锗钨酸晶体合成、 二维红外光谱和抗肿瘤活性研究  

Syntheses,Spectral Study and Antitumor Properties of Two Polyoxogermanotungstates

作　　者：黄晓辉 黄晓星 应少明 毕文超 高小梅 陈义平 孙燕琼 HUANG Xiao-hui;HUANG Xiao-xing;YING Shao-ming;BI Wen-chao;GAO Xiao-mei;CHEN Yi-ping;SUN Yan-qiong(College of Chemistry,Fuzhou University,Fuzhou 350116,China;Fujian Provincial Key Laboratory of Featured Materials in Biochemical Industry,College of Chemistry and Materials,Ningde Normal University,Ningde 352100,China;Fujian Key Laboratory of Tumor Microbiology,Department of Medical Microbiology,Fujian Medical University,Fuzhou 350116,China)

机构地区：[1]福州大学化学学院,福建福州350116 [2]福建省特色生物化工材料重点实验室,宁德师范学院化学与材料学院,福建宁德352100 [3]消化道恶性肿瘤教育部重点实验室,福建医科大学基础医学部,福建福州350116

出　　处：《光谱学与光谱分析》2021年第12期3733-3739,共7页Spectroscopy and Spectral Analysis

基　　金：国家自然科学基金项目(21971040);宁德师范学院科研项目(2019ZX404)资助。

摘　　要：通过水热法合成两个同构新型锗钨酸化合物[M(phen)_(3)]_(2)[GeW_(12)OH_(40)]·2H_(2)O[M=Zn(1),Co(2)]。属于正交晶系,空间群为Pnma,配体与簇阴离子间的氢键构成二维层状结构,层与层之间通过配体邻菲罗啉(phen)的π…π和C—H…π分子间作用力连结成三维超分子。利用X射线粉末衍射(PXRD)、红外光谱(FTIR)、磁微扰及热微扰下的动态红外光谱(2D-IR COS)和热重分析(TGA)等方法对化合物进行研究。PXRD显示化合物测试谱图和单晶结构数据模拟谱图主要峰位重合,峰形基本一致,表明合成的化合物较纯。FTIR显示在3400 cm^(-1)附近出现较宽的吸收峰是νas(O—H)吸收峰,在1650~1350 cm^(-1)之间出现的峰是phen芳环的骨架伸缩振动峰,在1100~700 cm^(-1)出现了饱和Keggin结构4个特征振动吸收峰;5~50 mT磁场变化下的2D-IR COS显示,在1300~1500和3000~3300 cm^(-1)范围内,化合物1和化合物2出现明显差异,可能是化合物中过渡金属(Zn(Ⅱ),Co(Ⅱ))造成配体phen苯环中C—C骨架振动伴随C—H…π氢键中νas(C—H)振动时偶极矩随磁场的变化。TGA显示失重过程分为3个阶段,第1阶段主要失去游离的水,第2阶段失去配位邻菲罗啉,第3阶段620℃后钨氧簇骨架开始坍塌。探讨了化合物对五种人体肿瘤细胞系(胃癌细胞HGC-27、SNU668,肝癌细胞Huh7,肠癌细胞HCT116、SW480)的体外抑制作用。发现两个化合物对这五种人体肿瘤细胞的半抑制浓度IC50都小于100μmol·L^(-1),有机配体和锗钨氧酸簇的协同作用使得化合物1、2的体外抗肿瘤活性大大增强;化合物1、2对于这五种人体肿瘤细胞具有一定的选择性,两种化合物对肠癌细胞SW480的抗肿瘤活性最高,对胃癌细胞SNU668的抑制作用最低。虽然化合物1和2同构,但是过渡金属的不同,导致于它们的抗肿瘤活性差别较大,化合物2对五种人体肿瘤细胞的抑制作用都比化合物1强,其中化合物2对于肠癌细胞SW480的抑制�Two Keggin-type polyoxogermanotungstates[M(phen)_(3)]_(2)[GeW_(12)OH_(40)]·2H_(2)O(M=Zn(1),Co(2))were synthesized by hydrothermal method.Compounds 1 and 2 are isomorphic,with the Pnma space group.2D layers are linked by the hydrogen bonds between ligands and cluster anions.The layers were connected to form a three-dimensional supramolecule by strong molecular inter-atomic forces between adjacent phenanthroline.The compounds were characterized by XRD,FTIR,two-dimensional(2D)correlation infrared spectroscopy under magnetic and thermal perturbation,TG,etc.XRD showed that the spectrum was consistent with the simulation by single crystal structure data,and the main peaks were the same,indicating that the synthesized compound was relatively pure.The FTIR spectrum indicated that the wide absorption peak wasνas(O—H)near 3400 cm^(-1),the peak between 1650 and 1350 cm^(-1) was the skeleton stretching vibration peak of the aromatic ring,and there was four characteristic stretching vibrations of Keggin cluster anion skeleton in the range of 1100 to 700 cm^(-1).Furthermore,the two-dimensional infrared correlation spectroscopy under 5~50 mT magnetic showed that the obvious difference between compound 1 and compound 2 in the range of 1300~1500 and 3000~3300 cm^(-1) may be caused by the transition metal(Zn(Ⅱ),Co(Ⅱ))in the compounds which assigned to the C—C skeleton of phen and C—H…πhydrogen bond varies.TGA showed that the weight loss process could be divided into three stages.In the first stage,the free water was lost,and in the second,the coordinated phen was lost.At last,in the third stage,the framework of the tungsten oxide cluster began to collapse from 620℃.Results of the experiment on antitumor activities in vitro showed that two compounds inhibited five different human cancer cell lines(gastric cancer cell line,HGC-27 and SNU668;liver cancer cell line Huh7;and colon cancer cell line HCT116 and SW480)demonstrated dose dependency and selectivity.It was found that the IC 50 of the two compounds against the

关 键 词：锗钨酸 KEGGIN结构 二维红外光谱 抗肿瘤活性 

分 类 号：O644.1[理学—物理化学]