CN110204535B - 一种香豆素类水合肼荧光探针及其制备方法 - Google Patents

一种香豆素类水合肼荧光探针及其制备方法 Download PDF

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CN110204535B
CN110204535B CN201910645960.6A CN201910645960A CN110204535B CN 110204535 B CN110204535 B CN 110204535B CN 201910645960 A CN201910645960 A CN 201910645960A CN 110204535 B CN110204535 B CN 110204535B
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侯琳熙
姜行宗
郭英雄
卢振
上官明沁
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Abstract

本发明属于荧光探针制备技术领域，具体涉及一种香豆素类荧光探针及其制备方法。本发明利用7‑羟基‑4‑甲基香豆素和酰氯噻吩为原料，在三乙胺催化下反应得到荧光探针化合物。在紫外光激发下，该探针化合物本没有荧光，当其与水合肼作用时，脂键发生断裂，探针发出蓝色的荧光，从而实现对水合肼的检测。该探针对水合肼具有很强的选择性和很高的灵敏性，能在复杂环境中对水合肼实现响应，是一类优异的“Turn‑on”型荧光探针，具有很好的应用前景。

Description

一种香豆素类水合肼荧光探针及其制备方法
技术领域
本发明属于荧光探针制备技术领域，具体涉及一种香豆素类荧光探针及其制备方法。
背景技术
水合肼(N2H4)是一种无机二元胺，无色且具有氨气味的液体。作为一种具有高反应活性的还原剂、弱碱，水合肼在制药、杀虫剂、纺织染料、化学化工方面有重要的作用。由于水合肼具有易燃、易爆、燃烧焓高的特性，通常也被用于火箭、导弹推进***。水合肼作为一种重要的工业原料有着广泛的应用，但是它是一种高毒性化学物质，在操作、使用、处理过程中容易造成环境污染以及人体伤害。水合肼作为一种神经毒素、致癌物，可以对肾脏、肺、肝脏、中枢神级***造成伤害。吸入高浓度的水合肼会造成咽喉、鼻子、眼睛感染，严重的会导致短暂的失明、头晕、恶心、血液病等慢性疾病。在人体内，水合肼虽然不是内生的，但是可以通过一些简单的途径如皮肤，呼吸***等被人体摄入吸收。由于具有很好的水溶性，易于入侵人体，造成伤害。美国环境署设定了饮用水中水合肼的容许最高浓度值为10 ppb。用于检测水合肼的常规方法有色谱法、电势法、电化学方法、滴定法。但是常规方法方法具有一些缺陷如：需要昂贵的仪器设备、复杂的操作过程、样品前处理繁琐等。荧光探针作为一种新型的分析方法，具有高选择性、高灵敏性可以实现在细胞组织内实时检测分析物的优点。但是关于检测水合肼的荧光探针的报道数量有限，而且很多探针合成复杂，容易受到干扰离子影响。因此，发明新的兼具选择性和灵敏性的水合肼探针十分必要。
发明内容
本发明的目的在于提供一类新颖的水合肼荧光探针及其制备方法，其合成简单、选择性好、灵敏度高、能够快速识别水合肼。
为了达到上述目的，本发明采取以下技术方案：
具体而言，本发明提供了一种水合肼荧光探针，其为香豆素类化合物，其结构如下：
Figure 100002_DEST_PATH_IMAGE001
其中：R为卤素、氢原子或甲基。
香豆素类水合肼荧光探针的制备方法包括以下步骤：
将7-羟基-4-甲基香豆素和酰氯噻吩溶解在丙酮中，滴加一定量的催化剂，在室温下回流搅拌30-60 min；反应完毕后减压蒸馏，得到白色粗产物；干燥后用二氯甲烷/石油醚体系进行柱色谱分离得到纯品探针。
其中7-羟基-4-甲基香豆素与酰氯噻吩按摩尔比计为1: 1-1.5。
所述步骤中的催化剂为三乙胺。
所述酰氯噻吩为噻吩-2-甲酰氯、5-氯噻吩-2-甲酰氯、5-甲基噻吩-2-甲酰氯、5-溴噻吩-2-甲酰氯中的任意一种。
所述的催化剂的用量，按摩尔比计，7-羟基-4-甲基香豆素：三乙胺=5: 0.8-1。
所述的柱色谱分离二氯甲烷/石油醚的体积比为：二氯甲烷：石油醚=1: 1。
本发明的有益效果有：
（1）本发明的水合肼荧光探针可与水合肼进行特异性作用，产生荧光光谱的变化，从而实现对水合肼的定量检测。
（2）本发明的水合肼荧光探针对水合肼具有很高的选择性，与其他物质进行作用均不能导致荧光光谱的明显改变。
（3）本发明的水合肼荧光探针的稳定性好，进而能够长期保存使用。
（4）本发明的水合肼荧光探针是快速高选择性水合肼探针，且合成简单，成本低廉，有利于商业化的推广应用。
附图说明
图1是实施例1探针样品对水合肼的时间响应曲线。
图2是不同浓度水合肼对实施例2探针样品荧光光谱的响应曲线。
图3是不同水合肼浓度对实施例2探针样品荧光强度的线性拟合曲线。
图4是不同分析物对实施例3探针样品荧光强度响应。其中编号0–21依次为空白，钠离子，钾离子，锂离子，钴离子，锌离子，亚铁离子，铜离子，镁离子，氯离子，磷酸根离子，碳酸根离子，硫酸根离子，氟离子，硝酸根离子，碘离子，三乙胺,乙醇胺，二正丁胺，二乙胺，氨水，水合肼。
图5是实施例2探针样品的核磁氢谱图。
具体实施方式
本发明提供了上述高灵敏高选择性水合肼荧光探针的制备方法及其光谱性能。下面将通过借助以下实施例来更详细地说明本发明。以下实施例仅是说明性的，应该明白，本发明并不受下述实施例的限制。
实施例1：
将263mg（1.5 mmol）7-羟基-4-甲基香豆素和218mg（1.5 mmol）噻吩-2-甲酰氯溶解在25 mL的丙酮中，滴加30mg（0.3 mmol）三乙胺，在室温（25 ℃）下回流搅拌30 min；反应完毕后减压蒸馏，得到白色粗产物；干燥后用二氯甲烷/石油醚体系（v/v, 1:1）进行柱色谱分离得到纯品探针。
实施例2：
将263mg（1.5 mmol） 7-羟基-4-甲基香豆素和271mg（1.5 mmol）5-氯噻吩-2-甲酰氯溶解在30 mL的丙酮中，滴加30mg（0.3 mmol）三乙胺，在室温（25 ℃）下回流搅拌1h；反应完毕后减压蒸馏，得到白色粗产物；干燥后用二氯甲烷/石油醚体系（v/v, 1:1）进行柱色谱分离得到纯品探针。
实施例3：
将526mg（3mmol）7-羟基-4-甲基香豆素和542mg（3 mmol）5-氯噻吩-2-甲酰氯溶解在25 mL的丙酮中，滴加48 mg（0.48 mmol）三乙胺，在室温（25 ℃）下回流搅拌30 min；反应完毕后减压蒸馏，得到白色粗产物；干燥后用二氯甲烷/石油醚体系（v/v, 1:1）进行柱色谱分离得到纯品探针。
实施例4：
将526mg（3mmol）7-羟基-4-甲基香豆素和473mg（3 mmol）5-甲基噻吩-2-甲酰氯溶解在20 mL的丙酮中，滴加60mg（0.6 mmol）三乙胺，在室温（28 ℃）下回流搅拌40 min；反应完毕后减压蒸馏，得到白色粗产物；干燥后用二氯甲烷/石油醚体系（v/v, 1:1）进行柱色谱分离得到纯品探针。
实施例5：
将263mg（1.5 mmol）7-羟基-4-乙基香豆素和336mg（1.5 mmol）5-溴噻吩-2-甲酰氯溶解在25 mL的丙酮中，滴加24mg（0.24 mmol）三乙胺，在室温（25 ℃）下回流搅拌50min；反应完毕后减压蒸馏，得到白色粗产物；干燥后用二氯甲烷/石油醚体系（v/v, 1:1）进行柱色谱分离得到纯品探针。
实施例6：
将263mg（1.5 mmol） 7-羟基-4-乙基香豆素和236mg（1.5 mmol）5-甲基噻吩-2-甲酰氯溶解在25 mL的丙酮中，滴加30mg（0.3 mmol）三乙胺，在室温（25 ℃）下回流搅拌30min；反应完毕后减压蒸馏，得到白色粗产物；干燥后用二氯甲烷/石油醚体系（v/v, 1:1）进行柱色谱分离得到纯品探针。
性能测试：
探针对水合肼和不同分析物的荧光光谱响应的测定是在DMSO-PBS（v/v=3:1, pH=7.4）中进行的，所使用的探针是实施例1-6中所制备的探针样品，探针配制的浓度为5 μM，水合肼和不同分析物的浓度为50 μM。光谱和核磁氢谱测试结果参见附图1-5，核磁数据为1H NMR (500 MHz, DMSO-d6): δ (ppm): 7.98 (d, J = 4.1 Hz, 1H), 7.88 (d, J = 8.7Hz, 1H), 7.47 (d, J = 2.3 Hz, 1H), 7.41 (d, J = 4.1 Hz, 1H), 7.36 (dd, J =8.6, 2.3 Hz, 1H), 6.43 (d, J = 1.2 Hz, 1H), 2.47 (d, J = 1.2 Hz, 3H)。
虽然用上述实施方式描述了本发明，应当理解的是，在不背离本发明的精神的前提下，本发明可进行进一步的修饰和变动，且这些修饰和变动均属于本发明的保护范围之内。

Claims (1)

1.一种香豆素类水合肼荧光探针在水合肼检测上的应用，其特征在于：香豆素类水合肼荧光探针具有如下分子结构：
Figure DEST_PATH_IMAGE001
；
其中： R为氯原子或氢原子。
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