CN111606933A - 一种含邻菲罗啉配体的Cd(II)配合物及其制备方法和应用 - Google Patents
一种含邻菲罗啉配体的Cd(II)配合物及其制备方法和应用 Download PDFInfo
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Abstract
Description
技术领域
本发明涉及配合化合物技术领域,具体涉及一种含邻菲罗啉配体的Cd(II)配合物及其制备方法和应用。
背景技术
具有d10电子结构Cd离子具有独特的光谱学特征,使得它们在生命科学和发光材料研究中起着重要作用。在过去的几年中,顺铂的临床成功及其应用引起了人们对新型金属基抗癌药物研究的广泛兴趣,但是,铂类抗癌药极其昂贵,易产生严重的副作用,并且这类化合物的选择性有限,除了其有效性外还获得了耐药性。因此,需要开发具有不同作用机理的新型金属基抗癌抗炎症、抑菌治疗药物,克服铂基化学治疗剂的上述缺点。近年来,基于氨基酸的过渡金属配合物具有物理化学性能稳定、功能可调、应用范围广,在生物无机医用材料及其在许多科学领域中的潜在应用,引起了广泛注目和研究兴趣。应用于多个领域,例如气体存储,分子识别与分离,化学催化,传感,离子交换和药物传递。已成为新型发光材料研究和发展的新方向。目前,含氮杂环化合物由于其广泛的生物活性,例如杀虫,杀菌,除草,抗病毒,抗癌特性。引起了在现代超分子化学领域的极大兴趣。噻唑类化合物是含氮杂环的重要成分,由于其独特的结构被广泛用于农药和药物中。其中许多用作商业杀虫剂,杀菌剂和杂草剂。高效简便的合成方法这种超分子功能化合物是在很大程度上取决于适当的选择精心设计的有机构建基作为终端组件或桥接基团作为节点。
金属有机超分子化学是一个涉及无机化学、有机化学和配位化学等多学科的崭新科研课题,引起了世界范围内的关注,基于d10电子构型的金属有机框架化合物,杂环化合物如唑类、噻唑类可以与特别是一些生命必须的氨基酸离子,如甘氨酸、谷氨酸结合而成蛋白,而具有生物活性。同时,1,10-邻菲罗啉(缩写为phen)通常作为简单的次级N受体构建基块,可以协调环境并稳定结构,也是一种常用的氧化还原指示剂。它是一个双齿杂环化合物配体,这些分子的引入,常常因共轭结构增大对光的吸收。因为芳香环的存在,有利于的形成π-·π堆积或氢键相互作用,改善可以改善化合物的稳定性,改善化合物的结构。金属有机框架化合物具有可修改、功能可调的优势,但是大多过渡金属和稀土金属的有机框架化合物,因为分子聚合而水溶性很差,造成在生物抑菌过程难以完成。
发明内容
本发明的目的是为解决上述技术问题及不足,提供一种含邻菲罗啉配体的Cd(II)配合物及其制备方法和应用。
本发明为解决上述技术问题的不足,所采用的技术方案是:一种含邻菲罗啉配体的Cd(II)配合物,化学式为Cd(phen)2ASBA·H2O,其中ASBA为4-氨基-N-(5-甲基-1,2-硫代噻唑-3-基)苯磺酰胺,phen为1,10-邻菲罗啉,配合物晶体属于三斜晶系,空间群为P-1,晶胞参数为:α=105.116(4)°,β=97.181(3)°,γ=98.744(4)°,Z=4。
一种含邻菲罗啉配体的Cd(II)配合物的制备方法,包括以下步骤:
(1)、取有机配体ASBA加入水与乙醇的混合溶液中,搅拌混合,得到溶液A;
(2)、取Cd(ClO4)2·6H2O加入水和有机溶剂的混合溶液中,搅拌混合,得到溶液B;
(3)、取溶液B中加入溶液A,搅拌后得到浑浊液C,然后向浑浊液C中加入配体phen,并调节pH为6.5-7.5,搅拌后,得到混合液D,将混合液D用磁力搅拌器在常温常压下搅拌后,得到前驱液E;
(4)、将前驱液E转移至带有聚四氟乙烯的水热反应釜中,密封反应釜,并将反应釜放入烘箱中,选择控温模式进行反应,温度控制在60-100℃反应60-90h,反应结束后,控制反应釜以5℃/h的冷却速率冷却至室温,并收集反应釜内底部出现的无色结晶,然后将收集到的结晶经洗涤和干燥,得到无色菱形块状晶体配合物。
作为本发明一种含邻菲罗啉配体的Cd(II)配合物的制备方法的进一步优化:所述步骤(1)中有机配体ASBA和混合溶液的加入量之比为:每10ml的混合有溶液中加入0.1-0.5mmol有机配体。
作为本发明一种含邻菲罗啉配体的Cd(II)配合物的制备方法的进一步优化:所述步骤(2)中水与有机溶剂的体积比为0.5:1-3:1,有机溶剂为甲醇、乙醇、DMF或DMSO。
作为本发明一种含邻菲罗啉配体的Cd(II)配合物的制备方法的进一步优化:所述步骤(2)中Cd(ClO4)2·6H2O和混合溶液的加入量之比为:每10ml的水和有机溶剂混合液中加入0.1mmolCd(ClO4)2·6H2O。
作为本发明一种含邻菲罗啉配体的Cd(II)配合物的制备方法的进一步优化:所述步骤(3)中溶液B、溶液A和配体phen的加入量之比为:每10ml溶液A中加入10-50ml的溶液B和0.1-0.2mmol的phen。
作为本发明一种含邻菲罗啉配体的Cd(II)配合物的制备方法的进一步优化:所述步骤(3)中使用稀硝酸和氢氧化钠调节溶液pH值。
作为本发明一种含邻菲罗啉配体的Cd(II)配合物的制备方法的进一步优化:所述所述步骤(5)中真空干燥箱的干燥温度控制在50-70℃。
含邻菲罗啉配体的Cd(II)配合物在抑菌方面的应用。
含邻菲罗啉配体的Cd(II)配合物在荧光发光材料方面的应用。
本发明具有以下有益效果:
一、本发明的配合物材料晶体结晶性较好,无毒、无污染,热稳定性高,抑菌性能优良,原料成本低;
二、本发明的配合物材料合成工艺设备简单,方法简便,适合大量可控生产;
三、本发明的配合物材料可满足环境消毒,抑菌,社区、家庭抗菌使用,并且在光致发光材料方面也具有一定的用途。
附图说明
图1是本发明实施例1所制备产物的粉末X-射线衍射(PXRD)图谱与单晶衍射数据模拟的XRD的比较图;
图2是本发明实施例1所制备产物的傅里叶变换红外光谱图;
图3是本发明实施例1所制备产物的分子基本单元结构图;
图4是本发明实施例1所制备产物的热重分析图;
图5是本发明实施例1所制备产物的溶液里的激发/发射荧光光谱图;
图6是本发明实施例1所制备产物(10%DMSO)的抑菌效果图;
图7是本发明实施例1所制备产物(15%DMSO)的抑菌效果图;
图8是本发明实施例1所制备产物(20%和30%DMSO)的抑菌效果图。
具体实施方式
下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述。
实施例1
一种含邻菲罗啉配体的Cd(II)配合物的制备方法:包括以下步骤:
(1)、取有机配体ASBA(0.1mmol)加入水与乙醇的混合溶液(10ml)中,搅拌混合,得到溶液A;
有机配体ASBA的结构式如下:
(2)、取Cd(ClO4)2·6H2O(0.1mmol)加入水和有机溶剂的混合溶液(10ml)中,搅拌混合,得到溶液B;水和有机溶剂的混合溶液中有机溶剂为甲醇,且水与甲醇的体积比为0.5:1。
(3)、取溶液B(10ml)中加入溶液A(10ml),搅拌后得到浑浊液C,然后向浑浊液C中加入配体phen(0.2mmol),并调节pH为7.0,搅拌后,得到混合液D,将混合液D用磁力搅拌器在常温常压下搅拌后,得到前驱液E;
配体phen的结构式如下:
(4)、将前驱液E转移至带有聚四氟乙烯的水热反应釜中,密封反应釜,并将反应釜放入烘箱中,选择控温模式进行反应,温度控制在80℃,反应80h后,控制反应釜以5℃/h的冷却速率冷却至室温,并收集反应釜内底部出现的无色结晶,然后将收集到的结晶采用乙醇与水的混合溶液洗涤2-3次,然后置于真空干燥箱中干燥(50℃)2h后,得到无色菱形块状晶体。
将所得产物Cd(phen)2ASBA·H2O,用德国的BrukerSMARTAPEXII型单晶X射线衍射仪进行分析,如图1所示:发现产物XRD图谱与单晶衍射数据模拟的PXRD图谱相吻合,在2θ为8.7,12.2,17.3,21.2,26.9,32.1等处,出现强的特征衍射峰,同时得到产物单晶,其结构数据如下表所示:
将所得产物Cd(phen)2ASBA·H2O,用美国Nicolet6700傅立叶变换红外光谱仪进行分析,测得的红外光谱如图2所示,从红外光谱上看,在3400-3500cm-1左右观察到配位水分子OH-的振动峰,3100,2900cm-1观察到-CH3和NH2的C-H和N-H伸缩振动峰,1600cm-1附近观察到氨基C=N的振动峰,1370,1120,630cm-1处的峰归属于SOOH的对称振动峰,2200cm-1出现的峰证明弱的S=N键的存在,在1710cm-1没有峰存在证明磺酸基团脱去质子,在650-800cm-1出现的系列振动峰对应l、10邻菲啰琳芳香环环骨架振动峰。
通过Diamond3D模拟晶体画图软件模拟出产物的晶体结构,如图3所示。单晶分析显示该化合物为单核结构,配位单元由一种ASBA有机配体和2个邻菲罗琳分子片段,1个Cd(II)离子,1个配位水分子和1个游离的带负一价的NO3-离子。中心Cd(II)离子,展示了6配位数的配位模式,呈现变形八面体的几何构型,赤道面由3个N原子和一个O原子构成,这些供体中的3个N来自不同的邻菲罗琳和4-氨基-N-(5-甲基-1,2-硫代噻唑-3-基)苯磺酰胺配体,O原子来自配位水分子。轴向的位置被两个N原子占领,中心离子与邻菲罗琳片段和噻二唑的N原子结合,键长分别是2.281和而在赤道平面上,Cd(II)离子与1个水分子的O和邻菲罗琳片段的3个N原子结合,Cd-O3;Cd-N5;Cd-N6键长分别是2.374(2);2.324(2);而Cd-N5;Cd-N6;Cd-N7的键长分别是2.324(2);346(2);作为ASBA配体的一部分,磺酸基和氨基没有参与配位。金属Cd(II)的配位单元带有一个单位的正电荷,与NO3-离子负电荷抗衡。
将所得产物用意大利的FlashEA-2000元素分析仪进行元素分析,分析表明,材料由以下成分组成:化合物为C33H28CdN9O6S2,理论计算元素含量百分比:C40.59,H2.01,N3.64,实际测定:C41.10,H2.07,N3.66。热重分析在氮气气氛下进行TGA实验,以每分钟10℃的速率,在25-900℃的温度范围内的升温,如图4所示,加热到约150℃时化合物失去游离水分子,约300℃时化合物失去配位水分子,约400℃以下时化合物框架保持稳定,当进一步加热时,重量损失为28.37%,其对应于ASBA有机配体的分解,与晶体结构分析是一致的。将所得产物用日本的F7000荧光光谱仪进行分析,该产物在362nm的近紫外光条件下激发,在可见绿光区域518nm出现强大发射光谱。
将晶态化合物材料研磨,得到粉末。我们以DH5-α葡萄糖大肠杆菌作为模板细菌种类,通过培养基扩散法研究化合物的抑菌性能及对细菌种选择性。取化合物分别分散在用蒸馏水和一定浓度DMSO(N,N二甲基亚砜)溶液中,使其浓度大约为1x10-3mol/L。制备抑菌片,用消毒过的棉栻子蘸取试验菌悬浊液,进行试验菌的接种。用无菌镊子取样品贴片于染菌平板表面,盖在培养皿里面,至于培养箱37℃,保温24小时后,观察抑菌圈及范围,用游标卡尺测量抑菌环的直径。发现Cd的化合物样品在10%的DMSO溶解,抑菌圈的直径平均值在13.5mm左右(图6),样品在15%的DMSO水溶液中,抑菌圈的直径平均值在20.5mm左右(图7),具有较好的抑菌性能,同时我们做了对对比实验:继续增大DMSO的浓度,在20%和的30%DMSO水溶液中(图8),却发现菌性能没有太大的变化,证明抑菌效果主要来自于配位化合物。随着DMSO溶液的加入,牛津杯子,白色抑菌圈向外周移动,证明制得新型化合物,在DMSO/水混合溶液中溶解度增大。
实施例2
一种含邻菲罗啉配体的Cd(II)配合物的制备方法:包括以下步骤:
(1)、取有机配体ASBA(0.5mmol)加入水与乙醇的混合溶液(10ml)中,搅拌混合,得到溶液A;
(2)、取Cd(ClO4)2·6H2O(0.5mmol)加入水和有机溶剂的混合溶液(50ml)中,搅拌混合,得到溶液B;水和有机溶剂的混合溶液中有机溶剂为甲醇,且水与甲醇的体积比为1:1。
(3)、取溶液B(10ml)中加入溶液A(50ml),搅拌后得到浑浊液C,然后向浑浊液C中加入配体phen(0.1mmol),并调节pH为6.5,搅拌后,得到混合液D,将混合液D用磁力搅拌器在常温常压下搅拌后,得到前驱液E;
(4)、将前驱液E转移至带有聚四氟乙烯的水热反应釜中,密封反应釜,并将反应釜放入烘箱中,选择控温模式进行反应,温度控制在70℃,反应90h后,控制反应釜以5℃/h的冷却速率冷却至室温,并收集反应釜内底部出现的无色结晶,然后将收集到的结晶采用乙醇与水的混合溶液洗涤2-3次,然后置于真空干燥箱中干燥(50℃)2h后,得到无色菱形块状晶体。
实施例3
一种含邻菲罗啉配体的Cd(II)配合物的制备方法:包括以下步骤:
(1)、取有机配体ASBA(0.1mmol)加入水与乙醇的混合溶液(10ml)中,搅拌混合,得到溶液A;
(2)、取Cd(CH3COO)2·4H2O(0.1mmol)加入水和有机溶剂的混合溶液(10ml)中,搅拌混合,得到溶液B;水和有机溶剂的混合溶液中有机溶剂为甲醇,且水与甲醇的体积比为5:1。
(3)、取溶液B(10ml)中加入溶液A(20ml),搅拌后得到浑浊液C,然后向浑浊液C中加入配体phen(0.1mmol),并调节pH为7.5,搅拌后,得到混合液D,将混合液D用磁力搅拌器在常温常压下搅拌后,得到前驱液E;
(4)、将前驱液E转移至带有聚四氟乙烯的水热反应釜中,密封反应釜,并将反应釜放入烘箱中,选择控温模式进行反应,温度控制在100℃,反应60h后,控制反应釜以5℃/h的冷却速率冷却至室温,并收集反应釜内底部出现的无色结晶,然后将收集到的结晶采用乙醇与水的混合溶液洗涤2-3次,然后置于真空干燥箱中干燥(50℃)2h后,得到无色菱形块状晶体。
以上对本发明的具体实施例进行了描述。需要理解的是,本发明并不局限于上述特定实施方式,本领域技术人员可以在权利要求的范围内做出各种变形或修改,这并不影响本发明的实质内容。
Claims (10)
2.如权利要求1所述一种含邻菲罗啉配体的Cd(II)配合物的制备方法,其特征在于:包括以下步骤:
(1)、取有机配体ASBA加入水与乙醇的混合溶液中,搅拌混合,得到溶液A;
(2)、取Cd(ClO4)2·6H2O或者Cd(CH3COO)2·4H2O加入水和有机溶剂的混合溶液中,搅拌混合,得到溶液B;
(3)、取溶液B中加入溶液A,搅拌后得到浑浊液C,然后向浑浊液C中加入配体phen,并调节pH为6.5-7.5,搅拌后,得到混合液D,将混合液D用磁力搅拌器在常温常压下搅拌后,得到前驱液E;
(4)、将前驱液E转移至带有聚四氟乙烯的水热反应釜中,密封反应釜,并将反应釜放入烘箱中,选择控温模式进行反应,温度控制在60-100℃反应60-90h,反应结束后,控制反应釜以5℃/h的冷却速率冷却至室温,并收集反应釜内底部出现的无色结晶,然后将收集到的结晶经洗涤和干燥,得到无色菱形块状晶体配合物。
3.如权利要求2所述一种含邻菲罗啉配体的Cd(II)配合物的制备方法,其特征在于:所述步骤(1)中有机配体ASBA和混合溶液的加入量之比为:每10ml的混合有溶液中加入0.1-0.5mmol有机配体。
4.如权利要求2所述一种含邻菲罗啉配体的Cd(II)配合物的制备方法,其特征在于:所述步骤(2)中水与有机溶剂的体积比为0.5:1-3:1,有机溶剂为甲醇、乙醇、DMF或DMSO。
5.如权利要求1所述一种含邻菲罗啉配体的Cd(II)配合物的制备方法,其特征在于:所述步骤(2)中Cd(ClO4)2·6H2O、Cd(CH3COO)2·4H2O和混合溶液的加入量之比为:每10ml的水和有机溶剂混合液中加入0.1mmolCd(ClO4)2·6H2O或Cd(CH3COO)2·4H2O。
6.如权利要求1所述一种含邻菲罗啉配体的Cd(II)配合物的制备方法,其特征在于:所述步骤(3)中溶液B、溶液A和配体phen的加入量之比为:每10ml溶液A中加入10-50ml的溶液B和0.1-0.2mmol的phen。
7.如权利要求1所述一种含邻菲罗啉配体的Cd(II)配合物的制备方法,其特征在于:所述步骤(3)中使用稀硝酸和氢氧化钠调节溶液pH值。
8.如权利要求1所述一种含邻菲罗啉配体的Cd(II)配合物的制备方法,其特征在于:所述所述步骤(5)中真空干燥箱的干燥温度控制在50-70℃。
9.如权利要求1所述一种含邻菲罗啉配体的Cd(II)配合物在抑菌方面的应用。
10.如权利要求1所述一种含邻菲罗啉配体的Cd(II)配合物在荧光发光材料方面的应用。
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