甲硫富瓦烯为介体的碳纤维束葡萄糖氧化酶微电极的研究

本研究了一种将电子介体四硫富瓦烯（ＴＴＦ，Ｔｅｔｒａｔｈｉａｆｕｌａｌｅｎｅ）引入葡萄糖氧化酶微电极的新方法，制成了ＴＴＦ为介体的碳纤维束葡萄氧化酶微电极。该电极制作简单，响应迅速，灵敏，电极寿命可达１５天。葡萄糖浓度在１．０×１０＾－＾４－１．５×１０＾－＾３ｍｏｌ／Ｌ范围内有线性关系，检出限为７×１０＾－＾５ｍｏｌ／Ｌ。用于人体血样中葡萄糖测获得满意结果。     

四氰基醌二甲烷修饰碳糊电极催化氧化测定多巴胺

以四氰基醌二甲烷（ＴＣＮＱ）作介体,制成ＴＣＮＱ修饰碳糊电极。研究该电极的性能。该电极对多巴胺（ＤＡ）有良好的电催化氧化作用,在ＤＡ浓度６．７５×１０＾－５－６．７５×１０＾－３ｍｏｌ·Ｌ＾－１内。催化电流与ＤＡ浓度呈线性关系,响应时间小于１０ｓ。该电极用于针剂中多巴胺测量,结果较好。     

四氰基醌二甲烷修饰碳糊电极电催化氧化测定抗坏血酸

本用四氰基醌二甲烷作价体，制成ＴＣＮＱ－碳糊电极，研究了该电极的性能。电极对水溶液中的抗坏血酸在较宽的ｐＨ和浓度范围内均有良好的电催化氧化作用，电极的稳定性良好，在ＡＨ２浓度５．０×１０＾－５－５．０×１０－２ｍｏｌ／Ｌ范围内，催化峰电流与ＡＨ２浓度呈线性关系，响应时间小于３０ｓ．     

铅基磷酸铅化学修饰电极的研究

本研制了铅基磷酸铅化学饰电极，并研究了该ＣＭＥ的性能。实验发现，该ＣＭＥ是一种磷酸根离子敏感电极。电极对磷酸盐有类能斯特响应，在ＰＨ４．０和６．０下，其线性范围分别为１×１０＾－３－１×１０＾－１和１×１０＾－４－１×１０＾－２ｍｏｌ／Ｌ磷酸盐，电极响应斜率为２３－２７ｍＶ／ｄｅｃ．电极有较好的稳定性重现性，可望用于磷酸盐的实际分析。     

乙醇酸菠菜组织电极和马兰组织电极的研究

分别以菠菜和马兰叶为生物催化材料，将其叶浆组织与氧电极相结合，首次制成乙醇酸电极，本研究了这两种电极的响应性能。菠菜组织电极线性范围为５．０×１０＾－６－１．０＾１０＾－４ｍｏｌ／Ｌ；响应时间为３ｍｉｎ；寿命为１０天，马兰组织电极线性范围为２．０×１０＾－６－１．０×１０＾－４ｍｏｌ／Ｌ；响应时间为３ｍｉｎ；寿命至少３０天。这两种电极对底物乙醇酸钠皆有良好的选择性。     

聚吡咯碳糊电极的研制及应用

研制了聚吡咯电极，探讨了该电极的性能和实用性，实验结果表明，该电极可用于伏安法快速测定Ｌ－抗坏血酸，在０．１ｍｏｌ／ＬＫＮＯ３底液中，线性范围为１．０×１０＾－１１～９．０×１０＾－９ｍｏｌ／Ｌ检测限为５．０×１０＾－１２ｍｏｌ／Ｌ，电极具有具有良好的重现性和高选择性，响应迅速，使用寿命３个月以上。     

聚氯乙烯膜氧氟沙星和曲马多选择电极的研制与应用

报道了以氧氟沙星碘化物与碘化铋的分子缔合物为电活性物的新型聚氯乙烯膜氧氟沙星选择电极。并以类似的方法报道了曲马多选择电极。氧氟沙星电极的特响应范围为１．０×１０＾－２－２．２×１０＾－５ｍｏｌ／Ｌ，斜率为３０ｍＶ／ＰＣ，检测限为１．６×１０＾－５ｍｏｌ／Ｌ。     

大蒜中抗坏血酸的半微分伏发法测定

将工作电极直接插入大蒜瓣中，采用半微分伏安法研究了抗坏血酸的测定方法。用微铂盘电极作为工作电极，在ｐｈ６．８的磷酸氢二钠－柠檬酸介质中，抗坏血酸在７．０×１０＾－２－３．２×１０＾２ｍｇ／Ｌ范围内与半微分伏安曲线阳极峰的峰高呈线性关系，其最低检出浓度为４．９×１０＾２ｍｇ／Ｌ。     

铁的单点络合滴定法研究

本研究了Ｆｅ＾３＋的单点络合滴定法，导出了定量关系式，比较了以铂电极为指示电极和以ＰＶＣ膜四氯络铁（Ⅲ）阴离子电极为指示电极时电位测量的稳定性及所得的分析结果。在Ｆｅ＾３＋浓度为１．０００×１０＾－３ｍｏｌ／Ｌ时，１８次实验的平均值为１．０２×１０＾－４ｍｏｌ／Ｌ，相对偏差小于１．７％；Ｆｅ＾３＋在５．０×１０＾３ｍｏｌ／Ｌ以上时，相对偏差小于０．１％；其浓度小于１０＾－３ｍｏｌ／Ｌ而大于５×１     

苄氧基甲基12—冠—3的合成与锂离子选择性电极研究

报道了苄氧基甲基－１２－冠－３－的合成，并以此化合物作载体研制成锂离子选择电极。用苄氧基甲基－１２冠－３－为载体的电极对锂离子响应拇性范围为１．０×１０＾－１－８．３×１０＾－５ｍｏｌ／Ｌ．检测限为４．２×１０＾－５ｍｏｌ／Ｌ，斜率为５７．４ｍＶ／ｐＬｉ。电极具有好的稳定性和重现性。     

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.     

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.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.