CN115124519B - 用于检测氯磷酸二甲酯的荧光试剂及其制备方法 - Google Patents
用于检测氯磷酸二甲酯的荧光试剂及其制备方法 Download PDFInfo
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Abstract
本发明属于化学分析测试领域,具体涉及一种用于检测氯磷酸二甲酯的荧光试剂及其制备方法。该荧光试剂为基于5‑氨基喹啉衍生物为靶点的香豆素类化合物。靶点部分以5‑氨基喹啉为原料,与氯乙酰氯发生酰化反应,再与N‑Boc‑1,4‑苯二胺发生取代,通过脱Boc得到靶点部分;荧光染料7‑(二乙基氨基)香豆素‑3‑甲酸与靶点部分在N,N‑二异丙基乙胺碱性条件下,在1H‑苯并三唑‑1‑基氧三吡咯烷基六氟磷酸盐催化下得到最终化合物。本发明荧光试剂具有良好的水溶性与优异的光学性能,能够对氯磷酸二甲酯进行荧光响应识别检测。
Description
技术领域
本发明属于化学分析测试领域,具体涉及一种用于检测氯磷酸二甲酯的荧光试剂及其制备方法。
背景技术
有机磷酸酯(organophosphate esters,OPEs)是一类碳磷键相连的化合物或含有机基团的磷酸衍生物,通常情况下为无色无味透明的液体。OPEs的结构通式如式1-1所示,不同类型的OPEs是通过3个取代基团(R1、R2、X)取代磷酸上的H得到的。
式1-1OPEs结构式,R1、R2、X分别代表不同或相同的取代基
根据与P相连的取代基X不同,有机磷酸酯会呈现出不同的理化性质。当X基团为卤素或者氰基等这类电负性很强的取代基时,OPEs会表现出很强的毒性,通常被用作“神经毒剂”,最著名的为G系列神经毒剂包括塔崩(GA)、沙林(GB)、梭曼(GD),它们的结构如式1-2所示,这一类G系列神经毒剂能与乙酰胆碱酯酶结合,该过程不可逆,导致乙酰胆碱分解受到阻碍,胆碱能突触神经受到破坏,神经系统出现瘫痪,器官衰竭,导致迅速死亡。
式1-2G系列神经毒剂结构
由于以G类神经毒素为代表的OPEs具有剧毒,它们的使用受到严格的管控,所以在实际的研究过程中常常选用式1-3中氯磷酸二甲酯等具有相似的化学结构但毒性较小的OPEs来代替剧毒的G类神经毒素作为模拟物。它们的化学活性通常小于G类神经毒素为代表的OPEs。通过荧光检测法进行检测,开发一种快速简便、灵敏度好、水溶性优异的检测氯磷酸二甲酯的荧光试剂。
式1-3氯磷酸二甲酯结构式
目前针对有机磷酸酯的检测方法主要有液相色谱-质谱联用、拉曼光谱法等,但是检测都需要依靠大型的仪器设备,同时样品的前处理比较麻烦,也不能适应样品现场的快速检测。
发明内容
本发明提供了一种用于检测氯磷酸二甲酯的荧光试剂,该荧光试剂的结构式为:
本发明还提供了一种用于检测氯磷酸二甲酯的荧光试剂的制备方法,其反应如下式所示:
具体反应步骤如下:
(1)将氯乙酰氯的无水二氯甲烷溶液加入到5-氨基喹啉和碳酸钾的无水二氯甲烷溶液中,冰浴搅拌,随后室温搅拌反应,反应结束后,通过重结晶,得到淡黄色固体;
其中,5-氨基喹啉、氯乙酰氯与碳酸钾的摩尔当量比为:1:1~10:3;冰浴搅拌时间为15分钟;室温搅拌时间为4小时;重结晶的良性溶剂为二氯甲烷,惰性溶剂为石油醚。
(2)将步骤(1)中得到的淡黄色固体与N-Boc-1,4-苯二胺,加入碳酸钾和碘化钾,在乙腈溶液中加热回流,反应结束后,冷却至室温,旋蒸除去溶剂,通过柱层析法与薄层色谱法,得到淡黄色固体;
其中,步骤(2)中淡黄色固体、N-Boc-1,4-苯二胺、碳酸钾与碘化钾的摩尔当量比为:1:0.8~0.9:1~3:0.1。回流温度为85℃~105℃,反应时间为16小时;采用柱层析分离提纯化合物,柱填料采用100~200目的碱性氧化铝。
(3)将步骤(2)中得到的淡黄色固体溶解在二氯甲烷中,加入盐酸-二氧六环溶液,室温搅拌,反应结束后,旋蒸除去溶剂,加入碱溶液溶解,用乙酸乙酯萃取,有机相浓缩,通过薄层色谱法得到黄色固体靶点部分;
其中,4M的盐酸二氧六环溶液与二氯甲烷的体积比为1:1;反应时间为2~16小时;碱溶液为5%的碳酸钾溶液。
(4)将步骤(3)中的黄色固体与1H-苯并三唑-1-基氧三吡咯烷基六氟磷酸盐(PyBOP)和N,N-二异丙基乙胺,在N,N-二甲基甲酰胺(DMF)中搅拌,再加入7-(二乙基氨基)香豆素-3-甲酸,室温下搅拌16小时,反应结束后,用乙酸乙酯萃取,用无水硫酸钠干燥有机相,旋蒸除去有机溶剂,通过薄层色谱法得到用于检测有机磷酸酯的荧光试剂;
其中,黄色固体、1H-苯并三唑-1-基氧三吡咯烷基六氟磷酸盐(PyBOP)、N,N-二异丙基乙胺、7-(二乙基氨基)香豆素-3-甲酸的摩尔当量比为:1:1~3:3:0.8~0.9。
本发明还提供了一种上述化合物荧光试剂的应用:所制备的基于5-氨基喹啉衍生物为识别靶点的香豆素类化合物在去离子水为溶剂时,能够通过荧光增强的方式来选择性识别以氯磷酸二甲酯(DMECP)为代表的有机磷酸酯。
本化合物结构中采用了香豆素作为荧光基团,在香豆素的7号位上取代供电子基团(氮二甲基),在3号位上取代吸电子基团(羧基),使香豆素形成电子推拉的同时,更加增强了香豆素衍生物的水溶性。靶向受体结构主要为氨基喹啉,喹啉骨架是氮杂环化学的主要种类之一,喹啉结构能在多个位点进行取代,取代基团不同,导致不同的物理和化学性质。
所制备的化合物的结构中,5-氨基喹啉衍生物为靶点能与氯磷酸二甲酯(DMECP)相互作用,在去离子水中由单体形态转变为聚集形态,导致XDS5A的结构固化,光诱导电子转移(PET)受到抑制,导致XDS5A荧光增强,从而达到识别氯磷酸二甲酯(DMECP)的作用。
本技术解决了荧光试剂在水相体系中,通过荧光增强对氯磷酸二甲酯(DMECP)选择性识别的问题。从反应现象上看,XDS5A本身的荧光强度很微弱,在加入其他有机膦酸酯后,荧光强度基本没有发生变化,而在加入氯磷酸二甲酯(DMECP)后,荧光强度显著增强。
本发明的有益效果在于:本发明原料价格便宜,容易获得,合成路线较短,方法较简单,反应条件容易控制,反应结束后能通过简单的后处理方式得到较纯的目标产物;基于5-氨基喹啉衍生物为识别靶点的香豆素类化合物在去离子水中能够高效并且专一地识别氯磷酸二甲酯(DMECP)。
附图说明:
图1为实施例1制备的化合物在去离子水中与不同有机磷酸酯作用后的荧光光谱图。
图2为实施例1制备的化合物在去离子水中与不同浓度的氯磷酸二甲酯(DMECP)作用后的荧光谱图。
图3为实施例1制备的化合物的氢谱。
图4为实施例1制备的化合物的碳谱。
具体实施方式
本发明下面结合实施例作进一步详述:
实施例1:
(1)称取5-氨基喹啉(1g,6.93mmol)和碳酸钾(2.873g,20.79mmol)溶于20mL无水二氯甲烷,将氯乙酰氯(4.26g,34.65mmol)溶于10mL无水二氯甲烷,在0℃时,将含有氯乙酰氯的二氯甲烷溶液滴加到含有5-氨基喹啉和碳酸钾的溶剂体系中,冰浴搅拌15分钟后,常温搅拌4小时,反应结束,过滤除去不溶固体,旋蒸除去溶剂;再加入二氯甲烷,使固体刚好完全溶解,加入大量石油醚(PE),搅拌16小时,发现有大量固体析出,过滤收集1.27g固体化合物2,产率为:91.3%。
(2)将步骤(1)中得到的化合物2(0.2g,0.906mmol)与N-Boc-1,4-苯二胺(0.151g,0.725mmol),加入碳酸钾(0.25g,1.812mmol)和碘化钾(0.015g,0.096mmol),溶解在10mL乙腈溶液中,加热至90℃,回流16小时,反应结束后,冷却至室温,旋蒸除去溶剂,通过碱性氧化铝柱层析法进行初步提纯(洗脱剂为二氯甲烷:甲醇体积比=100:1),再通过薄层色谱法进一步提纯,得到0.31g淡黄色固体化合物3,产率为:87.1%。
(3)将步骤(2)中得到的化合物3(0.077g,0.196mmol)溶解在2mL二氯甲烷中,加入2Ml 4M盐酸-二氧六环溶液(CAS号:7647-01-0),室温搅拌4小时,反应结束后,旋蒸除去溶剂,加入5%碳酸钾溶液溶解,用乙酸乙酯萃取,有机相浓缩,通过薄层色谱法得到0.054g黄色固体靶点部分化合物4,产率为:94.1%。
(4)将步骤(3)中的化合物4(0.016g,0.055mmol)与1H-苯并三唑-1-基氧三吡咯烷基六氟磷酸盐(PyBOP)(0.043g,0.0825mmol)和N,N-二异丙基乙胺(0.021g,0.165mmol),溶解在3mL的N,N-二甲基甲酰胺(DMF)溶剂中搅拌均匀,再加入7-(二乙基氨基)香豆素-3-甲酸(0.0115g 0.044mmol),室温下搅拌16小时,反应结束后,用乙酸乙酯萃取,旋蒸除去有机溶剂,通过薄层色谱法得到0.098g黄色固体香豆素化合物XDS5A,产率为:41.5%。
具体应用方法为:向96孔板中分别加入2uL的磷酸三甲酯(TMP)、磷酸三乙酯(TEP)、磷酸三丁酯(TBP)、氯磷酸二甲酯(DMECP)、氯甲基膦酸二乙酯(DMMCP)、甲基磷酸二甲酯(DMMP)溶液,有机磷酸酯浓度为10mM,加入196uL的去离子水和2uL的基于5-氨基喹啉衍生物为识别靶点的香豆素类化合物(浓度为2mM),总体积保持为200μL,使得XDS5A在96孔板中最终浓度为20μM,有机磷酸酯的最终浓度为100μM。加样完成后混合均匀,使用多功能微孔板检测仪Spark(瑞士)进行荧光的光学检测,测得每个孔的荧光强度,结果显示:当氯磷酸二甲酯(DMECP)加入体系中时,XDS5A在波长为485nm处的荧光强度增强并且荧光强度为空白对照组的荧光强度的10倍,而当其他有机磷酸酯加入体系时,XDS5A在去离子水中的荧光强度变化不大。从而显示出,在去离子水中XDS5A对氯磷酸二甲酯(DMECP)有显著的选择性识别作用。
图1为实施例1制备的化合物在去离子水中与不同有机磷酸酯作用后的荧光光谱图。图中结果显示,滴加浓度为10mM的不同有机磷酸酯2uL于含有100uM的探针水溶液后,探针的荧光强度变化情况,当加入10mM的氯磷酸二甲酯(DMECP)2uL时,探针在485nm处的荧光强度发生了显著的升高(箭头所指曲线);而该化合物在去离子水中,对于其他有机磷酸酯无特别明显的荧光的变化,从而显示出在该体系中化合物对于氯磷酸二甲酯(DMECP)的选择性识别作用。
图2为实施例1制备的化合物在去离子水中与不同浓度的氯磷酸二甲酯(DMECP)作用后的荧光谱图。图中结果显示,随着加入的DMECP的浓度的增加,探针化合物的荧光强度逐渐增加,表明探针化合物的荧光表现跟加入的DMECP的浓度相关。
图3为实施例1制备的基于5-氨基喹啉衍生物为靶点的香豆素类化合物的氢谱。1HNMR(400MHz,CDCl3)δ=10.76(s,1H),9.20(s,1H),8.87(d,J=3.0,1H),8.75(s,1H),8.01(d,J=4.0,1H),7.96(d,J=8.5,1H),7.90(d,J=8.5,1H),7.71(t,J=8.1,1H),7.65(d,J=8.7,2H),7.43(d,J=9.0,1H),7.33(dd,J=8.6,4.2,1H),6.80(d,J=8.7,2H),6.66(dd,J=9.0,2.3,1H),6.51(d,J=2.0,1H),4.07(s,2H),3.46(q,J=7.1,4H),1.24(d,J=6.5,6H).
图4为实施例1制备的基于5-氨基喹啉衍生物为靶点的香豆素类化合物的碳谱。13CNMR(75MHz,DMSO)δ=170.85,162.76,160.31,157.70,153.01,150.97,148.54,148.16,145.55,134.11,132.16,131.90,129.55,128.68,126.74,123.47,122.28,121.75,121.40,113.02,110.78,109.93,108.37,96.37,47.93,44.85,12.80.。
实施例2
(1)称取5-氨基喹啉(0.108g,0.75mmol)和碳酸钾(0.311g,2.25mmol)溶于5mL无水二氯甲烷,将氯乙酰氯(0.085g,0.75mmol)溶于5mL无水二氯甲烷,在0℃时,将含有氯乙酰氯的二氯甲烷溶液滴加到含有5-氨基喹啉和碳酸钾的溶剂体系中,冰浴搅拌15分钟后,常温搅拌4小时,反应结束,过滤除去不溶固体,旋蒸除去溶剂;再加入二氯甲烷,使固体刚好完全溶解,加入大量石油醚(PE),搅拌16小时,发现有大量固体析出,过滤收集0.098g固体化合物2,产率为:59.4%。
(2)将步骤(1)中得到的化合物2(0.098g,0.44mmol)与N-Boc-1,4-苯二胺(0.054g,0.36mmol),加入碳酸钾(0.061g,0.44mmol)和碘化钾(0.007g,0.044mmol),溶解在5mL乙腈溶液中,加热至90℃,回流16小时,反应结束后,冷却至室温,旋蒸除去溶剂,通过碱性氧化铝柱层析法进行初步提纯(洗脱剂为二氯甲烷:甲醇体积比=100:1),再通过薄层色谱法进一步提纯,得到0.108g淡黄色固体化合物3,产率为:62.3%。
(3)将步骤(2)中得到的化合物3(0.1g,0.255mmol)溶解在3mL二氯甲烷中,加入3mL盐酸-二氧六环溶液,室温搅拌2小时,反应结束后,旋蒸除去溶剂,加入5%碳酸钾溶液溶解,用乙酸乙酯萃取,有机相浓缩,通过薄层色谱法得到0.066g黄色固体靶点部分化合物4,产率为:89%。
(4)将步骤(3)中的化合物4(0.032g,0.109mmol)与1H-苯并三唑-1-基氧三吡咯烷基六氟磷酸盐(PyBOP)(0.057g,0.109mmol)和N,N-二异丙基乙胺(0.042g,0.327mmol),溶解在4mL的N,N-二甲基甲酰胺(DMF)溶剂中搅拌均匀,再加入7-(二乙基氨基)香豆素-3-甲酸(0.023g 0.087mmol),室温下搅拌12小时,反应结束后,用乙酸乙酯萃取,旋蒸除去有机溶剂,通过薄层色谱法得到0.016g黄色固体香豆素化合物XDS5A,产率为:33.4%。
实施例3
(1)称取5-氨基喹啉(0.5g,3.47mmol)和碳酸钾(1.44g,10.41mmol)溶于7mL无水二氯甲烷,将氯乙酰氯(4.26g,34.7mmol)溶于8mL无水二氯甲烷,在0℃时,将含有氯乙酰氯的二氯甲烷溶液滴加到含有5-氨基喹啉和碳酸钾的溶剂体系中,冰浴搅拌15分钟后,常温搅拌4小时,反应结束,过滤除去不溶固体,旋蒸除去溶剂;再加入二氯甲烷,使固体刚好完全溶解,加入大量石油醚(PE),搅拌16小时,发现有大量固体析出,过滤收集0.633g固体化合物2,产率为:82.7%。
(2)将步骤(1)中得到的化合物2(0.3g,1.36mmol)与N-Boc-1,4-苯二胺(0.226g,1.09mmol),加入碳酸钾(0.563g,4.08mmol)和碘化钾(0.022g,0.136mmol),溶解在15mL乙腈溶液中,加热至95℃,回流24小时,反应结束后,冷却至室温,旋蒸除去溶剂,通过碱性氧化铝柱层析法进行初步提纯(洗脱剂为二氯甲烷:甲醇体积比=100:1),再通过薄层色谱法进一步提纯,得到0.426g淡黄色固体化合物3,产率为:79.8%。
(3)将步骤(2)中得到的化合物3(0.114g,0.29mmol)溶解在4mL二氯甲烷中,加入4mL盐酸-二氧六环溶液,室温搅拌16小时,反应结束后,旋蒸除去溶剂,加入5%碳酸钾溶液溶解,用乙酸乙酯萃取,有机相浓缩,通过薄层色谱法得到0.079g黄色固体靶点部分化合物4,产率为:93.7%。
(4)将步骤(3)中的化合物4(0.016g,0.096mmol)与1H-苯并三唑-1-基氧三吡咯烷基六氟磷酸盐(PyBOP)(0.15g,0.288mmol)和N,N-二异丙基乙胺(0.037g,0.288mmol),溶解在4.5mL的N,N-二甲基甲酰胺(DMF)溶剂中搅拌均匀,再加入7-(二乙基氨基)香豆素-3-甲酸(0.02g 0.077mmol),室温下搅拌16小时,反应结束后,用乙酸乙酯萃取,旋蒸除去有机溶剂,通过薄层色谱法得到0.015g黄色固体香豆素化合物XDS5A,产率为:38.2%。
Claims (8)
1.一种基于5-氨基喹啉衍生物为靶点的香豆素类化合物荧光试剂,其特征在于:所述荧光试剂的结构式为:
。
2.一种基于5-氨基喹啉衍生物为靶点的香豆素类化合物荧光试剂的制备方法,其特征在于:所述制备方法步骤如下:
(1)将氯乙酰氯的无水二氯甲烷溶液加入到5-氨基喹啉和碳酸钾的无水二氯甲烷溶液中,冰浴搅拌,随后室温搅拌反应,反应结束后,通过重结晶,得到淡黄色固体;
(2)将步骤(1)得到的淡黄色固体与N-Boc-1,4-苯二胺,加入碳酸钾和碘化钾,在乙腈溶液中加热回流,反应结束后,冷却至室温,旋蒸除去溶剂,通过柱层析法与薄层色谱法,得到淡黄色固体;
(3)将步骤(2)得到的淡黄色固体溶解在二氯甲烷中,加入盐酸-二氧六环溶液,室温搅拌,反应结束后,旋蒸除去溶剂,加入碱溶液溶解,用乙酸乙酯萃取,有机相浓缩,通过薄层色谱法得到黄色固体靶点部分;
(4)将步骤(3)中的黄色固体与1H-苯并三唑-1-基氧三吡咯烷基六氟磷酸盐和N,N-二异丙基乙胺,在N,N-二甲基甲酰胺溶剂中搅拌,再加入7-(二乙基氨基)香豆素-3-甲酸,室温下搅拌16h,反应结束后,用乙酸乙酯萃取,用无水硫酸钠干燥有机相,旋蒸除去有机溶剂,通过薄层色谱法得到用于检测有机磷酸酯的荧光试剂。
3.如权利要求2所述的荧光试剂的制备方法,其特征在于:步骤(1)中5-氨基喹啉、氯乙酰氯与碳酸钾的摩尔比为:1:1~10:3;冰浴搅拌时间为15分钟;室温搅拌时间为4小时;重结晶的良性溶剂为二氯甲烷,惰性溶剂为石油醚。
4.如权利要求2所述的荧光试剂的制备方法,其特征在于:步骤(2)中,步骤(1)得到的淡黄色固体、N-Boc-1,4-苯二胺、碳酸钾与碘化钾的摩尔比为:1:0.8~0.9:1~3:0.1;回流温度为85℃~105℃,反应时间为16小时;柱层析的固体相为100~200目的碱性氧化铝。
5.如权利要求2所述的荧光试剂的制备方法,其特征在于:步骤(3)中淡黄色固体溶解于体积比为1:1的盐酸-二氧六环溶液与二氯甲烷混合溶液中;反应时间为2 ~16小时。
6.如权利要求2所述的荧光试剂的制备方法,其特征在于:步骤(4)中黄色固体、1H-苯并三唑-1-基氧三吡咯烷基六氟磷酸盐、N,N-二异丙基乙胺、7-(二乙基氨基)香豆素-3-甲酸的摩尔比为:1:1~3:3:0.8~0.9。
7.一种如权利要求1所述的基于5-氨基喹啉衍生物为靶点的香豆素类化合物荧光试剂的应用,其特征在于:所述荧光试剂用于检测氯磷酸二甲酯。
8.如权利要求7所述的荧光试剂的应用,其特征在于:所述荧光试剂在去离子水为溶剂时,通过荧光增强的方式选择性识别氯磷酸二甲酯。
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