CN115043855A - 一种检测重水中水含量的荧光探针及其应用 - Google Patents
一种检测重水中水含量的荧光探针及其应用 Download PDFInfo
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Abstract
Description
技术领域
本发明属于有机小分子荧光探针技术领域,具体涉及一种检测重水中水含量的荧光探针及其应用。
背景技术
重水(Deuterium oxide)是由氘和氧组成的化合物,分子式D2O,相对分子质量20.0275,比水(H2O)的分子量18.0153高出约11%,因此叫做重水。在天然水中,重水的含量约占0.015%。由于氘与氢的性质差别极小,因此重水和普通水也很相似。
由于目前重水一般采用从轻水中蒸馏的办法制备,且重水具有很强的亲水性,重水中经常会含有一定量的轻水。检测重水中的轻水含量对于重水的安全应用具有很重要的意义。相比于传统的原子吸收、核磁共振等检测方法,荧光分析法具有灵敏度高、选择性好、响应迅速、操作简单等优点,已广泛用于各种小分子检测。目前,荧光法结合传统的传感机制如分子内电荷转移、光致电子转移、准分子和激基复合物、聚集诱导发射、席夫碱、二茂铁衍生物的水解反应以及醛的水合等,已经开发出许多用于检测水含量的荧光探针,包括有机小分子荧光探针、金属有机骨架、碳点、聚合物和铜纳米团簇等。尽管荧光法在该领域取得了显著成功,然而纵观文献报道,当然大多数的荧光方法仍然存在荧光信号输出关闭、灵敏度低以及环境因素干扰等问题。
因此开发新的具有高灵敏度、光稳定性,能够实时快速检测重水中的轻水含量的荧光探针具有重要的意义。
发明内容
本发明的目的在于提供一种检测重水中水含量的荧光探针及其应用,该荧光探针具有优异的荧光发光能力,应用于重水中检测轻水含量,表现出优异的灵敏性和精确度,且具有更佳的抗干扰性,检测限低,实际应用价值高。
本发明为实现上述目的所采取的技术方案为:
一种荧光探针,包括如式I所示的结构:
式I中,R选自以下结构中的一种:
X选自卤元素中的一种。本发明以噻唑并噻唑类结构为基础,采用3,4-亚甲基二氧苄基氯反或5-(4-溴苯基)糠醛通过化学反应对其进行衍生,得到两种具有新型结构的荧光探针材料,具有良好的荧光检测性能,尤其对水分子具有高敏感性,能够很好地应用于检测重水中水的含量,并且具有高灵敏度,检测方法的检测限可低至0.015%;具有高稳定性,能够有效抵抗常见阳离子、阴离子、活性氧物质和常见氨基酸等物质的干扰。其原因可能在于本发明制备的新型结构的荧光探针,其分子结构包含多种能够形成氢键的活性原子,可与水分子中的氢原子形成氢键,从而引起探针产生明亮荧光信号。并且采用5-(4-溴苯基)糠醛衍生得到的荧光探针对水信号的响应更高,且抗干扰能力更强。同时,本发明制备的荧光探针不仅能够用于检测重水中水含量的检测,也可以应用于有机溶剂中水含量的检测,具有广阔的应用前景和较高的实际应用价值。
于某一实施例中,荧光探针的化学结构如式II所示:
于某一实施例中,荧光探针的化学结构如式III所示:
本发明公开了式II所示结构的制备方法,包括:
-取4-吡啶甲醛、二硫代草酰胺混合,在无水DMF回流条件下反应得到产物E1;
-取E1与3,4-亚甲基二氧苄基氯反应得到式II所示结构。
具体的,式II所示结构的制备方法,步骤为:
取4-吡啶甲醛、二硫代草酰胺混合,加入无水DMF回流反应5~8h;静置过夜,过滤、水洗涤5~8次,并在230~260℃下减压升华收集黄色产物E1;
取E1加入3,4-亚甲基二氧苄基氯,125~140℃油浴条件下搅拌反应10~12h;之后静置过夜,加入甲醇并用正己烷洗涤5~8次得到荧光探针。
于某一实施例中,4-吡啶甲醛、二硫代草酰胺的质量比为1:0.7~0.8;4-吡啶甲醛与无水DMF的固液比为0.025~0.04g:1mL。
于某一实施例中,E1与3,4-亚甲基二氧苄基氯的固液比为0.02~0.03g:1mL。
本发明又公开了式III所示结构的制备方法,包括:
-取4-吡啶甲醛、二硫代草酰胺混合,在无水DMF回流条件下反应得到产物E1;
-取E1与5-(4-溴苯基)糠醛混合,在丙酮回流条件下反应得到式III所示结构。
具体的,式III所示结构的制备方法,步骤为:
取实施例1制备的E1加入5-(4-溴苯基)糠醛混合,接着加入丙酮回流反应4~6h;静置过夜,过滤、丙酮洗涤5~8次得到荧光探针。
于某一实施例中,E1与5-(4-溴苯基)糠醛的摩尔比为1:2.2~2.8;E1与丙酮的固液比为0.02~0.03g:1mL。
于某一实施例中,4-吡啶甲醛、二硫代草酰胺的质量比为1:0.7~0.8。
本发明的又一目的在于,提供了上述荧光探针在检测重水中轻水含量中的应用。
本发明又公开了上述荧光探针检测重水中轻水含量的方法,包括:
-将上述荧光探针溶于有机溶剂中制备成荧光探针溶液;
-设置荧光分光光度计中的激发波长,将上述荧光探针溶液与待测样品混匀,并置于荧光分光光度计中,进行扫描得到荧光光谱图;
-根据荧光光谱图判断待测样品中的轻水的含量。
于某一实施例中,有机溶剂包括DMSO。
于某一实施例中,荧光探针对轻水的检测限≤0.028%。
优选地,荧光探针对轻水的检测限为0.015%。
本发明的又一目的在于,公开了上述荧光探针在检测有机溶剂中水含量中的应用。
于某一实施例中,上述有机溶剂至少包括二甲基亚砜、1,4-二氧六环、四氢呋喃、N,N-二甲基甲酰胺。本发明制备的荧光探针不仅能够用于检测重水中水含量的检测,也可以应用于多种有机溶剂中水含量的检测,具有优异的灵敏度,检测限低,精确度高,进一步拓展其应用范围。
相比于现有技术,本发明具有如下有益效果:
本发明以噻唑并噻唑类结构为基础,采用3,4-亚甲基二氧苄基氯反或5-(4-溴苯基)糠醛通过化学反应对其进行衍生,得到荧光探针材料,具有良好的荧光检测性能,尤其对水分子具有高敏感性,能够很好地应用于检测重水中水的含量,并且具有高灵敏度,检测方法的检测限可低至0.015%;具有高稳定性,能够有效抵抗常见阳离子、阴离子、活性氧物质和常见氨基酸等物质的干扰。同时,本发明制备的荧光探针也可以应用于有机溶剂中水含量的检测,具有广阔的应用前景和较高的实际应用价值。
因此,本发明提供了一种检测重水中水含量的荧光探针及其应用,该荧光探针具有优异的荧光发光能力,应用于重水中检测轻水含量,表现出优异的灵敏性和精确度,且具有更佳的抗干扰性,检测限低,实际应用价值高。
附图说明
图1为本发明实施例3中荧光探针在不同轻水含量(0-99%)的重水中的荧光发射光谱;
图2为本发明实施例3中荧光探针在不同轻水含量(0-20%)的重水中的荧光发射光谱;
图3为本发明实施例3中荧光探针在的重水中的荧光强度随轻水含量增加的线性关系图;
图4为本发明实施例4中荧光探针在的重水中的荧光强度随轻水含量增加的线性关系图;
图5为本发明实施例5中式I所示结构荧光探针在干扰物质存在条件下荧光发射柱状图;
图6为本发明实施例5中式II所示结构荧光探针在干扰物质存在条件下荧光发射柱状图;。
具体实施方式
以下结合具体实施方式和附图对本发明的技术方案作进一步详细描述:
实施例1:
荧光探针(式II所示结构)的制备:
按照质量比为1:0.76的比例取4-吡啶甲醛、二硫代草酰胺混合,加入无水DMF(4-吡啶甲醛与无水DMF的固液比为0.032g:1mL)回流反应6h;静置过夜,过滤、水洗涤6次,并在240℃下减压升华收集黄色产物E1;1H NMR(400MHz,d6-DMSO),δppm∶8.73(d,4H),7.99(d,4H);
取E1加入3,4-亚甲基二氧苄基氯,其中,E1与3,4-亚甲基二氧苄基氯的固液比为0.025g:1mL;130℃油浴条件下搅拌反应12h;之后静置过夜,加入甲醇并用正己烷洗涤6次得到荧光探针;1H NMR(400MHz,d6-DMSO),δppm∶9.07(d,4H),8.85(d,4H),6.75~6.92(m,6H),5.63、5.41(s,8H)。
实施例2:
荧光探针(式III所示结构)的制备:
按照摩尔比为1:2.5的比例取实施例1制备的E1加入5-(4-溴苯基)糠醛混合,接着加入丙酮(E1与丙酮的固液比为0.025g:1mL)回流反应5h;静置过夜,过滤、丙酮洗涤6次得到荧光探针;1H NMR(400MHz,d6-DMSO),δppm∶9.71(s,2H),9.12(d,4H),8.96(d,4H),8.01、7.68(d,8H),7.59、7.38(d,4H)。
实施例3:
荧光探针检测重水中轻水含量的测试
配制系列不同轻水含量的10μM探针(实施例1制备的)重水溶液,其中包含0.35%DMSO,轻水含量分别为(v/v)0%、10%、20%、30%、40%、50%、60%、70%、80%、90%、99%;再配制0-20%轻水含量的重水溶液,浓度分别为0%、2%、4%、6%、8%、10%、12%、14%、16%、18%、20%。之后放置于荧光分光光度计中进行荧光检测,设置激发波长为400nm,激发与发射带宽均为5nm,扫描记录400-650nm范围内的荧光发射光谱。
测试结果如图1-3所示。从图1中分析可知,随着含水量的增加,实施例1制备的探针在490nm处的荧光强度不断增强;由图2分析可知,在0-20%含轻水量范围内荧光强度与轻水含量成正比例增加,且具有优异的线性关系(如图3所示),线性曲线为y=5.34x+14.55,r2=0.9965;式中,y代表荧光增强因子的对数,x代表含轻水量。然后,根据3σ/n法则(S/N=3)计算得到该检测方法的检测限为0.028%。
实施例4:
荧光探针检测重水中轻水含量的测试
配制系列不同轻水含量的10μM探针(实施例2制备的)重水溶液,其中包含0.35%DMSO,轻水含量分别为(v/v)0%、10%、20%、30%、40%、50%、60%、70%、80%、90%、99%;再配制0-20%轻水含量的重水溶液,浓度分别为0%、2%、4%、6%、8%、10%、12%、14%、16%、18%、20%。之后放置于荧光分光光度计中进行荧光检测,设置激发波长为400nm,激发与发射带宽均为5nm,扫描记录400-650nm范围内的荧光发射光谱。
从测试结构中分析可知,随着含水量的增加,实施例2制备的探针在475nm处的荧光强度不断增强;并且在0-20%含轻水量范围内荧光强度与轻水含量成正比例增加,且具有优异的线性关系(如图4所示),线性曲线为y=7.66x+16.20,r2=0.9966;式中,y代表荧光增强因子的对数,x代表含轻水量。然后,根据3σ/n法则(S/N=3)计算得到该检测方法的检测限为0.015%。
实施例5:
荧光探针选择性测试
选择性离子的溶液配制:取0.01mol各种金属盐、阴离子的钠盐,加入少量去离子水溶解后,再用去离子水定容,得到浓度为10mM的溶液。
配制10mL的10μM探针(实施例1或2制备的)重水溶液,其中包含0.35%DMSO;然后加入100μL浓度为200μM的无机离子(Fe2+、Fe3+、Ca2+、Cu2+、Mg2+、Na+、F-、HSO3 -、H2O2、Cys)水溶液,然后放置于荧光分光光度计中进行荧光检测,设置激发波长为400nm。最后计算相应荧光波长处的荧光强度,评估不同物质对荧光探针溶液的干扰性。
分别对实施例1和实施例2制备的荧光探针进行上述测试,结果如图5-6所示。从图中分析可知,常见阳离子、阴离子、活性氧物质和常见氨基酸的存在几乎不引起探针在检测荧光强度的变化,表明本发明制备得到的荧光探针应用于重水中轻水含量的检测,该检测方法具有优异的抗干扰能力,具有较高的实际应用价值。同时式III所示结构的荧光探针抗干扰能力要优于式II所示结构的荧光探针。
实施例6:
荧光探针检测有机溶剂中水含量的测试
配制系列不同水含量的10μM探针(实施例1或2制备的)DMF溶液,水含量分别为(v/v)0%、10%、20%、30%、40%、50%、60%、70%、80%、90%、99%;再配制0-20%轻水含量的重水溶液,浓度分别为0%、2%、4%、6%、8%、10%、12%、14%、16%、18%、20%。之后放置于荧光分光光度计中进行荧光检测,设置激发波长为400nm,激发与发射带宽均为5nm,扫描记录400-650nm范围内的荧光发射光谱。
分别对实施例1和实施例2制备的荧光探针进行上述测试,得到如下测试结果:
由实施例1制备的荧光探针进行上述测试的结果可知,随着含水量的增加,实施例1制备的探针在475nm处的荧光强度不断增强;并且在0-20%含水量范围内荧光强度与水含量成正比例增加,且具有优异的线性关系,线性曲线为y=3.428x+9.436,r2=0.9821;式中,y代表荧光增强因子的对数,x代表含水量。然后,根据3σ/n法则(S/N=3)计算得到该检测方法的检测限为0.174%。表明本发明实施例1制备的荧光探针材料对有机溶剂中含水量的检测具有良好的灵敏度。
由实施例2制备的荧光探针进行上述测试的结果可知,随着含水量的增加,实施例1制备的探针在470nm处的荧光强度不断增强;并且在0-20%含水量范围内荧光强度与水含量成正比例增加,且具有优异的线性关系,线性曲线为y=7.689x+18.437,r2=0.9889;式中,y代表荧光增强因子的对数,x代表含水量。然后,根据3σ/n法则(S/N=3)计算得到该检测方法的检测限为0.102%。表明本发明实施例2制备的荧光探针材料对有机溶剂中含水量的检测具有良好的灵敏度,并且其检测能力由于实施例1制备的荧光材料。
上述实施例中的常规技术为本领域技术人员所知晓的现有技术,故在此不再详细赘述。
以上所述,仅为本发明的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,可轻易想到变化或替换,都应涵盖在本发明的保护范围之内。因此,本发明的保护范围应以所述权利要求的保护范围为准。
Claims (9)
4.式II所示结构的制备方法,包括:
-取4-吡啶甲醛、二硫代草酰胺混合,在无水DMF回流条件下反应得到产物E1;
-取E1与3,4-亚甲基二氧苄基氯反应得到式II所示结构。
5.式III所示结构的制备方法,包括:
-取4-吡啶甲醛、二硫代草酰胺混合,在无水DMF回流条件下反应得到产物E1;
-取E1与5-(4-溴苯基)糠醛混合,在丙酮回流条件下反应得到式III所示结构。
6.根据权利要求4或5所述的结构的制备方法,其特征在于:所述4-吡啶甲醛、二硫代草酰胺的质量比为1:0.7~0.8。
7.权利要求1所述荧光探针在检测重水中轻水含量中的应用。
8.根据权利要求7所述的用途,其特征在于:所述荧光探针对轻水的检测限≤0.028%。
9.权利要求1所述荧光探针在检测有机溶剂中水含量中的应用。
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