CN110885339A - 一种锌配合物合成及作为荧光探针、铁电材料的应用 - Google Patents
一种锌配合物合成及作为荧光探针、铁电材料的应用 Download PDFInfo
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Abstract
本发明提供一种锌金属配合物制备及其在荧光探针、铁电材料的应用。所述配合物的化学式为[Zn(L)·H2O]n；其中，H2L＝1，1′‑(4‑羧基苯基)‑2，2′‑联咪唑。所述锌金属配合物为锌离子通过L2‑配体自组装而成三维结构。该锌配合物对三价铁离子、重铬酸根离子、抗生素呋喃西林和呋喃妥因表现出明显的荧光猝灭效应，可作为其荧光探针，在环境监测和生命科学领域具有潜在的应用价值。此外该锌配合物具有优异的铁电性质：当外加电场1200V时，其剩余极化为1.84μC/cm2，矫顽场为714V/cm，饱和极化为2.15μC/cm2，有望成为新型铁电材料在信息存储领域有广阔的应用前景。
Description
关于资助研究或开发的声明：本发明是在江苏省政策引导类计划(产学研合作)-前瞻性联合研究项目(Grant no.BY2016066-08)的资助下进行的。
技术领域
本发明属于有机合成和金属有机化学技术领域，具体涉及到一种以1，1′-(4-羧基苯基)-2，2′-联咪唑为配体的三维锌配位聚合物的制备及作为三价铁离子(Fe3+)、重铬酸根离子(Cr2O7 2-)、呋喃西林(NZF)以及呋喃妥因(NFT)抗生素荧光探针并且可作为铁电材料的锌配合物的应用。
背景技术
相比于传统发光材料，配合物荧光材料因同时具有无机材料高化学稳定性和有机材料高量子产率而备受关注。配合物荧光性能受自身金属离子的电子构型和能级、配位构型和配位环境、配体以及外界条件如溶剂(溶液荧光)、温度等因素影响。特别是结构中具有孔道、裸露金属位点、具有路易斯酸或者碱性位点的活性有机基团的配合物，他们能够有效与客体分子(包含阴离子、金属阳离子和有机小分子)进行主客体相互作用，并将作用结果直接反映在该物质荧光变化中，使其在有机物检测、金属离子检测、温度探针、pH探针和活性探针等方面表现出良好的应用价值。一系列的荧光探针配合物已被报道，但是能同时检测多种客体分子的荧光探针配合物报道比较少。
金属离子的存在与现代人类的生活密切相关：一方面，随着现代工业的迅速发展，采矿、工业废气、废水排放等环境污染问题日趋严重，并使重金属离子进入生物体内，造成生物体的慢性中毒。另一方面，金属离子也是生物和人体必不可少的组成元素。因此，快速、方便、准确检测金属离子非常重要的。
铁是一种生物体中微量的过渡金属元素，在人体内参与多种酶和免疫系统的组成，也是血红蛋白的主要组成部分，体内铁元素不足或者过量将引起诸多疾病，影响人体健康。但是如果人体内的铁含量过剩，则会导致人体脏器的结构发生变化导致病变；如肝纤维化等，严重者会危及生命。铬是人类必须的微量元素之一，同时也是重金属污染物之一。自然界中的铬一般以三价和六价两种形式存在，但其毒性相差很大，六价铬的毒性超过三价铬100倍，是一种剧毒的环境污染物，容易进入人体细胞，对肝、肾等内脏器官和DNA造成损伤，在人体内蓄积具有致癌性并可能诱发基因突变。因此，快速、方便、准确检测三价铁离子和重铬酸根离子非常重要的。
通俗地讲，抗生素就是用于治疗各种非病毒感染的药物。呋喃西林(NZF)是一种人工合成的抗菌药，它可以干扰细菌糖代谢的早期阶段，导致细菌代谢紊乱而死亡，其抗菌谱较广，体外能抑制一般的细菌，高浓度时可杀菌，外用冲洗或湿敷可以处理体表感染和皮肤疾病，但是呋喃西林在动物源性食品中的残留可以通过食物链传递给人类，长期摄入会引起各种疾病，对人体有致癌、致畸胎等副作用。呋喃妥因(NFT)是国家基本药物，有广谱抗菌作用，可有效地杀灭下尿路感染的革兰阳性菌和革兰阴性菌。临床上主要用于敏感菌引起的急性下尿路感染、慢性菌尿症及反复发作的慢性尿路感染。呋喃妥因的不良反应涉及多个器官系统，包括消化系统：恶心、呕吐、腹泻等；呼吸系统：急性肺炎、肺间质纤维化等；神经系统：三叉神经痛、周围神经病变以及血液系统：溶血、慢性溶血性贫血；全身的高敏反应：皮疹、发热、黄疸、肝损伤等。国外已有国家如美国已经禁止临床使用呋喃妥因片剂，可见人们对其安全性的担忧和警惕。基于上述原因，实现对呋喃西林、呋喃妥因的选择性荧光识别很有研究价值。
铁电材料是一类具有铁电性质的相变材料。该类材料不仅具有自发极化，且在一定温度范围内，其自发极化强度能随外施电场的方向改变而改变，能在外界电场、磁场、光波、压力和温度的刺激下会做出相应的响应，实现机械能、电能、热能、光能、电磁能等能量之间的转换，在当今信息功能材料和微电子领域备受重视，在国防、探测、通信等领域具有极为重要的用途。
传统的含铅类的陶瓷铁电体以及钙钛矿类型的无机型铁电体因具在生产中需要煅烧，耗能大、产率低，废弃物环境污染严重，成薄膜难且易脆而不断被革新。与传统的无机型铁电体相比，配合物在铁电材料方面具有合成简单、成本低、绿色环保、性质多样等优势越发受到人们的关注。因此，配合物是一种理想的铁电材料。
1，1′-(4-羧基苯基)-2，2′-联咪唑是配位能力较强的桥连配体：在这个配体的两端具有两个羧酸基，两个苯环之间通过联咪唑连接，有利于配合物的合成；它可以部分或完全去质子化，允许与金属离子有不同的配位模型，易合成具有不同维数的金属配合物，而合成不同维数的结构是完成器件化至关重要的一步。
本发明属于有机合成和金属有机化学技术领域，涉及具有三维锌金属荧光配合物的合成，更具体的说是以1，1′-(4-羧基苯基)-2，2′-联咪唑为配体的锌配位聚合物的合成及其作为荧光探针、铁电材料应用。本文分别采用二价锌离子作为主体，以1，1′-(4-羧基苯基)-2，2′-联咪唑为配体，探究不同溶剂分子对金属配合物的荧光性能影响，同时具有三维结构的锌荧光配合物对三价铁离子、重铬酸根离子和抗生素都表现出明显的荧光淬灭效应，作为荧光探针材料可以应用在金属离子、抗生素分子检测和分析研究，具有一个广阔的应用前景。此外，在本发明中，我们合成的配合物具有优异的铁电性质：当外加电场1200V时，其剩余极化Pr为1.84μC/cm2，矫顽场Ec为714V/cm，饱和极化Ps为2.15μC/cm2。本发明合成的配合物饱和极化强度远远大于经典的铁电体材料NaKC4H4O6·4H2O(罗谢尔盐：Ps为0.25μC/cm2)。
总结来说，具有荧光和铁电性质的配合物已经分别有了大量报道，但是能同时具有对Fe3+、Cr2O7 2-、NZF及NFT都有响应且具有优异铁电性质的配合物的报道是非常少的。在本发明中，我们合成的金属配合物具有成本低、效率高、重现性好、检测灵敏、易于分离、收益高的优点，在Fe3+、Cr2O7 2-、NZF及NFT检测和铁电材料方面具有一个广阔的应用前景。
发明内容
本发明旨在提供一种用作三价铁离子、重铬酸根离子、呋喃西林和呋喃妥因荧光探针并具有优异铁电性质的三维锌配合物及其制备方法。本发明选用1，1′-(4-羧基苯基)-2，2′-联咪唑配体和六水合硝酸锌构筑锌配位聚合物。该化合物对三价铁离子、重铬酸根离子、抗生素呋喃西林、抗生素呋喃妥因有荧光识别的功能，能检测水溶液中微量三价铁离子、重铬酸根离子、抗生素呋喃西林和呋喃妥因的存在，且具有优异的铁电性质。该化合物合成工艺简单、成本低、效率高、重现性好、检测灵敏、易于分离、收益高，可应用于工业化生产，在环境监测、生命科学及铁电材料领域具有潜在的应用前景。
本发明所涉及的用作三价铁离子、重铬酸根离子、抗生素呋喃西林和呋喃妥因荧光探针及铁电材料的锌配合物的化学式为：[Zn(L)·H2O]n，其中，H2L＝1，1′-(4-羧基苯基)-2，2′-联咪唑。H2L的结构式如下：
本发明所涉及的用作三价铁离子、重铬酸根离子、抗生素呋喃西林和呋喃妥因荧光探针及铁电材料的三维锌配合物结构如图1(a)所示，它的基本结构参数为：
本发明的锌配合物的晶体属于三方晶系，空间群为R-3，晶胞参数为：
α＝β＝90°，γ＝120°。中心离子锌为四配位的四面体构型；锌离子与1，1′-(4-羧基苯基)-2，2′-联咪唑羧基氧原子、咪唑基氮原子配位，形成了复杂的三维锌配位聚合物，如图1(b)所示。
本发明所涉及的锌配合物的制备方法包括下述步骤：
(1)将14.8mg的六水合硝酸锌(Zn(NO3)2·6H2O)、18.7mg的1，1′-(4-羧基苯基)-2，2′-联咪唑(H2L)、7.81mg的4，4′-联吡啶(4，4′-Bipyridine)放入水热25mL反应釜的聚四氟乙烯内胆中混合，再加入浓度为0.15mol·L-1的盐酸溶液调节pH至1.2，调节后的水溶液体积至10mL，常温搅拌30分钟后，得到混合液；
(2)将上述混合液在100℃下烘制72小时，取出产物后将固体分离；
(3)用乙醇将上述固体洗涤三次，得到无色透明块状晶体。
进一步地，本发明提供上述锌配合物用作三价铁离子、重铬酸根离子、抗生素呋喃西林和呋喃妥因荧光探针的应用，用于监测环境和生物体中的三价铁离子、重铬酸根离子、呋喃西林和呋喃妥因。除此之外，本发明提供的上述锌配合物还可用作铁电体材料。
本发明的优点是：该制备方法工艺简单，产率高、易于分离、重现性好、灵敏度高、铁电性质优异、收率高，可以得到单一晶型、高纯度的晶体材料，易工业化生产；该产品对三价铁离子、重铬酸根离子、呋喃西林和呋喃妥因具有荧光识别的功能，可以用于水溶液中微量三价铁离子、重铬酸根离子、呋喃西林和呋喃妥因的检测，与传统的检测法相比，该方法具有定性、快速、灵敏、高效、操作简便等优点；该产品具有优异的铁电性质，当外加电场1200V时，其剩余极化Pr为1.84μC/cm2，矫顽场Ec为714V/cm，饱和极化Ps为2.15μC/cm2，远远优于经典的铁电体材料NaKC4H4O6·4H2O。
附图内容
图1(a)本发明锌配合物的晶体结构图；图1(b)本发明锌配合物的三维结构图。
图2为本发明锌配合物的固体荧光图。
图3为本发明锌配合物对不同溶剂的荧光强度图。
图4(a)为本发明锌配合物对不同金属溶液的荧光发射强度图；图4(b)为本发明锌配合物对不同浓度三价铁离子溶液的荧光强度图。
图5(a)为本发明锌配合物对不同阴离子溶液的荧光发射强度图；图5(b)为本发明锌配合物对不同浓度重铬酸根离子溶液的荧光强度图。
图6(a)为本发明锌配合物对不同种类抗生素溶液的荧光发射强度图；图6(b)为本发明锌配合物对不同浓度的呋喃西林溶液荧光发射强度图。
图7为本发明锌配合物的电滞回线图。
具体实施方式
为了更好的理解本发明，下面结合实施实例进一步阐述本发明的内容，但本发明的内容不仅仅局限于下面的实施例。本发明的所述原料均有市售。
实施例中的所用原料均可从市场获得。六水合硝酸锌，分析纯，国药集团；4，4′-联吡啶，分析纯，国药集团；1，1′-(4-羧基苯基)-2，2′-联咪唑，济南恒化。
实施例1配合物的合成：
将14.8mg的六水合硝酸锌(Zn(NO3)2·6H2O)、18.7mg的1，1′-(4-羧基苯基)-2，2′-联咪唑(H2L)、7.81mg的4，4′-联吡啶(4，4′-Bipyridine)溶于10mL水中，再加入浓度为0.15mol·L-1的盐酸溶液调节pH至1.2，搅拌半小时，转移至25mL水热反应釜的聚四氟乙烯内胆中，在100℃温度条件下反应72小时，所得产物用乙醇洗涤三次(2mL/次)，得到无色透明块状晶体。基于金属Zn计算的产率45.3％。
实施例2配合物的结构表征：
晶体结构采用Bruker Smart CCD X-射线单晶衍射仪，在296(2)K下，挑选尺寸为0.31×0.14×0.13mm的晶体，使用经过石墨单色化的MoKα射线(λ＝0.07107nm)为入射辐射光源，以ω/2θ扫描方式收集衍射点，晶胞参数经最小二乘法精修，用SADABS程序对收集到的数据进行吸收校正。用直接法解出配合物的结构，运用全矩阵最小二乘法对非氢原子坐标和各向异性温度因子进行精修，用SHELXTL程序完成全部计算。详细的晶体学参数列于表1。[Zn(L)·H2O]n的晶体结构图及三维结构图如图1(a)和图1(b)所示。
表1配合物的晶体学数据
实施例3配合物的荧光性质：
采用LS-55型荧光光谱仪，在室温下测试配合物的荧光性质。图2为实施例1所制备锌配合物的固体荧光图，表明材料具有较强的荧光性质。如图3所示，该配合物在水溶液中表现出很强的发光性能。
从图4(a)可以看出，在所选金属离子水溶液中，实施例1所制备锌配合物的荧光强度表现出对金属离子的依赖性，对Fe3+表现出完全的荧光淬灭效果，有望成为Fe3+的荧光探针。
从图5(a)可以看出，在所选阴离子水溶液中，实施例1所制备锌配合物的荧光强度表现出对阴离子类型的依赖性，只有Cr2O7 2-表现出完全的荧光淬灭效果，有望成为Cr2O7 2-的荧光探针。
从图6(a)可以看出，在所选抗生素水溶液中，实施例1所制备锌配合物的荧光强度表现出对抗生素类型的依赖性，呋喃西林、呋喃妥因表现出完全的荧光淬灭效果，可望成为呋喃西林和呋喃妥因的荧光探针。
为了研究实施例1所制备锌配合物识别水溶液中Fe3+、Cr2O7 2-、NZF和NFT的灵敏度，把Fe3+、Cr2O7 2-、NZF和NFT加入到该材料的水悬浊液中，配制成不同浓度的悬浊液，记录其荧光强度的变化。如图4、5和6所示，荧光强度随着Fe3+、Cr2O7 2-、NZF和NFT的浓度增大呈现下降趋势。当Fe3+、Cr2O7 2-、NZF和NFT的的浓度分别为1.96×10-5mmol·L-1、2.60×10-5mmol·L-1、4.00×10-5mmol·L-1、4.76×10-5mmol·L-1时，配合物的荧光就基本被完全淬灭了，表明该配合物在水溶液检测Fe3+、Cr2O7 2-、NZF和NFT的过程中具有很高的灵敏度。
实施例4配合物的铁电性质：
当外加电场1200V时，实施例1所制备锌配合物表现出优异的铁电性质，其剩余极化Pr为1.84μC/cm2，矫顽场Ec为714V/cm，饱和极化Ps为2.15μC/cm2(如图7)，有望成为新型铁电材料在信息存储领域有广阔的应用前景。
Claims (3)
1.一种用作三价铁离子、重铬酸根离子、抗生素呋喃西林和呋喃妥因荧光探针且具有优异铁电性能的锌配合物，其特征在于，其化学式为[Zn(L)·H2O]n，其中，H2L＝1，1′-(4-羧基苯基)-2，2′-联咪唑；所述的锌配合物的晶体属于三方晶系，空间群为R-3，晶胞参数为：
α＝β＝90°，γ＝120°；中心离子锌为四配位的四面体构型；锌离子与1，1′-(4-羧基苯基)-2，2′-联咪唑羧基氧原子、咪唑基氮原子配位，形成了复杂的三维锌配位聚合物。
2.根据权利要求1所述的锌金属的制备方法，其特征在于，步骤如下：在密封条件下，有机配体1，1′-(4-羧基苯基)-2，2′-联咪唑、4，4′-联吡啶与六水合硝酸锌在水溶液中，经由水热反应得到晶体结构的锌配合物。
3.根据权利要求2所述的制备方法，其特征在于，其中：1，1′-(4-羧基苯基)-2，2′-联咪唑、4，4′-联吡啶和六水合硝酸锌的摩尔比为1∶1∶1，每0.05mmol的六水合硝酸锌对应10mL的去离子水，热反应的条件为100℃，反应时间为三天。
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