作者利用化学沉积法在低合金铸铁表面分别制取了Ni-P镀层和Ni-P-SiC复合镀层,并就两者的耐磨性与铸铁、磷化处理表面及Cr镀层的进行了对比试验研究。结果表明,Ni-P镀层的耐磨性比铸铁及磷化处理的好,但比Cr镀层和Ni-P-SiC复合镀层的差,并以后者的为最佳。     

卫星编队飞行动力学与控制研究

简要介绍了卫星编队飞行的动力学与控制研究的最新进展，对今后研究工作的重点提出了建议．     

二维GeSe纳米片五族和七族原子掺杂的受主和施主杂质态

采用第一性原理的计算方法研究GeSe纳米片结构掺杂V和VII族元素对其电子结构、形成能和跃迁能级的影响.结果表明：无论是掺杂V族还是VII族元素,体系的形成能均随杂质半径的增加而增加.V族元素掺杂体系的跃迁能级随杂质原子半径的增加而降低,而VII元素掺杂的体系却随杂质原子半径的增加而增加.其中,F、Cl、Br和I的掺杂为n型施主浅能级杂质,而N、P和As掺杂为p型受体深能级杂质.为相关的实验研究提供了理论参考.