预镀铋膜修饰铂电极差分脉冲溶出伏安法测定痕量铅、镉

采用预镀铋膜法修饰铂电极,用该电极对痕量Pd、Cd同时进行了差分脉冲溶出伏安法测定,Pd、Cd在富集中和铋形成类似于汞齐的合金,溶出峰良好。讨论了在不同沉积液和沉积时间下得到的铋膜电极的性能和富集时间、富集电位及底液pH对金属离子测定的影响。在优化的实验条件下,分别对10~100μg/L、20~200μg/L和50~500μg/L3个不同浓度系列的Pb2 、Cd2 进行了同时测定,Pb、Cd溶出峰电流与Pb2 、Cd2 浓度呈良好的线性关系(r≥0.999),Pb2 、Cd2 浓度的线性范围均为10~500μg/L;富集时间为180 s时,Pb2 、Cd2 的检出限分别为0.38μg/L和0.82μg/L。利用本方法测定了蔬菜中Pb的含量,并与原子荧光分析法做了对比,结果令人满意。     

预镀铋膜修饰碳糊电极差分脉冲伏安法测定废水中铅和镉

采用预镀铋膜法制得铋膜修饰碳糊电极,当沉积时间为540s得到最优铋膜。采用差分脉冲伏安法(DPV)实现了对痕量Pb2+、Cd2+的同时测定。优化了DPV测定条件,当富集时间为150s、富集电位为-1.25V、HAc-NaAc缓冲底液的pH为4.5时,Pb2+、Cd2+的峰电流最大。在最优的实验条件下,Pb2+和Cd2+的峰电流与其浓度呈良好的线性关系,线性相关系数R分别为0.9912和0.9937,线性范围分别为1~10μmol/L和5~50μmol/L,Pb2+和Cd2+的检出限分别为0.32μmol/L和2.01μmol/L。对实际废水样品进行了加标回收实验,其中Pb2+和Cd2+的回收率分别为98.4%~102.6%和95.4%~104.6%。     

石墨烯/铋复合膜修饰玻碳电极检测板蓝根中的铅和镉

采用滴涂法制备石墨烯(GR)修饰的玻碳电极(GCE),通过电化学富集Bi沉积在GR表面,得到GR/Bi-GCE修饰电极.用方波溶出伏安法研究了Cd2+和Pb2+在GR/Bi-GCE上的电化学行为.在0.1 mol/LpH 4.5的醋酸缓冲溶液中,在-1.1 V富集0.5 mg/L Bi(NO3)3溶液210 s后,溶出峰电流与Cd2+和Pb2+的浓度在0.01～85.0 μmol/L范围内呈良好的线性关系,检出限均为0.003 μmol/L.实验结果表明,此修饰电极对Cd2+和Pb2+均有较好的电化学活性,可对两种物质实现同时测定,具有较高的灵敏度和稳定性.将此电极用于板蓝根中Cd2+和Pb2+的含量测定,结果令人满意.     

铋膜修饰玻碳电极伏安法测定微量铅(Ⅱ)

以铋膜修饰玻碳电极为工作电极,采用阳极溶出伏安法对微量Pb(Ⅱ)进行测定。考察了铋离子浓度、支持电解质pH、沉积时间等因素对测定的影响。实验结果表明,铋膜修饰电极对痕量Pb(Ⅱ)具有良好的电化学响应。在实验选定条件下,Pb(Ⅱ)在10～260!g/L范围内与峰电流呈良好的线性关系,检出限为1.98!g/L。用同一支铋膜电极对50!g/L Pb(Ⅱ)平行测定10次,相对标准偏差(RSD)为2.82%。该电极可应用于井水中铅的测定。     

以镍铬合金为基体的铋膜电极的构建及其应用

采用循环伏安法以镍铬合金为基体构建了铋膜/镍铬合金电极,以扫描电镜表征其表面形貌,利用线性扫描伏安法研究了Pb(II)、Cd(II)在该电极上电化学行为。结果表明:在0.20 mol/L HAc-NaAc缓冲溶液(pH4.5)中,该电极对Pb(II)、Cd(II)离子有较好的电催化活性,Pb(II)、Cd(II)的阳极溶出峰电流与其浓度分别呈良好的线性关系,检出限分别为6.39μg/L和3.52μg/L。     

锑电极电位溶出法测定锌、镉、铅

提出了采用锑电极作为工作电极同时测定痕量重金属锌、镉、铅的电位溶出法。探讨了同时测定锌、镉、铅的最佳条件。在pH=5.0的HAc-NaAc缓冲溶液中,Zn2+、Cd2+、Pb2+分别在-1.07、-0.70、-0.52 V得到灵敏的电位溶出峰。沉积时间为60 s时,锌、镉、铅的质量浓度分别在0~16.0、0~1.6、0~0.08 μg/mL范围内,与各自微分电位溶出峰高呈线性关系,检出限分别为4.0、0.3、0.03 μg/L。测定了水样中痕量锌、镉、铅的含量,结果令人满意。     

基于脱氢枞胺基希夫碱-多壁碳纳米管修饰电极测定铅

采用脱氢枞胺基希夫碱和多壁碳纳米管复合材料修饰玻碳电极,以循环伏安法和示差脉冲阳极溶出伏安法研究此修饰电极的导电性能,及Pb2+在此电极上的电化学行为。结果表明,修饰电极在0.2 mol/L HAc-NaAc缓冲体系(pH 5.5)中,于!1.1 V下沉积250 s,Pb2+在1.0×10!8~1.0×10!6mol/L范围内与溶出峰电流呈良好的线性关系,线性回归方程为I(μA)=6.6173C(μmol/L)+0.2597(R=0.9971),检出限为5.0×10!9mol/L(S/N=3)。将此修饰电极用于水样品中Pb2+检测,结果令人满意。本方法操作简便,耗时短,具有很好的准确性、灵敏度和选择性,实现了水样中低浓度铅的准确、快速测定。     

基于溶出伏安法的铋微阵列电极检测饮料中的铅和镉

建立了基于溶出伏安法的铋微阵列电极检测饮料中重金属的方法。该传感器采用三电极体系,铋微阵列电极为工作电极,铂薄膜电极为对电极,Ag/AgCl电极为参比电极。铋是一种低毒的重金属,采用铋作为反应物质可以使检测过程更加安全。微阵列电极具有高通量测定、便于微型化、抗干扰性等优点。实验表明,该传感器可同时检测出Pb2+和Cd2+,检出限分别为0.067和0.064 mg/L,且具有很好的重复性。此传感器用于检测橙汁中的Pb2+和Cd2+,结果令人满意。     

基于纳米金修饰的两种无汞型重金属微传感器的对比研究

采用微加工技术制备了集成有工作电极和对电极的两种重金属微传感电极芯片,工作电极表面采用电沉积法修饰纳米金(Gold nanoparticles,GNPs),由半胱氨酸(L-cysteine,Cys)和天冬氨酸(L-aspartic acid,Asp)修饰制备Asp/Cys/GNPs/微传感电极芯片,并利用原位镀锡膜(Sn film)的方法,制成Sn/GNPs/微传感电极芯片。采用方波伏安法和方波溶出伏安法考察了两种微传感电极芯片对重金属离子Cu2+,Pb2+和Zn2+的响应特性。Asp/Cys/GNPs/微传感电极芯片可有效识别Cu2+和Pb2+,线性范围为5～2000μg/L,检出限为1μg/L;Sn/GNPs/微传感电极芯片可有效识别Cu2+,Pb2+和Zn2+,线性检测范围分别为5～500μg/L,5～500μg/L和10～500μg/L,检出限分别为2,3和5μg/L。相比而言,Asp/Cys/GNPs/微传感电极芯片具有较宽的检测范围,而Sn/AuNPs/微传感电极芯片具有较高的灵敏度,两种传感器绿色环保、制备简单、更新简便、易于集成,在水质在线监测方面具有应用前景。     

复合铋膜电极阳极溶出法测定水样中的痕量铟

在玻碳电极上采用电化学沉积法制备了新型铕离子掺杂普鲁士蓝复合铋膜电极,建立了用示差脉冲阳极溶出法测定环境水样中痕量铟的分析方法。讨论了铟在常规铋膜电极和复合铋膜电极上的溶出性能,对铋膜的厚度、支持电解质、测定底液的pH、富集时间和富集电位等参数进行了优化。在最佳实验条件下,铟的阳极溶出峰电流与其浓度在2~20μg/L和20~100μg/L范围内分别呈良好的线性关系,检测下限为0.15μg/L(S/N=3),相对标准偏差RSD2.0%。该法用于实际水样中痕量铟的测定,样品回收率为97.5%~103%。     

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.