CN109574977A - 一种香豆素类次氯酸荧光探针及其制备方法 - Google Patents
一种香豆素类次氯酸荧光探针及其制备方法 Download PDFInfo
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- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
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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8‑醛基‑7‑羟基香豆素和丙二腈为原料,在碱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,当其与次氯酸作用时,碳碳双键被氧化而发生断裂,探针发出蓝色的荧光,从而实现对次氯酸的检测。该探针对次氯酸具有很强的选择性和很高的灵敏性,能快速对次氯酸实现响应,是一类优异的“Turn‑on”型荧光探针,具有很好的应用前景。
Description
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
次氯酸根(ClO-)、次氯酸(HClO)是生物体内最重要的活性氧化物之一,在许多生理过程中具有重要的作用。生物体内生的次氯酸盐是由过氧化氢与氯离子在亚铁血红素酶、髓过氧化物酶催化作用发生生物化学反应产生。研究表明,生物体内次氯酸盐浓度偏离正常值通常会导致心血管疾病,动脉粥样硬化,骨关节炎,类风湿性关节炎,肺损伤和癌症等疾病。同时在日常生活中,次氯酸的使用非常广泛,它常用于漂白剂和卫生消毒剂,例如用于饮用水和游泳池水等。在水中残留的次氯酸会引起水体污染,对人体健康存在潜在危害。因此,检测实际水体和生物体系中次氯酸的浓度已成为一个重要的课题,现亟待发展快速、灵敏、高选择性检测次氯酸的手段。
当前,常见的次氯酸检测手段主要是碘还原滴定法、分光光度法、化学发光分析法、库伦法等。但这些分析手段在实际应用中既昂贵又繁琐,且常常需要特殊的昂贵实验仪器和高技能专业操作人员。因此,高效、廉价、简捷的次氯酸检测手段成为重要的研究课题。
在各种离子/分子的检测方法中,荧光探针检测法由于具有高灵敏度、高选择性、操作简便和实时分析等独特的优势而成为研究者关注的焦点。但是目前报道的荧光探针仍存在一些问题,包括灵敏度低、选择性差以及合成复杂等。总之,发展具有高灵敏度、高选择性、合成步骤简单的次氯酸荧光探针是本领域技术人员急需解决的问题。为此,本领域急需制备一种简单的快速高选择性次氯酸荧光探针,从而能够有效检测次氯酸。
发明内容
本发明的目的在于提供一类新颖的次氯酸荧光探针及其制备方法,其合成简单、选择性好、灵敏度高、能够快速识别次氯酸。
具体而言,本发明提供了一种次氯酸荧光探针,其为香豆素类化合物,其结构如下:;
其中:R1,R2,R3,R4为氢原子或碳原子数为1-4的烷基;且其中的R1,R2,R3和R4可以相同或不同。
香豆素类次氯酸荧光探针的制备方法包括以下步骤:
(1)将454 mg(2.8 mmol) 7-羟基香豆素和841 mg(6 mmol)六亚甲基四胺溶解在30 ml的冰乙酸中,在90℃回流搅拌6 h后加入5 ml盐酸,继续反应1 h;反应完毕后用乙酸乙酯和水萃取三次,得到8-醛基-7-羟基香豆素;
(2)在单口烧瓶中将8-醛基-7-羟基香豆素与丙二腈溶于40 ml二氯甲烷中,加入碱后加热回流搅拌,控制温度在40-50℃,反应5-10 h,然后使用石油醚/乙酸乙酯体系进行柱色谱分离得到纯品探针。
其中8-醛基-7-羟基香豆素与和丙二腈的摩尔比为1∶3。
所述碱的用量,按摩尔比计,8-醛基-7-羟基香豆素∶碱=1∶6;
所述的碱为三乙胺或碳酸钠;
所述的柱色谱分离石油醚/乙酸乙酯的体积比为:石油醚∶乙酸乙酯=4∶1。
本发明的有益效果有:
(1)本发明的次氯酸荧光探针可与次氯酸进行特异性作用,产生荧光光谱的变化,从而实现对次氯酸的定量检测。
(2)本发明的次氯酸荧光探针对次氯酸具有很高的选择性,与其他物质进行作用均不能导致荧光光谱的明显改变。
(3)本发明的次氯酸荧光探针的稳定性好,进而能够长期保存使用。
(4)本发明的次氯酸荧光探针是快速高选择性次氯酸探针,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探针样品对次氯酸的时间响应曲线。
图2是不同浓度次氯酸对实施例2探针样品荧光光谱的响应曲线。
图3是不同次氯酸浓度对实施例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1–20分别为空白、钾离子、钙离子、锌离子、铜离子、二价铁离子、三价铁离子、硝酸根离子、亚硝酸根离子、氯离子、亚硫酸根离子、亚硫酸氢根离子、硫酸根离子、半胱氨酸、谷胱甘肽、过氧化氢、羟基自由基、过氧自由基、过氧化亚硝酸盐、次氯酸钠。
图5是实施例2探针样品的核磁氢谱图。
具体实施方式
本发明提供了上述快速高灵敏高选择性次氯酸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:
(1)将454 mg(2.8 mmol) 7-羟基香豆素和841 mg(6 mmol)六亚甲基四胺溶解在30 ml的冰乙酸中,在90℃回流搅拌6 h后加入5 ml盐酸,继续反应1 h;反应完毕后用乙酸乙酯和水萃取三次,得到8-醛基-7-羟基香豆素;
(2)将190.17 mg(1 mmol) 8-醛基-7-羟基香豆素与198.09 mg(3 mmol)丙二腈溶于40ml二氯甲烷中,然后加入607.17 mg(6 mmol)三乙胺回流5 h,反应温度控制在40℃,使用石油醚/乙酸乙酯体系(v/v,4∶1)进行柱色谱分离,得到纯品探针化合物。
实施例2:
(1)将493 mg(2.8 mmol) 7-羟基-4-甲基香豆素和841 mg(6 mmol)六亚甲基四胺溶解在30 ml的冰乙酸中,在90℃回流搅拌6 h后加入5 ml盐酸,继续反应1 h;反应完毕后用乙酸乙酯和水萃取三次,得到8-醛基-7-羟基-4-甲基香豆素;
(2)将204.17 mg(1 mmol) 8-醛基-7-羟基-4-甲基香豆素与198.09 mg(3 mmol)丙二腈溶于40 ml二氯甲烷中,然后加入607.17 mg(6 mmol)三乙胺回流10 h,反应温度控制在40℃,使用石油醚/乙酸乙酯体系(v/v,4∶1)进行柱色谱分离,得到纯品探针化合物。
实施例3:
(1)将454 mg(2.8 mmol) 7-羟基香豆素和841 mg(6 mmol)六亚甲基四胺溶解在30 ml的冰乙酸中,在90℃回流搅拌6 h后加入5 ml盐酸,继续反应1 h;反应完毕后用乙酸乙酯和水萃取三次,得到8-醛基-7-羟基香豆素;
(2)将190.17 mg(1 mmol) 8-醛基-7-羟基香豆素与198.09 mg(3 mmol)丙二腈溶于40ml二氯甲烷中,然后加入607.17 mg(6 mmol)三乙胺回流10 h,反应温度控制在50℃,使用石油醚/乙酸乙酯体系(v/v,4∶1)进行柱色谱分离,得到纯品探针化合物。
实施例4:
(1)将454 mg(2.8 mmol) 7-羟基香豆素和841 mg(6 mmol)六亚甲基四胺溶解在30 ml的冰乙酸中,在90℃回流搅拌6 h后加入5 ml盐酸,继续反应1 h;反应完毕后用乙酸乙酯和水萃取三次,得到8-醛基-7-羟基香豆素;
(2)将190.17 mg(1 mmol) 8-醛基-7-羟基香豆素与198.09 mg(3 mmol)丙二腈溶于40ml二氯甲烷中,然后加入607.17 mg(6 mmol)碳酸钠回流5 h,反应温度控制在40℃,使用石油醚/乙酸乙酯体系(,v/v,4∶1)进行柱色谱分离,得到纯品探针化合物。
实施例5:
(1)将493 mg(2.8 mmol) 7-羟基-4-甲基香豆素和841 mg(6 mmol)六亚甲基四胺溶解在30 ml的冰乙酸中,在90℃回流搅拌6 h后加入5 ml盐酸,继续反应1 h;反应完毕后用乙酸乙酯和水萃取三次,得到8-醛基-7-羟基-4甲基香豆素;
(2)将204.17 mg(1 mmol) 8-醛基-7-羟基-4-甲基香豆素与198.09 mg(3 mmol)丙二腈溶于40 ml二氯甲烷中,然后加入607.17 mg(6 mmol)碳酸钠回流10 h,反应温度控制在40℃,使用石油醚/乙酸乙酯体系(v/v,4∶1)进行柱色谱分离,得到纯品探针化合物。
实施例6:
(1)将454 mg(2.8 mmol) 7-羟基香豆素和841 mg(6 mmol)六亚甲基四胺溶解在30 ml的冰乙酸中,在90℃回流搅拌6 h后加入5 ml盐酸,继续反应1 h;反应完毕后用乙酸乙酯和水萃取三次,得到8-醛基-7-羟基香豆素;
(2)将190.17 mg(1 mmol) 8-醛基-7-羟基香豆素与198.09 mg(3 mmol)丙二腈溶于40ml二氯甲烷中,然后加入607.17 mg(6 mmol)碳酸钠回流10 h,反应温度控制在50℃,使用石油醚/乙酸乙酯体系(v/v,4∶1)进行柱色谱分离,得到纯品探针化合物。
性能测试:
探针对次氯酸和不同分析物的荧光光谱响应的测定是在水溶液中进行的,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,次氯酸和不同分析物的浓度为15 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, CDCl3) δ10.63 (s, 1H), 7.73 (d, J = 9.0 Hz, 1H), 7.26 (s, 1H), 6.91 (d, J = 9.0 Hz,1H), 6.21 (d, J = 1.1 Hz, 1H), 2.43 (d, J = 1.1 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 (6)
1.一种香豆素类次氯酸荧光探针,其特征在于:香豆素类荧光探针具有如下分子结构:
其中:R1,R2,R3,R4为氢原子或碳原子数为1-4的烷基。
2.一种制备如权利要求1所述的香豆素类次氯酸荧光探针的方法,其特征在于:包括以下步骤:
(1)将2.8 mmol 7-羟基香豆素和6 mmol六亚甲基四胺溶解在30 ml的冰乙酸中,在90℃回流搅拌6 h后加入5 ml盐酸,继续反应1 h;反应完毕后用乙酸乙酯和水萃取三次,得到8-醛基-7-羟基香豆素;
(2)在单口烧瓶中将8-醛基-7-羟基香豆素与丙二腈溶于40 ml二氯甲烷中,加入碱后加热回流搅拌,控制温度在40-50℃,反应5-10 h,然后使用石油醚/乙酸乙酯体系进行柱色谱分离得到纯品探针。
3.根据权利要求2所述的香豆素类荧光探针的制备方法,其特征在于:按摩尔比计,8-醛基-7-羟基香豆素∶丙二腈=1∶3。
4.根据权利要求2所述的香豆素类荧光探针的制备方法,其特征在于:所述碱的用量,按摩尔比计,8-醛基-7-羟基香豆素∶碱=1∶6。
5.根据权利要求2所述的香豆素类荧光探针的制备方法,其特征在于:所述的碱为三乙胺或碳酸钠。
6.根据权利要求2所述的香豆素类荧光探针的制备方法,其特征在于:所述的柱色谱分离石油醚/乙酸乙酯的体积比为:石油醚∶乙酸乙酯=4∶1。
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