超流Fermi气体在非简谐势阱中的集体激发

研究了非谐振势中超流Fermi气体的集体激发. 基于一维超流流体动力学模型, 采用变分法获得了体系从分子Bose-Einstein凝聚端渡越到Cooper对凝聚端时系统的两个低能激发模, 即偶极模和呼吸模. 分析发现: 在整个跨越区偶极模和呼吸模都发生了频移现象, 且在BCS端频移更加显著. 进一步研究发现在不同驱动振幅激发下超流Fermi气体质量中心和宽度变化呈现出了复杂动力学特性, 由于非谐振势的贡献,超流Fermi气体两低能模发生耦合, 使宽度变化产生量子拍频现象, 且拍频频率随着驱动振幅的增加而增大. 这种非线性耦合对外部驱动的响应在幺正区尤其显著. 关键词： 超流Fermi气体 非谐振势 集体激发     

伽马CuX(X=Cl,Br,I)的电子结构和光学性质的第一性原理计算

基于第一性原理赝势平面波方法对伽马晶体CuCl, CuBr, CuI的体模量、体模量对压强的一阶偏导 数、电子结构、折射率等光学性质进行了计算.计算结果表明,广义梯度近似(GGA)下CuX(X = Cl, Br, I) 晶体的晶格常数与体模量的计算值与实验相差较小.与局域密度近似(LDA)相比, GGA更适合于 CuX(X = Cl, Br, I)晶体 的计算.这三者的价带都来源于Cu的3d态,导带部分主要来自Cu和卤素的s电子贡献,很少部分来自卤素的p电子 贡献.计算得到CuCl, CuBr, CuI的折射率分别为1.887, 2.015, 2.199,与应用Gladstone-Dale半经验关系得到 的结果符合得很好.     

Synthesis and Biological Evaluation of 3-Aryl-quinoxaline-2-carbonitrile 1,4-Di-<em>N</em>-oxide Derivatives as Hypoxic Selective Anti-tumor Agents

A series of 3-aryl-2-quinoxaline-carbonitrile 1,4-di-N-oxide derivatives were designed, synthesized and evaluated for hypoxic and normoxic cytotoxic activity against human SMMC-7721, K562, KB, A549 and PC-3 cell lines. Many of these new compounds displayed more potent hypoxic cytotoxic activity compared with TX-402 and TPZ in the tumor cells based evaluation, which confirmed our hypothesis that the replacement of the 3-amine with the substituted aryl ring of TX-402 increases the hypoxic anti-tumor activity. The preliminary SAR revealed that 3-chloro was a favorable substituent in the phenyl ring for hypoxic cytotoxicity and 7-methyl or 7-methoxy substituted derivatives exhibited better hypoxic selectivity against most of the tested cell lines. The most potent compound, 7-methyl-3-(3-chlorophenyl)-quinoxaline-2-carbonitrile 1,4-dioxide (9h) was selected for further anti-tumor evaluation and mechanistic study. It also exhibited significant cytotoxic activity against BEL-7402, HepG2, HL-60, NCI-H460, HCT-116 and CHP126 cell lines in hypoxia with IC₅₀ values ranging from 0.31 to 3.16 μM, and preliminary mechanism study revealed that 9h induced apoptosis in a caspase-dependent pathway.     

Mechanism of thio acid/azide amidation

A combined experimental and computational mechanistic study of amide formation from thio acids and azides is described. The data support two distinct mechanistic pathways dependent on the electronic character of the azide component. Relatively electron-rich azides undergo bimolecular coupling with thiocarboxylates via an anion-accelerated [3+2] cycloaddition to give a thiatriazoline. Highly electron-poor azides couple via bimolecular union of the terminal nitrogen of the azide with sulfur of the thiocarboxylate to give a linear adduct. Cyclization of this intermediate gives a thiatriazoline. Decomposition to amide is found to proceed via retro-[3+2] cycloaddition of the neutral thiatriazoline intermediates. Computational analysis (DFT, 6-31+G(d)) identified pathways by which both classes of azide undergo [3+2] cycloaddition with thio acid to give thiatriazoline intermediates, although these paths are higher in energy than the thiocarboxylate amidations. These studies also establish that the reaction profile of electron-poor azides is attributable to a prior capture mechanism followed by intramolecular acylation.     

耦合动力系统的预测投影响应

提出了耦合动力系统的预测投影响应,通过选择不同的函数以及改变比例因子可以构建一系列不同的驱动响应系统.详细研究了该系统的一种特殊情况——加速预测投影响应.在该系统中,响应系统与驱动系统的输出轨迹在幅度上成比例关系,并且具有更快的演化速度.同时,还进一步证明了该系统在驱动信号和驱动项有微小扰动以及参数失配的情况下具有鲁棒性.     

A query on crystallization temperature‐dependent cooling function under nonisothermal condition

The cooling function (κ) in Ozawa model was investigated through theoretic analysis and experimental method. Different from the fact accepted by researchers over past decades that κ(T) depends only on the crystallization temperature (T) and consequently the parameters for nonisothermal crystallization kinetics could be obtained by plotting ln[? ln(1 ? X(T))] versus ln λ at a given T, we found that κ at a given T was also dependent on onset temperature (T₀) of crystallization process. Because T₀ varies with cooling rate (λ) in nonisothermal crystallization, we conclude that κ is a binary function of T and λ, which was validated by our kinetic data from differential scanning calorimetry measurement in a wide λ range from 1 to 80 °C/min. It is suggested that the conventional method for calculating kinetic parameters based on Ozawa model, by plotting ln[? ln(1 ? X(T))] versus ln λ, might not be exact for nonisothermal crystallization. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44:795–800, 2006     

Structure Determination of Alkynyl-Protected Gold Nanocluster Au22(tBuC≡C)18 and Its Thermochromic Luminescence

An alkynyl-protected gold nanocluster, Au₂₂(^tBuC≡C)₁₈ ( 1 ), has been synthesized and its structure has been determined by single-crystal X-ray diffraction. The molecular structure consists of a Au₁₃ cuboctahedron kernel and three [Au₃(^tBuC≡C)₄] trimeric staples. The cluster 1 has strong luminescence in the solid state with a 15 % quantum yield, and it displays interesting thermochromic luminescence as revealed by temperature-dependent emission spectra. The enhanced room-temperature emission is characterized as thermally activated delayed fluorescence.     

Formation of an Alkynyl-Protected Ag112 Silver Nanocluster as Promoted by Chloride Released In Situ from CH2Cl2

By directly reducing alkynyl–silver precursors, we successfully obtained a large alkynyl-protected silver nanocluster, (C₇H₁₇ClN)₃[Ag₁₁₂Cl₆(C≡CAr)₅₁], which is hitherto the largest structurally characterized silver nanocluster in the alkynyl family. The cluster exhibits four concentric core–shell structures (Ag₁₃@Ag₄₂@Ag₄₈@Ag₉), and four types of alkynyl–silver binding modes are observed. Chloride was found to be critical for the stabilization and formation of the silver nanocluster. The release of chloride ions in situ from CH₂Cl₂ solvent has been confirmed by mass spectrometry. This study suggests that the combination of alkynyl and halide ligands will pave a new way for the synthesis of large silver nanoclusters.     

Some intriguing upper bounds for separating hash families

An N ×n matrix on q symbols is called {w_1,...,w_t}-separating if for arbitrary t pairwise disjoint column sets C_1,..., C_t with |C_i|=w_i for 1 ≤i≤t, there exists a row f such that f(C_1),...,f(C_t) are also pairwise disjoint, where f(C_i) denotes the collection of componentn of C_i restricted to row f. Given integers N, q and w_1,...,w_t, denote by C(N,q,{w_1,...,w_t}) the maximal a such that a corresponding matrix does exist.The determination of C(N,q,{w_1,...,w_t}) has received remarkable attention during the recent years. The main purpose of this paper is to introduce two novel methodologies to attack the upper bound of C(N, q, {w_1,...,w_t}).The first one is a combination of the famous graph removal lemma in extremal graph theory and a Johnson-type recursive inequality in coding theory, and the second onc is the probabilistic method. As a consequence, we obtain several intriguing upper bounds for some parameters of C(N,q,{w_1,...,w_t}), which significantly improve the previously known results.     

In situ One-Pot Fabrication of MoO3-x Clusters Modified Polymer Carbon Nitride for Enhanced Photocatalytic Hydrogen Evolution

Developing low-cost and high-efficient noble-metal-free cocatalysts has been a challenge to achieve economic hydrogen production. In this work, molybdenum oxides (MoO\begin{document}$_{3-x}$\end{document}) were in situ loaded on polymer carbon nitride (PCN) via a simple one-pot impregnation-calcination approach. Different from post-impregnation method, intimate coupling interface between high-dispersed ultra-small MoO\begin{document}$_{3-x}$\end{document} nanocrystal and PCN was successfully formed during the in situ growth process. The MoO\begin{document}$_{3-x}$\end{document}-PCN-\begin{document}$X$\end{document} (\begin{document}$X$\end{document}=1, 2, 3, 4) photocatalyst without noble platinum (Pt) finally exhibited enhanced photocatalytic hydrogen performance under visible light irradiation (\begin{document}$\lambda$\end{document}\begin{document}$>$\end{document}420 nm), with the highest hydrogen evolution rate of 15.6 μmol/h, which was more than 3 times that of bulk PCN. Detailed structure-performance revealed that such improvement in visible-light hydrogen production activity originated from the intimate interfacial interaction between high-dispersed ultra-small MoO\begin{document}$_{3-x}$\end{document} nanocrystal and polymer carbon nitride as well as efficient charge carriers transfer brought by Schottky junction formed.