CN115260509B - 基于硼酸功能化的多发射金属有机骨架化合物Eu-MOF及其在没食子酸检测中的应用 - Google Patents
基于硼酸功能化的多发射金属有机骨架化合物Eu-MOF及其在没食子酸检测中的应用 Download PDFInfo
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Abstract
本发明公开了一种基于硼酸功能化的多发射金属有机骨架化合物Eu‑MOF及其在没食子酸检测中的应用,其中Eu‑MOF是由硼酸配体与金属铕离子配位聚合获得的铕金属有机骨架化合物;所述硼酸配体为3,5‑二羧基苯硼酸。所述Eu‑MOF具有单波长激发下多发射的特性,在270nm的紫外激发下,于454nm和615nm处产生双发射而显示红色荧光。加入GA后,由于GA中的酚羟基与硼酸的羟基之间形成了硼酸酯特殊共价结构,使Eu‑MOF中能量转换效率发生变化,在紫外灯下Eu‑MOF由红色变为蓝色。本发明中的Eu‑MOF具有良好的发光性能、高灵敏度和视觉检测的快速响应,对GA的检出限低至22nM。
Description
技术领域
本发明涉及一种基于硼酸功能化的多发射金属有机骨架化合物Eu-MOF及其在没食子酸检测中的应用,属于材料合成、可视化检测、食品质量监测等领域。
背景技术
食品添加剂具有改善食品感官特性和保持或提高食品营养价值的作用,特别是具有抗氧化作用的食品添加剂受到了社会各年龄段人们的广泛关注。没食子酸因其在茶和鲜果汁中的还原特性而具有多种生物活性。它通过清除活性氧(reactive oxygen species,ROS)等自由基离子对人体具有抗氧化作用,并能显著降低ROS指数。GA不仅天然存在于绿茶、红茶等多种植物中,而且由于其抗自由基活性和抗氧化作用,被广泛应用于食品和保健品中。GA具有很强的抗诱变、抗癌和抗氧化活性,是评价食品抗氧化能力的重要指标,因此对其进行快速、直观的检测具有重要的分析化学意义。
目前已经发展了流动注射分析、共振光散射、薄层色谱、反相高压液相色谱、电化学、分光光度法、毛细管电泳等检测方法。如Souza等采用碳纳米管修饰电极,对葡萄酒样品中没子酸的检出限为0.3M。Ghaani等人使用纳米银/飞燕草色素修饰的玻碳电极检测商业饮料中的没食子酸,检测限为280nM。然而这些方法往往在灵敏度和稳定性方面存在一定的局限性,检测过程耗时或仪器昂贵,操作要求复杂。因此,有必要开发一种成本低、操作简单、发光效率高、敏感、特异性高的GA检测方法。
金属有机骨架(Metal organic frameworks,MOFs)由于其可调节的孔径、可设计的结构以及丰富的功能配体,近年来受到越来越多的关注。MOFs可以通过多种金属簇和有机配体设计合成得到目标性质,在气体吸附分离、目标分子的富集、发光传感器、光学器件和多相催化等方面都有广泛的应用前景。发光MOFs由于其丰富的金属离子、配体和客体分子的发射源而具有多种发光性质,并在荧光可视化检测和生物成像方面表现出优异的性能。然而,MOFs缺乏特异性识别反应位点和发光机理不明确限制了其在食品添加剂检测中的应用。因此,制备能够结合特定官能团来调节能量水平的GA特异识别的MOFs有待进一步研究。
发明内容
本发明旨在提供一种基于硼酸功能化的多发射金属有机骨架化合物Eu-MOF及其在没食子酸检测中的应用。本发明提供的多发射金属有机骨架化合物Eu-MOF能够实现快速可视化检测食品、保健品中的GA,可以在不进行复杂样品前处理的情况下进行灵敏、准确的检测。
本发明基于硼酸功能化的多发射金属有机骨架化合物Eu-MOF,是由硼酸配体与金属铕离子(Eu3+)配位聚合获得的铕金属有机骨架化合物;所述硼酸配体为3,5-二羧基苯硼酸(BBDC)。
所述Eu-MOF具有单波长激发下多发射的特性,具体是在270nm的紫外激发下,于454nm和615nm处产生双发射而显示红色荧光。
所述多发射金属有机骨架化合物Eu-MOF是采用简单优化的溶剂热法制备获得,包括如下步骤:
在DMF/H2O体积比为7:3的混合溶剂中,将0.1~0.4mM的EuCl3·6H2O与0.1~0.3mM的BBDC混合,剧烈搅拌10~30min;将反应液置于含有50~70mL聚四氟乙烯内衬的不锈钢高压釜中,120~150℃加热反应12~24h,室温冷却,分别用DMF和乙醇清洗样品后离心,40~60℃真空干燥,得到白色的Eu-MOF粉末。
本发明多发射金属有机骨架化合物Eu-MOF的应用,是在没食子酸的检测过程中作为检测试剂使用。
本发明以3,5-二羧基苯基硼酸(BBDC)和EuCl3·6H2O为原料,通过简单的溶剂热法制备了硼酸功能化的多发射金属有机骨架化合物Eu-MOF。GA与Eu-MOF反应将MOF配体中的-B(OH)2转化为-BOO-,从BBDC配体到Eu3+的系统转换效率降低使Eu3+的红色发射减弱,而与GA结合的BBDC呈现的蓝色发射增强,其Eu-MOF探针颜色呈现出由红色到蓝色的连续变化,通过Eu-MOF荧光体系中荧光变化程度来检测食品和保健品中GA的含量。
具体的,设置激发波长为240~280nm,采用荧光分光光度法进行检测。激发和发射的狭缝宽度均设为5~20nm。在300~800nm范围内记录其荧光光谱。将2~5mg的Eu-MOF分散到10~40mL去离子水中,制备探针溶液。将一定量没食子酸溶于无水乙醇中,得到浓度为1.0~5.0μM的分析溶液。随后使1~3mL Eu-MOF探针溶液与GA分析溶液混合,并用去离子水稀释并充分混匀后,转移到石英比色皿中,在紫外灯下进行荧光检测。荧光颜色变化的图像是在黑暗的环境中使用相机拍摄,为保证实验结果的可靠性,每个样本至少测量三次,取平均值后再进行下一步实验。
通过软件获取荧光照片的红-绿-蓝值(RGB值)对应的颜色信息,通过分析RGB值来定量检测没食子酸。为了保证数据的准确性,反复实验三次,得到R/B的平均值,R/B表示红色和蓝色信息的比例。
进一步地,检测体系的pH=6。
本发明多发射金属有机骨架化合物Eu-MOF在270nm的紫外激发下,于454nm和615nm处产生双发射而显示红色荧光。GA的加入使Eu-MOF配体的硼酸基与其共价结和形成了硼酸酯,导致Eu-MOF在615nm处红色发光逐渐减少,而在454nm处蓝色发光逐渐增加,从而在紫外灯下产生了由红到蓝显著的颜色变化。
本发明基于硼酸配体与金属铕离子的聚合,制备了单波长激发下多发射的Eu-MOF,实现了食品和保健品中GA的可视化、实时和定量检测。作为传感系统的核心,通过硼酸基团功能化修饰构建的Eu-MOF在270nm的单激发下于454nm和615nm表现出两个发射中心。加入GA后,硼酸基团的羟基于GA中苯环上的羟基共价结合。随着GA浓度的增加,Eu-MOF在615nm处的红色荧光逐渐降低,而454nm处的蓝色荧光逐渐增加,Eu-MOF探针在紫外灯照射下呈现出由红到蓝的清晰颜色变化,通过智能手机的颜色识别器APP可识别出相应的颜色信息进行定量检测。同时,Eu-MOF探针可用于茶叶、果汁等实际样品中GA的检测,在构建可靠、方便的实时可视化检测平台提供了理论依据,在化学和分析传感领域具有巨大的应用潜力。
本发明中Eu-MOF具有良好的发光性能、高灵敏度和视觉检测的快速响应,对GA的检出限低至22nM。将Eu-MOF荧光探针结合智能手机比色器对茶叶和果汁样品中的GA进行目视定量检测,并将检测结果与高效液相色谱(HPLC)相比较,提出有效的食品添加剂监管策略,从而保障食品安全和健康,在化学分析和传感领域具有巨大的潜力和广阔的应用前景。
附图说明
为了便于本领域技术人员理解,下面结合附图对本发明作进一步的阐述说明。
图1Eu-MOF的合成及添加GA后的变色过程。
图2基于硼酸功能化的多发射金属有机骨架化合物对没食子酸的荧光可视化检测。
图3(a)Eu-MOF在无GA时的荧光传感机理;(b)Eu-MOF在GA存在下的荧光传感机理;(c)Eu-MOF的吸收、迁移和发射示意图;(d)Eu-MOF的吸收、迁移和发射示意图,其中A表示270nm处的吸收,F表示荧光,P表示磷光。(ISC:系统间交叉;ET:能量转移;S:单线态;T:三线态)。
图4(a)Eu-MOF的SEM图像表征;(b)Eu-MOF构建单元中Eu3+离子配位环境的EDX元素映射;(c)BBDC和Eu-MOF的傅立叶变换红外光谱;(d)Eu-MOF、Eu-MOF 2和BBDC的粉末XRD图谱。
图5(a)不加GA的Eu-MOF荧光探针在20~40℃时的荧光光谱;(b)40mM GA比色荧光探针在20~40℃处的荧光光谱;(c)温度对Eu-MOF检测GA的影响。(I615/I454)为添加40mM GA时的荧光强度比,(I615/I454)0为未添加GA时的荧光强度比。
图6(a)不加GA的情况下Eu-MOF在pH值为2~13时的荧光光谱;(b)加入GA的情况下Eu-MOF在pH为2~13时的荧光光谱;(c)pH对Eu-MOF检测GA的影响。(I615/I454)为添加40mMGA时的荧光强度比,(I615/I454)0为未添加GA时的荧光强度比。
图7(a)室温下2mg mL-1Eu-MOF的荧光稳定性;(b)Eu-MOF荧光探针对GA的响应时间。
图8(a)Eu-MOF在加入不同浓度GA后的荧光光谱(Ex=270nm,c=0.2mg mL-1);(b)(I615/I454)强度比与GA浓度的曲线图。
图9Eu-MOF对不同干扰物质的选择性和抗干扰性。黑色直方图显示了Eu-MOF对不同样本的选择性,红色直方图显示了Eu-MOF对不同样本的抗干扰能力。在365nm紫外光照射下拍摄相应的荧光图像。
图10(a)智能手机RGB颜色识别APP在24孔石英板上对GA进行视觉检测;(b)在RGB颜色识别App上添加不同浓度的GA和线性关系拟合图得到相应的识别色块。
具体实施方式
下述实施例是对于本发明内容的进一步说明以作为对本发明技术内容的阐释,但本发明的实质内容并不仅限于下述实施例所述,本领域的普通技术人员可以且应当知晓任何基于本发明实质精神的简单变化或替换均应属于本发明所要求的保护范围。
本发明提供出一种基于硼酸功能化的多发射金属有机骨架化合物对没食子酸的荧光可视化检测,设计的Eu-MOF荧光探针具有灵敏度高,选择性好等特点。
实施例:
1、Eu-MOF的制备
采用简单优化的溶剂热法制备了具有硼酸功能的Eu-MOF。在DMF/H2O体积比为7:3的溶液中,将0.1~0.4mM的EuCl3·6H2O与0.1~0.3mM的BBDC混合,剧烈搅拌10~30min。将产物置于含有50~70mL聚四氟乙烯内衬的不锈钢高压釜中,120~150℃加热12~24h,室温冷却,分别用DMF和乙醇清洗样品后离心。产品在40~60℃真空烘箱中干燥,得到了白色的Eu-MOF粉末。
2、没食子酸的荧光检测
设置激发波长为240~280nm,采用荧光分光光度法进行检测。激发和发射的狭缝宽度均设为5~20nm。在300~800nm范围内记录其荧光光谱。将2~5mg的Eu-MOF分散到10~40mL去离子水中,制备探针溶液。将一定量没食子酸溶于无水乙醇中,得到浓度为1.0~5.0μM的分析溶液。随后使1~3mL Eu-MOF探针溶液与GA分析溶液混合,并用去离子水稀释并充分混匀后,转移到石英比色皿中,在紫外灯下进行荧光检测。荧光颜色变化的图像是在黑暗的环境中使用相机拍摄,为保证实验结果的可靠性,每个样本至少测量三次,取平均值后再进行下一步实验。
3、Eu-MOF的传感机制、组分表征、检测条件的优化和对GA的响应
3a、Eu-MOF荧光体系传感机制
Eu-MOF在270nm紫外激发下具有明显的双发射峰。一方面,Eu-MOF中的配体对Eu3+离子的发光具有敏化和协同增强作用,另一方面,配体中的硼酸基对Eu-MOF中不完全的能量转移效率具有调节作用。由于硼酸基可以与苯环上的羟基共价结合,当GA加入体系中时,配体中的硼酸基与GA形成硼酸酯键。结果导致配体的荧光强度增强,而Eu3+离子的荧光强度明显降低。通过调节自身的能量传递效率,可以实现Eu-MOF对GA的检测,并很容易在紫外灯下观察到荧光颜色的明显变化,实现对GA的准确、快速可视化检测。
3b、Eu-MOF荧光体系组分表征
考虑到探针对分析物的检测灵敏度与其本身的性质有关,分别使用FT-IR,UV-vis和荧光光谱研究了Eu3+、BBDC配体和Eu-MOF探针的结构特征和光谱特性。此外,使用SEM和EDX来确定Eu-MOF的形貌以及其Eu3+在其中的分布情况。
3c、Eu-MOF荧光体系对GA的响应
由于荧光探针对分析物的检测与其荧光强度有关,通过适当的配比,制备了Eu-MOF荧光探针,该探针在紫外光照射下发出强烈的红色荧光。由于眼睛对红色很敏感,加入GA后,在270nm激发下,荧光探针在紫外光照射下呈现蓝色荧光,由此产生较为明显的视觉颜色变化。此外,荧光光谱也被用于研究Eu-MOF荧光探针的稳定性,它们在24h内的稳定性都很好。所设计的Eu-MOF荧光探针用于GA的检测是可行的。
3d、温度和pH对荧光探针的影响
温度和pH值对Eu-MOF探针的荧光强度有一定的影响。温度的变化对合成的比例荧光探针的荧光强度影响不大。加入GA后,不同温度下Eu-MOF探针的荧光强度相似。从图5还可以看出,不同温度下I615/I454与(I615/I454)0的比值相似,说明温度对GA检测的影响不大。所以综合考虑,本发明中Eu-MOF探针的合成选择20℃作为最佳温度。
同样,当溶液体系的pH<6时,Eu-MOF探针的荧光强度在454nm和615nm处下降。Eu-MOF探针在pH=6的270nm激发下荧光强度最大,这是因为Eu-MOF与GA在弱酸性条件下容易发生反应。当溶液pH>6时,在pH=7~9和pH=11~13时,Eu-MOF探针的荧光强度分别在454nm和615nm处下降。虽然pH=9时,Eu-MOF探针在454nm处的荧光强度高于pH=6时,但在615nm处的荧光强度远低于pH=6时。基于以上原因,本发明最终选择pH=6作为最佳反应条件。
3e、Eu-MOF荧光体系的选择性和抗干扰能力
对于出色的荧光传感系统,重要的是要对GA具有良好的选择性,即使在存在干扰物的情况下也可以保持对GA的选择性响应。因此,进行了一系列实验以探索Eu-MOF传感系统在检测GA中的选择性和抗干扰能力。在相同条件下,选择Cu2+,Fe3+,Ca2+,Mg2+,K+,Cl-,F-,HCO3 -,NO3 -,SO4 2-,谷氨酸,赖氨酸,丙氨酸,甘氨酸和精氨酸等物质,评价了Eu-MOF荧光传感系统对GA的选择性。
4、利用智能手机颜色识别器对GA的检测
将含有0.5~1.0mg mL-1的Eu-MOF悬浊液超声处理1~3min,使溶液呈现均匀状态。将Eu-MOF悬浊液均匀滴入石英多孔板的凹槽中,然后加入不同浓度的GA标准溶液。当含有Eu-MOF的石英板中GA达到一定含量时,在紫外灯下可观察到明显的荧光颜色变化。荧光照片的红-绿-蓝值(RGB值)对应的颜色信息可以通过智能手机的颜色识别应用程序(APP)获取。因此,通过分析RGB值来定量检测没食子酸。为了保证数据的准确性,反复实验三次,得到R/B的平均值,R/B表示红色和蓝色信息的比例。
5、Eu-MOF对实际样品中GA的分析
为评价其可行性,采用Eu-MOF探针测定不同类型茶和橙汁中GA的含量。准确称取1.0~3.0g绿茶、红茶、乌龙茶,用60~90mL沸水浸泡三次,过滤后移入100mL烧瓶中。取0.5~1.0mL样品溶液测定红茶、绿茶等实样中GA的含量。另外,在实际样品中加入不同量的GA标准品进行了回收试验。在进行橙汁中GA的测定时,取橙汁样品20~50mL,过滤后转至100mL容量瓶中,稀释至刻度作为样品储备液。后续测定方法与红茶、绿茶的测定方法一致。
表1Eu-MOF和HPLC对茶和果汁中GA的分析结果
Claims (6)
1.一种基于硼酸功能化的多发射金属有机骨架化合物Eu-MOF,其特征在于:
所述多发射金属有机骨架化合物Eu-MOF是由硼酸配体与金属铕离子配位聚合获得的铕金属有机骨架化合物;所述硼酸配体为3,5-二羧基苯硼酸;
所述多发射金属有机骨架化合物Eu-MOF是采用溶剂热法制备获得,包括如下步骤:
在混合溶剂中,将0.1~0.4mM的EuCl3·6H2O与0.1~0.3 mM的3,5-二羧基苯硼酸混合,剧烈搅拌10~30 min;将反应液置于含有聚四氟乙烯内衬的不锈钢高压釜中,120~150℃加热反应12~24 h,室温冷却,分别用DMF和乙醇清洗样品后离心,真空干燥,得到白色的Eu-MOF粉末;
EuCl3·6H2O与3,5-二羧基苯硼酸的投料比为1-4:1-3。
2.根据权利要求1所述的多发射金属有机骨架化合物Eu-MOF,其特征在于:
所述Eu-MOF具有单波长激发下多发射的特性,在270 nm的紫外激发下,于454 nm和615nm处产生双发射而显示红色荧光。
3.根据权利要求1所述的多发射金属有机骨架化合物Eu-MOF,其特征在于:
所述混合溶剂是由DMF和H2O按体积比7:3的比例复配构成。
4.权利要求1-3中任一项所述多发射金属有机骨架化合物Eu-MOF的应用,其特征在于:
所述多发射金属有机骨架化合物Eu-MOF在没食子酸的检测过程中作为检测试剂使用。
5.根据权利要求4所述的应用,其特征在于:
没食子酸与Eu-MOF反应将MOF配体中的-B(OH)2转化为-BOO-,从BBDC配体到Eu3+的系统转换效率降低使Eu3+的红色发射减弱,而与没食子酸结合的BBDC呈现的蓝色发射增强,其Eu-MOF探针颜色呈现出由红色到蓝色的连续变化,通过Eu-MOF荧光体系中荧光变化程度来检测样品中没食子酸的含量。
6.根据权利要求4或5所述的应用,其特征在于:
检测体系的pH=6。
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