二氧化锆/石墨烯复合材料对亚硝酸盐的电化学传感研究

制备了一种二氧化锆/还原氧化石墨烯(ZrO2NPs/rGO)复合材料修饰电极的亚硝酸盐电化学传感器,并成功用于亚硝酸盐的检测.采用循环伏安法和电流-时间曲线考察了修饰电极的电化学行为.实验结果表明,ZrO2NPs/rGO复合材料修饰电极对亚硝酸盐具有良好的电流响应.在最优实验条件下,电流-时间曲线中的电流响应信号与亚硝酸盐浓度在3.0×10Symbolm@@_7～1.0×10Symbolm@@_6 mol/L和1.0×10Symbolm@@_6～6.0×10Symbolm@@_6 mol/L的范围内呈良好的线性关系,检测限为1.0×10Symbolm@@_7 mol/L(S/N 3).该传感器灵敏性高、稳定性和重现性好.使用此传感器检测实际样品香肠中的亚硝酸盐的回收率为93.7％～110.4％,相对标准偏差为1.6％～2.1％.     

基于氯化血红素复合材料的过氧亚硝酸阴离子电化学传感器的构建

构建了一种基于氯化血红素/金纳米粒子/聚三聚氰胺/多壁碳纳米管复合材料修饰玻碳电极的过氧亚硝酸阴离子电化学传感器,并成功用于过氧亚硝酸阴离子的检测.采用循环伏安法和电流-时间曲线考察了过氧亚硝酸阴离子在传感器上的电化学行为,并对传感器的制备条件及过氧亚硝酸阴离子的检测条件进行了优化.结果表明,碳纳米管滴涂量为5 μL,金沉积时间为20 s,工作电位为0.8V时,所制传感器对过氧亚硝酸阴离子的响应最大.在优化实验条件下,此传感器检测过氧亚硝酸阴离子的线性范围为1.0×10-5～3.5×10-4 mol/L和3.5×10-4～1.1×10-3 mol/L,灵敏度为0.13 A/(mol/L),检出限为1.2×10-7 mol/L(S/N=3).     

聚四氨基酞菁铜微型传感器及其在一氧化氮测定中的应用

利用电化学聚合的方法制备了聚四氨基酞菁酮微型传感器，并探讨了微型传感器对一氧化氮（ＮＯ）的电化学响应。结果表明，电化学聚合Ｃｕ（ＴＡＰｃ）微型传感器对ＮＯ具有良好的催化氧化作用。     

基于石墨烯-甲苯胺蓝复合物癌胚抗原电化学免疫传感器

研究了在PBS缓冲介质中,一种检测癌胚抗原的新型免标记电化学免疫传感器的制备及应用,石墨烯与甲苯胺蓝复合物饰于玻碳电极表面,通过循环伏安法对修饰的电极进行表征.基于以[Fe(CN)6]3-/4-为氧化还原探针,癌胚抗原抗体反应引起[ Fe(CN)6] 3-/4-探针的电流响应的变化,来实现癌胚抗原的检测,癌胚抗原的浓度...     

电化学聚合吡咯掺杂蛋白A固定抗体的安培型沙门氏菌微传感器

基于电化学聚合将蛋白A(staphylococcal protein A)与吡咯掺杂后共聚于电极表面的新方法设计传感界面,结合采用微机电系统(micro electro mechanical systems, MEMS)技术制备的两电极系统,开发了一种新型的利用电聚合引入蛋白A进而固定抗体、提高检测性能的安培型免疫微传感器,并应用于沙门氏菌(Salmonella typhimurium, S.typhi)的检测.考察了传感器检测沙门氏菌的响应特性,优化了相关实验条件及参数,并结合扫描电镜(scanning electron microscopy,SEM)图像验证了该抗体固定方法的有效性.实验表明,采用电化学聚合方法固定蛋白A进行敏感膜修饰,操作简便省时(<10 min)、可控性强,试剂用量少(10 μL),能够有效改善抗体固定效果,提高传感器检测性能,适于微型免疫传感器的表面修饰研究.以此设计的安培型免疫微传感器能够检测100 cfu/mL沙门氏菌溶液,具有良好的重复性和特异性.     

基于石墨烯和金纳米笼修饰的无标记型微囊藻毒素免疫传感器的研制

利用石墨烯及中空结构的金纳米笼构建了无标记型电化学免疫传感器,并用于微囊藻毒素的检测。利用多元醇还原法合成制备了导电性好、催化性强、生物相容性好的金纳米笼;再利用高分散的石墨烯将其固定于玻碳电极表面,进一步吸附固定微囊藻毒素抗体。在无微囊藻毒素存在时,电化学探针[Fe(CN)6]3!/4!在传感器界面上能获得较高的电流响应信号。当培育了微囊藻毒素后,抗体与微囊藻毒素形成免疫结合物,增加了电极表面的电荷密度和传质阻力,阻碍[Fe(CN)6]3!/4!扩散到电极表面,导致[Fe(CN)6]3!/4!的电流响应信号明显降低,电流减小的程度间接地与微囊藻毒素的浓度成比例,可实现对微囊藻毒素的检测。实验考察了抗原培育时间,抗体浓度等条件对该传感器响应性能的影响。结果表明,此传感器对微囊藻毒素的线性响应范围为0.05~1000μg/L,检出限为0.017μg/L,优于文献报道。此传感器操作简单,并且具有良好的稳定性,将其用于实际水样中微囊藻毒素的检测,平均加标回收率为94.1%。     

光电化学传感器的研究进展

光电化学传感器以光作为激发源,以光电流或光电压作为检测信号,具有响应快速、灵敏度高、设备简单等特点,目前已在环境、食品、医学等多个领域的分析测试中得到广泛应用。该文阐述了光电转换材料与光电化学传感器的制备方法,介绍了光电化学传感器的原理和分类。光电化学传感器包含光寻址电位型传感器和电流型光电化学传感器,其中,电流型光电化学传感器由于优良的光电性能、检出限低、所需材料低廉且易加工等优势而被广泛应用。文中着重介绍了电流型光电化学传感器在金属离子、有机污染物、核酸、蛋白质、细胞等方面的应用,并对光电化学传感器的发展前景进行了展望。     

基于聚邻苯二胺@单壁碳纳米管修饰电极用于全血pH测定

开发了一种新型的电流型pH传感器。聚邻苯二胺(PoPD)通过原位电化学聚合法沉积在单壁碳纳米管(SWCNT)修饰的玻碳电极(GCE)表面。利用扫描电子显微镜(SEM)和傅里叶变换红外光谱(FTIR)对所得电极GCE/SWCNT/PoPD进行表征。通过循环伏安法(CV)优化扫描聚合电位和扫描圈数,在最佳实验条件下,研究该传感器对pH的电化学响应。结果表明,该传感器对pH在4.5～8.2具有良好的比率型电流响应。该传感器已成功用于人全血样品pH的直接测定。     

无酶葡萄糖传感器

利用葡萄糖在镍电极上的电化学氧化．制备了无酶葡萄糖传感器,研究了其电化学氧化机理．并测定了血清中葡萄糖的含量。在较高的pH值和570 mV的电位条件下,镍电极上产生的Ni(Ⅲ)具有氧化剂的作用,能直接氧化葡萄糖为葡萄糖酸内酯,产生的正比于葡萄糖浓度的电流响应可以定量样品中的葡萄糖含量。传感器由镍棒、铂丝对极和Ag/AgCl参比电极构成;对葡萄糖的响应时间小于1 min,进样间隔时间为3 min;对葡萄糖的电流响应范围为1．96×10~(-5)～1．80×10~(-4)mol/L,检测限为9．80×10~(-6)mol/L。传感器未使用葡萄糖氧化酶或其他生物酶,受温度的影响较小,样品中的氧对测定没有影响。在镍电极上,抗坏血酸、尿酸和多巴胺等物质不干扰血清中葡萄糖的测定。传感器用于测定血清中葡萄糖含量,相对标准偏差为4．3％。与己糖激酶法的测定结果一致。传感器制备简单,无需特殊保管,经简单处理后可重复使用。     

纳米碳管修饰铂结合溶胶-凝胶固定酶制备高性能胆碱生物传感器

为了提高胆碱传感器的灵敏度和抗干扰性,以纳米碳管修饰铂电极为基础电极,采用溶胶-凝胶法固定胆碱氧化酶(ChOx),构建了电流型胆碱检测生物传感器,对纳米碳管修饰电极的电化学特征进行分析,得知纳米碳管的引入不仅使电极对H2O2的催化电流增大,同时降低了电催化所需的恒定电位。讨论了缓冲液介质、pH值、酶负载量对传感器响应的影响。研究表明,所制备的传感器在pH 7.2、电位为0.15V条件下对氯化胆碱的线性响应范围为5.0×10-6~1.0×10-4mol/L;检出限为5.0×10-7mol/L;灵敏度为9.48μA/mmol/L。传感器的稳定性好,经过1个月,仍可保持初始电流的85%。抗干扰能力有很大提高。用于人体血清中的胆碱浓度测定,结果令人满意。     

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.     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

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.     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.