HNO与（HF）1≤n≤3分子间的蓝移与红移氢键

运用量子化学从头算方法研究了HNO与分子簇(HF)1≤n≤3形成的蓝移与红移氢键.在这些体系中,F…H-N都是蓝移氢键,重极化与重杂化和分子内超共轭导敛了氰键的蓝移;所有的X…H-F(X=O,N,F)氢键都是红移的,分子问超共轭导致了氢键的红移.在多分子体系形成的氢键链中,分子问超共轭作用呈现规律性递变,它导致了氢键强度与频率位移的规律性变化,电子密度拓扑分析结果反映和支持了这种规律性变化.     

Synthesis and Isolation of Diastereomers of Optically Active Cyclomercurated Ferrocenylimines

IntroductionOrganomercurials have been used extensively in organic synthesis and synthesis of other organometallics due to their ability to accommodate practically all the important organic functional groups and their ease in undergoing transmetallation for syntheses of transition metal organometallics which are very useful in organic synthesis. Recently, we reported the synthesis of optically active 1,2-disubstituted cyclomercurated ferrocenylimines by transmetallation reaction of planar chir…     

Detection of the photochemical intermediate processes in phycobiliproteins

The delayed luminescence was applied to detect the intermediate processes of the excitedstate decay in the selectively excited phycobiliproteins. Phosphorescence spectra of the five types of phycobiliproteins, R-PE, CPC, APC, R-PC, PEC were reported in this article. The five phycobiliproteins showed different phosphorescence yields, the sequence of which was the same as that of the singlet oxygen yields. Based on the observation, it can be concluded that each of the chromophores possesses a characteristic phosphorescence emission. The delayed luminescence spectra of APC at different aggregation states (trimer, monomer and denatured APC) are researched. The lower aggregation APC showed less phosphorescence because of relative loose structures and less interaction with the surrounding proteins, while the denatured APC showed delayed fluorescence instead of phosphorescence because of triplet-triplet annihilation.     

航天探测器CO2两相主动热控系统试验及分析

本文设计了一种以机械泵驱动的CO2两相散热系统,用于高热流密度航天探测器的高精度温度控制.分别对其稳态特性包括散热热流密度、流动阻力特性和动态性能包括启动特性、控温特性试验研究发现:机械泵CO2两相控温系统控温精度不低于1.5℃,启动性能和控温实时性能良好.     

纳米科学技术及其在军事领域的应用展望

本文对作21世纪高新技术之一的纳米科学技术进行了阐述，并结合当前国内外的进展，就其在军用新材料技术，隐身技术，武器研制技术和军用电子技术等四个领域中在未来军事战争中的应用进行了阐述和展望。     

翠绿亚胺聚合物高压下芳环扭角和能隙的缩减

利用改进的Ginder-Epstein模型计算了翠绿亚胺聚合物在参数V4,0取值于1.8～35.8 eV的自洽变分基态,并通过芳环扭角的变化来估算聚合物压强,给出了V4,0,芳环扭角及能隙与理论压强之间的最小二乘拟合.结果表明随此参数的增大,芳环扭角和能隙都缩减而理论压强升高.当理论压强由零压增至3.0 GPa左右时,能隙先快后慢从2.0 eV减小至最小值0.87 eV.这理论与该聚合物的高压电导测试结果一致.     

Two‐injection workflow for a liquid chromatography/LTQ‐Orbitrap system to complete in vivo biotransformation characterization: demonstration with buspirone metabolite identification

The relatively high background matrix in in vivo samples typically poses difficulties in drug metabolite identification, and causes repeated analytical runs on unit resolution liquid chromatography/mass spectrometry (LC/MS) systems before the completion of biotransformation characterization. Ballpark parameter settings for the LTQ‐Orbitrap are reported herein that enable complete in vivo metabolite identification within two HPLC/MS injections on the hybrid LTQ‐Orbitrap data collection system. By setting the FT survey full scan at 60K resolution to trigger five dependent LTQ MS² scans, and proper parameters of Repeat Duration, Exclusion Duration and Repeat Count for the first run (exploratory), the Orbitrap achieved the optimal parallel data acquisition capability and collected maximum number of product ion scans. Biotransformation knowledge based prediction played the key role in exact mass ion extraction and multiple mass defect filtration when the initial data was processed. Meanwhile, product ion extraction and neutral loss extraction of the initial dependent data provided additional bonus in identifying metabolites. With updated parent mass list and the data‐dependent setting to let only the ions on the parent mass list trigger dependent scans, the second run (confirmatory) ensures that all precursor ions of identified metabolites trigger not only dependent product ion scans, but also at or close to the highest concentration of the eluted metabolite peaks. This workflow has been developed for metabolite identification of in vivo or ADME studies, of which the samples typically contain a high level of complex matrix. However, due to the proprietary nature of the in vivo studies, this workflow is presented herein with in vitro buspirone sample incubated with human liver microsomes (HLM). The major HLM‐mediated biotransformation on buspirone was identified as oxidation or hydroxylation since five mono‐ (+16 Da), seven di‐ (+32 Da) and at least three tri‐oxygenated (+48 Da) metabolites were identified. Besides the metabolites 1‐pyrimidinylpiperazine (1‐PP) and hydroxylated 1‐PP that formed by N‐dealkylation, a new metabolite M308 was identified as the result of a second N‐dealkylation of the pyrimidine unit. Two new metabolites containing the 8‐butyl‐8‐azaspiro[4,5]decane‐7,9‐dione partial structure, M240 and M254, were also identified that were formed apparently due to the first N‐dealkylation of the 1‐PP moiety. Copyright © 2009 John Wiley & Sons, Ltd.     

Construction of triangular DP surface and its application

In this paper, a new type of bivariate basis on a triangle is presented, which is constructed by extending the univariate NTP basis proposed by Delgado and Peña. Some algebraic properties and its recursive formulae are given. Then a new type of surfaces that is called triangular DP surface is defined, and its recursive evaluation algorithm is obtained. Also, in the case of low degree, its subdivision algorithm and degree elevation algorithm are derived. It is shown that this type of surfaces is obviously more advantageous than triangular Bézier surface, and hence extremely useful for geometric design, especially for the situation in which the surface needs to be evaluated quickly.     

Investigation into the rotational bands of ~(185)Pt with the particle-rotor model

Theoretical calculations have been performed for the ν9/2+[624](i13/2) and ν7/2-[503](f7/2) bands of 185Pt in the framework of particle-rotor model. The band properties of signature splitting and configuration mixing have been analyzed. The level energy and signature splitting before the band crossing can be well interpreted by introducing triaxiality. The positive-parity yrast band is pro posed to be dominated by the ν9/2+[624](i13/2) component, while the negative-parity band shows strong mixing of ν7/2-[5...