Eastman—AQ／四硫富瓦烯修饰碳纤维微秀电极

利用新型摄影了了聚合物膜将以富瓦烯修饰到电极表面上，并研究了修饰电极的电化学行为，研究了浸泡时间、扫描速度和支持电解质对修饰电极性能的影响；循环伏安法、计时电流法和交流阻抗法表明四硫富瓦烯在膜中的扩展是控制步骤。四硫富瓦烯在膜中的第一对氧化还的峰呈现可逆的，单电子反应。用循环伏安法测得了ＴＴＦ＋ＴＴＦ＋＋＝２ＴＴＦ＋的反应的平衡常数。     

Eastman-AQ/四硫富瓦烯修饰碳纤维微盘电极

利用新型的阳离子聚合物膜将四硫富瓦烯修饰到电极表面上，并研究了修饰电极的电化学行为。研究了浸泡时间、扫描速度和支持电解质对修饰电极性能的影响；循环伏安法、计时电流法和交流阻抗法表明四硫富瓦烯在膜中的扩散是控制步骤。四硫富瓦烯在膜中的第一对氧化还原峰呈现可逆的、单电子反应。用循环伏安法测得了ＴＴＦ＋ＴＴＦＺＴＴＦ反应的平衡常数。     

四硫富瓦烯四硫醇盐对纳米硫化物表面的修饰

本文报道用四硫富瓦烯四硫醇盐(TTFS₄^4-，简写TTFS₄)修饰CdS、NiS的纳米微粒的方法，通过TEM、FT-IR等手段对修饰的纳米微粒进行了表征。实验发现CdS/TTFS₄的固体荧光强度随着修饰量的增加而逐渐减弱。表面修饰后的CdS和NiS的电导率比修饰前都有提高，后者更为明显。     

四硫富瓦烯为电子媒介体的葡萄糖生物传感器的研究

本采用四硫富瓦烯（ＴＴＦ）作为葡萄糖氧化酶与玻碳电极之间的电子媒介体，把葡萄糖氧化酶因定在Ｎａｆｉｏｎ－ＴＴＦ修饰电极上，制成葡萄糖生物传感器。用这种传感器测定人体血清中葡萄糖的含量，其线性范围在４．０×１０＾－５～１０＾－３ｍｏｌ／Ｌ之间，响应时间为２０ｓ。该传感器具有选择性、重现性好，灵敏度高等优点。     

Nafion—四硫富瓦烯修饰蜡浸石墨电极的葡萄糖传感器

本文用四硫富瓦烯（ＴＴＦ）作为酶与电极之间的电子传递体，通过牛血清蛋白和戊二醛交联剂，把葡萄糖化氧化酶固定在Ｎａｆｉｏｎ－ＴＴＦ修饰石墨电极上，最后在电极修饰一层Ｎａｆｉｏｎ膜，制备成葡萄糖传感器。Ｎａｆｉｏｎ膜不仅能防止四硫富瓦燃流失，而且能氢抗坏血酸，尿酸等电活生物质阻挡在电极外，防止其干扰，同时具有防污性能。通过实验表明ＴＴＦ＾＋，ＴＴＴ＾２＾＋都能够氧化葡萄糖氧化酶中的辅酶（ＦＡＤＨ２）。     

以四硫富瓦烯为电子媒介体的电流式葡萄糖传感器

用四硫富瓦烯作为酶与电极之间的电子传递体，通过Ｎａｆｉｏｎ水溶液把葡萄糖氧化酶固定在Ｎａｆｉｏｎ－ＴＴＦ修饰玻碳电极上，最后在电极上装饰一层Ｎａｆｉｏｎ膜，制备成葡萄糖传感器。Ｎａｆｉｏｎ膜不仅能防止四硫富瓦烯流失，而且能把抗坏血酸、尿酸等电活性物质阻挡在电极外，防止其干扰，同时具有防污性能。通过实验表明ＴＴＦ＾＋１、ＴＴＴ＾＋２都能够氧化葡萄糖氧化酶中的辅酶。该传感器的线性范围为３．０×１０＾－     

不对称四硫富瓦烯衍生物合成新方法及其电化学性质的研究

以2,3－二（2′－氰乙硫基）－6,7－亚烷硫基四硫富瓦烯为原料,在醇钠的作用下消去氰乙基生成的二元硫负离子与对－二（氯甲基）苯反应除了生成两种新的不对称四硫富瓦烯衍生物外,还得到两种新的“二桥”－双四硫富瓦烯衍生物,为四硫富瓦烯衍生物的合成提供了一种新的方法。并对不对称四硫富瓦烯衍生物和“二桥”－双四硫富瓦烯衍生物的循环伏安图、电化学性质和UV－Vis光谱进行了研究。     

“A-C≡C-TTF-C≡C-A”型四硫富瓦烯衍生物的合成与性质研究

四硫富瓦烯及其衍生物是性能优良的电子给体.本文利用Sonogashira反应将吡啶基团连接在四硫富瓦烯单元上,合成了"A-C≡C-TTF-C≡C-A"型四硫富瓦烯共轭体系衍生物4,4′(5′)-二-(4-吡啶乙炔基)-四硫富瓦烯(TTF4N).吸收光谱、电化学和Pb2+配位键合研究表明,三键作为桥基能够有效实现分子内的电荷转移.金属Pb2+离子与吡啶基团的配位能够引起TTF4N的吸收光谱、核磁氢谱和电化学性质的显著变化.     

双（亚烷二硫基)四硫富瓦烯衍生物的合成及其电化学性质

以四(氰乙硫基)四硫富瓦烯为原料经醇钠消去氰乙基生成四硫富瓦烯四硫盐， 再与二元卤代烷烃化反应，除了得到三种文献报道的双(亚烷二硫基)四硫富瓦烯衍 生物外，还得到三种新的“四桥”双—四硫富瓦烯衍生物，为“桥式”双—四硫富 瓦烯衍生物的合成提出了一种新的方法．并研究了它们的循环伏安图、电化学性质 和紫外—可见光光谱．     

新型I型五聚四硫富瓦烯衍生物的合成和性质

利用2,3-二(2'-氰乙基硫基)-6,7-二烷硫基四硫富瓦烯在甲醇钠的作用下消除一个保护基团生成四硫富瓦烯单钠盐,与1,4-二(氯甲基)苯反应,形成单桥-双(四硫富瓦烯)衍生物,生成的单桥-双(四硫富瓦烯)衍生物再次在甲醇钠的作用下消除剩下的保护基团,形成单桥-双(四硫富瓦烯)衍生物二钠盐,最后与四(3'-碘丙硫基)四硫富瓦烯反应形成新型I型五聚TTF衍生物,并通过循环伏安法和化学氧化法分别对其氧化还原性质和紫外光谱进行了研究.     

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.