CN112079852B - 基于ASBSA和4,4’联吡啶配体的Zn(II)配合物及其制备方法和应用 - Google Patents
基于ASBSA和4,4’联吡啶配体的Zn(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
本发明涉及配位化合物技术领域,具体涉及一种基于ASBSA和4,4’联吡啶配体的Zn(II)配合物及其制备方法和应用。
背景技术
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,在现代超分子化学领域引起了广泛关注。噻唑类化合物是含氮杂环的重要成分,由于其独特的结构和性能,而被广泛用作农药和药物,其中许多用作商业杀虫剂、杀菌剂和杂草剂,但是,由于有机化合物的不稳定性对其运输和应用带来些不便。具有D10电子结构的Zn离子具有独特的光谱学特征,Zn离子无毒无害,还是多个生理活动的积极参与者,使得它们在生命科学研究中起着重要作用。有机体缺锌也是全球面临的问题,人体机体缺锌会导致基础代谢下降、蛋白质利用率降低与消化功能低下。近年研究成果发现,真正在体内发挥作用的是有机锌,与锌离子螯合生成肽和氨基酸锌而不是无机锌。但是由于生产微量元素氨基酸Zn螯合物成本较高,也是制约其发展的因素。
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。在分子识别与分离、化学催化、配位反应、稳定剂染料和颜料、摄影、电光显示以及农业等领域都有着重要的作用。获得这种超分子功能化合物在很大程度上取决于选择适当的有机构建基团作为终端组件或桥接基团作为节点。氨基酸具有多个N、O配位原子的特殊结构,是一类重要的生物配体,它也是细胞生长所必需的。而癌变细胞比正常细胞对氨基酸的需求量大得多,因而磺酸基氨基酸就可能将抗癌基运载到癌变细胞内,从而增大杀伤癌变细胞的选择性。人们对这类化合物的合成、表征、结构测定、热力学和动力学性质及具有抗癌、抗炎、抗癌活性等进行了大量的富有成效的研究。含杂环化合物,如氮唑类、噻唑类可以与一些生命必须的氨基酸离子,如丙氨酸、谷氨酸的结合成蛋白,而具有生物活性。金属有机配位化合物具有可修改、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,提供一种基于ASBSA和4,4’联吡啶配体的Zn(II)配合物及其制备方法和应用。
本发明解决上述技术问题,所采用的技术方案是:4-氨基-N-(5-甲基-1,2-硫代噻唑-3-基)苯磺酰胺和4,4’联吡啶的Zn(II)配合物,化学式为Zn(ASBSA)2(bipy)2,其中ASBSA为bipy为4,4’-联吡啶,该配合物晶体属单斜晶系,空间群为P21/c,晶胞参数为:β=103.132(4)°,晶胞体积Z=4。
基于ASBSA和4,4’联吡啶配体的Zn(II)配合物的制备方法,包括以下步骤:
(1)、取有机配体ASBSA,加入水与乙醇的混合溶液中,分散混合,得到溶液A;
(2)、取Zn(CH3COO)2·4H2O或Zn(ClO4)2·6H2O或Zn(NO3)2·6H2O加入水与有机溶剂的混合溶液中,搅拌混合,得到溶液B;
(3)、取溶液B,加入溶液A中,搅拌后得到浑浊液C,然后调节pH为4.0-8.0,得到混合液D;
(4)、向混合液D中分散加入bipy,然后在常温常压下搅拌后,得到前驱液E;
(5)、将前驱液E转移至反应容器内进行反应,反应结束后收集反应瓶内出现的无色结晶,然后冷却、过滤、洗涤,然后置于真空干燥箱中干燥,即得到无色菱形块状晶体配合物。
作为本发明一种基于ASBSA和4,4’联吡啶配体的Zn(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ASBSA和水与乙醇的混合溶液的加入量为:每10ml的水与乙醇的混合溶液中加入0.1~0.5mmol有机配体ASBSA。
作为本发明一种基于ASBSA和4,4’联吡啶配体的Zn(II)配合物的制备方法的进一步优化,所述步骤(2)水与有机溶剂的混合液,有机溶剂为甲醇、二氯甲烷、乙醇、乙腈、DMF或DMSO中的一种或几种,且水与有机溶剂的体积比为0.5:1~2:1之间。
作为本发明一种基于ASBSA和4,4’联吡啶配体的Zn(II)配合物的制备方法的进一步优化,所述步骤(2)中Zn(CH3COO)2·4H2O或Zn(ClO4)2·6H2O或Zn(NO3)2·6H2O的物质的量:每10ml的水和有机溶剂混合液中加入0.1mmol Zn(CH3COO)2·4H2O或Zn(ClO4)2·6H2O或Zn(NO3)2·6H2O。
作为本发明一种基于ASBSA和4,4’联吡啶配体的Zn(II)配合物的制备方法的进一步优化,所述步骤(3)和步骤(4)中溶液B、溶液A和bipy的加入量为:每10ml溶液A中加入10~50ml的溶液B和0.1-0.2mmol的bipy。
作为本发明一种基于ASBSA和4,4’联吡啶配体的Zn(II)配合物的制备方法的进一步优化,所述步骤(5)中的反应容器为带有温度计的三颈反应瓶,且通过用磁力搅拌器搅拌,选择控温模式进行反应,反应温度为50-100℃,反应时间为8h。
作为本发明一种基于ASBSA和4,4’联吡啶配体的Zn(II)配合物的制备方法的进一步优化,所述步骤(5)中的反应容器为带有聚四氟乙烯衬的水热反应釜,其反应方式为密封反应釜,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80-140℃,反应40-70h后,控制反应釜以5℃/h的冷却速率冷却至室温。
所述步骤(5)中将过滤后的结晶采用乙醇与水的混合溶液洗涤2-3次,真空干燥箱的干燥温度控制在50-70℃。
本发明所述的基于ASBSA和4,4’联吡啶配体的Zn(II)配合物在抑菌方面的应用。
本发明所述的基于ASBSA和4,4’联吡啶配体的Zn(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、本发明制备的一种基于4-氨基-N-(5-甲基-1,2-硫代噻唑-3-基)苯磺酰胺Zn(II)的抑菌活性配位化合物,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,原料成本低廉。
二、本发明的配合物材料合成工艺设备简单,方法简便,适合大量可控合成,该材料可满足环境消毒,抑菌,社区、家庭抗菌使用。
三、本发明的配合物材料在显示方面,荧光发光材料等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所制备产物的配位聚合物一维连状堆积结构图;
图5是本发明实施例1所制备产物的热重分析图;
图6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7是本发明实施例1所制备产物的抑菌效果图;
图8是本发明实施例1所制备产物在DMSO溶液中的抑菌效果图。
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
基于ASBSA和4,4’联吡啶配体的Zn(II)配合物,化学式为Zn(ASBSA)2(bipy)2,该配合物可被近紫外光激发,并发射出强的绿色荧光。其中ASBSA为bipy为4,4’-联吡啶,该配合物晶体属单斜晶系,空间群为P21/c,晶胞参数为:β=103.132(4)°,晶胞体积Z=4。本发明的配体4,4’联吡啶(bipy)可以协调环境并稳定结构,其作为一个双齿杂环化合物配体,其共轭结构可以增大对光的吸收。本发明的金属有机框架化合物,在芳香环的存在下,形成p-π、π-π的堆积作用,可以改善化合物的稳定性,改善化合物的结构。
基于ASBSA和4,4’联吡啶配体的Zn(II)配合物的制备方法,包括以下步骤:
(2)、取Zn(CH3COO)2·4H2O(0.1mmol)加入水与有机溶剂的混合溶液中,每10ml的水和有机溶剂混合液中加入0.1mmol Zn(CH3COO)2·4H2O,有机溶剂为甲醇,且水与甲醇的体积比为0.5:1,搅拌混合,得到溶液B;
(3)、取溶液B(10ml),加入溶液A(10ml)中,搅拌后得到浑浊液C,然后用三乙胺调节pH为6.0-8.0,得到混合液D;
(5)、将前驱液E转移至带有温度计的三颈反应瓶中,用磁力搅拌器搅拌,选择控温模式在温度为50-100℃条件下进行回流反应,反应时间为8h,反应结束后收集反应瓶内出现的无色结晶,然后冷却、过滤,并采用乙醇与水的混合溶液将结晶洗涤2-3次,然后置于真空干燥箱中干燥,干燥温度控制在50-70℃,即得到无色菱形块状晶体配合物。
PXRD测试
将所得产物Zn(ASBSA)2(bipy)2·H2O,使用德国的Bruker D8 Advance仪器(CuKα,)在上收集X射线粉末衍射(XRPD)数据,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6.8,9.4,10.6,13.2,16.3,18.5,19.4,20.4,21.2,23.8 25.7°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:
表1:产物化合物晶胞数据及晶体精修细节
红外光谱分析:将所得产物Zn(ASBSA)2(bipy)2,用美国Nicolet 6700傅立叶变换红外光谱仪进行分析,采用KBr压片,在4000-400cm-1范围内摄谱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,3100cm-1附近观察到-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,1630cm-1处产生的吸收峰,对应于位亚胺基的νC=N振动峰,同时当金属Zn(II)与配体配位后,吸收峰发生红移动。545cm-1左右出现了νZn-N的吸收峰。1370,1120cm-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没有峰的存在,证明磺酸基团脱去质子,在650-800cm-1出现的系列振动峰对应与芳香环环骨架振动峰。
分子结构分析:通过Diamond 3D模拟晶体画图软件模拟出产物的晶体结构,如图3所示。单晶分析显示化合物属于单斜晶系,p2(1)点群。化合物的基本结构,配位单元由2个ASBSA有机配体和2个bipy分子片段、1个Zn(II)离子组成,分子内没有配位和游离的水分子。核心组成ZnN4,中心Zn(II)离子展示了4配位数的配位模式,呈现变形四面体的几何构型,电子给体4个N原子中,2个来自不同的4-氨基-N-(5-甲基-1,2-硫代噻唑-3-基)苯磺酰胺配体的噻二唑片段,2个来自bipy的N原子,而在赤道平面上,中心离子被bipy分子片段和噻二唑的N原子结合,Zn-N3,Zn1-N6,Zn1-N9,Zn1-N101的键长分别是1.987(2),1.987(2),2.042(2),2.051(2)和与吡啶N原子相连的化学键稍长一些。与中心原子链接的化学键的键角在102.27(10)和113.10(10)°之间。金属Zn(II)原子经由O3N1供体组成球状结构,这些供体中的三个羧基氧原子O(1)、O(2)和O(6)分别来自于三个ASBSA配体的一部分,而N(1)原子则位于第四个ASBSA配体吡啶环官能团的C3晶体学轴上。bipy分别利用两端的N9、N10原子,作为两个端基连接点把Zn的配位单元连成一维“之”字链状结构,如图4所示,Zn两侧的bipy成大约120°角度分布。含有N、O原子的ASBSA作为三齿配位体提供较强的配位能力,连接三个Zn(II)离子,没有为客体水分子的引入提供空间。同一个4,4’联吡啶分子内部,两个吡啶片段稍有扭曲,它们的二面角大约20.33°,而不是在同一平面上。另外,在化合物内部存在非共价化学键,如S...H-N,O...H-N,也对化合物的稳定性有所贡献。
热重、元素分析、荧光性能分析:将所得产物化合物在CHN-O-Rapid分析仪或Elementar Vario MICRO上进行元素分析,分析表明,材料由以下成分组成:化合物为C33H28ZnN9O6S2,理论计算元素含量百分比:C 44.12,H 3.70,N 18.38,实际测定:C44.10,H3.68,N18.56。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5示,加热到约200℃时化合物框架保持稳定,当进一步加热时,重量损失为62.37%,其对应于ASBSA有机配体的分解(理论值62.2%),随着温度的进一步升高,到750°质量损失21.20%,对应于联吡啶片段的分解(理论值20.47%),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(如图6所示),因为与中心离子配位的单元没有溶剂部分,减少了非辐射跃迁的电荷转移,使其荧光增强。对比分析表明,化合物的荧光来自于配体到金属中心的电荷跃迁。测试发现,激发态半衰期为8.7ns。
抑菌性能分析:将晶态化合物材料研磨,得到无色粉末。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,用消毒过的棉拭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,至于培养箱中,于37℃条件下保温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,在水溶液中,目标Zn的化合物抑菌圈12mm,溶解在10%(质量比)DMSO的,抑菌圈的直径平均值大约为15.5mm(如图7),较好的抑菌性能;同时我们做了对对比实验,在15%的的N,N–二甲亚砜(DMSO)溶液中,抑菌圈的直径平均值为20.5mm(图8),证明抑菌效果主要来自于配位化合物。加入DMSO溶液,牛津杯子,白色抑菌圈向外周移动,证明制得的新型化合物在DMSO/水混合溶液中溶解度增大。
实施例2
基于ASBSA和4,4’联吡啶配体的Zn(II)配合物的制备方法,包括以下步骤:
(1)、取有机配体ASBSA(1mmol),加入水与乙醇的混合溶液(50ml)中,水与乙醇的体积比为1:1.5,分散混合,得到溶液A;
(2)、取Zn(ClO4)2·6H2O(1mmol)加入100ml水与有机溶剂的混合溶液中,有机溶剂为甲醇、乙醇和乙腈的混合液,且水与有机溶剂的体积比为1.5:1-2.5:1,搅拌混合,得到溶液B;
(3)、取溶液B(50ml),加入溶液A(10ml)中,搅拌后得到浑浊液C,然后用稀硝酸(氨水)调节pH为5.5-7.5,得到混合液D;
(4)、将0.2mmol 4,4’联吡啶用少量乙醇分散加入混合液D中,用磁力搅拌器在常温常压下搅拌2h后,得到前驱液E;
(5)、将前驱液E转移至带有聚四氟乙烯衬的水热反应釜中,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80-140℃,反应50-70h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,然后冷却、过滤,并采用乙醇与水的混合溶液将结晶洗涤2-3次,然后置于真空干燥箱中干燥,干燥温度控制在60℃以下,即得到无色菱形块状晶体配合物。
实施例3
基于ASBSA和4,4’联吡啶配体的Zn(II)配合物的制备方法,包括以下步骤:
(1)、取有机配体ASBSA(1mmol),加入水与乙醇的混合溶液(100ml)中,水与乙醇的体积比为1:0.8,分散混合,得到溶液A;
(2)、取Zn(NO3)2·6H2O(1mmol)加入(100ml)水与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,搅拌混合,得到溶液B;
(3)、取溶液B(20ml),加入溶液A(10ml)中,搅拌后得到浑浊液C,然后用稀硝酸(稀氨水)调节pH为4.5-7.0,得到混合液D;
(4)、将0.2mmol 4,4’联吡啶用少量乙醇分散加入混合液D中,用磁力搅拌器在常温常压下搅拌2h后,得到前驱液E;
(5)、将前驱液E转移至带有聚四氟乙烯衬的水热反应釜中,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90-140℃,反应40-60h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(40-60℃)后,即得到无色菱形块状晶体配合物。
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所述的基于ASBSA和4,4’联吡啶配体的Zn(II)配合物的制备方法,其特征在于:
所述Zn(II)配合物由以下方法制备得到:
(1)、取有机配体ASBSA,加入水与乙醇的混合溶液中,分散混合,得到溶液A;
(2)、取Zn(CH3COO)2·4H2O或Zn(CIO4)2·6H2O或Zn(NO3)2·6H2O加入水与有机溶剂的混合溶液中,搅拌混合,得到溶液B;
(3)、取溶液B,加入溶液A中,搅拌后得到浑浊液C,然后调节pH为4.0-8.0,得到混合液D;
(4)、向混合液D中分散加入bipy,然后在常温常压下搅拌,得到前驱液E;
(5)、将前驱液E转移至反应容器内进行反应,反应结束后收集反应瓶内出现的无色结晶,然后冷却、过滤、洗涤,然后置于真空干燥箱中干燥,即得到无色菱形块状晶体配合物。
3.如权利要求2所述的基于ASBSA和4,4’联吡啶配体的Zn(II)配合物的制备方法,其特征在于:所述步骤(1)中有机配体ASBSA和水与乙醇的混合溶液的加入量为:每10ml的水与乙醇的混合溶液中加入0.1~0.5mmol有机配体ASBSA。
4.如权利要求2所述的基于ASBSA和4,4’联吡啶配体的Zn(II)配合物的制备方法,其特征在于:所述步骤(2)水与有机溶剂的混合液,有机溶剂为甲醇、二氯甲烷、乙醇、乙腈、DMF或DMSO中的一种或几种,且水与有机溶剂的体积比为0.5∶1~2∶1之间。
5.如权利要求2所述的基于ASBSA和4,4’联吡啶配体的Zn(II)配合物的制备方法,其特征在于:所述步骤(2)中Zn(CH3COO)2·4H2O或Zn(CIO4)2·6H2O或Zn(NO3)2·6H2O的物质的量:每10ml的水和有机溶剂混合液中加入0.1mmolZn(CH3COO)2·4H2O或Zn(CIO4)2·6H2O或Zn(NO3)2·6H2O。
6.如权利要求2所述的基于ASBSA和4,4’联吡啶配体的Zn(II)配合物的制备方法,其特征在于:所述步骤(3)和步骤(4)中溶液B、溶液A和bipy的加入量为:每10ml溶液A中加入10~50ml的溶液B和0.1-0.2mmol的bipy。
7.如权利要求2所述的基于ASBSA和4,4’联吡啶配体的Zn(II)配合物的制备方法,其特征在于:所述步骤(5)中的反应容器为带有温度计的三颈反应瓶,且通过用磁力搅拌器搅拌,选择控温模式进行回流反应,反应温度为50-100℃,反应时间为8h。
8.如权利要求2所述的基于ASBSA和4,4’联吡啶配体的Zn(II)配合物的制备方法,其特征在于:所述步骤(5)中的反应容器为带有聚四氟乙烯衬的水热反应釜,其反应方式为密封反应釜,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80-140℃,反应40-70h后,控制反应釜以5℃/h的冷却速率冷却至室温。
9.如权利要求1所述的基于ASBSA和4,4’联吡啶配体的Zn(II)配合物在制备抑菌剂方面的应用。
10.如权利要求1所述的基于ASBSA和4,4’联吡啶配体的Zn(II)配合物在荧光发光材料方面的应用。
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