CN112079861B - 一种荧光淬灭检测氟离子的分子探针及其制备方法 - Google Patents
一种荧光淬灭检测氟离子的分子探针及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种荧光猝灭检测氟离子的分子探针及其制备方法。所述荧光分子探针以4‑(二乙氨基)‑2‑羟基苯甲醛为原料，引入叔丁基二甲基氯硅烷，再与丙二腈缩合而成。合成简便，反应条件温和。该探针分子光学性能稳定，合成产率高；对氟离子检测灵敏度高，检测下限低，响应范围为宽，检测限极低，检测范围宽，选择性好，对常见的阳离子，干扰性阴离子无响应；并且适合裸眼检测。该荧光分子探针在生物化学，环境科学等领域具有实际的应用价值。
Description
技术领域
本发明涉及的是化学分析检测技术领域，具体涉及一种荧光淬灭检测氟离子分子探针及其制备方法。
背景技术
氟化物阴离子因其在人类活动的许多领域中的重要性而在其对健康和环境的影响方面受到重视，因此在科学界得到了广泛的关注。尽管过去在***研究中忽略了氟化物，但氟化物现已成为阴离子识别领域的热门目标。F-具有强烈的亲核特性，作为最小的卤化物，它具有最高的电荷密度，然而，由于其离子半径与K+的离子半径大致相同，因此不能认为其尺寸最小。所有这些都使得氟化物以氢键(HB)配偶体。近几年发表的大量科学报告，在极性和水性介质中寻求与氟化物建立有效和特异性的相互作用。
氟离子(F-)是人体必不可少的微量元素，因为低浓度的F-已被证明对龋病的预防和骨质疏松症的临床治疗有效。F-的主要来源是食物和地下水的摄入量。然而，过量摄入F-可引起胃部和肾脏疾病，例如牙齿和骨骼氟中毒，***，甚至死亡。此外，地方性氟中毒广泛存在，影响数百万人。考虑到环境问题，氟离子化学传感器可以对氟离子进行定性定量的测定，对环境保护和人类健康具有重要的意义。
在目前用于F-检测的方法中，离子选择性电极和离子色谱法的标准Willard-Winter方法常用于F-分析，他们通常需要复杂的程序和昂贵的仪器。因此，开发出高选择性，敏感性和快速性的F-检测方法变得非常重要。荧光探针是用于测试各种分析物的新兴方法，因为它们可用于具有最小干扰，以及高灵敏度和选择性。
发明内容
根据上述现有技术存在的问题，本发明的目的之一是提供一种合成简单、反应条件温和、成本低廉的荧光探针的合成方法；目的之二是提供一种选择性好，灵敏度高，能够可视化监测及荧光淬灭检测氟离子的荧光探针。
为了实现上述目的，本发明采用以下技术方案：
一种荧光猝灭检测氟离子的分子探针，其结构式为：
所述分子探针以4-(二乙氨基)-2-羟基苯甲醛衍生物为荧光团，叔丁基二甲基氯硅烷醚为氟离子识别基团的化合物。
所述快速检测氟离子的新型分子探针的制备方法，具体采用以下工艺路线：
所述快速检测氟离子的新型分子探针的制备方法，具体包括以下步骤：
(1)将化合物I(4-(二乙氨基)-2-羟基苯甲醛)溶于DMF中，加入咪唑后室温下搅拌，之后将叔丁基二甲基氯硅烷加入到上述反应液中搅拌，反应完成后，加入去离子水淬灭反应，用二氯甲烷萃取，将所得有机相用无水硫酸钠干燥，减压蒸馏除去溶剂，得到红色混合物，纯化制得黄色固体，即为化合物II；
(2)将上述化合物II和丙二腈溶于DMF中，加入无水碳酸钠，在室温下搅拌；反应完成后，加入去离子水淬灭反应，用二氯甲烷萃取，所得有机相用无水硫酸钠干燥，减压蒸馏除去溶剂，纯化制得黄色固体化合物III，即为荧光分子探针。该荧光分子探针具有很强的荧光性。
本发明的荧光分子探针使用方法没有特殊限制。通常可以将探针分子溶解在合适的有机溶剂中，如，四氢呋喃(THF)或1,4-二氧六环，室温下进行测试。
本发明的荧光分子探针对氟离子的检测原理如下式所示：探针具有PET机制，在未加入F-时，PET被抑制，因此具有强烈的荧光，当加入F-时，PET被打开，生成氧负离子基团，以及硅氟键，从而荧光淬灭。探针在未加入F-前为无色液体，当加入F-后，变为黄色液体，荧光由蓝色变为绿色。
与现有技术相比，本发明制备的荧光分子探针具有很强的荧光性，探针具有PET机制实现对氟离子的快速、可视化检测。该探针分子光学性能稳定，合成产率高；对氟离子检测灵敏度高，检测限极低，检测范围宽，选择性好，对常见的阳离子，干扰性阴离子无响应；并且适合裸眼检测。该荧光分子探针在生物化学，环境科学等领域具有实际的应用价值。
附图说明
图1为本发明探针在有机体系下，加入不同浓度的氟离子的荧光发射光谱图。
图2为本发明探针在有机体系下，加入不同干扰离子的荧光发射光谱图。
图3为本发明探针在有机体系下，加入一定浓度的氟离子，响应时间的变化图。
图4为本发明探针在PBS缓冲体系下，加入不同浓度的氟离子荧光发射光谱图。
图5为本发明探针在PBS缓冲体系下，加入不同浓度的氟离子的浓度线性方程，R2＝0.9937。
图6为本发明探针在PBS缓冲体系下，加入干扰离子,荧光发射光谱图。
具体实施方式
以下结合附图和具体实施例对本发明的进行说明，应当理解，此处所描述的优选实施例仅用于说明和解释本发明，并不用于限定本发明。
实施例1：
(1)化合物2的制备
在单颈圆底烧瓶中，加入化合物I(4-(二乙氨基)-2-羟基苯甲醛)和咪唑和DMF，室温搅拌。将叔丁基二甲基氯烷加入到上述反应体系中，搅拌反应完全，加入去离子水淬灭反应。然后用二氯甲烷萃取、分离得到有机相，再用无水硫酸钠干燥，蒸馏除去溶剂，得到红色固体混合物，用硅胶柱层析分离纯化，得黄色固体，为化合物II。(产率63％)
(2)分子荧光探针的制备
在单颈烧瓶中，将化合物II和丙二腈溶于DMF中，加入无水Na2CO3，室温反应。将反应液倒入水中，用二氯甲烷萃取，再用去离子水洗涤，分离得到有机相用无水硫酸钠干燥，蒸馏除去溶剂，得到固体混合物，用硅胶柱层析分离纯化，得黄色固体，化合物III，即为分子荧光探针。(产率45％)
化合物III核磁检测结果如下所示：
1H NMR(400MHz,CDCl3)，δ7.97(s，1Η)，7.32-7.30(d，1H)，6.65-6.63(d，1H)，6.47(s，1H)，3.44-3.50(m，4H)，1.57(s，9H)，1.25-1.27(t，6H)，1.23(s，6H)。
实施例2：裸眼识别检测氟离子荧光分子探针的应用
分别将实施例1制备的分子探针溶于THF溶液和THF溶液+PBS混合溶液中，加入不同的阴离子(磷酸二氢根、溴离子、硫酸氢根、碳酸根、碘离子、氯离子、硝酸根等)以及阳离子(铁离子、汞离子、锌离子、钾离子、钙离子、铜离子等)溶液，测试荧光发射光谱变化。
图1-图3表明，在荧光发射光谱中荧光分子探针对氟离子具有很高的灵敏度。在有机体系中(THF溶液)，加入氟离子后，荧光发射由460nm红移到480nm，荧光强度淬灭，溶液颜色发生显著变化(淡黄色变为黄色)，荧光由蓝色变为绿色，可以用裸眼检测；同时在紫外灯下照射下，荧光分子探针在加入氟离子后荧光淬灭。并且不受阴离子的影响，且探针对氟离子具有很好的选择性。在缓冲体系中，加入氟离子后，荧光发射由480nm红移到486nm，荧光强度淬灭。两种体系中都具有荧光淬灭性，且荧光强度变化与氟离子浓度呈线性关系，适用于氟离子的检测。
所述荧光分子探针用于有机体系中氟离子含量的测定，具体方法如下：
将所述分子探针加入有机溶剂中，如THF，1,4二氧六环，DMF，DMSO等，得到分子探针母液，然后配置不同氟离子浓度的标准溶液。向标准溶液中加入母液，放置1分钟后，在激发波长420nm，发射波长为460nm处分别测定不同氟离子浓度时的荧光强度，做成滴定曲线，拟合460nm处荧光强度与氟离子浓度的函数关系。再向待测氟离子溶液中加入等量的母液，将荧光强度带入上述滴定曲线，得到待测氟离子含量。
所述荧光分子探针用于缓冲体系中氟离子含量的测定，具体方法如下：
将所述分子探针加入有机溶剂中，如THF，1,4二氧六环，DMF，DMSO等，用THF:PBS＝1：9(pH＝7.4)的混合缓冲溶液配制探针分子母液。然后配置不同氟离子浓度的标准溶液。向标准溶液中加入母液，放置1分钟后，在激发波长440nm，发射波长为480nm处分别测定不同氟离子浓度时的荧光强度，做成滴定曲线，拟合480nm处荧光强度与氟离子浓度的函数关系。再向待测氟离子溶液中加入等量的母液，将荧光强度带入上述滴定曲线，得到待测氟离子含量。
最后应说明的是：以上所述仅为本发明的优选实施例而已，并不用于限制本发明，尽管参照前述实施例对本发明进行了详细的说明，对于本领域的技术人员来说，其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (3)
1.一种荧光猝灭检测氟离子的分子探针，其特征在于，结构式为：
2.一种权利要求1所述荧光猝灭检测氟离子的分子探针的制备方法，其特征在于，具体采用以下工艺路线：
3.根据权利要求2所述荧光猝灭检测氟离子的分子探针的制备方法，其特征在于，具体包括以下步骤：
(1)将化合物I溶于DMF中，加入咪唑后室温下搅拌，之后将叔丁基二甲基氯硅烷加入到上述反应液中搅拌，反应完成后，加入去离子水淬灭反应，用二氯甲烷萃取，将所得有机相用无水硫酸钠干燥，减压蒸馏除去溶剂，得到红色混合物，纯化制得黄色固体，即为化合物II；
(2)将上述化合物II和丙二腈溶于DMF中，加入无水碳酸钠，在室温下搅拌；反应完成后，加入去离子水淬灭反应，用二氯甲烷萃取，所得有机相用无水硫酸钠干燥，减压蒸馏除去溶剂，纯化制得黄色固体化合物III，即为荧光分子探针。
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