近红外菁染料敏化的准固态太阳电池的光电化学研究

一个新型的近红外五甲川菁染料敏化剂(Cy)通过3,3-二甲基-1-乙基-2-[4-(N-苯乙酰氨基]-1,3-丁二烯-1-基]-3H-苯并[e]吲哚碘盐和5-羧基-1-丁基-2,3,3-三甲基-3H-吲哚碘盐的Knoevenagel缩合反应合成, 其结构用核磁、质谱和紫外等方法进行了确定; 使用疏水性气相法纳米SiO2 R974固化1-丁基-3-丙基咪唑碘离子液体制备了一种新的准固态电解质, 将其应用于菁染料(Cy)敏化的太阳电池, 对该染料敏化的准固态太阳电池的光电化学性能进行了研究. 在AM1.5G标准光源下, 得到1.49%的光电转换效率. 此方法对拓展准固态染料敏化太阳电池的研究具有一定的意义.     

半菁类染料敏化太阳能电池的光电化学性能研究

研究了三种不同长度碳链取代的半菁类染料2-[4-(N,N-二羧乙基)氨基]苯乙烯基-1,3,3-三甲基苯并吲哚鎓碘(BIDC1)、2-[4-(N,N-二羧乙基)氨基]苯乙烯基-1-丁基-3,3-二甲基苯并吲哚鎓碘(BIDC2)和2-[4-(N,N-二羧乙基)氨基]苯乙烯基-1-辛基-3,3-二甲基苯并吲哚鎓碘(BIDC3)敏化太阳能电池的光电化学性能。其中BIDC1的敏化效果最好,在100mW/cm2氙灯光源下,开路电压、短路电流、填充因子和转换效率分别是430mV、1.31mA/cm2、0.52、0.29%。研究表明,随着半菁染料碳链取代基的增长,光电转换效率逐渐降低。     

苯并咪唑-噻碳菁染料的合成及性质

2-(β-苯胺基乙烯基)-5-R-3-(γ-磺酸丙基)苯并噻唑内铵盐同5,6-二氯-1-乙基-2-甲基-3-(γ-磺酸丙基)苯并咪唑内铵盐在乙酸酐-三乙胺存在下缩合生成苯并咪唑-噻碳菁染料, 合成并表征了七个不对称苯并咪唑-噻碳菁, 其中六个为新化合物. 测试了它们的紫外可见吸收光谱和荧光发射光谱, 结果表明 不对称染料的Brooker偏离值与取代基R的Hammettσ~m常数呈线性关系. 取代的苯并噻唑杂环碱性顺序: 4,5-苯并＞5-CH~3＞5-H＞5-OCH~3＞5-F＞5-Cl＞5-CF~3 .     

吲哚碳菁染料的合成及其光谱特性的研究

将(未)确定的1-(3'-磺酸丙基)2,3,3-三甲基吲哚啉内盐与原乙酸三乙酯在吡啶或酸酐中回流合成了五个氮原子上带有磺酸丙基的取代吲哚碳菁染料. 这些染料和杂环氮原子上带有烷基取代的吲哚碳菁相比, 它们具有较高的熔点, 在极性溶剂中具有较高的溶解度. 这些染料的最大吸收值在540～580nm之间, 并具有较高的消光系数(1～2×10^5L·mol·cm^-^1) .     

冠醚硒菁染料的合成

合成了对称和非对称两个新的冠醚硒菁染料2,2'-二乙基-45,4'5'-双并-(15-冠-5)硒碳菁碘化季铵盐和2,2'-二乙基-4,5-并-(15-冠-5)硒碳菁碘化季铵盐以用三种新的中间体2,2'-二硝基-4,5,4',5'-双并-(15-冠-5)二苯基二硒化物, 2-甲基-5,6-并-(15-冠-5)苯并硒唑和2-甲基-3-乙基-5,6-并-(15-冠-5)苯并硒碘化季铵盐。报道了它们的红外、紫外、核磁共振、质谱数据。     

新型花菁染料-蛋白质散射体系的研究与应用

基于蛋白质对花菁染料的共振散射效应,以新型水溶性碳菁染料(1,1′-丙磺酸-3,3,3′,3′-四甲基吲哚三次甲基碳菁-5,5′-二磺酸钾)为探针,建立了一种新的蛋白质共振散射检测体系.在最优条件下,蛋白质对该碳菁染料具有明显的散射增强作用,散射强度与蛋白质浓度成良好的线性关系,牛血清蛋白BSA和人血清蛋白HSA线性响应范围分别为0.20～15.0μg/mL和0.50～10.0μg/mL,检测灵敏度(3σ/K)为0.05、0.10μg/mL.测定了BSA血清合成样品,回收率94.5%～104.0%;测定HSA血清合成样品,回收率95.6%～103.0%,测定相对标准偏差为1.1%～1.9%,测定较为稳定、准确.     

近红外吸收菁染料光氧化反应机理的研究

本文选择了三种分子结构相同而母核杂原子不同的近红外吸收菁染料,对它们的光谱性能特征及光氧化稳定性能进行了研究。结果表明,具有三种不同母核杂原子的菁染料,其光氧化稳定性顺序为:苯并 唑>苯并噻唑>苯并硒唑。通过猝灭实验给出,在三种菁染料的光氧化反应机制中,具有反应活性的单线态氧和超氧负离子同时存在,其中单线态氧是导致菁染料褪色的主要因素。     

方酸菁染料掺杂聚对苯乙炔太阳电池研究

本文把方酸菁染料掺杂在聚[2-甲氧基-5(2-乙基己氧基)对苯乙炔](MEH-PPV)共轭聚合物中,利用方酸菁染料在可见光的良好吸收以提高器件对光谱的利用。用Ti(OC3H7)4作为纳米TiO2前驱物直接和MEH-PPV、方酸菁染料(Hydroxy Squaraine,Sq)混合旋涂来制作连续的互穿网络器件。通过紫外-可见光吸收光谱得到掺杂后体系在650nm左右吸收得到加强,通过荧光测试发现体系MEH-PPV(5mg/mL)∶Sq(0.1mg/1mL)为4∶1(v∶v)掺杂Ti(OC3H7)4(80μL/mL)体积为50%时,荧光几乎被完全淬灭。测试了器件ITO/MEH-PPV/∶Sq∶TiO2/A,ITO/TiO2/MEH-PPV∶Squaraine∶TiO2/A l的光电性能,在AM=1.5,1000W/m2白光下单层器件的FF为0.31,Voc=54Mv,Isc=1.4mA,能量转换效率为0.008%。在同样条件下双层器件FF为0.12,Voc=203mV,Isc=0.048mA,能量转换效率为0.009%。     

新型含羧戊基不对称五甲川菁染料的合成及蛋白标记

以磺酸基苯肼和7-甲基-8-氧代壬酸为原料合成了2,3-二甲基-3-羧戊基-3H-吲哚-5-磺酸;以2,3,3-三甲基-3H-吲哚-5-磺酸和1,3-丙磺酸内酯为原料合成了1-磺酸丙基-2,3,3-三甲基-3H-吲哚-5-磺酸;然后通过半菁合成法合成了一种新型水溶性不对称五甲川吲哚菁染料(Cy5)。产物经C18反相硅胶柱分离,收率57%,其结构经1H NMR、HRMS进行确证。并检测了目标化合物的光谱性质,初步探讨了其在生物标记方面的应用。染料具有良好的水溶性和光稳定性,水溶液的最大紫外吸收波长和最大荧光发射波长分别为646和666 nm,荧光量子产率为0.2,用n(活化菁染料)∶n(牛血清蛋白)=2∶1标记蛋白,D/P值为1.56。     

冠醚菁染料的研究 Ⅳ.一些新冠醚菁染料的合成

冠醚菁染料的合成及其光谱增感作用已有报道.带有冠醚结构因子的新型菁染料具有良好的增感效应和稳定性. 为进一步研究冠醚菁某些基本结构因素对感光和理化性能的影响,根据冠醚空腔和菁甲川链的可调性,参照前文合成路线,研究了单苯并-18-冠-6的溴化、硝化、二硫化及还原缩合反应,制得了关键中间体2-甲基-5,6-并-18-冠-6-苯并噻唑(3),经两种季铵化反应后合成各种菁染料. 本工作合成的中间体(1～7)以及不同盐基的,对称和不对称及中位取代的苯并-18-冠-6型的冠醚菁(9～12,15)和苯并-15-冠-5型的冠醚菁(13,14)均未见文献报道.这些新化合物均经元素分析、红外光谱和紫外光谱鉴识.     

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.     

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.     

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.     

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.