CN109265412B - 一种用于检测氟离子的探针化合物及其检测方法 - Google Patents

一种用于检测氟离子的探针化合物及其检测方法 Download PDF

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CN109265412B
CN109265412B CN201811377135.4A CN201811377135A CN109265412B CN 109265412 B CN109265412 B CN 109265412B CN 201811377135 A CN201811377135 A CN 201811377135A CN 109265412 B CN109265412 B CN 109265412B
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尹静梅
崔颖娜
贾颖萍
李慎敏
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Abstract

一种用于检测氟离子的探针化合物及其检测方法，本发明涉及一种具有氟离子检测用途的荧光探针化合物N‑3‑羟基‑4‑2’‑苯并噻唑苯‑3,5‑二苯甲氧苯甲酰胺，以及该化合物作为比率荧光探针检测氟离子的方法。本发明的氟离子荧光探针化合物检测范围较宽，响应范围2×10‑5～2×10‑3mol/L；选择性好，醋酸根、磷酸二氢根、硫酸氢根和氯离子对氟离子浓度的测定无明显干扰。适用于生物化学和环境化学等领域中氟离子的检测。

Description

一种用于检测氟离子的探针化合物及其检测方法
技术领域
本发明属于阴离子荧光分析检测技术领域，尤其是涉及一种具有氟离子(F-)检测用途的荧光探针化合物N-3-羟基-4-2’-苯并噻唑苯-3,5-二苯甲氧苯甲酰胺，以及该化合物作为比率荧光探针检测氟离子的方法。
背景技术
阴离子广泛存在于生物体系中，在生物学、化学、医学和环境科学等领域扮演着重要的角色，因此，人们对阴离子的选择性识别和检测越来越感兴趣。在众多阴离子中，氟离子是电负性最强、离子半径最小的阴离子，广泛存在自然界之中，也是人体必需的微量元素之一，由于在龋齿预防、骨质疏松症治疗等领域的显著作用而受到特别关注。但是过量氟离子的摄入将引起氟中毒，对人体有极大的危害，导致氟斑牙，氟骨癌等疾病。因此，氟离子的识别与检测显得尤为重要。
传统的检测氟离子的方法主要有氟离子选择电极法、离子色谱法、19F NMR谱、氟试剂比色法和荧光探针法，其中，荧光探针法因具有选择性好、灵敏度高、方便快捷等特点而备受关注。目前已经报道的氟离子荧光探针多为荧光增强型探针[1-7]，此类探针的量子效率易受环境影响，因此在实际应用中有一定的局限性，而比率型荧光探针可以避免检测环境的影响，实现对氟离子动态变化过程的定量检测，但是利用比率型荧光探针检测氟离子含量的报道较少[8,9]，而且已报道的这类探针存在一些缺陷，如灵敏度低[8]、响应范围窄[9]等，所以发展测定氟离子的新的比率荧光探针十分重要。
[1]Cho E J,Moon J W,Ko S W,et al.Anew fluoride selective fluorescentas well as chromogenic chemosensor containing naphthalene urea derivative[J].J.Am.Chem.Soc.,2003,125(41):12376-12377.
[2]Xu G,Tarr M A.A novel fluoride sensor based on fluorescenceenhancement[J].Chem.Commun.2004,9:1050-1051.
[3]Liu X Y,Bai D R,Wang S.Charge-transfer emission in nonplanarthree-coordinate organoboron compounds for fluorescent sensing of fluoride[J].Angew.Chem.,2006,118:5601-5604.
[4]Sokkalingam P,Lee C H.Highly sensitive fluorescence“turn-on”indicator for fluoride anion with remarkable selectivity in organic andaqueous media[J].J.Org.Chem.,2011,76:3820–3828.
[5]Ke B,Chen W,Ni N,et al.A fluorescent probe for rapid aqueousfluoride detection and cell imaging[J].Chem.Commun.2013,49:2494-2496.
[6]Sui B,Kim B,Zhang Y,et al.Highly selective fluorescence turn-onsensor for fluoride detection[J].ACS Appl.Mater.Interfaces,2013,5(8):2920-2923.
[7]Sakamoto T,Hasegawa D,Fujimoto K.Fluorine-modified bisbenzimidederivative as a molecular probe for bimodal and simultaneous detection ofDNAsby19F NMR and fluorescence[J].Chem.Commun.2015,51:8749-8752.
[8]Badugu R,Lakowicz J R,Geddes C D.Awavelength-ratiometric floride-sensitive probe based on the quinolinium nucleus and boronic acid moiety[J].Sensor.Actuat.B:Chemical,2005,104(1):103-110.
[9]Yang X F,Qi H P,Wang L P,et al.Aratiometric fluorescent probe forfluoride ion employing the excited-state intramolecular proton transfer[J].Talanta,2009,80(1):92-97.
发明内容
为弥补现有技术不足，本发明提供了一种具有F-检测用途的化合物N-3-羟基-4-2’-苯并噻唑苯-3,5-二苯甲氧苯甲酰胺(简称为a)。
本发明提供的探针化合物的结构为：
Figure BDA0001871025940000021
本发明的探针化合物检测F-浓度的方法：
将探针化合物溶于DMSO配成浓度为1×10-3mol/L的溶液A，取溶液A溶于含有乙腈的样品池中，混合均匀后得到探针化合物浓度为1×10-5mol/L的混合液B，向混合液B中逐渐滴加含F-的乙腈溶液，使得加入后F-的摩尔浓度依次是探针化合物的2，5，10，50，80，100，150，200，230倍，分别测定每次滴加含F-的乙腈溶液后激发波长为370nm的荧光光谱，以450nm与500nm荧光强度的比值(I450/I500)为纵坐标，F-浓度与探针化合物浓度比值([F-]/[a])为横坐标做工作曲线，趋势线方程为：
I450/I500＝0.0012[F-]/[a]+0.0562(R2＝0.9938)。
探针化合物对F-的工作浓度范围2×10-5～2×10-3mol/L，AcO-、H2PO4 -、HSO4 -和Cl-对F-浓度的测定无明显干扰。
进一步的，所述的含F-的乙腈溶液为四丁基氟化铵的乙腈溶液。
本发明的探针化合物对F-的选择性很高，能够选择性识别F-，适用于生物化学和环境化学等领域中F-的检测。本发明的探针化合物是F-检测的比率荧光识别探针，从而消除了荧光增强型探针等受外界不稳定带来的仪器的系统误差、背景误差等，使其灵敏度提高。
附图说明
图1是本发明实施例1中探针化合物的乙腈溶液在加入不同阴离子后的荧光吸收光谱图；
图2是本发明实施例2中探针化合物的乙腈溶液在加入0-230摩尔倍数的四丁基氟化铵后的荧光吸收光谱图；
图3是本发明实施例2中探针化合物在乙腈溶液中450nm与500nm荧光强度的比值(I450/I500)和F-摩尔浓度与探针化合物a摩尔浓度比值([F-]/[a])的工作曲线。
具体实施方式
下面通过具体实施例详述本发明，但不限制本发明的保护范围。如无特殊说明，本发明所采用的实验方法均为常规方法，所用实验器材、材料、试剂等均可从化学公司购买。
实施例1
将探针化合物N-3-羟基-4-2’-苯并噻唑苯-3,5-二苯甲氧苯甲酰胺溶于DMSO配成浓度为1×10-3mol/L的溶液A，取30μL溶液A溶于含有3mL乙腈的样品池中，将溶液混合均匀后得到探针化合物的浓度为1×10-5mol/L的混合液B。分别制备含有不同阴离子的乙腈溶液，即四丁基氟化铵乙腈溶液、四丁基磷酸二氢铵乙腈溶液、四丁基硫酸氢铵乙腈溶液、四丁基乙酸铵乙腈溶液和四丁基氯化铵的乙腈溶液，向混合液B中分别加入上述五种溶液，使得加入后四丁基氟化铵的浓度为探针化合物的200倍，其它四种四丁基铵盐的浓度为探针化合物的1000倍，分别测定各溶液在激发波长为370nm的荧光光谱(如图1)。从图1可以看出，探针化合物对AcO-的响应非常弱，H2PO4 -、HSO4 -和Cl-都不能引起探针化合物的荧光光谱的变化，而只有F-在500nm处荧光发射峰猝灭的同时，在450nm处出现了新峰，呈现出比率荧光的特征。以上结果说明探针化合物作为F-的荧光探针具有很好的选择性。
实施例2
将探针化合物N-3-羟基-4-2’-苯并噻唑苯-3,5-二苯甲氧苯甲酰胺溶于DMSO配成浓度为1×10-3mol/L的溶液A，取30μL溶液A溶于含有3mL乙腈的样品池中，将溶液混合均匀后得到探针化合物的浓度为1×10-5mol/L的混合液B，向混合液B中逐步滴加四丁基氟化铵的乙腈溶液，使得加入后四丁基氟化铵的浓度分别是探针化合物的2，5，10，50，80，100，150，200，230倍，分别测定每次滴加后激发波长为370nm的荧光光谱(如图2)。随着氟离子浓度的增加，荧光光谱上500nm处荧光峰强度逐渐减弱，而在450nm处出现了一个新峰，且荧光峰强度逐渐增强，以450nm与500nm荧光强度的比值(I450/I500)为纵坐标，F-浓度与探针化合物浓度比值([F-]/[a])为横坐标做工作曲线，如图3所示，趋势线方程为：I450/I500＝0.0012[F-]/[a]+0.0562(R2＝0.9938)。
以上所述，仅为本发明创造较佳的具体实施方式，但本发明创造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创造披露的技术范围内，根据本发明创造的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明创造的保护范围之内。

Claims (2)

1.一种用于检测氟离子的探针化合物检测氟离子的方法，其特征在于，氟离子探针化合物的化学名称为N-3-羟基-4-2’-苯并噻唑苯-3,5-二苯甲氧苯甲酰胺，结构式如下：
Figure FDA0002445167890000011
具体步骤为：
(1)将探针化合物溶于DMSO配成浓度为1×10-3mol/L的溶液，取30μL上述溶液溶于含有3mL乙腈的样品池中，将溶液混合均匀后得到探针化合物的浓度为1×10-5mol/L的混合液；
(2)向上述混合液中滴加四丁基氟化铵的乙腈溶液，并逐渐加大浓度，使得加入后四丁基氟化铵的浓度分别是探针化合物的2，5，10，50，80，100，150，200，230倍，分别测定每次滴加后激发波长为370nm的荧光光谱，以450nm与500nm荧光强度的比值I450/I500为纵坐标，氟离子浓度与探针化合物浓度比值[F-]/[a]为横坐标做工作曲线；
工作曲线为：I450/I500＝0.0012[F-]/[a]+0.0562(R2＝0.9938)。
2.根据权利要求1所述的氟离子探针化合物检测氟离子的方法，其特征在于，溶液中还可以存在AcO-、H2PO4 -、HSO4 -和Cl-。
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