螺旋共轭分子2，2‘—螺二茚—1，1’,3,3‘—四酮及其衍生物的二阶非线性光学性质与分子结构关系的研究

采用AM1和ZINDO系列方法研究了螺旋共轭分子2，2‘-螺二茚－1，1‘,3,3‘-四酮及其含氮衍生物的几何构型和各分子的稳定构型，并以稳定构型为基础，计算了这些分子的电子光谱、二阶非线性光学系数βμ，β0为电荷转移，考察了取代堪变化对βμ的影响。计算结果表明，所设计分子兼具较大的二阶非线性光学系数和较高的透过率，有希望成为一类新型的二阶非线性光学材料。     

硼羰基取代螺旋共轭化合物电子结构的理论研究

在AM1方法优化的几何结构基础上,用INDO/CI-SOS方法深入探讨硼羰基(B—CO)螺旋共轭化合物的二阶非线性光学性质,讨论了硼羰基的不同取代位置对螺旋共轭体系的电子光谱、二阶非线性光学系数的影响.结果表明硼羰基的引入可改善体系的非线性光学性质,随着硼羰基个数的增加,二阶非线性光学系数增大,大入射波长为1064nm时,β绝对值比未被取代的螺旋共轭化合物的β值增大一个数量级,达到13 84×10-40C·m.     

N-取代吩噻嗪衍生物分子的结构和二阶非线性光学性质的理论研究

在ZINDO方法基础上, 按完全态求和(SOS)公式, 编制了计算分子二阶非线性光学系数βijk的程序。研究了各种取代基在吩噻嗪的氮上取代后衍生物的结构和二阶非线性光学系数。结论是N上取代推电子基对增大二阶光学非线性有利, N上取代吸电子基对增大二阶光学非线性不利。扩大共轭范围对增大二阶光学非线性有利。对上述结果在微观上给予了解释。     

螺旋共轭化合物及其相对应的多烯及联苯连接合物的结构,？…

用ＡＭ１和ＩＮＤＯ／ＣＩ方法研究了螺旋共轭化合物Ｉ的结构和电子光谱，并在此基础上，用完全态求和公式（ＳＯＳ，自编程序）计算了二阶非线性光学系数βμ，把结果与其对应的多烯及联苯连接的化合物Ⅱ和Ⅲ用同一方法计算得到的结果加以比较，发现螺旋共轭化合物Ⅰ的二阶非线性光学系数βμ虽然小于ⅡⅢ，但其透明性均比化合物Ⅱ和Ⅲ好。     

螺旋共轭化合物及其相对应的多烯及联苯连接化合物的结构、光谱和二阶非线性光学性质的比较研究

用ＡＭ１和ＩＮＤＯ／ＣＩ方法研究了螺旋共轭化合物Ⅰ的结构和电子光谱,并在此基础上,用完全态求和公式（ＳＯＳ,自编程序）计算了二阶非线性光学系数βμ．把结果与其对应的多烯及联苯连接的化合物Ⅱ和Ⅲ用同一方法计算得到的结果加以比较,发现螺旋共轭化合物Ⅰ的二阶非线性光学系数βμ虽然小于Ⅱ和Ⅲ,但其透明性均比化合物Ⅱ和Ⅲ好     

甲氧基苯基偶氮衍生物电子结构与二阶NLO性质的HF/FF方法研究

采用量子化学HF方法在6-31G水平上优化6个甲氧基苯基偶氮衍生物分子的几何构型，利用HF／6-31G。方法计算它们的偶极矩、电荷分布、前线分子轨道能级并结合有限场(FF)方法计算二阶非线性光学系数．结果表明，偶氮苯衍生物分子具有很好的共轭性，在给吸电子基团作用下，电荷转移明显，展现示出较强的极性．偶氮苯衍生物分子与苯乙烯、Schiff碱类衍生物相似，也具有很好二阶非线性光学活性，同时六元杂环取代的偶氮苯衍生物分子二阶非线性光学系数比未取代的大，五元杂环取代结果相反．     

含1,3-方酸苯螺旋共轭分子的设计及其电子光谱和非线性光学性质的理论研究

以量子化学半经验方法PM3优化构型为基础,利用INDO/CI方法研究了嵌入1,3-方酸的苯螺旋共轭分子的电子光谱,同时利用INDO/CI-SOS程序计算了它们的二阶非线性光学系数β_ijk和β_μ值,从而探索分子结构与电子光谱及非线性光学性质的关系.理论计算结果表明:在苯螺旋共轭分子中适当地嵌入方酸后,其二阶非线性光学系数增大.与苯螺旋共轭分子和1,3-方酸的比较表明,方酸环处于左端的体系有很好的二阶非线性光学性质,可能成为较好的光学材料.     

新型非线性光学材料的分子设计: 系列螺旋共轭化合物的结构、光谱及二 阶非 线性光学性质的理论研究

采用AM1和ZINDO系列方法研究了螺旋共轭分子2,2'-螺二茚-1,1',3,3'-四酮及其腈基衍生物的几何构型,研究了各分子的稳定构型,并以稳定为基础,计算了这些分子的电子光谱,二阶非线性光学系数βμ,β0,及电荷转移,考察了取代基变化对βμ的影响,计算结果表明所设计分子兼具较大的二阶非线性光学系数和较高的透过率,有希望成为一类新型的二阶非线性光学材料。     

新型合偶氮功能团的双炔类衍生物非线性光学性质的理论研究

在SM1和ZINDO方法基础上，按完全态求和公式计算分子二阶非线性光学系数β(ijk)和三阶非线性光学系数γ(ijkl)，并对含偶氛功能团的双快类衍生物的二阶、三阶非线性光学性质进行了系统的理论研究．即在基础上，在分子左端引入推电子基N（CH3）2，右端分别引入推电子基CH2OH、2，5-二氮-4-硫甲苯基，研究取代基变化时β、γ变化的规律．对计算结果所反映的规律性在微观上给予了解释．     

若干有机共轭分子二阶非线性光学系数和结构的关系

利用CNDO/S-CI程序计算了四类结构近似的有机共轭分子的二阶非线性光学系数,系统地研究了分子结构、共轭链链长、取代基的电子性质、取代位置等对有机共轭大分子二阶非线性光学性质的影响。研究结果表明,四类化合物的二阶非线性光学性质与其分子结构有着密切的关系。     

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.     

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.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.