铜(Ⅱ)与咪唑及2-羰基丙酸水杨酰腙混配体配合物的合成、晶体结构及热分解研究

以2-羰基丙酸水杨酰腙、咪唑与五水硫酸铜在水中反应,首次制得混配体配合物Cu(C10H8N2O4)(C3H4N2)(H2O)[C10H8N2O42-为2-羰基丙酸水杨酰腙负离子;C3H4N2为咪唑],并在甲醇溶剂中培养出单晶.该单晶为深绿色,属单斜晶系,空间群为P2(1)/c,晶胞参数a=1.50583(5)nm,b=1.08411(3)nm,c=0.94366(2)nm,a=90°,β=101.5583(11).,γ=90°,V=1.50927(7)nm3,Z=4,μ=1.479 mm-1,Dc=1.628 Mg/m3,F(000)=756.00,R=0.0340,ωR=0.0777,GOF=1.025.晶体测试结果表明,配合物中Cu(Ⅱ)的配位数为5,处于四方锥配位环境,其中配体2-羰基丙酸水杨酰腙的羧基以单齿配位,腙基上C=N的N配位以及羰基(C=O)的O配位,咪唑的3位N参与了配位,这四个配位原子处于四方锥的锥底,另一个配位原子来自H2O中的O,它处于四方锥的锥顶.在晶胞中,除分子内存在氢键外,分子间也存在氢键.根据TG-DTG曲线研究了配合物的热分解过程,利用Kissinger公式计算了配合物主要分解阶段的表观活化能.     

离子液体(1-甲基-3-羧甲基咪唑)钴配合物的合成和晶体结构

由离子液体1-甲基-3-羧甲基咪唑硫酸氢盐([C6H9N2O2][HSO4])和氯化钴合成了一种新的配合物[Co(H2O)4(C6H8N2O2)2]Cl2.2H2O;采用单晶X射线衍射方法测定了配合物的晶体结构.结果表明,所合成的配合物C12H28Cl2CoN4O10属于三斜晶系,空间群P-1,a=0.66753(5)nm,b=0.91751(6)nm,c=1.80604(13)nm,α=85.618(5)°,β=83.385(5)°,γ=83.443(5)°,V=1.08934(13)nm3,Z=2,Mr=520.23,F(000)=538,Dc=1.580g.cm-3,μ(Mo-Kα)=1.088mm-1,R1=0.0861,wR2=0.2878.单晶X射线分析结果表明,在所合成的配合物中,每个1-甲基-3-羧甲基咪唑除羧基外其它原子均位于同一平面,咪唑环带正电荷,而羧基氢原子消失;即整个1-甲基-3-羧甲基咪唑分子不带电荷.总体而言,配合物的内界[Co(H2O)4(C6H8N2O2)2]2+带两个正电荷,外界游离的两个氯离子起平衡电荷作用.     

模拟含双锌核的甲烷单加氧酶催化甲烷和乙烷羟基化理论研究

采用密度泛函B3LYP方法,研究含双锌核的甲烷单加氧酶催化底物CH3X (X=H,CH3) 羟基化的反应机理.用cis-(HCOO)(C3N2H4)Zn2(μ-O)2(COOH)(C3N2H4)(其中C3N2H4＝咪唑)模拟双锌核甲烷单加氧酶中的关键化合物Q.研究表明,反应通过自由基回弹机理发生.首先,底物CH3X (X=H,CH3)与Q中的一个桥形氧发生相互作用生成分子复合物QCH3X.然后,Q中的一个桥形氧进一步夺取底物中的氢原子,生成QH和XCH2双自由基.这两种双自由基很容易结合生成醇类分子复合物PXCH2OH,其中P= cis-(HCOO)(C3N2H4)Zn(μ-O)Zn(COOH)(C3N2H4).最后,分子复合物PXCH2OH脱去羟基化合物XCH2OH生成P.在298.15K和1atm的条件下,含双锌核甲烷单加氧酶Q催化CH4和CH3CH3羟基化反应在蛋白质溶液中的速率常数分别为6.414×10-19和1.542×10-6 dm3·mol-1·s-1.     

邻香草醛缩组氨酸Schiff碱及其镧配合物的合成与生物活性

合成了2个新的化合物——邻香草醛缩组氨酸Schiff碱及其镧配合物.通过元素分析、X射线衍射、红外光谱、紫外-可见光谱、热重-差热分析及化学分析等对它们进行了表征.结果表明,邻香草醛缩组氨酸Schiff碱为2-[(2-羟基-3-甲氧基-苯亚甲基)-氨基]-3-(2-咪唑基)-丙酸一水合物(C14H15N3O4·H2O),Schiff碱镧配合物为二氯-{2-[(2-羟基-3-甲氧基-苯亚甲基)-氨基]-3-(2-咪唑基)-丙酸}合镧(Ⅲ)三水合物[La(C14H15N3O4)Cl2·3H2O].应用生物微量热法研究了这2个化合物的生物活性,在301.15 K下测定了2个化合物存在时粟酒裂殖酵母细胞代谢的产热曲线,计算得到了粟酒裂殖酵母细胞生长速率常数(k)、传代时间(tG)、总热效应(Qtotal)、抑制率(I)及半抑制浓度(IC50)等热动力学参数.结果表明,随着C14H15N3O4·H2O和La(C14H15N3O4)Cl2·3H2O浓度的增加,k和Qtotal减小,tG和I增加,IC50分别为0.2585和0.2488mmol/L.     

镧三元配合物的合成、热稳定性及生物活性

在甲醇介质中,用La(ClO4)3•nH2O与丙氨酸（CH3CHNH2COOH,简称Ala）及咪唑（C3H4N2,简称Im）或苯并咪唑(C7H6N2,简称BenIm)合成出两个新三元配合物La(Ala)3Im(ClO4)3•3H2O(简称La1)和La(Ala)3BenIm(ClO4)3•H2O(简称La2).对配合物进行了容量分析及元素分析，确定了其组成.通过IR、UV、XRD及TG-DTG、DSC进一步研究了配合物的配位行为及热稳定性.生物活性试验表明该类配合物对5种菌均具有不同程度的抑制作用.     

高振动激发态吡嗪碰撞传能的QCT计算研究

用准经典轨线(QCT)方法计算了高振动激发态吡嗪(C4N2H4)与N2、O2、NH3、基态吡嗪之间的碰撞传能. C4N2H4通过计算发现, 高振动激发态C4N2H4与N2、O2碰撞发生的主要是V-V传能, 与NH3碰撞发生的主要是V-R传能, 与基态C4N2H4碰撞发生的主要是V-V(R)传能. 通过比较高振动激发态C4N2H4、C6F6、C6H6与其基态分子的碰撞传能， 发现此类碰撞传能中, 若分子的对称性高， 则V-V传能更容易实现.     

一类六核三价铁簇化合物的合成及结构表征（英文）

选择3种不同尺寸含氮配体(哌嗪、咪唑和三氮唑)与三羟甲基丙烷(H3tmp)和Fe Cl3采用溶剂热反应合成3例六核Fe髥合物:(C5H14N2)[Fe6(μ6-O)Cl6(tmp)4]·2H2O·CH3OH(1)、(C3H5N2)2[Fe6(μ6-O)Cl6(tmp)4](2)和(C4H8N3)3(C2H4N3)[Fe12(μ6-O)2Cl12(tmp)8]·3CH3OH(3),并对它们的结构进行表征。发现三元醇配体有利于合成高核金属簇。3个化合物具有相同的阴离子簇[Fe6(μ6-O)Cl6(tmp)4]2-。通过晶体学参数,元素分析,红外等手段证实,在化合物1和3的体系中,氮杂环配体经历了N-和C-烷基化反应。     

四核Cu(Ⅰ)配合物[Cu4(imdt)9](NO3)4·6H2O的合成与晶体结构

近年来,硫脲类金属配合物在配位化学、生物化学、医药等领域的研究一直受到广泛重视[1,2]。四氢化咪唑-2-硫酮(imdt)又称乙撑硫脲,是乙撑双二硫代氨基甲酸酯类农药的代谢产物。它属于硫酰胺杂环化合物,含—N(H)—C(=S)—=—N=C(—SH)—结构互变活性基团,表现出配位多样性,与金属铜可以形成单核[3]和双核[4,5]配合物。本文合成了四核Cu(I)配合物[Cu4(imdt)9](NO3)4·6H2O,对该配合物进行了元素分析和红外光谱表征,用单晶X-射线衍射测定了晶体结构。1实验部分1·1试剂与仪器配体四氢化咪唑-2硫酮(C3H6N2S,imdt)按文献合成[6],其它药品…     

[Mn3O(O2CC6H5)6(C3H4N2)3]·C6H5CO2·0.5H2O的 合成、晶体结构及磁性质

Mn(O2CMe)2·4H2O、咪唑、苯甲酸和N(n-Bu)4MnO4在无水乙醇溶剂中反应,制备得到锰的三核μ3-O桥联配位化合物[Mn3O(O2CC6H5)6(C3H4N2)3]·C6H5CO2·0.5H2O.该配位化合物的X射线单晶衍射表明,其属于单斜晶系,空间群P21/C,晶胞参数：a=1.52832(19)nm,b=1.9722(2)nm,c=2.1023(3)nm,β=92.597(3)°,Z=4.变温磁化率(5～280K)研究表明,该配位化合物中3个锰离子在低温下存在弱的反铁磁性耦合,交换积分J=-2.34cm^-1。     

m-4-m型Gemini表面活性剂对铂电极上亚甲蓝吸附溶出伏安行为的影响

在0.050 mol·L-1磷酸盐缓冲溶液(PBS)中(pH=6.4), 亚甲蓝(MB)在铂电极上于-0.2 V产生一对不明显的伏安峰. 当向溶液中加入阳离子型Gemini表面活性剂Br-C16H33N+(CH3)2-C4H8-N+(CH3)2C16H33Br-, Br-C12H25N+(CH3)2-C4H8-N+(CH3)2C12H25Br-或Br-C8H17N+(CH3)2-C4H8-N+(CH3)2C8H17Br-后, 亚甲蓝的氧化峰显著增高, 还原峰降低, 氧化还原峰峰电位均正移, 这和表面活性剂与MB在电极表面的协同吸附有关. 联接基团相同的Gemini表面活性剂, 其影响程度随烷基链的增长而逐渐增强. 增大表面活性剂的浓度, MB的氧化峰先升高后缓慢降低. 如当Br-C16H33N+(CH3)2-C4H8-N+(CH3)2C16H33Br-的浓度为15 μmol·L-1 时, 5 μmol·L-1 MB的氧化峰峰电流达到最大值. 此外,溶液pH值和富集电位等对MB及表面活性剂的吸附亦有影响.     

铜(Ⅰ，Ⅱ)配合物的合成、结构与性质

在室温、有关配体存在下,利用金属铜粉和过氧化苯甲酰的氧化加成配位反应合成了四种铜(Ⅱ)配合物(配体分别为联吡啶、双二苯基膦乙烷、2-氨基吡啶、苯并咪唑)。同时又利用双齿有机膦配体(dppm=双二苯基膦甲烷,dppe=双二苯基膦乙烷,dppp=双二苯基膦丙烷,dppb=双二苯基膦丁烷)和金属铜盐的还原取代反应合成了四种一价铜(Ⅱ)配合物。通过元素分析确定了配合物的组成,经X射线四圆单晶衍射确定了配合物的分子结构,配合物的晶体结构由直接法和Fourier合成方法解出。利用电子光谱等手段研究了氧化加成配位和还原取代配位反应的机理。初步建立了一套简单有效的合成铜(Ⅰ,Ⅱ)配合物的新方法。     

烯烃环丙烷化反应催化研究

本文研究了用Cu(CH3CCHCCH3)2, Ph3PCuX, Cu(O2CCF3)2等催化剂催化四甲基乙烯和重氮乙酸乙酯的环丙烷化反应。结果表明配体吸电子能力越强, 立体位阻越小, 其催化活性也越强。考察了反应物与Cu(O2CCF3)2的配比, 反应温度对Cu(O2CCF3)2催化反应活性的影响。通过对Cu(O2CCF3)2催化活性中心的研究表明,催化活性中心是一价铜配合物, 并推断四甲基乙烯环丙烷化机理是经由金属卡宾机理。     

氟烷基化和氟烷氧基化的研究 32. 铜存在下氟砜基二氟碘甲烷与烯烃的反应─一个电子转移引发同时存在自由基和卡宾的过程

在催化量的铜粉存在下, 氟砜基二氟碘甲烷在DG、乙酐或不加溶剂时与烯烃反应,得到加成产物(3,4)和三元环产物。对反应机理作了初步探讨, 3,4经自由基加成得到而三元环产物是涉及二氟卡宾中间体。     

Atomic-scale characterization of graphene grown on copper (100) single crystals

Growth of graphene on copper (100) single crystals by chemical vapor deposition has been accomplished. The atomic structure of the graphene overlayer was studied using scanning tunneling microscopy. A detailed analysis of moire? superstructures present in the graphene topography reveals that growth occurs in a variety of orientations over the square atomic lattice of the copper surface. Transmission electron microscopy was used to elucidate the crystallinity of the grown graphene. Pristine, defect-free graphene was observed over copper steps, corners, and screw dislocations. Distinct protrusions, known as "flower" structures, were observed on flat terraces, which are attributed to carbon structures that depart from the characteristic honeycomb lattice. Continuous graphene growth also occurs over copper adatoms and atomic vacancies present at the single-crystal surface. The copper atom mobility within vacancy islands covered with suspended graphene sheets reveals a weak graphene-substrate interaction. The observed continuity and room-temperature vacancy motion indicates that copper mobility likely plays a significant role in the mechanism of sheet extension on copper substrates. Lastly, these results suggest that the quality of graphene grown on copper substrates is ultimately limited by nucleation at the surface of the metal catalyst.     

Initial Stages of Copper Electrocrystallization on a Glassy-Carbon Ring–Disk Electrode from Sulfate Electrolytes of Various Acidity: Potentiostatic Current Transients

Initial stages of copper electrocrystallization on glassy carbon from sulfuric acid electrolytes of pH 0.3 and 3.7 are studied by the method of potentiostatic current transients on rotating and stationary ring–disk electrode. The rate of copper deposition in a 0.5 M Na₂SO₄ + 0.01 CuSO₄ (pH 3.7) solution is marginally higher than in a 0.5 M H₂SO₄ + 0.01 CuSO₄ acid electrolyte (pH 0.3) at the expense of adsorption of sulfate and hydroxide ions on the substrate surface and the copper crystals. Regularities governing the multistage discharge of copper ions, the formation of the new phase nuclei, and the deposit dissolution are analyzed. The results of the study are compared with the data on the kinetics of copper electrocrystallization on a platinum electrode. The acceleration of the copper deposition on glassy carbon in the acid solution of pH 0.3, as compared with platinum, is due to accelerated discharge of copper ions and increased number of univalent copper ions in the near-electrode layer of solution. The oxygen-containing surface groups of glassy carbon (quinone–hydroquinone, carbonyl, etc.) are probably active centers for the discharge of copper ions and three-dimensional nucleation.     

Nanocomposite forming on the cathode in electrochemical reduction of copper ions from a polymer solution

Copper electrodeposition from a solution of a mixture of copper(II) sulfate and poly(N-vinylpyrrolidone) is accompanied by the formation of a nanocomposite on the cathode. The nanocomposite contains copper nanoparticles and up to 20 wt % polymer. The composite forms by a noncovalent interaction of polymer macromolecules with the surface of copper particles growing on the cathode.     

配位化学中的直线自由能关系XXI: 铜(II)-13-取代苄基-1, 4, 8, 11-四氮杂环十四烷-12, 14-二酮配合物的生成及酸分解行为研究

采用pH法, 在25.0±0.1℃, I=0.1 mol.dm^-^3 (KNO3)条件下, 测定了13-取代苄基-1, 4, 8, 11-四氮杂环十四烷-12,14-二酮的质子化常数及其与Cu(II)配位的平衡常数。讨论了配体与金属离子的配位方式。在25.0±0.1℃, 离子强度为0.1mol.dm^-^3 (KNO3)下, 采用分光光度法, 研究了这些配体铜(II)配合物的酸分解动力学行为。探讨了配合物酸分解机理,得到了速控步的速率常数。发现配位反应平衡常数与配体的质子化常数及配合物酸分解反应速率常数之间存在较好的Hammett型和Bronsted型直线自由能关系。同时探讨了取代基对配合物生成及酸分解的影响情况。     

焦磷酸盐电镀铜初始过程研究

应用恒电流法研究了铁基体上焦磷酸盐电镀铜电位时间变化类型与镀层结合强度之间的关系.提出了临界起始电流密度(DKC)概念.当起始工作电流DKI大于DKC时,铁电极首先被极化至铁表面的活化电位,即基体表面被活化,随后极化至铜的析出电位,使铜层沉积在活化的铁基体表面上,形成具有良好结合强度的铜镀层.反之,如DKI小于DKC,则铜层只能在"钝化"的含氧层表面上析出,得到的镀层结合强度很差.由氩离子溅射深度刻蚀和X射线光电子能谱(XPS)检测出结合强度差的镀层和基体间界面含氧层的存在.调整工艺条件,优化了焦磷酸盐直接镀铜工艺,可降低工艺的DKC,得到与铁基体具有良好结合强度的电镀层.     

Spacer layer screening effect: a novel fluorescent film sensor for organic copper(II) salts

A fluorescent film sensor was prepared by chemical assembly of pyrene on a glass plate surface via a long flexible spacer. It was found that the film is highly selective for some organic Cu2+ salts, such as copper acetate and copper propionate. The presence of inorganic Cu2+ salts and other metal(II) acetates, including Ni2+, Co2+, Pb2+, Cd2+, Zn2+, etc., had little effect upon the sensing behavior of the film for copper acetate or copper propionate. The observation was explained by employing a proposed "two-dimensional solution" model. The quenching by copper acetate of the emission of the film is static in nature due to complexation of the spacers to the metal ions. Furthermore, the response of the film sensor to copper acetate is fully reversible. To the best of our knowledge, this film sensor may be the first one that can differentiate greasy copper salts from inorganic copper salts.     

Synthesis of copper dendrite nanostructures by a sonoelectrochemical method

Copper dendrites have been prepared by a sonoelectrochemical process from an aqueous solution of Cu(2+) in the presence of polyvinyl alcohol. A SEM image of the morpholohy of the copper formed on the electrode after one electric pulse is presented. A subsequent sonic pulse removes the copper from the electrode surface, cleaning it for the next step. The formation of the dendrites is accounted for by the "drying-mediated self-assembly of nanoparticles" theory.