CH_2Cl_2对离子液体BmimPF_6中二茂铁电化学行为的影响

应用循环伏安和交流阻抗法研究有机溶剂二氯甲烷对二茂铁在离子液体1-丁基-3-甲基咪唑六氟磷酸盐(Bm imPF6)中电化学行为的影响.实验表明,二氯甲烷可促进离子液体的离子解离,减小离子液体粘度,增加离子液体电导率,加速二茂铁在离子液体中的扩散,增大氧化还原峰电流.由于电极界面双电层结构的变化,导致双电层电容增大,电极反应电阻减小,从而加速了界面电子传递反应.     

双酚A在纳米金-离子液体复合修饰电极上的电化学行为及测定

该文制备了纳米金-离子液体修饰电极(GNP-[BMIM]PF6/GCE),用红外光谱对GNP和[BMIM]PF6进行了表征.采用交流阻抗法研究了GNP-[BMIM]PF6/GCE的表面电化学特性,同时研究了双酚A(BPA)在该修饰电极上的循环伏安行为.结果表明,BPA在该修饰电极上出现1个氧化峰,无还原峰,为不可逆电化...     

Nafion-离子液体-修饰碳糊电极在抗坏血酸和尿酸存在下选择性测定多巴胺

用Nafion和亲水性离子液体溴化1-辛基-3-甲基咪唑([OMIM]Br)作修饰剂制作了Nafion-离子液体-修饰碳糊电极;在0.1 mol/L磷酸盐缓冲溶液(pH 7.40)中,用循环伏安法(CV)和方波伏安法(SWV)研究了多巴胺在该修饰电极上的电化学行为,建立了抗坏血酸和尿酸存在下选择性测定多巴胺的新方法.研究表明,该修饰电极降低了多巴胺氧化、还原反应的过电位,增大了其氧化、还原反应的峰电流,而抗坏血酸和尿酸在该修饰电极上无响应;在方波伏安曲线上,多巴胺的氧化电流与其浓度在3.0×10-8～2.0×10-6 mol/L范围内呈线性关系,检出限为1.0×10-8 mol/L.该法可用于注射液和模拟生物样品中多巴胺的测定.     

含二茂铁离子液体电容器的电化学性能

对以含二茂铁(ferrocene, Fc)离子液体1-乙基-3-甲基咪唑四氟硼酸盐(1-ethyl-3-methylimidazolium tetra-fluoroborate, [BMIm]BF4)作为电解液, 高比表面积的多孔炭作为电极材料构成的电容器的电化学行为进行了探讨. 循环伏安和恒流充放电测试结果表明,含二茂铁离子液体在多孔炭中发生氧化还原反应, 并且该氧化还原反应是扩散控制, 高度可逆的过程. 0.01 mol·L-1 [BMIm]BF4/Fc在电流密度为1 mA·cm-2时的平均比电容为163 F·g-1, 比纯[BMIm]BF4的比电容高63%. 平均比电容的增加表明由Fc参与的氧化还原反应生成的法拉第电容对电容器的总电容有很大的贡献. 同时, 以0.01 mol·L-1 [BMIm]BF4/Fc作电解液的电容器的功率密度为400 W·kg-1, 能量密度高达37.5 Wh·kg-1, 达到了电池的水平.     

二茂铁基超支化聚氨酯的电化学性能

通过循环伏安法(CV)测定了二茂铁基超支化聚氨酯(HAPE-Fc)的电化学性能.结果表明:HPAE-Fc表现为单对氧化还原峰,在二茂铁接枝到超支化聚氨酯上以后,二茂铁基团依然保持着自身的氧化还原独立性,具有较强的电子转移速率,这是其具有电化学特性和催化作用的前提条件.通过分析扫描速率与HPAE-Fc电化学行为之间的关系,发现HPAE-Fc的电极过程既受扩散控制,同时也受电极反应的控制.     

10-羟基喜树碱在碳纳米管-离子液体修饰电极上的电催化氧化及电分析方法

用多壁碳纳米管(MWCNTs)和亲水性离子液体N-乙基吡啶四氟硼酸盐([Et Py]BF4)作修饰剂,构置了修饰玻碳电极(MWCNTs-[Et Py]BF4/GCE),并应用电镜扫描法(SEM)和电化学阻抗法(EIS)对MWCNTs-[Et Py]BF4/GCE进行了表征。MWCNTs在[Et Py]BF4离子液体中能有效分散,增加了电极表面的活性位点,与裸GCE和MWCNTs-DMF/GCE相比,MWCNTs-[Et Py]BF4/GCE电导率最高。在pH 6.8的PBS缓冲溶液中,用循环伏安法(CV)和差分脉冲伏安法(DPV)研究了10-羟基喜树碱在该修饰电极上的电化学行为,建立了一种测定10-羟基喜树碱注射液中10-羟基喜树碱含量的新方法。10-羟基喜树碱在MWCNTs-[Et Py]BF4/GCE上出现一对灵敏、可逆的氧化还原峰,峰电位差(△Ep)为40 m V,与MWCNTs-DMF/GCE相比减小了80 m V;10-羟基喜树碱在MWCNTs-[Et Py]BF4/GCE上的氧化、还原峰电流响应分别是在M WCNTs-DM F/GCE上的3.3倍和2.0倍,表明M WCNTs-[Et Py]BF4/GCE对10-羟基喜树碱的氧化还原反应有良好的电催化作用。在20~500 m V/s扫速范围内,氧化还原峰电流均与扫速平方根(v1/2)呈线性关系,表明该电极反应过程受扩散控制。在DPV曲线上,10-羟基喜树碱的氧化峰电流与其浓度在5.0×10-6~1.8×10-4g/L范围内呈良好的线性关系,检出限为1.0×10-6g/L。方法用于10-羟基喜树碱药物的含量测定,RSD为2.9%~3.5%,加标回收率为98.6%~105%。     

新型1-烷基-2,3-二甲基咪唑六氟磷酸盐离子液体/过氧化氢酶电极电化学性能研究与应用

合成了5种新型1-烷基-2,3-二甲基咪唑六氟磷酸盐类离子液体,并以离子液体为介质制备空白电极及过氧化氢酶电极.采用循环伏安法研究电极电化学行为,结果表明离子液体有优良的电化学性质.离子液体空白电极的基体峰电流都在数nA范围内,电化学窗口大于4 V;不同离子液体酶电极的电化学行为存在明显差异.在5种离子液体中,仅有1-戊基-2,3-二甲基咪唑六氟磷酸盐能很好地保持酶活,呈现灵敏的电化学响应.此外,该酶电极还具有良好的稳定性,4 ℃保存30 天后,电化学性质没有明显变化.在0.1 mol/L的H3PO4缓冲溶液(pH 7.0)中,该酶电极还原峰电流随溶液中H2O2浓度的增加而增大.当H2O2浓度在3.17×10-6～12.4×10-6 mol/L之间,酶电极的还原峰电流符合线性关系,其检出限为1.1×10-6 mol/L.方法已用于环境水中痕量H2O2的测定.     

氯化钽在离子液体1-丁基-3-甲基咪唑六氟磷酸盐中电化学行为

采用循环伏安法,研究了0.25 mol/L TaCl₅在离子液体1-丁基-3-甲基咪唑六氟磷酸盐([Bmim]PF₆)中的电化学行为。 实验结果表明,电沉积钽是受扩散控制、两步骤的不可逆电极反应过程,首先是Ta(Ⅴ)还原为Ta(Ⅲ),其次是Ta(Ⅲ)还原为金属钽和形成其它低价钽氯化物。 Ta(Ⅴ)/Ta(Ⅲ)和Ta(Ⅲ)/Ta在离子液体[Bmim]PF₆中的阴极传递系数分别为0.155和0.406。 Ta(Ⅴ)在离子液体[Bmim]PF₆中的扩散系数为1.629×10^-9 cm²/s。 在100 ℃和-1.25 V条件下,采用恒电势法在铂片上电沉积钽,扫描电子显微镜照片和EDS分析表明,沉积物为钽和钽的低价氯化物。     

花旗松素在碳纳米管-离子液体修饰碳糊电极上的电催化氧化及其测定

制备了碳纳米管(MWCNTs)和疏水性离子液体N-丁基吡啶六氟磷酸盐([Bu Py]PF6)复合修饰碳糊电极(MWCNTs-[Bu Py]PF6/CPE),利用循环伏安法研究了花旗松素在MWCNTs-[Bu Py]PF6/CPE上的电化学氧化行为。结果表明,花旗松素在修饰电极上出现一对灵敏、准可逆的氧化还原峰,氧化峰电位Epa=0.60 V,还原峰电位Epc=0.24 V,△Ep=0.46 V,氧化峰电流ipa=3.96μA,还原峰电流ipc=5.03μA,ipa/ipc=0.79,表明MWCNTs-[Bu Py]PF6/CPE对花旗松素具有良好的电催化氧化作用。用差分脉冲伏安法(DPV)测得花旗松素的氧化峰电流ipa与浓度c在1.2×10-5~4.0×10-2g·L-1范围内呈良好线性,检出限为2.2×10-6g·L-1。该法用于水红花子中花旗松素含量的测定,RSD为1.1%~1.5%,加标回收率为97.3%~101.3%。     

化学修饰电极的研究 Ⅵ.聚乙烯二茂铁膜电极的表面表征和组成

本文研究了用等离子体法在玻璃炭上制备聚乙烯二茂铁(PPVF)膜电极的伏安行为及其XPS分析.结果表明PPVF膜电极的伏安行为和组成均与其制备条件有关.PPVF膜电极的二茂铁与二茂正铁之间的氧化还原反应是在电极上快速进行电荷转移的电化学过程.PPVF膜电极的伏安特性受膜中电活性物量、膜的厚度和组成的影响.伏安法和XPS法都可以用来表征PPVF膜制备条件的变化.     

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.     

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.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.