偏最小二乘催化极谱法同时测定铂,钯,铑

应用Ｍ２７３Ａ电化学系统中的线性扫描技术，确定了０．７５ｍｏｌ／ＬＨ２ＳＯ４－１．５％ＮＨ４Ｃｌ－２．８ｍｍｏｌ／Ｌ（ＣＨ２）６Ｎ４－０．００２５％Ｎ２Ｈ４．Ｈ２ＳＯ４为偏最小二乘极谱法同时测定Ｐｔ、Ｐｄ、Ｒｈ的最佳极谱体系。Ｐｔ、Ｐｄ、Ｒｈ的线性范围为３．２ｍｇ／Ｌ、０－１５．０ｍｇ／Ｌ和０－１．０ｍｇ／Ｌ。模拟样品及实际样品的回收率在９０．３－１０７．７％之间。     

微分电位溶出法测定人发中铜铜镉锌的研究

本文报道了０．００２５ｍｏｌ．Ｌ＾－１ＨＣｌ－０．２ｍｏｌ．Ｌ＾－１ＮＨ４Ｃｌ底液中连续测定人发中铜、铅、镉、锌的微分电位溶出法。四元素峰电位分别为－０．２０Ｖ，－０．４６Ｖ，－０．６７Ｖ，－１．０２Ｖ（ＳＣＥ），峰形好，灵敏度高，干扰少，测定发样相对标准偏差≤４．３％，回收率为９７．６％－１０４．６％。并对ＨＮＯ３－ＨＣｌＯ４和ＮＨＯ３－Ｈ２Ｏ２消化发样进行了比较。     

含硫、氮Schiff碱配合物—二水二分之一二甲基亚砜醋酸四邻香草醛缩胺基硫脲合镉（Ⅱ）的合成及晶体结构

Ｘ射线单晶衍射结果表明，三核镉配合物Ｃｄ３［ＣＨ３Ｏ（Ｏ）Ｃ６Ｈ３ＣＨ＝ＮＮＨＣ（Ｓ）ＮＨ２］４·［ＣＨ３ＣＯＯ］２·１／２［ＣＨ３Ｓ（Ｏ）ＣＨ３］·２Ｈ２Ｏ为单斜晶系，空间群为Ｃ２／ｃ，ａ＝３．４２１４（４），ｂ＝１．１５８１（２），ｃ＝１．７９３２（５）ｎｍ，β＝１１９．７６（１）°，Ｖ＝６．１６８ｎｍ３，Ｍｒ＝１４２７．４３，Ｚ＝４，Ｄｃ＝１．５４ｇ／ｃｍ３，μ＝１２．４８ｃｍ（－１），Ｆ（０００）＝２８６０，最后偏离因子Ｒ＝０．０６６．     

微分电位溶出法测定人发中铜铅镉锌的研究

本文报道了０．００２５ｍｏｌ·Ｌ￣（－１）ＨＣｌ－０．２ｍｏｌ·Ｌ￣（－１）ＮＨ＿（４）Ｃｌ底液中连续测定人发中铜、铅、镉、锌的微分电位溶出法。四元素峰电位分别为－０．２０Ｖ，－０．４６Ｖ，－０．６７Ｖ，一１．０２Ｖ（ＳＣＥ），峰形好，灵敏度高，干扰少，测定发样相对标准偏差≤４．３％，回收率为９７．６％～１０４．６％。并对ＨＮＯ＿３－ＨＣｌＯ＿４和ＨＮＯ＿（３）Ｈ＿（２）Ｏ＿２消化发样进行了比较。     

4—CH3SC6H4NH2对α—磷酸锆的插层特性

制备了４－ＣＨ３ＳＣ６Ｈ４ＮＨ２（ＭＭＡ）插层的α－Ｚｒ９ＨＰＯ４）２．Ｈ２Ｏ，研究了不同实验条件下ＭＭＡ的插层特性，发现插层反应与ＭＭＡ和α－ＺｒＰ摩尔比Ｒ有关；（１）当Ｒ〉２时，有插层产物相产生，但是即使在ＭＭＡ大大过量的条件下，仍然有部分α－ＺｒＰ颗粒大小等有关；插层产物的层间距约为２．３６ｎｍ，，层间距的大小不随反应物浓度，温度等条件变化。     

精氨酸在苯甲醛存在下的吸附溶出伏安法研究

在０．２ｍｏｌ／ＬＮａＯＨ－０．０４ｍｏｌ／ＬＨ３ＰＯ４－０．０２ｍｏｌ／Ｌ（ＮＨ４）２ＳＯ４－０．０４ｍｏｌ／ＬＣＨ３ＣＯＯＨ溶液中，精氨酸（Ａｒｇ）在苯甲醛存在下产生一灵敏的吸附波。实验证明电活性物质为α－苯亚甲基精氨酸，其电极反应机理是分子内α－＞Ｃ＝Ｎ基团被还原为亚胺。用该吸附波可在１×１０（－３）～２×１０（－６）ｍｏｌ／Ｌ范围内分析蛋白质中的Ａｒｇ。     

过硫酸钾存在下人血清白蛋白的极谱平行催化氢波及其应用

报道 Ｋ２Ｓ２Ｏ８存在下人血清白蛋白（ＨＳＡ）的极谱平行催化氢波。在 ０．４ ｍｏｌ／Ｌ　ＮＨ３－ＮＨ４Ｃｌ（ｐＨ ８．５８）－０．０１ ｍｏｌ／Ｌ Ｋ２ｓ２Ｏ８支持电解质中，ＨＳＡ产生一个平行催化氢波，峰电位为－１．８５ Ｖ（ｖｓＡｇ／ＡｇＣｌ）。该平行催化氢波二阶导数峰电流与 ＨＳＡ浓度在 ２．６ × １０－９～９．６ × １０－９ｍｏｌ／Ｌ范围呈线性关系。用于人血清样和尿样中ＨＳＡ的测定，结果满意。     

若干Sc络合物的空间群

通过模拟结构因子计算将「（Ｃ４Ｈ９）４Ｎ」「Ｓｃ（ＮＣＳ）６」．３．５Ｈ２Ｏ的空间群从正交晶系的ｐｃａｂ修正为立方晶系的ｐａ３．将Ｓｃ（Ｃ１７Ｈ１３Ｎ２Ｏ２）３和「（Ｈ２Ｏ）１０（ＯＨ）２Ｓｃ２」（Ｃ６Ｈ５ＳＯ３）４．４Ｈ２Ｏ从Ｐ１修正为Ｃ２／ｃ。还将「Ｓｃ（ＮＯ３）３（Ｈ２Ｏ）３」．１８－Ｃｒｏｗｎ－６的Ｐｎａ２１修正为Ｐｎｍａ。     

4—氨基—3,5—二甲基—1,2,4—三唑水杨亚胺合铜[Ⅱ]配合物合成及其单…

４－氨基－３，５－二甲基－１，２，４－三唑与水杨醛缩合形成４－（邻羟苯基亚甲基）－亚胺－０３，５－二甲基－１，２，４－三唑Ｓｃｈｉｆｆ碱（ＳＡＴＺ），该Ｓｃｈｉｆｆ碱与Ｃｕ（ＣｌＯ４）２．６Ｈ２Ｏ形成配合物Ｃｕ（ｓａｔｚ）２．６Ｈ２Ｏ，分子式为Ｃ２２Ｈ２２ＣｕＮ８Ｏ２．６Ｈ２Ｏ。     

NH4HCO3对氧化铝孔结构的影响

ＮａＡｌＯ２溶液和ＣＯ２在低温下成胶,生成的沉淀为无定形氢氧化铝,拟薄水铝石或三水氧化铝;加入一定量的ＮＨ４ＨＣＯ３,控制一定的时间,温度和压力,氢氧化铝与ＮＨ４ＨＣＯ３作用生成片钠铝石ＮＨ４Ａｌ（ＯＨ）２ＣＯ３,经高温焙烧后可制香孔容为０．６－１．５ｍｌ／ｇ的大孔容氧化铝。     

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.     

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.     

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.     

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.     

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.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.