甘缬二肽-铜(Ⅱ)-多吡啶配合物合成、表征及与DNA的作用

本文合成了3个新的三元铜(Ⅱ)配合物：[Cu(Gly-L-Val)(Phen)]·3.5H₂O(1)、[Cu(Gly-L-Val)(TATP)]·2H₂O(2)和[Cu(Gly-L-Val)(DPPZ)]·1.5H₂O(3)[Gly-L-Val=甘缬二肽,Phen=1,10-邻菲咯啉,TATP=1,4,8,9-四氮三联苯,DPPZ=二吡啶并[3,2-a;2,3-c]吩嗪]。通过元素分析、红外光谱、紫外-可见光谱以及摩尔电导率测定对这些配合物进行了表征。采用电子吸收光谱、荧光光谱、粘度测定和琼脂凝胶电泳方法研究了这些配合物与DNA之间的相互作用。结果表明,这些配合物对DNA有较强的键合作用, 作用模式为插入作用;配合物在还原剂维生素C存在下对pBR322 DNA具有显著的断裂作用。配合物对DNA键合及断裂作用大小为配合物3＞2＞1。     

355 nm光照下大气液相中HNO2与C6H5Cl的反应机理

利用瞬态吸收光谱技术进行了有氧、无氧条件下氯苯与亚硝酸水溶液的交叉反应机理研究，初步考察了这些瞬态物种的生长与衰减等行为, 并对其光解产物进行了GC/MS分析.研究表明，HNO₂在355 nm紫外光的照射下可产生•OH自由基, •OH和氯苯反应生成C₆H₅Cl•••OH，反应速率常数为（6.6～7.0）×10⁹ L•mol^-1•s^-1; 在有氧条件下C₆H₅Cl•••OH可氧化为C₆H₅Cl•••OHO2, 反应速率常数为(1.6 ± 0.2)×109 L•mol^-1•s^-1,然后进一步分解; C₆H₅Cl•••OH衰减或与亚硝酸等作用可形成多种含硝基的化合物或醌类物质.     

硝酸锌与四种α-氨基酸配合物的恒容燃烧能测定

Ten solid complexes of zinc nitrate with L-α-leucine(Leu)， L-α-valine(Val)， L-α-tryptophan(Try) and L-α-threonine(Thr) were prepared in water. The compositions of these complexes are determined by chemical analysis and elemental analysis， which are identified as Zn(Leu)(NO₃)₂·2H₂O(A)， Zn(Leu)₂(NO₃)₂·H₂O(B)， Zn(Val)(NO₃)₂·2H₂O(C)， Zn(Val)₂(NO₃)₂·H₂O(D)， Zn(Val)₃(NO₃)₂·H₂O(E)， Zn(Try)(NO₃)₂·2H₂O(F)， Zn(Try)₂(NO₃)₂·H₂O(G)， Zn(Thr)(NO₃)₂·2H₂O(H)， Zn(Thr)₂(NO₃)₂·H₂O(I) and Zn(Thr)₃(NO₃)·H₂O(J). The constant-volume combustion energies of the complexes， Δ_cU(complex)， were determined by a precise rotating bomb calorimeter at 298.15K. Standard enthalpies of combustion，Δ_cH_m^?(complex， s， 298.15K)， and standard enthalpies of formation， Δ_fH_m^?(complex，s，298.15K) for these complexes were calculated as (4523.22±2.08)， (7208.86±4.28)， (3442.21±1.85)， (5971.21±3.32)， (9007.26±4.24)， (5802.35±2.14)， (10891.58±3.01)， (2147.40±1.28)， (4120.83±0.99)， (6444.68±3.85)kJ·mol^-1 and (615.67±2.27)， (1863.16±4.60)， (1017.34±2.00)， (1742.93±3.61)， (2245.70±4.73)， (1161.18±2.61)， (1829.71±4.20)， (1632.82±1.43)， (1885.55±1.50)， (2770.25±4.21)kJ·mol^-1， respectively.     

基于D-(—)-/L-(+)-对羟基苯甘氨酸的两对手性钴配合物的合成、晶体结构和电化学识别

采用常温溶液挥发法,以D-(—)-/L-(+)-对羟基苯甘氨酸(D-/L-Hhpg)为主配体,2种含氮吡啶配体4,4′-联吡啶(4,4′-bipy)和5,5′-二甲基-2,2′-联吡啶(5,5′-BM-2,2′-bipy)为辅助配体,与CoCl₂·6H₂O反应合成了2对手性配合物{[Co (D-hpg)(4,4′-bipy)(H₂O)]Cl·H₂O}_n(1-D)、{[Co (L-hpg)(4,4′-bipy)(H₂O)]Cl·H₂O}_n(1-L)、[Co (D-hpg)2(5,5′-BM-2,2′-bipy)]Cl·5.5H₂O (2-D)、[Co (L-hpg)₂(5,5′-BM-2,2′-bipy)]Cl·5.5H₂O (2-L)。通过单晶X射线衍射、元素分析、红外光谱、粉末X射线衍射等多种测试方法对其结构进行分析和表征。配合物的单晶X射线衍射数据表明,配合物1-D和1-L属于单斜晶系,P2₁手性空间群,分别呈现1D左手螺旋链和右手螺旋链,通过4,4′-bipy分子扩展为2D网状矩形格子结构。配合物2-D属于单斜晶系,P2₁手性空间群,为0D小分子,在氢键的作用下形成1D超分子双链,并以ABAB形式在a轴方向堆积排布。这些配合物的结构差异归因于辅助配体和Hhpg配位模式的影响。此外,还研究了配合物的电化学性质。配合物1-D表现出电化学可逆的氧化还原行为,并可作为电化学传感器用于有效地检测组氨酸对映体和定量测定组氨酸混合物中的对映体过量。     

3，3′-偶氮-二(6-羟基苯甲酸)镉和钴的配合物：[Cd(OSA)(Phen)(H2O)]n和[Co(OSA)(Phen)(H2O)]n的合成、表征及晶体结构

利用药物奥沙拉秦钠，邻菲罗啉与Cd(ClO₄)₂·6H₂O或Co(NO₃)₂·6H₂O水热反应分别得到其配合物的晶体[Cd(OSA)(Phen)(H₂O)]_n (1)(OSA=3，3′-偶氮-二(6-羟基苯甲酸))和[Co(OSA)(Phen)(H₂O)]_n (2)。单晶结构分析表明两化合物均为一维链状聚合结构，两者的晶体的空间群皆为C2/c。两化合物中，中心金属的配位几何构型均为五配位的五角双锥。3，3′-偶氮-二(6-羟基苯甲酸)通过羧基桥连金属离子形成一维链状聚合物结构。     

通过铜(II)、铁(III)和铁(II)与2,2'-联咪唑协同作用构筑的超分子及其结构的研究

在水和乙醇溶剂中, 通过Cu(II), Fe(III)和Fe(II)与2,2-联咪唑协同作用, 构筑了四种新的超分子配合物[Cu(H₂biim)(gly)(H₂O)]Cl•H₂O (1), [Cu(H₂biim)(C₃H₂O₄)(H₂O)]•1.5H₂O (2), [Fe₂(μ-O)(H₂biim)₄(H₂O)₂](NO₃)₄•C₂H₅OH (3)和[Fe(H₂biim)₃]SO₄ (4) (H₂biim＝2,2-联咪唑; gly^－＝甘氨酸根; C₃H₂O＝丙二酸根). 并通过元素分析, 红外光谱和X射线单晶衍射对其组成、结构和谱学性质进行研究. H₂biim配体, 丙二酸根和甘氨酸根三种配体都采用了双齿螯合方式与金属离子配位. 配合物1～4中, 通过H₂biim配体的N—H键与阴离子、水分子和溶剂分子形成多种氢键, 如R(7), R(9)和R(4)等, 以及H₂biim配体之间的π-π堆积, 阳离子不对称单元构筑了多维结构的超分子配合物.     

Schiff碱双核Mn配合物的合成、结构和性能研究

Five manganese complexes of Schiff base were synthesized： [Mn^Ⅳ，Ⅳ(μ-O)(Salen)]₂·DMF·H₂O (1)， [Mn^Ⅳ，Ⅳ(μ-O)(5-BrSalen)]₂·DMF·0.5H₂O (2)， {Mn^Ⅳ，Ⅳ(μ-O)[Sal(1，2-pn)]}₂·H₂O (3)， {Mn^Ⅳ，Ⅳ(μ-O)[5-Br-Sal(1，2-pn)]}₂·H₂O (4)， {Mn^Ⅳ，Ⅳ(μ-O)[5-CH₃-Sal(1，2-pn)]}₂·2H₂O (5)， and were characterized by element analysis， IR and UV-Vis spectra. The results of cyclic voltammogram show that Schiff base ligands can drop the potential of manganese and steady high oxide state of manganese. The magnetic properties of 1 and 3 have also been studied. The results show that there is a weak ferromagnetically coupling of Mn^Ⅳ₂ pair at room and low temperature， and the interactions of complex 3 are weaker than complex 1.     

3-((4，6-二甲基-2-嘧啶基)硫代)-丙酸和菲咯啉三元稀土配合物的晶体结构和发光性能

制备了以3-((4,6-二甲基-2-嘧啶基)硫代)-丙酸(HL)和菲咯啉(Phen)为配体的2个三元稀土配合物[Eu(L)₃(Phen)]₂·2H₂O(1)和[Tb(L)₃(Phen)]₂·2H₂O(2),并对其结构进行了表征。单晶X射线衍射分析表明它们是同构的。2个稀土离子(Ln)由4个羧酸配体桥接,形成二聚体排列。其余2个羧酸配体和Phen以双齿螯合方式与Ln配位。Ln的配位数为9,具有扭曲的单端方形反棱柱配位多面体构型。固态光致发光测试表明,这2种配合物都显示了金属中心的特征发射带。     

1,2,4-苯三甲酸铜二维网状配合物的合成及结构表征(英)

在室温下,MnSO₄·H₂O和1,2,4-苯三甲酸(H₃BTC)反应得到化合物[Mn(H₂BTC)₂(H₂O)₄]·2H₂O (1),化合物1和CuSO₄·5H₂O反应得到化合物[Cu(HBTC)(H₂O)_1.5]·H₂O (2)。化合物1是一个单核分子化合物。在化合物1中,每个锰离子和两个H₂BTC^－离子及四个水分子配位。化合物2中,每个铜离子和三个HBTC^2－及两个水分子配位,其中的一个水分子起桥联作用从而形成二维网状结构。     

菲咯啉与1-萘甲酸配体共同构筑的多核Ca(Ⅱ)、双核Mn(Ⅱ)配合物的合成、结构及性质

设计、合成了 2种配合物：[Ca(Phen)(Nap)₂]_n (1)和[Mn₂(Phen)₂(Nap)₄(H₂O)] (2)(Phen=菲咯啉,HNap=1-萘甲酸)。通过红外光谱、元素分析、X射线单晶衍射和热重对其进行了结构表征。测定了配合物的激发光谱、发射光谱,以及配合物对人肺癌细胞(NCI-H460)、人乳腺癌细胞(MCF-7)、人肝癌细胞(HepG2)的体外抑制活性;利用紫外吸收光谱、荧光分光光度法研究了配合物与小牛胸腺DNA的相互作用。结果表明：配合物1、2的激发光谱和发射光谱具有很好的镜像关系,且配合物2的斯托克斯位移大于配合物1;配合物对3种癌细胞都有较好的抑制作用,但是2更优于1;配合物1和2与小牛胸腺DNA以静电作用发生沟面结合,结合常数分别为5.83×10³和6.46×10³ L·mol^-1。     

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%.     

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.     

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.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

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.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.