ICAS-2006——分析科学国际大会（Ⅱ）

传感器组的报告有:(K1)K Suzuki,以新颖化学传感探针为基础的化学传感器;(K2)Yu G Vla-sov,分析化学中的传感阵列(电子鼻与电子舌)——历史与现状;(K3)S Dong,供传感器与传感技术用的生物材料与纳米结构集成体的整合;(K4)N El Murr,易适应还原氧化反应的氧化酶生物传感器——生     

Gd—Ba—Cu氯氧化物新相

在探索高Tc超导材料的过程中,人们采用替换元素的方法,试图寻找新体系的高温超导体。例如用钇取代La-Ba-Cu-O体系中的镧,结果使新体系的Tc(ρ=0)由原体系的30K提高到90K;在Y-Ba-Cu-O体系中掺入适量的氯后,观察到155K的超导电性。在此,我们对Gd-Ba-Cu-O体系掺氯后的物相变化情况,用X射线粉末衍射和电     

Two—dimensional Network Crown Ether Complex.Synthesis and Crystal Structure of 18—Crown—6 Complex：[K（18—C—6）]2[Cd—（nmt）2]

The novel complex [K(18-C-6)]2[Cd(mnt)2][18-C-6-18-crown-6,nmt=1,2-dicyanoethene-1,2-dithiolate,C2S2-(CN)2^2-] was synthesized and characterized by elemental analysis,IR spectrum and X-ray diffraction analysis.The complex displays two-dimensional network structure of [K(18-C-6)] complex segments and [Cd(nmt)2] complex segment bridged by S-K-S,S-K-N and N-K-N interactions between adjacent[K(18-C-6)] and [Cd(mnt)2]units.     

SYNTHESIS AND MOLECULAR STRUCTURE OF METHYL 1—BENZYL—6—PHENYLPIPERIDIN—2—ONE—5—CARBOXYLATE

<正> C20H21NO3,Mr=323.39,monoclinic, space group P21, a= 7. 338(2), b=15. 419(3),c=7. 515(1)A,β=95.98(1)°,V= 845. 7(2)A3,Dm(flotation in aq. KL)=1.267,Dx(Z=2)=1.270gcm-3,λ(MoKα)=0.71069A,μ=0.08cm-1,F(000)=344,T=295°K,final RF=0. 042 for 1651 observed reflections. The title compound was synthesized and established as the trans isomer, with the phenyl and carbomethoxy substituents occupying pseudo-axial and axial positions, respectively, of the piperidin-2-one ring in a half-chair conformation.     

4—氨基—三氮唑树脂对铬（Ⅵ）的吸附,机理及应用

4-氨基-三氮唑树脂(4-ATR)对Cr(Ⅵ)的吸附在pH=1时最佳,Cr~(3+)基本不被吸附。两者分离系数β_(CrVI/Cr~(3+)=5.52×10~3.静态饱和容量为179.4mg Cr(Ⅵ)/g树脂。用5mol/L HCl能还原洗脱。测得不同温度下的吸附速率常数k_(21·c)=1.59×10~(-3)S~(-1)、K_(25·c)=1.87×10~(-3)S~(-1)、K(30·c)=2.2×10~(-3)S~(-1);表观吸附活化能E_a=26.26kJ/mol;吸附热力学函数ΔH=6.16kJ/mol,ΔG~(298)=-15.1kJ/mol,ΔS~(298)=339.8J.mol·K.吸附机理表明4-ATR功能基上的N与Cr(Ⅵ)发生配位键合,配位摩尔比为1∶1.利用此树脂处理含Cr(Ⅵ)电镀废水,铬回收率可达95.7%。     

La—LaCl3—KCl熔体的计算机模拟研究

用Monte Carlo方法对La-LaCl_3-KC1体系在1223K时的结构进行了计算机模拟研究,得到了熔体中诸离子对的偏径向分布函数和体系在1223K的势能和内能。结果表明,在熔体中La(Ⅲ)有相当一部分以LaCl_6~3六配位形式存在,而La(Ⅱ)则主要以LaCl_4~2四配位形式存在。结果还表明,熔体中的自由体积分布不均匀,存在许多不规则的空孔和缝隙,其中XK~+·YC1~-集团内的缝隙比纯KC1熔体中的缝隙明显增多。     

TRANSFORMING GENES IN DUCK HEPATIC CARCINOMA——mht(raf) AND Ha-ras

The transfection of NIH 3T3 cells was performed with DNAs from 2 duck primary hepatic carcinomas (DHC 40K, 9K) and I tumor-adjacent liver tissue (TAL, 9N). Transfectants were found from 40K, 9K and 9N DNAs. The secondary transfectants were obtained after transfection of RAT-1 cells with DNAs from primary transfectants. After hybridization with Ha-ras, Ki-ras, N-ras and mht oncogenes, it was found that duck mht (5.2 and 3.2 kb EcoRI fragments) and duck Ha-ras (3.4 kb EcoRI fragments) were present in all these transformants.This is the first report on transforming genes in duck primary hepatic cancer as well as tumoradjacent liver tissue     

Low temperature heat capacities and thermodynamic properties of rare earth triisothiocyanate hydrates——Pr(NCS)_3· 7H_2O and Nd(NCS)_3· 7H_2O

Heat capacities of Pr(NCS)3·7H2O and Nd(NCS)3· 7H2O haw been measured from 13 to 300 K by using a fully automated adiabatic calorimeter. Schottky anomaly was observed for Pr(NCS)3·7H2O below 50 K. The polynomial equations for calculating the heat capacity values of the two compounds in the range of 13-300 K were obtained by the least-squares fitting based on the experimental Cp data. The Cp values below 13 K were estimated by using the Debye-Einstein and Schottky heat capacity functions. The standard molar thermodynamic functions were computed from 0 to 300 K. The standard entropies and Gibbs energies of formation of the two compounds were also calculated.     

Salen Zn对氨基酸甲酯体系的手性分子识别研究

用光谱滴定法测定了手性SalenZn与D-和L-氨基酸甲酸客体在CHCl3中的分子识别反应的缔合常数,其大小顺序为K(LeuOMe)>K(ValOMe)>K(AlaOMe);K(ThrOMe)>K(SerOMe)>K(TyrOMe);且X(D型)>K(L型).根据van'tHoff方程确定了反应体系的热力学函数,并对体系的熵-焓补偿关系和对映体选择性进行了讨论.用分子力学和量子化学方法,对体系 的识别行为进行了计算研究,从理论上对实验现象及识别过程的规律性给予了合理解释.     

A NOVEL IRON—SULFUR—THIOLATE BASKET CLUSTER：CRYSTAL STRUCTURE OF Fe6S5（μ—SPh）（P—n—Bu3）4（SPh）2

<正> Fe6S5 (u-SPh) (P-n-Bu3)A (SPh )2, Mr = 1632. 21 , triclinic, P1, a = 11.877(3), b=14. 302(3), c= 24. 920(2) A ,a= 94. 84 (2), B = 96. 59 (2), y = 100. 44(2),V= 4111.7(13)A3,Z=2,Dx==1. 32gcm3,MoKa(0. 71069A),u=13.4 cm-1,F(000) = 1726,T=293K,R(Ru) = 0. 077(0. 060) for 6042 observed (I>3o(I)) reflections.     

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.