双亲性希土-邻苯二甲酸正十四醇单酯-邻菲咯啉三元配合物的合成、表征、荧光特性及成膜性能

合成了双亲性的铕、铽-邻苯二甲酸正十四醇单酯-邻菲咯啉三元混配配合物，用红外光谱及差热-热重谱进行了表征。考察了发光性能。研究了它们在空气-水界面上的单分子膜行为，结果表明均具有良好的成膜行为。     

Transport properties of alkanes through ceramic thin zeolite MFI membranes

Polycrystalline randomly oriented defect free zeolite layers on porous α-Al₂O₃ supports are prepared with a thickness of less than 5 μm by in situ crystallisation of silicalite-1. The flux of alkanes is a function of the sorption and intracrystalline diffusion. In mixtures of strongly and weakly adsorbing gases and a high loadings of the strongly adsorbing molecule in the zeolite poze, the flux of the weakly adsorbing molecule is suppressed by the sorption and the mobility of the strongly adsorbing molecule resulting in pore-blocking effects. The separation of these mixtures is mainly based on the sorption and completely different from the permselectivity. At low loadings of the strongly adsorbing molecules the separation is based on the sorption and the diffusion and is the same as the permselectivity. Separation factors for the isomers of butane (n-butane/isobutane) and hexane (hexane/2,2-dimethylbutane) are respectively high (10) and very high (> 2000) at 200°C. These high separation factors are a strong evidence that the membrane shows selectivity by size-exclusion and that transport in pores larger than the zeolite MFI pores (possible defects, etc) can be neglected.     

非水滴定法测定苯唑醇含量的研究

建立了农药中间体苯唑醇的分析方法，用指示剂法和电位法对苯唑醇进行了非水滴定的研究，测定结果与高效液相色谱(HPLC)法基本一致，相对标准偏差≤0．20％。     

Synthesis of methylenedioxy-bearing 1-aryl-3-carboxylisoquinolines using a modified Ritter reaction procedure

This paper describes original approaches aimed at the preparation of electron-rich 1-aryl-3-carboxylisoquinolines. Our first attempt led to an efficient preparation of 1-hydroxyisoquinoline-3-carboxylic acid methyl ester starting from bromophthalide via a rearrangement of 2-acetylamino-2-(3-oxo-1,3-dihydroisobenzofuran-1-yl)-malonic acid dimethyl ester. However, as its eventual application to the synthesis of methylenedioxy-bearing substrates seemed rather long, a second approach involving an extension of the Ritter reaction to safrole was devised. We thus report that, under proper experimental settings, the use of 54% tetrafluoroboric acid in ether enables a Ritter reaction between safrole and 3,4,5-trimethoxybenzonitrile yielding 17% of 7-methyl-5-(3,4,5-trimethoxyphenyl)-7,8-dihydro-[1,3]dioxolo[4,5-g]isoquinoline. This acidic reagent avoids the extensive decomposition seen when using the classical Ritter reaction conditions (i.e.: concentrated sulfuric acid). Further chemical transformations of this methyl-bearing dihydroisoquinoline led to the methylenedioxy-bearing 1-aryl-3-carboxylisoquinoline. These derivatives are related to the peripheral benzodiazepine receptor ligand PK 11195 as well as falcipain-2 inhibitors and other potential antitumor agents.     

微量元素叶面肥料中硼的测定

研究了在 pH 6 .5乙酸铵缓冲溶液中 ,硼与 3 甲氧基 甲亚胺H的显色反应条件 ,最大吸收在 4 2 0nm处 ,摩尔吸光系数为 8.1× 10 3,硼含量在 0～ 10 μg/ 10ml范围内符合比耳定律。用于微量元素叶面肥料中硼的测定 ,获得了与国标法一致的结果     

Crystal chemistry of protonated 1,2-bis(di-R-aminomethyl)benzenes. Part V. [1,2-bis(diethylaminomethyl)-3,6-dichlorobenzene:1,2-bis(diethylaminomethyl)-3,4,6-trichlorobenzene]perchlorate mixed crystals

The mixed crystals of 1,2-bis(diethylaminomethyl)-3,6-di- and 3,4,6-trichloro-benzene perchlorate at 0.5:0.5 ratio have been studied using X-ray diffraction and FT-IR spectroscopy. The molecules of di- and tri-chloro derivatives are distributed randomly in the crystal lattice; however, this disorder manifested mainly by a partial occupation of the chlorine atom at C(4) and by relatively big atomic temperature parameters even at 99 K, particularly for the oxygens of the perchlorate anion. The proton in the [NHN]⁺ bond refined close to the equidistant position between the nitrogens. The conformations of the diethylaminomethyl substituents are pseudo-symmetrical relative to the plane and twofold axis passing through the midpoint of the hydrogen bond. The IR spectrum of the crystals shows a broad intense band and an intense continuous absorption indicating relatively high proton polarizability in the intramolecular hydrogen bond. In acetonitrile and in chloroform, the proton in the intramolecular hydrogen bond also shows a very high proton polarizability demonstrated by the continuous absorption in the IR spectrum.     

Reaction of 1,2-Diamino-4,5-diphenylimidazole with 1,3-Diarylpropenones and Their Dibromo Derivatives

The reaction of 1,2-diamino-4,5-diphenylimidazole with 1,3-diarylpropenones and 1,3-diaryl-2,3-dibromopropenones gives dihydro- and heteroaromatic derivatives of 6-hydroxyimidazopyrimidines and also imidazopyrimidines which do not contain the 6-hydroxy group. It was found that the structure of the products depended on the conditions for carrying it the reaction.     

Selective Pre-concentration and Solid Phase Extraction of Mercury（Ⅱ） from Natural Water by Silica Gel-loaded （E）-N-（1-Thien-2＇-ylethylidene）-1,2-phenylenediamine Phase

Silica gel-loaded （E）-N-（1-thien-2＇-ylethylidene）-1,2-phenylenediamine （TEPDA） phase was synthesized based on physical adsorption approaches. The stability of a chemically modified TEPDA especially in concentrated hydrochloric acid that was then used as a recycling and preconcentration reagent allowed the further uses of silica gel-loaded immobilized TEPDA phase. The application of this silica gel-loaded phase to sorption of a series of metal ions was performed by using different controlling factors such as the pH of the metal ion solution and the equilibration shaking time by the static technique. This difference was interpreted on the basis of selectivity incorporated in these sulfur containing silica gel-loaded TEPDA phases. Hg（Ⅱ） was found to exhibit the highest affinity towards extraction by these silica gel-loaded TEPDA phases. The pronounced selectivity was also confirmed by the determined distribution coefficients （Kd） of all the metal ions, showing the highest value reported for mercury（Ⅱ） extraction by the silica gel immobilized TEPDA phase. The potential applications of the silica gel immobilized TEPDA phase to selective extraction of mercury（Ⅱ） from aqueous solution were successfully accomplished and preconcentration of low concentration of Hg（Ⅱ） （30 pg·mL^-1） from natural tap water with a preconcentration factor of 200 for Hg（Ⅱ） off-line analysis was conducted by cold vapor atomic absorption analysis.     

Reactions of Polycyclic Ketones with Dimethoxycarbene; a Convenient Route for a ‘One‐Pot’ Preparation of Some α‐Hydroxycarboxylic Acid Esters

Polycyclic ‘cage’ ketones, such as pentacyclo[5.4.0.0^2,6.0^3,10.0^5,9]undecan‐8‐one ( 10 ), pentacyclo[5.4.0.0^2,6.0^3,10.0^5,9]undecane‐8,11‐dione ( 11 ), and adamantan‐2‐one ( 16 ) were treated with the nucleophilic dimethoxycarbene (DMC; 1 ), which was generated thermally from 2,5‐dihydro‐2,2‐dimethoxy‐5,5‐dimethyl‐1,3,4‐oxadiazole ( 4a ) in boiling toluene. In this ‘one‐pot’ procedure, the α‐hydroxycarboxylic acid ester 12 or a corresponding derivative 15 or 17 was obtained (Schemes 4–7). Additionally, ‘cage’ thione 21 was treated with DMC under the same conditions yielding dimethoxythiirane 22 (Scheme 8). Subsequent hydrolysis or desulfurization (followed by hydrolysis on silica gel) of 22 gave α‐mercaptocarboxylate 25 and the corresponding desulfurized ester 24 , respectively. In all cases, the addition of DMC occurred stereoselectively, and the addition from the exo‐face is postulated to explain the structures of the isolated products.     

Synthesis and Crystal Structure of the Binuclear Complex [Pr2(C10H8N2O4)2(C10H9N2O4)2(H2O)4]·3H2O·C6H6

The binuclear praseodymium(III) complex with N‐(1‐carboxyethylidene)‐salicylhydrazide (C₁₀H₁₀N₂O₄, H₂L) was prepared in H₂O‐C₂H₅OH mixed solution, and the crystal structure of [Pr₂L₂(HL)₂(H₂O)₄]·3H₂O·C₆H₆ was determined by X‐ray single crystal diffraction. The crystal complex crystallizes in the triclinic system with space group P‐1, and in the structure each Pr atom is 9‐coordinated by carboxyl O and acyl O and azomethine N atoms of two tridentate ligands to form two stable five‐membered rings sharing one side in keto‐mode and two water molecules. The coordination polyhedron around Pr³⁺ was described as a monocapped square antiprism geometry. In an individual molecule, four tridentate ligands were coordinated by two negative univalent (HL) and two bivalent forms (L) respectively. Two negative univalent ligands were coordinated via μ₂‐bridging mode.