偶氮氯膦Ⅲ—希土极谱络合吸附波的研究

在０．０６ｍｏｌ／Ｌ ＮａＡｃ－ＨＡｃ ｐＨ４．５的缓冲底液中，偶氮氯膦Ⅲ（ＣＰＡⅢ）在－０．２５Ｖ（ｖｓ．Ａｇ／ＡｇＣｌ）有一良好的微分脉冲极谱还原波，加入希土（ＲＥ）后期峰高电流（ｉｐ）降低，轻希土浓度在１×１０＾－６～６×１０＾－６ｍｏｏ／Ｌ，钇和重希土浓度在２×１０＾－７～３×１０＾－６ｍｏｌ／Ｌ范围中，ｉｐ的降低与浓度呈线性关系，表明ＣＰＡⅢ亦是可用的希土极谱分析试剂。实验证明它们是不可     

3,3‘—四亚甲基—双—（1—苯基—5—吡啶酮—4—羟酸酯）极谱行为研究

ＴＰＰＣ在０．０８ｍｏｌ／ＬＣＨ３ＣＯＯＮａ和０．４ｍｏｌ／ＬＣＨ３ＣＯＯＨ（ＮａＡｃ－ＨＡｃ下同）底液条件下，在电位－１．５７Ｖ附近产生一尖锐的导数波，峰高在３．７×１０＾－６－５．６×１０＾－５ｍｏｌ／Ｌ范围内呈线性关系，同时，讨论了极谱波的性质及电极反应机理。     

铜—腺嘌呤络合物吸附波的研究

了在０．０８ｍｏｌ／ＬＮａＡｃ～０．０２ｍｏｌ／ＬＨＡｃ缓冲溶液铜与腺嘌呤（Ａｄｅ）络合物的极谱行为，结果表明，扫描电压为－０．２Ｖ～－０．７Ｖ时铜－腺嘌呤络合物在单扫示波极谱上有一络合物吸附波，其一阶导数峰电位主－０．４Ｖ（ｖｓ．ＳＣＥ），腺嘌呤浓度在１．０×１０＾－６～１．０×１０＾－５ｍｏｌ／Ｌ范围内与一阶导数波高呈良好的线性关系，检出限为１．０×１０＾－７ｍｏｌ／Ｌ，实验证明，该峰具有吸附     

大黄酚的电化学行为及其应用研究

大黄酚在０．１５ｍｏｌ／Ｌ ＨＡｃ－ＮａＡｃ（ｐＨ４．９）底液中，出现一灵敏的示波极谱导数峰，峰电位为－０．４５Ｖ（ｖｓ，ＳＣＥ），峰电流与大黄酚浓度在２．０×１０＾－７－５．０×１０＾－６ｍｏｌ／Ｌ范围内成线性关系，检测限为２．０×１０＾－６ｍｏｌ／Ｌ。用于生药大黄中大黄酚的测定，回收率为９２．４％－１０８．４％。用多种电化学手段研究体系的电化学行为，测得电极反应电子数ｎ＝２。体系具有吸附性，并     

阿霉素在钴离子注入修饰电极上的电化学行为及其应用

阿霉素在０．１ｍｏｌ／Ｌ ＨＡｃ－ＮａＡｃ（ｐＨ４．６２）缓冲溶液中用注入钴的修饰玻碳电极为工作电极进行伏安测定,得到一良好的还原峰;Ｅｐ＝－０．５２２Ｖ（ｖｓ．ＳＣＥ）。峰电流与阿霉素浓度在１．４×１０＾－６－１．４×１０＾－６ｍｏｌ／Ｌ和１．４×１０＾－６－５．６×１０＾－５ｍｏｌ／Ｌ范围内呈线性关系,。     

哌仑西平的单扫描示波极谱法测定

本报道一种测定哌仑西平的单扫描示波极谱法，在０．１ｍｏｌ／ＬＮＨ４Ｃｌ－ＮＨ３．Ｈ２Ｏ（ｐＨ８．０±０．１）缓冲液中，哌仑西平有一极谱还原波，其峰电位为－１．５１Ｖ（ｖｓ．ＳＣＥ），其一阶导数峰高与哌仑西闰浓度在６．６×１０＾－７－４．６×１０＾－６ｍｏｌ／Ｌ（ｒ＝０．９９８１）和６．６×１０＾－６－１．６×１０＾－５ｍｏｌ／Ｌ（ｒ＝０．９９９１）范围内有线性关系，检测限为３．４×１０－７ｍｏｌ     

单扫描示波极谱法测定甘草酸

本文报道测定甘草酸的单扫描法波极谱方法，在０．１ｍｏｌ／ＬＮａＡｃ－ＨＡｃ（ｐＨ４．１±０．１）缓冲液中，甘草酸还原波峰电位为－１．３８Ｖ（ｖｓ．ＳＣＥ），峰高与其浓度在２．０×１０＾－６～１．０ ×１０＾－４ｍｏｌ／Ｌ范围内有线性关系，检测限为１．２×１０＾－６ｍｏｌ／Ｌ。甘氨酸，半胱氨酸等不干扰测定。应用本方法测定强力宁注射液中甘草酸含量，结果令人满意。本文还讨论了电极过程机理。     

钒（Ⅴ）—向红菲咯啉的络合吸附波

在ＰＨ４．０２的０．０２ｍｏｌ／ＬＨＡｃ－ＮａＡｃ介质中，研究了钒（Ⅴ）向红菲咯啉（ＢＰＴ）的极谱行为。钒（Ⅴ）－ＢＰＴ络合物在滴汞电采上于－０．３６Ｖ得到一良好的吸附还原波，在聚乙烯醇（ＰＶＡ）存在下，其二阶导数值一钒（Ⅴ）浓度在５．０×１０６－８－４．０×１０＾－６ｍｏｌ／Ｌ范围内呈线性关系；检出限可达９．０×１０＾－９ｍｏｌ／Ｌ。应用该法测定饮用水及碳素钢中微量钒，结果较好讨论了ＰＶＡ的影响     

一阶导数差示脉冲极谱法测定氢氯噻嗪的研究

本研究了一阶导数差示脉冲极谱法用于氢氯噻嗪及其制剂的定量分析。在０．００２ｍｏｌ／Ｌ盐酸－０．００２ｍｏｌ／Ｌ氯化钾底液中，于０．０５０Ｖ（ｖｓ．Ａｇ／ＡｇＣｌ）处出现良好的一阶导数极谱峰，氢氯噻嗪浓度在０～６．０×１０＾－４ｍｏｌ／Ｌ范围内，与峰高呈线性关系，检测限为４．０×１０＾－９ｍｏｌ／Ｌ。方法操作简便、快速、灵敏、结果准确。     

淋必治的极谱研究

在０．１ｍｏｌ／Ｌ ＨＡｃ－ＮａＡｃ（ｐＨ４．５０）支持电解质中，淋必治（ＳＰＥ）有一灵敏的示波极谱导数还原峰，峰电位Ｅｐ＝－０．９８Ｖ（ｖｓ．ＳＣＥ）。峰电流与ＳＰＥ的浓度在２．０×１０＾－７￣８．０×１０＾－５ｍｏｌ／Ｌ范围内呈线性关系，最低检出限为５．０×１０＾－８ｍｏｌ／Ｌ。该法用于注射针剂中ＳＰＥ含量的测定。，结果良好。文中对ＳＰＥ的极谱行为、电极过程及反应机理进行了探讨。     

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.     

关于"对‘燃料电池物理及化学性能的有限时间热力学分析方法'的讨论”答复

把有限时间热力学理论用于化学过程的研究,将会得到一系列新的结论,开展这方面的研究是很有意义的.文献[1]以燃料电池为例,在同时考虑化学反应及传热不可逆性的情况下,研究了燃料电池的性能界限,文献[2]指出了文献[1]计算化学反应及传热不可逆性而引起系统与有关环境的总熵产生率的错误以及由此而导致的结论所存在的问题,并进行了富有启发性的分析与讨论.但文献[2]对于系统与有关环境的总熵产生率的计算也是不正确的,由此得到的其它结论自然不能成立.本文将就此情况下系统与有关环境的总熵产生率的计算再次进行讨论,并给出电池功率和效率的有限时间热力学性能界限.