含有机配体的活性双过氧钒配合物与组氨酸的相互作用研究

在合成和表征了4种具有较强生物活性双过氧钒配合物K_3[VO(O_2)_2(ox)]· 2H_2O，Na[VO(O_2)_2(bipy)]·5H_2O，K[VO(O_2)_2(phen)]·3H_2O和K_2[VO (O_2)_2(pic)]·2H_2O[分别缩写为pV(ox)，pV(bipy)，pV(phen)和pV(pic)，其中 ox为草酸根，bipy为2,2'-联吡啶，phen为邻菲咯啉，pic为2-羧酸吡啶负离子]的 基础上，利用多种NMR技术和电喷雾质谱（ESI-MS）研究了这4种含有机配体双过氧 钒酸合物与组氨酸（His）在溶液中的相互作用以及反应物浓度、时间、pH等对相 互作用体系的影响。~(51)V NMR跟踪监测的结果表明：双过氧钒配合物pV(ox)和 pV(pic)与His在中性水溶液中存在强配位相互作用，而pV(bipy)和pV(phen)与His 在中性水溶液中无明显作用。我们还利用谱学方法确定了pV(ox)和His相互作用后 所生成产物是pV(ox)分别与His在中性水溶液中无明显作用。我们还利用谱学方法 确定了pV(ox)和His相互作用后所生成产物是pV(ox)分别与His咪唑基上的3-N和1- N配位的一对异构体。     

迎头色谱程序升温脱附快速测定吸附热新方法

在Ｐｏｌａｎｙｉ吸附势理论基础上，结合程序升温脱附曲线的测定，建立了一个快速测定吸附热的新方法，详细讨论了该方法的原理，通过微机采样和数据处理，测定一条吸附热与覆盖度的曲线仅需１ｈ左右。     

Synthesis and Asymmetric Enantioselective Addition of Chiral Polybinaphthyl and Polybinaphthol I.igands

Four chiral polymers P-1, P-2, P-3 and P-4 were synthesized by the polymerization of （S）-2,2＇-dioctoxy-1,1＇- binaphthyl-6,6＇-boronic acid （S-M-3） with （S）-6,6＇-dibromo-1,1＇-binaphthol （S-M-1）, （R）-6,6＇-dibromo-1,1＇- binaphthol （R-M-1）, （S）-3,3＇-diiodo-1,1＇-binaphthol （S-M-2） and （R）-3,3＇-diiodo-1,1＇-binaphthol （R-M-2） under Pd-catalyzed Suzuki reaction, respectively. All four polymers can show good solubility in some common solvents due to the nonplanarity of the polymers in the main chain backbone and flexible alkyl groups in the side chain. The analysis results indicate that specific rotation and circular dichroism （CD） spectral signals of the alternative S-S chiral polymers P-1 and P-3 are larger than those of S-R chiral polymers P-2 and P-4, but their UV-Vis and fluorescence spectra are almost similar. The results of asymmetric enantioselectivity of four polymers for diethylzinc addition to benzaldehyde indicate that catalytically active center is （R） or （S）-1, 1＇-binaphthol moieties.     

Macro-, Micro-, Nano- and Crystal Structures of a Homodinuclear Complex [NH3（ CH2）3NH3]2{Na2[（C6H4O2）2]（C6H4O2H）2}

A homodinuclear complex （NH3CH2CH2CH2NH3）2 {Na2[（C6H4O2）2] （C6H4O2H）2} （1） has been synthesized by a solution-based self-assembly route. It crystallized in monoclinic system with space group P21/c. Every sodium ion coordinates in a tetragonal prism fashion with two O atoms of a terminal chelating catecholate ligand and three O atoms from two bridging catecholate ligands. Two neighboring NaO5 tetragonal prisms are edge-shared and centrosymmetric with regard to the inversion center to form a binuclear cluster {Na2[（C6H4O2）2]（C6H4OOH）2}^4- anion. The complex anions were aligned parallelly by n-n interaction and linked with the protonated 1,3-propylenediamine through hydrogen bonds which were assembled into a multi-lamellar structure with channels. The crystal exhibits rectangular geometry with an interior triangle hollow structure under optical microscopy. And the scanning electron microscopy （SEM） indicates that the wall of the tubes shows multi-lamella morphologies. Further, the transmission electron microscopy （TEM） reveals that the crystal is composed of multi-lamellar nano-tubes with diameters less than 100 nm. The molecular structure of the complex was compared with that of its isomer complex 2.     

Theoretical Study of the Photochemical Reaction Mechanism of Bicyclo [4.1.0 ] heptane

IntroductionPhotochemical reactions, which involve a three-membered ring, have been of great interest to experi-mental photochemists[1—10]. A main reason for thisphenomenon is that the cyclopropane ring exhibits somereaction characteristics of double bon…     

微生物传感器—高效液相色谱联用研究

本文用自制的单一或复合的微生物传感器作检测器,与高效液相色谱结合,对7种氮基酸,5种有机醇,以及同化糖与醇,维生素等7种混合体系进行分离硷测,取得较好的结果。     

Synthesis, Crystal Structure, UV-vis and EPR Studies of（ NH3CH2CH2NH2 ） 2.5 [ Mo0.5^（V）W0.5^（VI）O2 （ OC6H4O ） 2]

Cis-dioxo-metal complex ( NH3CH2CH2NH2 ) 2.5 [ Mo0.5^(V)W0.5^(VI)O2 ( OC6H4O ) 2] 1 was obtained by the reaction of tetra-butyl ammonium hexamolybdotungstate with 1, 2-dihydroxybenzene in the mixed solvent of CH3OH, CH3CN and ethylenediamine,and characterized by X-ray diffraction, UV-vis and EPR analysis. Compared with its analogous complexes (NH3CH2CH2NH2)3[Mo^(V)O2(OC6H40)2] 2 and (NH3CH2CH2NH2)2[W^(VI)O2(OC6H4O)2] 3, the results show that tungsten(VI) is less active in redox than molybdenum (VI) and that the change of the valence induced by substitution of W(VI) for Mo(V) in EMO2(OC6H40)2]n- does not influence the coordination geometry of the complex anion in which the metal center exhibits distorted octahedral coordination with cis-dioxo catechol. The responses to EPR of complexes 1 and 2 are active but complex 3 is silent,and the UV-vis spectra exhibited by the three complexes are obvious different because of the different electronic configuration between the central Mo(V) and W(VI) ions in the complexes.It is noteworthy that complexes 1 and 2 have the similar EPR signal to flavoenzyme, suggesting that the three complexes have the same coordination geometry feature with the co-factor of flavoenzyme.     

环状缩醛对某些含官能团烯烃的自由基加成反应

率的加成产物。这些产物通常是不易制备的,因而该反应在这一类酯的合成中将是有效的方法。结果和讨论我们应用的1和含官能团的烯烃2反应,结果列于表1。显然,在体系中存在着多个反应的竞争。要使得上述加成成为主要反应,首先要减少2的自聚和调聚反应,其次要使如下的链反应能够实现(见 p.176)。     

基于聚类分析的初三化学学业质量发展研究

以2013-2016年广州市各区（县级市）中考化学成绩的4种数据为指标，运用聚类分析研究广州市区域初三化学学业质量的发展状况。研究发现各区（县级市）主要分为3大类，部分区在不同年份的类别中移动，倾向于建立一个包括越来越多区域的第1大类。广州市区域初三化学学业质量逐步向优质均衡发展。系统的中学生化学探究活动和化学教师研训活动是实现这一发展的重要原因。     

LC-ESI-MS Determination of Bilobalide and Ginkgolides in Canine Plasma

A sensitive and selective method using liquid chromatography with electrospray ionization mass spectrometric detection was developed for the quantification of bilobalide and ginkgolides in canine plasma. The analytes were extracted with diethyl ether-dichloromethane-isopropanol (6:3:1, v/v) after spiking the samples with daidzein (internal standard). The lower limit of quantification (LLOQ) of the method was 2.5 μg L⁻¹ for ginkgolide B and 10.0 μg L⁻¹ for bilabolide, ginkgolide A and ginkgolide C. The accuracy of the method was within 15% of the actual values over a wide range of plasma concentrations. The intra-day and inter-day precision was better than 15% (R.S.D.). Finally, the LC-ESI-MS method was successfully applied to study the pharmacokinetics of ginkgolides and bilabolide after administration of Ginkgo biloba extracts to dogs.