新型酰基吡唑啉酮配合物的合成、表征及生物活性研究

以1-苯基-3-甲基-5-吡唑啉酮和苯甲酰氯为原料,二氧六环为溶剂,回流反应合成了4-酰基吡唑啉酮配体及4种过渡金属配合物,通过元素分析、红外光谱、差热一热重分析、紫外光谱等对其结构进行了表征,表明配合物组成分别为:Cu(L)2、Zn(L)2、Ni(L)2、Mn(L)2;同时利用抑菌圈大小对2种细菌和4种真菌进行了生物...     

酰基吡唑啉酮缩邻氯苯胺席夫碱Ni(Ⅱ)、Al(Ⅲ)配合物的合成与表征

酰基吡唑啉酮缩有机胺是新型席夫碱配体,对金属离子具有较好的萃取性能,具有一定的传递电子作用、光致发光作用及较强的抗菌抗病毒生物活性。为进一步拓宽酰基吡唑啉酮类配合物的研究领域,合成了1-苯基-3-甲基-4-(α-呋喃甲酰基)吡唑啉酮-5缩邻氯苯胺新型席夫碱试剂及其镍和铝配合物。元素分析、摩尔电导数据表明配合物的组成分别为:Ni(L)2.2H2O、Al(L)3.H2O。通过红外光谱、紫外光谱、差热-热重分析对配合物进行表征。     

取代苯基酰基吡唑啉酮Zn(Ⅱ)、Ni(Ⅱ)配合物的合成与表征

合成新型酰基吡唑啉酮化合物及其金属配合物,研究其热稳定性。在非水溶剂中,对硝基苯肼与乙酰乙酸乙酯反应制得酰基吡唑啉酮。通过回流新配体和金属醋酸盐合成了配合物。合成了新β-双酮试剂,1-对硝基苯基-3-甲基-4-(α-呋喃甲酰基)吡唑啉酮-5(HL)及其锌和镍的配合物。元素分析及摩尔电导值表明配合物的组成为[NiL2]·2C2H5OH·[ZnL2]·2C2H5OH。通过红外光谱、紫外光谱、差热—热重分析对配合物进行了表征。结果表明配合物的中心离子均为4配位。它们加热至185℃分解。     

酰基吡唑酮缩氨基硫脲Cu(Ⅱ)、Ag(Ⅰ)配合物的合成及表征

合成了含硫席夫碱试剂1-苯基-3-甲基-4-(α-呋喃甲酰基)吡唑啉酮-5缩氨基硫脲(L)及其铜,银的配合物。元素分析及摩尔电导值表明新配合物的组成为[CuL2]·4H2O,[AgL]NO3·C2H5OH。通过红外光谱、紫外光谱、差热-热重对配合物进行表征。     

吡唑啉酮类钐配合物的合成及其光谱分析

通过1-取代苯基-3-甲基-4-α-噻吩甲酰基-5-吡唑啉酮配体与稀土离子钐进行络合反应制备了二元及三元吡唑啉酮类钐配合物,并通过核磁共振、红外光谱和元素分析对其进行表征,证明二元配合物的化学式为Sm(L)3(C2H5OH)2,三元配合物的化学式为Sm(L)3(Phen)2(L=1-取代苯基-3-甲基-4-(α-噻吩甲酰基)-5-吡唑啉酮)。经过研究其紫外吸收光谱和荧光光谱表明配合物的吸收光谱主要来源于第一配体,配合物具有荧光。     

二苯基呋喃甲酰基吡唑啉酮及铜、铅配合物的合成与表征

合成了新β-双酮试剂,1-对甲苯基-3-苯基-4-(α-呋喃甲酰基)吡唑啉酮-5(HL)及其Cu(Ⅱ)和Pb(Ⅱ)配合物。根据元素分析、化学方法、摩尔电导结果推出配合物的组成为[ML2]。通过红外光谱、紫外-可见光谱、差热-热重分析和X-射线衍射分析对其配位结构和一般性质进行了研究。     

新型PMNAP缩胺类席夫碱及其铜配合物的合成与表征

在非水溶剂中合成了3种基于1-苯基-3-甲基-4-萘乙酰基-5-吡唑啉酮(PMNAP)缩胺类新型席夫碱及其铜配合物。由元素分析、络合滴定法、质谱和摩尔电导值推测出配合物的组成为CuL2[L=L1,L2,L3],通过红外光谱、紫外光谱、热重分析和核磁共振氢谱对配体和配合物进行了结构表征。结果表明:在测试条件下,3种新配体均以酮式和烯醇式结构共存,配位时酮式可能转化为烯醇式结构按去质子的方式以烯醇负离子的O和亚胺基上的N与铜中心离子配位,配合物的配位数均为4。     

新型酰基吡唑啉酮钬(Ⅲ)、钕(Ⅲ)配合物的合成与表征

酰基吡唑啉酮配合物在分析化学、金属侵蚀、催化,生物,发光材料等领域具有广泛的应用。研究了酰基吡唑啉酮钬(Ⅲ)、钕(Ⅲ)配合物的各种性质。利用1-苯基-3-甲基-吡唑啉酮-5为母体设计合成出了1-苯基-3-甲基-4-己酰基吡唑啉酮-5(HL),再将HL与金属钬和钕的三价盐发生化合反应制备这两种金属的酰基吡唑啉酮配合物,并使用部分光学仪器对化合物进行表征。通过红外光谱分析发现钬(Ⅲ)配合物在476cm-1处有O-Ho键生成、钕(Ⅲ)配合物在469cm-1处有O-Nd键生成;通过差热-热重分析测试可以看出这两种配合物的分解温度较高;通过荧光性能测试得到钬(Ⅲ)配合物,钕(Ⅲ)配合物的最大激发波长和最大发射波长,且发现它们的荧光强度较大。     

己酰基吡唑啉酮锌配合物的合成与表征

酰基吡唑啉酮配合物在功能材料、金属离子萃取、生物活性等领域应用广泛。以1-苯基-3-甲基-吡唑啉酮-5(PMP)为母体,设计合成出4-己酰基吡唑啉酮(HL),通过4-己酰基吡唑啉酮配体(HL),非水溶剂法与金属Zn盐成功合成金属配合物,应用光学和热学分析检测仪对HL与金属配合物进行性能表征。红外光谱中发现,烯醇羟基已去质子化发生配位,吡唑啉酮环共轭形成大的离域键。热重分析测试表明金属配合物在107℃时开始失去水分子,配合物存在并且应用环境不高于107℃。     

PMNAP缩2-氨基苯并噻唑席夫碱及其过渡金属配合物的合成与抑菌活性

在非水溶剂中合成出一种未见报道的新型席夫碱试剂(HL):1-苯基-3-甲基4-萘乙酰基-吡唑啉酮-5(PMNAP)缩2-氨基苯并噻唑及其4种过渡金属配合物.由元素分析、化学方法、质谱和摩尔电导值推测出配合物的组成为ML·H2O[M=Cu2+、Pb2+、Ni2+、Zn2+],通过红外光谱、紫外光谱、热重谱和核磁共振氢谱等手段对配体和配合物进行了结构表征并做了初步的抑菌活性实验.表征结果显示:配体在测试条件下以酮式和烯醇式结构共存,配位时酮式可能转化为烯醇式结构按去质子的方式以1分子吡唑啉酮环羟基和1分子H2O上的两个0原子以及亚胺基和苯并噻唑环上的两个N原子与过渡金属中心离子成键,配合物的配位数为4;抑菌实验结果表明:配合物比配体对枯草杆菌、大肠杆菌、酵母菌和金黄色葡萄球菌具有更强的抑制作用.     

糠醛缩邻氨基苯甲酸Schiff碱稀土配合物的合成与表征

合成了糠醛缩邻氨基苯甲酸Schiff碱及其4种稀土配合物,并通过元素分析、IR、UV、1H NMR和热失重分析对其组成和结构进行表征,结果表明,配体是以四齿的形式参与配位,配位数为8,配合物的组成为Re(L)2.2.5H2O(Re=Eu、Sm、La、Y)。     

Guanine and plasmid DNA binding of mono- and trinuclear fac-[Re(CO)3]+ complexes with amino acid ligands

We have synthesized and fully characterized four new complexes comprising the fac-[Re(CO)3]+ moiety and the ligands NH3, L-proline (Pro), or N,N-dimethylglycine (dmGly). The reaction of [Re(H2O)3(CO)3]+ with the two amino acids gives trinuclear complexes of general formula [Re(L)(CO)3]3 (where L = amino acid). We have studied the in vitro behavior of these compounds with guanine and DNA in order to understand whether the cytotoxicity exhibited by certain rhenium complexes based on the fac-[Re(CO)3]+ core is due to the formation of nucleobase complexes and inter- or intrastrand links between DNA bases. We have performed model studies with guanine and studied the structural effects induced by different rhenium(I) tricarbonyl complexes on PhiX174 plasmid DNA by electrophoretic methods. Our results show that rhenium complexes with two available coordination sites interact with plasmid DNA to form a stable adduct that is likely to involve two bases.     

1, 2-苯并-异噻唑啉-3-酮与锌(Ⅱ)、铜(Ⅱ)配合物的合成及其抑菌性

1,2-苯并-异噻唑啉-3-酮(BIT)与醋酸锌、醋酸铜反应得到配合物[Zn(BIT-H)2](1)及[Cu(BIT)(BIT-H)(CH3COO)](2);通过元素分析、核磁共振、红外光谱和紫外可见分析等手段对配合物结构进行表征。将配合物1和配合物2分别做抑菌实验,它们对大肠杆菌的最小抑菌质量浓度分别为2.344×10-3、1.172×10-3 g/L,对金黄色葡萄球菌的最小抑菌质量浓度分别为5.86×10-4、5.86×10-4 g/L,配合物的抑菌性能很好。     

间硝基苯胺水杨醛Schiff碱过渡金属配合物的合成及性质

合成了4种间硝基苯胺水杨醛Schiff碱过渡金属配合物,其结构经UV-Vis、IR、元素分析、摩尔电导率测定等表征。荧光光谱表明,4种配合物都能强烈猝灭牛血清白蛋白（BSA）的内源荧光。生物活性实验表明,配合物对金黄色葡萄球菌（S.aureus）、大肠杆菌（E.coli）、枯草芽孢杆菌（B.subtilis）、绿脓杆菌（P.aeruginosa）均有不同程度的抑菌作用,其中对绿脓杆菌的抑菌活性较强。4种配合物的抑菌活性均大于配体的抑菌活性。     

无溶剂法合成氨基酸水杨醛席夫碱锌的配合物

以L-丙氨酸或L-亮氨酸及水杨醛、乙酸锌为原料,通过无溶剂一步法合成了氨基酸水杨醛席夫碱锌(Ⅱ)配合物[ZnL(H2O)].nH2O(L=sal-ala,sal-leu),用EDTA滴定法、元素分析、红外光谱、X射线粉末衍射、热分析等手段对配合物的组成和结构进行了表征。结果表明,锌分别与席夫碱配体中的亚氨基氮、羧基氧、酚羟基氧以及水分子中的氧形成了配位数为4的配合物,其热分解包括失水、配体的氧化分解过程,最后完全分解为氧化锌。     

Controlled ring‐opening polymerization of ε‐caprolactone initiated by in situ formed yttrium trisalicylaldimine complexes,and their study by density functional theory

A series of yttrium trisalicylaldimine complexes formed in situ by the reaction of trialkyl complex [Y(CH₂SiMe₃)₃(THF)₂] (THF is tetrahydrofuran) with three equivalent salicylaldimines were used as initiators for the ring‐opening polymerization of ε‐caprolactone. Electronic and steric effects of the salicylaldimine ligand played important roles on the catalytic properties of the yttrium complexes. The yttrium trisalicylaldimine complex Y( L7 )₃ ( L7 = (S)‐2,4‐di‐tert‐butyl‐6‐[(1‐phenylethylimino)methyl]phenol) most effectively initiated controlled ring‐opening polymerization of ε‐caprolactone to prepare poly(ε‐caprolactone)s with high molecular weights and moderate molecular weight distributions. Obtained by density functional theory calculations, the optimized geometries of the four different active centers with four salicylaldimine ligands explained the experimental results. Copyright © 2011 Society of Chemical Industry     

电解铜箔添加剂配方优化

在高电流密度下用直流电沉积法制备了电解铜箔。电解液基础成分为:Cu2+80～90g/L,H2SO4120～130g/L和Cl-30～40mg/L。用正交试验法研究了聚乙二醇、2–巯基苯并咪唑、硫脲、明胶等4种添加剂对电解铜箔力学性能的影响。最佳配比为:聚乙二醇0～5.5mg/L,2–巯基苯并咪唑0～6.0mg/L,硫脲0～3.0mg/L,明胶0～4.5mg/L。由此制备的铜箔,其常温抗拉强度与延伸率分别是411.3MPa和9.3%,高温抗拉强度与延伸率分别是209.2MPa和2.9%。     

Symmetric 1,1'-Dimethylferrocene-Derived Amino Acids: Their Synthesis, Characterization, Ligational and Biological Properties With Cu(II), Co(II) and Ni(II) Ions

Some novel symmetric 1,1'-dimethylferrocene derived amino acids have been prepared by the reaction of 1,1'-ferrocenedimethyldichloride with amino acids (glycine, alanine, phenylalanine and tyrosine). Their Cu(II), Co(II) and Ni(II) complexes, of the type [M(L)] where [M = Cu(II) and L = L(1)-L(5)] and [M(L)Cl(2)] where [M-Co(II)and Ni(II), L = L(1)-L(5)] have been prepared. The dicarboxylic acids and their metal complexes were characterized by their physical, analytical and spectral data. The [M(L)] complexes showed a square planar geometry whereas an octahedral geometry was observed for [M(L)Cl(2)] complexes. The title dicarboxylic acids and their metal complexes have also been screened for their antibacterial activity.     

Catalyst Stability Determines the Catalytic Activity of Non‐Heme Iron Catalysts in the Oxidation of Alkanes

A series of iron(II) bis(triflate) complexes [Fe(L)(OTf)₂] containing linear tetradentate bis(pyridylmethyl)diamine ligands with a range of ligand backbones has been prepared. The backbone of the ligand series has been varied from a two‐carbon linkage [ethylene ( 1 ), 4,5‐dichlorophenylene ( 2 ) and cyclohexyl ( 3 )] to a three‐carbon [propyl ( 4 )) and a four‐carbon linkage (butyl ( 5 )]. The coordination geometries of these complexes have been investigated in the solid state by X‐ray crystallography and in solution by ¹H and ¹⁹F NMR spectroscopy. Due to the labile nature of high‐spin iron(II) complexes in solution, dynamic equilibria of complexes with different coordination geometries (cis‐α, cis‐β and trans) are observed with ligands 2 – 5 . In these cases, the geometry observed in the solid state does not necessarily represent the only or even the major geometry present in solution. The ligand field strength in the various complexes has been investigated by variable temperature magnetic moment measurements and UV‐vis spectroscopy. The strongest ligand field is observed with the most rigid ligands 1 and 2 , which generate complexes [Fe(L)(OTf)₂] with a cis‐α coordination geometry and the corresponding complexes [Fe(L)(CH₃CN)₂]²⁺ display spin crossover behaviour. The catalytic properties of the complexes for the oxidation of cyclohexane, using hydrogen peroxide as the oxidant, have been investigated. An increased flexibility in the ligand results in a weaker ligand field, which increases the lability of the complexes. The activity and selectivity of the catalysts appear to be related to the strength of the ligand field and the stability of the catalyst in the oxidising environment.