Asymmetric michael addition of aromatic thiols to 2-cyclohexenone and maleic acid esters via formation of crystalline cyclodextrin complexes

The asymmetric Michael addition of aromatic thiols to 2-cyclohexenone and maleic acid esters has been carried out by utilizing their crystalline cyclodextrin complexes suspended in water. The best chiral induction, 30% enantiomeric excess (ee), was achieved in combinations of 2-cyclohexenone and octyl maleate with the crystalline -cyclodextrin complex of benzenethiol (method A) to afford (S)-3-phenylthiocyclohexanone and (S)-octyl-2-phenylthiosuccinate, respectively, whereas the reaction of benzenethiol with 2-cyclohexenone included in -cyclodextrin (method B) inversely induced the chiral recognition to give the (R)-adduct with 4–9% ee.     

锰（Ⅱ）—邻菲口罗啉配合物极谱吸附波及其应用

在ｐＨ９．５ＮＨ３ＮＨ４Ｃｌ缓冲溶液中，Ｍｎ（Ⅱ）与邻菲口罗啉形成的配合物在－１．３６Ｖ（ｖｓ．ＳＣＥ）处产生一灵敏的吸附波，一阶导数峰电流与Ｍｎ（Ⅱ）浓度在５×１０－８５×１０－６ｍｏｌ／Ｌ范围内呈线性关系，检出限为２×１０－８ｍｏｌ／Ｌ对极谱性质及反应机理进行了研究，用该法测定了大豆和茶叶中的微量锰，结果满意     

配合物[Cu_2(TS)(H_2O)]·H_2O的自组装制备、晶体结构和电化学性质

利用单核配合物Na2 CuTS·H2 O在溶剂中的不稳定性质 ,自分解并重新组装得到了双核配合物 [Cu2 (TS)(H2 O) ]·H2 O .配合物为单斜晶系 ,空间群P2 1/C ,晶胞参数为a =0 .80 830 (16 )nm ,b =1.70 79(3)nm ,c =1.4 0 73(3)nm ,β =10 5 .0 8(3)° ,V =1.86 5 4 (6 )nm3 ,Z =4 ,最终一致性因子R =0 .0 6 4 4 .该分子结构为双核单元 ,金属原子通过两个酚氧原子桥联在一起 .结合晶体结构对配合物作了电化学研究     

Geometries and properties of bimetallic phosphido-bridged complex Cp(CO)2W(μ-PPh2)W(CO)5 and Cp(CO)3W(μ-PPh2)W(CO)5

Complete geometry optimizations were carried out by HF and DFT methods to study the molecular structure of binuclear transition-metal compounds (Cp(CO)₃W(μ-PPh₂)W(CO)₅) (I) and (Cp(CO)₂W(μ-PPh₂)W(CO)₅) (II). A comparison of the experimental data and calculated structural parameters demonstrates that the most accurate geometry parameters are predicted by the MPW1PW91/LANL2DZ among the three DFT methods. Topological properties of molecular charge distributions were analyzed with the theory of atoms in molecules. (3, −1) critical points, namely bond critical point, were found between the two tungsten atoms, and between W1 and C10 in complex II, which confirms the existence of the metal–metal bond and a semi-bridging CO between the two tungsten atoms. The result provided a theoretical guidance of detailed study on the binuclear phosphido-bridged complex containing transition metal–metal bond, which could be useful in the further study of the heterobimetallic phosphido-bridged complexes.     

Screening of antagonists based on induced dissociation of a calmodulin-melittin interaction entrapped in a sol-gel derived matrix

Sol-gel derived materials offer a unique advantage for the development of sensing and screening platforms in that they allow for the entrapment of multiple species within a confined space. In this work, we show that it is possible to entrap an intact protein-peptide interaction, consisting of bovine calmodulin (bCaM) and melittin, into a sol-gel derived silicate material. Fluorescence emission data demonstrate that the entrapped complex behaves similarly to the complex in solution, and can undergo reversible dissociation upon introduction of the denaturant guanidine hydrochloride. Screening of antagonists of the bCaM-melittin complex was accomplished based on induced dissociation of the entrapped complex, which was followed by measuring the loss of sensitization of Tb(III) luminescence originating from energy transfer from the Trp of melittin to Tb(III) bound in the loops of bCaM. This study shows that entrapped protein-peptide complexes can be used as targets for drug screening or for fluorescence-based biosensing.     

Quantum chemical models of alkali metal hydroxide-water-dimethylsulfoxide superbasic media (MOH-H<Subscript>2</Subscript>O-DMSO,M = Li,Na, K)

Models of alkali metal hydroxide-water-dimethylsulfoxide superbasic media have been constructed using Hartree Fock and DFT (B3LYP) quantum chemical methods; the structure and energies of anion complexes are considered. The hydroxide anion in the models is stabilized as complexes of OH^?·H₂O and OH^?· 2H₂O types.     

配位聚合物{[Co2(HBTC)2(H2O)6]·C4H10N2·2H2O}n的水热合成、结构表征及荧光性质

采用水热法合成了配位聚合物[Co2(HBTC)2(H2O)6]·C4H10N2·2H2O}n(H3BTC为1,3,5-均苯三羧酸,C4H10N2为哌嗪),通过X射线单晶衍射、红外光谱和荧光光谱进行表征,并用TGA研究了该配位聚合物的热稳定性.晶体属三斜晶系,P1空间群,a=1.05437(9)nm,b=1.05485(9)nm,c=0.71482(5)nm,α=102.4623(28)°,β=91.3500(42)°,γ=111.0186(29)°,V=0.72018(10)nm3,Mr=764.37,Dc=1.762g·cm-3,Z=1,μ(MoKα)=1.25mm-1,F(000)=394,R=0.0307,wR=0.0815.晶体的基本构建单元中包含2个Co()中心、2个配位的HBTC分子和6个配位的水分子.基本构建单元通过相互链接形成具有“Z”型结构的一维配位聚合链,链间通过两种不同的氢键(O—H…O和N—H…O)相互作用,进而形成具有三维骨架结构的微孔晶体,微孔大小为0.71nm×0.82nm.荧光光谱表明,常温下用λex=312nm的光激发后,配位聚合物在329nm处出现强烈的荧光发射.     

EDTA—Cu配合物用于还原糖的测定

首次报道了应用ＥＤＴＡ（乙二胺四乙酸二钠盐）－铜配合物（ＥＣ）测定还原糖的分光光度法，结果表明，ｐＨ４～１１时ＥＣ的最大吸收波长为７３２ｎｍ，在ＨＣＯ－３ＣＯ２－３缓冲介质中，配合物ＥＣ的吸光度与还原糖在０７７～１６１ｍｇ（六碳糖）范围内有很好的线性关系，相关系数大于０９９８，样品测定回收率在９５％～１０５％之间。该法试剂易得、性质稳定，操作方便，灵敏度较高，取样量少于５ｍＬ。     

Solid-solute phase equilibria in aqueous solution. VI. Solubilities,complex formation,and ion-interaction parameters for the system Na+−Mg2+−ClO 4 − −CO2−H2O at 25°C

The stoichiometric solubility constant of eitelite (NaMg _0.5 CO ₃ +2H⁺ ⇄ Na⁺+0.5Mg ²⁺ +CO ₂ (g)+H ₂ O, log^*K _pso ^I =14.67±0.03 was determined at I=3 m (mol kg⁻¹) (NaClO ₄ ) and 25°C. The stability of magnesium (hydrogen-)carbonato complexes in this ionic medium was explicitely taken into account. Consequently, trace activity coefficients of free ionic species, calculated from the Pitzer model with ion-interaction parameters from the literature, were sufficient for an evaluation of the thermodynamic solubility constants and Gibbs energies of formation for eitelite (−1039.88±0.60), magnesite (−1033.60±0.40), hydromagnesite (−1174.30±0.50), nesquehonite (−1724.67±0.40), and brucite (−835.90±0.80 kJ-mol ⁻¹ ). The increasing solubilities of nesquehonite and eitelite at higher sodium carbonate molalities were explained by invoking a magnesium dicarbonato complex (Mg²⁺+2CO ₃ ²⁻ ⇄ Mg(CO₃) ₂ ²⁻ , log β_z = 3.90 ± 0.08). A set of ion-interaction parameters was obtained from solubility and dissociation constants for carbonic acid in 1 to 3.5 m NaClO ₄ media which reproduce these constants to 0.02 units in log K. The following Pitzer parameters are consistent with the previously studied formation of magnesium (hydrogen-)carbonato complexes in 3m NaClO ₄ . The model and Gibbs functions of solid phases derived here reproduce original solubility data (−log [H⁺], [Mg ²⁺ ] _tot ) measured in perchlorate medium within experimental uncertainty. Presented at the XXII International Conference on Solution Chemistry, July 14–19, 1991, Linz, Austria.     

Effect of arrangement of the styryl fragment on the optical properties and complexation of mono-and bis(styryl)-substituted <Emphasis Type="Italic">N</Emphasis>-methylpyridinium perchlorates containing benzo-15-crown-5 ether moieties

Using ¹H NMR spectroscopy and steady-state and time-resolved electronic spectroscopy, the optical properties of mono-and bis(styryl)pyridinium perchlorates and their complexes with Mg²⁺, Ba²⁺ cations were studied. The stability constants of the complexes were determined using spectrophotometric titration. The formation of inclusion complexes for Mg²⁺ and sandwich type complexes for Ba²⁺ results in fluorescence enhancement and increases the lifetimes of the excited states of the initial bis-styryl ligands. The variation of position of the styryl fragment in the pyridinium aromatic ring gives rise to photochromic crown ethers with different optical and photophysical characteristics and is also an easy route to bis(crown-ethers) of symmetrical and unsymmetrical structure. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2092–2100, November, 2007.