CN109266330A - 一种亚硫酸根稀土荧光探针及其制备方法和应用 - Google Patents
一种亚硫酸根稀土荧光探针及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种亚硫酸根稀土荧光探针,所述亚硫酸根稀土荧光探针是通过三价稀土铽离子和四价稀土铈离子与间苯二甲酸通过溶剂热反应生成的金属有机框架纳米粒子。该亚硫酸根荧光探针利用铈离子氧化亚硫酸根的氧化还原反应敏化稀土铽离子的发光的新原理检测亚硫酸根离子。本发明还公开了这种亚硫酸根荧光探针的制备方法和测定亚硫酸根的应用。本发明的亚硫酸根稀土荧光探针特异性强、能快速、高灵敏测定溶液中的亚硫酸根离子,可应用于生物样品、环境水等中的亚硫酸根的测定。
Description
技术领域
本发明涉及一种检测亚硫酸根的稀土荧光探针,还涉及这种荧光探针的制备方法和应用,属于发光检验技术领域。
背景技术
二氧化硫是一种主要的大气污染物,常以亚硫酸根形式存在。然而过量的亚硫酸根会危害人类健康,比如导致呼吸系统问题,神经系统紊乱,引发肺癌等。因此亚硫酸根的监测对环境保护具有重要的意义。在检测亚硫酸根的各种方法中,荧光探针因为高选择性和高灵敏性被广泛应用于亚硫酸根离子的检测。
已报道的亚硫酸根检测方法有:中国专利公布号CN 105466894A,2016年,瞿金清,杨小东,刘瑞源,一种应用三苯胺类染料检测亚硫酸根的方法,公开了一种用三苯胺类染料检测亚硫酸根离子的方法;中国专利公布号CN 108299424A,2018年,葛燕青,段桂运,吉瑞雪,董建,咪唑并吡啶吲哚类亚硫酸根离子比率荧光探针及其应用,公开了一种3,3-二甲基-1-乙基-2-(N-(1-氯-3-丁基-7-咪唑并[1,5-a]吡啶甲酰基)-4-(哌嗪基)-苯基乙烯)吲哚碘化物测定亚硫酸根离子的方法;中国专利公布号CN 104804729A,2015年,宋相志,一种荧光增强型亚硫酸根荧光探针的制备及应用,公开了一种2-羟基-6-乙酰基萘分子探针荧光检测亚硫酸根的方法;中国专利公布号CN 105136695A,2015年,梁英,陈嫚,伍婵翠,一种基于OPA-NH4 +-SO3 2-反应的亚硫酸根离子的分光测定方法及其应用,公开了一种用邻苯二甲醛和氨氮溶液分光光度法测定亚硫酸根离子的方法;中国专利号CN 102659677A,2012年,宋相志,陈颂,一种裸眼和荧光比值检测亚硫酸根离子荧光分子探针及其合成和应用,公开了一种以4-羟基萘酰亚胺为原料与乙酰丙酸缩合而成的荧光分子探针,可目视和荧光检测亚硫酸根离子;王姣亮,龙立,平谢丹,魏太保报道了一种以香豆素343和2-苯并噻唑乙腈为原料合成的基于香豆素343的荧光探针检测亚硫酸根的方法(应用化学,2016,7,841-847),;刘彩,马卫兴,路源报道了基于亚硫酸根离子可将三价铁离子还原为亚铁离子,后者与2,2'-联吡啶形成红色的配合物,分光光度法测定烟气中二氧化硫的新方法(化学试剂,2017,39,501-504),X.Yang等报道了一种基于罗丹明的荧光探针在乙醇溶液中测定亚硫酸根离子的方法(Sensors and Actuators B:chemical,2011,152,8-13);M Gómez等报道了一种基于异恶唑衍生物的荧光探针检测二氧化硫衍生物的方法(Sensors and ActuatorsB:Chemical,2017,238,578-587)。报道的这些亚硫酸根检测方法大多使用合成的分子探针,分子探针需复杂的有机合成,且常常难溶于水,不得不使用有机溶剂-水混合相测定。因此,有必要开发制备方法简单、测定快速、在水溶液中应用的亚硫酸根探针。
发明内容
发明目的:本发明的目的是提供一种检测亚硫酸根(SO3 2-)的稀土荧光探针,能在水溶液中简单快速地测定亚硫酸根浓度。
本发明的第二个目的是提供这种亚硫酸根稀土荧光探针的制备方法,一种简便、快速的制备方法。
本发明的第三个目的是提供上述稀土荧光探针检测亚硫酸根的应用。
技术方案:为实现上述第一个目的,本发明采用的技术方案为:一种亚硫酸根稀土荧光探针,所述的亚硫酸根稀土荧光探针是通过三价稀土铽离子(Tb3+)和四价稀土铈离子(Ce4+)与间苯二甲酸(PA)通过溶剂热反应生成的金属有机框架纳米粒子。
其中,所述的亚硫酸根稀土荧光探针中间苯二甲酸作为桥连配体分别配位连接稀土铽离子和铈离子,生成的金属有机框架纳米粒子为球形纳米粒子,粒径大小50-250nm。
其中,所述荧光探针通过四价稀土铈离子和亚硫酸根离子的氧化还原反应敏化稀土铽离子的发光检测亚硫酸根。
具体的,本发明的亚硫酸根稀土荧光探针利用四价铈离子氧化亚硫酸根离子的氧化还原反应能量敏化稀土铽离子的发光原理检测亚硫酸根离子。
为实现上述第二个目的,本发明采用的技术方案为:一种亚硫酸根稀土荧光探针的制备方法,包括以下步骤:向间苯二甲酸的N,N'二甲基甲酰胺溶液中加入硝酸铽水溶液和硝酸铈铵水溶液,构成间苯二甲酸:铽离子:铈离子的摩尔比为2:1:1的混合液;搅拌20分钟后转入反应釜,在130℃高温反应5小时之后离心收集浅黄色沉淀,沉淀用乙醇、纯水洗涤后干燥备用。
上述方法合成制备的产物经元素分析含有铽离子、铈离子和间苯二甲酸;红外光谱分析显示C=O峰和C-O峰分别从1695和1257cm-1移动到1627和1161cm-1,表明铽离子和铈离子通过与间苯二甲酸的羧基配位相连。
为实现上述第三个目的,本发明还提供了一种亚硫酸根稀土荧光探针在检测亚硫酸根离子中的应用。
其中,用亚硫酸根稀土荧光探针检测水溶液中亚硫酸根离子具体的应用为:取一定量的亚硫酸根稀土荧光探针悬浮液加入到样品溶液中,加入磷酸缓冲溶液,混合后用荧光分光光度计测定混合液在545nm波长下铽离子的特征荧光强度,根据铽离子荧光强度与亚硫酸根离子浓度的工作曲线测得待测样品的亚硫酸根离子含量。
本发明还提供了一种通过化学反应敏化稀土离子发光的方法,通过四价铈离子和亚硫酸根离子的氧化还原反应敏化稀土铽离子的发光。
本发明的一种氧化还原反应敏化稀土离子发光的方法,不局限于上述氧化还原反应对稀土离子发光的敏化,所有的通过化学反应敏化稀土离子发光的方法均包含在本发明的保护范围之内。
有益效果:与现有技术相比,本发明具有如下的特色及优点:
1)与已报道的亚硫酸根探针或测定方法相比,本发明制备的亚硫酸根荧光探针采用了新的测定原理,利用四价铈离子氧化亚硫酸根离子的氧化还原反应能量敏化稀土铽离子的发光原理检测亚硫酸根离子。
2)本发明的亚硫酸根荧光探针利用稀土离子发光,稀土离子长的荧光寿命允许通过时间分辨荧光技术消除各种非特异性荧光(如背景荧光或干扰荧光)的干扰,能获得高的信噪比,对测定具有很强的背景荧光的样品(如生物样品)中亚硫酸根离子具有优势。
3)本发明的亚硫酸根荧光探针的制备方法简便、无需复杂的有机合成。
4)本发明的亚硫酸根荧光探针响应亚硫酸根小于30秒,速度快具有即时选择性荧光指示亚硫酸根浓度的功能;灵敏度高,检测限低达1nM;为检测生物样品、环境水、生产废水中的亚硫酸根离子提供了一种简便、快速的方法。
附图说明
图1、亚硫酸根稀土荧光探针Tb-PA-Ce的透射电镜图;
图2、亚硫酸根稀土荧光探针Tb-PA-Ce对亚硫酸根浓度的荧光响应;
图3、亚硫酸根稀土荧光探针Tb-PA-Ce测定亚硫酸根的工作曲线;
图4、亚硫酸根稀土荧光探针Tb-PA-Ce测定亚硫酸根的响应时间;
图5、亚硫酸根稀土荧光探针Tb-PA-Ce测定亚硫酸根的选择性。
具体实施方式
下面结合附图和实施例,对本发明的技术方案进行详细说明。
实施例1亚硫酸根稀土荧光探针Tb-PA-Ce的制备
将1mL间苯二甲酸水溶液(20mM)加入5mL N,N'二甲基甲酰胺(DMF)溶液中,再加入1mL浓度为10mM的Tb(NO3)3水溶液和1mL浓度为10mM的Ce(NH4)2(NO3)6水溶液,构成间苯二甲酸:铽离子:铈离子的摩尔比为2:1:1的混合液。搅拌20分钟后转入高温反应釜,在130℃温度下反应5个小时,之后冷却至室温离心收集浅黄色沉淀,沉淀用乙醇、超纯水分别洗涤三次后于80℃烘箱中干燥后备用。图1是制备的亚硫酸根稀土荧光探针Tb-PA-Ce的透射电镜图,Tb-PA-Ce为球形纳米粒子,平均粒径约为100nm。
实施例2亚硫酸根稀土荧光探针Tb-PA-Ce对水溶液中亚硫酸根离子的荧光响应
取20μL的实施例1制备的亚硫酸根稀土荧光探针Tb-PA-Ce悬浮液(1.5mg/mL)加入到960μL的磷酸缓冲溶液中得到混合液,将20μL一定浓度的亚硫酸根离子溶液分别加入到上述混合液中,分别制成含亚硫酸根0,1,10,50,80,100,150,200,300μM的混合溶液,测定这些混合溶液在545nm波长下铽离子的荧光强度。图2是这些混合溶液的荧光光谱图,亚硫酸根稀土荧光探针Tb-PA-Ce的荧光强度随溶液中亚硫酸根离子浓度的增加而增加,并且在0-200μM浓度范围内,亚硫酸根稀土荧光探针Tb-PA-Ce的荧光强度与亚硫酸根离子的浓度成线性关系(图3),可作为测定亚硫酸根离子的工作曲线,检测亚硫酸根离子的检测限低达1nM。
本发明制备的亚硫酸根稀土荧光探针Tb-PA-Ce具有良好的测定选择性,如图4所示,在100μM的阴离子PO4 3-、CO3 2-、Ac-、ClO-、Cl-、NO3 -、NO2 -、SO3 2-和SO4 2-存在下,用亚硫酸根稀土荧光探针Tb-PA-Ce测定亚硫酸根离子无干扰。
本发明制备的亚硫酸根稀土荧光探针Tb-PA-Ce测定亚硫酸根离子具有快的响应时间,在30秒内能迅速响应亚硫酸根离子的存在(图5)。
实施例3亚硫酸根稀土荧光探针Tb-PA-Ce测定人血清中亚硫酸根离子
取人血清样本1mL,用水稀释20倍后备用。将10μL一定浓度的亚硫酸根离子溶液和10μL人血清样本加入到960μL的磷酸缓冲溶液中制成分别含亚硫酸根20,100,500nM的人血清样品溶液。取20μL实施例1制备的亚硫酸根稀土荧光探针Tb-PA-Ce悬浮液(2mg/mL)分别加入到配置好的人血清样品溶液中,分别测定这些样品溶液在545nm波长下Tb3+的荧光强度,根据实施例2中的亚硫酸根稀土荧光探针的荧光强度与亚硫酸根浓度的工作曲线及测得的样品溶液的荧光强度得到亚硫酸根的浓度。表1是测定人血清样品中亚硫酸根离子的结果。
表1
结果显示制备的亚硫酸根稀土荧光探针可测定具有复杂成分的人血清样品中的亚硫酸根浓度,具有高的灵敏度。
显然,上述实施例仅仅是为清楚地说明本发明所作的举例,而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动,这里无需也无法对所有的实施方式予以穷举,这些引伸出的变化或变动也处于本发明的保护范围之中。
Claims (8)
1.一种亚硫酸根稀土荧光探针,其特征在于,所述亚硫酸根稀土荧光探针是通过三价稀土铽离子和四价稀土铈离子与间苯二甲酸通过溶剂热反应生成的金属有机框架纳米粒子。
2.根据权利要求1所述的一种亚硫酸根稀土荧光探针,其特征在于,所述金属有机框架纳米粒子为球形纳米粒子,粒径大小50~250 nm。
3.根据权利要求1所述的一种亚硫酸根稀土荧光探针,其特征在于,所述间苯二甲酸:铽离子:铈离子的摩尔比为2:1:1。
4.根据权利要求1所述的一种亚硫酸根稀土荧光探针,其特征在于,所述荧光探针通过四价稀土铈离子和亚硫酸根离子的氧化还原反应敏化稀土铽离子的发光检测亚硫酸根。
5.权利要求1~3任一项所述的一种亚硫酸根稀土荧光探针的制备方法,其特征在于,包括以下步骤:向间苯二甲酸的N,N'二甲基甲酰胺溶液中加入硝酸铽水溶液和硝酸铈铵水溶液,构成间苯二甲酸:铽离子:铈离子的摩尔比为2:1:1的混合液;搅拌20分钟后转入反应釜,在130℃高温反应5小时之后离心收集浅黄色沉淀,沉淀用乙醇、纯水洗涤后干燥备用。
6.权利要求1~3任一项所述的一种亚硫酸根稀土荧光探针在检测亚硫酸根中的应用。
7.根据权利要求5所述的应用,其特征在于:通过将亚硫酸根稀土荧光探针悬浮液加入到样品溶液中,混合后用荧光分光光度计测定混合液的铽离子特征荧光强度,根据铽离子荧光强度与亚硫酸根离子浓度的工作曲线测得样品溶液的亚硫酸根离子含量。
8.一种通过化学反应敏化稀土离子发光的方法,其特征在于,通过四价铈离子和亚硫酸根离子的氧化还原反应敏化稀土铽离子的发光。
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