纳米金-还原氧化石墨烯修饰葡萄糖氧化酶传感器的制备及其电流法检测饮料中的葡萄糖

利用纳米金(Au NPs)与还原氧化石墨烯(rGO)复合纳米材料制备了葡萄糖氧化酶生物传感器并用于饮料中葡萄糖含量的检测。将壳聚糖作为还原剂及稳定剂,通过一步法合成了Au NPs-rGO复合材料,并通过物理吸附固定葡萄糖氧化酶(GOx)来制作GOx生物传感器。该传感器在磷酸盐缓冲溶液(0.1 mol/L,p H6.0)中,-0.45 V(vs.Ag/Ag Cl)电位下电流法检测葡萄糖含量,线性检测范围为0.01~0.88 mmol/L,灵敏度为22.54μA·mmol-1·L·cm-2,检出限为1.01μmol/L,且表观米氏常数为0.497 mmol/L。该传感器用于多种饮料中葡萄糖含量的直接检测,结果满意。     

基于聚锂均苯三甲酸/多壁碳纳米管复合膜的葡萄糖生物传感器的研究

利用电聚合方法在裸玻碳(GC)电极上修饰一种新型金属有机框架化合物锂均苯三甲酸(Li-BTC),并采用滴涂技术制备了Nafion/GOx/MWNTs/poly-Li-BTC/GC葡萄糖生物传感器。利用扫描电镜分析了复合膜(含MWNTs和poly-Li-BTC)的形貌,采用循环伏安和交流阻抗方法对修饰电极的电化学性能进行了研究。结果表明,此复合膜可增大裸玻碳电极的有效表面积、改善电极的电催化活性。利用循环伏安法和计时安培法研究了葡萄糖在Nafion/GOx/MWNTs/poly-Li-BTC/GC电极上的电化学特性。结果表明:葡萄糖的浓度在0.02～1.56 mmol/L范围内,此修饰电极的电流响应与葡萄糖的浓度呈线性关系,其相关系数为0.9992,检出限为5.1μmol/L(信噪比为3∶1)。修饰电极的米氏常数为0.832 mmol/L,回收率为96.3#～100.3#。本研究制备的葡萄糖生物传感器具有较好的重复性、重现性、选择性与稳定性,用于葡萄糖注射液中葡萄糖含量的检测,结果满意。     

基于二氧化钛/碳纳米管/壳聚糖纳米复合薄膜制备葡萄糖生物传感器

利用壳聚糖(CHI)溶液分散了纳米二氧化钛(nano-TiO2)和多壁碳纳米管(MWCNT),将该分散液修饰于玻碳电极表面形成纳米复合薄膜;用戊二醛为交联剂在该纳米复合层上固定了葡萄糖氧化酶(GOx),同时以二茂铁为电子媒介体构建了一种新型葡萄糖传感器。利用扫描电镜(SEM)、交流阻抗(AC)对所制备的传感器进行了表征,同时用循环伏安法(CV)和计时电流法(CA)考察了其对葡萄糖的电催化氧化性能。实验结果表明,在优化测试条件下该传感器对葡萄糖在0.5～20.0 mmol.L-1范围内有线性响应,检出限为0.2 mmol.L-1;电流达到95%的稳态时间小于5 s;此生物传感器具有良好的重现性和选择性,能有效排除抗坏血酸、尿酸等常见干扰物的影响并成功应用于饮料中葡萄糖含量的测定。     

基于掺杂碳纳米管的复合体系电化学生物传感器研究

制备了含有铂纳米颗粒(NSPt)的壳聚糖(CHIT)和正硅酸四乙酯(TEOS)溶胶-凝胶溶液,将多壁碳纳米管(MWCNTs)分散于制备的CHIT和TEOS溶胶-凝胶混合物体系,并用高倍透射电镜(TEM)和扫描电子显微镜(SEM)对NSPt-CHIT表面和MWCNTs进行了表征。此种复合膜修饰玻碳电极对过氧化氢有灵敏的电化学响应。通过在此复合膜修饰的玻碳电极上固定葡萄糖氧化酶(GOx)制备了葡萄糖生物传感器。该传感器对葡萄糖在0.05~8 mmol/L范围有线性响应,相关系数为0.996,检出限(S/N=3)为10μmol/L。传感器对葡萄糖有灵敏响应,并有很好的重现性和稳定性,应用于实际样品体系的回收试验,结果良好。     

非图案化法制备柔性连续葡萄糖监测传感器

以聚多巴胺作为前驱体,在聚酰亚胺薄膜表面化学沉积一层牢固致密的金层,以该镀金薄膜两面的金层作为基体电极,在其中一面镀铂黑作为参比-对电极,在另一面依次电沉积铂黑层、电泳形成Nafion/碳纳米管网络层、电吸引形成葡萄糖氧化酶层构成工作电极,并整体涂覆聚氨酯外膜,制备了一种柔性葡萄糖传感器.考察了此传感器对葡萄糖的检测性能,以及各层表面形态结构对传感器性能的影响.传感器在0.3V的工作电位下对葡萄糖的线性响应范围是2.0 ～ 32.0 mmol/L,响应灵敏度为25 μA· (mmol/L)-1·cm-2,检出限为0.05 mmol/L (S/N=3),且传感器有良好的长期稳定性和抗干扰性,可用于皮下连续血糖监测.     

以高氯酸·三-2,2′-联吡啶合钴(Ⅲ)作为电子媒介体金纳米颗粒增强的葡萄糖生物传感器

用纳米金溶胶与聚乙烯醇缩丁醛(PVB)构成复合固酶基质,采用溶胶-凝胶法固定葡萄糖氧化酶(GOx)于铂电极表面,并在葡萄糖溶液中加入高氯酸·三-2,2′-联吡啶合钴(Ⅲ)作为电子媒介体,制成了高灵敏的葡萄糖生物传感器.葡萄糖氧化酶吸附在纳米金颗粒表面上稳定且保持其生物活性;而电子媒介体的存在,显著提高了传感器的响应灵敏度.该传感器对葡萄糖响应的线性范围为1.2×10-8～6.2×10-6 mol/L,检出限6.2×10-9 mol/L(S/N=3).该生物传感器有效消除了抗坏血酸、尿酸的干扰,可用于人体血清中葡萄糖的测定.     

生物/化学同步聚合法制备纤维蛋白纳米复合物及传感研究

本文以有效提高生物分子包埋率为目的,基于生物/化学同步聚合的新方法制备了一种新型纤维蛋白聚合物基纳米复合物,并研究了该复合物修饰电极的传感性能。该方法在凝血仿生聚合的同时,采用NaAuCl4作为氧化剂化学氧化聚合生成聚多巴胺(PDA),在PDA膜内原位合成纳米金(AuNPs),同时在PDA-纤维蛋白凝胶生长时包埋葡萄糖氧化酶(GOx)。生物/化学同步聚合法操作简单,条件温和。该纳米复合物引入了AuNPs的优异性质,有效提升了GOx的包埋量,所制电化学生物传感器对葡萄糖的检测灵敏度高达117μA/(cm2·mmol/L),检测限为57nmol/L。     

基于立方体纳米氧化亚铜修饰的安培型葡萄糖生物传感器的制备及性能研究

将合成的立方体纳米氧化亚铜用于修饰玻碳电极,在其上固定葡萄糖氧化酶,构建了高灵敏的安培型葡萄糖生物传感器.采用X射线衍射(X RD)、扫描电镜(SEM)对合成的立方体纳米氧化亚铜及其修饰电极进行了表征.结果表明,合成的纳米氧化亚铜为均匀的立方体形状.采用循环伏安法(CV)、交流阻抗谱(EIS)、差分脉冲伏安法(DPV)及计时电流法(CA)考察了修饰电极的电化学行为.在含0.1 mmol/L葡萄糖的磷酸盐缓冲溶液(pH 7.4)中研究了立方体纳米氧化亚铜修饰电极的循环伏安(CV)响应,实验结果表明,此修饰电极对葡萄糖显示出良好的电催化性能.DPV响应电流与葡萄糖的浓度在5.0×10-6 ～4.0× 10-3mol/L范围内呈良好的线性关系,线性相关系数R2=0.9983,检出限为6.8×10-7 mol/L(S/N=3).CA实验结果表明,尿酸、抗坏血酸、D-果糖对传感器不产生干扰.本传感器具有较好的重现性和稳定性,可用于实际样品中葡萄糖的检测.     

天青Ⅰ为电子媒介体金纳米颗粒修饰葡萄糖生物传感器

用纳米金溶胶与聚乙烯醇缩丁醛(PVB)构成复合固酶基质,采用溶胶凝胶法固定葡萄糖氧化酶(GOx)于铂金电极表面,并在葡萄糖溶液中加入天青Ⅰ作为电子媒介体,制成了新型葡萄糖生物传感器。实验证明,葡萄糖氧化酶吸附在纳米金颗粒表面上稳定且保持其生物活性;而电子媒介体的存在,显著提高了传感器的响应灵敏度。该传感器对葡萄糖响应的线性范围为2.5×10-5～7.5×10-3mol/L;检出限为8.5×10-6mol/L(S/N=3)。该生物传感器用于人体血清中的葡萄糖测定,结果令人满意。     

基于对氨基苯甲酸/硫堇/纳米金共价修饰玻碳电极的葡萄糖生物传感器

实验制备了以对氨基苯甲酸(4-ABA)、硫堇(TH)、纳米金(Au NPs)共价键合葡萄糖氧化酶的新型葡萄糖生物传感器. 主要采用循环伏安法, 以羟基二茂铁作为电子媒介体, 对含葡萄糖和未含葡萄糖的电解液进行了研究. 结果表明: 传感器的响应电流值随葡萄糖氧化酶膜层数的不同而变化. 考虑到酶电极的长期稳定性与构造简单性, 我们制作了两层葡萄糖氧化酶膜的酶电极. 该传感器对1×10^－2 mol/L葡萄糖的响应电流达2.47 μA, 响应时间仅4.7 s. 该生物传感器检测的线性范围为3×10^－5～1×10^－3 mol/L, 最低检测浓度可达5.8×10^－6 mol/L. 该传感器制备简单, 稳定好, 具有一定的使用价值.     

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.     

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.     

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.     

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.     

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.     

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.