对氨基二乙基苯胺全差示光度法测定微量铬

详细实验了铬（Ⅵ）与对氨基二乙基苯胺氧化显色反应的条件。实验结果表明：铬（Ⅵ）与对氨基二乙基苯胺反应形成的红色产物在５５４ｎｍ处有最大吸收。表观摩尔吸收系数为３．３×１０＾４Ｌｍｏｌ＾－１．ｃｍ＾－１线性范围为０－１．６ｍｇ／Ｌ。实验了采用全差示光度法测定水中铬的条件，用于某湖水中４．０７μｇ／Ｌ的铬测定时，相对标准偏差为３．４％。测定结果与二苯胺基脲法的测定结果相比令人满意。     

人工神经网络分光光度法同时测定钼和铬

在钼，铬－二溴邻硝基苯基荧光酮－ＣＴＭＡＢ显色体系中，应用三层ＡＮＮ－ＢＰ网络解析钼和铬的吸收光谱，不经分离分光光度法同时测定钼和铬。钼和铬的表观摩尔吸光系数分别为ε５４５＝ ６．４８×１０４Ｌ·ｍ ｏｌ－ １·ｃｍ － １，ε５４７＝ １．５４×１０４Ｌ·ｍ ｏｌ－ １·ｃｍ － １。对合成样品和合金钢中钼和铬进行了同时测定，结果满意。使用改进的ＢＰ算法，避免了神经网络学习过程中可能产生的麻痹现象。提出了目标向量的简单变换方法及便于网络参数选择的收敛评价函数。     

某些偶氮胂类试剂高灵敏光度法测定铬(Ⅵ)

研究了氮胂Ⅲ,二溴硝基偶氮胂和二溴羧基偶氮胂３种偶氮胂类试剂与Ｃｒ２Ｏ＾２－７的褪色反应。发现它们在硝酸介质中具有高灵敏的褪色反应,摩尔吸光系数均达１×１０＾５Ｌ．ｍｏｌ＾－１．ｃｍ＾－１以上,是目前光度法测定Ｃｒ灵敏度最高的方法之一。可用于水中铬的测定。     

3,3‘,5,5’—四甲基联苯胺分光光度法测定水和废水中总铬

提出了３，３‘，５，５’－四甲基联苯胺测定水和废水中总铬的分光光度法。在Ｈ２ＯＳ４介质中，用ＫＭｎＯ４将水中所有铬氧化成六价铬，而铬能定量氧化ＴＭＢ生成黄色化合物。该化合物的最大吸收波长位于４５０ｎｍ，表观摩尔吸光系数为１．０４×１０＾５Ｌ．ｍｏｌ＾－１．ｃｍ＾－１，铬量在０－０．５０ｍｇ／Ｌ范围内服从比尔定律，用本文提出了方法测定了河水和电镀废水中的总铬，结果满意。     

3,3′,5,5′-四甲基联苯胺分光光度法测定水和废水中总铬

提出了３，３′，５，５′－四甲基联苯胺（ＴＭＢ）测定水和废水中总铬的分光光度法。在Ｈ２ＳＯ４介质中，用ＫＭｎＯ４将水中所有铬氧化成六价铬，而铬（Ⅵ）能定量氧化ＴＭＢ生成黄色化合物。该化合物的最大吸收波长位于４５０ｎｍ，表观摩尔吸光系数为１．０４×１０５Ｌ·ｍｏｌ－１·ｃｍ－１，铬量在０～０．５０ｍｇ／Ｌ范围内服从比尔定律，用本文提出的方法测定了河水和电镀废水中的总铬，结果满意。     

长光路萃取光度法测定痕量氟

以新型氟树脂长光纤作吸收池，用二甲苯胺的异戊醇作萃取剂，氟、硝酸镧与茜素络合剂形成三元络合物。为保持有机相的清澈，加入０．１０ｍＬ无水乙醇代替ＨＡｃ－ＮａＡｃ缓冲溶液洗涤有机相，并以乙醇稀释有机相后测定。用１１０ｃｍ长的毛细管５８０ｎｍ处测定吸收，氟的线性范围在０－３２μｇ／Ｌ服从比尔定律。该法具有高灵敏度，高稳定性等优点，于天然水中氟，对含氟０．１０ｍｇ／Ｌ－０．１３ｍｇ／Ｌ的水样，其回收率在９     

铬（Ⅵ）－SAF－H_2O_2褪色光度法测定污水中微量铬（Ⅵ）

在硼砂－氢氧化钾介质中，铬（Ⅵ）对过氧化氢氧化水杨基荧光酮褪色有催化作用，加入三乙醇胺可阻止催化反应。以此建立了微量铬（Ⅵ）的褪色光度法测定，该法不需加热，允许干扰量较大，灵敏度为１．０×１０￣（－９）／ｍＬ，ε＝１×１０￣５Ｌ．ｍｏｌ￣（－１）．ｃｍ￣（－１），０．０５～５．０μｇ／２５ｍＬ铬符合比尔定律，用于测定某些污水中之铬（Ⅵ），不需分离富集，其结果与二苯碳酰二肼法相符，加样回收９６～１０３％。     

离子交换树脂比色法在金属分析中的应用研究——Ⅰ.钨中铬的测定

吉村于1976年提出以离子交换树脂作载体直接对显色树脂进行光度测定的离子交换树脂比色法,并首先用二苯碳酰二肼作显色剂测定了水中微量铬,郭文生,李世豫用国产树脂分别测定了洗涤塔脲液和水中的铬。大関邦夫和Ohzeki用凝聚树脂比色法测定了水中ppb级的铬,但在金属分析中的应用尚未见报导。本文将此法应用于金属分析,可不经分离直接测定钨中的铬,测定下限达0.5×10~(-4)％。试验结果表明,离子交换树脂比色法所具有的选择性高,灵敏和快速的特点在金属分析中同     

国产大网状吸附树脂的应用 Ⅱ.上试402富集分光光度法测定水…

本文研究了用上试４０２吸附树脂富集铬－二苯卡巴腙（Ｃｒ－ＤＰＣ）分光光度法测定水中痕量铬（Ⅵ）的方法。结果表明水中ｐｐｂ级的Ｃｒ－ＤＰＣ在酸性条件下能吸着于上试４０２树脂上，用数毫升乙醇将Ｃｒ－ＤＰＣ定量淋洗下来，用可见分光光度法测定，实样的加标回收率＞９０％，结果令人满意。     

3－［（对－苯偶氮苯）－三氮烯］苯甲酸与镉和系的显色反应研究及其应用

本文合成了一种新的选择性显色剂：３－［（对－苯偶氮苯）－三氮烯］苯甲酸（ＰＡＢＴＢ）、该试剂在碱性介质中，在非离子表面活性剂存在下，能与镉和汞产生灵敏显色反应。其配合物的组成为ＣｄＬ２ＨｇＬ。摩尔吸光系数分别为εｃｄ＝１．３１×１０５和８．４４×１０４　Ｌ·ｍｏｌ－１·ｃｍ（－１）。共存离子中仅钯和铬有干扰。利用此反应建立了测定水中痕量镉与汞的分光光度法。     

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.