分子间相互作用研究的APF-D密度泛函SAM色散校正方法改进

APF密度泛函色散校正（APF-D）是由B3PW91和PBE0杂化的APF泛函,加上球形原子模型（SAM）色散校正构成的一种有别于Grimme经验色散校正的密度泛函理论色散校正（DFT-D）方法,计算稀有气体及其与小分子复合物结合能和势能面准确性很高,但对常见氢键、C―H…π和π…π等复合物结合能计算结果明显偏大,在一般性分子间相互作用问题研究中一直未被认可和采纳。我们发现APF-D结合能计算结果偏大的原因是APF泛函与SAM色散校正重复计入了一定量的长程色散能;通过引入不依赖于体系的SAM色散能阻力因子ζ,简单而有效地解决了APF-D色散能过度补偿问题,提出了APF-D改进方案APF-D^*;通过S66和L7标准测试集的对照计算表明,APF-D^*结合能准确性远高于原始APF-D,达到和超过目前常用的B3LYPD3和ωB97X-D方法水平,并具有较好的计算效率,期待在大体系分子间相互作用研究中得到广泛应用。     

基于双吡啶脲类Cd(Ⅱ)、Zn(Ⅱ)、Hg(Ⅱ)配合物的合成及晶体结构

间苯二胺和3-吡啶异氰酸酯在甲苯中加热回流得到双吡啶脲类配体L,然后将配体分别与CdSO_4·8H_2O,ZnI_2,HgI_2,HgCl_2进行配位反应,得到4个配合物{[Cd(L)(SO_4)(H_2O)_3]·H_2O}n(1),{[Zn(L)I_2]·2C_2H_5OH}n(2),{[Hg(L)I_2]·C_2H_5OH}n(3),[Hg(L)Cl_2]·H_2O(4),并用元素分析、FT-IR、X射线单晶衍射、粉末衍射对其进行了表征。配合物1形成一维螺旋链结构,配合物2和3形成一维"之"字链结构,配合物4形成32元环状结构。     

一种同时分辨识别Zn2+和F-离子的双功能探针

由8-甲酰基-7-羟基香豆素与碳酰肼经一步缩合反应可制得探针1。研究发现,探针1对Zn²⁺和F^-离子均呈现荧光增强和比率比色的高灵敏和高选择性响应,检出限低至10^-8 mol·L^-1。通过光谱、ITC、¹H NMR滴定及质谱分析,详细地研究了探针与离子形成的配合物性质。在不同的介质中,探针不仅同时表现出对金属阳离子Zn²⁺和对阴离子F^-的识别,而且吸收和发射波长均有显著的差异：1-Zn²⁺配合物的最大吸收波长为360 nm,而1-F^-配合物为400 nm;1-Zn²⁺配合物的荧光激发和发射波长分别为360和454 nm,而1-F^-配合物分别为400和475 nm。此外,探针1还能应用于活体PC3细胞中Zn²⁺的荧光成像。     

Visualization observation of cells growth in low-density polyethylene foaming processes

Low-density polyethylene (LDPE)/p, p-oxybis (benzenesulfonylhydrazide) (OBSH) system was carried out to investigate the cell growth during foaming process with a visualization apparatus at a constant temperature. The results showed that the cells growth of LDPE foams follows the Logistic function with a higher correlation coefficient of 0.96738. Here, a method was adopted to establish the relationships between cell growth and foaming process with first and second derivatives of cell mean diameter vs. time, which reflected the cells growth rate and driving force during cell growth, respectively. Moreover, we elucidated the interactions of cells growth at less-foamed, better-foamed and over-foamed stages were asymmetric during foaming process, which resulted from the greater cells deformation. This revealed the method in describing cells growth provided a visual comprehension of the mechanisms for foaming process.     

二维晶格模型研究皂荚素二元体系形成混合胶束的分子交换能

利用二维晶格模型和相分离模型，由正规溶液理论首先推导出了二元表面活性剂形成混合胶束的分子交换能(ε~m)与混合胶束中组分A的超额化学位(μ^E~m~,~A)的关系式：μ^E~m~,~A=ε~m~gN~0(1-x~A)^2。然后导出ε~m与混合胶束中表面活性剂分子间的相互作用参数(β~m)的关系：ε~m=gRTβ~m/N~0。用该结论对皂荚素(GS)与十二烷基磺酸钠(C~1~2H~2~5SO~3Na)、十二烷基聚氧乙烯醚硫酸钠[C~1~2H~2~5(OC~2H~4)~3SO~4Na]、全氟辛酸钠(C~7F~1~5CO~2Na)、十二烷基脂肪醇聚氧乙烯(9)醚[C~1~2H~2~5(EO)~9OH]、辛基酚聚氧乙烯(10)醚[C~8H~1~7Ph(EO)~1~0OH]及十六烷基三甲基溴化铵(C~1~6H~3~3NMe~3Br)等表面活性剂混合体系的研究和计算表明：含皂荚素的二元表面活性剂形成的混合胶束，ε~m均为负值，表面活性剂分子间具有较强的协同效应。     

Lu掺杂AlN的电子结构和光学性质的第一性原理研究

为了探索 AlN在光电器件中的潜在应用,采用第一性原理计算了不同 Lu掺杂浓度(以原子分数 x表示)的 AlN(Al_1-xLu_xN)的电子结构和光学性质。研究结果表明,Al_1-xLu_xN的超胞体积随着Lu掺杂浓度的增加而增加,而带隙则相反。Al_1-xLu_xN的静态介电常数在低能区随掺杂浓度的提高而提高,随后逐渐趋向一致。随着Lu掺杂浓度的增加,反射率和吸收系数的峰值强度降低,峰值向较低能量方向移动。Al_1-xLu_xN的能量损失光谱表现出明显的等离子体振荡特性,且峰值低于本征AlN。Al_1-xLu_xN的光电导率在低能区随能量的增加而急剧增加。     

电沉积法制备镍与镧、铈的非晶态合金及其晶化动力学

稀土元素(La、Ce)的标准还原电位较负,在水溶液中很难电沉积出来.通过选用合适的络合剂和工艺条件制备出Ni-La、Ni-La-P、Ni-Ce、Ni-Ce-P以及Ni-P合金,除Ni-Ce外,均具有非晶态的结构;并对这几种非晶态合金进行了晶化动力学研究,用差示扫描量热法(DSC)测定了它们的晶化活化能以及所遵守的动力学方程.     

Development a multiplex panel of AISNPs,multi-allelic InDels,microhaplotypes, and Y-SNP/InDel loci for multiple forensic purposes via the NGS

Recently, next generation sequencing has shown the promising application value in forensic research. In this study, we constructed a multiplex amplification system of different molecular genetic markers based on the previous selected ancestry informative single nucleotide polymorphisms (SNPs), multi-allelic insertion/deletion (InDel) polymorphisms, microhaplotypes, and Y-chromosomal SNP/InDel loci, and evaluated forensic efficiencies of the system in Chinese Shaanxi Han, Chinese Hui, and Chinese Mongolian groups via the next generation sequencing platform. Ancestry information analyses of Shaanxi Han, Hui, and Mongolian groups revealed that most Mongolian individuals could be differentiated from Shaanxi Hans and Huis based on the selected ancestry informative SNPs. Multi-allelic InDels and microhaplotypes showed the multiple allele variations and possessed relatively high genetic polymorphisms in these three groups, indicating these loci could provide higher forensic efficiencies for individual identification and paternity testing. Based on Y-chromosomal SNPs, different haplogroup distributions were observed among Shaanxi Han, Hui, and Mongolian groups. In conclusion, the self-developed system could be used to simultaneously carry out the individual identification, paternity analysis, mixture deconvolution, forensic ancestry information analysis, and Y-chromosomal haplogroup inference, which could provide more valuable investigative clues in forensic practices.     

Chemical profiling and quantification of multiple components in Jin-Gu-Lian capsule using a multivariate data processing approach based on UHPLC-Orbitrap Exploris 240 MS and UHPLC-MS/MS

The Jin-Gu-Lian capsule, a Chinese Miao herbal compound, is widely used to treat rheumatoid arthritis. In this study, a rapid, selective, and sensitive UHPLC-Orbitrap Exploris 240 MS method was developed to analyze the chemical composition of Jin-Gu-Lian capsules. A total of 88 compounds were identified, including 23 flavonoids, 23 organic acids, 14 phenylpropanoids, 12 phenols, eight alkaloids, four terpenes, three quinones, and one ketone. Among these, 21 compounds were clearly detected based on a comparison with reference standards and selected as quality control markers. Thereafter, these compounds were simultaneously determined in the Jin-Gu-Lian capsules. The established method was successfully validated and applied for the simultaneous determination of 21 biologically active compounds in Jin-Gu-Lian capsules of 27 sample batches. Quantitative data of the analytes were analyzed using multivariate statistical analysis to determine the quality of the Jin-Gu-Lian capsules. Four compounds (JGLC6 [salidroside], JGLC8 [chlorogenic acid], JGLC12 [liriodendrin], JGLC19 [quercetin]) were identified as chemical markers for quality control of Jin-Gu-Lian capsules. Altogether, the established method was validated as a novel and efficient tool, that can be used for rapid analysis of Jin-Gu-Lian capsules. Accordingly, this study serves as a reference for scientific research on traditional Chinese and ethnic medicine.     

吲唑衍生物及其生物活性研究进展

吲唑衍生物具有抗肿瘤、抗菌、抗炎及治疗骨质疏松等多种生物活性,因此,在药物化学领域受到广泛的关注,具有巨大研究前景及价值。本文总结归纳了近几年来与吲唑衍生物相关的文献,对单取代、双取代及多取代吲唑衍生物及其生物活性的最新研究进展进行了综述,希望能为开发高效低毒的吲唑衍生物提供一定的理论基础。