对乙酰氨基酚在多壁碳纳米管修饰电极上的电化学行为

制备了多壁碳纳米管修饰玻碳电极,研究了对乙酰氨基酚在多壁碳纳米管修饰电极上的循环伏安行为,并建立了测定对乙酰氨基酚含量的电化学分析方法。在pH为6.89的磷酸盐缓冲液中,多壁碳纳米管修饰电极对对乙酰氨基酚有明显的电催化作用,其氧化峰电流与对乙酰氨基酚浓度在1.0×10-6～1.0×10-4mol·L-1范围内呈良好的线性关系,检测限为2.0×10-7mol·L-1。     

对乙酰氨基酚在单壁碳纳米管/聚甘氨酸复合膜修饰玻碳电极上的电化学行为及测定

采用循环伏安法在玻碳电极上先聚合甘氨酸,再用滴涂法修饰单壁碳纳米管制备单壁碳纳米管/聚甘氨酸复合膜修饰玻碳电极。研究了对乙酰氨基酚在修饰电极上的电化学行为,结果表明,修饰电极对对乙酰氨基酚的氧化还原具有很好的电催化作用。采用差分脉冲伏安法测定不同浓度的对乙酰氨基酚,氧化峰电流与对乙酰氨基酚浓度在0.3~90μmol·L~(-1)范围内呈良好线性关系,检测限(S/N=3)为0.1μmol·L~(-1)。该法用于实际样品中对乙酰氨基酚的测定RSD小于2.5%,回收率范围为98.1~98.8%,结果令人满意。     

聚L-半胱氨酸/多壁碳纳米管复合修饰电极同时测定邻苯二酚和对苯二酚

将羧基化多壁碳纳米管分散在L-半胱氨酸溶液中并滴涂在玻碳电极表面.将上述电极在pH 6.9的B-R缓冲溶液中,于-1.0～2.5 V的电位范围内进行电聚合,制备了聚L-半胱氨酸/多壁碳纳米管复合修饰电极(Pol-L-Cys/MWCNTs/GCE).研究发现,邻苯二酚和对苯二酚在聚L-半胱氨酸/多壁碳纳米管复合修饰电极上分别出现了一对氧化还原峰,且两者的氧化峰电位差达101 mV,提出了用微分脉冲伏安法同时测定邻苯二酚和对苯二酚的方法.氧化峰电流与邻苯二酚和对苯二酚的浓度在1.0×10-5～1.0×10-3mol·L-1呈线性关系,检出限(3S/N)均达1.0×10-5mol·L-1.修饰电极用于模拟样品中邻苯二酚和对苯二酚的测定,回收率在82.0%～107.0%之间.     

六氰合铁酸铜钴-多壁碳纳米管修饰电极研究

采用电沉积方法制备六氰合铁酸铜钴-多壁碳纳米管复合修饰电极(CuCoHCF-MWCNTs/GCE).研究碳纳米管用量、电解液组成对该修饰电极性能的影响.结果表明,与单一的六氰合铁酸铜钴薄膜修饰电极相比,六氰合铁酸铜钴-多壁碳纳米管复合修饰电极具有更优良的电化学特性,以其催化氧化过氧化氢,峰电流与过氧化氢浓度在3.16×10-5～2.92×10-3mol·L-1范围内呈良好的线性关系,线性回归方程为ip(μA)=0.5529+1.1299C(×10-4mol·L-1),相关系数r=0.9966,检出限为1.75×10-5mol·L-1.     

碳纳米管负载钴/铁混合氧化物修饰电极碱性条件下测定葡萄糖

以碳纳米管为模板,采用电化学方法制备了碳纳米管负载的钴/铁混合氧化物修饰电极,并研究了该修饰电极在碱性介质中对葡萄糖的电催化活性。结果表明,该修饰电极对葡萄糖具有良好的电催化氧化活性。在优化条件下,安培法检测葡萄糖的线性范围为2.0×10-7~4.2×10-5mol·L-1和4.2×10-5~4.9×10-4mol·L-1,检出限(3sb,n=7)为5.0×10-8mol·L-1,灵敏度分别为242.7μA·(mmol·L-1)-1和114.8μA·(mmol·L-1)-1,响应时间小于5 s。     

石墨烯/碳纳米管复合膜修饰电极检测亚硝酸根

本研究先采用滴涂法制备了多壁碳纳米管修饰电极,然后采用电化学沉积技术从含有氧化石墨烯的溶液中制备了石墨烯(GR)/多壁碳纳米管(MWCNT)复合膜修饰电极(GR/MWCNT/GCE)。研究了亚硝酸根(NO2-)在该修饰电极上的电化学行为。结果表明,该修饰电极对亚硝酸根的电氧化具有高的催化活性。在pH 7.00的PBS缓冲溶液中,微分脉冲伏安法测定亚硝酸根的线性范围为1.0×10-7mol·L-1~1.7×10-3mol·L-1,检出限为5.0×10-8mol·L-1(S/N=3)。用该法测定了土壤中亚硝酸根的含量,结果令人满意。     

钴配合物/单壁碳纳米管修饰电极对尿酸的检测

采用滴加单壁碳纳米管(SWCNTs)悬浮液和电沉积钴配合物[Co(phen)3]2+(phen=邻菲啰啉)的方法,制备了钴配合物-单壁碳纳米管修饰玻碳电极([Co(phen)3]2+-SWCNTs/GCE),研究了尿酸(UA)在该修饰电极上的电化学行为。结果表明,修饰电极对UA具有良好的电催化作用,在1~249μmol·L-1浓度范围内,氧化峰电流与UA浓度之间存在良好的线性关系,检出限(S/N=3)为1μmol·L-1,加标回收率在98%~102%之间。该修饰电极的稳定性和重现性好,可用于UA的定量分析。     

盐酸克伦特罗在纳米ZnO和多壁碳纳米管修饰玻碳电极上的电化学行为

制备了纳米ZnO与多壁碳纳米管(MWNTs)复合修饰玻碳电极(ZnO-MWNTs/GCE),考察了盐酸克伦特罗(CLB)在该修饰电极上的电化学行为。实验结果表明:纳米ZnO与MWNTs显著增强了修饰电极对盐酸克伦特罗的伏安响应,增加了电极的有效表面积,改善了电极的导电性和电催化活性。在2~30μmol·L-1和30~500μmol·L-1浓度范围内,CLB在所制备的修饰电极上的电流响应与其浓度线性关系良好,且该电极具有较好的重现性和稳定性。     

基于新型二氧化锰-碳纳米管复合材料的高灵敏过氧化氢传感器

本文以多壁碳纳米管(MWCNTs)和KMnO4为原料,通过直接氧化还原反应合成了一种新型MnO2-C纳米复合材料,将其滴涂在玻碳(GC)电极表面,成功制备出一种非酶型H2O2传感器。采用循环伏安法和计时电流法研究了该传感器对H2O2的电催化氧化行为。实验结果表明,与GC电极和MWCNTs修饰电极相比,该电极对H2O2氧化显示出更好的催化活性。实验对影响电极性能的各种参数,包括pH值、工作电位及MnO2-C修饰量进行了探讨。在最佳实验条件下,传感器对H2O2响应的线性范围为5.0×10-7～0.2mol·L-1,检测限(S/N=3)为1.4×10-7 mol·L-1。该传感器选材新颖,制备方法简单,重现性好,稳定性和抗干扰能力强。     

生物合成纳米金与MWCNTs/L-Cys复合修饰玻碳电极测定左旋多巴

利用荷叶萃取液生物合成纳米金,并与多壁碳纳米管/L-半胱氨酸复合成修饰电极材料,研究了左旋多巴在该修饰电极上的电化学行为.在0.2 mol/L乙酸-乙酸钠体系(pH=2.6)中,氧化峰电流与左旋多巴浓度在0.6~40μmol/L及60~120μmol/L范围内呈良好的线性关系,检出限达5.2×10-8mol/L.实验结果表明,生物合成纳米金复合多壁碳纳米管/L-半胱氨酸修饰电极具有良好的稳定性和高灵敏度,对实际样品测定的回收率在91.2%~102.5%之间.     

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.