再生丝素固定葡萄糖氧化酶及其传感器应用

再生丝素固定葡萄糖氧化酶及其传感器应用钱江红，刘永成，刘海鹰，于同隐，邓家祺（复旦大学化学系高分子科学系，上海，２００４３３）关键词再生丝素，葡萄糖氧化酶，传感器，酶电极酶电报的各项性能在很大程度上取决于酶的固定比方法，葡萄糖氧化酶的固定化方法很多１...     

Nafion膜固定的麦尔多拉蓝为介体的过氧化氢、葡萄糖和乳糖生物传感器

以Nafion膜修饰玻碳电极固定的麦尔多拉蓝为辣根过氧化物酶和电极间的电子传递介体，成功地制成了性能优良的电流型单酶过氧化氢生物传感器；在此基础上通过固定双酶（辣根过氧化物酶－葡萄糖氧化酶）和三酶（辣根过氧化物酶－葡萄糖氧化酶－半乳糖苷酶）分别制成了葡萄糖和乳糖生物传感器；探讨了工作电位、pH、温度和干扰物质等对这3种生物传感器的影响。     

基于微带阵列电极的微型葡萄糖传感器研究

用微电子薄膜技术制作了微带阵列电极（ＭＡＥ）,考察了该电极在铁氰化钾,过氧化氢溶液中的电化学行为。在微带阵列电极表面,修饰一层全氟代磺酸酯膜作为基底电极,并把电子介体二茂铁及葡萄糖氧化酶固定在基底电极上制备了微型葡萄糖传感器,探讨了微酶电极对葡萄糖氧化过程的催化作用。该微酶电极响应时间小于１０ｓ,检测线性上限为８ｍｍｏｌ／Ｌ。     

聚乙烯－葡萄糖氧化酶膜的制备和性能研究

聚乙烯－葡萄糖氧化酶膜的制备和性能研究朱如瑾，殷弘浩，刘永盛，黄家湛（成都高分子材料国家重点实验室成都科技大学高分子研究所成都６１００６５）关键词聚乙烯，等离子体，固定化酶，葡萄糖氧化酶固定化酶是６０年代发展起来的生物工程技术Ｉ‘］．酶的固定化方法主...     

聚乙烯－葡萄糖氧化酶膜的制备和性能研究

聚乙烯－葡萄糖氧化酶膜的制备和性能研究朱如瑾，殷弘浩，刘永盛，黄家湛（成都高分子材料国家重点实验室成都科技大学高分子研究所成都６１００６５）关键词聚乙烯，等离子体，固定化酶，葡萄糖氧化酶固定化酶是６０年代发展起来的生物工程技术Ｉ‘］．酶的固定化方法主...     

Nafion—四硫富瓦烯修饰蜡浸石墨电极的葡萄糖传感器

本文用四硫富瓦烯（ＴＴＦ）作为酶与电极之间的电子传递体，通过牛血清蛋白和戊二醛交联剂，把葡萄糖化氧化酶固定在Ｎａｆｉｏｎ－ＴＴＦ修饰石墨电极上，最后在电极修饰一层Ｎａｆｉｏｎ膜，制备成葡萄糖传感器。Ｎａｆｉｏｎ膜不仅能防止四硫富瓦燃流失，而且能氢抗坏血酸，尿酸等电活生物质阻挡在电极外，防止其干扰，同时具有防污性能。通过实验表明ＴＴＦ＾＋，ＴＴＴ＾２＾＋都能够氧化葡萄糖氧化酶中的辅酶（ＦＡＤＨ２）。     

聚吡咯葡萄糖氧化酶电极的生物电化学响应

采用分步骤合过程，制备了以聚吡咯膜为载体的葡萄糖氧化酶电极，探讨了其生物电化学响应特性，计算了酶催化反应的有关动力学参数。与溶解态酶相比，该电极表现出良好的生物电化学特征，而且酶蛋白对溶液温度的稳定性有显著提高。     

亲水金和憎水二氧化硅纳米颗粒对葡萄糖生物传感器响应灵 …

用亲水金、憎水二氧化硅纳米颗粒固定葡萄糖氧化酶（ＧＯＤ）,采有聚乙烯醇缩丁醛（ＰＶＢ）为辅助固酶膜基质来制备葡萄糖生物传感器,并考察了亲水金、憎水二氧化硅纳米颗粒对酶电极电流响应的影响。实验表明,引入纳米粒子可显著增强电极响应灵敏度,并对两种不同性质纳米所起作用的可能机理进行讨论,从理论和实验上辛 明了纳米颗粒对固定酶的作用。为制备有实用价值的葡萄糖生物传感器提供了可供参考的实验和理论依据。     

微酶电极的研制及在流动注射分析中的应用

利用铂化电极的大表面吸附葡萄糖氧化酶（简称ＧＯＤ）构建了一种具有良好操作性能的微酶电极，在０～１０ｍｍｏｌ／Ｌ葡萄糖浓度具有很好线性，相关系数γ＝０．９９８，响应时间短（＜２０ｓ），精度高。利用该电极组成三电极流动注射分析系统，这种系统同样有较好的线性范围，分析频率达４５ｈ＾－１，使用寿命在一周以上。     

生物功能电极（Ⅴ）：—葡萄糖氧化酶在环糊精聚合物中的固…

将葡萄糖氧化酶固定在α－环糊精聚合物中，而电子传递体分子被包含在环糊精腔穴中，固定化酶膜的ＦＴＩＲ测定表明，ＧＯＤ与环糊精聚合物发生共价连接，制备了含电子传递体的不同ＧＯＤ酶电极并比较了它们的性能，含四硫代富瓦烯的酶电极具有良好的电流响应特性，可望成为第二代葡萄糖酶电极的新构型。     

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%.     

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.     

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.     

Copper catalyzed/mediated synthetic methodology for ebselen and related isoselenazolones

Scope of the copper catalyzed/mediated selenium-nitrogen coupling reaction has been studied for the synthesis of isoselenazolones. It is noticed that the 2-chloro, 2-bromo-, and 2-iodo-aryl amides substrates can be exploited in the selenium-nitrogen coupling reaction by employing 25-100 mol % of CuI/1,10-phenanthroline (L) and potassium carbonate as a base in DMF. Furthermore, electron rich 2-chloro-arylamides also underwent selenium-nitrogen coupling reaction to give biologically important selenium-nitrogen heterocycles. Also, copper-catalyzed selenium-nitrogen coupling reaction has been meticulously applied for the synthesis of diaryl diselenides having methoxy, amine, and amide functionality from respective aryl iodides in the presence of stoichiometric amount of succinimide as an external Se-N coupling partner.     

Knoevenagel condensation catalyzed by novel Nmm-based ionic liquids in water

A series of novel N-methyl morpholine (Nmm) based ionic liquids with 1,2-propanediol group were synthesized and used as catalysts for Knoevenagel condensation at room temperature in water. Under the effect of the catalyst, various aldehydes or aliphatic ketones could react with a wide range of activated methylene compounds well, including malononitrile, alkyl cyanoacetate, cyanoacetamide, β-diketone, barbituric acid, 2-arylacetonitrile and thiazolidinedione. Furthermore, most of the products could be separated just by filtrating and washing with water. Additionally, the catalyst is recyclable and applicable for the large-scale synthesis.     

Construction of polyheterocyclic spirotetrahydrothiophene derivatives via sulfa-Michael/aldol cascade reaction

A series of polyheterocyclic spirotetrahydrothiophene derivatives were obtained in moderate to excellent yields via a catalyst-free sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 under mild conditions. We also present the first asymmetric sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 with moderate to good enantioselectivities catalyzed by readily available chiral phase-transfer catalysts (PTCs).     

Suzuki-Miyaura reactions of the soluble guanylate cyclase inhibitor NS2028: a non-product specific route to C-8 substituted analogues

Both soluble guanylate cyclase (sGC) inhibitors ODQ 1 and NS2028 2 are synthesized via improved protocols. In the former case treating 3,4-dihydroquinoxalin-2(1H)-one oxime 8, which can be prepared in two steps from 1,2-benzenediamine, with 1,1′-carbonyldiimidazole (CDI) gives the dihydro-ODQ 10 that in the presence of KMnO₄ oxidises to give ODQ 1 in an overall yield of 46% starting from 1,2-benzenediamine. In the latter case, the synthesis affords NS2028 2 from 2-amino-4-bromophenol 3 in three steps with an overall yield of 85% and avoids the need for chromatography. Furthermore, Suzuki-Miyaura reaction conditions are described that enable the preparation of 8-aryl and 8-heteroaryl derivatives of NS2028 directly from NS2028 2. Finally, demethylation of the 8-(methoxyphenyl) substituted analogues afforded the 8-(hydroxyphenyl) derivatives 40-42. All new products are fully characterised.