离子色谱的抑制系统及相关技术的发展

抑制系统是抑制型(双柱型)离子色谱系统极为重要的一个组成部分,也是离子色谱有别于其它类型的液相色谱的最重要特点之一。抑制器的发展经历了多个发展时期,而目前商品化的离子色谱仪亦分别采用不同形式的抑制手段。近年来,还发展了一些特殊的辅助抑制器,如接在抑制器后面CO2除去装置,用于提高被测离子的信号或进一步降低背景电导值。     

离子色谱的抑制及相关技术的发展

对于抑制型(双柱型)离子色谱系统,抑制系统是极为重要的一个组成部分,也是离子色谱有别于其它类型的液相色谱的最重要特点之一。抑制器的发展经历了多个发展时期,而目前商品化的离子色谱仪亦分别采用不同形式的抑制手段。近年来,还发展了一些特殊的辅助抑制器,接在抑制器的后面的CO2除去装置,都用于提高被测离子的信号或进一步降低背景电导值。     

1,2-二硒-3，4-二硫方酸的从头计算

在RHF／STO－3G、STO－3G和3－21G（仅对ZE型）水平上，用abinitioSCF方法优化得到1，2－二硒－3，4－二硫方酸（3，4－二巯基－3－环丁烯－1，2－二硒酮）三种平面异构体的平衡构型，进一步用3－21G／／STO－3G（对ZZ和EE型）方法计算总能量，发现三种平面导构体中ZZ型是最稳定构象，ZE型次之，并与1，2－二硒方酸和3，4－二硫方酸从头算结果作了比较，用abinitio数值方法在STO－3G水平上计算了三种异构体的谐振动频率．     

三电极电致膜阴离子抑制器的构建

制作了一个三电极电致膜抑制器,考察了加电方式、串连电阻阻值、电极间距对改善噪声的影响。相较于传统两电极抑制器,优化得到的三电极抑制器在抑制CO_3~(2-)-淋洗液时在噪声(～2.5倍)和信噪比(2.5～3.6倍)方面皆有一定程度的改善;所得三电极抑制器稳定性好,可与离子色谱结合后检测饮料中6种常见阴离子含量。     

无机物晶格能及其它理化性质的定量构效关系研究

于邻接矩阵和原子或离子的极化力参数（gi)建立新的连接性指数（^mG)，其中^0G,^1G的定义式为：^0G=∑（gi)^0.5,^1G=∑(gi.gj)^0.5。涉及14种离子（如X^-,O^2-,S^2-,Se^2-,Te^2-,PO4^3-,SiO4^4-,N^3-等）的192种无机物晶格能与^0G,^1G的线性性回归方程为：U＝－381.11 310.20^1G 354.45^0G,R=0.9975其估算值与实验值基本吻合，^1G不仅计算简单，对无机分子结构差异具有很强的区分能力，而且而碱金属卤化物的理化性质（如晶格能、熔点、磁化主、M－X键长，反应微分截面等）显著相关。     

聚合物支载的甘氨酸与Cu^2＋离子的络合性能

本文用N-（3-聚苯乙烯磺酰基-2-羟基丙基）甘氨酸为模型，研究了聚合物支载的氨基酸与Cu2 离子的络合作用性能。树脂与铜离子络合的介质最佳pH值在2～3之间。按照方程：－1n（1－F）=KTt处理求得吸附速率下数K288＝2．47X10－4sec－1。根据Boyd液膜扩散理论，这一吸附过程主要受液膜扩散控制。而且这个反应过程是一种Freundlish吸附过程。G=－30．91KJ／mole和S=129．90J／moleK表明，吸附反应是自发进行的。用斜率法和容量法求得树脂支载的氨基酸基因与铜离子之间的配位比为2:1。     

1，2－二甲氧基乙烷的真空紫外光电离和光解离

利用同步辐射真空紫外光对1，2－二甲氧基乙烷进行光电离解离研究，得到了 该分子的电离势为（9.33±0.04)eV，碎片离子CH_3OCH_2CH_3~+和CH_3OCH_2~+的 出现势分别为(9.83±0.05)eV, (9.99±0.05)eV，根据实验结果和B3LYP／6－31＋ G(d)理论计算的结果，分析了可能的解离通道，并得到了离子生成焓、键解离能这 些重要的热力学数据。     

钒离子与乙烷反应的理论研究

用量子化学方法在UB3LYP／6－311＋＋G（3df,3pd)水平上研究了一阶钒离子与乙烷的反应，找到了[VC2H6]^ 势能面上各驻点的结构，分析了反应过程中有关的电子转移性质，给出了CH4和H2的还原消队理。结果表明：CH4消除反应一般按加成－消除机理进行，在高能条件下也可按协同机理进行；H2分子消除反应，一般按1，2－H2分子消除机理进行，在高能条件下也可按1，1－H2分子消除机理进行。计算表明：能量最有利的反应通道是V^ C2H6→V(C2H4)^ H2，该反应放热11.82kJ/mol。     

聚氧乙烯型非离子表面活性剂Triton X-100和Tween-60的毛细管超临界流体色谱分析

对辛基苯酚惭烯型非离子表面活性剂ＴｒｉｔｏｎＸ－１００和聚氧乙烯失水山梨醇脂肪?酯型非离子表面活性剂Ｔｗｅｅｎ－６０进行毛细管超临界流体色谱法（ＣＳＦＣ）分析条件的研究，用ＣＳＦＣ连接通用型ＦＩＤ检测器研究了二种表面活性剂的组成和分子量，实验结果表明，ＴｒｉｔｏｎＸ－１００中含量最多的低聚物的ＥＯ数（聚合的环氧乙烷数目）为９－１０，分子量约６００，Ｔｗｅｅｎ－６０的分子量约为１５００，与理论计算值     

毛细管离子色谱进展

从毛细管离子色谱柱制备和毛细管离子色谱仪器研制两方面评述了毛细管离子色谱目前的发展状况。毛细管离子色谱柱包括开管离子色谱柱，毛细管颗粒填充离子色谱柱以及最近几年发展起来的整体毛细管离子色谱柱。对毛细管离子色谱仪的总结包括微流量泵、小体积进样器、适合毛细管离子色谱系统的小体积抑制器、电导和光学检测器等。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.