{[Gd(DMF)_3(DMSO)(H_2O)_3](μ-CN)[Fe(CN)_5]}·2H_2O的合成,结构表征和磁性(英文)

0IntroductionThefirstmolecule鄄basedmagnetswerereportedin1986[1].Duringthelasttwodecades,moreandmoreattentionhasbeenpaidtothesynthesisofmolecule鄄basedmagnets,especiallytoPrussianBlueanalogu鄄es[2].TheoldPrussianBlueanalogueshavebeenbroughtuptodateduetoth…     

新型含葡萄糖基手性Salen配体及其Mn3+、Fe3+、Co2+、Cu3+配合物的合成与表征

A novel chiral Salen ligand with a glucose moiety was synthesized from the condensation of 1,2:5,6-di-O-isopropylidene-3-O-methylene-[5-(3-tert-butyl-2-hydroxy benzaldehyde)]-α-D-glucofuranose with (1R,2R)-1,2-diaminocyclohexane. Several chiral complexes of Mn³⁺, Fe³⁺, Co²⁺ and Cu²⁺ were prepared from this ligand. Both the ligand and the complexes were characterized by elemental analysis, NMR, IR, MS, and UV-Vis.     

Characterization and Crystal Structure of a New Holmium(Ⅲ) Complex with the Macrocyclic Ligand Derived from 2,6-Dfformyl-4-methylphenol and Diethylenetriamine

The title compound (13,27-dimethyl-3,6,9,17,20,23-hexaazatricyclo-[23.3.1.111,15]-triaconta- 1 (29),2,9,11,13,15(30), 16,23,25,27-decaene-29,30-diol-N3,N6,N9,O29,O30)-bis(nitrato-O,O')-holmium(Ⅲ) nitrate hydrate has been prepared and characterized by elemental analysis, infrared spectra, and electrospray mass spectra. Its crystal and molecular structures were determined by X-ray diffraction methods. The crystal crystallizes in the monoclinic system, space group C2/c with a = 23.737(12), b = 14.237(7), c = 19.801(10) (A), β = 91.36(1)°, Mr = 831.57, V = 6690(6) (A)3, Z = 8,Dc = 1.651 g/cma, F(000) = 3344, R = 0.0482 and wR = 0.0923. The holmium ion is located in one of the compartments of the macrocyclic ligand and presents a distorted tricapped trigonal prismatic coordination geometry. The macrocycle is coordinated with two oxygen and three nitrogen atoms.Two nitrates are chelated in the opposite positions of the macrocycle, and the third one is ionic.     

若干中性配体对Mo—Fe—S簇合物自兜的影响

通过电子吸收光谱的变化研究了一些含N和含P中性配体对MoS_4~(2-)-nFeCl_2-DMF体系形成立方烷型Mo-Fe-S簇合物的可能影响。     

Protein-ligand binding free energy estimation using molecular mechanics and continuum electrostatics. Application to HIV-1 protease inhibitors

A method is proposed for the estimation of absolute binding free energy of interaction between proteins and ligands. Conformational sampling of the protein-ligand complex is performed by molecular dynamics (MD) in vacuo and the solvent effect is calculated a posteriori by solving the Poisson or the Poisson-Boltzmann equation for selected frames of the trajectory. The binding free energy is written as a linear combination of the buried surface upon complexation, SASbur, the electrostatic interaction energy between the ligand and the protein, Eelec, and the difference of the solvation free energies of the complex and the isolated ligand and protein, deltaGsolv. The method uses the buried surface upon complexation to account for the non-polar contribution to the binding free energy because it is less sensitive to the details of the structure than the van der Waals interaction energy. The parameters of the method are developed for a training set of 16 HIV-1 protease-inhibitor complexes of known 3D structure. A correlation coefficient of 0.91 was obtained with an unsigned mean error of 0.8 kcal/mol. When applied to a set of 25 HIV-1 protease-inhibitor complexes of unknown 3D structures, the method provides a satisfactory correlation between the calculated binding free energy and the experimental pIC5o without reparametrization.     

手性钯络合物催化下2-硝基环酮的不对称烯丙基化反应

在用氮杂冠醚改良的手性二茂铁膦与钯的络合物催化下, 2-硝基环酮可进行不对称烯丙基化反应. 讨论了配位基的形状, 反应物的构造, 碱的类型以及反应时间对反应速率和立体选择性的影响. 通过增加反应的空间位阻改进了反应的立体选择性 .     

苯二甲酰基桥联铁硫配合物［（μ－RS）Fe_2（CO）_6］_2（μ－OCC_6

通过由Ｆｅ３（ＣＯ）１２、ＲＳＨ和Ｅｔ３Ｎ所形成的［（μ－ＣＯ）（μ－ＲＳ）Ｆｅ２（ＣＯ）６］Ｅｔ３ＮＨ于室温下分别与对或间苯二甲酰氯的原位反应，首次合成６个结构新颖的苯二甲酰基桥联铁硫配合物［（μ－ＲＳ）·Ｆｅ２（ＣＯ）６］２（μ－ｐ－ＯＣＣ６Ｈ４ＣＯ－ｐ－μ）（Ｒ＝Ｅｔ，ｎ－Ｂｕ，ｔ－Ｂｕ）以及［（μ－ＲＳ）Ｆｅ２（ＣＯ）６］２（μ－ｍ－ＯＣＣ６Ｈ４ＣＯ－ｍ－μ）（Ｒ＝ｎ－Ｐｒ，ｎ－Ｂｕ，ｔ－Ｂｕ）。经元素分析、ＩＲ光谱及１ＨＮＭＲ表征了它们的结构，并讨论了产物的生成过程。此外，还提出了合成对苯二甲酰氯的一种新方法。     

Kinetic studies of nickel speciation in model solutions of a well-characterized humic acid using the competing ligand exchange method

Publications on the binding characteristics of metals with humic acid (HA) are sparse. Here we investigated the release of nickel from Ni(II)-HA complexes using model solutions of three different [Ni(II)]/[HA] mole ratios at three different pH values; we also compared the results with those of [Ni(II)]/[FA] complexes from previous work in this laboratory. Ligand exchange kinetics using the competing ligand exchange method (CLEM) were studied using two different techniques: graphite furnace atomic absorption spectrometry (GFAAS) with Chelex 100 resin as the competing ligand, and adsorptive cathodic stripping voltammetry (AdCSV) with dimethylglyoxime as the competing ligand to measure the rate of dissociation of Ni(II)-HA complexes. The results of the kinetic studies showed that as the [Ni(II)]/[HA] mole ratio was decreased, the rate of dissociation of Ni(II)-HA complexes decreased, and the proportion of free Ni²⁺ ions plus very labile nickel complexes decreased while the proportion of the less labile kinetically distinguishable components increased. Generally, the rate of dissociation of Ni(II)-HA complexes was slower than that of Ni(II)-FA complexes. Studies on the validity of the kinetic model showed that the concentrations of chemical species varied in a reasonable way with pH and the [Ni(II)]/[HA] mole ratios, indicating that the kinetically distinguishable components have chemical significance and the kinetic model is valid.     

Synthesis and Crystal Structure of a New 2D Honeycomb-like Cadmium(II) Complex with Tripodal Ligand

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