CN114539159A - 一种脱氢枞酸基席夫碱多离子功能型荧光探针及其制备方法和应用 - Google Patents
一种脱氢枞酸基席夫碱多离子功能型荧光探针及其制备方法和应用 Download PDFInfo
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- CN114539159A CN114539159A CN202210264914.3A CN202210264914A CN114539159A CN 114539159 A CN114539159 A CN 114539159A CN 202210264914 A CN202210264914 A CN 202210264914A CN 114539159 A CN114539159 A CN 114539159A
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- Prior art keywords
- dehydroabietic acid
- methyl ester
- reaction
- acid methyl
- bromo
- Prior art date
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Abstract
本发明公开了一种脱氢枞酸基席夫碱多离子功能型荧光探针及其制备方法和应用,脱氢枞酸经过酰氯化、甲酯化、溴代和双硝化反应,铁粉还原,制得12‑溴‑13‑氨基脱异丙基脱氢枞酸甲酯,邻苯二胺与5‑溴水杨醛经过成环反应再与三氟乙酸反应制得3‑(1H‑苯并[d]咪唑‑2‑基)‑2‑羟基‑5‑甲基苯甲醛,12‑溴‑13‑氨基脱异丙基脱氢枞酸甲酯与3‑(1H‑苯并[d]咪唑‑2‑基)‑2‑羟基‑5‑甲基苯甲醛反应制得荧光探针;该化合物能识别Hg2+、Cu2+、ClO-,加入Cu2+后,绿色荧光逐渐减弱直至猝灭,加入ClO-绿色荧光逐渐减弱,逐渐出现蓝色荧光并逐渐增强,加入Hg2+绿色荧光逐渐减弱逐渐猝灭,在日光下溶液由黄色变成红褐色,检测结果准确。
Description
技术领域
本发明属于设计精细有机合成领域,具体涉及到一种脱氢枞酸基席夫碱多离子功能型荧光探针及其制备方法和应用。
背景技术
汞离子属于一种有毒离子,它的所有存在的形势都危害生命健康,它通过细菌的作用转化为剧毒甲基汞,可以通过食物链在生物体内富集。常见的疾病有肾脏衰竭、水俣病以及运动和神经性障碍等。
铜离子在基本生理过程中发挥着许多重要的作用,如酶的功能、血液的形成、呼吸和生物过程的转录。然而一旦失去稳态会导致各种疾病,如冠心病、肝病、贫血等。次氯酸(HClO)是活性氧(ROS)的重要成分,当细菌侵入人体或表皮受损时,体内白细胞中性粒细胞会分泌内源性HClO,通过破坏这些外来细菌和病毒的细胞壁,使其无法存活,从而抵抗外来细菌和病毒。大量的HClO对机体的健康存在很大的危害,导致组织坏死和疾病,例如动脉粥样硬化和癌症。
虽然目前有很多检测金属离子的方法,如原子吸收法、分光光度法、循环伏安法等,但这些方法存在着一系列的问题限制,例如检测环境严格,样品标准要求高,操作专业性高等,荧光探针法具有检测速度快,检测环境广,灵敏度高等优点。
近年来,人们研究很多的荧光探针用于金属检测技术,如香豆素类荧光探针检测汞离子,罗丹明类荧光探针检测三价铁离子,但没有合成脱氢枞酸席夫碱类荧光探针检测汞离子、铜离子、次氯酸根离子的相关报道。
发明内容
本部分的目的在于概述本发明的实施例的一些方面以及简要介绍一些较佳实施例。在本部分以及本申请的说明书摘要和发明名称中可能会做些简化或省略以避免使本部分、说明书摘要和发明名称的目的模糊,而这种简化或省略不能用于限制本发明的范围。
鉴于上述和/或现有技术中存在的问题,提出了本发明。
因此,本发明的目的是,克服现有技术中的不足,提供一种脱氢枞酸基席夫碱多离子功能型荧光探针。
为解决上述技术问题,本发明提供了如下技术方案:一种脱氢枞酸基席夫碱多离子功能型荧光探针,该化合物名称为(E)-7-((3-(1H-苯并[d]咪唑-2-基)2-羟基-5-苄亚胺)氨基)6-溴-1,4a-二甲基-1,2,3,4,4,9,10,10a-八氢菲罗-1-甲酯,结构式为:
本发明的再一个目的是,克服现有技术中的不足,提供一种脱氢枞酸基席夫碱多离子功能型荧光探针的制备方法。
为解决上述技术问题,本发明提供了如下技术方案:一种脱氢枞酸基席夫碱多离子功能型荧光探针的制备方法,包括,
脱氢枞酸经过酰氯化、甲酯化、溴代和双硝化反应,制得12-溴-13-硝基脱氢枞酸甲酯;
12-溴-13-硝基脱氢枞酸甲酯经过Fe/HCl还原,制得12-溴-13-氨基脱异丙基脱氢枞酸甲酯;
邻苯二胺与5-溴水杨醛经过成环反应后,再与三氟乙酸反应制得3-(1H-苯并[d]咪唑-2-基)-2-羟基-5-甲基苯甲醛;
12-溴-13-氨基脱异丙基脱氢枞酸甲酯与3-(1H-苯并[d]咪唑-2-基)-2-羟基-5-甲基苯甲醛反应制得所述荧光探针。
作为本发明所述脱氢枞酸基席夫碱多离子功能型荧光探针的制备方法的一种优选方案,其中:所述12-溴-13-硝基脱氢枞酸甲酯,其制备方法,包括,
向脱氢枞酸甲苯溶液中加入二氯亚砜进行反应,反应结束后真空旋干,加入甲醇进行甲酯化反应,反应结束后旋干,加入乙醇溶解结晶,得到脱氢枞酸甲酯;其中,所述脱氢枞酸甲苯溶液的浓度为0.4~0.6g/mL,脱氢枞酸与二氯亚砜的用量比为1g:0.2~0.3mL,脱氢枞酸与甲醇的用量比为1g:1~3mL;所述脱氢枞酸与二氯亚砜的反应温度为75~80℃,反应时间为2~4h;所述甲酯化反应温度为75~80℃,反应时间为2~4h;
向脱氢枞酸甲酯的乙腈溶液中加入N-溴代丁二酰亚胺NBS,避光常温反应,反应结束后旋蒸,二氯甲烷洗涤两次,甲醇溶解结晶,得到12-溴代脱氢枞酸甲酯;其中,所述脱氢枞酸甲酯乙腈溶液的浓度为0.15~0.20g/mL,脱氢枞酸甲酯与NBS的用量比1:1.2~1:1.5,反应时间为20~24h;
在冰浴条件下,将12-溴脱氢枞酸甲酯加入到浓硝酸与浓硫酸充分混合的混酸中,进行搅拌,反应结束后直接倒入冰水中静置,减压抽滤,水洗多次,用石油醚:乙酸乙酯的体积比500:1-200:1过柱提纯,制得纯12-溴-13-硝基脱氢枞酸甲酯;其中,浓硝酸由发烟硝酸和水按照体积比5:1调配而成,12-溴脱氢枞酸甲酯与发烟硝酸用量比为1g:6~7ml,12-溴脱氢枞酸甲酯与浓硫酸的用量比为1~3g:1ml,所述消化反应在冰浴条件下反应0.5~1.5h。
作为本发明所述脱氢枞酸基席夫碱多离子功能型荧光探针的制备方法的一种优选方案,其中:所述12-溴-13-氨基脱异丙基脱氢枞酸甲酯,其制备方法包括,
在无水乙醇中,将12-溴-13-硝基脱氢枞酸甲酯与铁粉、浓盐酸反应,搅拌回流,反应结束,过滤铁粉,用饱和碳酸氢钠中和至中性,用石油醚:乙酸乙酯体积比为28:1,过柱提纯,制得纯12-溴-13-氨基脱异丙基脱氢枞酸甲酯;
其中,12-溴-13-硝基脱氢枞酸甲酯与蒸馏水的用量比0.22g:1ml,12-溴-13-硝基脱氢枞酸甲酯与铁粉用量比0.22g:0.5g,12-溴-13-硝基脱氢枞酸甲酯与浓盐酸的用量比0.22g:800μl,反应时间为4.5h。
作为本发明所述脱氢枞酸基席夫碱多离子功能型荧光探针的制备方法的一种优选方案,其中:所述3-(1H-苯并[d]咪唑-2-基)-2-羟基-5-甲基苯甲醛,其制备方法包括,
在氮气保护下,无水乙醇作为有机溶剂,将邻苯二胺与5-甲基水杨醛反应,亚硫酸钠作为催化剂,搅拌回流反应结束后用无水乙醇进行重结晶,制得纯苯并咪唑2-(1H-苯并[d]咪唑-2-基)-4-甲酚;其中,邻苯二胺与5-甲基水杨醛用量比为1.22g:1.56g,邻苯二胺与无水硫酸钠用量比为1.22g:1.59g,反应温度为78℃,反应时间为12h;
三氟乙酸与苯并咪唑2-(1H-苯并[d]咪唑-2-基)-4-甲酚反应,六亚甲基四胺作为催化剂,反应结束后,用石油醚:乙酸乙酯体积比100-20:1过柱提纯,制得纯3-(1H-苯并[d]咪唑-2-基)-2-羟基-5-甲基苯甲醛;其中,三氟乙酸与苯并咪唑2-(1H-苯并[d]咪唑-2-基)-4-甲酚的用量比为0.3g:5ml,六亚甲基四胺与苯并咪唑2-(1H-苯并[d]咪唑-2-基)-4-甲酚的用量比为0.3g:0.9g,反应温度为110℃,反应时间为12h。
作为本发明所述脱氢枞酸基席夫碱多离子功能型荧光探针的制备方法的一种优选方案,其中:所述12-溴-13-氨基脱异丙基脱氢枞酸甲酯与3-(1H-苯并[d]咪唑-2-基)-2-羟基-5-甲基苯甲醛反应,其中,以无水乙醇作为有机溶剂,3-(1H-苯并[d]咪唑-2-基)-2-羟基-5-甲基苯甲醛与纯12-溴-13-氨基脱异丙基脱氢枞酸甲酯反应用量比为1:1,反应时间为10~12h;反应结束后,在室温下静置析出固体,制得纯的探针。
本发明的另一个目的是,克服现有技术不足,提供一种脱氢枞酸基席夫碱多离子功能型荧光探针在检测铜离子、次氯酸根离子和汞离子中的应用。
作为本发明所述应用的一种优选方案,其中:荧光探针在铜离子和汞离子的作用下,荧光强度降低至猝灭,对铜和汞离子的最低检测限低至nM级别,达到1.37nM和14.3nM;
在次氯酸根离子的作用下,荧光有黄绿色变为蓝色,最低检测限为0.52μM。
作为本发明所述应用的一种优选方案,其中:荧光探针对汞离子的检测不受其他共存离子的干扰。
作为本发明所述应用的一种优选方案,其中:所述(E)-7-((3-(1H-苯并[d]咪唑-2-基)2-羟基-5-苄亚胺)氨基)6-溴-1,4a-二甲基-1,2,3,4,4,9,10,10a-八氢菲罗-1-甲酯作为荧光探针在细胞成像和斑马鱼成像中的应用。
本发明有益效果:
本发明利用天然可再生资源歧化松香中提取的脱氢枞酸为原料制备的(E)-7-((3-(1H-苯并[d]咪唑-2-基)2-羟基-5-苄亚胺)氨基)6-溴-1,4a-二甲基-1,2,3,4,4,9,10,10a-八氢菲罗-1-甲酯(CPY),能选择性的与Hg2+、Cu2+络合,荧光发生猝灭,与ClO-反应,荧光发生蓝移,该化合物可作为荧光探针检测Hg2+、Cu2+、ClO-;加入Hg2+后,探针颜色实际发生了红移,由于红色荧光强度较弱,探针本身颜色与红移后颜色的荧光强度不在一个量级范围内,因此将探针加入汞离子视为猝灭型,但在实际生物成像应用当中,细胞内和斑马鱼体内的生物成像可得荧光颜色为红色;加入ClO-,荧光颜色由黄绿色变为蓝色,加入Cu2+,黄绿色逐渐消失,以此在生物成像中有效鉴别Hg2+、Cu2+、ClO-。
附图说明
为了更清楚地说明本发明实施例的技术方案,下面将对实施例描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动性的前提下,还可以根据这些附图获得其它的附图。其中:
图1为本发明实施例中合成(E)-7-((3-(1H-苯并[d]咪唑-2-基)2-羟基-5-苄亚胺)氨基)6-溴-1,4a-二甲基-1,2,3,4,4,9,10,10a-八氢菲罗-1-甲酯的工艺图;
图2为本发明实施例中荧光探针CPY溶液中加入Hg2+的荧光吸收光谱图。
图3为本发明实施例中荧光探针CPY溶液中加入Cu2+的荧光吸收光谱图。
图4为本发明实施例中(荧光探针CPY溶液中加入ClO-的荧光吸收光谱图。
图5为本发明实施例中荧光探针CPY在日照下和365nm紫外灯下与Hg2+、Cu2+、ClO-发生反应的前后对比图;其中,a为365nm紫外灯下加入探针、Cu2+、ClO-、Hg2+前后的照片,b为日照下加入探针、Cu2+、ClO-、Hg2+前后的照片;a为在365nm紫外灯照射下,纯探针的颜色为黄绿色,当加入汞离子和铜离子,荧光猝灭,当加入ClO-时,荧光颜色由黄绿色变为蓝色。b为在日光灯照射下,纯探针溶液颜色为黄色,加入Cu2+和ClO-,溶液仍为黄色,当加入Hg2+,溶液由黄色变为橙红色。
图6为本发明实施例中荧光探针CPY与不同离子作用的荧光吸收光谱图。
图7为本发明实施例中探针以及加入不同检测离子在MCF-7细胞内荧光成像图;可以看出,CPY进入细胞显示出黄绿色荧光,表明探针可以穿透细胞膜,并有效进行细胞成像;而加入Cu2+、Hg2+、ClO-后细胞内的荧光分别猝灭和变成蓝色荧光,说明离子可以扩散到细胞,并对探针发生作用,说明该探针成功用于细胞成像,具有检测Cu2+、ClO-、Hg2+的作用。
图8为本发明实施例中加入不同检测离子在斑马鱼内荧光成像图;可以看出,探针CPY在鱼体内显示出黄绿色荧光,表明探针可以进入鱼体内,并有效进行成像,而加入Cu2+、Hg2+、ClO-后体内的荧光分别猝灭和变成蓝色荧光,说明离子可以扩散到鱼体内,并对探针发生作用,说明该探针成功用于生物成像,具有检测Cu2+、ClO-、Hg2+的作用。
具体实施方式
为使本发明的上述目的、特征和优点能够更加明显易懂,下面结合说明书实施例对本发明的具体实施方式做详细的说明。
在下面的描述中阐述了很多具体细节以便于充分理解本发明,但是本发明还可以采用其他不同于在此描述的其它方式来实施,本领域技术人员可以在不违背本发明内涵的情况下做类似推广,因此本发明不受下面公开的具体实施例的限制。
其次,此处所称的“一个实施例”或“实施例”是指可包含于本发明至少一个实现方式中的特定特征、结构或特性。在本说明书中不同地方出现的“在一个实施例中”并非均指同一个实施例,也不是单独的或选择性的与其他实施例互相排斥的实施例。
本发明中歧化松香,购于广东封开华林有限公司(脱氢枞酸含量为59.93%);层析硅胶(300-400目),购于青岛海洋化工厂,化学纯;乙醇胺,购于安徽泽生科技有限公司,分析纯;铁粉,购于天津市风船化学试剂科技有限公司,分析纯;邻苯二胺,购于成都科龙化工试剂厂,分析纯;5-甲基水杨醛,购于萨恩化学技术有限公司,分析纯;三氟乙酸,购于安徽泽生科技有限公司,分析纯。
实施例1
本实施例提供一种脱氢枞酸基席夫碱多离子功能型荧光探针的制备方法,具体步骤如下:
(1)12-溴-13-硝基脱氢枞酸甲酯的制备:脱氢枞酸经过甲酯化、溴代和硝化反应制得,参见图1,具体过程如下:
称取30g脱氢枞酸溶于60mL的甲苯中,加入11mL的二氯亚砜在78-80℃中反应3h,真空旋干,加入60mL甲醇,在78-80℃下反应3h,旋干,加入30mL乙醇溶解结晶,得到脱氢枞酸甲酯;
准确称取5g脱氢枞酸甲酯,溶于30mL乙腈中,加入4gN-溴代丁二酰亚胺,避光常温反应24h,旋蒸,二氯甲烷洗涤两次,100mL甲醇溶解结晶,得到12-溴代脱氢枞酸甲酯;
12-溴-13-硝基脱氢枞酸甲酯:在冰浴条件下,将12-溴脱氢枞酸甲酯加入到浓硝酸与浓硫酸充分混合的混酸中,进行搅拌,反应结束后直接倒入冰水中静置,减压抽滤,水洗多次,用石油醚:乙酸乙酯的体积比500:1-200:1过柱提纯,制得纯12-溴-13-硝基脱氢枞酸甲酯;其中,浓硝酸由发烟硝酸和水按照体积比5:1调配而成,12-溴脱氢枞酸甲酯与发烟硝酸用量比为1g:6ml,12-溴脱氢枞酸甲酯与浓硫酸的用量比为2g:1ml,所述消化反应在冰浴条件下反应1h;
12-溴-13-氨基脱异丙基脱氢枞酸甲酯:准确称量0.22g12-溴-13-硝基脱氢枞酸甲酯溶于10mL无水乙醇中,向混合溶液中依次加入蒸馏水1mL、铁粉0.5g、浓盐酸800μl,搅拌回流4.5h,反应结束后,过滤除去铁粉,饱和碳酸氢钠中和至中性,用乙酸乙酯萃取,再用蒸馏水洗涤,干燥后减压蒸出溶剂得到黄色油状物,用硅胶柱对其进行层析分离,洗脱剂选用石油醚乙酸乙酯体系(体积比28:1),得到纯化合物12-溴-13-氨基脱异丙基脱氢枞酸甲酯。
(2)3-(1H-苯并[d]咪唑-2-基)-2-羟基-5-甲基苯甲醛的制备:邻苯二胺与5-溴水杨醛反应后再与三氟乙酸反应制得,具体过程如下:
准确称量邻苯二胺1.22g,5-甲基水杨醛1.56g和亚硫酸钠1.59g,混合在22ml无水乙醇中,温度为78℃,氮气保护下搅拌回流17小时,反应结束后静置于室温下重结晶,得到纯的苯并咪唑2-(1H-苯并[d]咪唑-2-基)-4-甲酚。
准确称量0.3g六亚甲基四胺,与0.9g苯并咪唑2-(1H-苯并[d]咪唑-2-基)-4-甲酚超声于5ml的三氟乙酸中,温度为110℃,回流搅拌过夜,反应结束后用乙酸乙酯萃取三次,水洗三次,饱和碳酸氢钠水溶液洗一次,饱和食盐水洗一次,无水硫酸钠干燥除水,旋干得到黄色油状物,经过硅胶柱过柱提纯得到纯的3-(1H-苯并[d]咪唑-2-基)-2-羟基-5-甲基苯甲醛。
(3)探针CPY的制备,12-溴-13-氨基脱异丙基脱氢枞酸甲酯与3-(1H-苯并[d]咪唑-2-基)-2-羟基-5-甲基苯甲醛反应制得,具体过程如下:
准确称量0.1g 12-溴-13-氨基脱异丙基脱氢枞酸甲酯和0.052g3-(1H-苯并[d]咪唑-2-基)-2-羟基-5-甲基苯甲醛,超声于10ml无水乙醇中,滴三滴乙酸,温度为78℃,回流搅拌过夜,反应结束后置于室温下重结晶得到纯的探针CPY。
产物的表征数据为:M.p.161.2-162.3℃;1H NMR(600MHz,DMSO-d6)δ1.21(d,J=20.8Hz,6H),1.42-1.31(q,J=12.5,10.3Hz,2H),1.57-1.86(m,5H),2.05(d,J=12.0Hz,1H),2.32-2.44(m,4H),2.96-2.74(dd,J=59.9,7.6Hz,2H),3.63(s,3H),7.12(s,1H),7.22-7.35(m,2H),7.56(s,1H),7.75-7.59(s,2H),7.75(s,1H),8.23(s,1H),8.94(s,1H),12.78(s,1H),14.32(s,1H).13C NMR(151MHz,CDCl3)δ178.84,161.80,157.33,150.81,149.62,142.72,135.98,134.56,133.93,129.22,129.05,128.22,122.64,119.38,119.05,117.29,116.88,115.68,52.10,47.51,44.44,37.88,37.37,36.63,29.53,25.02,21.31,20.24,18.42,16.52.ESI-MS:m/z calcd for C33H35BrN3O3[M+H]+600.1862,found600.1859。
实施例2
脱氢枞酸基席夫碱衍生物的制备方法的优化:
试验1:准确称量0.1g 12-溴-13-氨基脱异丙基脱氢枞酸甲酯和0.052g 3-(1H-苯并[d]咪唑-2-基)-2-羟基-5-甲基苯甲醛,超声于10ml无水乙醇中,温度为78℃,回流搅拌12小时,反应结束后置于室温下重结晶得到纯的探针CPY,产率为72%。
试验2:准确称量0.1g 12-溴-13-氨基脱异丙基脱氢枞酸甲酯和0.052g 3-(1H-苯并[d]咪唑-2-基)-2-羟基-5-甲基苯甲醛,超声于10ml无水乙醇中,温度为90℃,回流搅拌12小时,反应结束后置于室温下重结晶得到纯的探针CPY,产率为62%。
试验3:准确称量0.1g 12-溴-13-氨基脱异丙基脱氢枞酸甲酯和0.052g 3-(1H-苯并[d]咪唑-2-基)-2-羟基-5-甲基苯甲醛,超声于10ml无水乙醇中,滴三滴冰乙酸,温度为78℃,回流搅拌12小时,反应结束后置于室温下重结晶得到纯的探针CPY,产率为90%。
试验4:准确称量0.1g 12-溴-13-氨基脱异丙基脱氢枞酸甲酯和0.052g 3-(1H-苯并[d]咪唑-2-基)-2-羟基-5-甲基苯甲醛,超声于10ml无水乙醇中,滴三滴氢氧化钠溶液,温度为78℃,回流搅拌12小时,反应结束后置于室温下重结晶得到纯的探针CPY,产率为45%。
试验5:准确称量0.1g 12-溴-13-氨基脱异丙基脱氢枞酸甲酯和0.052g 3-(1H-苯并[d]咪唑-2-基)-2-羟基-5-甲基苯甲醛,超声于10ml甲醇中,温度为78℃,回流搅拌12小时,反应结束后置于室温下重结晶得到纯的探针CPY,产率为60%。
表1不同条件下探针CPY的产率
注:/表示无催化剂。
从表1可以看出,试验3的条件相对于其他反应条件较高的反应得率,因此采用此优选条件进行反应。
实施例3
将探针CPY溶于无水乙醇中,配制成1×10-3M的溶液,取200μL原液加入10ml乙醇水溶液(乙醇:水7:3)中,配制成2×10-5M的溶液,每次加入5μL Cu2+(1×10-3M),50μL ClO-(1×10-3M),20μL Hg2+(1×10-2M),测得不同浓度离子对探针CPY吸收光谱图。
如图2所示,加入Hg2+后,随着Hg2+浓度的增加,520nm处绿色荧光逐渐减弱逐渐猝灭,在日光下溶液由黄色变成红褐色。可以看出,在0~150μM的Hg2+浓度范围内,化合物CPY的荧光强度与离子的浓度具有很好的线性相关性,线性回归方程y=-5.32324x+829.08382,R2=0.98702,计算得Hg2+的检测限为14.3nM。
如图3所示,加入不同浓度Cu2+后,随着Cu2+浓度的增加可以看出,520nm处的绿色荧光逐渐减弱直至猝灭,在0~15μM的Cu2+浓度范围内,化合物CPY的荧光强度与离子的浓度具有很好的线性相关性,线性回归方程y=-55.3864x+829.08382,R2=0.96116,计算得Cu2+的检测限为13.7nM。
如图4所示,随着ClO-浓度的增加,520nm处的绿色荧光逐渐减弱,而412nm处的蓝色荧光逐渐增强。在5~25μM和30~55μM的ClO-两个浓度范围内分别成线性关系。线性方程分别为y=-0.14462x+4.61477,R2=0.9789,y=-0.01012x+0.36832,R2=0.97391。ClO-最低检测限为0.52μM。
上述结果说明CPY能与Cu2+和Hg2+发生络合,与ClO-发生反应。
实施例4
将探针CPY溶于无水乙醇中,配制成1×10-3M的溶液,取200μL原液加入10ml乙醇水溶液(乙醇:水7:3)中,配制成2×10-5M的溶液,每次加入5μL Cu2+(1×10-3M),50μL ClO-(1×10-3M),20μL Hg2+(1×10-2M),在日光灯下,逐渐加入Cu2+和ClO-离子,随着离子浓度的增加,溶液变为淡黄色,逐渐加入Hg2+,溶液变为橙红色。在365nm紫外灯下观察,如图5所示,a:日照下化合物加入Cu2+、ClO-和Hg2+离子前后的照片;b:365nm紫外灯下化合物加入Cu2+、ClO-和Hg2+离子前后照片,加入Cu2+后,绿色荧光逐渐减弱直至猝灭,加入ClO-绿色荧光逐渐减弱,逐渐出现蓝色荧光并逐渐增强,加入Hg2+绿色荧光逐渐减弱逐渐猝灭,说明化合物与Cu2+、Hg2+络合,与ClO-反应。
从而可以检测出Cu2+,ClO-,Hg2+离子。通过加入等摩尔量的HPO4-,NH4+,F-,I-,Cl-,Br-,SO3 2-,SO4 2-,NO2 -,NO3 -,SCN-,OAC-,HCO3-,S2-,苏氨酸,天冬氨酸,甘氨酸,精氨酸,谷氨酸,高胱氨酸,半胱氨酸,水合肼,H2O2,Cs2+,Ca2+,Na+,Fe3+,Co2+,Sn2+,Mg2+,Pb2+,K+,Mn2+,Zn2+,Cd2+,Ni2+,Cr3+,Ag+等,通过荧光分光光度计测量,谱图显示不会导致化合物荧光的变化,如图6所示。说明该化合物可以作为一种有效识Cu2+、ClO-、Hg2+离子的荧光探针。
实施例5
探针的生物成像应用
为探究CPY对活细胞Cu2+、ClO-、Hg2+传感适用性,采用MCF-7细胞进行荧光成像实验,MCF-7细胞在含10%胎牛血清(FBS),1%青霉素和链霉素DMEM培养基中培养,在温度为37℃的孵化箱中孵化,把细胞铺在六孔板中(1×104个/孔)中,37℃孵育约24h。然后加入50μl CPY(1×10-3mol/L)探针孵3h,PBS缓冲液吸去多余CPY。先加入50μl EDTANa2孵化30分钟,以除去细胞内源性Cu2+、ClO-、Hg2+。然后分别加入Cu2+、ClO-、Hg2+50μl(1×10-3mol/L)孵化细胞30分钟,用基础培养基洗3次除去多余离子。随后在激光共聚焦显微镜下成像。如图7所示,CPY进入细胞显示出黄绿色荧光,表明探针可以穿透细胞膜,并有效进行细胞成像。加入Hg2+后,黄绿色荧光猝灭,加入ClO-,由黄绿色变为蓝色,加入Cu2+黄绿色逐渐消失,说明离子可以扩散到细胞,并对探针发生作用,说明该探针成功用于细胞成像,具有检测细胞内Cu2+、ClO-、Hg2+的作用。
实施例6
将斑马鱼卵倒入烧杯中,加入营养液,将烧杯置于装有水的恒温水浴锅中,温度调至26℃,放置1-3天进行孵化,待斑马鱼孵化,在六孔板中放置幼鱼,分别加入探针,其中一个孔不加离子作对照,在另外三孔中分别加入50μl的Cu2+、ClO-、Hg2+(1×10-3mol/L),继续恒温培养3h。
随后在激光共聚焦显微镜下成像,如图8所示,CPY在鱼体内显示出黄绿色荧光,加入ClO-后,荧光颜色由黄绿色变为蓝色,加入Cu2+后,荧光颜色由黄绿色逐渐消失,加入Hg2+后,黄绿色荧光猝灭,说明离子可以扩散到鱼体内,并对探针发生作用,说明该探针成功用于生物成像,具有检测Cu2+、ClO-、Hg2+的作用。
应说明的是,以上实施例仅用以说明本发明的技术方案而非限制,尽管参照较佳实施例对本发明进行了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的精神和范围,其均应涵盖在本发明的权利要求范围当中。
Claims (10)
2.如权利要求1所述脱氢枞酸基席夫碱多离子功能型荧光探针的制备方法,其特征在于:包括,
脱氢枞酸经过酰氯化、甲酯化、溴代和双硝化反应,制得12-溴-13-硝基脱氢枞酸甲酯;
12-溴-13-硝基脱氢枞酸甲酯经过Fe/HCl还原,制得12-溴-13-氨基脱异丙基脱氢枞酸甲酯;
邻苯二胺与5-溴水杨醛经过成环反应后,再与三氟乙酸反应制得3-(1H-苯并[d]咪唑-2-基)-2-羟基-5-甲基苯甲醛;
12-溴-13-氨基脱异丙基脱氢枞酸甲酯与3-(1H-苯并[d]咪唑-2-基)-2-羟基-5-甲基苯甲醛反应制得所述荧光探针。
3.如权利要求2所述脱氢枞酸基席夫碱多离子功能型荧光探针的制备方法,其特征在于:所述12-溴-13-硝基脱氢枞酸甲酯,其制备方法,包括,
向脱氢枞酸甲苯溶液中加入二氯亚砜进行反应,反应结束后真空旋干,加入甲醇进行甲酯化反应,反应结束后旋干,加入乙醇溶解结晶,得到脱氢枞酸甲酯;其中,所述脱氢枞酸甲苯溶液的浓度为0.4~0.6g/mL,脱氢枞酸与二氯亚砜的用量比为1g:0.2~0.3mL,脱氢枞酸与甲醇的用量比为1g:1~3mL;所述脱氢枞酸与二氯亚砜的反应温度为75~80℃,反应时间为2~4h;所述甲酯化反应温度为75~80℃,反应时间为2~4h;
向脱氢枞酸甲酯的乙腈溶液中加入N-溴代丁二酰亚胺NBS,避光常温反应,反应结束后旋蒸,二氯甲烷洗涤两次,甲醇溶解结晶,得到12-溴代脱氢枞酸甲酯;其中,所述脱氢枞酸甲酯乙腈溶液的浓度为0.15~0.20g/mL,脱氢枞酸甲酯与NBS的用量比1:1.2~1:1.5,反应时间为20~24h;
在冰浴条件下,将12-溴脱氢枞酸甲酯加入到浓硝酸与浓硫酸充分混合的混酸中,进行搅拌,反应结束后直接倒入冰水中静置,减压抽滤,水洗多次,用石油醚:乙酸乙酯的体积比500:1-200:1过柱提纯,制得纯12-溴-13-硝基脱氢枞酸甲酯;其中,浓硝酸由发烟硝酸和水按照体积比5:1调配而成,12-溴脱氢枞酸甲酯与发烟硝酸用量比为1g:6~7ml,12-溴脱氢枞酸甲酯与浓硫酸的用量比为1~3g:1ml,所述消化反应在冰浴条件下反应0.5~1.5h。
4.如权利要求2所述脱氢枞酸基席夫碱多离子功能型荧光探针的制备方法,其特征在于:所述12-溴-13-氨基脱异丙基脱氢枞酸甲酯,其制备方法包括,
在无水乙醇中,将12-溴-13-硝基脱氢枞酸甲酯与铁粉、浓盐酸反应,搅拌回流,反应结束,过滤铁粉,用饱和碳酸氢钠中和至中性,用石油醚:乙酸乙酯体积比为28:1,过柱提纯,制得纯12-溴-13-氨基脱异丙基脱氢枞酸甲酯;
其中,12-溴-13-硝基脱氢枞酸甲酯与蒸馏水的用量比0.22g:1ml,12-溴-13-硝基脱氢枞酸甲酯与铁粉用量比0.22g:0.5g,12-溴-13-硝基脱氢枞酸甲酯与浓盐酸的用量比0.22g:800μl,反应时间为4.5h。
5.如权利要求2所述脱氢枞酸基席夫碱多离子功能型荧光探针的制备方法,其特征在于:所述3-(1H-苯并[d]咪唑-2-基)-2-羟基-5-甲基苯甲醛,其制备方法包括,
在氮气保护下,无水乙醇作为有机溶剂,将邻苯二胺与5-甲基水杨醛反应,亚硫酸钠作为催化剂,搅拌回流反应结束后用无水乙醇进行重结晶,制得纯苯并咪唑2-(1H-苯并[d]咪唑-2-基)-4-甲酚;其中,邻苯二胺与5-甲基水杨醛用量比为1.22g:1.56g,邻苯二胺与无水硫酸钠用量比为1.22g:1.59g,反应温度为78℃,反应时间为12h;
三氟乙酸与苯并咪唑2-(1H-苯并[d]咪唑-2-基)-4-甲酚反应,六亚甲基四胺作为催化剂,反应结束后,用石油醚:乙酸乙酯体积比100-20:1过柱提纯,制得纯3-(1H-苯并[d]咪唑-2-基)-2-羟基-5-甲基苯甲醛;其中,三氟乙酸与苯并咪唑2-(1H-苯并[d]咪唑-2-基)-4-甲酚的用量比为0.3g:5ml,六亚甲基四胺与苯并咪唑2-(1H-苯并[d]咪唑-2-基)-4-甲酚的用量比为0.3g:0.9g,反应温度为110℃,反应时间为12h。
6.如权利要求2所述脱氢枞酸基席夫碱多离子功能型荧光探针的制备方法,其特征在于:所述12-溴-13-氨基脱异丙基脱氢枞酸甲酯与3-(1H-苯并[d]咪唑-2-基)-2-羟基-5-甲基苯甲醛反应,其中,以无水乙醇作为有机溶剂,3-(1H-苯并[d]咪唑-2-基)-2-羟基-5-甲基苯甲醛与纯12-溴-13-氨基脱异丙基脱氢枞酸甲酯反应用量比为1:1,反应时间为10~12h;反应结束后,在室温下静置析出固体,制得纯的探针。
7.如权利要求1所述脱氢枞酸基席夫碱多离子功能型荧光探针在检测铜离子、次氯酸根离子和汞离子中的应用。
8.如权利要求7所述的应用,其特征在于:荧光探针在铜离子和汞离子的作用下,荧光强度降低至猝灭,对铜和汞离子的最低检测限低至nM级别,达到1.37nM和14.3nM;
在次氯酸根离子的作用下,荧光有黄绿色变为蓝色,最低检测限为0.52μM。
9.如权利要求7所述的应用,其特征在于:荧光探针对汞离子的检测不受其他共存离子的干扰。
10.权利要求1所述(E)-7-((3-(1H-苯并[d]咪唑-2-基)2-羟基-5-苄亚胺)氨基)6-溴-1,4a-二甲基-1,2,3,4,4,9,10,10a-八氢菲罗-1-甲酯作为荧光探针在细胞成像和斑马鱼成像中的应用。
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