三氮宾分子的磁性设计

采用量子化学ＧＡＵＳＳＩＡＮ９４ａｂｉｎｉｔｉｏＵＨＦ方法和ＳＴＯ－３Ｇ基组设计一系列三氮宾分子，讨论分子的几何结构和取代基对其磁性的影响，计算结果表明，这些分子都具有铁磁性并有高自旋基态，有效交换积分值随代基的变化而变化，其中一种具有较代的总能量和高的有效交换积分值的分子，可期望被合成。     

环境元素与健康

通过一些分析数据，说明了环境元素与健康的关系。     

The absolute sign of J coupling constants determined using the order matrix calculation

A novel methodology using the order matrix calculation to determine the absolute sign of spin-spin couplings based on the structure of organic compounds is presented. The sign of the residual dipolar coupling (RDC) depends on the sign of corresponding scalar spin-spin coupling constant and the sign of the RDC has a dramatic influence on the order matrix calculation. Therefore, the sign of the spin-spin coupling constant can be obtained by an order matrix calculation through the corresponding RDC. Six types of spin-spin coupling constants, including 2J(H,H), 1J(C,F), 2J(C,F), 3J(C,F), 2J(F,H) and 3J(F,H), were obtained simultaneously. Except for 3J(C,F) where the measured RDCs have very small magnitudes, the signs were determined unambiguously.     

Two dimensional mapping of cancer cell extracts by liquid chromatography-capillary electrophoresis with ultraviolet absorbance detection

A two-dimensional liquid chromatography/capillary electrophoresis technique was developed for rapid and comprehensive mapping of cell extracts. The cell extracts were first separated by reversed-phase HPLC based on hydrophobicity. Fractions of the effluent from the HPLC system were collected into 96-well microtiter plates and dried under vacuum. The fractions were reconstituted with deionized water, separated by capillary array electrophoresis based on charge-to-size ratio, and detected by UV absorption at 214 nm. Prior to analysis by multiplexed capillary electrophoresis, the reconstituted fractions were concentrated on-column using large volume sample stacking with polarity switching. In this way, high-resolution analysis of even the minor components in the complicated mixture was possible.     

动力学光度法测定痕量钴的研究

催化动力学法测定微量Co~(2+)已有报道,方法灵敏度一般在10~(-6)～10~(-10g)数量级,多数用于测定水、血液和高纯物质中的Co~(2+),而测定中药內的痕量CO~(2+)还未见报道。本文研究了氨水介质中Co~(2+)催化二苯偶氮酰肼氧化褪色的新指示反应及动力学条     

CTMAB胶束体系中反离子缔合度的测定

对十六烷基三甲基淡化按（CTMAB）水胶束体系，不同方法测得其反离子缔合度产值不同【‘－＼且很高于由股团电化学理论所得q值0．67问．本文以离子选择性电极法测定CTMAB水胶束体系中反离子缩合度（仁0．65），并研究了外加盐和乙醇的影响·1实验部分1．工试剂和仪器十六烷基三甲基漠化技（CP）在无水乙醇中重结晶两次，纯化物经帕环法测其表面张力在CMC附近无最低声、·淡化钾（AR），水为。次蒸馏水，PXJIC型离子计，302型PB，电极（响应范围为PB，＝1．6～3．3，响应时间为5分钟）222型甘汞电极·1．2实验方法在CMCV／de的稀…     

Theoretical Study on the Isomerization Mechanism of Enol Ester from 2-Acyl-1, 3-cyclohexanediones

The present paper employed density function theory to investigate two reaction pathways for isomerization of enol ester proposed by Yang(path a) and the present authors(path a), respectively. The base catalytic effects of solvent triethylamine on these two reactions were also evaluated. It is demonstrated that path B is more preferable than path a due to low barrier height for the rate-determining step.     

Copper(II), nickel(II) and cobalt(II) complexes of 4-cyanobenzonic acid: syntheses, crystal structures and spectral properties

Three new metal complexes, Cu(4-Hcba)₂(4-cba)₂(Py)₂ (4-Hcba=4-cyanobenzoic acid) 1 and M[H(4-cba)₂]₂(Py)₂ (M=Ni 2, Co 3), have been prepared by the treatment of 4-Hcba with the respective metal nitrate M(NO₃)₂ (M=Cu, Ni, Co) in the presence of pyridine (Py). Single-crystal X-ray diffraction analyses (3 is isostructural to 2) show that the obtained complexes are of isolated mononuclear and the metal atoms have distorted octahedral coordination environment. Two different types of intramolecular hydrogen bonds exist: asymmetrical O–HO for 1 and symmetrical OHO for 2 and 3. The crystal packing between the molecular complexes is controlled mainly by T-shaped C–Hπ interactions between pyridine and phenyl rings. Preliminary discussions on IR, UV–VIS and fluorescent spectra have also been carried out.     

Synthesis, reaction and structure of a series of chromium(III) complexes containing oxalate ligand

A series of chromium(III) complexes [Cr(bipy)(HC₂O₄)₂]Cl·3H₂O (1), [Cr(phen)(HC₂O₄)₂]Cl·3H₂O (2), [Cr(phen)₂(C₂O₄)]ClO₄ (3), [Cr₂(bipy)₄(C₂O₄)](SO₄)·(bipy)_0.5·H₂O (4) and [Mn(phen)₂(H₂O)₂]₂[Cr(phen)(C₂O₄)₂]₃ClO₄·14H₂O (5) were synthesized (bipy=4,4′-bipyridine, phen=1,10-phenanthroline), while the crystal structures of 1 and 3–5 have been determined by X-ray analysis. 1 and 3 are mononuclear complexes, 4 contains binuclear chromium(III) ions and 5 is a 3D supromolecule formed by complicated hydrogen bonding. 1–3 are potential molecular bricks of chromium(III) building blocks for synthesis heterometallic complexes. When we use these molecular bricks as ligands to react with other metal salts, unexpected complexes 4 and 5 are isolated in water solution. The synthesis conditions and reaction results are also discussed.     

Density functionals for inorganometallic and organometallic chemistry

We present a database of 21 bond dissociation energies for breaking metal-ligand bonds. The molecules in the metal-ligand bond energy database are AgH, CoH, CoO+, CoOH+, CrCH3+, CuOH2+, FeH, Fe(CO)5, FeO, FeS, LiCl, LiO, MgO, MnCH3NiCH2+, Ni(CO)4, RhC, VCO+, VO, and VS. We have also created databases of metal-ligand bond lengths and atomic ionization potentials. The molecules used for bond lengths are AgH, BeO, CoH, CoO+, FeH, FeO, FeS, LiCl, LiO, MgO, RhC, VO, and VS and the ionization potentials are for the following atoms: C, Co, Cr, Cu, Ni, O, and V. The data were chosen based on their diversity and expected reliability, and they are used along with three previously developed databases (transition metal dimer bond energies and bond lengths and main-group molecular atomization energies) for assessing the accuracy of several kinds of density functionals. In particular, we report tests for 42 previously defined functionals: 2 local spin density approximation (LSDA) functionals, 14 generalized gradient approximation (GGA) methods, 13 hybrid GGA methods, 7 meta GGA methods, and 8 hybrid meta GGA methods. In addition to these functionals, we also examine the effectiveness of scaling the correlation energy by testing 13 functionals with scaled or no gradient-corrected correlation energy, and we find that functionals of this kind are more accurate for metal-metal and metal-ligand bonds than any of the functionals already in the literature. We also present a readjusted GGA and a hybrid GGA with parameters adjusted for metals. When we consider these 57 functionals for metal-ligand and metal-metal bond energies simultaneously with main-group atomization energies, atomic ionization potentials, and bond lengths we find that the most accurate functional is G96LYP, followed closely by MPWLYP1M (new in this article), XLYP, BLYP, and MOHLYP (also new in this article). Four of these five functionals have no Hartree-Fock exchange, and the other has only 5%. As a byproduct of this work we introduce a convenient diagnostic, called the B1 diagnostic, for ascertaining the multireference character in a bond.