二茂铁及其衍生物作为电化学传感器的研究进展

本文对近二十年来国内外对二茂铁及其衍生物作为电化学传感器的研究进展做了较全面的综述。主要讨论了二茂铁及其衍生物修饰电极的制备、表征,介绍了二茂铁及其衍生物作为电化学传感器的应用情况,并探讨了今后的研究方向。     

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。     

Solid-state Synthesis of Aryl and Vinyl of Ferrocene Derivatives via Wittig Reaction

Organometallic structure possessing extensively conjugated π-electron system are an interesting class of potentially highly nonlinear molecular blocks and photoactive semiconductor^[1,2]. The title compounds were synthesized following Wittig reaction or palladium-catalyzed reaction of olefines and iodoferrocene, which proceed in solution and refluxing^[3]. However, there are always some disadvantages such as long reaction time, difficult work-up and low yield. Herein we report a free-solvent synthesis of aryl and vinyl ferrocene derivatives. As shown in the table, the phosphoning salt (1mol),NaOH (1.5mol) and formylferrocene (1mol) were mixed by grinding at room temperature to 65℃ in dry state to give the corresponding title compounds in 60-90% yield. The reaction was usually completed within a few minutes. The product thus obtained is mainly E-isomer. It could be emphasized that solid-state Wittig reaction is fast, cleaner and efficient.     

二茂铁及其衍生物的合成与应用研究进展

近年来二茂铁及其衍生物的合成与应用研究是金属有机化学研究的热点.本文不仅对二茂铁及其衍生物的性质、合成及其应用研究现状作了归纳和评述,而且简要概括了二茂铁及其衍生物的未来研究方向.     

Reaction of Epichlorohydrin with 2-Aminobenzothiazole and Its Derivatives

We have shown that 2-aminobenzothiazoles when reacted with epichlorohydrin form 3-hydroxytetrahydropyrimido[2,1-b]benzothiazolium chlorides, while 2-iminobenzothiazolines form 2-(-chloro--hydroxypropyl)iminobenzothiazolines.     

Ferrocene Derivatives of Valine and Leucine

Methyl and ethyl esters of valine and leucine were reacted with ferrocenecarbaldehyde to obtain azomethines (C₅H₅)Fe(C₅H₄CH=NCHRCOOR′) whose reactions with sodium borohydride provide ferrocenylmethyl derivatives (C₅H₅)Fe(C₅H₄CH₂NHCHR⋅COOR′) [R=(CH₃)₂CH, (CH₃)₂CHCH₂; R′ = CH₃, C₂H₅]. The latter compounds react with sodium hydroxide to give, after treatment of the reaction mixtures with acetic acid, N-substituted amino acids (C₅H₅)Fe(C₅H₄CH₂NHCHRCOOH).__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 6, 2005, pp. 1046–1048.Original Russian Text Copyright © 2005 by Popova, Yurashevich, Cherevin, Gulevich, Reshetova, Knizhnikov.     

Reaction of 1-Hydroxybenzotriazole and Its Organotin Derivatives with Vanadocene

1-Hydroxynbenzotriazole, 1-(N-tributylstannyloxy)benzotriazole, or bis(1-benzotriazolyloxy)dibutylstannane react with vanadocene (Cp₂V) to give as the major product 1-[(⁵-cylcopentadienyl)vanadiooxy]benzotriazole in high yields.     

1,1′-二硒取代二茂铁衍生物的合成

由1,2,3-三硒[3]桥二茂铁(Ferrocenophane)经LiAlH_4还原生成二硒酚,不经分离直接与一亲电试剂在三乙胺存在下反应,得到7种1,1′-二硒醚二茂铁,4种1,n-二硒[n]桥二茂铁(n=3～5)和1种螺形化合物[Fe(C_5H_4Se)_2]_2Sn。这12种化合物中有7种尚未见文献报道,对其中几种产物进行了~(77)Se NMR谱及质谱分析。讨论了影响产率的因素和核磁共振图谱。     

二茂铁及其与DNA复合物的电化学行为

在Tris-NaCl(pH=7.2)缓冲溶液中, 应用循环伏安法、微分脉冲伏安法、旋转圆盘电极实验、电化学阻抗谱等技术研究了二茂铁在旋转碳纳米管(CNT)修饰电极上的电化学行为及其与小牛胸腺DNA的相互作用. 结果表明, 二茂铁及其与双链DNA的电活性产物在静止的CNT修饰电极上均呈现一对基本可逆的氧化还原峰；在旋转电极上呈现出明显的极限扩散电流, 电化学阻抗谱呈现一个压扁的半圆. 二茂铁与DNA的作用在扩散控制过程中表现为峰电流和极限扩散电流随DNA浓度增大而减小；电化学控制过程则表现为电化学反应电阻随DNA浓度增大而增大, 条件电位下的速度常数也有一定程度的减小.     

青霉烯二茂铁衍生物的合成与抗菌活性研究

为了探寻更具活性的青霉烯类抗生素,设计并合成了8个新的青霉烯二茂铁衍生物,并进行了结构表征与确认.采用琼脂平皿二倍稀释法测定了它们和法罗培南对金黄色葡萄球菌等菌种的最小抑菌浓度(MIC),并对此类化合物的构效关系进行了探讨.结果显示,C-2位被二茂铁基团取代的青霉烯类化合物的抗菌活性优于法罗培南或与其相当,尤其是含有杂环取代基的化合物8h抗菌活性显著.     

Novel Product and Its Derivatives from the Reaction of Lappaconitine with HIO_4

Lappaconitine l, a bisnorditerpenoid alkaloid, was isolated from many plants ofAconitum and Delphinium species such as A. barbatum var. puberulum, A.sinomontanuml' 2. It is now used in the clinical practice as an analgesic in China', andantiarrhythmic drugs in Uzbekistan4' 5. In our attempts to prepare the 10-oxygenatedderivatives by treating lappaconitine I with HIO. followed by bromination, unexpectedby-products were obtained in modest yields. This communication described the isolationan…     

Synthesis and Stereoselective Reactions of New Stable α-Ferrocenyllithium Derivatives. An Umpolung of the Ferrocene Reactivity

The reductive lithiation of various α-ferrocenylcarbinol derivatives yields stable α-ferrocenyllithium species (see scheme). These can be quenched with different electrophiles with complete retention of configuration.     

二茂铁及其胺甲基类取代衍生物的紫外光解自由基的研究

本文用自旋捕捉-ESR技术研究了二茂戊铁、环二烯和胺甲基类取代二茂铁的紫外光解过程中的活泼自由基。结果表明,二茂铁光解初级过程中生成的自由基为(C_5H_5Fe)·和C_5H_5·,其衍生物光解则生成(C_5H_5Fe)·和RC_5H_4·,而(C_5H_5Fe)·还可以进一步分解给出C_5H_5和Fe。     

Flame-retardancy and Smoke-suppression Studies on Ferrocene Derivatives in PVC

A range of substituted ferrocenes has been synthesized and studied for flame retardancy and smoke suppression on incorporation into plasticized PVC at 0.1–5.0 phr. Smoke suppression by up to 50 and enhancement of the limiting oxygen index by up to 4 units were observed. The differences in performance could not be correlated with char formation, thermal analysis or chemical structure of the additive. A negative correlation was found between smoke suppression and flame retardancy. The most effective smoke suppressant additive appears to accelerate the rate of dehydrochlorination of PVC while the most effective flame retardant appears to have little effect on the dehydrochlorination process.     

Reactivity of Benzofuran Derivatives

This review presents a systematic and comprehensive survey of the chemical reactivity of benzofurans. These compounds are important intermediates for the synthesis of a variety of useful and novel heterocyclic systems that are otherwise difficult to obtain synthetically.     

异维A酸二茂铁基衍生物的合成及其细胞毒活性的研究

为降低异维A酸的毒副作用并提高其癌细胞毒活性以及增加其在生物体内的吸收, 通过Mitsunobu反应, 以高于80%的收率合成了8种新异维A酸二茂铁基衍生物, 并进行了结构表征与确认. 采用3-(4,5-二甲基噻唑-2)-2,5-二苯基四唑溴盐(MTT)法测试了它们对肺癌细胞(A549)等的癌细胞毒活性. 结果显示, 引入二茂铁基团后的异维A酸二茂铁基衍生物具有很好的癌细胞毒活性.     

NaBH_3CN－ZnCl_2体系对含氧二茂铁衍生物的选择性还原

ＮａＢＨ＿３ＣＮ－ＺｎＣｌ＿２体系对含氧二茂铁衍生物的选择性还原林欣欣（中国科学院广州化学研究所广州５１０６５０）ＷＥＬｉｎｄｓｅｌｌ（ＤｅｐａｒｔｍｅｎｔｏｆＣｈｅｍｉｓｔｒｙ，Ｈｅｒｉｏｔ－ＷａｔｔＵｎｉｖｅｒｓｉｔｙ，ＵｎｉｔｅｄＫｉｎｇｄｏｍ...     

焦脱镁叶绿酸的Knoevenagel反应及其杂环取代衍生物的合成

以焦脱镁叶绿酸-d甲酯(MPPd)为起始原料, 通过其醛基与连有五元杂环的β-二酮、α-氰基酮和丙二腈的活性亚甲基进行Knoevenagel反应, 完成3-位五元杂环取代的焦脱镁叶绿酸-a甲酯衍生物. 所合成的新化合物均经UV, IR, ¹H NMR及元素分析证明其结构.