酰腙化合物及其过渡金属配合物的高生物活性和低毒性使其在医药和农药领域的应用越来越广泛，因此构筑新颖结构的酰腙化合物成为了此类化合物更新换代的趋势。 本文将萘环基团引入酰腙分子结构中，旨在通过两类基团的叠加，获得兼具两者生物活性的新型酰腙化合物及其金属配合物。主要工作如下： (1) 制备了7种萘甲酰腙化合物及其3种过渡金属配合物，均获得了单晶 7种萘甲酰腙化合物均是通过分步合成法得到，即先以6-溴-2-萘甲酸甲酯和水合肼(80%)为原料，制备了6-溴-2-萘甲酰肼(C11H9BrN2O)，然后利用6-溴-2-萘甲酰肼与7种醛反应制备7种萘甲酰腙，分别是4-甲氧基苯甲醛-6-溴-2-萘甲酰腙(C19H15BrN2O2，I)、4-甲基苯甲醛-6-溴-2-萘甲酰腙(C19H15BrN2O，II)、3-吡啶甲醛-6-溴-2-萘甲酰腙(C17H12BrN3O，III)、2-吡啶甲醛-6-溴-2-萘甲酰腙(C17H12BrN3O，IV)、4-氟苯甲醛-6-溴-2-萘甲酰腙(C18H12BrFN2O，V)、4-氯苯甲醛-6-溴-2-萘甲酰腙(C18H12BrClN2O，VI)、4-溴苯甲醛-6-溴-2-萘甲酰腙(C18H12Br2N2O，VII)。 3种过渡金属配合物是以I和IV与过渡金属盐反应得到，其中Co配合物(C36H26Br2CoN7O5，VIII)和Cr配合物(C36H26Br2CrN6O2，IX)是以I和2-乙酰吡啶的混合溶液分别与六水合硝酸钴和六水合氯化铬反应得到，Ni配合物(C34H23Br2NiN6O2，X)是通过IV和六水合硝酸镍反应得到。 (2) 利用X-射线单晶衍射技术对I~X进行了单晶结构表征 单晶衍射结果表明I、IX和X属于三斜晶系，P-1空间群，其余均属于单斜晶系，P21/c(n)空间群。I~VII均以酮羰基形式存在，VIII~IX均以烯醇形式存在，X以酮羰基和烯醇式并存的形式存在。3个配合物均是单核配合物，中心金属原子以六配位的形式与两个配体进行螯合，形成畸形的八面体配位构型。 (3) 通过热重实验研究了I~X的热稳定性 探索了I~X在3种不同升温速率下(5，10和15 ℃•min-1)的热分解过程，并通过Kissinger和Ozawa方程计算了它们主要热分解阶段的表观活化能(Ea)，根据表观活化能大小得到它们的热稳定性顺序为：VIII>X>V>IX>VI>I>III>VII>IV>II；其中X比相应配体IV的热稳定性要高。 (4) 利用光谱法和热谱法探究了I~X和生物大分子牛血清白蛋白(BSA)和小牛胸腺DNA (ct-DNA)的作用方式和能力 荧光滴定光谱实验结果发现I~X均对BSA内源荧光产生了静态猝灭，说明了I~X可以与BSA进行有效结合，并形成了非辐射基态复合物。微量热实验结果表明VIII和IX与BSA的相互作用为吸热反应，作用力主要为疏水作用；其余化合物与BSA的相互作用为放热反应，作用力以氢键和范德华力为主。 利用紫外滴定光谱法和溴化乙锭(EB)置换荧光猝灭实验探究了I~X与ct-DNA相互作用，结果表明I~IX与ct-DNA的相互作用方式为沟槽作用，X与ct-DNA的相互作用方式为嵌插作用。微量热实验结果表明I~IX与ct-DNA的相互作用过程为吸热反应，作用方式为沟槽作用；X与ct-DNA的相互作用过程为放热反应，作用方式为嵌插作用，与紫外和荧光实验结果一致。 (5) 采用琼脂扩散法测定了I~X对大肠杆菌、金黄色葡萄球菌、枯草芽孢杆菌和铜绿假单胞菌的抑制活性 抑菌结果表明I~X对四种细菌的抑制效果良好，最小抑制浓度均为50 μg•mL-1。在200 μg•mL-1浓度下，除了IV、VIII和X，其余化合物对大肠杆菌的抑制能力均强于市售抑菌药物硫酸庆大霉素；II对金黄色葡萄球菌的抑制能力强于硫酸庆大霉素；V、VI和X对枯草芽孢杆菌的抑制能力略强于硫酸庆大霉素；除了VIII，其余化合物对铜绿假单胞菌的抑制能力均强于硫酸庆大霉素。 (6) 根据密度泛函理论(DFT)进行量化计算预测I~X的生物活性及活性位点 利用Gaussian 09程序对I~X的几何构型进行全参数优化，再利用Multiwfn和VMD程序包计算了I~X的前线轨道能量和分布以及静电势，发现I~X均具有较强的生物活性，与生物活性实验的结果基本一致。I~X的羰基氧原子和亚氨基氮原子为主要的亲电作用位点，I~VII及X的N-H基团为主要的亲核作用位点，VIII和IX中萘环、吡啶环和甲基的C-H基团为亲核作用位点。

Acylhydrazone compounds and its transition metal complexes have been widely applied in the fields of medicine and pesticide due to their high biological activity and low toxicity. Therefore, the construction of acylhydrazone compounds with novel structures has become a trend of the renewal of these compounds. In this paper, naphthalene ring group was introduced into the molecular structure of acylhydrazone to obtain novel acylhydrazone compounds and their metal complexes possessing biological activities of both groups. The main tasks were as follows: (1) Seven naphthohydrazones and three transition metal complexes were prepared, and their single crystals were all obtained. Seven naphthohydrazones were synthesized by two-step method. First, 6-bromo-2-naphthalic acid methyl ester and hydrazine hydrate (80%) were used as raw materials to prepare 6-bromo-2-naphthoyl hydrazide (C11H9BrN2O). Then 6-bromo-2-naphthoyl hydrazide was reacted with seven aldehydes to prepare seven naphthohydrazones, which were 4-methoxybenzaldehyde-6-bromo-2-naphthohydrazone (C19H15BrN2O2, I), 4-methylbenzaldehyde-6-bromo-2-naphthohydrazone (C19H15BrN2O, II), 3-pyridinecarboxaldehyde-6-bromo-2-naphthohydrazone (C17H12BrN3O, III), 2-pyridinecarboxaldehyde-6-bromo-2-naphthohydrazone (C17H12BrN3O, IV), 4-fluorobenzaldehyde-6-bromo-2-naphthohydrazone (C18H12BrFN2O, V), 4-chlorobenzaldehyde-6-bromo-2-naphthohydrazone (C18H12BrClN2O, VI) and 4-bromobenzaldehyde-6-bromo-2-naphthohydrazone (C18H12Br2N2O, VII), respectively. Three transition metal complexes were prepared from the reaction of transition metal salts with I and IV. Among them, Co complex (C36H26Br2CoN7O5, VIII) and Cr complex (C36H26Br2CrN6O2, IX) were prepared through the mixture of I and 2-acetylpyridine reacting with cobalt nitrate hexahydrate and chromium chloride hexahydrate, respectively. Ni complex(C34H23Br2NiN6O2, X) was prepared by IV and nickel nitrate hexahydrate respectively. (2) The single crystal structures of I~X were characterized by X-ray single crystal diffraction technique. The results showed that I, IX and X belonged to triclinic system and P-1 space group, the others belonged to monoclinic system and P21/c(n) space group. I~VII existed in the form of keto-carbonyl, while VIII~IX in the form of enol, X in the forms of keto-carbonyl and enol coexistence. All of three complexes were mononuclear complexes. Deformed octahedral coordination configuration were formed by the chelation of the central metal atoms and two ligands by six coordinations. (3) The thermal stabilities of I~X were studied by thermogravimetric experiments. The thermal decomposition processes of I~X at three heating rates(5, 10 and 15 ℃ min-1) were explored. The apparent activation energies(Ea) of their main thermal decomposition stages were calculated by Kissinger and Ozawa equation. According to the apparent activation energies, the order of their thermal stability was as follows: VIII>X>V> IX>VI>I>III>VII>IV>II. The thermal stability of X was higher than that of corresponding ligand IV. (4) The interaction modes and abilities of I~X with bovine serum albumin (BSA) and calf thymus DNA(ct-DNA) were investigated by spectroscopy and thermography. The results of fluorescence titration spectra indicated that all I~X quenched the intrinsic fluorescence of BSA through a static process, which suggested that I~X could bind to BSA effectively and form the nonradiative ground-state complex. Microcalorimetric experiments showed that the binding processes between VIII~IX and BSA were endothermic, and the primary binding pattern was hydrophobic interaction; the binding processes between other compounds with BSA were exothermic, and the binding forces were mainly hydrogen bond and van der Waals force. The interactions between I~X and ct-DNA were investigated by ultraviolet absorption titration and ethidium bromide displacement assay. The results showed that I~IX bounded to ct-DNA via groove binding mode, however, X bounded to ct-DNA with an intercalative interaction. The results from microcalorimetry revealed that the binding processes between I~IX with ct-DNA were endothermic and the binding mode were groove binding, however, the binding process between X and ct-DNA was exothermic and the binding mode was intercalation interaction, which was consistent with the results of ultraviolet and fluorescence experiments. (5) The inhibition activities of I~X against Escherichia coli, Staphylococcus aureus, Bacillus subtilis and Pseudomonas aeruginosa were determined by agar diffusion method. I~X showed strong inhibition activities against Escherichia coli, Staphylococcus aureus, Bacillus subtilis and Pseudomonas aeruginosa, and the minimum inhibitory concentration were 50 μg•mL-1. At the concentration of 200 μg•mL-1, except VIII and X, the inhibition activities of other compounds against Escherichia coli were stronger than that of gentamycin sulfate, a commercially available bacteriostatic drug; the inhibition activity of II against Staphylococcus aureus was stronger than that of gentamicin sulfate; the inhibition activities of VI and X against Bacillus subtilis were stronger than that of gentamicin sulfate; except VIII, the inhibition activities of other compounds against Pseudomonas aeruginosa were all stronger than gentamycin sulfate. (6) The biological activities and active sites of I~X were predicted through quantum chemistry calculation on the basis of the density functional theory(DFT). The geometric configurationand of I~X were full-optimized by Gaussian 09 package. The frontier orbital energy and distribution as well as electrostatic potential of I~X were calculated by using Multiwfn and VMD programs. It was found that I~X had strong biological activity, which were basically consistent with the results of biological activity experiments. The carbonyl O atoms and imino N atoms of I~X were the main electrophilic sites, the N-H groups of I~VII and X were the main nucleophilic sites, and the C-H groups of naphthalene ring, pyridine ring and methyl in VIII and IX were the main nucleophilic sites.