物理化学学报 >> 2017, Vol. 33 >> Issue (2): 356-363.doi: 10.3866/PKU.WHXB201610191

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三种2-羟基-1-萘醛酰腙的晶体结构、热分解及其与CT-DNA的相互作用

赵顺省,李兰兰,刘向荣*(),丁作成,杨再文   

  • 收稿日期:2016-09-05 发布日期:2017-01-12
  • 通讯作者: 刘向荣 E-mail:xkchemistry@163.com
  • 基金资助:
    国家自然科学基金(21103135,21073139,21301139);陕西省自然科学基础研究计划(2016JM2011);陕西省教育厅自然科学专项(15JK1492)

Crystal Structure, Thermal Decomposition and Interaction with CT-DNA of Three 2-Hydroxy-1-naphthaldehyde Acyl Hydrazones

Shun-Sheng ZHAO,Lan-Lan LI,Xiang-Rong LIU*(),Zuo-Cheng DING,Zai-Wen YANG   

  • Received:2016-09-05 Published:2017-01-12
  • Contact: Xiang-Rong LIU E-mail:xkchemistry@163.com
  • Supported by:
    the National Natural Science Foundation of China(21103135,21073139,21301139);Natural Science Basic Research Plan in Shaanxi Province, China(2016JM2011);Scientific Research Program Funded by Shaanxi Provincial Education Commission, China(15JK1492)

摘要:

合成了2-羟基萘醛苯乙酰腙(1)、2-羟基萘醛-4-羟基苯乙酰腙(2)和2-羟基萘醛-2-甲氧基苯乙酰腙(3)三种新型酰腙化合物,通过单晶X射线衍射(XRD)、元素分析和傅里叶变换红外(FTIR)光谱对化合物结构进行了表征。单晶X射线衍射结果表明,化合物23结晶为单斜晶系,空间群C2/c。而化合物1结晶为正交晶系,空间群为Pbca。热重(TG)分析结果表明,化合物1、2、3分子骨架热分解的温度分别为318.23、319.04、323.01℃,对应的热分解过程表观活化能分别为115.90、145.18、129.38 kJ·mol-1。微量热研究表明,三种酰腙及其前驱体酰肼与小牛胸腺脱氧核糖核酸(CT-DNA)相互作用均为吸热作用,但作用时间(1.00-50.0 min)和反应熵变(0.47-15.50 kJ·mol-1)有较大的差异。化合物1和2与CT-DNA的反应焓变均大于其前驱体酰肼ab与CT-DNA的反应焓变,而化合物3与CT-DNA的反应焓变却小于其前驱体酰肼c与CT-DNA的反应焓变。

关键词: 酰腙, 晶体结构, 热重, 微量热, DNA作用

Abstract:

Three acyl hydrazones N'-((2-hydroxynaphthalen-1-yl)methylene)-2-phenylacetohydrazide (1), N'-((2-hydroxynaphthalen-1-yl) methylene)-2-(4-hydroxyphenyl)acetohydrazide hydrate (2), and N'-((2-hydroxynaphthalen-1-yl) methylene)-2-(2-methoxyphenyl) acetohydrazide hydrate (3) were synthesized and then characterized by elemental analysis and single-crystal X-ray diffraction. The crystallographic data indicated that both compounds 2 and 3 crystallized in the monoclinic crystal lattice, space group C2/c, while compound 1 crystallized in the orthorhombic space group Pbca. The thermal decomposition processes of the three hydrazones were studied by thermogravimetry. The thermal decomposition temperatures of compounds 1, 2, and 3 were 318.23, 319.04, and 323.01℃, respectively. Meanwhile, the apparent activation energies for thermal decomposition for compounds 1, 2, and 3 were 115.90, 145.18, and 129.38 kJ·mol-1, respectively, calculated according to the Kissinger and Ozawa equations. The interactions of compounds 1-3 with calf thymus (CT)-DNA were evaluated by microcalorimetry. The results indicated these interactions were homogenous endothermic processes with non-identical interaction time (1.00-50.0 min) and interaction enthalpies (0.47-15.50 kJ·mol-1). The interaction enthalpies of compounds 1 and 2 were higher than those of their precursors, while the interaction enthalpy of compound 3 was lower than that of its precursor.

Key words: Acyl hydrazone, Crystal structure, Thermogravimetry, Microcalorimetry, DNA binding

MSC2000: 

  • O641