NaIO4-肾上腺色腙体系化学发光法测定肾上腺色腙

利用ＮａＩＯ４－Ｈ＾＋－Ｈ２Ｏ２－肾上腺色腙化学发光体系,结合流动注射技术建立了一种测定肾上腺色腙的化学发光新方法。方法的线性范围为８．０＊１０＾－９－１．０＊１０＾－６ｇ／ｍＬ肾上腺色腙,检出限为２．７＊１０＾－９ｇ／ｍＬ,相对标准偏差为０．９７％。     

水杨酸甲酯制备实验的改进

"水杨酸甲酯的制备"是一个经典的有机化学实验，作为考核实验考查学生操作技能，并根据产品的质量和纯度给予学生成绩。教材中提供的实验方案不合理，导致学生制备产品的收率很低。对传统实验方法的不足之处进行分析，提出了先用碳酸钠中和硫酸（去除催化剂），再蒸馏分离甲醇的实验路线。改进的实验方案设计更合理，避免了水杨酸甲酯分解，提高了产品的收率，达到了良好的教学效果。     

Studies on Salicylate Complexes of Lanthanum

Stoichiometric determination of complexes of La (III) with some derivatives of salicylic acid by monovariation and Job's method of continuous variation have shown formation of 1:3 complex in each case. The dissociation constants of these complexes have been determined by conductometric and spectrophotometric methods.     

Zur Bestimmung der Alkalibenzoate und Salicylate

Ohne Zusammenfassung     

新型水杨酸根离子选择性电极的研究

本文报道了基于Mn(Ⅲ)Schiff碱为中心载体的新型溶剂聚合膜离子选择性电极。电极对水杨酸根离子(Sal-)具有优良的电位响应特性并呈现反Hofmeister选择性行为。电极在pH5.5的磷酸盐缓冲体系中,对Sal-在1.0×10-1～2.0×10-5mol·L-1浓度范围内呈近能斯特响应,斜率为-51mV/p[Sal-],检出限为8.0×10-6mol·L-1。电极具有响应快、重现性好、制备简单等优点。将电极初步应用于药物分析,得到较满意的结果。     

创新化学实验:水杨酸异戊酯的制备*

酯化反应是有机化学教学实验中最重要的实验种类,不同的酯合成方法有很大区别,这些实验培养了学生的实践能力,在教学实验的基础上,对水杨酸和异戊醇的酯化反应进行了研究探索。水杨酸异戊酯是一种前景广阔,极具开发价值的产品,研究其合成方法具有很大的潜在经济效益和社会效益。采用分水分馏方法,以环己烯为带水剂,高效合成水杨酸异戊酯,产品收率达85.9%。通过研究水杨酸异戊酯的合成方法,培养了学生独立思考的创新能力和勇于探索的科学精神,达到了良好的教学效果。     

A Fluorescence Spot Test for Salicylate Determination

Abstract

A procedure based on a spot test for salicylate is presented. The method is simple, rugged and is based on the salycilate native fluorescence measurement on the surface of a filter paper by using optical fibers for light conduction. The fluorescence was linear at concentration range of 0.01–0.4 mmol l^?1. The relative standard deviation of 5% (n=10) was observed. Detection and quantification limits were 4 and 14 µmol l^?1, respectively. The results obtained in pharmaceutical salicylate determinations showed that practically no statistical difference existed with the pharmacopeical method (95% confidence level). The recovery studies in biological samples spiked with salicylic acid at overdose concentration levels showed that the matrix sample did not interfere in the method.     

水杨酸钴非等温热分解动力学研究

用热分析(TG/DTG)、X射线衍射(XRD)技术研究了固态物质水杨酸钴在空气中热分解的过程。热分析结果表明,水杨酸钴在空气中分两步分解,其失重率与理论计算失重率相吻合;XRD结果表明,水杨酸钴分解的终产物为Co3O4。用Friedman法和Flynn-Wall-Ozawa(FWO)法求取了分解过程的活化能E,并用多元线性回归和多元非线性回归法给出了可能的机理函数,由这些方法得到的动力学数据相互比较吻合。     

赝势平面波计算铀及铀化合物结构研究

Ultrasoft pseudopotential was generated for uranium and the plane waves pseudopotential formalism was used to study its crystal structures at zero temperature as a function of pressure. The alpha phases of uranium were fully relaxed. The zero-pressure zero-temperature equilibrium volumes and bulk moduli are consistent with previous calculations, and in excellent agreement with the experiment. This is also the case for cell parameters and pressure-induced phase transitions. In the calculation of NaCl and CaF2 structure type of compound of uranium, the difference of theoretical lattice constant and the experimental value is less than 3%. For UO2+x the trend of the lattice shinking with the x value increase is in accord with the experiment. For large U2C3 and U2N3 complex cells the difference of theoretical lattice constant and the experimental value is less than 3%, and the difference of coordination of atom is less than 5%.     

Hydrotropic Behavior of Sodium Salicylate in Presence of Additives

It is well known that, like surfactants aggregating at a certain concentration (called critical micelle concentration, CMC), hydrotropes also have minimum hydrotrope concentration (MHC). However, unlike surfactant CMC, this MHC value is usually very high, thereby reducing their application. In this paper we report the results of conductivity and viscosity measurements with a well known hydrotrope sodium salicylate (NaSal) solutions in presence and absence of additives (propanol, PrOH; butanol, BuOH; pentanol, PeOH and tetrabutylammonium bromide, Bu₄NBr). We have found that MHC value of NaSal decreases in presence of additives. Alcohols increase the hydrophobic interactions and decrease the MHC while Bu₄NBr, in addition to ameliorating the hydrophobic interactions, reduces the charge on head groups and MHC decreases more steeply in its presence. Increased solubility of riboflavin in NaSal containing the above additives corroborates the results.     

解密铀元素

简介了铀元素的发现历史、基本核性质、独特的电子结构以及相关的配位化学性质;同时,还介绍了铀元素在核燃料、分子催化、单分子磁体、超导等方面的应用。     

水杨酸-2′-乙基己基酯在胶束中的增溶位点

考察了阳离子、非离子和阴离子表面活性剂存在下水杨酸-2′-乙基己基酯(EHS)的吸收光谱和激发态分子内质子转移(ESIPT)荧光光谱.结果表明,EHS可增溶在胶束中,2′-乙基己基碳链朝向胶束内核,而水杨酸基朝向胶束-水界面;胶柬环境有利于EHS分子对紫外光的吸收和分子内氢键的形成,从而使ESIPT荧光显著增强,激发态分子以发射可见光和非辐射去活化方式衰减;并根据EHS和表面活性剂分子的结构和大小,解释了EHS分子在胶束中的结合位点,荧光猝灭和酯水解的光谱测量进一步为此结合位点提供了佐证.     

Salicylate metal-binding isosteres as fragments for metalloenzyme inhibition

Metalloenzyme inhibitors typically share a common need to possess a metal-binding pharmacophore (MBP) for binding the active site metal ions. However, MBPs can suffer from physicochemical liabilities, impeding the pharmacological properties and drug-likeliness of inhibitors. To circumvent this, problematic features of the MBP can be identified and exchanged with isosteric replacements. Herein, the carboxylic and hydroxyl group of the salicylic acid MBP were replaced and a total of 27 salicylate metal-binding isosteres (MBIs) synthesized. Of these 27 MBIs, at least 12 represent previously unreported compounds, and the metal-binding abilities of >20 of the MBIs have not been previously reported. These salicylate MBIs were examined for their metal-binding features in model complexes, physicochemical properties, and biological activity. It was observed that salicylate MBIs can demonstrate a range of attractive physicochemical properties and bind to the metal in a variety of expected and unexpected binding modes. The biological activity of these novel MBIs was evaluated by measuring inhibition against two Zn²⁺-dependent metalloenzymes, human glyoxalase 1 (GLO1) and matrix metalloproteinase 3 (MMP-3), as well as a dinuclear Mn²⁺-dependent metalloenzyme, influenza H1N1 N-terminal endonuclease (PA_N). It was observed that salicylate MBIs could maintain or improve enzyme inhibition and selectivity. To probe salicylate MBIs as fragments for fragment-based drug discovery (FBDD), an MBI that showed good inhibitory activity against GLO1 was derivatized and a rudimentary structure–activity relationship was developed. The resulting elaborated fragments showed GLO1 inhibition with low micromolar activity.

Metal-binding isosteres (MBIs) of salicylic acid have been developed for metalloenzyme drug development.     

Microbiosensor for Salicylate Based on Modified Carbon Fibre

ABSTRACT

A microbiosensor is proposed for a quick and easy amperometric determination of salicylate. The methodology involves the use of the enzyme salicylate hydroxylase (SH) to convert salicylate to catechol, which is then oxidised at the carbon fibre electrode. The covalent immobilisation of the enzyme onto a carbon fibre electrode via carbodiimide results in an amperometric biosensor with high sensitivity, low detection limit and good stability. The response of the biosensor is linearly proportional to the salicylate concentration between 1.0 10^?7 and 2.0 10^?6 mol L^?1, at an applied potential of 300 mV vs SCE, with a response time of 3.5 s and a detection limit of 3.3 10^?8 mol L^?1. The relative standard deviation for the determination was 4.1% for n=10. The biosensor was applied to determine salicylate in urine and pharmaceutical samples and compared to the reference method with a good correlation.     

水杨酸-2’-乙基己基酯在胶束中的增溶位点

考察了阳离子、非离子和阴离子表面活性剂存在下水杨酸-2’-乙基己基酯(EHS)的吸收光谱和激发态分子内质子转移(ESIPT)荧光光谱. 结果表明, EHS可增溶在胶束中, 2’-乙基己基碳链朝向胶束内核, 而水杨酸基朝向胶束-水界面; 胶束环境有利于EHS分子对紫外光的吸收和分子内氢键的形成, 从而使ESIPT 荧光显著增强, 激发态分子以发射可见光和非辐射去活化方式衰减; 并根据EHS和表面活性剂分子的结构和大小, 解释了EHS分子在胶束中的结合位点, 荧光猝灭和酯水解的光谱测量进一步为此结合位点提供了佐证.     

Thiosemicarbazone Complexes of Uranium

Acetylpyridine thiosemicarbazone, HAPTSC ( 1 ), reacts with uranyl nitrate in MeOH under formation of (H₂APTSC)[UO₂(NO₃)₂(μ‐OH)]₂ ( 2 ) or [ UO₂(APTSC)(MeOH)(MeO)]₂ ( 3 ) depending on the experimental conditions applied. Protonation of 1 and precipitation of the [UO₂(NO₃)₂(μ‐OH)]₂^2— dianion as acetylpyridinium thiosemicarbazone salt is observed when the reaction is performed without the addition of a base. The metal atoms are situated in the centres of distorted hexagonal bipyramids. The U—U distance is 3.892(1)Å. Addition of triethylamine results in deprotonation of HAPTSC and the formation of 3 which is an unusual dimer with four methanol/methanolato ligands of two metal sites sharing two protons. The U—U distance in this dimer is 5.313(1)Å. (Bu₄N)[UO(APTSC)Cl₂] ( 4 ) is obtained when (Bu₄N)₂[UO₂Cl₄] is used as precursor. The uranium atoms in 3 and 4 are seven co‐ordinate. Their co‐ordination polyhedra can best be described as pentagonal bipyramids. Compounds 3 and 4 represent the first examples of thiosemicarbazone complexes with actinide elements which haven been studied by X‐ray analysis.     

Atomistic Model of Uranium

The electronic state and potential data of U₂ molecules are performed by first principle calculations with B3LYP hybrid exchange-correlation functional, the valence electrons of U atom are treated with the (5s4p3d4f)/[3s3p2d2f] contraction basis sets, and the cores are approximated with the relativistic effective core potential. The results show that the ground electronic state is X⁹∑⁺_g . The pair potential data are fitted with a Murrell-Sorbie analytical potential function. The U-U embedded atom method (EAM) interatomic potential is deter-mined based on the generalized gradient approximation calculation within the framework of the density functional theory using Perdew-Burke-Ernzerhof exchange-correlation functional at the spin-polarized level. The physical properties, such as the cohesive energy, the lattice constant, the bulk modulus, the shear modulus, the sc/fcc relative energy, the hcp/fcc rela-tive energy, the shear modulus and the monovacancy formation energy are used to evaluate the EAM potential parameters. The U-U pair potential determined by the first principle calculations is in agreement with that defined by the EAM potential parameters. The EAM calculated formation energy of the monovacancy in the fcc structure is also found to be in close agreement with DFT calculation.