CN116283563A - 用于二甲硝咪唑和四环素检测的铽配合物及其制备方法 - Google Patents
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Abstract
本发明涉及无机和材料化学科学领域，公开了一种用于二甲硝咪唑和四环素检测的铽配合物及其制备方法。所述的铽配合物为晶体材料，化学式为[Tb(L)0.5(H2O)2]·7H2O，式中L为[1,1':3',1”‑三联苯]‑3,3”,4',5,5”,6'‑六羧酸的负六价阴离子配体。本发明使用的配体结合三联苯和多羧酸的优势，有利于构建结构独特且稳定性良好的配合物材料。本发明所述的铽配合物具有稳定的荧光发射，可检测水溶液中的二甲硝咪唑和四环素且检测灵敏，检出限低，可回收性好，在抗生素的快速检测方面具有良好的应用前景。
Description
技术领域
本发明涉及无机和材料化学科学领域，具体涉及一种用于二甲硝咪唑和四环素检测的铽配合物及其制备方法。
背景技术
抗生素作为治疗细菌感染的一类药物，广泛应用于畜牧业、农业和医药领域。人类和动物服用的抗生素中，大多数并不能被机体充分吸收，约有20.0％～97.0％以活性物质形式代谢至体外进入环境中。另外，畜禽水产养殖、制药和医用废水的排放均会导致抗生素在生物圈的积累，不仅危害生物的生存和繁殖，影响生态系统功能，而且有引发“超级细菌”的风险，对人类生存环境安全和生命健康造成严重威胁。我国人口众多，农业和畜牧业发达，抗生素引起的环境污染问题日益严峻。有研究表明，仅在地表水中检出的抗生素就有61种。另外，老人、儿童和孕妇这些特殊群体也受到抗生素的危害，甚至12％的新生儿对抗生素表现出耐药性。四环素是一种广谱抗菌素，其毒性不大，但副作用较多见，如恶心、呕吐、食欲减退等。二甲硝咪唑对原虫及各种厌氧细菌抑制作用显著，由于潜在的致癌性和致突变性，其残留对食品安全构成威胁。因此，抗生素的灵敏、快速检测技术在临床诊断、制药、食品和环境监测等领域具有重要意义。
目前，抗生素的检测方法主要有高效液相色谱、液相色谱-串联质谱、离子迁移谱和毛细管电泳等，这些方法大多需要依赖复杂的仪器且耗时长、价格昂贵，极大限制了其在常规分析中的应用。基于配合物的新型发光传感器因其操作简便、灵敏度高、响应快以及抗干扰能力强等优点得到研究者的青睐。镧系金属配合物通常具有长的发光寿命、优异的发光单色性，是良好的化学传感器。大多数已报道的镧系金属配合物荧光探针仅可用于有机溶剂等非水体系。配合物在水溶液中的稳定性显著影响其应用。苯环属于疏水性基团，丰富的苯基和羧基有利于构建结构独特且稳定性良好的配合物。目前，研制水稳定良好的镧系金属配合物荧光材料用于水体中抗生素的检测仍然面临挑战。
发明内容
针对现有技术存在的上述不足，本发明的目的在于提供一种用于二甲硝咪唑和四环素检测的铽配合物及其制备方法。
为实现以上目的，本发明采用如下技术方案：
用于二甲硝咪唑和四环素检测的铽配合物，为晶体材料，化学式为[Tb(L)0.5(H2O)2]·7H2O，式中L为[1,1':3',1”-三联苯]-3,3”,4',5,5”,6'-六羧酸的负六价阴离子配体，所述铽配合物属于正交晶系Cmca空间群，晶胞参数为：
α＝90°，β＝90°，γ＝90°，所述铽配合物分子式为TbC12H22O15。
进一步地，所述的用于二甲硝咪唑和四环素检测的铽配合物，其特征在于，不对称单元包含一个Tb3+离子，二分之一完全脱质子的L6-配体，两个配位水分子和七个游离水分子；所述铽配合物含有双核[Tb2(COO)2]簇，相邻簇之间通过L6-配体拓展形成三维网络结构；所述铽配合物为(6,6)-连接的三维网络结构，拓扑符号为(48.66.8)(49.66)。
进一步地，所述的用于二甲硝咪唑和四环素检测的铽配合物，其特征在于，其制备方法为：在密封条件下，将六水合硝酸铽和[1,1':3',1”-三联苯]-3,3”,4',5,5”,6'-六羧酸溶于有机溶剂中，通过溶剂热方法反应后得到。
优选的，所述六水合硝酸铽和[1,1':3',1”-三联苯]-3,3”,4',5,5”,6'-六羧酸的摩尔比为2:1，所用溶剂为N-甲基甲酰胺。
优选的，所述的反应温度为120℃，反应时间为72小时，反应结束后，将反应混合物以8℃/小时的速度冷却到室温。
进一步地，所述的用于二甲硝咪唑和四环素检测的铽配合物，具有稳定的荧光发射，荧光寿命为1324.86μs，能够用于荧光检测。
进一步地，所述的用于二甲硝咪唑和四环素检测的铽配合物，能够应用于水溶液中二甲硝咪唑和四环素的检测。
与现有技术相比，本发明具有以下有益效果：
(1)本发明用于二甲硝咪唑和四环素检测的铽配合物，使用的配体结合三联苯和多羧酸的优势，构筑的配合物可作为一种潜在的荧光探针材料应用于水溶液中抗生素的检测领域。
(2)本发明使用三联苯多羧酸配体，丰富的苯基和羧基有利于构建结构独特且稳定性良好的配合物材料。
(3)本发明使用三联苯多羧酸配体制备得到一例具有新颖三维拓扑网络结构的配合物材料。
(4)本发明用于二甲硝咪唑和四环素检测的铽配合物，具有稳定的荧光发射，可检测水溶液中的二甲硝咪唑和四环素且检测灵敏，检出限低，可回收性好，在抗生素的快速检测方面具有良好的应用前景。
(5)本发明所述铽配合物材料制备工艺简单、操作简便、安全、成本低；材料具有良好的稳定性和优异的发光性能。
附图说明
通过阅读参照以下附图对非限制性实施例所作的详细描述，本发明的其它特征、目的和优点将会变得更明显：
图1为所述铽配合物材料中Tb3+离子的配位环境，对称代码：#1-x+1/2,y,-z+1/2；#2x,-y+3/2,z-1/2；#3x,y-1/2,-z+1/2；#4-x,y,z；
图2为所述铽配合物材料a)沿a轴方向形成的一维链结构，b)沿c轴方向的三维结构图以及c)三维拓扑网络结构图；
图3为所述铽配合物材料的PXRD图；
图4为所述铽配合物材料的发射光谱图；
图5为所述铽配合物材料的荧光寿命图；
图6为所述铽配合物材料在不同抗生素水溶液中的荧光光谱；
图7为所述铽配合物材料在DMZ和TET水溶液中不同时间间隔的荧光响应速度；
图8a)为所述配合物材料对DMZ检测的非线性拟合方程，b)为所述配合物材料对TET检测的非线性拟合方程(插图：低浓度范围内拟合曲线)；
图9a)加入TET和DMZ后不同抗生素溶液中所述配合物材料的相对荧光强度，b)循环实验图。
具体实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。
实施例1
用于二甲硝咪唑和四环素检测的配位聚合物材料，化学式为[Tb(L)0.5(H2O)2]·7H2O，式中L为[1,1':3',1”-三联苯]-3,3”,4',5,5”,6'-六羧酸(H6L)的负六价阴离子配体；所述配合物中含有双核Tb配位单元，并且通过L6-的配位延伸，形成含有一维孔道的三维框架；所述配合物材料具有良好的稳定性和优异的发光性能，可在水溶液中快速检测二甲硝咪唑和四环素。
其中L6-结构式如下：
用于二甲硝咪唑和四环素检测的铽配合物的合成：将六水合硝酸铽(0.091g，0.20mmol)和[1,1':3',1”-三联苯]-3,3”,4',5,5”,6'-六羧酸(0.049g，0.10mmol)以摩尔比2:1加入到N-甲基甲酰胺(6mL)溶剂中搅拌均匀。将混合物密闭在25mL的高压反应釜中，加热到120℃并保持72小时，然后以8℃/小时的速度冷却到室温。取出后，得到透明米粒状晶体，即为所述配合物材料。
对合成得到的晶体进行结构表征和解析，确定其晶胞和空间结构，该晶体属正交晶系Cmca空间群，晶胞参数为：
α＝90°，β＝90°，γ＝90°。最小不对称单元包含一个Tb3+离子，二分之一完全脱质子的L6-配体，两个配位水分子和七个游离水分子。具体的晶体学数据如下表1所示：
表1铽配合物的晶体学数据表
如图1所示，Tb中心为八配位，其中六个氧原子来自四个H6L配体中的四个羧基，另外两个氧原子来自两个配位水分子。两个Tb原子通过来自不同配体的两个羧基桥连形成双核[Tb2(COO)2]簇。相邻簇之间通过L6-配体中的羧基以螯合和单齿桥连方式相连，沿a轴方向形成一维链状结构(图2a)。相邻一维链之间通过L6-配体的芳环进一步延伸构成三维网络结构(图2b)。拓扑计算表明该配合物是一个新颖的(6,6)-连接的三维网络结构(图2c)，符号为(48.66.8)(49.66)。如附图3所示，合成的铽配合物的X-射线粉末衍射(PXRD)数据与从晶体结构拟合得到的数据相吻合，说明所制备配合物材料具有很高的物相纯度。
荧光性质测试：
在254nm紫外灯照射下制备得到的配合物材料表现出明显的绿色发光，进一步将制备的配合物材料利用型号为F-4500Hitachi的荧光光谱仪测定荧光数据，如图4所示，在352nm激发波长下，分别在490，544，584和622nm处出现较强发射峰，最强发射峰出现在544nm处。荧光寿命测试结果表明该配合物符合单指数衰减，寿命为1324.86μs(图5)。该铽配合物材料浸泡在去离子水中5天后仍然能保持其荧光强度。将该配合物材料加入土霉素(OTC)，呋喃西林(NFZ)，甲硝唑(MDZ)，四环素(TET)，二甲硝咪唑(DMZ)，呋喃妥因(NFT)，阿莫西林(ACL)，磺胺甲恶唑(SMZ)，磺胺噻唑(STZ)，红霉素(ERM)10种抗生素水溶液中，通过荧光光谱仪记录其发光光谱。与不含抗生素的空白实验相比，在TET和DMZ溶液中发光强度明显下降，猝灭效率分别为86.9％和87.9％(图6)，并且荧光响应可在1分钟后达到最小值(图7)。使用Stern-Volmer方程计算得到该配合物材料对DMZ的猝灭常数Ksv值为6.18×104mol·L-1(图8a)，对TET的猝灭常数为6.08×104mol·L-1(图8b)，相同条件下，这些值优于多数已报道的配合物材料的数值。基于3σ/Ksv(其中σ代表标准差)计算得到该铽配合物材料对DMZ和TET的检测限分别为5.33ppm和5.42ppm。另外，该配合物材料具有良好的选择性和可回收利用性(图9)。所述铽配合物材料特异性检测DMZ和TET归因于光电子诱导转移和共振能量转移的共存过程。检测灵敏，选择性强，检出限低等优势使得该配合物材料作为发光传感器能够应用于工业水环境中DMZ和TET的有效检测。
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 (7)
1.一种用于二甲硝咪唑和四环素检测的铽配合物，其特征在于，为晶体材料，化学式为[Tb(L)0.5(H2O)2]·7H2O，式中L为[1,1':3',1”-三联苯]-3,3”,4',5,5”,6'-六羧酸的负六价阴离子配体，所述铽配合物属于正交晶系Cmca空间群，晶胞参数为：
α＝90°，β＝90°，γ＝90°，所述铽配合物分子式为TbC12H22O15。
2.根据权利要求1所述的用于二甲硝咪唑和四环素检测的铽配合物，其特征在于，不对称单元包含一个Tb3+离子，二分之一完全脱质子的L6-配体，两个配位水分子和七个游离水分子；所述铽配合物含有双核[Tb2(COO)2]簇，相邻簇之间通过L6-配体拓展形成三维网络结构；所述铽配合物为(6,6)-连接的三维网络结构，拓扑符号为(48.66.8)(49.66)。
3.根据权利要求1～2任一项所述的用于二甲硝咪唑和四环素检测的铽配合物，其特征在于，其制备方法为：在密封条件下，将六水合硝酸铽和[1,1':3',1”-三联苯]-3,3”,4',5,5”,6'-六羧酸溶于有机溶剂中，通过溶剂热方法反应后得到。
4.根据权利要求3所述的用于二甲硝咪唑和四环素检测的铽配合物，其特征在于，所述六水合硝酸铽和[1,1':3',1”-三联苯]-3,3”,4',5,5”,6'-六羧酸的摩尔比为2:1，所用溶剂为N-甲基甲酰胺。
5.根据权利要求3所述的用于二甲硝咪唑和四环素检测的铽配合物，其特征在于，所述的反应温度为120℃，反应时间为72小时，反应结束后，将反应混合物以8℃/小时的速度冷却到室温。
6.根据权利要求1～2任一项所述的用于二甲硝咪唑和四环素检测的铽配合物，其特征在于，具有稳定的荧光发射，荧光寿命为1324.86μs，能够用于荧光检测。
7.根据权利要求1～2任一项所述的用于二甲硝咪唑和四环素检测的铽配合物，其特征在于，能够应用于水溶液中二甲硝咪唑和四环素的检测。
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