Comparison study of several numerical integration schemes used in calculations of density functional theory

Several numerical integration schemes for the evaluation of matrix elements in density functional theory calculations have been studied and compared by computational practice. The best scheme was found to be the combination of the atomic partition function proposed by Becke with the scaled generalized Gauss-Laguerre quadrature formula for radial integration suggested by Yang, which achieve the highest convergence rate to the numerical integration. With the same number of integration points, the accuracy of the calculated results by this scheme is higher by 1 to 2 orders of magnitudes than that by other schemes. The reason for achieving higher accuracy by this scheme has been proposed preliminarily.     

Si(CH3)3Cl修饰的HZSM-5酸性及正己烷芳构化的催化性能研究

随着芳烃需求量的增加,低分子烃的芳构化受到广泛重视.由于HZSM-5的独特骨架结构及酸性,使其对低分子烃有良好芳构化性能~[1～3],但研究工作大多放在HZSM-5本身的硅铝比调变及加入某些金属(如Ga,Zn)来提高其芳构化性能~[4～7],而以非金属对其进行改性处理则很少见.本文以Si(CH_3)_3CI对HZSM-5进行CVD处理,并对其酸性及对正已烷芳构化能力进行了考察,研究了催化剂的结焦情况.     

湿化学法制备硅纳米线阵列及其光电化学产氢性能分析

为了探究不同方法条件下制备的硅纳米线阵列电极产氢性能异同,文中分别采用了两步金属辅助催化无电刻蚀法、一步金属辅助催化无电刻蚀法以及阳极氧化法来制备硅纳米线阵列用作为光电分解水电池光阴极材料.通过FESEM、XRD和UV-Vis-IRDRS等手段对实验样品的形貌、晶型、减反性表征,发现相比于其他2种方法所得硅纳米线样品,两步金属辅助催化无电刻蚀法制备的硅纳米线结构晶型保持更好,表面缺陷更少.光电化学测试表明两步金属辅助催化无电刻蚀法制备的硅纳米线光电化学性能表现最优,其光电流密度值是一步法的4倍,阳极氧化法的40倍;转移电荷电阻仅是一步法制备的硅纳米线阵列阻值的1/3,阳极氧化法制备的1/1000.     

湿化学法制备硅纳米线阵列及其光电化学产氢性能分析

为了探究不同方法条件下制备的硅纳米线阵列电极产氢性能异同,文中分别采用了两步金属辅助催化无电刻蚀法、一步金属辅助催化无电刻蚀法以及阳极氧化法来制备硅纳米线阵列用作为光电分解水电池光阴极材料。通过FESEM、XRD和UVVis-IR DRS等手段对实验样品的形貌、晶型、减反性表征,发现相比于其他2种方法所得硅纳米线样品,两步金属辅助催化无电刻蚀法制备的硅纳米线结构晶型保持更好,表面缺陷更少。光电化学测试表明两步金属辅助催化无电刻蚀法制备的硅纳米线光电化学性能表现最优,其光电流密度值是一步法的4倍,阳极氧化法的40倍;转移电荷电阻仅是一步法制备的硅纳米线阵列阻值的1/3,阳极氧化法制备的1/1 000。     

正交设计-偏最小二乘光度法同时测定磷和硅

采用正交设计法研究了磷、硅在酸性钼酸铵和混合还原剂中的最佳显色条件,建立了多波长紫外可见光度法同时测定磷、硅的方法。试验中采集多个波长下的吸光度构成校正矩阵,用偏最小二乘法对该矩阵进行解析,得出了校正模型。该模型与通过主成分回归法得到的模型相比,预测结果更准确。     

Problems encountered with the routine application of HPLC to the analysis of carbamate pesticides

Summary This paper describes the determination of all carbamate pesticides mentioned in the Austrian regulations for pesticides and of some other carbamates commonly used in the EEC. Clean-up procedure is carried out by ethyl acetate extraction. Purification is by a liquid-liquid extraction step followed by use of a florisil column. Final detection of the carbamates is carried out by HPLC on silica gel and GLC respectively The method works well for all carbamates under consideration. Only benzimidazolamine-2, the decomposition product of benomyl and carbendazime cannot be determined by the method described. Therefore determination of benomyl, carbendazime and benzimidazolamine-2 was by hydrolysis of benomyl and carbendazime to benzimidazolamine-2, which is then determined by reversed-phase chromatography.     

铂非均匀掺杂二氧化钛薄膜的光催化性能

采用溶胶-凝胶法制备了铂非均匀掺杂的二氧化钛薄膜, 并用UV-vis分光光度计及电化学工作站表征了薄膜的光吸收性能和光电化学行为, 通过对甲基橙的光催化降解动力学来表征催化剂的光催化活性. 结果表明 Pt非均匀掺杂可以明显增强二氧化钛的光催化活性, 而均匀掺杂的效果较差; Pt非均匀掺杂的最佳量为0.3 mol%. 催化剂薄膜的电化学行为显示: Pt非均匀掺杂二氧化钛薄膜的开路电压高, 交流阻抗小. 并从半导体的PN结原理探讨了Pt非均匀掺杂二氧化钛的催化活性机理.     

New designer drug 2,5-dimethoxy-4-ethylthio-beta-phenethylamine (2C-T-2): studies on its metabolism and toxicological detection in rat urine using gas chromatography/mass spectrometry

Studies are described on the metabolism and the toxicological analysis of the phenethylamine-derived designer drug 2,5-dimethoxy-4-ethylthio-beta-phenethylamine (2C-T-2) in rat urine using gas chromatography/mass spectrometry (GC/MS) after enzymatic cleavage of conjugates, liquid-liquid extraction and derivatization. The structures of 14 metabolites were assigned tentatively by detailed interpretation of their mass spectra. Identification of these metabolites indicated that 2C-T-2 was metabolized by sulfoxidation followed by N-acetylation and either hydroxylation of the S-ethyl side chain or demethylation of one methoxy group, O-demethylation of the parent compound followed by N-acetylation and sulfoxidation, deamination followed by reduction to the corresponding alcohol followed by partial glucuronidation and/or sulfation or by oxidation to the corresponding acid followed either by partial glucuronidation or by degradation to the corresponding benzoic acid derivative followed by partial glucuronidation. Furthermore, 2C-T-2 was metabolized by N-acetylation of the parent compound followed either by O-demethylation and sulfoxidation or by S-dealkylation, S-methylation and sulfoxidation. The authors' systematic toxicological analysis (STA) procedure using full-scan GC/MS after acid hydrolysis, liquid-liquid extraction microwave-assisted acetylation allowed the detection of an intake of a dose of 2C-T-2 in rat urine, which corresponds to a common drug users' dose. Assuming similar metabolism, the described STA procedure should be suitable for proof of an intake of 2C-T-2 in human urine.     

方波伏安法评估聚苯胺膜修饰电极的电荷传输速度

研究导电聚合物的电荷传输机制与速度对于其在应用方面的研究极为重要［‘］．例如在电池的研究中，充放电的速度决定于导电聚合物的电荷传输速度；在电致变色器件的研究中，响应时间也是决定于导电聚合物在氧化还原态间的变化速度，即电荷传输速度．显然较低的电荷传输速度不利于器件的实用化，因此人们必须找到一种能够迅速准确评价电荷传输速度的方法，由于导电聚合物是一个特殊的体系，用一般的电化学方法对其电荷传输速度进行测定时常常遇到这样或那样的问题［‘j．一般说来，导电聚合物的氧化还原过程中均伴随着抗衡离子的运动．体系…     

TiO2纳米粒子膜表面性质的研究

ＴｉＯ_２纳米粒子膜在光催化降解大气和水中的污染物［１］、光电转换［２］、光致变色［３］等方面有广阔的应用前景,近年来受到了科学界的高度重视．研究表明,膜的表面性质对如上应用有着重要影响．本文采用等离子体化学气相沉积法（ＰＥＣＶＤ法）［４］制备了ＴｉＯ２的纳米粒子膜,分别采用ＴｉＣｌ４等离子体或Ｏ２等离子体处理膜表面,获得两种不同表面性质的ＴｉＯ２纳米粒子膜;并利用表面光电压谱（ＳＰＳ）和电场诱导表面光电压谱（ＥＦＩＳＰＳ）技术对膜的表面性质进行具体分析,探讨了其在光催化领域的可能应用．１实验部…     

Fermented Oyster Extract Attenuated Dexamethasone-Induced Muscle Atrophy by Decreasing Oxidative Stress

It is well known that oxidative stress induces muscle atrophy, which decreases with the activation of Nrf2/HO-1. Fermented oyster extracts (FO), rich in γ-aminobutyric acid (GABA) and lactate, have shown antioxidative effects. We evaluated whether FO decreased oxidative stress by upregulating Nrf2/HO-1 and whether it decreased NF-κB, leading to decreased IL-6 and TNF-α. Decreased oxidative stress led to the downregulation of Cbl-b ubiquitin ligase, which increased IGF-1 and decreased FoxO3, atrogin1, and Murf1, and eventually decreased muscle atrophy in dexamethasone (Dexa)-induced muscle atrophy animal model. For four weeks, mice were orally administered with FO, GABA, lactate, or GABA+Lactate, and then Dexa was subcutaneously injected for ten days. During Dexa injection period, FO, GABA, lactate, or GABA+Lactate were also administered, and grip strength test and muscle harvesting were performed on the day of the last Dexa injection. We compared the attenuation effect of FO with GABA, lactate, and GABA+lactate treatment. Nrf2 and HO-1 expressions were increased by Dexa but decreased by FO; SOD activity and glutathione levels were decreased by Dexa but increased by FO; NADPH oxidase activity was increased by Dexa but decreased by FO; NF-κB, IL-6, and TNF-α activities were increased by Dexa were decreased by FO; Cbl-b expression was increased by Dexa but restored by FO; IGF-1 expression was decreased by Dexa but increased by FO; FoxO3, Atrogin-1, and MuRF1 expressions were increased by Dexa but decreased by FO. The gastrocnemius thickness and weight were decreased by Dexa but increased by FO. The cross-sectional area of muscle fiber and grip strength were decreased by Dexa but increased by FO. In conclusion, FO decreased Dexa-induced oxidative stress through the upregulation of Nrf2/HO-1. Decreased oxidative stress led to decreased Cbl-b, FoxO3, atrogin1, and MuRF1, which attenuated muscle atrophy.     

聚丙烯酰胺的改性和表征

用甲醛(F)和二氰二胺(D)改性聚丙烯酸胺(PAm),制得新型阳离子聚电解质PAm·MG,对PAm·MG的合成和表征进行了研究。合成反应通过两步进行,先使PAm与F反应,生成羟甲基化产物PAm·M,然后在酸性条件下使PAm·M与D反应,制得PAm·MG.控制F用量,得到不同取代度的PAm·M.和PAm·MG。PAm·MG在水溶液中能与阴离子聚电解质形成复合物沉淀证明PAm·MG带有阳离子基团。元素分析及电位、浊度滴定结果表明PAm·M中的羟基完全与D发生了反应。SALLS测得的M_w证实了PAm在改性过程中分子链未发生降解。     

Role of binding entropy in the refinement of protein-ligand docking predictions: analysis based on the use of 11 scoring functions

We present results of testing the ability of eleven popular scoring functions to predict native docked positions using a recently developed method (Ruvinsky and Kozintsev, J Comput Chem 2005, 26, 1089) for estimation the entropy contributions of relative motions to protein-ligand binding affinity. The method is based on the integration of the configurational integral over clusters obtained from multiple docked positions. We use a test set of 100 PDB protein-ligand complexes and ensembles of 101 docked positions generated by (Wang et al. J Med Chem 2003, 46, 2287) for each ligand in the test set. To test the suggested method we compared the averaged root-mean square deviations (RMSD) of the top-scored ligand docked positions, accounting and not accounting for entropy contributions, relative to the experimentally determined positions. We demonstrate that the method increases docking accuracy by 10-21% when used in conjunction with the AutoDock scoring function, by 2-25% with G-Score, by 7-41% with D-Score, by 0-8% with LigScore, by 1-6% with PLP, by 0-12% with LUDI, by 2-8% with F-Score, by 7-29% with ChemScore, by 0-9% with X-Score, by 2-19% with PMF, and by 1-7% with DrugScore. We also compared the performance of the suggested method with the method based on ranking by cluster occupancy only. We analyze how the choice of a clustering-RMSD and a low bound of dense clusters impacts on docking accuracy of the scoring methods. We derive optimal intervals of the clustering-RMSD for 11 scoring functions.     

系列甘露糖醛酸寡糖的制备与鉴定

用酸降解法制备了系列甘露糖醛酸寡糖(聚合度2～8),并分析测定了寡糖的结构. 褐藻胶经部分酸水解,于pH=2.85处分级获得聚甘露糖醛酸. 继续用酸降解法降解聚甘露糖醛酸,经凝胶柱层析分离纯化,获得系列甘露糖醛酸寡糖. 用荧光标记糖电泳(FACE)对寡糖进行了分析,并用电喷雾离子化质谱(ESI-MS)、 核磁共振波谱(NMR)及红外光谱(FTIR)进行了结构表征. 本研究用酸降解法制备饱和甘露糖醛酸寡糖,用凝胶柱层析法分离获得系列聚合度的寡糖,为褐藻胶大分子构效关系研究和药物的筛选与发现提供了重要的基础资料.     

镧对青菜生物量、植株氮磷钾含量及土壤酶活性的影响

利用盆栽试验,研究了镧对青菜生物量、植株氮磷钾含量及土壤酶活性的影响.结果表明,施用镧显著增加了青菜生物量,与对照相比地上部干重提高了5.49%～19.78%,根干重提高了13.51%～51.35%.在低浓度下,随镧浓度的升高,青菜茎叶和根的氮、磷、钾含量逐渐增加,到一定浓度后,随着镧浓度的继续升高,含量反而逐渐降低.镧施入土壤后对脲酶、酸性磷酸酶、转化酶活性表现出刺激作用并随浓度的升高而增强,而对过氧化氢酶活性有轻微的抑制作用,对脱氢酶活性有强烈的抑制作用.     

锰离子控制掺杂二氧化钛薄膜光催化活性增强的机理探讨

采用溶胶-凝胶法通过工艺控制制备了锰离子以不同形式掺杂TiO₂的光催化剂薄膜,并通过XPS和SEM对薄膜的结构进行表征.通过UV-Vis分光光度计及电化学工作站表征了薄膜的光吸收性能和光电化学性能,通过甲基橙溶液的光催化降解脱色率来表征催化剂薄膜的光催化活性.结果表明,以锰离子MT掺杂方式制备的TiO₂薄膜可明显增强TiO₂的光催化活性,而以MM掺杂方式制备的TiO₂薄膜反而降低了TiO₂的光催化活性;锰离子MT掺杂方式的最佳掺杂质量分数为0.8%.催化剂薄膜的电化学行为显示,薄膜具有p-n结的电容-电压特性,锰离子MT掺杂TiO₂薄膜的开路电位和瞬时光电流信号较强,说明其光生载流子易于生成并且分离效果较好.依据半导体的p-n结原理探讨了锰离子控制掺杂TiO₂的光催化活性机理.     

Mechanistic model of disproportionation of nitrogen monoxide on CaHY-type zeolite

Infrared spectra produced by adsorbing, by evacuating and by readsorbing NO on CaHY-type zeolite were examined. The absorption peaks were identified by comparing the spectra produced by adsorbing and by evacuating N₂O and NO₂. Based upon the experimental evidence, an eight-step mechanism was proposed for the behavior of NO on CaHY-type zeolite. A mechanistic model of the disproportionation reaction of NO was deduced from the variation of the spectra with time.     

Novel Synthetic Approach to Thiophosphinates Incorporating Different N-Heterocycles

Eight new cycloiminylidenamidothiophosphinates incorporating pyridine, pyrimidine, thiazole, and benzothiazole heterocycles were synthesized by phosphorylation of the quaternary iminium salts of the heterocycles by diphenylchlorophosphine followed by in situ sulfurization by elemental sulfur. Crystalline solid products were well characterized by elemental analysis and NMR spectroscopy.     

中波紫外线与化学致癌物诱导下HaCaT细胞的蛋白表达应答

对角质形成细胞HaCaT分别进行中波紫外线(UVB)照射、2,4-二硝基苯磺酸(DNBS)刺激及UVB+DNBS(UD)共同刺激, 利用二维荧光差异胶内凝胶电泳(2D DIGE)、DeCyder定量分析软件和HPLC-nESI-MS/MS分析技术, 对HaCaT细胞产生的差异表达蛋白进行了鉴定. 有65个蛋白质点发生了明显表达差异(P<0.05), 与UVB或DNBS单独处理细胞相比, 有41个蛋白点表现为UVB和DNBS的正协同效应, 13个蛋白点表现为负协同效应, 5个蛋白点与UVB单独处理相近, 6个蛋白点与DNBS单独处理相近. HPLC-nESI-MS/MS从65个差异表达蛋白质点中共鉴定出60种单一(Unique)蛋白. 采用生物信息学方法对这些鉴定蛋白所涉及的分子功能、参与的生物学过程及信号通路进行了系统分析. 实验得到了与紫外辐射和化学诱导损伤的直接相关蛋白, 有助于研究不同环境条件下皮肤癌的形成及皮肤疾病的有效防护与治疗.