CN110627756B - 一种用于检测次氯酸根的比色-荧光探针及其制备方法和用途 - Google Patents
一种用于检测次氯酸根的比色-荧光探针及其制备方法和用途 Download PDFInfo
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Abstract
本发明提供了一种用于检测次氯酸根的比色‑荧光探针及其制备方法和用途,该比色‑荧光探针由醛基化的苯胺与2‑(3‑氰基‑4,5,5‑三甲基呋喃‑2(5H)‑酰基)丙烯腈吸电子基团通过克脑文盖儿缩合,即得到比色‑荧光探针(E)‑((4‑(2‑(4‑氰基‑5‑(二氰基亚甲基)‑2,2‑二甲基‑2,5‑二氢呋喃‑3‑基)乙烯基)苯基)氮烷二基)双(乙烷‑2,1‑二基)二丙烯酸酯,该探针对次氯酸根的响应基团为C=C双键,单独的探针在有机溶剂与水的混合溶液中,其荧光发射峰位在632 nm,紫外吸收峰位在544 nm,用于对次氯酸根的检测时,表现出明显的荧光猝灭和褪色响应,响应速度快,可实现次氯酸根的实时检测;检测灵敏度高,检测限低达0.19 uM;可以准确地测定环境中水样及非制式爆炸物原料中的次氯酸根含量。
Description
技术领域
本发明属于环境和非制式爆炸物检测领域,提供了一种用于检测次氯酸根的比色-荧光探针及其制备方法和用途。本比色-荧光探针检测限低、抗干扰性强和反应时间短,可实现低成本、实时比色-荧光双模检测次氯酸根的目的。
背景技术
由于次氯酸根的氧化性,被广泛用于水的净化、纸浆漂白,医药工业中制氯胺等领域。而次氯酸根作为一种非常重要的活性氧,无论是在生物体内还是饮用水中都具有不可替代的作用。生物体内产生或积累过量的次氯酸根,会引起多种疾病,如心血管疾病,炎症性疾病,癌症等病症的发生。除此之外,美国FBI部门将Ca(ClO)2列为非制式爆炸物的一种重要氧化剂;英国国防科技实验室Marshall将Ca(ClO)2列为爆炸物组分的潜在原料。因此,实现对环境中水样及非制式爆炸物原料中次氯酸根的高灵敏、快速、专一性检测至关重要。
目前,国内外的科学家们主要从生物健康和环境卫生角度考虑,采取了很多方法对生物体内及饮用水、游泳池中的次氯酸根进行检测。常见的次氯酸根检测手段主要是分光光度法、化学发光分析法、电位滴定法、库仑滴定法和电流分析法等。这些分析方法需要昂贵的仪器及专业的操作人员。因此,快捷、廉价、准确、实时的次氯酸根检测手段的开发成为研究的重点。
与上述检测方法相比,荧光探针检测由于其高灵敏度、高选择性、操作简单、实时分析等优点而被广泛地应用,其分子结构主要是在荧光团上连接上述可与次氯酸根发生特异性反应的活性位点,如硫原子,酰肼,C=N,缺电子烯烃,对甲氧基苯酚,1,8-萘酰亚胺等,常使用的荧光团包括罗丹明,荧光素,硼-二吡咯亚甲基(BODIPY),花青染料,萘酮,香豆素,铱(III)络合物,萘二甲酰亚胺,苯并噻唑衍生物,苯并恶唑等。然而,大多数荧光探针仍然存在检测限差,量子产率低,摩尔吸光系数低,氧化反应时间延迟以及抗干扰性差等缺点。
本发明从探针分子本身的结构分析,设计制备了以苯胺为电子给体,以2-(3-氰基-4,5,5-三甲基呋喃-2(5H)-酰基)丙烯腈强吸电子基团作为电子受体,以不饱和烯烃作为次氯酸根反应位点的D-π-A型结构的比色-荧光双模检测探针,可以增加摩尔吸光系数及荧光强度,从而实现对次氯酸根的现场、快速、专一、痕量、可视化检测。
发明内容
本发明目的在于,针对现有技术中存在的不足,提供一种用于检测次氯酸根的比色-荧光探针及其制备方法和用途,所述的比色-荧光探针化学名称为(E)-((4-(2-(4-氰基-5-(二氰基亚甲基)-2,2-二甲基-2,5-二氢呋喃-3-基)乙烯基)苯基)氮烷二基)双(乙烷-2,1-二基)二丙烯酸酯,由醛基化的苯胺与2-(3-氰基-4,5,5-三甲基呋喃-2(5H)-酰基)丙烯腈吸电子基团通过克脑文盖儿缩合得到,该荧光探针对次氯酸根的响应基团为C=C双键,单独的探针在有机溶剂与水的混合溶液中,其荧光发射峰位在632nm,紫外吸收峰位在544nm,用于对次氯酸根的检测时,表现出明显的荧光猝灭和褪色响应,响应速度快,可实现次氯酸根的实时检测;检测灵敏度高,检测限低达0.19uM;对次氯酸根具有较高的选择性,其他常见氧化性物质无干扰;利用标准曲线,可以准确地测定环境中水样及非制式爆炸物原料中的次氯酸根含量。
本发明所述的一种用于检测次氯酸根的比色-荧光探针,该荧光探针的化学结构式为(Ⅰ):
其中该荧光探针的化学名称为:(E)-((4-(2-(4-氰基-5-(二氰基亚甲基)-2,2-二甲基-2,5-二氢呋喃-3-基)乙烯基)苯基)氮烷二基)双(乙烷-2,1-二基)二丙烯酸酯。
所述一种用于检测次氯酸根的比色-荧光探针的制备方法,按下列步骤进行:
a、将N-苯基二乙醇胺溶于有机溶剂乙醚、氯仿、四氢呋喃或二氯甲烷,加入有机碱为三乙胺、哌啶或吡啶,温度0℃下加入丙烯酰氯,反应12h,萃取,去离子水洗至中性、无水硫酸镁干燥、抽滤、旋干后得中间产物1(苯基氮杂二基)双(乙烷-2,1-二基)二丙烯酸酯,其中N-苯基二乙醇胺与丙烯酰氯和有机碱的摩尔比为1:2-4:2-4;
b、将三氯氧磷滴入N,N-二甲基甲酰胺中,反应2h后滴入步骤a得到的中间产物1,升温至75℃,反应12h后冷却至室温,加入有机溶剂乙醚、氯仿、四氢呋喃或二氯甲烷,温度0℃,滴入乙酸钠的水溶液,室温反应12h,萃取,得中间产物2((4-甲酰基苯基)氮杂二基)双(乙烷-2,1-二基)二丙烯酸酯,其中中间产物1与三氯氧磷和N,N-二甲基甲酰胺的摩尔比为1:1:2-5;
c、将步骤b得到的中间产物2溶于有机溶剂乙醇、二氯甲烷、氯仿、四氢呋喃、N,N-二甲基甲酰胺或N,N-二甲基乙酰胺中,加入2-(3-氰基-4,5,5-三甲基呋喃-2(5H)-酰基)丙烯腈,其中中间产物2与2-(3-氰基-4,5,5-三甲基呋喃-2(5H)-酰基)丙烯腈的摩尔比为1:1-1.2,回流6h,冷却至室温后旋干,加入溶剂10mL二氯甲烷,再加入100mL甲醇,室温下旋干,抽滤重结晶后,即得检测次氯酸根的比色-荧光探针分子(E)-((4-(2-(4-氰基-5-(二氰基亚甲基)-2,2-二甲基-2,5-二氢呋喃-3-基)乙烯基)苯基)氮烷二基)双(乙烷-2,1-二基)二丙烯酸酯。
所述一种用于检测次氯酸根的比色-荧光探针在检测环境中水样及非制式爆炸物原料中次氯酸根的定性或定量中的用途。
本发明所述的一种用于检测次氯酸根的比色-荧光探针及其制备方法和用途,其中比色-荧光探针(E)-((4-(2-(4-氰基-5-(二氰基亚甲基)-2,2-二甲基-2,5-二氢呋喃-3-基)乙烯基)苯基)氮烷二基)双(乙烷-2,1-二基)二丙烯酸酯,其结构式为:
所述的检测次氯酸根比色-荧光探针(E)-((4-(2-(4-氰基-5-(二氰基亚甲基)-2,2-二甲基-2,5-二氢呋喃-3-基)乙烯基)苯基)氮烷二基)双(乙烷-2,1-二基)二丙烯酸酯的合成路线为:
该比色-荧光探针(E)-((4-(2-(4-氰基-5-(二氰基亚甲基)-2,2-二甲基-2,5-二氢呋喃-3-基)乙烯基)苯基)氮烷二基)双(乙烷-2,1-二基)二丙烯酸酯能与次氯酸根发生专一性反应,在544nm处出现褪色,在632nm处出现荧光猝灭;
检测方法为:
将本发明所述的探针分子(E)-((4-(2-(4-氰基-5-(二氰基亚甲基)-2,2-二甲基-2,5-二氢呋喃-3-基)乙烯基)苯基)氮烷二基)双(乙烷-2,1-二基)二丙烯酸酯溶解于水与四氢呋喃的混合体系中,分别加入浓度为5uM、10uM、20uM、30uM、40uM、50uM、100uM、500uM、1mM、2mM、3mM、4mM、5mM、6mM、7mM的次氯酸根溶液,测试其在632nm处的荧光强度和544nm处的紫外吸收强度,然后以溶液在632nm处的荧光发射强度和544nm处的紫外吸收强度对次氯酸根的浓度做标准图,根据标准图,定量检测环境中水样及非制式爆炸物原料中次氯酸根的含量。结果表明:该比色-荧光探针可实现对环境中水样及非制式爆炸物原料中的次氯酸根的现场、快速、专一、痕量、可视化检测;
本发明用N-苯基二乙醇胺和2-(3-氰基-4,5,5-三甲基呋喃-2(5H)-酰基)丙烯腈吸电子基为原料,通过克脑文盖儿缩合反应制备D-π-A型比色-荧光探针(E)-((4-(2-(4-氰基-5-(二氰基亚甲基)-2,2-二甲基-2,5-二氢呋喃-3-基)乙烯基)苯基)氮烷二基)双(乙烷-2,1-二基)二丙烯酸酯,该系列探针能专一性地识别次氯酸根,在544nm处出现褪色,在632nm处出现荧光猝灭,反应位点为C=C双键。
与现有技术相比,本发明的有益效果是:
本发明中制备的比色-荧光探针(E)-((4-(2-(4-氰基-5-(二氰基亚甲基)-2,2-二甲基-2,5-二氢呋喃-3-基)乙烯基)苯基)氮烷二基)双(乙烷-2,1-二基)二丙烯酸酯可实现对环境中水样及非制式爆炸物原料中的次氯酸根的现场、快速、专一、痕量、可视化检测,在632nm处出现荧光猝灭,在544nm处出现褪色变化;无需将待测物进行前处理即可实现检测,操作简单,便捷,高效。
附图说明
图1为本发明在四氢呋喃和水的混合溶剂中,比色-荧光探针分子的浓度为5uM的检测液3mL,分别与30uL的5uM-7mM的次氯酸根水溶液反应后的紫外吸收光谱图;
图2为本发明在四氢呋喃和水的混合溶剂中,比色-荧光探针分子的浓度为5uM的检测液3mL,分别与30uL的5uM-7mM的次氯酸根水溶液反应后的荧光光谱图;
图3为本发明在四氢呋喃和水的混合溶剂中,3mL的5uM的比色-荧光探针分子,分别加入30uL的7mM的次氯酸根、氯酸根+次氯酸根、高氯酸根+次氯酸根、硝酸铵+次氯酸根、过硫酸根+次氯酸根水溶液反应后的紫外吸收光谱图;
图4为本发明在四氢呋喃和水的混合溶剂中,3mL的5uM的比色-荧光探针分子,分别加入30uL的7mM的次氯酸根、氯酸根+次氯酸根、高氯酸根+次氯酸根、硝酸铵+次氯酸根、过硫酸根+次氯酸根水溶液反应后的荧光光谱图;
图5为本发明在四氢呋喃和水的混合溶剂中,3mL的5uM的比色-荧光探针分子,分别加入30uL的7mM的次氯酸根、氯酸根、高氯酸根、硝酸铵、过硫酸根水溶液反应后的紫外吸收光谱图;
图6为本发明在四氢呋喃和水的混合溶剂中,3mL的5uM的比色-荧光探针分子,分别加入30uL的7mM的次氯酸根、氯酸根、高氯酸根、硝酸铵、过硫酸根水溶液反应后的荧光光谱图;
图7为本发明中比色-荧光探针检测不同浓度次氯酸根时吸收峰强随次氯酸根浓度变化的曲线;
图8为本发明中比色-荧光探针检测不同浓度次氯酸根时荧光峰强随次氯酸根浓度变化的曲线。
具体实施方式
下面通过具体实施例对本发明做进一步的说明,但发明不限制于这些实施例。
实施例1
a、将5mmol N-苯基二乙醇胺溶于50mL有机溶剂乙醚中,加入20mmol有机碱为三乙胺,温度0℃加入20mmol丙烯酰氯,室温反应12h,萃取,去离子水洗至中性、无水硫酸镁干燥、抽滤、旋干后得中间产物1(苯基氮杂二基)双(乙烷-2,1-二基)二丙烯酸酯4.6mmol,产率为92%;
b、将4.6mmol三氯氧磷在温度0℃下滴入23mmol N,N-二甲基甲酰胺中,反应2h后滴入步骤a得到的4.6mmol中间产物1,升温至75℃,反应12h后冷却至室温,加入有机溶剂乙醚,温度0℃,取30mmol无水乙酸钠溶于50mL去离子水中配制乙酸钠的水溶液,再将配制的乙酸钠的水溶液滴入反应物中,室温反应12h,萃取,得中间产物2((4-甲酰基苯基)氮杂二基)双(乙烷-2,1-二基)二丙烯酸酯4.186mmol,产率91%;
c、将步骤b得到的4.186mmol中间产物2溶于10mL有机溶剂乙醇中,加入4.186mmol2-(3-氰基-4,5,5-三甲基呋喃-2(5H)-酰基)丙烯腈,回流6h,冷却至室温后旋干,加入溶剂10mL二氯甲烷,再加入100mL甲醇,室温下旋干,抽滤重结晶后,即得比色-荧光探针分子(E)-((4-(2-(4-氰基-5-(二氰基亚甲基)-2,2-二甲基-2,5-二氢呋喃-3-基)乙烯基)苯基)氮烷二基)双(乙烷-2,1-二基)二丙烯酸酯3.47mmol,产率83%。
实施例2
a、将5mmol N-苯基二乙醇胺溶于50mL有机溶剂氯仿中,加入10mmol有机碱为哌啶,温度0℃下加入10mmol丙烯酰氯,反应12h,萃取,去离子水洗至中性、无水硫酸镁干燥、抽滤、旋干后得中间产物1(苯基氮杂二基)双(乙烷-2,1-二基)二丙烯酸酯4.5mmol,产率为90%;
b、将4.5mmol三氯氧磷在温度0℃下滴入22.5mmol N,N-二甲基甲酰胺中,反应2h后滴入步骤a得到的4.5mmol中间产物1,升温至75℃,反应12h后冷却至室温,加入有机溶剂氯仿,温度0℃,取30mmol无水乙酸钠溶于50mL去离子水中配制乙酸钠的水溶液,再将配制的乙酸钠的水溶液滴入反应物中,室温反应12h,萃取,得中间产物2((4-甲酰基苯基)氮杂二基)双(乙烷-2,1-二基)二丙烯酸酯4.12mmol,产率91.6%;
c、将步骤b得到的4.12mmol中间产物2溶于10mL有机溶剂二氯甲烷中,加入4.12mmol2-(3-氰基-4,5,5-三甲基呋喃-2(5H)-酰基)丙烯腈,回流6h,冷却至室温后旋干,加入溶剂10mL二氯甲烷,再加入100mL甲醇,室温下旋干,抽滤重结晶后,即得比色-荧光探针分子(E)-((4-(2-(4-氰基-5-(二氰基亚甲基)-2,2-二甲基-2,5-二氢呋喃-3-基)乙烯基)苯基)氮烷二基)双(乙烷-2,1-二基)二丙烯酸酯3.3mmol,产率80.1%。
实施例3
a、将5mmol N-苯基二乙醇胺溶于50mL有机溶剂四氢呋喃,加入15mmol有机碱为吡啶,温度0℃下加入15mmol丙烯酰氯,反应12h,萃取,去离子水洗至中性、无水硫酸镁干燥、抽滤、旋干后得中间产物1(苯基氮杂二基)双(乙烷-2,1-二基)二丙烯酸酯4.7mmol,产率94%;
b、将4.7mmol三氯氧磷在温度0℃下滴入23.5mmol N,N-二甲基甲酰胺中,反应2h后滴入步骤a得到的4.7mmol中间产物1,升温至75℃,反应12h后冷却至室温,加入有机溶剂四氢呋喃,温度0℃,取30mmol无水乙酸钠溶于50mL去离子水中配制乙酸钠的水溶液,再将配制的乙酸钠的水溶液滴入反应物中,室温反应12h,萃取,得中间产物2((4-甲酰基苯基)氮杂二基)双(乙烷-2,1-二基)二丙烯酸酯4.31mmol,产率91.7%;
c、将步骤b得到的4.31mmol中间产物2溶于10mL有机溶剂氯仿中,加入4.31mmol2-(3-氰基-4,5,5-三甲基呋喃-2(5H)-酰基)丙烯腈,回流6h,冷却至室温后旋干,加入溶剂10mL二氯甲烷,再加入100mL甲醇,室温下旋干,抽滤重结晶后,即得比色-荧光探针分子(E)-((4-(2-(4-氰基-5-(二氰基亚甲基)-2,2-二甲基-2,5-二氢呋喃-3-基)乙烯基)苯基)氮烷二基)双(乙烷-2,1-二基)二丙烯酸酯3.5mmol,产率81.2%。
实施例4
a、将5mmol N-苯基二乙醇胺溶于50mL有机溶剂二氯甲烷中,加入20mL有机碱为吡啶,温度0℃下加入20mL丙烯酰氯,反应12h,萃取,去离子水洗至中性、无水硫酸镁干燥、抽滤、旋干后得中间产物1(苯基氮杂二基)双(乙烷-2,1-二基)二丙烯酸酯4.56mmol,产率91.2%;
b、将4.56mmol三氯氧磷在温度0℃下滴入22.8mmol N,N-二甲基甲酰胺中,反应2h后滴入步骤a得到的4.56mmol中间产物1,升温至75℃,反应12h后冷却至室温,加入有机溶剂二氯甲烷,温度0℃,取30mmol无水乙酸钠溶于50mL去离子水中配制乙酸钠的水溶液,再将配制的乙酸钠的水溶液滴入反应物中,室温反应12h,萃取,得中间产物2((4-甲酰基苯基)氮杂二基)双(乙烷-2,1-二基)二丙烯酸酯4.23mmol,产率92.8%;
c、将步骤b得到的4.23mmol中间产物2溶于10mL有机溶剂乙醇、二氯甲烷、氯仿、四氢呋喃、N,N-二甲基甲酰胺或N,N-二甲基乙酰胺中,加入2-(3-氰基-4,5,5-三甲基呋喃-2(5H)-酰基)丙烯腈,其中中间产物2与2-(3-氰基-4,5,5-三甲基呋喃-2(5H)-酰基)丙烯腈的摩尔比为1:1-1.2,回流6h,冷却至室温后旋干,加入溶剂10mL二氯甲烷,再加入100mL甲醇,室温下旋干,抽滤重结晶后,即得比色-荧光探针分子(E)-((4-(2-(4-氰基-5-(二氰基亚甲基)-2,2-二甲基-2,5-二氢呋喃-3-基)乙烯基)苯基)氮烷二基)双(乙烷-2,1-二基)二丙烯酸酯3.4mmol,产率80.4%。
实施例5
a、将5mmol N-苯基二乙醇胺溶于50mL有机溶剂乙醚中,加入10mL有机碱为三乙胺,温度0℃下加入10mL丙烯酰氯,反应12h,萃取,去离子水洗至中性、无水硫酸镁干燥、抽滤、旋干后得中间产物1(苯基氮杂二基)双(乙烷-2,1-二基)二丙烯酸酯4.48mmol,产率89.6%;
b、将4.48mmol三氯氧磷在温度0℃下滴入8.96mmol N,N-二甲基甲酰胺中,反应2h后滴入步骤a得到的4.48mmol中间产物1,升温至75℃,反应12h后冷却至室温,加入有机溶剂乙醚、氯仿、四氢呋喃或二氯甲烷,温度0℃,取30mmol无水乙酸钠溶于50mL去离子水中配制乙酸钠的水溶液,再将配制的乙酸钠的水溶液滴入反应物中,室温反应12h,萃取,得中间产物2((4-甲酰基苯基)氮杂二基)双(乙烷-2,1-二基)二丙烯酸酯4.12mmol,产率92.0%;
c、将步骤b得到的4.12mmol中间产物2溶于10mL有机溶剂N,N-二甲基甲酰胺中,加入4.12mmol 2-(3-氰基-4,5,5-三甲基呋喃-2(5H)-酰基)丙烯腈,回流6h,冷却至室温后旋干,加入溶剂10mL二氯甲烷,再加入100mL甲醇,室温下旋干,抽滤重结晶后,即得比色-荧光探针分子(E)-((4-(2-(4-氰基-5-(二氰基亚甲基)-2,2-二甲基-2,5-二氢呋喃-3-基)乙烯基)苯基)氮烷二基)双(乙烷-2,1-二基)二丙烯酸酯3.24mmol,产率78.6%。
实施例6
a、将5mmol N-苯基二乙醇胺溶于50mL有机溶剂四氢呋喃中,加入15mL有机碱为哌啶,温度0℃下加入15mL丙烯酰氯,反应12h,萃取,去离子水洗至中性、无水硫酸镁干燥、抽滤、旋干后得中间产物1(苯基氮杂二基)双(乙烷-2,1-二基)二丙烯酸酯4.51mmol,产率90.2%;
b、将4.51mmol三氯氧磷在温度0℃下滴入13.53mmol N,N-二甲基甲酰胺中,反应2h后滴入步骤a得到的4.51mmol中间产物1,升温至75℃,反应12h后冷却至室温,加入有机溶剂二氯甲烷,温度0℃,取30mmol无水乙酸钠溶于50mL去离子水中配制乙酸钠的水溶液,再将配制的乙酸钠的水溶液滴入反应物中,室温反应12h,萃取,得中间产物2((4-甲酰基苯基)氮杂二基)双(乙烷-2,1-二基)二丙烯酸酯4.11mmol,产率91.1%;
c、将步骤b得到的4.11mmol中间产物2溶于10mL有机溶剂N,N-二甲基乙酰胺中,加入4.11mmol 2-(3-氰基-4,5,5-三甲基呋喃-2(5H)-酰基)丙烯腈,回流6h,冷却至室温后旋干,加入溶剂10mL二氯甲烷,再加入100mL甲醇,室温下旋干,抽滤重结晶后,即得比色-荧光探针分子(E)-((4-(2-(4-氰基-5-(二氰基亚甲基)-2,2-二甲基-2,5-二氢呋喃-3-基)乙烯基)苯基)氮烷二基)双(乙烷-2,1-二基)二丙烯酸酯3.19mmol,产率77.6%。
实施例7
取实施例1-6任意一种制备的比色-荧光探针分子(E)-((4-(2-(4-氰基-5-(二氰基亚甲基)-2,2-二甲基-2,5-二氢呋喃-3-基)乙烯基)苯基)氮烷二基)双(乙烷-2,1-二基)二丙烯酸酯溶于体积比为4:1得四氢呋喃和水的混合溶剂中,比色-荧光探针分子的浓度为5uM;取检测液3mL,分别加入30uL的5uM-7mM的次氯酸根水溶液,反应后进行紫外吸收光谱的测试,如图1所示,由图1可以看出随着次氯酸根浓度的增加,544nm处的吸收峰值逐渐降低,直至消失,其颜色变化由紫色慢慢褪为无色;
取实施例1-6任意一种制备的比色-荧光探针分子(E)-((4-(2-(4-氰基-5-(二氰基亚甲基)-2,2-二甲基-2,5-二氢呋喃-3-基)乙烯基)苯基)氮烷二基)双(乙烷-2,1-二基)二丙烯酸酯溶于体积比为4:1的四氢呋喃和水的混合溶剂中,比色-荧光探针分子的浓度为5uM;取检测液3mL,分别加入30uL的5uM-7mM的次氯酸根水溶液,反应后进行荧光光谱的测试,如图2所示,由图2可以看出随着次氯酸根浓度的增加,632nm处的发射峰值逐渐降低,直至消失。
实施例8
取实施例1-6任意一种制备的比色-荧光探针分子(E)-((4-(2-(4-氰基-5-(二氰基亚甲基)-2,2-二甲基-2,5-二氢呋喃-3-基)乙烯基)苯基)氮烷二基)双(乙烷-2,1-二基)二丙烯酸酯溶于体积比为4:1的四氢呋喃和水的混合溶剂中,比色-荧光探针分子的浓度为5uM;取检测液3mL,分别加入30uL的7mM的次氯酸根、氯酸根+次氯酸根、高氯酸根+次氯酸根、硝酸铵+次氯酸根、过硫酸根+次氯酸根水溶液,反应后进行紫外吸收光谱的测试,如图3所示,由图3可以看出只要次氯酸根的存在,544nm处的吸收峰皆消失,说明其他氧化性物质对紫外吸收检测性能无影响,抗干扰性强;
取实施例1-6任意一种制备的比色-荧光探针分子(E)-((4-(2-(4-氰基-5-(二氰基亚甲基)-2,2-二甲基-2,5-二氢呋喃-3-基)乙烯基)苯基)氮烷二基)双(乙烷-2,1-二基)二丙烯酸酯溶于体积比为4:1的四氢呋喃和水的混合溶剂中,比色-荧光探针分子的浓度为5uM;取检测液3mL,分别加入30uL的7mM的次氯酸根、氯酸根+次氯酸根、高氯酸根+次氯酸根、硝酸铵+次氯酸根、过硫酸根+次氯酸根水溶液,反应后进行荧光光谱的测试,如图4所示,由图4可以看出只要次氯酸根的存在,632nm处的发射峰值皆消失,说明其他氧化性物质对荧光检测性能无影响。
实施例9
取实施例1-6任意一种制备的比色-荧光探针分子(E)-((4-(2-(4-氰基-5-(二氰基亚甲基)-2,2-二甲基-2,5-二氢呋喃-3-基)乙烯基)苯基)氮烷二基)双(乙烷-2,1-二基)二丙烯酸酯溶于体积比为4:1的四氢呋喃和水的混合溶剂中,比色-荧光探针分子的浓度为5uM;取检测液3mL,分别加入30uL的7mM的次氯酸根、氯酸根、高氯酸根、硝酸铵、过硫酸根水溶液,反应后进行紫外吸收光谱的测试,如图5所示,由图5可以看出仅在加入次氯酸根时,544nm处的吸收峰才消失,说明其他氧化性物质与比色-荧光探针不反应,专一性强;
取实施例1-6任意一种制备的比色-荧光探针分子(E)-((4-(2-(4-氰基-5-(二氰基亚甲基)-2,2-二甲基-2,5-二氢呋喃-3-基)乙烯基)苯基)氮烷二基)双(乙烷-2,1-二基)二丙烯酸酯溶于体积比为4:1的四氢呋喃和水的混合溶剂中,比色-荧光探针分子的浓度为5uM;取检测液3mL,分别加入30uL的7mM的次氯酸根、氯酸根、高氯酸根、硝酸铵、过硫酸根水溶液,反应后进行荧光光谱的测试,如图6所示,由图6可以看出仅在加入次氯酸根时,632nm处的发射峰才消失,说明其他氧化性物质与比色-荧光探针不反应。
实施例10
取实施例1-6任意一种制备的比色-荧光探针分子(E)-((4-(2-(4-氰基-5-(二氰基亚甲基)-2,2-二甲基-2,5-二氢呋喃-3-基)乙烯基)苯基)氮烷二基)双(乙烷-2,1-二基)二丙烯酸酯溶于体积比为4:1的四氢呋喃和水的混合溶剂中,比色-荧光探针分子的浓度为5uM;取检测液3mL,分别加入30uL不同浓度的次氯酸根水溶液,反应后进行紫外吸收光谱和荧光光谱的测试,以溶液在544nm处的紫外吸收强度和632nm处的荧光发射强度对次氯酸根的浓度做标准图,根据紫外吸收标准图(如图7所示)和荧光光谱标准图(如图8所示),定量检测次氯酸根在待测溶液中的含量,利用公式LOD=3σ/K(K=-0.00151,σ=9.6115×10-5)计算的检测限为0.19uM。
本发明所述的一种用于检测次氯酸根的比色-荧光探针(E)-((4-(2-(4-氰基-5-(二氰基亚甲基)-2,2-二甲基-2,5-二氢呋喃-3-基)乙烯基)苯基)氮烷二基)双(乙烷-2,1-二基)二丙烯酸酯可实现对环境中水样及非制式爆炸物原料中次氯酸根的现场、快速、专一、痕量、可视化检测,在632nm处出现荧光猝灭,在544nm处出现褪色变化。
Claims (3)
2.根据权利要求1所述的一种用于检测次氯酸根的比色-荧光探针的制备方法,其特征在于按下列步骤进行:
a、将N-苯基二乙醇胺溶于有机溶剂乙醚、氯仿、四氢呋喃或二氯甲烷,加入有机碱为三乙胺、哌啶或吡啶,温度0℃下加入丙烯酰氯,反应12h,萃取,去离子水洗至中性、无水硫酸镁干燥、抽滤、旋干后得中间产物1(苯基氮杂二基)双(乙烷-2,1-二基)二丙烯酸酯,其中N-苯基二乙醇胺与丙烯酰氯和有机碱的摩尔比为1:2-4:2-4;
b、将三氯氧磷滴入N,N-二甲基甲酰胺中,反应2h后滴入步骤a得到的中间产物1,升温至75℃,反应12h后冷却至室温,加入有机溶剂乙醚、氯仿、四氢呋喃或二氯甲烷,温度0℃,滴入乙酸钠的水溶液,室温反应12h,萃取,得中间产物2((4-甲酰基苯基)氮杂二基)双(乙烷-2,1-二基)二丙烯酸酯,其中中间产物1与三氯氧磷和N,N-二甲基甲酰胺的摩尔比为1:1:2-5;
c、将步骤b得到的中间产物2溶于有机溶剂乙醇、二氯甲烷、氯仿、四氢呋喃、N,N-二甲基甲酰胺或N,N-二甲基乙酰胺中,加入2-(3-氰基-4,5,5-三甲基呋喃-2(5H)-酰基)丙烯腈,其中中间产物2与2-(3-氰基-4,5,5-三甲基呋喃-2(5H)-酰基)丙烯腈的摩尔比为1:1-1.2,回流6h,冷却至室温后旋干,加入溶剂10mL二氯甲烷,再加入100mL甲醇,室温下旋干,抽滤重结晶后,即得检测次氯酸根的比色-荧光探针分子(E)-((4-(2-(4-氰基-5-(二氰基亚甲基)-2,2-二甲基-2,5-二氢呋喃-3-基)乙烯基)苯基)氮烷二基)双(乙烷-2,1-二基)二丙烯酸酯。
3.根据权利要求1所述的一种用于检测次氯酸根的比色-荧光探针在检测环境中水样及非制式爆炸物原料中次氯酸根的含量中的用途。
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