新荧光试剂—3—邻甲苯基—5—（2‘—羧基苯偶氮）绕丹宁的荧光性质研究

本文报道新荧光试剂－３－邻甲苯基－５－（２’－羧基苯偶氮）绕丹宁（３ＯＭＲＡＣＰ）的荧光特性，建立了荧光分析测定铜的方法，在ｐＨ５．６时，３ＯＭＲＡＣＰ与铜（Ⅱ）形成螯合物，并在λｅｘ／λｅｍ＝３０８ｎｍ／４０５ｎｍ产生强烈荧光，其荧光强度与铜（Ⅱ）的浓度在０．１～４．０×１０＾－２μｇ／ｇ范围内呈线性关系，检测限达５×１０＾－４μｇ／ｇ。测定了人发中的痕量铜，结果满意。     

铬（VI）与5—溴水杨基荧光酮的显色反应及应用

本文研究了Ｃｒ（Ⅵ）与５－溴水杨基荧光酮（５－Ｂｒ－ＳＡＦ）的显色反应。在ｐＨ６．０ＫＨ２ＰＯ４－ＮａＯＨ缓冲溶液中，Ｃｒ（Ⅵ）与５－Ｂｒ－ＳＡＦ、ＣＴＭＡＢ形式稳定的三元络合物，其最大吸收波长为５７２ｎｍ，表观摩尔吸光系数为１．４２×１０＾５Ｌ·ｍｏｌ＾－１·ｃｍ＾－１。Ｃｒ（Ⅵ）浓度在０￣２．５μｇ／１０ｍＬ间服从比耳定律。用此法测定了环境水样中微量Ｃｒ（Ⅵ），获得满意结果。     

Fe（Ⅲ）—TEA—5—Br—PADAP—H2O2体系中催化波的研究及其应用

在０．２ｍｏｌ·Ｌ＾－１ＮＨ４Ｃｌ－ＮＨ３·Ｈ２Ｏ底液中，（ｐＨ为９．２６），得到一个极为灵敏的Ｆｅ（Ⅲ）－ＴＥＡ－５－Ｂｒ－ＰＡＤＡＰ－Ｈ２Ｏ２配合吸附催化波，其峰电位为－０．７１Ｖ（ｖｓ．ＳＣＥ）。铁浓度在１．８×１０＾－１０￣５．４×１０＾－６ｍｏｌ·Ｌ＾－１范围内与二阶导数波高呈线性关系。对该极谱波的性质进行了研究，证明是一种配合吸附催化波，并成功地应用于各类水样，钒催化剂中微量或痕量铁的     

3,3′,5,5′—四甲基联苯胺吸光光度法测定水中NO2^——N

提出用３,３′,５－５′－四甲基联苯胺（ＴＭＢ）吸光光度法测定水中ＮＯ２＾－－Ｎ。在ＨＯＡｃ－ＮａＯＡｃ缓冲液（ｐＨ３．６）中,ＴＭＢ与ＮＯ２＾－反应生成蓝色的ＴＭＢ－ＴＭＢ亚胺传荷络合物,其最大吸收波长为６５０ｎｍ,表观摩尔吸光系数为２．５９×１０＾４,ＮＯ２＾－－Ｎ与０～０．５μｇ·ｍｌ＾－１范围内服从比耳定律。运用此法测定了环境水样并进行了加标回收试验,结果满意。     

铍（Ⅱ）—均三溴偶氮胂配合物吸附波的研究

在ｐＨ９．２０的ＮＨ３．Ｈ２Ｏ－ＮＨ４Ｃｌ介质中，铍与均三溴偶氮胂（ＴＢＡ）的形成配合物，于－０．５５Ｖ（ｖｓ．ＳＣＥ）处产生一灵敏的配合物吸附波，峰电流与Ｂｅ浓度在８．０×１０＾－８～２．０×１０＾－６ｍｏｌ／Ｌ范围内呈线性关系。测得铍与均三溴偶氮胂的配合比为Ｂｅ（Ⅱ）：ＴＢＡ＝１：１，稳定常数β＝３．０×１０＾，电子转移数ｎ＝２，峰电流由配合物中配位体ＴＢＡ还原产生。可不经分离直接测定矿样中铍     

大量锆存在下铪镧钼杂多酸—耐尔蓝体系测定给

本文研究了耐尔蓝（ＮＢ）－给镧钼杂多酸（ＨｆＬａＭｏ－聚乙烯醇（ＰＶＡ）体系测定铪的超高灵敏光度法。在ＰＶＡ存在下，铪，镧和钼酸铵形成杂多酸，继而与耐尔蓝形成离子缔合物。其适宜条件为〔ＨＣｌｏ４〕＝１．２ｍｏｌ／Ｌ，〔Ｌａ×３＋〕＝２．９×１０＾－７ｍｏｌ／Ｌ，〔ＭｏＯ４×２－〕＝１．１×１０＾－３ｍｏｌ／Ｌ，〔ＮＢ〕＝２．７×１０＾－６ｍｏｌ／Ｌ，ＰＶＡ０．０８％。离子缔合物的最大吸收波长在５９     

葡萄糖脱氢酶微型生物传感器的研制及应用

以甲苯胺兰（ＴＢ）修饰碳糊微电极为基体，将葡萄糖脱氢酶（ＧＤＨ）用丝素蛋白膜固定于修饰微电极表面制成了生物传感器，在ｐＨ７．０的ＮａＯＨ－ＮａＨ２ＰＯ４缓冲溶液中，烟酰胺腺嘌呤二核苷酸（ＮＡＤ）的浓度为１．０４×１０＾－３ｍｏｌ／Ｌ的条件下，其响应电流与葡萄糖浓度在１．０×１０＾－４～３．２×１０＾－３ｍｏｌ／Ｌ范围内有良好线性关系，响应时间为２０ｓ；检测限为４．０×１０＾－５ｍｏｌ／Ｌ。该传感器     

钍钼杂多酸—丁基罗丹明B测定岩矿口痕量钍

本文报道了一个灵敏度高，选择性好的测定痕量钍的新光度分析法。在聚乙烯醇存在下，钍钼杂多酸和丁基罗丹明Ｂ形成离子缔合物，其适宜条件为ＣＨＣｌＯ４＝１．３ＭＯＬ／Ｌ，ＣＭｏＯ＾２－４＝６．８×１０＾－４ｍｏｌ／Ｌ，ＣＢＲＢ＝２．７×１０＾－５ｍｏｌ／Ｌ，ＰＶＡ０．０８％。     

铜（Ⅱ）—4,7—二苯基—1,10—邻菲罗啉二磺酸根—聚吡咯H2O2传感器的研制

通过电化学方法将４，７－二苯基－１，１０－邻菲罗啉二磺酸黄盐（ＤＰＳ）的Ｃｕ（Ⅱ）络阴离子掺入聚吡咯（ＰＰｙ）薄膜内，制成ＰＰｙ／（ＤＰＳ）２ＣｕＨ２Ｏ２传感器，该传感器对Ｈ２Ｏ２的电还原过程有明显催化作用，催伦电流和Ｈ２Ｏ２浓度在５．０×１０＾－６～１．０×１０＾－３ｍｏｌ／Ｌ，范围内呈良好性关系，用于模拟样品中Ｈ２Ｏ２的测定。     

特丁醇和水混合溶剂多组分电解质热力学HC1—NaCl—tert._C4H9OH—H2…

本在恒定特丁醇质量分数ｘ＝０．１０的条件下，应用电动势测定了无液接界电池（Ａ）和电池（Ｂ）的电动势：Ｐｔ，Ｈ２（１．０１３×１０＾５Ｐａ）｜ＨＣ（ｍ），ｔｅｒｔ．－Ｃ４Ｈ９ＯＨ（ｘ），Ｈ２Ｏ（１－ｘ）｜ＡｇＣｌ－Ａｇ （Ａ） Ｐｔ，Ｈ２（１．０１３×１０＾５Ｐａ）｜ＨＣｌ（ｍＡ），ＮａＣｌ（ｍＢ），ｔｅｒｔ．－Ｃ４ＨｏＯＨ，Ｈ２Ｏ（１－ｘ）｜ＡｇＣｌ－Ａｇ （Ｂ）根据电池（Ａ）电动势确定了     

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.