CN107760298A - 一种检测亚硫酸氢根的荧光探针及制备方法与应用 - Google Patents
一种检测亚硫酸氢根的荧光探针及制备方法与应用 Download PDFInfo
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Abstract
本发明公开了一种检测亚硫酸氢根离子的荧光探针及其制备方法和应用，该探针的分子式为：C52H42N4O6，其结构式如下所示：
Description
【技术领域】
本发明属于离子检测的分子探针领域，特别是一种用于选择性检测亚硫酸氢根的分子探针及其制备方法与应用。
【背景技术】
亚硫酸氢盐具有抗氧化性、抗菌性，可用做食用级产品的漂白剂、抗菌剂以及酶抑制剂，在食品以及制药行业有着广泛的应用。亚硫酸氢盐作为一种世界范围内广泛使用的食品添加剂，被用于食品、药品的抗氧化、防腐。过量的亚硫酸氢根离子会导致严重的过敏反应、腹泻、低血压等疾病。美国食品药品管理局规定需要表示含有>10μg/mL的产品。迄今为止，已有多种检测亚硫酸氢根的方法，包括电化学、色谱、毛细管电泳等。这些方法仪器昂贵、处理复杂、不能实时监测，具有很大的局限性。而荧光方法由于其检出限低、方便高效、实时监测等优势被广泛应用于分析检测领域。
荧光探针能够将离子存在信息转换成易被检测的光信号，进而获得特定离子的识别功能。在体系中与特定离子的相互作用会发生特定的物理化学变化，从而导致相应的光信号发生改变。荧光探针具有高灵敏度，简单易行等诸多优点。
【发明内容】
本发明的目的是针对上述技术分析和存在问题，提供了一种荧光探针及其制备方法，及其在亚硫酸氢根离子检测中的应用。
本发明的技术方案：
一种检测亚硫酸氢根离子的荧光分子探针，该探针的分子式为：C52H42N4O6，其结构如下：
上述所述用于检测亚硫酸氢根离子的荧光探针探针的制备方法，步骤如下：
(1)惰性气体保护下，乙二醇二甲醚与水的混合溶剂中，加入氢化螺烯化合物1、无水碳酸钾、4-甲酰基苯硼酸、四三苯基膦钯，加热回流。反应结束后用乙酸乙酯萃取，真空干燥，柱层析方法提纯得到化合物2。
(2)惰性气体保护下，乙醇溶液中加入化合物2、丙二腈，加入适量哌啶作为催化剂，室温搅拌。柱层析方法提纯得到探针分子I。
其中步骤(1)中所述反应需在惰性气体保护下进行；
所述化合物1、无水碳酸钾、4-甲酰基苯硼酸、四三苯基膦钯、乙二醇二甲醚与水的用量比为1mol:5-20mol:2-10mol:0.02-0.1mol:5-25L:5-25L，具体可为1mol:5-10mol:2-5mol:0.02-0.05mol:5-15L:5-15L
步骤(2)中所述反应需在惰性气体保护下进行；所述反应需加入哌啶作为催化剂；
所述化合物2、丙二腈的用量比为1mol:2-8mol，具体可为1mol:2-5mol
研究发现，本发明的荧光探针使用方法没有特殊限制，通常可在室温下将探针分子I溶解在乙醇和水的混合溶液(1:1，v/v)中进行测试，当加入亚硫酸氢根离子时，由于硫酸氢根离子对于碳碳双键时，会发生亲核加成，改变分子的电子结构，导致紫外光谱和荧光光谱发生明显变化，肉眼可见溶液由黄色变为无色，同时绿色荧光变为蓝色。
本发明的优点是：本发明制备的荧光探针I，合成简单方便，产率高，易于制备，适于放大合成及实际生产应用。能够利用紫外可见方法以及荧光方法检测亚硫酸氢根离子。选择性好，检测速度快，并且适合裸眼检测，不受醋酸根离子、硫氰酸根离子、亚硝酸根离子、硝酸根离子、硫酸氢根离子、碳酸根离子、氟离子、氯离子、溴离子、碘离子、半胱氨酸、高半胱氨酸、谷胱甘肽等阴离子以及生物硫醇的干扰。其作为新型探针可以应用于离子检测领域，有着广阔的应用前景。
【附图说明】
图1为探针I溶液中加入40当量不同阴离子以及含巯基化合物后的紫外吸收光谱。
图2为探针I溶液中加入40当量不同阴离子以及含巯基化合物后的荧光光谱。
【具体实施方式】
为了进一步说明本发明，给出以下系列具体实施例，但本发明并不受这些具体实施例的限制，了解该领域的技术人员对本发明的些许改动将可以达到类似的结果，这些改动也包含在本发明中。
实施例1：分子荧光探针I的制备
(1)化合物1(76mg，0.114mmol)，加入无水碳酸钾(0.157g，1.14mmol)，4-甲酰基苯硼酸(51.2mg，0.342mmol)，15mL二甲基甲酰胺，10mL水，13mg四三苯基膦钯，氮气保护下，加热回流12小时。后用乙酸乙酯萃取，柱层析方法纯化，得到化合物2(70mg，85％)。
(2)化合物2(0.3g，0.415mmol)，加入丙二腈(81.9mg，1.24mmol)，两滴哌啶，乙醇20mL，氮气保护下室温搅拌2小时。后经柱层析纯化得到荧光探针I(0.25g，73％)。
检测结果：
1H NMR(500MHz,CDCl3)δ7.95(d,J＝8.4Hz,4H),7.78(s,2H),7.72(d,J＝8.4Hz,4H),7.31(s,2H),6.77(s,2H),4.36–4.21(m,4H),3.32(s,6H),3.14–3.06(m,2H),2.92–2.84(m,4H),2.76–2.66(m,2H),1.83–1.74(m,4H),1.03(t,J＝7.4Hz,6H).
13C NMR(126MHz,CDCl3)δ170.43,153.87,153.47,148.97,148.74,135.05,133.91,132.89,128.85,128.71,128.54,127.51,126.13,125.80,125.73,125.68,124.79,123.85,123.75,120.83,118.01,107.27,106.74,98.05,66.33,44.26,12.68.
实施例2：亚硫酸氢根离子荧光探针的应用。
将该分子探针I溶于二甲基亚砜中，配置成1mmol/L的探针溶液，并稀释成乙醇和PBS缓冲液的混合溶液(二甲基亚砜：PBS＝1:1，v/v)，用紫外可见分光光度计和荧光分光光度计对探针I识别HSO3 -的性能进行了研究。探针I的浓度为1×10-5M及5×10-6M，分别用来进行紫外吸收以及荧光测试。
图1为探针I溶液中加入40当量不同阴离子以及含巯基化合物后的紫外吸收光谱。1×10-5M的探针I溶液中，分别加入40当量不同的阴离子以及巯基化合物(醋酸根离子、硫氰酸根离子、亚硝酸根离子、硝酸根离子、硫酸氢根离子、碳酸根离子、氟离子、氯离子、溴离子、碘离子、半胱氨酸、高半胱氨酸、谷胱甘肽)。发现探针分子I在加入亚硫酸氢根离子后，357nm-500nm处紫外吸收强度明显下降，285nm处紫外吸收峰明显上升，黄色溶液褪色。加入其它阴离子以及巯基化合物没有明显变化。
图2为探针I溶液中加入40当量不同阴离子以及含巯基化合物后的荧光光谱。5×10-6M的探针I的溶液中，分别加入40当量不同的阴离子以及巯基化合物(醋酸根离子、硫氰酸根离子、亚硝酸根离子、硝酸根离子、硫酸氢根离子、碳酸根离子、氟离子、氯离子、溴离子、碘离子、半胱氨酸、高半胱氨酸、谷胱甘肽)。选用350nm波长光作为激发光。发现探针I本身在527nm处有较弱的荧光发射峰，在加入亚硫酸氢根离子后，在450nm处出现新的荧光发射峰，荧光强度显著增强，由弱的绿色荧光变为强的蓝色荧光。加入其它阴离子以及巯基化合物没有明显变化。
结果表明，合成的荧光探针I对于亚硫酸氢根有很好的响应能力，同时能够避免常见的阴离子以及生物体内含巯基化合物的干扰，可以作为比色以及荧光探针选择性地检测亚硫酸氢根离子，有广泛的应用前景。
Claims (6)
1.一种检测亚硫酸氢根离子的荧光分子探针，该探针的分子式为：C52H42N4O6，其结构如下：
2.一种如权利要求1所述化合物的制备方法，
其特征在于包括下述步骤：
(1)惰性气体保护下，乙二醇二甲醚与水的混合溶剂中，加入氢化螺烯化合物1、无水碳酸钾、4-甲酰基苯硼酸、四三苯基膦钯，加热回流。反应结束后用乙酸乙酯萃取，真空干燥，柱层析方法提纯得到化合物2。
(2)惰性气体保护下，乙醇溶液中加入化合物2、丙二腈，加入适量哌啶作为催化剂，室温搅拌。柱层析方法提纯得到探针分子I。
3.根据权利要求2所述的方法，其特征在于：其中步骤(1)中所述反应需在惰性气体保护下进行；所述化合物1、无水碳酸钾、4-甲酰基苯硼酸、四三苯基膦钯、乙二醇二甲醚与水的用量比为1mol:5-20mol:2-10mol:0.02-0.1mol:5-25L:5-25L，具体可为1mol:5-10mol:2-5mol:0.02-0.05mol:5-15L:5-15L。
4.根据权利要求2所述的方法，其特征在于：步骤(2)中所述反应需在惰性气体保护下进行；所述反应需加入哌啶作为催化剂；所述化合物2、丙二腈的用量比为1mol:2-8mol，具体可为1mol:2-5mol。
5.一种如权利要求1所述荧光探针的应用，其特征在于，该荧光探针可以利用荧光光谱仪检测亚硫酸氢根离子。
6.一种如权利要求1所述荧光探针用于裸眼检测亚硫酸氢根离子的应用。
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