3-对甲苯基-5-(4′-硝基-2′-羧基苯偶氮)-2-硫代-4-噻唑啉酮的合成及用于铜的荧光光度测定

本文报道了新荧光试剂3-对甲苯基-5-（4’-硝基-2‘-羧基苯偶氮）-2-硫代-4-噻唑啉酮（MPNCPATTN）的合成。通过元素分析、红外光谱，核磁共振氢谱和质谱确证了其结构。在pH5．6时，它与铜（Ⅱ）形成稳定的荧光络合物，在λex／λem=308nm／403nm处产生强烈荧光，其荧光强度与铜（Ⅱ）的浓度在6．28×10－9～9．44×10-7mo1／L范围内呈线性关系，检测限为0.399μg／L的铜（Ⅱ）。测定了人发中的痕量铜，结果满意。     

苯并三唑和8-羟基喹啉对铜的缓蚀协同作用

通过电化学极化曲线和电化学阻抗谱研究了苯并三唑（BTA）和8 羟基喹啉（HQ）对铜的缓蚀协同作用， BTA和HQ复配使用后提高了电极的膜电阻，降低了电极的膜电容，增强了对铜腐蚀的抑制作用.通过MM2分子力学程序和PPP SCF量子化学方法优化计算了BTA和HQ的分子结构参数，分析讨论了它们之间的缓蚀协同效应.     

2-氨基-4-苯基-硒唑Ni（Ⅱ）、Cu（Ⅱ）配合物的合成与表征

合成了2-氨基-4-苯基-硒唑（L）配体与过渡金属镍（Ⅱ）、铜（Ⅱ）的配合物Ni（L）（NO3）2（1）和Cu（L）（Ac）2·H2O（2）．用元素分析、摩尔电导、红外光谱、紫外一可见光谱、核磁共振和热重分析进行了表征;确定了配合物的组成并推断了它们的结构。     

2，2＇-联吡啶在化学镀铜中的作用研究

研究了以次磷酸钠作还原剂的化学镀铜体系，添加剂2，2＇-联吡啶对化学镀铜沉积速率、次磷酸钠阳极氧化和铜离子阴极还原、以及镀层形貌、结构和组分存在状态的影响．结果表明，2，2＇-联吡啶对化学沉积起阻化作用．电化学线性伏安扫描实验显示，镀液中加入2，2＇-联吡啶，次磷酸钠的氧化峰电势有所负移，但峰电流减小；铜离子的还原峰电势负移，但峰电流逐渐增大．扫描电子显微镜（SEM）、能量色散谱（EDS）、X射线衍射（XRD）及X射线光电子能谱（XPS）等实验分别表明，添加剂使镀层致密和光亮、镍含量降低；镀层为Cu-Ni合金，呈面心立方结构，无明显晶面择优取向现象；镀层中铜和镍以金属态存在，磷的质量含量小于0．05％．     

N-苯基-α-氨基酸的微波合成及表征

以溴苯，α-氨基酸为原料，碘化亚铜为催化剂，DMF为溶剂，在碱性介质中微波辐射合成了目标化合物，并以颉氨酸与溴苯的偶联为模型反应进行条件优化，产物结构经IR，1H NMR表征。     

α,β不饱和酸铜与1,10-邻菲绕啉三元配合物的合成、表征及晶体结构

合成了丙烯酸铜和α-甲基丙烯酸铜与1，10-邻菲绕啉形成的三元配合物，通过元素分析、红外光谱、热谱等数据对配合物进行了表征．测定了Cu（C4H5O2）2（phen）·H2O的晶体结构．配合物的组成为CuL2（phen）·H2O（L=CH2＝HC-COO-,CH2=C(CH3)-COO-），结构为畸变的四方锥形，属单斜晶系，P21/n群，晶胞参数：a=0.7322nm，b=1.7948nmc=1，6014nm，β＝97．12（2）°;Z＝4．     

MMI作为铜的盐酸酸洗缓蚀剂作用机理的研究

用失重法研究了N-甲基-2-巯基咪唑（MMI）在5％盐酸中对铜的酸洗缓蚀性能.探讨了温度和MMI浓度对缓蚀效果的影响，从中得出了MMI在铜表面的吸附等温式，计算了吸附热及MMI的加入对铜在盐酸中腐蚀反应活化能的影响，进而探讨了MMI对铜缓蚀作用的机理.结果表明， 30 ℃下，在5％盐酸中，当MMI的浓度在3 mmol•L－1和8 mmol•L－1之间时,缓蚀率随MMI浓度的增加而迅速增加，当浓度达到8 mmol•L－1时，缓蚀率趋于定值，而当浓度小于3 mmol•L－1时， MMI的加入会加速铜的腐蚀；吸附在铜表面的MMI分子间的作用力整体表现为引力； MMI在铜表面的吸附是吸热反应； MMI的加入降低了铜的腐蚀反应活化能.     

5-苯基-1H-四氮唑对铜片缓蚀性能的研究

通过金相显微镜和接触角测试研究了5-苯基-1H-四氮唑在硫-乙醇体系中对铜的缓蚀性能。结果显示,缓蚀剂可以在铜片表面形成疏水性保护膜,有效抑制了铜片的腐蚀。电化学测试表明,当缓蚀剂浓度为70 mg/L时缓蚀效率达到87%,对铜电极有明显的缓蚀作用。通过量子化学密度泛函理论研究了缓蚀剂分子结构与缓蚀性能的关系,分析了缓蚀剂分子的活性位点。通过分子动力学模拟研究了缓蚀剂分子在Cu的(111)表面的吸附行为。     

油溶性缓蚀剂ω,ω’-双(1-辛基苯并咪唑-2-基)烷烃的合成及缓蚀性能研究

合成了系列ω,ω’-双(1-辛基苯并咪唑-2-基)烷烃油溶性缓蚀剂,并通过红外、质谱等进行结构表征。通过恒电位极化曲线,考察了此类缓蚀剂在2×10-4mol/L H2S-乙醇溶液中对铜电极极化曲线的影响。结果表明,此系列油溶性缓蚀剂对铜电极具有明显的缓蚀作用,且对金属铜的缓蚀效率高,作为润滑油添加剂具有很好的应用前景。     

1-（4-硝基苯基）-3-（2-苯并咪唑）-三氮烯的合成及与铜（Ⅱ）的显色反应

报道了1-（4-硝基苯基）-3-（2-苯并咪唑）-三氮烯（NPBMT）的合成及其与铜（Ⅱ）的显色反应。在非离子表面活性剂OP存在下,于pH11．5的Na2B4O7-NaOH缓冲介质中,NPBMT与铜（Ⅱ）形成2：1的桔红色络合物,络合物的最大吸收峰为417nm,表观摩尔吸光系数为2．62×10^4 L·mol^-1·cm^-1,10mL溶液中,铜（Ⅱ）量在0—15μg／mL范围内符合比尔定律。该法用于人发和食品中微量铜的测定,测定结果与AAS法相符。     

Synthesis and characterization of aryl substituted bis(2-pyridyl)amines and their copper olefin complexes: investigation of remote steric control over olefin binding

The aryl-functionalized pyridylamine 2-(i)PrC(6)H(4)N(H)py (1) and bis(2-pyridyl)amines of the type ArN(py)(2) for Ar = Mes (2), 2,6-Et(2)C(6)H(3) (3), 2-(i)PrC(6)H(4) (4), 2,6-(i)Pr(2)C(6)H(3) (5), and 1-naph (6), have been prepared by the palladium-catalyzed cross-coupling of substituted anilines with 2-bromopyridine, and have been characterized by (1)H and (13)C NMR NMR, FTIR, MS, and TGA. Complexes of these new N-aryl bis(2-pyridyl)amines have been prepared for the acid salts [H{ArN(py)(2)}]BF(4) where Ar = Mes (7) and 2-(i)PrC(6)H(4) (8), and the dimeric bridged complexes [Cu{ArN(py)(2)}(μ-X)(Y)](2) where X/Y = Cl(-) and Ar = Ph (9), 2-(i)PrC(6)H(4) (10), and 1-naph (11), in addition to X = OH(-), Y = H(2)O and Ar = Mes (12). The olefin complexes [Cu(Ar-dpa)(styrene)]BF(4) for Ar = Ph (13), Mes (14), 2-(i)PrC(6)H(4) (15), and 1-naph (16), in addition to the norborylene complexes of Ar = Mes (17) and 2-(i)PrC(6)H(4) (18) have been prepared and characterized by (1)H and (13)C NMR, FTIR, and TGA. The crystal structures have been determined for compounds 1-17. Secondary amine 1 crystallizes in hydrogen-bonded head-to-tail dimers, while the N-aryl bis(2-pyridyl)amines 2-6 crystallize in a three-bladed propellar conformation, having nearly planar geometries about the amine nitrogen. The geometry about copper centers in the dimeric complexes 9-12 is distorted trigonal bypyramidal, with the axial positions occupied by one of the two pyridyl nitrogens and one of the bridging ligands (i.e., Cl or OH). The copper atoms in each of the olefin complexes 13-17 are coordinated to the two pyridine nitrogen atoms and the appropriate olefin; consistent with a pseudo three-coordinate Cu(I) cation. Distortion of pyridyl ring geometries about the copper centers, and concomitant bending of the aryl groups away from the CuN(amine) vectors were found to correlate with the steric bulk of the aryl group present in both dimeric and olefin complexes. Such distortion is also observed to a lesser extent in the acid salts as well. The (1)H and (13)C NMR spectra of [Cu(Ar-dpa)(olefin)]BF(4) exhibit an upfield shift in the olefin signal as compared to free olefin. A good correlation exists between the (1)H and (13)C NMR Δδ values and olefin dissociation temperatures, confirming that the shift of the olefin NMR resonances upon coordination is associated with the binding strength of the complex.     

Synthesis, characterization and antioxidant activity of new copper(I) complexes of scorpionate and water soluble phosphane ligands

New copper(I) complexes have been synthesised from the reaction of CuCl with potassium hydrotris(4-bromo-1H-pyrazol-1-yl)borate, KTp4Br or lithium bis(3,5-dimethylpyrazol-1-yl)acetate, Li[L2CO2] ligands and 4- or 2-(diphenylphosphane)benzoic acid or tris(m-sulfonatophenyl)posphine trisodium salt (TPPTS) coligands. The complexes obtained have been characterized by elemental analyses and FT-IR in the solid state, and by NMR (1H and 31P[1H]) and electrospray mass spectrometry (ESI-MS) in solution. Single crystal structural characterisation was undertaken for the [Cu[PPh2(4-C6H4COOH)](Tp4Br)] derivative, an interesting dimeric supramolecular assembly. A chemiluminescence study has demonstrated the superoxide scavenging activity of these new copper complexes. The Comet assay was used to evaluate the impairment of DNA in rat epithelial cells exposed to different reactive nitrogen species. In addition, the same complexes were included in this study to determine their efficacy as antioxidants in mitigating oxidative DNA damage. The parameter tail moment, used as an index of DNA damage, showed that the complex [Cu[PPh2(4-C6H4COOH)](Tp4Br)] remarkably inhibited DNA strand breaks induced by the different nitrogen oxide species. The other copper complexes under study showed a different ability to reduce tail moment values depending on the type of RNOS donor used.     

The first stereochemically nonrigid monomeric two-coordinate copper(I) complexes with homoleptic and heteroleptic "N2" donor set

A novel set of stereochemically nonrigid monomeric two-coordinate copper(I) complexes, [Cu(eta(1)-H(2)CPz'(2))(2)]ClO(4) 1, [Cu(HPz')(2)]ClO(4) 2, and [Cu(HPz')(eta(1)-H(2)CPz'(2))]ClO(4) 3, where Pz' = 3,5-di-tert-butylpyrazolyl, has been synthesized and characterized by X-ray diffraction and variable-temperature (1)H NMR spectroscopy. Based on the (1)H NMR line shape analysis of complexes 1 and 2, the intramolecular fluxional process was proposed for these two-coordinate copper(I) complexes. Also, the mixed ligand complex 3 shows that these two different dynamic binding modes of the coordinated HPz' and H(2)CPz'(2) ligands can proceed simultaneously on a single copper(I) ion.     

Inorganic-organic hybrids of the p,p'-diphenylmethylenediphosphinate, pcp2-. Synthesis, characterization, and XRPD structures of [Sn(pcp)] and [Cu(pcp)

Two new inorganic-organic polymeric hybrids [Sn(pcp)] and [Cu(pcp)], pcp=CH2(PhPO2)2(2-), have been synthesized and structurally characterized. The tin derivative has been obtained by reaction of the p,p'-diphenylmethylenediphosphinic acid (H2pcp) in water with SnCl2.2H2O, while the copper derivative has been synthesized through a hydrothermal reaction from the same H2pcp acid and Cu(O2CMe)2.H2O. The structures of these compounds have been solved "ab initio" by X-ray powder diffraction (XRPD) data. [Sn(pcp)] has a ladder-like polymeric structure, with tin(II) centers bridged by diphenylmethylenediphosphinate ligands, and alternating six- and eight-membered rings. The hemilectic coordination around the metal shows the tin(II) lone pair to be operative, resulting in significant interaction mainly with a C-C bond of one phenyl ring. The [Cu(pcp)] complex displays a polymeric columnar structure formed by two intersecting sinusoidal ribbons of copper(II) ions bridged by the bifunctional phosphinate ligands. The intersections of the ribbons are made of dimeric units of pentacoordinated copper ions. Crystal data for [Sn(pcp)]: monoclinic, space group P2(1)/c, a=11.2851(1), b=15.4495(6), c=8.6830(1) A, beta=107.546(1) degrees, V=1443.44(9) A, Z=4. Crystal data for [Cu(pcp)]: triclinic, space group P, a=10.7126(4), b=13.0719(4), c=4.9272(3) A, alpha=92.067(5), beta=95.902(7), gamma=87.847(4) degrees, V=685.47(7), Z=2. The tin compound has been characterized by 119Sn MAS NMR (magic-angle spinning NMR), revealing asymmetry in the valence electron cloud about tin. Low-temperature magnetic measurements of the copper compound have indicated the presence of weak antiferromagnetic interactions below 50 K.     

4-氧代-3（4H）-喹唑啉-5-羧酸的合成

以2-氨基-6-甲基苯甲酸为起始原料,通过合环反应生成两种4-氧代-3(4H)-喹唑啉-5-羧酸衍生物(1a, 1b), 1a, 1b分别经高锰酸钾氧化合成了4-氧代-3(4H)-喹唑啉-5-羧酸（2a, 2b）,其结构经¹H NMR, ¹³C NMR和MS表征。研究了投料比｛r［n(高锰酸钾) :n(5-甲基-3(4H)-喹唑啉-4-酮)］｝和反应温度等对收率的影响。结果表明：在最佳反应条件（r=7:1,中性高锰酸钾氧化,于90 ℃反应）下合成2总收率可达66%。     

Synthesis,Characterisation and Reactivity of Copper(I) Amide Complexes and Studies on Their Role in the Modified Ullmann Amination Reaction

A series of copper(I) alkylamide complexes have been synthesised; copper(I) dicyclohexylamide ( 1 ), copper(I) 2,2,6,6‐tetramethylpiperidide ( 2 ), copper(I) pyrrolidide ( 3 ), copper(I) piperidide ( 4 ), and copper(I) benzylamide ( 5 ). Their solid‐state structures and structures in [D₆]benzene solution are characterised, with the aggregation state in solution determined by a combination of DOSY NMR spectroscopy and DFT calculations. Complexes 1 , 2 and 4 are shown to exist as tetramers in the solid state by X‐ray crystallography. In [D₆]benzene solution, complexes 1 , 2 and 5 were found by using ¹H DOSY NMR to exist in rapid equilibrium between aggregates with average aggregation numbers of 2.5, 2.4 and 3.3, respectively, at 0.05 M concentration. Conversely, distinct trimeric, tetrameric and pentameric forms of 3 and 4 were distinguishable by one‐dimensional ¹H and ¹H DOSY NMR spectroscopy. Complexes 3 – 5 are found to react stoichiometrically with iodobenzene, in the presence or absence of 1,10‐phenanthroline as an ancillary ligand, to give arylamine products indicative of their role as potential intermediates in the modified Ullmann reaction. The role of phenanthroline has also been explored both in the stoichiometric reaction and in the catalytic Ullmann protocol.     

制备方法对H2SO4固体酸结构和催化性能的影响

 以溶胶-凝胶法和浸渍法制备了H2SO4固体酸催化剂. FT-IR, XRD和 29Si MAS NMR结果表明,两种方法得到的催化剂结构不同. FT-IR和 29Si MAS NMR结果表明,溶胶-凝胶法制备的固体酸H2SO4-SiO2中H2SO4和载体SiO2间存在相互作用; 1H MAS NMR结果表明,H2SO4-SiO2固体酸的酸强度和液体浓硫酸相当. 通过对柠檬酸与正丁醇的液/固相催化酯化反应比较了溶胶-凝胶法与浸渍法制备的固体酸的催化性能,结果表明,浸渍法得到的固体酸重复使用4次后活性消失; 溶胶-凝胶法制备的H2SO4-SiO2固体酸重复使用6次后仍显示出较高的活性和选择性.     

Self‐Assembly of 3,6‐Bis(4‐triazolyl)pyridazine Ligands with Copper(I) and Silver(I) Ions: Time‐Dependant 2D‐NOESY and Ultracentrifuge Measurements

Two 3,6‐bis(R‐1H‐1,2,3‐triazol‐4‐yl)pyridazines (R=mesityl, monodisperse (CH₂ CH₂O)₁₂CH₃) were synthesized by the copper(I)‐catalyzed azide–alkyne cycloaddition and self‐assembled with tetrakis(acetonitrile)copper(I) hexafluorophosphate and silver(I) hexafluoroantimonate in dichloromethane. The obtained copper(I) complexes were characterized in detail by time‐dependent 1D [¹H, ¹³C] and 2D [¹H‐NOESY] NMR spectroscopy, elemental analysis, high‐resolution ESI‐TOF mass spectrometry, and analytical ultracentrifugation. The latter characterization methods, as well as the comparison to analog 3,6‐di(2‐pyridyl)pyridazine (dppn) systems and their corresponding copper(I) and silver(I) complexes indicated that the herein described 3,6‐bis(1H‐1,2,3‐triazol‐4‐yl)pyridazine ligands form [2×2] supramolecular grids. However, in the case of the 3,6‐bis(1‐mesityl‐1H‐1,2,3‐triazol‐4‐yl)pyridazine ligand, the resultant red‐colored copper(I) complex turned out to be metastable in an acetone solution. This behavior in solution was studied by NMR spectroscopy, and it led to the conclusion that the copper(I) complex transforms irreversibly into at least one different metal complex species.     

Cu(II)-氨基酸-核苷酸三元配合物 II: Cu(II)-L-组氨酸、L-赖氨酸－5'-嘌呤核苷酸三元配合物

合成和表征了新的三元配合物: [Cu(L-His)(5'-AMP)]Cl2.4H2O,[Cu(L-His)(5'-GMP)]Cl2, [Cu(L-His)(5'-IMP)]Cl2.2H2O,[Cu(l-Lys)2(5'-GMP)]Cl2.6H2O, Na2[Cu(L-Lys)2(5'-GMPH_2)].6H2O,Na2[Cu(L-Lys)2(5'-GTPH_2)].6H2O, Na2[Cu(L-Lys)2(5'-IMPH_2)].10H2O. IR及NMR谱表明, 5'-嘌呤核苷酸以嘌呤碱基上的7-N原子与Cu(II)配位。在5'-嘌呤核苷酸形成的配合物中, 磷酸根不参与配位, 但是Na2.5'-GMPH-2和Na.5'-GTPH-2的磷酸根参与配位, 而Na2.5'-IMPH-2的磷酸根不参与配位。     

4(3H)-喹唑啉酮类Schiff碱的合成与抗烟草花叶病毒活性

采用邻氨基苯甲酸经醋酐酰化闭环得2-甲基苯并噁嗪-4-酮, 水合肼回流合成2-甲基-3-氨基-4(3H)-喹唑啉酮, 在无水乙醇中与芳醛反应得4(3H)-喹唑啉酮类Schiff碱. 经元素分析, IR, 1H NMR, 13C NMR对所合成的化合物进行了结构确认和表征. 初步生物活性测试表明, 化合物3t具有较高的抗烟草花叶病毒活性.