基于四氧杂四烯衍生物荧光增强的苯酚传感器

苯酚对固定在增塑的聚氯乙烯（ＰＶＣ）敏感膜中的２，２，７，７，１２，１２，１７，１７－八甲基－２１，２２，２３，２４－四氧杂四烯（ＴＯＥ）有可逆荧光增强作用，据此研制了测定水溶液中苯酚含量的荧光化学传感器。该敏感膜最佳组成为：５０ｍｇ ＰＶＣ、１００ｍｇ癸二酸二异辛脂（ＤＯＳ）、１．５ ｍｇ ＴＯＥ。该传感器在ｐＨ７．４的 Ｔｒｉｓ／ＨＣｌ缓冲溶液中，对苯酚的线性响应范围为４．４７×ｌ０~（－６）～４．１７×１０~（－３）ｍｏｌ／Ｌ；检出限为６．３０×ｌ０~（－７）ｍｏｌ／Ｌ；其响应时间小于３０ｓ。该传感器具有良好的重现性、可逆性和选择性，常见阴离子和阳离子不干扰测定。该传感器应用于工业废水中苯酚含量的测定，结果满意。     

四(十二烷基)碘化铵-氯酸根FET传感器的研究

报道了以四(十二烷基)碘化铵作为电活性物质,对氯酸根离子响应的场效应晶体管化学传感器(氯酸根FET)。传感器电位响应的线性范围为1.00×10-1mol/L～3.98×10-6mol/L,斜率为55.0mV/pC,适应pH范围为3.5～10 0。该传感器全固态化、自身阻抗变换、易于微型化和集成化,已用于测定氯酸根离子。     

大环轮烯的合成及其NMR谱特征

论述了大环轮烯、去氢轮烯、架桥轮烯及氮杂轮烯、氧杂轮烯、硫杂轮烯的合成方法;轮烯、去氧轮烯[4n+2]、[4n]体系以及杂原子轮烯[4n+1]、[4n-1]体系的NMR谱的特征;还介绍了近两年大环轮烯研究成果及发展趋势。     

含四氮杂十四轮烯的Li／SOCl2电池的研究

含四氮杂十四轮烯的Ｌｉ／ＳＯＣｌ２电池的研究章福平胡祝庆纪佩珍吴俭俭（浙江丝绸工学院纤维分院杭州３１００３３）关键词锂电池亚硫酰氯四氮杂十四轮烯过渡金属离子的有机大环络合物如Ｍ－ＰＣ［１，２］，Ｍ－ｐｏｒｐｈ［２］，Ｃｏ－ＴＡＡ［３］等掺入炭阴极后，...     

杂原子烯反应研究进展

烯反应是有机合成中简单而用途广泛的反应之一。杂原子烯反应是该反应的重要组成部分。本文主要综述了含氮、氧、硫、磷、硅等杂原子烯组分参与的杂原子烯反应的研究现状。     

激光拉曼光谱法测定模拟高放废液中钼酸根

建立激光拉曼光谱法测定模拟高放废液中钼酸根的分析方法。考察了拉曼光谱法测量钼酸根的主要影响因素。以硝酸根作为内标物,在选定的实验条件下,钼酸根与硝酸根的拉曼光谱特征峰强度比值与钼酸根浓度呈良好的线性关系,钼酸根浓度分别为0.002~0.08,0.05~0.80 mol/L时,线性方程分别为y=247c–0.178 8,y=11.36c–0.112 8,r~20.999,方法检出限为0.001 mol/L。采用该方法测定模拟高放废液中的钼酸根,测定值与配制值相比,相对误差小于5%,测量结果的相对标准偏差小于4%(n=6)。该方法操作简便、检测快速、制样简单、取样量小。     

以四硫富瓦烯为电子媒介体的电流式葡萄糖传感器

用四硫富瓦烯作为酶与电极之间的电子传递体，通过Ｎａｆｉｏｎ水溶液把葡萄糖氧化酶固定在Ｎａｆｉｏｎ－ＴＴＦ修饰玻碳电极上，最后在电极上装饰一层Ｎａｆｉｏｎ膜，制备成葡萄糖传感器。Ｎａｆｉｏｎ膜不仅能防止四硫富瓦烯流失，而且能把抗坏血酸、尿酸等电活性物质阻挡在电极外，防止其干扰，同时具有防污性能。通过实验表明ＴＴＦ＾＋１、ＴＴＴ＾＋２都能够氧化葡萄糖氧化酶中的辅酶。该传感器的线性范围为３．０×１０＾－     

含四硫富瓦烯结构单元的酞菁和四氮杂卟啉衍生物的研究概况

综述了含四硫富瓦烯(TTF)结构单元的酞菁和四氮杂卟啉衍生物的合成、光物理和电化学性质以及聚集和自组装性能的研究概况.     

四硫富瓦烯为电子媒介体的葡萄糖生物传感器的研究

本采用四硫富瓦烯（ＴＴＦ）作为葡萄糖氧化酶与玻碳电极之间的电子媒介体，把葡萄糖氧化酶因定在Ｎａｆｉｏｎ－ＴＴＦ修饰电极上，制成葡萄糖生物传感器。用这种传感器测定人体血清中葡萄糖的含量，其线性范围在４．０×１０＾－５～１０＾－３ｍｏｌ／Ｌ之间，响应时间为２０ｓ。该传感器具有选择性、重现性好，灵敏度高等优点。     

四硫富瓦烯─多酸分子杂化材料化学研究进展

综述了一类有机－无机超分子组装体系四硫富瓦烯─多酸分子杂化材料近年来的研究进展。分述了Ｋｅｇｇｉｎ型杂多阴离子、Ｄａｗｓｏｎ－Ｗｅｌｓ型杂多阴离子、Ｌｉｎｄｇｕｉｓｔ型同多阴离子以及含有顺磁性过渡金属原子的多阴离子的四硫富瓦烯和双乙基四硫富瓦烯的荷移盐和游离基离子盐的结构特征与导电性质,有机与无机亚单元间的磁交换性质介绍了杂多阴离子的低聚四硫富瓦烯盐的新进展     

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.