无机物晶格能及其它理化性质的定量构效关系研究

于邻接矩阵和原子或离子的极化力参数（gi)建立新的连接性指数（^mG)，其中^0G,^1G的定义式为：^0G=∑（gi)^0.5,^1G=∑(gi.gj)^0.5。涉及14种离子（如X^-,O^2-,S^2-,Se^2-,Te^2-,PO4^3-,SiO4^4-,N^3-等）的192种无机物晶格能与^0G,^1G的线性性回归方程为：U＝－381.11 310.20^1G 354.45^0G,R=0.9975其估算值与实验值基本吻合，^1G不仅计算简单，对无机分子结构差异具有很强的区分能力，而且而碱金属卤化物的理化性质（如晶格能、熔点、磁化主、M－X键长，反应微分截面等）显著相关。     

价电子平均能级连接性指数及其应用

定义价电子平均能级（δi）为：δi=(ni-1)(ni+ΣEij)0.5/(1+mi)。由δi建构分子连接性指数（mQ）,其中,0Q=Σ(δi)-0.5、1Q=Σ(δiδj)-0.5。0Q与无机物总键能ΔE、0Q2与过渡元素卤化物的ΔfHmθ、1Q0.5与碱金属卤化物晶格能U、0Q及1Q与无机氢化物pKa的相关系数分别为0.9734、0.9769、0.9906、0.9945,均优于文献方法。mQ是一种结构选择性、性质相关性俱佳的拓扑指数。     

新的价连接性指数与烃标准熵和燃烧热的相关性研究

定义原子特征值βi=(ni-1)mi±hi.由βi建构新的价连接性指数mX=∑(βi·βi·βk…)0.5,其中0阶指数0X=∑(βi)0.5,1阶指数1X=∑(βi·βi)0.5.并计算了4个系列72个烃分子的0X、1X值.发现mX与烃的标准熵、标准燃烧热有良好的相关性,相关系数均在0.99以上.并采用Jackknife方法对模型稳健性进行了检验.     

碱土金属卤化物晶格能和磁化率的拓扑研究

定义一个拓扑指数 n F ,n F = ( Ei× Ej× Ek×… ) - 0 .5,E为价电子能级值。其中的 0 F = ( Ei) - 0 .5,1F = ( Ei× Ej) - 0 .5。0 F、1F与碱土金属卤化物晶格能 ( U)、磁化率 ( Xm)的回归方程为 :U =1 1 2 9.1 - 44 1 .80 F + 360 0 .5 1F,R =0 .9865 ;Xm=- 748.9+ 60 4 .70 F0 .5- 1 34.71F,R =0 .9646。本方法计算简单 ,使用方便 ,物理意义明确 ,预测结果令人满意     

主量子数拓扑指数研究烷基苯的定量构效关系

由主量子数(ni)定义成键原子化学特征的点价为ti=mi(ni-1) hi,在此基础上建构一个主量子数拓扑指数nQ=∑(ti·tj·tk…)0.5,其中,0Q=∑(ti)0.5, 1Q=∑(ti·tj)0.5,并以此为参数研究了烷基苯的燃烧热、等张比容、沸点、汽化热、标准生成自由能、标准熵、摩尔体积、溶解度、辛醇/水分配系数等10种物理化学性质,提出了一个通用的关系式:p=a b 0Q c 1Q.结果表明,0Q, 1Q与烷基苯的许多物理化学性质具有广泛良好的相关性,相关系数均大于0.99.     

多氯代二苯并呋喃的结构信息连接性指数与其在不同柱上的气相保留行为的关系

在分子连接性指数的基础上 ,建立了化合物结构信息连接性指数 nχH(n =0 ,1,2 ,… ,m) ,即 nχH =∑(δiH·δjH·δkH·… ·δmH) -0 5,其中 1阶和 2阶结构信息连接性指数为 :1χH =∑(δiH·δjH) -0 5,2 χH =∑(δiH·δjH·δkH) -0 5,并计算了 135个多氯代二苯并呋喃分子的1χH 和2 χH 值。发现1χH 或2 χH 或1χH 和2 χH 与多氯代二苯并呋喃在不同柱上的气相保留指数 (RI)和相对保留时间 (RRT)有很好的相关性。各样本总体模型即定量结构 保留关系 (QSRR)相关模型的相关系数均在 0 96以上 ,且物理意义明确 ,计算简单.     

多氯代二苯并呋喃的结构信息连接性指数与其在不同柱上的气相保留行为的关系

 在分子连接性指数的基础上 ,建立了化合物结构信息连接性指数 nχH(n =0 ,1,2 ,… ,m) ,即 nχH =∑(δiH·δjH·δkH·… ·δmH) -0 5,其中 1阶和 2阶结构信息连接性指数为 :1χH =∑(δiH·δjH) -0 5,2 χH =∑(δiH·δjH·δkH) -0 5,并计算了 135个多氯代二苯并呋喃分子的1χH 和2 χH 值。发现1χH 或2 χH 或1χH 和2 χH 与多氯代二苯并呋喃在不同柱上的气相保留指数 (RI)和相对保留时间 (RRT)有很好的相关性。各样本总体模型即定量结构 保留关系 (QSRR)相关模型的相关系数均在 0 96以上 ,且物理意义明确 ,计算简单.     

价电子轨道能量拓扑指数mZ及其应用

受Randic分子连接性拓扑指数^mZ的启发,本文构建了价电子轨道能量拓扑指数^mZ。用^mZ的0、1阶指数分别与无机氢化物的pKa1值、20种碱金属卤化物的晶格能U、生成焓△rHm、水化能△rG^0m和气态碱金属卤化物核间距R0关联,拟合的回归方程的相关系(指)数,满足优级或良级标准。预测取得较好的结果。     

无机氢化物的酸性与分子拓扑指数(mYz)的关系

定义一种新原子点价izδ,在izδ的基础上建构新的分子连接性指数mYz,其0阶指数0Yz、1阶指数1Yz的计算公式分别为:0Yz=∑(izδ)0.5;1Yz=∑(ziδ.izδ)0.5.0Yz,1Yz对13种无机氢化物呈现惟一性表征,0Yz,1Yz与无机氢化物pKa1值的一元相关系数和二元相关指数分别为0.993 6和0.995 2.以0Yz,1Yz,和相对分子质量Mr为自变量的三元线性回归方程的相关指数为0.995 7,对无机氢化物pKa1的预测结果十分令人满意.     

CsBr与SmBr3在氢溴酸介质中反应的相化学

由于稀碱稀土卤化物特殊的材料性能，正日益受到各国科学家的关注［‘－3］．动年代初，M：y：：提出了下述4种类型卤化物A’RE？X7（1：2型）、AIREyXgta：2型）、AIRE”X6ta：l型）及AgRE”X。（2：l型）的合成方法（A为碱金属）分析Meyer等人的合成方法网；发现其初始反应是     

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.