CN105418560A - 长波长肼比色荧光探针及其制备方法 - Google Patents
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Abstract
本发明涉及长波长肼比色荧光探针及其制备方法。具体而言，本发明涉及作为长波长肼比色荧光探针的一类4-溴丁酸酯三氰基呋喃苯乙烯类化合物及其制备方法。这类探针不仅能够高选择性地识别肼而且能够在长波长处用荧光法对肼进行灵敏的定量和定性分析。这类探针可以快速对肼实现响应，可以实现对肼的即时检测，可以仅用“裸眼”观察实现对肼的定性和定量分析。这类探针性质稳定，可以长期保存使用。此外，这类探针还具有较强的抗干扰能力。这类探针的合成条件相对温和，只需一步反应，合成简单。
Description
技术领域
本发明涉及4-溴丁酸酯三氰基呋喃苯乙烯类化合物作为肼高选择长波长比色荧光探针及其制备方法。
背景技术
肼(NH2NH2)因其具有较强的还原性而广泛的应用于有机合成等工业领域中。此外，肼作为抗菌药物在医药领域也得到了应用。但是，研究表明肼具有强毒性，能够增强肺癌、鼻炎癌以及肝癌的发病率。现在肼已被美国环保署和世界卫生组织列为人类一个潜在的致癌物质。众所周知，肼具有较强的挥发性，易于引起包括大气和水在内的环境污染。因此，开发高选择灵敏检测肼的方法是非常必要的。
目前，检测肼的传统分析方法主要包括气相色谱法、液相色谱法和电化学方法等。最近，荧光探针由于其灵敏度高、操作方便等优点而得到了快速发展，但是目前报道的肼荧光探针仍存在一些不足，例如选择性差、灵敏度低、响应速度慢、合成复杂以及激发和发射波长相对较短等。另外，比色探针由于不需要借助先进的昂贵仪器仅用“裸眼”观察即可达到定量和定性分析的目的而受到广泛关注。因此，发展高选择性、高灵敏度、合成简单的长波长肼比色荧光探针是本领域技术人员研究的热点。
发明内容
本领域急需一种制备简单的高选择高灵敏长波长肼比色荧光探针，从而能够有效检测肼。为此，本发明合成了一类新颖的长波长肼比色荧光探针，其合成简单、稳定性高、和/或选择性高，和/或能够识别肼。
具体而言，本发明提供了一种长波长肼比色荧光探针，其为4-溴丁酸酯三氰基呋喃苯乙烯类化合物。
本发明还提供了肼比率荧光探针的制备方法，其是通过将相应的4-羟基三氰基呋喃苯乙烯类化合物与4-溴丁酸反应制得。
在本发明的长波长肼比色荧光探针的制备方法中，反应温度是20～150℃；反应时间是1h～24h；4-羟基三氰基呋喃苯乙烯类化合物与4-溴丁酸的摩尔比为约1：1至1：8。
本发明的长波长肼比色荧光探针可与肼进行作用，引起荧光和吸收光谱的变化(同时伴随着颜色的变化)，从而实现对肼的定性和定量检测。
具体而言，本发明的长波长肼比色荧光探针分别与其他分析物进行作用均不能导致荧光光谱的明显改变，从而实现对肼的选择性识别，进而可任选地用于排除其他分析物的存在对肼的定性和定量测定的干扰。
可选择地，本发明的长波长肼比色荧光探针的稳定性好，进而能够长期保存使用。
进一步的，本发明的长波长肼比色荧光探针是高选择肼比色长波长荧光探针，且合成简单，有利于商业化的推广应用。
附图说明
图1是不同浓度肼(0～500μM)对探针(20μM)吸收和荧光光谱的影响。
图2是不同浓度肼引起探针(40μM)溶液颜色的变化图
图3是不同分析物(200μM)对探针(20μM)荧光光谱以及探针利用荧光光谱法定量分析肼(200μM)的影响。
具体实施方式：
本发明提出了上述高选择性长波长肼比色荧光探针的合成路线、方法及其光谱性能。
本发明的长波长肼比色荧光探针是一类4-溴丁酸酯三氰基呋喃苯乙烯类化合物，其具有以下结构通式
上式中：R1，R2，R3，R4为氢原子，直链或支链烷基，直链或支链烷氧基，磺酸基，酯基，羧基；R1，R2，R3和R4可以相同或不同。
该类长波长肼比色荧光探针的合成路线和方法如下：
本发明的高选择性识别肼长波长比色荧光探针的显著特征是能够在长波长处高选择性地识别肼，和/或在其他高浓度分析物的存在下能够准确对肼进行定性和定量分析。重要的是，本发明的长波长肼比色荧光探针还能够用“裸眼”观察的方法进行定性和定量分析。
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
(方案1)将4-羟基苯乙烯三氰基呋喃(303mg，1.0mmol)、4-溴丁酸(166mg，1.0mmol)、4-二甲氨基吡啶(122mg，1.0mmol)和二环己基碳二亚胺(412mg，2.0mmol)溶于20mL干燥的二氯甲烷中，50℃下反应4h后，减压蒸发得到粗产品，然后使用二氯甲烷进行柱色谱分离，得到浅黄色纯净产品140mg，产率为31﹪。
(方案2)将4-羟基苯乙烯三氰基呋喃(303mg，1.0mmol)、4-溴丁酸(166mg，1.0mmol)、4-二甲氨基吡啶(122mg，1.0mmol)和二环己基碳二亚胺(412mg，2.0mmol)溶于20mL干燥的二氯甲烷中，50℃下反应10h后，减压蒸发得到粗产品，然后使用二氯甲烷进行柱色谱分离，得到浅黄色纯净产品293mg，产率为65﹪。
(方案3)将4-羟基苯乙烯三氰基呋喃(303mg，1.0mmol)、4-溴丁酸(166mg，1.0mmol)、4-二甲氨基吡啶(122mg，1.0mmol)和二环己基碳二亚胺(412mg，2.0mmol)溶于20mL干燥的二氯甲烷中，50℃下反应15h后，减压蒸发得到粗产品，然后使用二氯甲烷进行柱色谱分离，得到浅黄色纯净产品320mg，产率为71﹪。
(方案4)将4-羟基苯乙烯三氰基呋喃(303mg，1.0mmol)、4-溴丁酸(332mg，2.0mmol)、4-二甲氨基吡啶(224mg，2.0mmol)和二环己基碳二亚胺(824mg，4.0mmol)溶于20mL干燥的二氯甲烷中，50℃下反应15h后，减压蒸发得到粗产品，然后使用二氯甲烷进行柱色谱分离，得到浅黄色纯净产品401mg，产率为89﹪。
1H-NMR(400MHz,CDCl3)δ(*10-6):1.81(s,6H),2.28-2.34(m,2H),2.82(t,J＝6Hz,2H),3.56(t,J＝6Hz,2H),7.00(d,J＝16Hz,2H),7.24(s,1H),7.63-7.70(m,3H).13C-NMR(100MHz,CDCl3)δ(*10-6):26.44,27.39,32.36,32.55,58.16,97.77,100.35,110.12,110.78,111.52,115.03,122.83,130.32,131.45,146.03,153.87,170.56,173.57,175.15.ESI-MScalcdforC22H19BrN3O3[M+H]+452,found452.
实施例2
本发明的发明人进行了如下测试：(a)不同浓度肼(0～500μM)对探针(20μM)吸收光谱的影响，插入图是595nm处吸光度与410nm处吸光度的比值与加入的肼浓度之间的线性关系。(b)不同浓度肼(0～500μM)对探针(20μM)荧光光谱的影响；插入图是610nm处荧光强度与加入的肼浓度之间的线性关系。上述测定是在乙醇和水(5:5，V/V)含有5mM磷酸盐缓冲溶液(PBS)，pH值7.4的体系中，且所有光谱测试都是在25℃下肼加入作用20min后测得的。结果参见图1。
从图1a可以看出，伴随着探针溶液中肼浓度的增加，410nm处的吸收峰逐渐降低，同时595nm处产生新的吸收峰并逐渐升高，且在120～250μM肼浓度范围内和595nm处吸光度与410nm处吸光度的比值成良好的线性关系。从图1b可以看出，伴随着探针溶液中肼浓度的增加，610nm处荧光发射峰逐渐升高，且在50～500μM肼浓度范围内和610nm处荧光强度成良好的线性关系。因此，本发明的探针能较精确地确定待测样本中肼的含量。
实施例3
由图2可以清晰的看出：不同浓度肼(从左至右:0,0.2,0.4,0.6,0.8,1.0mM)存在下探针溶液(40μM)的颜色由黄色逐渐变成蓝色。因此，本发明的探针仅用“裸眼”观察即可完成样本中肼的定性和定量分析检测。
实施例4
不同分析物(200μM)对探针(20μM)荧光光谱的影响。分析物包括：乙二胺EDA、二乙胺DEA、三乙胺TEA、正丁胺nBA、氯离子Cl-、硫酸根离子SO4 2-、硝酸根离子NO3 -、亚硝酸根离子NO2 -和肼，它们的浓度均为200μM。所有测试条件是在乙醇和水(5:5，V/V)含有5mM磷酸盐缓冲溶液(PBS)，pH值7.4的体系中完成，且所有光谱都是在25℃下分析物加入作用20min后测得的。移取10μL的探针储备液(10mM)放进5mL比色管中，然后加入2.5mL乙醇，250μL100mMPBS，再移取10μL上述分析物储备液(100mM)加入比色管内，然后用超纯水定容至5mL。摇匀，静置20min，即可测定。结果如图3灰色柱状图所示。
从图3灰色柱状图可以看出，探针对肼具有很高的选择性，能够专一性地和肼进行反应。其原因可能是腈首先与溴原子发生分子间的亲核取代反应，然后肼上的另外一个氮原子又发生了分子内亲核取代反应胺解掉了酯基导致的。
不同分析物(200μM)对探针(20μM)荧光光谱法定量分析肼(200μM)的影响。分析物包括：乙二胺EDA、二乙胺DEA、三乙胺TEA、正丁胺nBA、氯离子Cl-、硫酸根离子SO4 2-、硝酸根离子NO3 -、亚硝酸根离子NO2 -和肼，它们的浓度均为200μM。所有测试条件是在乙醇和水(3:7，V/V)含有5mM磷酸盐缓冲溶液(PBS)，pH值7.4的体系中完成，且所有光谱都是在25℃下分析物加入作用20min后测得的。结果如图3黑色柱状图所示。
从图3黑色柱状图可以看出，环境中存在的其他常见分析物不会明显干扰探针对肼的定性与定量检测。
Claims (10)
1.化合物，其具有以下结构
其中：R1，R2，R3，R4为独立地选自由氢原子、直链或支链烷基、直链或支链烷氧基、磺酸基、酯基和羟基组成的组；且其中的R1，R2，R3和R4可以相同或不同。
2.根据权利要求1所述的化合物，其为如下结构的化合物：
3.制备权利要求权利要求1或2的化合物的方法，其中包括将如下的物质进行反应：
(1)反应试剂：4-羟基三氰基呋喃苯乙烯类化合物和4-溴丁酸化合物；
(2)有机碱催化剂4-二甲氨基吡啶、三乙胺或哌啶；
(3)有机酸活化试剂二环己基碳二亚胺；和
(4)反应溶剂二氯甲烷、三氯甲烷、四氢呋喃或乙腈；
反应完成后进行减压蒸发得到粗产品，即是化合物的粗产品；以及
任选地，使用二氯甲烷进行柱色谱分离将粗产品继续进行纯化。
4.根据权利要求3的方法，其中反应温度是20℃～150℃。
5.根据权利要求4的方法，其中的反应时间是1h～24h。
6.根据权利要求5的方法，其中4-羟基三氰基呋喃苯乙烯类化合物与4-溴丁酸化合物的摩尔比为1：1至1：8。
7.根据权利要求6的方法，其中4-羟基三氰基呋喃苯乙烯类化合物与4-溴丁酸化合物的摩尔比为1：1至1：6。
8.根据权利要求7的方法，其中4-羟基三氰基呋喃苯乙烯类化合物与4-溴丁酸化合物的摩尔比为1：1至1：3。
9.根据权利要求3-8中任一项的方法，其中所述的4-羟基三氰基呋喃苯乙烯类化合物是4-羟基苯乙烯三氰基呋喃。
10.根据权利要求9的方法，其中所制备的化合物为：
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