CN113698361B - 一种用于检测氟离子的比色荧光探针化合物及其检测方法 - Google Patents
一种用于检测氟离子的比色荧光探针化合物及其检测方法 Download PDFInfo
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Abstract
本发明公开了一种用于检测氟离子的比色荧光探针化合物及其检测方法,属于分析化学技术领域。该比色荧光探针结构为在苝湾位置含有N‑H和O的七原子环的苝四羧酸酯。本发明的比色荧光探针在有机溶剂中具有良好的溶解性和荧光性能,在F‑离子存在下吸收峰红移,表现出明显的颜色变化和强烈的荧光猝灭;选择性好,氯离子、溴离子、碘离子、硫酸根、醋酸根、高氯酸根和磷酸二氢根对氟离子浓度的测定无明显干扰,可以作为比色和荧光探针用于氟离子检测。
Description
技术领域
本发明属于分析化学技术领域,涉及一种用于检测氟离子(F-)的比色荧光探针化合物及其检测方法。
背景技术
构建具有高选择性和高灵敏度的具备阴离子识别能力的有机分子传感探针是超分子化学的研究热点。在各种类型的阴离子中,F-在不同的环境、生物和工业过程中发挥着重要作用,少量F-对预防使用正畸器引起的牙釉质脱矿和龋齿非常重要,还可用于治疗骨质疏松症。然而,大量F-则可导致氟中毒、机体尿石症、肾毒性改变甚至癌症。美国环境保护署(EPA,USA)建议水中F-的允许浓度为2ppm。因此,开发具有高灵敏度的比色和荧光传感系统,获取F-的定性和定量信息具有重要意义。苝二酰亚胺(PDI)及其衍生物因具有优异的光、热和化学稳定性,广泛应用在工业颜料领域。近年来,它们作为荧光探针的应用受到了极大的关注。然而,由于苝核容易发生π-π聚集,许多PDI溶解性差、荧光量子产率低,限制了它们的应用。苝四羧酸酯(PTAC)具有四个缺电子羧基酯链,在有机溶剂中具有良好的溶解性和荧光性能。为了进一步改善PTAC的光学和电子性能,湾位扩展PTAC衍生物的开发在过去的几年中受到极大的关注,湾位扩展能够得到具有平面结构和共轭大π键的芳香体系,这种构象有助于电子从电子给体(F-识别基团)到电子受体(湾位扩展PTAC)的有效分子内电荷转移(ICT),苝骨架中含有S-、O-和N-等杂原子的五元或六元杂环PTAC荧光探针已经有了相关报道,然而,在苝湾位置含有七原子环的PTAC探针尚未见报道。
发明内容
针对上述现有技术,本发明提供了一种用于检测氟离子的比色荧光探针化合物。
本发明提供的比色荧光探针化合物的结构为:
本发明的比色荧光探针化合物检测氟离子的方法:
将探针化合物溶于二氯甲烷配成浓度为1×10-5mol/L的探针溶液,向上述探针溶液中用移液枪加入四丁基氟化铵的乙腈溶液,并逐渐增加浓度,使得加入后四丁基氟化铵的浓度分别是探针化合物浓度的3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20倍,分别测定每次滴加后激发波长为501nm的荧光光谱,以574nm荧光强度I574nm为纵坐标,氟离子浓度与探针化合物浓度比值为横坐标做工作曲线;工作曲线为:y = -77.8x + 1937.8(R2=0.9986),其中y为574 nm的荧光强度,x为F-的浓度与探针化合物浓度比值。探针化合物对氟离子的工作浓度范围3×10-5~2×10-4mol/L,Cl-、Br-、I-、SO4 2-、AcO-、ClO4 -和H2PO4 -对氟离子浓度的测定无明显干扰。
本发明的有益效果:
本发明所涉及的一种氟离子比色荧光探针,识别机理为F-和H原子(位于七元原子环的N位)之间的分子间质子转移过程以及随后的从N·基团向苝基团的分子内电荷转移跃迁。探针在F-存在下吸收峰红移,表现出明显的颜色变化和强烈的荧光猝灭,选择性好,常见阴离子对氟离子浓度的测定无明显干扰,可以作为比色和荧光探针用于F-检测。
附图说明
图1是比色荧光探针的分子结构图;
图2是比色荧光探针的1H NMR谱图;
图3是比色荧光探针的13C NMR谱图;
图4是本发明的比色荧光探针在CH2Cl2溶液中(浓度为10 µM)仅存在F-离子(0-30当量)时的吸收光谱变化(a)和不同阴离子(当量为100)存在下的吸收光谱(b)。嵌入图显示的是自然光下对应的照片;
图5是本发明的比色荧光探针在CH2Cl2溶液中(浓度为10 µM,激发波长501 nm),在0 ~ 30当量探针浓度的F-离子存在下的荧光变化图,嵌入图为手持紫外线灯照射下对应的溶液荧光照片(a)。本发明的比色荧光探针最大荧光峰强度(I574 nm)与加入F-离子浓度的对应关系曲线(b);
图6是本发明的比色荧光探针在CH2Cl2溶液中(浓度为10 µM)加入各种阴离子(F-为30当量,其他阴离子为100当量)后的荧光变化图示。嵌入图为手持紫外线灯照射下对应溶液的荧光照片。
具体实施方式
实施例 1. 比色荧光探针的制备
合成路线如下式所示:
将化合物3(1.0 g,1.44 mmol)、锌粉(0.5 g,8.0 mmol)、氯化铵(0.8 mg,16.0mmol)溶于100 mL四氢呋喃中。将混合物在室温下搅拌3 h,过滤除掉氯化铵和锌粉。滤液粗产物经硅胶柱层析纯化,得到深褐色固体化合物2(0.76 g,80%)。将化合物2(0.4 g,5.0mmol)、多聚甲醛(0.12 g,4.0 mmol)催化的甲酸溶于100 mL乙醇中,加热回流12 h。过滤收集沉淀,粗产物经硅胶柱层析(二氯甲烷:乙酸乙酯,2%)纯化,得到本发明的比色荧光探针P1(0.25 g,62%,M.p.:300-302℃)。1H NMR(400 MHz,CDCl3,δ ppm):8.17(d,1H,J = 7.7Hz),7.98(d,1H,J = 7.7 Hz),7.91(d,1H,J = 7.2 Hz),7.88(s,1H),7.80(s,1H),7.52(s,1H),6.00(m,1H),5.03(d,2H,J = 7.2 Hz),4.34(m,8H),1.80-1.73(m,8H),1.57-1.46(m,8H),1.02-0.98(m,12H)。13C NMR(100 MHz, CDCl3,δ ppm):169.01,168.96,168.03,167.82,157.15,144.18,131.76,129.47,128.45,125.67,122.15,120.82,79.45,65.37,65.29,65.25,65.21,30.70,30.68,30.62,29.72,19.31,19.26,13.85。
本发明对实施例1得到的比色荧光探针进行了效果测试:
1.对F-的吸收光谱响应
将氟离子的四丁基铵盐标准溶液加入到本发明比色荧光探针的CH2Cl2溶液中,用分光光度滴定法研究了探针与F-离子的相互作用。单体探针在501 nm处有强吸收带,在379nm处有弱吸收带(图4中(a))。在探针溶液中加入F-(0 - 30.0当量)后,探针溶液中501 nm和379 nm处的吸收带逐渐减弱,577 nm和413 nm处出现新的吸收带,在436 nm和530 nm处观察到两个清晰的等吸收点,探针溶液的浅橙黄色变成了蓝灰色(图4中(a)插图)。对Cl-、Br-、I-、SO4 2-、AcO-、ClO4 -、H2PO4 -等多种阴离子进行了类似的研究。其中,在加入100当量浓度的各种阴离子(除F-离子外)后,探针的吸收光谱没有明显变化(图4中(b)插图)。本发明的荧光探针可用于F-的比色定性分析。
2.对F-的荧光光谱响应
在501nm波长光激发下,单体探针在574nm处出现最大荧光发射峰,随着F-浓度的增加,探针在574nm处的荧光强度逐渐减弱(图5中(a))。图5中(b)为P1在574nm处的发射峰与F-浓度之间的对应关系,发射强度(I574 nm)随F-浓度从3×10-5到2×10-4 mol/L呈线性下降。线性方程为y = -77.8x + 1937.8(R2=0.9986),其中y为574 nm的荧光强度,x为F-的浓度。F-离子识别过程不仅可以通过自然光下的颜色变化,还可以通过紫外灯下的荧光变化清楚地看到。用F-离子对探针进行荧光滴定时,探针的亮橘黄色溶液变为深蓝色(图5中(a)嵌入图)。本发明的荧光探针可用于F-的荧光定量分析。
3.探针对F-识别的选择性
对30倍量探针浓度的F-和100倍量探针浓度的其它阴离子(Cl-、Br-、I-、SO4 2-、AcO-、ClO4 -、H2PO4 -)进行了选择性识别实验。观察到,当添加其它阴离子后,探针的荧光光谱没有发生显著变化(图6)。本发明的荧光探针可以作为F-高选择性的荧光探针。
Claims (2)
1.一种比色荧光探针化合物非治疗目的的和非诊断目的的检测氟离子的方法,所述比色荧光探针化合物的化学结构式如下所示:
其特征在于,具体步骤为:
(1)将探针化合物溶于二氯甲烷配成浓度为1×10-5mol/L的探针溶液;
(2)向上述探针溶液中用移液枪加入四丁基氟化铵的乙腈溶液,并逐渐增加浓度,使得加入后四丁基氟化铵的浓度分别是探针化合物浓度的3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20倍,分别测定每次滴加后激发波长为501nm的荧光光谱,以574nm荧光强度I574nm为纵坐标,氟离子浓度与探针化合物浓度比值为横坐标做工作曲线;
工作曲线为:y = -77.8x + 1937.8, R2=0.9986,其中y为574 nm的荧光强度,x为氟离子的浓度与探针化合物浓度比值。
2.根据权利要求1所述的一种比色荧光探针化合物非治疗目的的和非诊断目的的检测氟离子的方法,其特征在于,溶液中还可以存在Cl-、Br-、I-、SO4 2-、AcO-、ClO4 -和H2PO4 -。
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