硅钼钒和硅钨钒杂多酸催化过氧化氢直接氧化苯制苯酚的活性研究

以自制的两种Keggin型杂多酸,硅钼钒杂多酸和硅钨钒杂多酸作催化剂,冰醋酸作溶剂,过氧化氢作氧化剂,研究了由苯直接羟基化制苯酚的催化活性,发现对于所研究的体系,即苯为0.02mol,过氧化氢为0.16mol,冰醋酸为0.24mol,当杂多酸的用量为0.10~0.15mmol、反应温度323K、反应时间80min时,硅钼钒和硅钨钒上苯酚的收率分别可达17.2%和4.3%,选择性达90.3%和87.4%.     

9—钼—3钒硅酸钾的合成与表征

钼钒硅杂多化合物作为氧化还原型催化剂应用于某些有机合成反应已引起化学工作者的关注,其合成与分离均有一定的难度,一钒及二钒取代的钼钒硅杂多化合物已有文献报道,但三钒取代的钼钒硅杂多化合物尚未见报道,本文采用正交设计方法,成功地合成了标题杂多化合物,并通过IR、UV、TG-DTA、~(51)V NMR和ESR等测试手段进行了表征。     

Keggin型磷钼钒季铵盐催化氧化苯制苯酚反应研究

采用分步反应、分步酸化法制备了磷钼钒缺位型杂多酸,用（C4H9）4N^＋（以下简写为Bu4N^＋）阳离子取代杂多酸中H^＋作为反荷离子合成了杂多季铵盐（用于苯氧化制苯酚反应）．FT-IR分析反应前后催化剂结构的变化．以苯为原料,乙酸为溶剂,30％H2O2作氧化剂,系统考察了催化剂类型、催化剂用量、氧化剂用量、反应时间及温度对反应的影响．实验结果表明,56．4mmol苯在（Bu4N）5PMo10V2O40用量0．25mmol,30％H2O2用量10mL,溶剂乙酸10mL,70℃条件下回流反应6h,苯酚收率可达到27．9％．     

钒改性六方介孔硅分子筛催化苯羟基化制苯酚

以偏钒酸铵为钒源,采用溶胶-凝胶法合成了不同钒含量的六方介孔硅（V-HMS）分子筛,利用X射线衍射、N2吸附-脱附和程序升温还原(H2-TPR)对合成的催化剂进行了表征,考察了V-HMS对苯羟基化反应的影响。 结果表明,钒进入了分子筛骨架,并且在HMS分子筛上具有较好的分散性。 V-HMS对苯羟基化反应具有良好的催化活性;高分散的钒氧物种有利于提高苯的羟基化反应性能,溶剂乙腈对反应促进作用明显。 乙腈为溶剂,w(V(5.8)-HMS)=2%,60 ℃反应5 h,苯酚收率达到18.55%,选择性达到100%。     

钒钼磷杂多酸催化苯直接羟化为苯酚的动力学研究

以钒钼磷杂多酸作为催化剂,用紫外可见分光光度法研究了过氧化氢直接将苯氧化羟基化为苯酚反应的动力学行为。结果表明,该氧化羟化反应速率对底物苯、氧化剂和催化剂都是一级反应,反应的活化能为57.73kJ.mol-1。本文推测了杂多酸配合物催化苯氧化羟化为苯酚反应的过程,建立了该反应动力学数学模型,模型很好地解释了实验结果。     

钼钒砷三元杂多酸氧化还原性能研究

杂多酸应用十分广泛 ,作为催化剂是迄今为止的一项最广泛、最重要、最具前途的应用。已经用杂多化合物作为催化剂实现工业化的大型项目有八个[1] ,创造了良好的经济效益和社会效益。杂多酸具有酸性和氧化性 ,作为酸型、氧化型或双功能催化剂 ,应用于许多均相和多相催化反应中。其中 ,具有 Keggin结构的杂多酸显示出良好的催化活性 ,是被广泛应用的酸种之一。杂多酸组成元素众多 ,可以通过调变元素的组成和比例来调变其氧化还原性 ,以适应各种不同的催化需要 ,这对于开发新型催化剂具有重要意义。本文合成了四种钼钒砷三元杂多酸 ,经表征确…     

高含量钒的钼钒磷杂多化合物的合成和性质研究

本工作改进了文献[4]报导的几种原料同时混合、加热煮沸合成的方法采用分步加入原料,控制反应温度、多次重结晶的方法合成了6、7、8个钒原子取代的钼钒磷杂多酸铵;并以铵盐为原料,用离子交换、冷冻分离和真空抽吸相结合的提纯方法制备了未见文献报导的相应的固体杂多酸;H₅[PMo₅V₇O_37.5]·xH₂O,H₆[PMo₄V₈O_37.5]·xH₂O。通过元素组成分析确定了它们的组成。这些杂多酸在水溶液、非水溶液中的电位滴定表明,杂多阴离子在分解前没有发生自电离、水解等情况,它们在水溶液中是稳定的。酸的碱度分别为5、5、6。通过纸上色谱实验,讨论了杂多酸的分解过程。由热重分析和溶解性实验得到它们的分解温度,本文还讨论了这些化合物的红外、紫外光谱,x光粉末衍射及极谱性质。光谱结果表明,它们可能具有Keggin结构,由导数脉冲极谱得到它们的峰电位。     

镱钼钒磷四元杂多化合物催化苯酚羟化分应的研究

合成了具有Keggin结构镱钼钒磷杂多化合物,用IR,UV,XRD,ICP等手段对其结构进行了表征,并研究了该杂多化合物对苯酚过氧化氢羟化反应的催化活性。实验结果表明：以甲醇为溶剂,用镱钼钒磷杂多化合物为催化剂,当（n(phOH):n(H2O2)=1:2,反应体系的pH=5.0,反应时间4h,苯酚转化率为41．66％,对苯二酚产率可达到40．24％。     

ICP-AES法测定1J22软磁材料中的锰、硅、镍、铜、钒

用电感耦合等离子体发射光谱仪(ICP)测定软磁材料1J22中的锰、硅、镍、铜、钒.通过试验选择了适宜的测试条件,针对1J22软磁材料中常见元素对锰、硅、镍、铜、钒谱线的光谱干扰选择了合适的分析谱线,并进行了精密度和准确度试验.选用Mn 257. 610 nm、Si 251. 611 nm、Ni 351. 505 nm、Cu 224. 700 nm、V 292. 402 nm为分析线时.合成溶液的回收率为92. 0%～114. O%,RSD为0. 33%～7. 73%(n=6).本方法适合1J22软磁材料中锰、硅、镍、铜、钒元素的测定.     

磷钨钒杂多酸相转移催化剂的制备及其深度氧化脱硫性能

以钒原子取代的Keggin型磷钨杂多酸与不同的季铵类阳离子表面活性剂反应合成了一系列磷钨钒杂多酸相转移催化剂,采用红外和X射线衍射对催化剂进行了表征。以H_2O_2为氧化剂,对模型柴油的氧化脱硫反应进行了研究,考察了季胺类表面活性剂种类、不同季胺盐含量、催化剂用量、氧硫比、反应温度等参数对反应的影响。结果表明,所制备的杂多酸相转移催化剂保留有杂多酸阴离子和季铵盐阳离子的结构特征。[(C_(16)H_(33)(CH_3)_3) N]_3H[PW_(11)VO_(40)]催化剂具有最佳的氧化脱硫性能和重复使用性能,在n(催化剂)/n(模型柴油)=1∶80,n(H_2O_2)/n(模型柴油)=8∶1,反应温度50℃,反应时间3 h的反应条件下,二苯并噻吩的转化率可达到100%;催化剂重复使用五次后,转化率为99.7%。反应过程中,该催化剂与反应物形成微乳体系,如同一个均相混合物,而反应结束体系静置一段时间后,催化剂和产物又形成两相,通过离心法就可以快速分离和回收催化剂。     

Enantioselective rhodium-catalysed addition of boronic acids using C2-symmetric aryl diphosphite ligands

The enantioselective rhodium-catalysed conjugate addition of aryl boronic acids to dehydroalanine derivatives has been successfully carried out in the presence of C₂-symmetric aryl diphosphite ligand (R,R,R-4) to prepare unnatural amino acid esters. The products have been obtained in up to 72% ee and with good isolated yield.     

Application of HPLC to characterization and control of individual acids in apple extracts and ciders

Summary Three HPLC methods have been tested in order to compare their separation of apple and cider organic acids. Optimum results for simultaneous determination of malic, citric, quinic, succinic, lactic and shikimic acids have been obtained using an RP-18 column with phosphate buffer as the mobile phase.This method was applied to organic acids monitoring during the ripening of apples and throughout the fermentation process. After filtration and degasification the organic acids in the sample were separated, and quantified by using a diode array detector.Recovery studies show good results for all solutes (88%–106%). The coefficients of variation show excellent precision (5%).     

氨基酸在甲醇—水混合溶剂中的气液平衡

采用改进的Ｒｏｓｅ釜测定了在３３３Ｋ和３３８Ｋ下，氨基乙酸、ＤＬ－氨基丙酸及Ｌ－氨基异戊酸在甲醇－水混合溶剂中的气液平衡数据。实验结果表明，当甲醇－水混合溶剂的相对组成固定时，体系的平衡压力与加入的氨基酸的浓度间存在线性关系，使已建立的含盐混合溶剂的“广义线性定理”进一步扩展到含有非挥发性物质的混合溶剂中。用热力学原理导出了线性方程的数学解析式；讨论了引入氨基酸对混合溶剂结构及性质的影响规律。     

七氟丁酰氨基酸正丁酯的GC/MS分析

本文报道了19种蛋白质氨基酸的七氟丁酰正丁酯衍生物的GC/MS分析方法;优选了衍生反应条件;建立了GC分离、定量分析方法,最小检测量为0.1ng;研究了衍生物的EI质谱数据,确定了可作为定性依据的特征离子;测定了儿童用复方氨基酸注射液及儿童血清样品,得到了满意的结果。     

临床化学上氨基酸、有机酸及核苷类的二维薄层色谱多相分离

在同一块薄层板上多相二维分离３０余种氨基酸、４０余种非挥发性有机酸和２０余种碱基。核苷类化合物。应用一对新的展开剂,用紫外灯－吖啶试剂－镉茚三酮试剂组合显色定位分析,改良了尿液非挥发性有机酸的溶剂萃取。尿液中此三类化合物提取物的多相二维色谱分离效果良好。     

Determination of free amino acids by precolumn derivatization with phenylisothiocyanate. Application to wine samples

Summary A method to determine free amino acids by pre-column derivatization with phenylisothiocyanate is discussed. The method has been applied to determine free amino acids in wine samples, and the results have been compared with those obtained by means of an automatic orthophthal-aldehyde-9-fluorenylmethyloroformate (OPA-FMOC) method.     

Preconcentration and separation of haloacetic acids by ion chromatography

A comparative study was made of the chromatographic behaviour of five haloacetic acids (mono-, dibromoacetic and mono-, di-, trichloroacetic acids). The techniques investigated included reversed-phase ion interaction chromatography with UV detection, suppressed and non-suppressed anion-exchange chromatography. The systems are discussed studying the retention as a function of the mobile phase parameters and the stationary phases used (LiChrospher 100 RP-18, IonPac AS9, AS10 and AS11). A preconcentration step, performed on different substrates, namely LiChrolut-EN and activated vegetal carbon, has been optimized in order to reduce the method detection limits. Results obtained for drinking water samples are shown.     

Ion-pair chromatography on a porous graphitic carbon stationary phase for the analysis of twenty underivatized protein amino acids

The analysis of twenty underivatized protein amino acids has been achieved on porous graphitic carbon packing material (Hypercarb). Five perfluoroalkyl carboxylic acids (trifluoroacetic, heptafluorobutyric, nonafluoropentanoic, tridecafluoroheptanoic and pentadecafluorooctanoic acid) have been studied as ion-pairing reagent. Several parameters (equilibration time, quantities adsorbed onto the chromatographic support, concentration and nature of the ion-pairing reagent, as well as temperature effect) have been studied leading to the complete separation of these compounds in gradient elution mode. Evaporative light scattering detector has allowed the detection of these non UV–visible absorbent molecules. The chromatographic methodology developed can also be easily coupled with pneumatically assisted electrospray mass spectrometry.     

Separation of some amino acids by supercritical fluid chromatography after a pre-derivatization step with classical reagents

Summary The separation of polar compounds by supercritical fluid chromatography is a difficult problem to solve. In this work, we have used a pre-derivatization method to obtain apolar or less polar compounds. Amino acids have been chosen as model polar compounds of biological interest, and 9-fluorenylmethyl chloroformate (FMOC) and (+)-1-(9-fluorenyl)ethyl chloroformate (FLEC) have been used as derivatizating reagents.With this procedure, the amino acids studied have been separated in less than 40 minutes with a good efficiency. Furthermore, with FLEC reagent, the enantiomeric separation was rapid in comparison with liquid chromatography techniques and the selectivities obtained were in the same order of magnitude.