基于平面薄膜型电极的介体型半乳糖传感器的制备

以微电子薄膜技术制作的平面薄膜型电极为基底电极，β-环糊精与戊二醛缩合成的β-环糊精聚合物与二茂铁甲醇形成稳定的包络物，以此包络物中的二茂铁甲醇为电子介体，制成了半乳糖传感器。传感器的最佳工作电位0．3V，适宜的pH值范围7．0-9．0。传感器对半乳糖测定的线性范围为0．5-5．0mmol/L，响应时间1min。该传感器在两个星期内连续使用，响应电流无明显变化。保存一个月后测试仍有较好的电流响应。由于低测定电位和β-环糊精聚合膜的阻挡作用，能有效减少抗坏血酸、尿酸的干扰。     

离子结合物在二茂铁介体电流型葡萄糖生物传感器中的应用研究

二茂铁及其衍生物由于氧化还原可逆性好,不溶于水,因此可利用其作介体电流型生物传感器的电子转移介体。但该类传感器的重现性、稳定性差。本文首次提出以含(C_6H_5)_4·(CH_3)_4离子缔合物的碳糊电极为基础电极,以二茂铁(FeCp_2)为电子转移介体制成葡萄糖生物传感器。该传感器重现性、稳定性好,响应迅速,测量准确度高。     

二茂铁及其衍生物在传感器上的应用进展

二茂铁是一类具有夹心结构的有机金属配合物,有良好的氧化 还原特性,可有效改善传感器电极上的电子传递效率。 本文评述了近年来二茂铁及其衍生物在酶生物传感器、免疫传感器和离子传感器上的研究状况,并对其今后的发展方向做出展望。     

过氧化物模拟酶生物传感器—二茂铁衍生物为介体

本文用三种二茂铁衍生物－双羟基乙基二茂铁、单羟基乙基二茂铁和羧基二茂铁为介体，在过氧化物模拟酶－ｍｅｓｏ－四（４－磺基苯）卟啉锰存在下，检测过氧化氢，以双羟基，单羟基乙基二茂铁为介体时，获得了良好的结果。     

自组装单层界面β-环糊精非电活性客体的电化学测定

提出了用电化学技术测定非电活性物质的新方法.利用合成的β-CD对甲苯磺酸基衍生物(Ts-β-CD)获得新型β-CD单层.虽然β-CD的覆盖率只有10%左右,但该单层对二茂铁表现出有效的主客体响应.界面上二茂铁的包络符合Langmuir吸附响应.利用Langmuir吸附等温式,得到二茂铁与β-环糊精形成包络物的包络常数为4.2×10~4mol-1·L二茂铁在该单层上的最大表面覆盖度为8.6×10~(-12)mol/cm2.当二茂铁溶液中含有非电活性物质间甲苯甲酸(mTA)或十二烷基磺酸钠(SDS)时,mTA和SDS与包络在电极表面的二茂铁发生客体竞争反应而使二茂铁的氧化还原峰电流降低.利用该原理,分别测定了非电活性物质mTA和SDS,线性范围分别为0.8~2.7μmol/L和5~100nmol/L.     

异丙嗪—β—环糊精包络物性质及手性分离

１引言异丙嗪为组胺Ｈ１受体拮抗剂，其分子结构中含一个手性中心，即存在对映异构体。β－环糊精（β－ＣＤ）与大多数药物分子形成包络物，使药物分子水溶性增加和药效延长。本文研究了异丙嗪与β-ＣＤ形成包络物的紫外光谱性质，比较了异丙嗪和异丙嗪－β-ＣＤ包络物最大吸收波长的变化。利用玻碳电极循环伏安法研究了异丙嗪与β－ＣＤ生成包络物的电化学行为，采用“电位法测定了包络物的配位比ｍ和解离常数Ｋｄ。利用高效毛细管区带电泳技术，通过向背景电解质中加入β－ＣＤ对异丙嗪的对映异构体进行了手性分离。２实验部分２．１仪器…     

β—环糊精和α—萘乙酸包络物的荧光光谱研究

本文研究了水溶液中β－环糊精和α－萘乙酸包络反应，研究了包络物的荧光光谱性质，测定了包络物的形成常数，讨论了各种水溶性一元醇对该包络物形成及荧光性质的影响，并对其应用了作了预测。     

酰基二茂铁在液相中的电子传递性质

酰基二茂铁在液相中的电子传递性质蒋朝阳邰子厚＊季斌（南京大学配位化学国家重点实验室，南京２１００９３）关键词：酰基二茂铁三相氧化还原体系电子传递二茂铁及其衍生物在生物模拟和光电材料中有着极高的应用价值［１－４］。本文合成了一系列的酰基二茂铁ＦｃＸ（Ｘ...     

二茂铁-Nafion修饰葡萄糖传感器的研究

1 引言 第二代电流式酶传感器采用非生理的氧化还原介体如二茂铁及其衍生物、铁氰化钾、四硫富瓦烯、醌及其衍生物、钉化合物及麦尔多蓝等代替氧,起着酶与电极之间的电子传递作用,克服了第一代电流式酶传感器背景电流大,响应特性差,易受环境中氧浓度的影响,干扰大等缺点。但目前第二代电流式酶电极还存在着介体流失,电极污染及一些电活性物质干扰等问题。商品化的Nafion甲醇溶液不易溶解酶且能使部分酶失活,本文把Nafion甲醇溶液制成Nafion水溶液,将葡萄糖氧化酶溶解在Nafion水溶液,然后把它修饰在修饰有二茂铁的玻碳电极的表面,最后再修饰一层Nafion膜,成功地制备了二茂铁-Nafion修饰葡萄糖传感器,Nafion膜不仅能把抗坏血酸、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,而且能防止二茂铁的流失,提高电极的稳定性。该传感器具有抗干扰能力强,响应快等特点。     

荧光光谱法研究β—环糊精与L—酪氨酸的主客体包络反应

以荧光光谱法系统地研究了水溶液中β－环糊精与Ｌ－酪氨酸的主客体包络反应条件，包络物的荧光光谱性质，利用改进的Ｂｅｎｅｓｉ－Ｈｉｌｄｅｂｒａｎｄ法测定了包络物的形成常数，初步了探讨了某些水溶性一元醇的存在对该包络物形成常数及荧光性质的影响。检出限为２×１０＾－７ｍｏｌ／Ｌ，平均回收率为９９．１％。     

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%.     

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.     

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.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

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.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.