苏丹红I号在纳米金/碳球修饰硼掺杂金刚石电极上的电化学行为

采用纳米金/碳球(Au/CS)复合物修饰硼掺杂金刚石(BDD)电极,研究了苏丹红I号在Au/CS修饰BDD电极上的电化学行为,并据此建立了实际样品中的苏丹红I号的测定方法.结果表明,与裸BDD电极相比,苏丹红I号在Au/CS修饰BDD电极上的氧化峰电流由0.24μA增加到0.83μA,峰电位由0.809V负移到0.743V.在最优测试条件下,苏丹红I号浓度与其峰电流在4~100μmol/L范围内呈线性关系,线性方程为Ip=0.011 26c+0.116(R2=0.999),检出限为8.33μmol/L.采用本方法对实际样品中的苏丹红I号进行测定,测定结果及平均回收率均优于BDD电极法.     

金刚石薄膜电化学

金刚石由于其特殊的物理与化学性质,早在几百年前就吸引了人们对它的关注.化学气相沉积(chemical vapor deposition,CVD)法制备的高掺杂硼复合多晶金刚石薄膜,为金刚石薄膜在电化学中的应用开辟了新的领域.作为新型碳素电极材料,高掺杂硼复合多晶金刚石薄膜具有许多目前使用的电极材料所不可比拟的优异特性如:宽电化学势窗,低残留电流,极好的电化学稳定性以及表面不易被污染等.本文综述了高掺杂硼复合多晶金刚石薄膜电极在电化学中的几个重要应用,包括电分析、电合成及电化学法处理废水等.     

掺硼金刚石膜/碳膜平面式复合电极的制备及电化学性能

采用微波等离子体化学气相沉积法在本征硅上制备掺硼金刚石膜/碳膜平面式复合电极,其中硅片的一面为掺硼金刚石膜,另一面为碳膜。通过SEM和拉曼光谱分析了薄膜的表面形貌和成分,掺硼金刚石膜为纳米级金刚石,碳膜表面有均匀分布的凹坑;利用四探针、循环伏安法和交流阻抗法表征电极导电性和电化学性能,随着沉积时间增加,电极方阻减小;在铁氰化钾溶液中电极发生准可逆氧化还原反应,电势差为119mV,在103Hz附近阻抗为113Ω;多巴胺的检测限为5μmol·L-1。     

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 000μmol·L^-1,检测限低至0.03μmol·L^-1,具有良好的抗干扰能力及长期稳定性。     

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。     

三种碳基电极材料的电化学性质对比研究(英文)

对硼掺杂纳米金刚石(BDND),硼掺杂微米金刚石(BDMD)和玻碳(GC)电极的电化学性质做了对比研究.利用扫描电子显微镜表征了BDMD和BDND电极,其表面粒子大小分别为1-5μm和20-100nm.利用Raman光谱对两种金刚石薄膜的成分进行了表征,结果表明利用热丝化学气相沉积法得到了高质量的BDND和BDMD薄膜.采用0.5mol·L-1H2SO4溶液测定了三种电极的电化学窗口,BDND和BDMD电极的电化学窗口分别为3.3和3.0V,远比GC电极(2.5V)的要宽.[Fe(CN)6]3-/[Fe(CN)6]4-溶液的循环伏安和交流阻抗测定表明,在BDND、BDMD和GC电极上的峰间距(△Ep)分别为73、92和112mV,且其电子传递电阻(Ret)分别为(98±5)、(260±19)和(400±25)Ω.我们也研究了0.1mmol·L-1双酚A在三种电极上的电化学氧化行为.上述的电化学测定结果表明,两种金刚石电极均比GC电极表现出了更宽的电化学窗口、更好的电化学可逆性质、更快的电子传递速度和更高的电化学稳定性,更为重要的是与BDMD相比BDND的电化学性质有进一步的提高.     

碳薄膜电极材料在电分析化学中的应用*

由于具有一系列的优点,碳材料被广泛地应用于电分析化学。新型碳电极材料的开发及其性质研究对电分析化学的发展起着重要的推动作用。最近文献报道了一些制备新型碳薄膜电极材料的方法,因为制备方法不同,这些碳薄膜材料的电化学性质如电位窗、稳定性、导电性也显著不同。人们对电位窗宽、背景电流低、稳定性高、表面不易被电极产物钝化的碳薄膜电极材料的研究非常活跃。本文综述了采用不同方法制备的一些碳薄膜电极材料如硼掺杂的金刚石薄膜、无定形碳和纳米晶体碳薄膜材料等在电分析化学中应用。     

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。     

掺硼纳米TiO_2对农药毒死蜱的光催化降解作用

采用溶胶-凝胶法制备了掺杂硼的纳米TiO2,并用X射线衍射、红外光谱表征了产物的组成和结构.用制备好的掺硼纳米TiO2作为光催化剂对农药毒死蜱进行了光催化降解研究.结果表明:通过掺硼可以显著提高TiO2对毒死蜱的光催化效率.在硼掺杂量为3%,催化剂煅烧温度为500℃,煅烧时间为1 h,催化剂用量为15%时,毒死蜱的降解率最高.     

纳米硫化镉的合成及其电化学催化性能测试

采用CS2-SDS-正辛醇-水微乳体系制备了硫化镉纳米棒。利用XRD、SEM、TEM对产物进行表征，测试了其对多硫化物电极还原反应的催化性能，并与常规方法合成的大粒度CdS晶体进行对比．结果表明，纳米棒为六方型CdS晶体，直径约12nm．常规法合成的CdS为立方型晶体，平均粒度约为1μm．CdS纳米棒电极对硫化钠／多硫化钠电极反应的电催化活性明显高于大粒度CdS晶体电极．     

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.     

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%).     

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.     

Synthesis of N-substituted carbazolones from α-iodo enaminones via Pd(0)-catalyzed intramolecular coupling under microwave irradiation

A variety of N-aryl and N-alkyl carbazolones were conveniently achieved in good to high yields via Pd₂(dba)₃-mediated intramolecular coupling of N-substituted α-iodo enaminones under microwave irradiation. The Pd(0)-catalyzed cyclization was found to proceed favorably with the more electron-deficient phenyl ring during the reactions involving unsymmetrical N,N-diaryl α-iodo enaminones. This unique property enables the construction of carbazolone skeleton containing nitro substituted benzenoid ring.     

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 substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles by intramolecular nitrilimine cycloaddition

Both substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles have been synthesized by the 3+2 intramolecular dipolar cycloaddition of nitrilimines to alkynes. This cyclization has been extended to more versatile 3-bromo derivatives by the use of alkynylbromides as dipolarophiles.