硼-氮共掺杂垂直石墨烯电极的制备及其葡萄糖检测性能

采用电子辅助热丝化学气相沉积技术制备了垂直石墨烯(VG)、硼掺杂垂直石墨烯(BVG)、氮掺杂垂直石墨烯(NVG)及硼-氮共掺杂垂直石墨烯(BNVG)薄膜,采用扫描电子显微镜、透射电子显微镜、X射线光电子能谱及Raman光谱仪表征了形貌、微结构及成分,并采用电化学方法分析了其作为表皮传感电极的电化学性能。结果表明,BNVG薄膜由垂直于基片生长的二维纳米片排列成了三维多孔网结构,这些纳米片的硼和氮原子分数达到3.78%和2.75%。BNVG薄膜电极的皮肤接触电阻低至4.5 kΩ,对于葡萄糖的响应浓度范围在 0.001~10 000 μmol·L^-1,检测限低至 0.03 μmol·L^-1,具有良好的抗干扰能力及长期稳定性。     

石墨烯/类金刚石碳复合薄膜的电化学沉积及其场发射性能

采用液相电化学方法在硅基底上制备了石墨烯掺杂的类金刚石碳复合薄膜,探讨了电化学沉积复合薄膜的机理。利用扫描电子显微镜（SEM）、拉曼光谱（Raman）、透射电子显微镜（TEM）和傅里叶变换红外（FTIR）光谱技术对薄膜表面形貌和微观结构进行了分析表征。结果表明,石墨烯片均匀分散沉积在含氢类金刚石碳（a-C：H）基体中,沉积的石墨烯/类金刚石（G/a-C：H）复合薄膜表面相对均匀平整。场发射测试显示石墨烯掺杂使开启电场从4.7 V·μm^-1增加至5.8 V·μm^-1,场发射电流密度从384 μA·cm^-2显著增加至876 μA·cm^-2。     

差分脉冲伏安法同时检测硝苯地平和尼群地平

采用绿色环保的还原剂聚二烯丙基二甲基氯化铵,制备石墨烯(GR)/聚二烯丙基二甲基氯化铵(PDDA)/铂纳米粒子(PtNPs)复合材料,在此基础上制备了GR/PDDA/PtNPs复合修饰电极,并采用透射电镜、电化学等方法对GR/PDDA/PtNPs进行表征。以pH=8.5的B.R缓冲溶液为支持电解质,采用循环伏安法研究了硝苯地平(Nifedipine,NF)和尼群地平(Nitrendipine,NT)在复合修饰电极上的电化学行为,并优化了电化学测量条件。NF溶液浓度为4.0×10(-7)~1.6×10(-4) mol·L^-1,NT溶液浓度为1.0×10^-6~1.4×10^-4 mol·L^-1,它们的还原峰电流与浓度成线性关系,检出限分别为5.0×10^-8 mol·L^-1,3.7×10^-7 mol·L^-1。所建立的方法成功应用于血药中NF、NT的测定,获得可靠满意的结果。     

自支撑石墨烯/聚苯胺纳米纤维薄膜的制备及其电化学电容行为

用真空抽滤氧化石墨（GO）与聚苯胺（PANI）纳米纤维的混合分散溶液,流动组装得到自支撑GO/PANI复合薄膜,再利用气态水合肼还原其中的GO,最后重新氧化和掺杂还原态PANI,制备了自支撑石墨烯（GN）/PANI薄膜.扫描电子显微镜（SEM）结果显示,GN/PANI薄膜为层状结构,且PANI纳米纤维均匀插层于GN片间.PANI纳米纤维在复合薄膜中的存在有效增大了GN之间的层间距,有利于电解液离也GN充分接触.GN的高电导性则有利于PANI氧化还原过程中的电荷传输.电化学测试表明,GN/PANI薄膜在1 mol·L^-1HCl电解液中具有良好的电化学电容性能,在0.1 A·g^-1的电流密度下的比容量为495 F·g^-1,在3A·g^-1时为313 F·g^-1.经过2000次连续充放电,其具有90%的电容保持率,表明该复合材料具有良好的电化学稳定性.     

Ag-Co3O4@MWCNTs纳米复合材料的合成及其在多巴胺检测中的应用

本文使用水热法制备了Ag-Co₃O₄@MWCNTs纳米复合材料,使用扫描电镜和能谱仪对材料进行了表征。将Ag-Co₃O₄@MWCNTs纳米复合材料与壳聚糖超声混合均匀,并修饰到玻碳电极(GCE)表面,得到Ag-Co₃O₄@MWCNTs/GCE电化学传感器。电化学测定结果表明,该修饰电极对多巴胺的电化学反应具有显著的催化作用。峰电流与多巴胺浓度在0.5~377.5μmol·L^-1范围内具有良好的线性关系,检出限为0.16μmol·L^-1(S/N=3)。该传感器具有线性范围宽、检出限低、灵敏度高等优点,可用于人体血清样品中多巴胺的含量分析。     

氮掺杂石墨烯/多酚氧化酶修饰电极检测苯酚

制备了基于氮掺杂石墨烯的多酚氧化酶修饰电极,并将其应用于苯酚的检测。首先利用改进的Hummers方法制备氧化石墨,然后以聚苯胺为氮源,采用水热还原法制备了氮掺杂石墨烯材料,采用扫描电子显微镜、原子力显微镜对制备得到的氮掺杂石墨烯进行微观结构表征。将制备得到的氮掺杂石墨烯与多酚氧化酶复合,利用戊二醛交联的方法制备酶修饰电极,采用循环伏安法、差示脉冲伏安法等电化学方法研究了该酶修饰电极的电化学性能及最优运行条件,结果表明在pH值为6.5时酶修饰电极性能最优;该酶修饰电极对苯酚的检出限为1.21×10~(-6)mol·L~(-1)(S/N=3),线性检测范围为2×10~(-5)～7.7×10~(-4)mol·L~(-1)。同时,该酶修饰电极具有很好的抗干扰性能,可用于水中苯酚含量的检测。     

纳米Cu_2O/氮掺杂石墨烯复合修饰电极对多巴胺的电化学分析研究

本文通过化学还原法制备纳米Cu_2O/氮掺杂石墨烯(NG)复合材料,用于构建一种新型的多巴胺(DA)电化学传感器。采用X射线衍射法和扫描电镜对纳米Cu_2O/氮掺杂石墨烯复合材料进行表征。在pH为7.0的磷酸盐缓冲液中,采用循环伏安法和计时电流法分别研究了DA在纳米Cu_2O/氮掺杂石墨烯复合修饰电极上的电化学行为。结果表明,该修饰电极对DA表现出显著的电催化活性,且DA在修饰电极上的反应受吸附控制。在最佳实验条件下,催化电流与DA的浓度在0.5~700μmol/L之间呈线性关系(r=0.9943),检测限达0.17μmol/L。该修饰电极的选择性高、重复性和再现性好。方法用于实际样品中DA的检测,获得结果较好。     

基于氧化石墨烯增敏的聚邻苯二胺分子印迹电化学传感器测定多巴胺

本工作结合分子印迹技术和电化学检测方法对多巴胺(DA)进行了快速测定。以DA为模板分子,邻苯二胺(o-phenylenediamine,oPD)为功能单体,在氧化石墨烯(GO)修饰电极表面通过一步电聚合法制备分子印迹电化学传感器。采用透射电镜(TEM)和扫描电镜(SEM)对GO的形貌进行了表征,通过循环伏安法(CV)和差分脉冲伏安法(DPV)对传感器的电化学性能进行了分析。当DA的浓度在0.4～2000μmol·L^-1范围内时,DA在印迹电极上的DPV峰电流值与其浓度呈线性关系,检出限为8.0×10^-8 mol·L^-1;采用该方法对实际样品中的DA进行测定,回收率在92～108%之间。     

纳米钛酸锶薄膜电极的组装及其对不锈钢的光电化学缓蚀性能

研究了在铟锡氧化物（ITO）导电玻璃上组装的纳米钛酸锶薄膜光电极在模拟日光照射下对不锈钢的抗腐蚀保护性能.通过溶胶-凝胶法在添加和不添加十六烷基三甲基溴化铵（CTAB）表面活性剂的情况下制得了不同形貌的钛酸锶粉体.X射线衍射（XRD）和高分辨扫描电子显微镜（SEM）表征结呆表明,两种方法合成的钛酸锶均为钙钛矿型结构,但添加CTAB后得到的钛酸锶颗粒分散均匀,平均粒径为90 nm左右.采用紫外-可见漫反射光谱对钛酸锶薄膜的光物理性质进行了研究,发现其光吸收范围在紫外光区,而且通过CTAB协助合成的钛酸锶在小于380 nm光区较非CTAB协助合成的钛酸锶有更强的吸收.以0.1 mol·L^-1NaOH+0.2 mol·L^-1Na₂S溶液为光电极反应的电解质,测试了钛酸锶薄膜电极对304不锈钢在0.5 mol·L^-1的NaCI腐蚀溶液中的光电化学缓蚀性能.304不锈钢在CTAB改性钛酸锶薄膜光电化学保护或不保护条件在0.5 mol·L^-1NaCl+0.05 mol·L^-1HCl腐蚀溶液中腐蚀6h前后的表面金相图表明,钛酸锶薄膜具有优异的光电化学抗腐蚀性能.     

氮掺杂还原氧化石墨烯/四氧化三钴双功能催化剂的制备及表征

采用尿素作为氮源,通过热退火法制备氮掺杂还原氧化石墨烯,然后以乙酰丙酮钴作为钴源通过水热法制备氮掺杂还原氧化石墨烯/四氧化三钴杂化纳米片作为催化氧还原和氧析出反应的双功能催化剂。利用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线电子能谱仪(XPS)等对其进行形貌结构表征,通过旋转圆盘电极等电化学测试对其电催化性能进行分析,可以看出该催化剂具有良好的氧还原和氧析出催化性能。     

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.     

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.     

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.