LaMSb_2O_7:R~(3+)(M=Li,Na,K;R=Eu,Dy,Bi)的合成、组成、结构及发光性能

研究了激活离子Eu~(3+),Dy~(3+)和Bi~(3+)在具有相同结构的LaMSb_2O_7(M=Li,Na,K)中的发光特性,得到了发白光的磷光体LaNaSb_2O_7:Dy~(3+)。讨论了化学键的共价程度对Eu~(3+)和Dy~(3+)超灵敏跃迁强度比的影响。发现当用281nm激发试样时,Bi~(3+)对Eu~(3+)具有敏化作用并解释了其原因。

稀土元素对二次锂电池中Li-Al负极材料电化学行为的影响

用纯锂作二次锂电池的负板材料有形成锂枝晶和钝化膜的缺点,采用在铝或其他金属如钙、镁、锡上欠电位沉积锂形成锂合金代替纯锂,对克服上述缺点有一定效果.本文报导了以稀土铝合金代替纯铝作基底欠电位沉积锂,在LiClO_4/碳酸丙烯酯电解液中稀土对改进电极性能有有益的影响.

稀土-锂双金属配合物的研究——(LaCl)DME(μ_2-Cl)_5(μ_3-Cl)(La·DME)Li(THF)_2的合成及其晶体结构

在稀土有机化学中,[Cp_2LnCl]_2和[Cp_2LnCl_2LiL_2][Cp为取代或未取代的环戊二烯基,Ln为稀土离子(III),L为Lewis碱]型化合物是重要的中间物。对含锂烷基、芳基或烯丙基稀土化合物的研究也有着重要的意义。这类分子中含有型桥键结构。由于这类化合物难于结晶及其不稳定性,故很难进行系统的研究。 Rossmanith首先发现了NdCl_3-LiCl-THF溶液的存在。李毅用这一溶液很方便地合成了几个轻稀土-锂双金属有机化合物。但是,在稀土配位化学中,对氯化稀土-氯化锂配合物的研究还很少,对LnCl_3LiCl-THF溶液的认识也有待深化。本文合成了组成为(LaCl)DME(μ_2-Cl)_5(μ_3-Cl)(La·DME)Li(THF)_2的新型桥式链状配合物,并测定了晶体结构。这种类型的稀土双金属配合物尚未见报道。

Boundary Element Method (BEM) Analysis for Galvanic Corrosion of Hot Dip Galvanized Steel Immersed in Seawater

A numerical analysis of galvanic corrosion of hot-dip galvanized steel immersed in seawater was presented. The analysis was based on the boundary element methods (BEMs) coupled with Newton-Raphson iterative technique to treat the nonlinear boundary conditions, which were determined by the experimental polarization curves. Results showed that galvanic current density concentrates on the boundary of steel substrate and zinc coating, and the sacrificial protection of zinc coating to steel substrate results in overprotection of steel cathode. Not only oxygen reduction but also hydrogen reduction could occur as cathode reactions, which probably led up to the adsorption and absorption of hydrogen atoms. Flat galvanized steel tensile sample shows a brittle behavior similar to hydrogen embrittlement according to the SSRT (show strain rate test) in seawater.

2-(Benzotriazol-1-yl)-2-(alpha-hydroxybenzyl)-N-phenylthioacrylamide

In the title compound, C21H16N4OS, the dihedral angles between the planes of the benzotriazole and N-phenyl rings and the plane of the atoms that link these two rings are 79.56 (6) and 59.02 (5) degrees, respectively, while that between the two benzene rings is 64.12 (6) degrees. There are some inter- and intramolecular interactions in the crystal structure.

Aminic nitrogen-bearing polydentate Schiff base compounds as corrosion inhibitors for iron in acidic media: A quantum chemical calculation

Quantum chemical calculations based on DFT method were performed on three polydentate Schiff base compounds (PSCs) used as corrosion inhibitors for iron in acid media to determine the relationship between the molecular structure of PSC and inhibition efficiency. The structural parameters, such as the frontier molecular orbital energy HOMO (highest occupied molecular orbital) and LUMO (lowest unoccupied molecular orbital), the charge distribution of the studied inhibitors, the absolute electronegativity (chi) values, and the fraction of electrons (Delta N) transfer from inhibitors to iron, were also calculated and correlated with inhibition efficiencies. The results showed that the inhibition efficiency of PSCs increased with the increase in E-HOMO and decrease in E-LUMO-E-HOMO; and the areas containing N atoms are most possible sites for bonding the metal iron surface by donating electrons to the metal. (C) 2007 Elsevier Ltd. All rights reserved.

Nicotinic acid as a nontoxic corrosion inhibitor for hot dipped Zn and Zn-Al alloy coatings on steels in diluted hydrochloric acid

The inhibition effect of nicotinic acid for corrosion of hot dipped Zn and Zn-Al alloy coatings in diluted hydrochloric acid was investigated using quantum chemistry analysis, weight loss test, electrochemical measurement, and scanning electronic microscope (SEM) analysis. Quantum chemistry calculation results showed that nicotinic acid possessed planar structure with a number of active centers, and the populations of the Mulliken charge, the highest occupied molecular orbital (HOMO), and the lowest unoccupied molecular orbital (LUMO) were found mainly focused around oxygen and nitrogen atoms, and the cyclic of the benzene as well. The results of weight loss test and electrochemical measurement indicated that inhibition efficiency (IE%) increased with inhibitor concentration, and the highest inhibition efficiency was up to 96.7%. The corrosion inhibition of these coatings was discussed in terms of blocking the electrode reaction by adsorption of the molecules at the active centers on the electrode surface. It was found that the adsorption of nicotinic acid on coating surface followed Langmuir adsorption isotherm with single molecular layer, and nicotinic acid adsorbed on the coating surface probably by chemisorption. Nicotinic acid, therefore, can act as a good nontoxic corrosion inhibitor for hot dipped Zn and Zn-Al alloy coatings in diluted hydrochloric acid solution. (c) 2007 Elsevier Ltd. All rights reserved.

cis-Dichloridobis(1,10-phenanthroline-kappa N-2,N ')-cadmium(II) hemihydrate

The title compound, [ CdCl2( C12H8N2)(2)]center dot 0.5H(2)O, crystallizes with two independent complex molecules and one water molecule in the asymmetric unit. The Cd atoms in both independent complexes display a distorted octahedral coordination geometry formed by four N atoms from two phenanthroline ligands and two Cl atoms. In the crystal structure, pi-pi stacking interactions link complexes in two symmetry- independent ladders parallel to the c axis. Intermolecular O-H center dot center dot center dot Cl hydrogen bonds stabilize the crystal packing.

Triaqua(benzene-1,2-dicarboxylato-kO)-(1,10-phenanthroline-k(2)N,N ')zinc(II) monohydrate

The structure of the title compound, [Zn(C8H4O4)(C12H8N2)-(H2O)(3)]center dot H2O, displays a distorted octahedral coordination geometry, with two N atoms from the bidentate phenanthroline ligand, three O atoms from three meridional H2O molecules and one O atom from the monodentate phthalate ion.

Diisothiocyanatobis(1-vinyl-1H-imidazole-kappa N-3)-copper(II)

In the title compound, [Cu(NCS)(2)(C5H6N2)(2)], each Cu atom is coordinated by two N atoms from two Eim (Eim = 1-vinyl-1H-imidazole) ligands and two N atoms from two isothiocyanate groups. The Cu atom adopts a square-planar geometry. The mean Cu-N(Eim) and Cu-N(NCS) distances are 1.960 (6) and 1.993 (6) angstrom, respectively.

HPLC-APCI-MS determination of free fatty acids in Tibet folk medicine Lomatogonium rotatum with fluorescence detection and mass spectrometric identification

A simple and sensitive method for the determination of free fatty acids (FFAs) using acridone-9-ethyl-p-toluenesulfonate (AETS) as a fluorescence derivatization reagent by high performance liquid chromatography (HPLC) has been developed. Free fatty acid derivatives were separated on an Eclipse XDB-C-8 column with a good baseline resolution and detected with the fluorescence of which excitation and emission wavelengths of derivatives were set at lambda(ex) 404 and lambda(em) 440 nm, respectively. Identification of 19 fatty acid derivatives was carried out by online post-column mass spectrometry with an atmospheric pressure chemical ionization (APCI) source under positive-ion detection mode. Nineteen FFAs from the extract of Lomatogonium rotatum are sensitively determined. The results indicate that the plant Lomatogonium rotatum is enriched with an abundance of FFAs and FFAs of higher contents, which mainly focus on even carbon atoms, C-14, C-16, and C-18. The validation of the method including linearity, repeatability, and detection limits was examined. Most linear correlation coefficients for fatty acid derivatives are > 0.9989, and detection limits (at signal-to-noise of 3: 1) are 12.3-43.7 fmol. The relative standard deviations (RSDs) of the peak areas and retention times for 19 FFAs standards are < 2.24% and 0.45%, respectively. The established method is rapid and reproducible for the separation determination of FFAs from the extract of Lomatogonium rotatum with satisfactory results.

湖泊沉积物碳氧同位素和介形虫Li/Ca比值与古环境重建

了解过去是认识现在和预测未来的基础。晚全新世是PAGES研究的目标时段之一。寻找和解译最近2000年连续、高分辨率自然记录是古气候研究的热点与难点。本项研究有针对性地选择程海、草海和青海湖开展湖泊沉积物环境记录的精细研究，结合14C、210Pb和137Cs定年，系统探讨了碳酸盐碳氧同位素、纤维素碳氧同位素、有机质碳同位素以及介形虫壳体Li/Ca比值指标的古环境指示意义。 通过研究，本论文取得了如下成果和新的认识： 1. 建立了一套有效的四阶段湖泊沉积物有机质纤维素提取方法（5%NaOH碱洗、5%HCl酸洗、亚氯酸钠和冰醋酸混合溶液漂白以及17.5%NaOH碱洗），红外光谱鉴定提取物为纯的α-纤维素，表明该实验方法是可行的，为今后广泛开展湖泊沉积物纤维素稳定同位素研究打下了坚实基础。 2. 多指标综合辨识了程海和草海沉积物碳酸盐主要是自生碳酸盐。程海和草海沉积物有机质C/N比值结合有机质碳同位素结果表明两湖的有机质分别源于水生植物藻类和大型水草。程海和草海沉积物碳酸盐含量主要反映了湖区温度的变化。 3. 程海、草海沉积物碳酸盐与青海湖沉积物介形虫壳体氧同位素组成均反映了湖区降水/蒸发比。降水/蒸发比大的湿润期，碳酸盐δ18O值小；降水/蒸发比小的干旱期，碳酸盐δ18O值大。程海沉积物碳酸盐碳同位素组成影响因素复杂，除了受大气与湖水之间的CO2交换影响外，还受水生植物光合/吸收作用的影响；草海沉积物碳酸盐碳同位素组成更大的变化范围，反映了湖区水生植物光合/吸收作用的影响，其异常的正值可能指示了湖区细菌参与有机质碳同位素分馏过程。 4. 利用草海沉积物有机质纤维素氧同位素定量恢复了湖水氧同位素组成变化。在此基础上，结合碳酸盐氧同位素组成初步恢复了草海地区过去500年来温度变化历史：草海地区在过去500年明显存在四个冷期，包括1550－1610年，1670－1730年，1770－1870年和1890－1920年冷期，其中前三个发生在传统意义上的现代小冰期时段。与其它记录研究结果的一致性表明纤维素氧同位素结合碳酸盐氧同位素是恢复古温度变化的最有效途径之一，同时也为现代小冰期在中国西南地区的存在提供了湖泊沉积学方面的证据。 5. 不同类型水生植物湖泊，湖泊沉积物有机质δ13C值对湖泊初级生产力变化的响应过程不同。大型水草为主的湖泊（草海），其沉积物有机质δ13C值随湖泊生产力的增大呈现增加的变化趋势；藻类为主的湖泊（程海），其沉积物有机质δ13C随湖泊生产力的增大呈现减小的变化趋势，藻类易降解是导致δ13C值随湖泊生产力的增大呈现减小变化趋势的主要原因。 6. 程海沉积物碳酸盐和有机质碳同位素组成的正相关变化以及草海沉积物碳酸盐和有机质碳同位素组成的负相关变化.表明湖泊生产力变化并不是导致碳酸盐和有机质碳同位素正相关变化的主要原因，湖泊水生植物类型以及湖泊大小均起着重要作用。湖泊沉积物碳酸盐与有机质之间的碳同位素分馏（△δ13C）是一种有效的湖泊生产力指示剂，即使是在有微生物参与有机质碳同位素分馏过程的草海，△δ13C值也反映了湖泊生产力的变化过程。 7. 青海湖沉积物单一种属介形虫壳体胖真星介（Eucypris inflata）Li/Ca比值与气象记录以及邻近地区都兰和祁连山树轮宽度指数恢复的古温度变化序列的对比研究揭示，介形虫壳体Li/Ca比值与温度呈明显的负相关变化（Li/Ca比值高，温度低；Li/Ca比值低，温度高），表明介形虫壳体Li/Ca比值是一种有效的古温度代用指标。 8. 青海湖沉积物单一种属介形虫壳体胖真星介（Eucypris inflata）Li/Ca比值、氧同位素与反映太阳活动的大气14C含量和冰芯10Be含量的一致性变化表明青海湖地区温度和降雨量的同步变化主要受太阳活动控制。