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。     

Novel Zinc(II) Complexes [Zn(atc-Et)2] and [Zn(atc-Ph)2]: In Vitro and in Vivo Antiproliferative Studies

Cisplatin and its derivatives are the main metallodrugs used in cancer therapy. However, low selectivity, toxicity and drug resistance are associated with their use. The zinc(II) (Zn^II) thiosemicarbazone complexes [Zn(atc-Et)₂] (1) and [Zn(atc-Ph)₂] (2) (atc-R: monovalent anion of 2-acetylpyridine N4-R-thiosemicarbazone) were synthesized and fully characterized in the solid state and in solution via elemental analysis, Fourier transform infrared (FTIR), ultraviolet-visible (UV-Vis) and proton nuclear magnetic resonance (¹H NMR) spectroscopy, conductometry and single-crystal X-ray diffraction. The cytotoxicity of these complexes was evaluated in the HepG2, HeLa, MDA-MB-231, K-562, DU 145 and MRC-5 cancer cell lines. The strongest antiproliferative results were observed in MDA-MB-231 and HepG2 cells, in which these complexes displayed significant selective toxicity (3.1 and 3.6, respectively) compared with their effects on normal MRC-5 cells. In vivo studies were performed using an alternative model (Artemia salina L.) to assure the safety of these complexes, and the results were confirmed using a conventional model (BALB/c mice). Finally, tests of oral bioavailability showed maximum plasma concentrations of 3029.50 µg/L and 1191.95 µg/L for complexes 1 and 2, respectively. According to all obtained results, both compounds could be considered as prospective antiproliferative agents that warrant further research.     

Oxygen Binding by Co(II) Complexes with Oxime-Containing Schiff Bases in Solution

The present work describes the complexation properties of two oxime-containing Schiff bases (used as ligands), viz. 2-hydroxyimino-N′-[1-(2-pyridyl)ethylidene]propanohydrazone (Hpop) and 2-hydroxyimino-N′-[(pyridine-2-yl)methylidene]propanohydrazone (Hpoa), with Co(II) ions in DMSO/water solution. Volumetric (oxygenation) studies were carried out to determine the uptake of molecular oxygen O₂ in the formation of the complexes Co(II)-Hpop and Co(II)-Hpoa. The acquired data can be useful in the development of oxygen bioinorganic complexes of metal ions with Schiff base ligands in solution. Their properties allow them to be used as synthetic oxygen transporters. Moreover, the binding of dioxygen could play an important role in the research of catalytic activity by such systems.     

己酸二乙氨基乙醇酯亚慢性经口毒性

按照GB15670-1995的要求进行了己酸二乙氨基乙醇酯（DA-6）90d的亚慢性经口毒性试验。结果显示,与对照组相比,雌、雄性大鼠高剂量组的体重增长明显减慢（p〈0．05）;雄性大鼠高剂量组AST、ALB两项指标升高（p〈0．05）,肝、肺脏器系数增长（p〈0．05）。高、中剂量组雌、雄性大鼠发生心肌小灶炎症和肾脏小灶炎症的动物数明显增多。根据试验结果,受检样品己酸二乙氨基乙醇酯对大鼠的无作用剂量为：雄性40．2mg/kg bw／d,雌性49．1mg／kg bw／d。     

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。     

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.     

Pd(II) and Pt(II) Complexes of Schiff Thiobases Derived From 2-Carbonylpyridine

Pd(ll) and Pt(ll) complexes of three series of Schiff thiobases derived from 2- carbonylpyridine have been synthesized and characterized. The crystal structure of the Pt(ll) derivative of methyl-3-(2-pyridylmethylene)hydrazinecarbodithioate (HFp) was resolved. The ligand coordinates the platinum ion in tridentate fashion by heterocycle and imine nitrogen and thiocarbonyl sulfur. The fourth ligand is a chloride ion. The structure of the complexes is suitable for the formation of monofunctional adducts with DNA. Studies on the interaction of the complexes with Calf thymus DNA by CD reveal modifications in the B form of lineal DNA. Interaction with plasmid DNA was also confirmed in the images obtained by atomic force microscopy.     

Synthesis,Structure, Spectral-Luminescent Properties,and Biological Activity of Chlorine-Substituted N-[2-(Phenyliminomethyl)phenyl]-4-methylbenzenesulfamide and Their Zinc(II) Complexes

New azomethine compounds of 2-(N-tosylamino)benzaldehyde or 5-chloro-2-(N-tosylamino)benzaldehyde and the corresponding chlorine-substituted anilines, zinc(II) complexes based on them have been synthesized. The structures of azomethines and their complexes were determined by elemental analysis, IR, ¹H NMR, X-ray spectroscopy, and X-ray diffraction. It is found that all ZnL₂ complexes have a tetrahedral structure according to XAFS and X-ray diffraction data. The photoluminescent properties of azomethines and zinc complexes in methylene chloride solution and in solid form have been studied. It is shown that the photoluminescence quantum yields of solid samples of the complexes are an order of magnitude higher compared to the solutions and range from 11.34% to 48.3%. The thermal properties of Zn(II) complexes were determined by thermal gravimetric analysis (TGA) and differential scanning calorimetry. The TGA curves of all the compounds suggest their high thermal stability up to temperatures higher than 290 °C. The electrochemical properties of all complexes were investigated by the cyclic voltammetry method. The multilayered devices ITO/PEDOT:PSS/NPD/Zn complex/ TPBI/LiF/Al with wide electroluminescence (EL) color range spanning the range from bluish-green (494 nm) to green (533 nm) and the high values of brightness, current and power efficiency were fabricated. The biological activity of azomethines and zinc complexes has been studied. In the case of complexes, the protistocidal activity of the zinc complex with azomethine of 5-chloro-2-(N-tosylamino)benzaldehyde with 4-chloroaniline was two times higher than the activity of the reference drug toltrazuril.     

Dinuclear Zinc (II) Complexes of Macrocyclic Polyamine Ligands Containing an Imidazolium Bridge: Synthesis,Characterization, and Their Interaction with Plasmid DNA

Two novel macrocyclic polyamine ligands and their dinuclear zinc (II) complexes were synthesized and characterized. Their interaction with plasmid DNA was studied by gel electrophoresis and fluorescence quenching experiment. The result showed that these complexes could bind DNA efficiently under physiological conditions.     

Zinc(II) Complexes of Amino Acids as New Active Ingredients for Anti-Acne Dermatological Preparations

Zinc compounds have a number of beneficial properties for the skin, including antimicrobial, sebostatic and demulcent activities. The aim of the study was to develop new anti-acne preparations containing zinc–amino acid complexes as active ingredients. Firstly, the cytotoxicity of the zinc complexes was evaluated against human skin fibroblasts (1BR.3.N cell line) and human epidermal keratinocyte cell lines, and their antimicrobial activity was determined against Cutibacterium acnes. Then, zinc complexes of glycine and histidine were selected to create original gel formulations. The stability (by measuring pH, density and viscosity), microbiological purity (referring to PN-EN ISO standards) and efficacy of the preservative system (according to Ph. Eur. 10 methodology) for the preparations were evaluated. Skin tolerance was determined in a group of 25 healthy volunteers by the patch test. The preparations containing zinc(II) complexes with glycine and histidine as active substances can be topically used in the treatment of acne skin due to their high antibacterial activity against C. acnes and low cytotoxicity for the skin cells. Dermatological recipes have been appropriately composed; no irritation or allergy was observed, and the preparations showed high microbiological purity and physicochemical stability.     

含噻唑环席夫碱及其配合物的合成与性能研究进展

噻唑环具有良好的热稳定性和耐酸、碱及氧化等化学稳定性,而席夫碱拥有优良的配位能力,因而含噻唑环的席夫碱及其配合物已成为有机功能材料的研究热点之一.阐述了含噻唑环席夫碱的合成工艺及其在化学荧光、生物抑菌、模拟酶催化和电磁性能等方面的研究进展,最后对噻唑环席夫碱今后的研究方向作了简要的展望.     

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.     

木犀草素Zn(II)和Cu(II)配合物的合成及电化学性质研究

在无水乙醇溶液中,用木犀草素和醋酸铜、醋酸锌合成两种鲜见报道的木犀草素金属配合物,并通过元素分析、红外光谱、电子光谱和摩尔电导等表征手段,确定了配合物的结构。并研究了木犀草素Zn(II)和木犀草素Cu(II)配合物化学修饰碳糊电极在pH 5 B-R缓冲溶液中的电化学行为。     

1-(2-甲氧基苯基)哌嗪氢卤酸盐的合成研究

叙述了 1 (2 甲氧基苯基 )哌嗪盐酸盐 (Ⅱ )和氢溴酸盐 (Ⅳ )的合成研究结果。分别以双 (2 氯乙基 )胺盐酸盐 (Ⅰ )及双 (2 溴乙基 )胺氢溴酸盐 (Ⅲ )与邻甲氧基苯胺反应 ,合成了两个标题化合物 (Ⅱ ,Ⅳ ) ,合成收率分别达 5 9%和 80 % ,产品纯度达 98%以上。中间体 (Ⅰ )和 (Ⅲ )用二乙醇胺分别与SOCl2 和 4 0 %HBr反应来制备。还给出了化合物 (Ⅳ )的一釜合成法。     

1-(2,3-二氯苯基)哌嗪的合成研究

1-（2，3-二氯苯基）哌嗪是一种重要的医药中间体。本文描述了以2，6-二氯硝基苯和无水哌嗪为原料，经过烃化、乙酰化、硝基还原、重氮化与取代及水解等反应合成该中间体，总收率48．2％，同时重点讨论了烃化、乙酰化和硝基还原反应的影响因素。最终产物的结构通过红外光谱、核磁共振光谱得到了表征。     

Synthesis, Characterization and Biological Properties of Anions of Bivalent Transition Metal [Co(II) and Ni(II)] Complexes With Acylhydrazine Derived ONO Donor Schiff Bases

Some acylhydrazine derived ONO donor Schiff bases and their Co(II) and Ni(II) complexes have been prepared having the same metal ion (cation) but different anions. These synthesized metal(II) complexes have been characterized on the basis of their elemental analyses, magnetic moment, molar conductance, and IR and electronic spectral data. All of the Schiff base ligands function as tridentates and the deprotonated enolic form is preferred for coordination. In order to evaluate the effect of anions on the bactericidal activity, these synthesized complexes, in comparison to the uncomplexed Schiff bases have been screened against bacterial species., Escherichia coli, Staphylococcus aureus and Pseudomonas aeruginosa and the results are reported.     

双-8-羟基喹啉高分子配合物的合成与应用

用8-羟基喹啉在有相转移催化剂存在的碱性条件下,与氯仿作用合成5-甲酰基-8-羟基喹啉,然后将5-甲酰基-8-羟基喹啉分别与对苯二胺、联苯二胺,4,4＇-二氨基二苯砜反应,得到三种双-8-羟基喹啉-席夫碱配体,然后与金属离子配位,得到了一类新型的双-8-羟基喹啉-席夫碱-金属高分子配合物,再结合双-8-羟基喹啉-席夫碱配体与其它离子的显色反应,进行对比分析.利用红外光谱、紫外光谱对配体和配合物的结构进行表征,利用荧光光谱研究了高分子配合物的光致发光性能.     

2-（4-咪唑基苯乙烯基）-8-羟基喹啉锌的合成与光致发光特性

合成了一种新型的2-（4-咪唑基苯乙烯基）-8-羟基喹啉配体以及其金属锌配合物,用红外光谱（IR）、紫外光谱（UV）、元素分析（EA）、核磁共振氢谱（1H NMR）等确认了化合物的结构,通过荧光光谱测定了配合物的荧光性质,证实其具有良好的光致发光性能,最大发射波长为576 nm;热重分析实验也表明了金属锌配合物有很好的热稳定性。