含铁磁耦合Ni3单元的均苯三甲酸桥联双层镍(II)配合物

使用均苯三甲酸与碳酸镍在水热条件下反应得到了一例新的二维双层Ni(II)配位聚合物Ni3(BTC)2(μ-H2O)26H2O。二维层包含syn-syn羧酸桥和水桥连接的三核Ni3单元,进一步用均苯三甲酸上的苯环连接成二维层状结构。磁性研究表明,相邻Ni2+离子间存在弱的铁磁耦合作用。水桥连镍离子的桥联键角为122.8(3)deg,所以通过该水桥镍离子间应该呈现反铁磁耦合。因此,实验结果证明了syn-syn羧酸桥传递铁磁耦合,而且铁磁耦合大于反铁磁作用,最终配合物呈弱的铁磁耦合。基于本工作和文献报道的含syn-syn 羧酸混合桥联镍配合物的磁性,我们总结出下面结论：Ni–O–C–O–Ni的共面性与否决定了配合物的磁性。共面性好的Ni–O–C–O–Ni导致中等强度的反铁磁耦合,而共面性差会消弱反铁磁作用,甚至出现由反铁磁变为铁磁耦合。标题配合物中羧酸桥所传递的铁磁性可能就归因于Ni–O–C–O–Ni的不共平面性。因此,与含羧酸桥的混合桥联双核铜(II)配合物类似,轨道补偿效应(the orbital complementary effect (OCE))对于解释水/羧酸混合桥联镍(II)配合物的磁性也同样适用。     

Liquid chromatographic determination of dimethadione and trimethadione in human serum on octadecyl treated microporous glass columns

Summary The liquid chromatographic determination of trimethadione (TMO) and its methabolite, dimethadione (DMO) were studied by high-performance liquid chromatography (HPLC) on octadecyl-modified microporous glasses, prepared with toluene solution containing octadecyl-dimethylchlorosilane, using two types of microporous glass with various mean pore diameters and/or specific surface areas. Using acetonitrile-water mixtures as eluents, TMO and DMO in human serum were separated on the glasses studied, but with different degrees of resolution. In this present study, we report the development of a rapid and selective HPLC method for the simultaneous analysis of TMO and DMO in human serum.     

Boosting Efficiency for the Synthesis of Dimethyl Oxalate over Pd/MgAl2O4: Effect of Different Preparation Methods for MgAl2O4 Supports

High active Pd-based catalyst with low loading capacity for CO oxidative coupling with methyl nitrite (MN) to dimethyl oxalate (DMO) has aroused great interest in the large-scale production of DMO for the next hydrogenation to bring forth ethylene glycol (EG). Here, spinel composite oxide support, namely MgAl₂O₄, had been prepared through three different methods: solid combustion method (MAO-SC), hydrothermal method (MAO-HT) and co-precipitation method (MAO-CP), and further Pd nanoparticles were anchored to the surface of MgAl₂O₄ through a simple wetness impregnation method. In the CO direct esterification to DMO reaction, the Pd/MAO-SC catalyst, which used MgAl₂O₄ support prepared by solid combustion method, exhibited the highest intrinsic activity with Turnover frequency (TOF) value of 2.39 s⁻¹ and DMO weight space-time yield (956.8 g⋅kg_cat⁻¹⋅h⁻¹) with 44.1 % CO conversion and 97.8 % DMO selectivity, and showed negligible attenuation of activity during the process of continuous reaction for 100 h. The characterization results confirmed that abundant oxygen defect sites occurred in MAO-SC synthesized by combustion method not only can help to anchor the Pd nanoparticles with appropriate size and dispersion, but also can promote the interfacial electron transfer from MgAl₂O₄ support to Pd nanoparticles, thus significantly enhancing the metal-support interaction (MSI) and providing more CO bridge-adsorption sites that is favorable for the CO oxidative coupling with MN to DMO reaction.     

新荧光试剂双(2-苯并噻唑重氮氨基)-3,3′,5,5′-四甲基联苯的合成及其分析应用

将3,3′,5,5′-四甲基联苯胺和苯并噻唑类试剂结合, 并引入杂环三氮烯结构, 合成了新荧光试剂双(2-苯并噻唑重氮氨基) 3,3′,5,5′-四甲基联苯(BBTDTMB), 其结构经红外光谱、 核磁共振谱和元素分析证实. 研究结果表明, 在碱性介质中, 该试剂在λex/λem=342 nm/420 nm处产生强荧光, 并且Ag(Ⅰ)对其荧光有很好的猝灭作用, 因而建立了BBTDTMB测定Ag(Ⅰ) 的新荧光分析方法. 该方法的线性范围为1.0～240 μg/L, 检测限为 0.5 μg/L, 应用于人发、 茶叶中的Ag(Ⅰ) 的测定, 结果令人满意.     

5,5-Diethylbarbiturate tubular electrode for use in flow-injection detection systems

The construction, assessment and pharmaceutical appalications of a tubular potentiometric detector sensitive to the 5,5-diethylbarbiturate anion based on quaternary ammonium salt (tetraoctylammonium5,5-diethylbarbiturate) dissolved in o-nitrophenyl octyl ether immobilized in PVC are described. The intrinsic characteristics of the tubular electrode were determined in a low-dispersion manifold and compared with those of a conventional-shaped electrode with no internal reference solution and incorporating the same sensor. The behaviour of a double-channel flow-injection manifold with the same potentiometric detector was evaluated to assess its applicability to the determination of 5,5-diethylbarbiturate in pharmaceutical preparations. Data obtained in the determination of the anion in the latter matrices are presented and compared with those obtained by the conventional British Pharmacopoeia method.     

Flow injection determination of trace amounts of copper based on its catalytic effect on the oxidation of 3, 3′, 5, 5′-tetramethylbenzidine by cumene hydroperoxide

A sensitive and selective flow-injection method has been developed for the catalytic determination of copper(II). The method is based on the oxidation of 3,3′,5,5′-tetramethylbenzidine by cumene hydroperoxide as an organic oxidant in an acidic medium. A highly sensitivity has been achieved by adding 2,9-dimethyl-1,10-phenanthroline as an activator and benzyldimethyltetradecylammonium chloride (zephiramine) as a surfactant. The reaction was spectrophotometrically monitored by measuring the increase in absorbance of oxidation product of 3,3′,5,5′-tetramethylbenzidine at 650 nm. The calibration curve was linear over the range of 0.5–3.0 ng mL^?1 at a rate of 30 samples h^?1. Most of the diverse ions did not interfere with the determination of copper up to at least 50-fold excess. The serious interference by iron(III) was eliminated by addition of fluoride. The method was successfully applied to the determination of copper in water samples.     

Colorimetric method for determination of chlorine with 3,3',5,5'-tetramethylbenzidine

A new method is developed for the calorimetric determination in water of chlorine (free and combined) with 3,3′,5,5′-tetramethylbenzidine. The procedure proposed achieves a detection limit of 2 ng/ml and its sensitivity is greater than that of the methods used at present.     

Analytical investigations on cephalosporins--IV: application of Ellman's reagent

The application of 5,5'-dithiobis(2-nitrobenzoic acid) (Ellman's reagent) for the determination of microgram quantities of various selected cephalosporins in aqueous solution is described. Cephalosporin derivatives (cephalothin sodium, cephacetrile sodium, cefamandole lithium and nafate, cefoperazone sodium and ceftizoxime sodium) have to be treated with 0.5N sodium hydroxide before determination with Ellman's reagent, which reacts with free thiol groups. An aliquot of the solution is reacted with Ellman's reagent in pH 7.2 phosphate buffer and the absorbance of the resulting yellow solution is measured at 410 nm. The method, which is simple and precise, has been applied to determination of those cephalosporins in formulations, the results being compared with those obtained by the Ni-hydroxylamine method.     

Spectrophotometric determination of iron by extraction of the iron(II)-5,5-dimethyl-1,2, 3-cyclohexanetrione-1,2-dioxime-3-thiosemicarbazone complex

The iron (II)-5,5-dimethyl-1,2,3-cyclohexanetrione-1,2-dioxime-3-thiosemicarbazone complex can be extracted from a medium of high acidity into amyl alcohol. Measurement of the absorbance at 550 nm gives a determination limit for iron of 0.015 mu/ml. The method has been applied to the determination of iron in water, wine, beer and fruit juice.     

Analytical properties of 5,5-dimetyl 1,3-cyclohexanedione dithiosemicarbazone monohydrochloride; spectrophotometric determination of chromium(VI) in alloy steels and industrial effluents

The analytical properties of 5,5-dimethyl 1,3-cyclohexanedione dithiosemicarbazone monohydrochloride (5,5-DiMe-1,3-CHDT.HCl) are described. The reagent gives pink coloured solutions with chromium(VI) in acetic medium. The maximum colour intensity is observed in 0.5-2.5 pH range. This colour reaction (molar absorptivity, 1.63 x 10(4) 1 mol(-1) cm(-1) at 360 nm) has been used for the spectrophotometric determination of total chromium in alloy steels and industrial effluents.     

Sn改性TS-1分子筛催化草酸二甲酯和苯酚酯交换合成草酸二苯酯

 研究了Sn改性TS-1催化剂催化苯酚和草酸二甲酯（DMO）酯交换合成草酸二苯酯(DPO)反应。以Sn改性TS-1为催化剂时，Sn活性中心和Lewis酸中心协同作用催化苯酚和DMO酯交换合成DPO反应。因为Sn的加入，在保持MPO和DPO高选择性的同时，DMO转化率显著提高。而且Sn活性中心有利于MPO歧化反应生成DPO，从而大大提高了DPO的选择性。但是，当Sn负载量大于2％时，SnO2由均匀分布在TS-1表面改变为以晶体状态存在，从而导致DMO转化率的大幅降低。     

Determination of trace phosphate ion with 3,3',5,5'-tetramethylbenzidine using a flotation-extraction preconcentration method and spectrophotometric detection

A flotation-extraction method for sensitivity enhancement in spectrophotometry is proposed. The method is based on the reaction among molybdate, phosphate and 3,3',5,5'-tetramethylbenzidine (TMB) in acidic medium to form an color charge transfer complex ion. It forms an ion associate with positive ions and floated at the water/benzene interface simultaneously, and then extracted by the DMSO-formic acid directly and determined by spectrophotometry. The proposed method is simple and convenient. The apparent molar absorptivity is 4.03x10(5) L mol(-1) cm(-1) at 458 nm. The proposed method has been applied to the determination of phosphate in wastewater with satisfactory results.     

金(Ⅲ)与 3,3’,5,5’-四甲基联苯胺显色反应的研究和应用于微量金的测定

本文研究了An(Ⅲ)与 3,3′,5.5′-四甲基联苯胺(TMB)的显色反应,在0.02mol/L盐酸介质中,TMB于波长450nm处有最大吸收,摩尔吸光系数为1.03×10~5L·mol~(-1).cm~(-1).25ml溶液中0～40μg金(Ⅲ)符合比尔定律,本方法已用于粗铜中微量金的测定.     

Simultaneous quantification of olanzapine and its metabolite N‐desmethylolanzapine in human plasma by liquid chromatography tandem mass spectrometry for therapeutic drug monitoring

A simple, sensitive, and selective liquid chromatography tandem mass spectrometry (LC‐MS/MS) method was developed and validated for the simultaneous quantification of olanzapine (OLZ) and its metabolite N‐desmethylolanzapine (DMO) in human plasma for therapeutic drug monitoring. Sample preparation was performed by one‐step protein precipitation with methanol. The analytes were chromatographed on a reversed‐phase YMC‐ODS‐AQ C₁₈ Column (2.0 × 100 mm,3 µm) by a gradient program at a flow rate of 0.30 mL/min. Quantification was performed on a triple quadrupole tandem mass spectrometer via electrospray ionization in positive ion mode. The method was validated for selectivity, linearity, accuracy, precision, matrix effect, recovery and stability. The calibration curve was linear over the concentration range 0.2–120 ng/mL for OLZ and 0.5–50 ng/mL for DMO. Intra‐ and interday precisions for OLZ and DMO were <11.29%, and the accuracy ranged from 95.23 to 113.16%. The developed method was subsequently applied to therapeutic drug monitoring for psychiatric patients receiving therapy of OLZ tablets. The method seems to be suitable for therapeutic drug monitoring of patients undergoing therapy with OLZ and might contribute to prediction of the risk of adverse reactions. Copyright © 2014 John Wiley & Sons, Ltd.     

Carbon nanodots as peroxidase mimetics and their applications to glucose detection

Carbon nanodots (C-Dots) were found to possess intrinsic peroxidase-like activity, and could catalytically oxidize 3,3',5,5'-tetramethylbenzidine (TMB) by H(2)O(2) to produce a colour reaction. This offers a simple, sensitive and selective colorimetric method for glucose determination in serum.     

Spectrophotometric determination of molybdenum based on charge transfer complex in PVA medium

A very simple, selective and sensitive method was developed for the spectrophotometric determination of Mo in the presence of W. The method was based on the formation of color charge transfer complex, molybdotungstophosphate-3,3',5,5'-tetramethylbezidine anion, which was solubilized and stabilized in PVA medium. Following the recommended procedure, molybdenum could be determined in the linear range of 0.04-2.5 mug ml(-1) and the molar absorptivity was 1.47x10(4) l mol(-1) cm(-1) at 660 nm. The proposed method had been applied to the determination of trace molybdenum in tungsten ore with satisfactory results.     

Chemiluminescence flow injection analysis of 1,3-dichloro-5,5-dimethylhydantoin in swimming pool water

A new chemiluminescence (CL) flow-injection method is proposed for the determination of 1,3-dichloro-5,5-dimethylhydantoin (DDH). The method is based on the chemiluminescent reaction of DDH and luminol-H(2)O(2) in an alkaline medium (pH 12.0-12.5). The concentration of the analyte shows a good linear relationship with the produced luminescence intensity in the range of 3.0x10(-8) to 8.0x10(-6) mol l(-1). The detection limit of the proposed method is 1.0x10(-8) mol l(-1) and the relative standard deviation (R.S.D.) is 4.7% (n=5) at 5.0x10(-7) mol l(-1). This method was successfully applied to the determination of trace amounts of this disinfectant in water samples obtained from five different swimming pools. Satisfying recovery values were also obtained.     

Use of an Aqueous Micellar Medium to Improve the Spectrophotometry Determination of Cyanide Ion with 5,5′-Dithiobis(2-Nitrobenzoic Acid)

Abstract

The spectrophotometric method for the determination of cyanide, which is based on the reaction of cyanide ion with 5,5′-dithiobis(2-nitrobenzoic acid) to displace the corresponding absorbing thiol anion, has been reinvestigated using an aqueous cetyltrimethylammonium bromide micellar reaction medium. The rate of the analytical reaction is increased considerably in the presence of the cationic surfactant. Thus, the time required for the spectrophotometric determination of cyanide ion in the 0.18 – 2.80 μg/ml range using this procedure is decreased from 25 minutes to 1 – 3 minutes.     

A new indirect spectrophotometric procedure for determination of sulphur dioxide

An operationally inexpensive and sensitive spectrophotometric procedure for sulphur dioxide is proposed. The reagent 5,5-dimethyl-1,2,3-cyclohexanetrione-1,2-dioxime-3-thiosemicarbaz one is used to determine trace amounts of sulphur dioxide indirectly by means of the reduction of Fe(III) to Fe(II). The method can determine down to 0.032 microg/ml of sulphur dioxide in the final solution and recoveries are better than 98%. The method can be applied to the determination of atmospheric SO(2) provided that interfering gases such as nitrogen dioxide and hydrogen sulphide are eliminated.     

新型高性能Cu/HMS催化剂的合成及其在草酸二甲酯催化加氢合成 乙二醇反应中的应用

采用原位合成法合成了介孔Cu/HMS催化剂, 并以草酸二甲酯催化加氢合成乙二醇为探针反应考察了不同焙烧温度对反应催化性能的影响, 结果表明焙烧温度为650 ℃时合成的催化剂在该反应中表现出最佳的催化性能. 在反应温度为200 ℃、压力为3 MPa、氢酯比为50、液时空速为0.74 h－1的条件下, 草酸二甲酯的转化率达到100%, 并且乙二醇的选择性达到97%. 采用X射线粉末衍射、N2低温吸附、H2-TPR、N2O滴定、X射线光电子能谱及傅利叶变换红外光谱对系列催化剂进行了系统表征, 阐述了焙烧温度对催化性能影响的本质原因. 研究表明焙烧温度能够影响活性铜物种的分散度和铜物种与载体间的相互作用, 从而影响草酸二甲酯催化加氢的催化性能.