丙二酰肼席夫碱及其金属配合物合成与表征

合成了丙二酰肼缩双水杨醛席夫碱配体及与Cu(Ⅱ)、Ni(Ⅱ)和Zn(Ⅱ)的金属配合物。用元素分析、IR、摩尔电导和电子光谱对所有化合物进行了表征．对席夫碱配体还进行了^1HNMR和MS结构表征．给出了化合物可能的空间结构。     

Carbonic Anhydrase Inhibitors. Part 46 Inhibition of Carbonic Anhydrase Isozymes I, II and IV With Trifluoromethylsulfonamide Derivatives and Their Zinc(II) and Copper(II) Complexes

Reaction of aromatic/heterocyclic sulfonamides containing a free amino group with triflic anhydride afforded compounds possessing trifluoromethanesulfonamido moieties in their molecule. The Zn(II) and Cu(II) complexes of these new sulfonamides were prepared and characterized by standard procedures (elemental analysis, spectroscopic, magnetic, thermogravimetric and conductimetric measurements). The new derivatives showed good inhibitory activity against three isozymes of carbonic anhydrase (CA), i.e., CA I, II and IV.     

Homogenous and Heterogeneous Catalytic Activity of Azo-Linked Schiff Base Complexes of Mn(II), Cu(II) and Co(II)

Abstract  

Azo linked Schiff-base[L] complexes of Mn(II)(1), Cu(II)(2) and Co(II)(3) obtained by template method, in the reaction of 4-(benzeneazo) salicylaldehyde with 1,2-propanediamine in the present of metal acetate, respectively. Complexes are used as catalyst for oxidation of cyclohexene with tert-butylhydroperoxide (TBHP); oxidation of cyclohexene catalyzed by these complexes gave 2-cyclohexene-1-one and 2-cyclohexene-1-ol as major products. Conversion of cyclohexene achieved was 95–100% with (1), (2) and (3), with selectivity of 57, 92 and 100% for 2-cyclohexene-1-one, respectively. The encapsulated Cu(II) complex (Cu–NaY) catalyzes the oxidation of cyclohexene using TBHP as oxidant in good yield. (Cu–NaY) under optimized reaction condition gave three reaction products. A maximum of 100% conversion of cyclohexene has been achieved where selectivity of 2-cyclohexene-1-one was 83%.     

脱氢枞胺水杨醛Schiff碱及其铜配合物合成条件研究

脱氢枞胺与水杨醛反应合成脱氢枞胺水杨醛Schiff碱(Ⅰ),(Ⅰ)与醋酸铜反应合成了脱氢枞胺水杨醛Schiff碱铜配合物(Ⅱ).通过初步的合成条件探索之后,运用正交实验对合成条件优化,结果(Ⅰ)和(Ⅱ)的产率分别比文献值报道的最高产率高出3%和7%.     

Kharasch Addition and Vinylation Reactions Mediated by Ruthenium(II) Complexes Bearing Schiff Base Ligands

Ruthenium Schiff base complexes I.a-f mediated the Kharasch addition of carbon tetrachloride across olefins with high yields which markedly depended on the catalyst and the substrate used. Furthermore, 1,6-dienes undergo a highly stereoselective addition–cyclization process with these systems to give mixtures of cis- and trans-3-chloromethyl-4-(2,2,2-trichloroethyl)cyclopentanes in excellent yields. Finally, the catalytic performance of these systems in the vinylation reaction was checked. Dependent on the catalytic system and the reaction conditions used, enol esters or enynes can be obtained in high yields with moderate selectivities.     

Multifunctional Composites of Chiral Valine Derivative Schiff Base Cu(II) Complexes and TiO2

We have prepared four new Cu(II) complexes containing valine moieties with imidazole ligands at the fourth coordination sites and examined their photo-induced reactions with TiO₂ in order of understanding the reaction mechanisms. Under a nitrogen atmosphere, the intermolecular electron transfer reactions (essentially supramolecular interactions) of these systems, which resulted in the reduction of Cu(II) species to Cu(I) ones, occurred after UV light irradiation. In this study, we have investigated the conditions of the redox reactions in view of substituent effects of aldehyde moieties. The results of cyclic voltammetry (CV) on an rotating ring-disk electrode (RRDE) suggested that the substitution effects and redox potentials were correlated. Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations were also performed to simulate the UV–Vis and circular dichroism (CD) spectra; the results revealed a reasonably good correlation between the substituent effects and the highest occupied molecular orbitals and the lowest unoccupied molecular orbitals (HOMO-LUMO) gaps associated with the most intense transition bands. In addition, we summarized the substitution effects of Cu(II) complexes for their corresponding UV light-induced reactions.     

Synthesis, Crystal Structure, Fluorescence and Thermostability of Ni(II), Zn(II), Cd(II) Complexes with Schiff Base 2-Acetylpyridine-d-tryptophan

Three novel transition metal coordination polymers, [Ni(C₁₈H₁₆N₃O₂)₂·2CH₃OH] _n (1), [Zn(C₁₈H₁₆N₃O₂)₂·4CH₃OH] _n (2) and [Cd(C₁₈H₁₆N₃O₂)₂·2CH₃OH] _n (3) (C₁₈H₁₆N₃O₂=2-acetylpyridine-d-tryptophan) were synthesized and characterized by elemental analysis, IR, UV, ¹H NMR and X-ray diffraction single crystal analysis. The analyses of the structures indicate that all three materials crystallize in the tetragonal crystal system, space group P4₁2₁2. They have similar structures; i.e., the Schiff base coordinates in its deprotonated form and behaves as a hexadentate (4N+2O) coordinated ligand to form a distorted octahedron geometry. On the other hand, as a result of the alternate arrangement of chains through N–H···O intermolecular hydrogen bonds interactions, 2-D layers are formed for the three complexes. Furthermore, the luminescent properties and thermal stabilities of the three complexes were investigated.     

Spectroscopic Characterization and Biological Activity of Hesperetin Schiff Bases and Their Cu(II) Complexes

The three Schiff base ligands, derivatives of hesperetin, HHSB (N-[2,3-dihydro-5,7-dihydroxy-2-(3-hydroxy-4-methoxyphenyl)chromen-4-ylidene]isonicotinohydrazide), HIN (N-[2,3-dihydro-5,7-dihydroxy-2-(3-hydroxy-4-methoxyphenyl)chromen-4-ylidene]benzhydrazide) and HTSC (N-[2,3-dihydro-5,7-dihydroxy-2-(3-hydroxy-4-methoxyphenyl)chromen-4-ylidene]thiosemicarbazide) and their copper complexes, CuHHSB, CuHIN, and CuHTSC were designed, synthesized and analyzed in terms of their spectral characterization and the genotoxic activity. Their structures were established using several methods: elemental analysis, FT-IR, UV-Vis, EPR, and ESI-MS. Spectral data showed that in the acetate complexes the tested Schiff bases act as neutral tridentate ligand coordinating to the copper ion through two oxygen (or oxygen and sulphur) donor atoms and a nitrogen donor atom. EPR measurements indicate that in solution the complexes keep their structures with the ligands remaining bound to copper(II) in a tridentate fashion with (O^–, N, O_ket) or (O^–, N, S) donor set. The genotoxic activity of the compounds was tested against model tumour (HeLa and Caco-2) and normal (LLC-PK1) cell lines. In HeLa cells the genotoxicity for all tested compounds was noticed, for HHSB and CuHHSB was the highest, for HTSC and CuHTSC–the lowest. Generally, Cu complexes displayed lower genotoxicity to HeLa cells than ligands. In the case of Caco-2 cell line HHSB and HTSC induced the strongest breaks to DNA. On the other side, CuHHSB and CuHTSC induced the highest DNA damage against LLC-PK1.     

含噻吩双水杨醛希夫碱铜、镍配合物合成与表征

以5,5'-亚甲基双水杨醛缩-2-(2-氨基苯胺基)-3-氰基-5-甲基噻吩希夫碱(L)和乙酸铜或乙酸镍为原料,合成了含噻吩双水杨醛希夫碱铜(Ⅱ)、镍(Ⅱ)配合物,用滴定分析、元素分析、红外光谱、紫外-可见光谱和热分析对配合物进行了组成和结构表征。该双核配合物的组成为[M_2L(H_2O)_2](M=Cu~(2+),Ni~(2+)),中心离子与来自配体的亚胺基氮原子、酚羟基氧原子和氨基氮原子以及来自配位水分子中的氧原子形成了4配位的双核对称希夫碱配合物,其在空气气氛中的热分解反应包括脱水、配体的氧化分解过程,最后残余物为CuO或NiO。     

琥珀酰化壳聚糖-铜(Ⅱ)-苯并咪唑衍生物配合物的合成、表征及抗菌活性

文章利用琥珀酸酐对壳聚糖进行改性,并合成了两个新的配合物:sucts-Cu(Ⅱ)-hpb(1)和sucts-Cu(Ⅱ)-tbz(2)[sucts=琥珀酰化壳聚糖,hpb=2-(2’-吡啶)-苯并咪唑,tbz=2-(4′-噻唑基)苯并咪唑]。应用红外光谱,紫外-可见光谱,原子吸收光谱对配合物进行了表征,采用试管倍比稀释法研究了这些配合物对苏云金杆菌、枯草芽孢杆菌、大肠杆菌和金黄色葡萄球菌的抑制作用。结果表明,两种配合物对四种细菌均有较强的抑菌活性,配合物1、2,最小抑菌浓度(MIC)分别为62.5～125μg.mL-1和125～250μg.mL-1,抗菌效果明显强于自由配体。     

Synthesis and Inhibitory Activity of Schiff Base Surfactants Derived from Tannic Acid and Their Cobalt (II), Manganese (II) and Iron (III) Complexes Against Bacteria and Fungi

A series of tannic acid Schiff base surfactants and their iron, cobalt and manganese metal complexes were synthesized and their structures were elucidated by microelemental analysis, FTIR and ¹H-NMR data. The surface activities of the surfactants were increased by increasing the number of substituents, as represented from the surface tension measurements. The metal complexes showed higher critical micelle concentrations and surface tension reduction at critical micelle concentration. The antimicrobial activity in terms of inhibition zone diameter and minimum inhibitory concentrations showed increasing activity of the metal complexes over their parent compounds against Gram-positive, Gram-negative bacteria and fungi.     

3,4-二氨基苯甲酸水杨醛席夫碱合钴的制备

采用模板法,将3,4-二氨基苯甲酸、水杨醛和钴盐以1:2:1比例混合制备席夫碱合钴配合物,并对其进行了红外表征紫外及、摩尔电导和磁性等性质测定。数据分析结果表明:通过席夫碱合钴红外谱图和摩尔电导结果的对比和分析,表明金属与N原子进行了配位,钴盐中的阴离子并未参与配位;通过磁化率的测定,得出席夫碱合钴配合物中钴的单电子数为1,进而可以推测该配合物的分子构型是平面四边形。     

Uranium (VI) Complexes of Some Tridentate Schiff Bases

Protonation constants (log K^H₁ and log K^H₂) of N-acetylacetoneanthranilic acid (abbr. H₂ AA), N-salicylideneanthranilic acid (abbr. H₂SA) and N, (2-hydroxy-1-naphthalidene) anthranilic acid (abbr. H₂ NA), and formation constants of their uranium (VI) complexes have been determined potentiometrically in 50% dioxan (vol/vol) solutions (μ = 0.1 M NaClO₄) at 30 ± 0.1°C. The stabilities of these complexes were found to be in the order: UO₂⁺²-H₂NA > UO₂⁺²-H₂SA > UO₂⁺²-H₂AA.     

Synthesis, Characterisation and Anti-Fungal Activities of Some New Copper(II) Complexes of Octamethyl Tetraaza-Cyclotetradecadiene

The ligand Me(8)[14]diene, L, in its free state as well as in the dihydroperchlorate form, L.2HClO(4), coordinates copper(ll) in different salts to yield a series of [CuLX(x)] X(y)(H(2)O)(z) complexes where X = NO(3), ClO(4), NCS, Cl and Br; x and y may have values of 0 or 2 and z = 0, 1 or 2. The complex, [CuL(ClO(4))(2)].2H(2)O is found to undergo axial ligand substitution reactions with SCN(-), NO(3) and Cl(-) to give a variety of substitution derivatives: [CuL(ClO(4))(m) X(n)] where X = NCS, NO(3) and Cl; m = 0 or 1, and n = 1 or 2. The complexes .have been characterised on the basis of analytical, spectroscopic, magnetic and conductance data. The anti-fungal activities of the ligand and its complexes have been investigated against a range of phytopathogenic fungi.     

Biochemical Characterization of New Gemifloxacin Schiff Base (GMFX-o-phdn) Metal Complexes and Evaluation of Their Antimicrobial Activity against Some Phyto- or Human Pathogens

Four novel ligand-metal complexes were synthesized through the reaction of Fe(III), pleaseCo(II), Zn(II), and Zr(IV) with Schiff base gemifloxacin reacted with ortho-phenylenediamine (GMFX-o-phdn) to investigate their biological activities. Elemental analysis, FT-IR, ¹H NMR, UV-visible, molar conductance, melting points, magnetic susceptibility, and thermal analyses have been carried out for insuring the chelation process. The antimicrobial activity was carried out against Monilinia fructicola, Aspergillus flavus, Penicillium italicum, Botrytis cinerea, Escherichia coli, Bacillus cereus, Pseudomonas fluorescens, and P. aeruginosa. The radical scavenging activity (RSA%) was in vitro evaluated using ABTS method. FT-IR spectra indicated that GMFX-o-phdn chelated with metal ions as a tetradentate through oxygen of carboxylate group and nitrogen of azomethine group. The data of infrared, ¹H NMR, and molar conductivity indicate that GMFX–o-phdn reacted as neutral tetra dentate ligand (N₂O₂) with metal ions through the two oxygen atoms of the carboxylic group (oxygen containing negative charge) and two nitrogen atoms of azomethine group (each nitrogen containing a lone pair of electrons) (the absent of peak corresponding to ν(COOH) at 1715 cm⁻¹, the shift of azomethine group peak from 1633 cm⁻¹ to around 1570 cm⁻¹, the signal at 11 ppm of COOH and the presence of the chloride ions outside the complex sphere). Thermal analyses (TG-DTG/DTA) exhibited that the decaying of the metal complexes exists in three steps with the final residue metal oxide. The obtained data from DTA curves reflect that the degradation processes were exothermic or endothermic. Results showed that some of the studied complexes exhibited promising antifungal activity against most of the tested fungal pathogens, whereas they showed higher antibacterial activity against E. coli and B. cereus and low activity against P. fluorescens and P. aeruginosa. In addition, GMFX-o-phdn and its metal complexes showed strong antioxidant effect. In particular, the parent ligand and Fe(III) complex showed greater antioxidant capacity at low tested concentrations than that of other metal complexes where their IC₅₀ were 169.7 and 164.6 µg/mL, respectively.     

Synthesis and Catalytic Activities of Silica-Supported Multifunctional Azo-Containing Schiff Base Complexes with Cu(II), Co(II), Ni(II) and Mn(II)

A novel 4-((5-formyl-2,4-dihydroxyphenyl)diazenyl)benzylphosphonic acid (FPABP) ligand was synthesized and bound to silica-gel which was activated with 3-aminopropyltriethoxysilane (APTES). Cu(II), Co(II), Ni(II) and Mn(II) complexes of silica-supported ligand (FDPDABP) were synthesized. The ligand and its complexes were characterized by using NMR, FT-IR, elemental analysis, ICP-OES and scanning electron Microscope (SEM). Catalytic properties of the complexes were investigated for the selective oxidation of cyclohexane under microwave power. SiO₂-FDPDABP-Cu(II) complex showed good catalytic activitiy for the selective oxidation of cyclohexane to cyclohexanol with 35.61% yield and cyclohexanone with 7.74% yield.