CN111233917A - 一种氟离子检测小分子探针及其制备方法 - Google Patents
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Abstract
Description
技术领域
本发明属于氟离子检测技术领域,特别是涉及一种氟离子检测小分子探针及其制备方法。
背景技术
神经性毒剂中的沙林、梭曼等G类毒剂在分子结构中含有磷-氟键,在水解条件(尤其是碱性)下,这些毒剂的磷-氟键会发生断裂,氟会以氟离子释放出来。所以,对于氟离子的识别与定量检测,能对G类毒剂的存在提供判断,为对该类毒剂进行防护和处理提供依据。此外,氟离子在生物学、医学、食品科学以及环境科学中都具有重要的作用,氟离子的检测显得尤为重要。氟离子是最小的阴离子且电负性强,具有特殊的化学性质,因此开发氟离子分子探针一直是化学家和军事化学家研究的热点。
氟离子与硅原子具有极强的相互作用,可以形成稳定的Si—F键,因而氟离子或氟化物常被用于催化有机硅化合物的脱硅化反应。利用这种反应原理,可以制备基于有机硅化合物的氟离子分子探针。在氟离子的作用下,有机硅化合物发生硅氟加成或脱硅化反应,化学结构发生变化,从而导致光学性质的改变,达到检测的效果。然而,目前的有机硅类反应型氟离子分子探针的在水体系检测过程通常需要较长的反应时间,往往几十分钟之后反应才能完全,检测灵敏度和响应速度仍不太理想,这也在一定程度上限制了氟离子分子探针的应用研究。
综上所述,本发明基于氟离子与有机硅化合物反应,开发了一种氟离子检测小分子探针,该探针的制备反应条件温和,操作简单,能够实现在有水和无水体系中的氟离子的快速检测,具有响应速度快、灵敏度高和选择性好的优点。有望进一步发展成为现场快速检测含氟G类神经性毒剂的方法。
发明内容
本发明的目的是弥补现有技术的不足,提供一种氟离子检测小分子探针及其制备方法。本发明的小分子探针的制备反应条件温和,操作简单,能够实现在有水和无水体系中的氟离子的快速检测,具有响应速度快、灵敏度高和选择性好的优点。
为了达到上述的目的,本发明采取以下技术方案:
一种氟离子检测小分子探针,所述探针的分子结构如式(I)所示:
其中,所述R1、R3分别地选自C1-C3的烷基,所述R2选自C4-C6的烷基。
优选的,所述式(I)中R1、R3分别地选自甲基,所述R2为叔丁基。
一种氟离子检测小分子探针的制备方法,包括如下步骤:
(1)探针分子中间体的合成
水杨醛与邻氨基苯硫酚溶于乙醇溶液中,在室温下滴入双氧水和盐酸混合溶液,在室温下进行反应12-20小时,得到所述探针分子中间体;
(2)探针分子的合成
将分子结构如式(II)所示的氯硅烷的吡啶溶液逐滴加入至探针分子中间体的吡啶溶液中,加热搅拌,温度控制在65-70℃,反应12-24h后得到探针分子,
优选的,所述式(I)中R1、R3分别地选自甲基,所述R2为叔丁基。
优选的,所述步骤(1)中水杨醛、邻氨基苯硫酚、双氧水、盐酸的摩尔比为1:1:6:1.5。
优选的,所述步骤(1)中双氧水的质量浓度为30%,所述盐酸溶液的质量浓度为37%。
优选的,所述步骤(1)中反应结束后还包括抽滤、洗涤和重结晶的步骤。
优选的,所述步骤(1)中的洗涤的溶剂是无水乙醇。
优选的,所述步骤(2)中所述探针分子中间体与式(II)所示的氯硅烷的摩尔比为5:6。
优选的,所述步骤(2)中反应结束后还包括后处理步骤,所述后处理步骤包括萃取、洗涤和柱分离步骤。
本发明具有以下技术特点:
1)本发明设计了检测氟离子的有机小分子探针,以水杨醛和邻氨基苯硫酚为起始原料,制备得到目标探针分子,反应条件温和,操作简便。
2)本发明的探针在有水和无水体系中均实现了对氟离子的快速检测,在THF体系中检测,分别以361nm和398nm波长作为激发波长,在412nm和514nm处产生最大荧光发射,5分钟左右荧光强度达到最大,荧光强度与氟离子浓度存在一定的关系,最低检出限概略达到20ppm,具有响应速度快、灵敏度高和选择性好的优点。
附图说明
图1探针分子对氟离子检测过程中荧光强度对时间的响应;
图2探针分子在无氟条件下荧光的稳定性;
图3探针分子的稳定性与检测氟离子的快速性;
图4THF体系中探针的对不同浓度氟离子的荧光强度变化;
图520%水的THF体系中探针在0-500μM氟离子存在下的荧光光谱;
图610%水的DMF体系中探针P2在0-300μM氟离子存在下的荧光光谱。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚,下面将对本发明实施例的技术方案进行清楚、完整的描述。显然,所描述的实施例是本发明的一部分实施例,而不是全部的实施例。基于所描述的本发明的实施例,本领域普通技术人员在无需创造性劳动的前提下所获得的所有其他实施例,都属于本发明的保护范围。
除非另作定义,本公开所使用的技术术语或者科学术语应当为本发明所属领域内有一般技能的人士所理解的通常意义。
实施例1:R1、R3为甲基,R2为叔丁基的探针分子的制备方法
包括如下步骤:
(1)探针分子中间体的合成
称取1.37g(10mmol)4-氨基水杨醛与1.25g(10mmol)邻氨基苯硫酚溶于25ml乙醇中,在室温下滴入5ml(60mmol)的30%H2O2和2ml(30mmol)37%HCl混合溶液,室温反应一个小时,用油泵进行抽滤,滤除沉淀,用无水乙醇洗涤几次后,进行重结晶得探针中间体1.65g,产品收率为69.0%。
(2)探针分子的合成
称取探针分子探针分子中间体1.210g(5mmol),加入35ml吡啶,再称取0.45g(6mmol)的叔丁基二甲基氯硅烷溶于20ml吡啶中,然后逐滴加入至探针分子探针分子中间体中。加热搅拌,温度控制在60-70℃下,反应1h。TLC监测反应进程。再减压旋干,加入乙酸乙酯萃取,再加水30ml洗涤三次,20ml柠檬酸饱和溶液洗涤一次,水洗三次后用30ml饱和食盐水洗涤一次,加入无水硫酸钠干燥过夜;次日用旋转蒸发仪减压旋干后得到淡黄色粘稠液体,称重得粗品0.350g。
用薄层硅胶色谱分析。用乙酸乙酯装填碱性氧化铝柱对粗品进行柱分离,流动相为乙酸乙酯:石油醚=1:10。过柱后得到淡黄色硅醚化的探针分子为0.198g,产率为37.33%。
实施例2:探针分子在有机体系四氢呋喃(THF)中检测氟离子
(1)样品的配制及分析条件
分别准确称量探针分子0.356g溶解于10ml重蒸四氢呋喃中,配制成浓度为1mM的探针stock溶液,在使用前根据需要进行稀释。称量四丁基氟化铵30mg溶于10ml重蒸四氢呋喃(THF)中,再取100μL10 mMstock溶液加入900μL重蒸四氢呋喃进行稀释,制成1mMstock溶液,依此法再稀释制成0.1mMstock溶液。荧光光谱是在10mm宽度的石英荧光池中加入2.0ml的目标溶液,测量过程中引入的氟离子溶液体积之和不超过100μL,以尽量减少体积变化对荧光性质造成的影响。所有荧光光谱均在室温测得。通过预实验,确定了探针分子体系检测氟离子的荧光激发波长为398nm。激发光与发射光的狭缝宽度均为5nm。
(2)探针分检测氟离子的响应性测定
研究了反应时间对体系检测氟离子荧光强度的变化的影响,采用200μM浓度的探针与40μM浓度的氟离子发生反应,结果如图1所示,从图中可以看出探针分子的氟离子检测过程未出现任何的时间依赖性,反应速度极快,体系的荧光强度在1min内即可达到饱和。因此,这种快速的响应性使得探针分子可迅速检测出氟离子。而在无氟存在的条件下,探针的荧光强度基本不发生变化(图2),这也表明探针是个比较稳定的化合物。我们以探针分子检测氟离子过程中出现的特征峰(454nm)的峰值与时间、探针分子自身的特征峰(512nm)的峰值与时间作图(图3),能清楚地看出探针分子的稳定性与对氟离子检测的快速程度。
(3)探针分子在无水体系THF中对氟离子进行检测
我们研究了探针分子对不同浓度氟离子进行检测的荧光行为,我探针分子的浓度为200μM,氟离子浓度为0μM、0.5μM、1μM、5μM、10μM、20μM、30μM、40μM、50μM、100μM、200μM。在每次加入氟离子并震荡后于阴暗处放置五分钟,测量荧光发射光谱(激发波长为398nm)。所得结果如图4所示。从图4中可以看出,在THF体系中,检测氟离子的荧光特征峰的高度(454nm)随氟离子浓度的升高而增大。有机小分子探针能很好的在THF的体系中检测到氟离子。
实施例3:探针分子在有水体系中检测氟离子
为了进一步探索探针分子的实际应用价值,我们引入水对体系的荧光响应性的影响进行了测定。我们首先在探针分子的THF体系引入20%的水。我们采用的探针分子探针分子的浓度仍然为200μM,结果表明(图5),无论何种浓度氟离子的加入,没有发现探针分子与氟离子反应后产物的荧光特征峰(454nm)出现,这就表明在含有20%水的THF体系,探针分子很难克服氟离子的水合化作用。THF的含水体系不适合检测氟离子。
我们又选用探针分子的DMF有水体系对氟离子进行检测,有了上次的经验,我们将检测体系中的水含量降至10%,将探针分子的浓度升高为300μM,以克服氟离子的水合能。结果表明(图6),随着氟离子的加入,在40μM氟离子的存在下,出现了探针分子与氟离子反应后产物的荧光特征峰(454nm)出现,并且随着氟离子的继续加入,454nm峰的荧光强度不断增加,到加入氟离子的浓度为100μM时,荧光强度到达最高点。但随着氟离子的继续加入,454nm峰的荧光强度反而降低。这就表明在氟离子引入的同时,也有部分THF的引入(氟离子溶液由THF配制),THF的引入显然不利于454nm峰的出现。这里面有一种可能是,THF和水存在的条件下,氟离子会与探针分子反应生成物结构中的酚羟基发生氢键作用,从而无法使其在激发光的作用下发生分子内质子转移。但我们的结果表明,探针分子具有水体系中检测氟离子的能力。
以上实施例的说明只是用于帮助理解本发明方法及其核心思想。应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以对本发明进行若干改进和修饰,这些改进和修饰也落入本发明权利要求保护范围内。
Claims (10)
2.根据权利要求1所述的氟离子检测小分子探针,其特征在于,所述式(I)中R1、R3分别地选自甲基,所述R2为叔丁基。
4.根据权利要求3所述的制备方法,其特征在于,所述式(I)中R1、R3分别地选自甲基,所述R2为叔丁基。
5.根据权利要求3所述的制备方法,其特征在于,所述步骤(1)中水杨醛、邻氨基苯硫酚、双氧水、盐酸的摩尔比为1:1:6:1.5。
6.根据权利要求3所述的制备方法,其特征在于,其特征在于,所述步骤(1)中双氧水的质量浓度为30%,所述盐酸溶液的质量浓度为37%。
7.根据权利要求3所述的制备方法,其特征在于,所述步骤(1)中反应结束后还包括抽滤、洗涤和重结晶的步骤。
8.根据权利要求3所述的制备方法,其特征在于,所述步骤(1)中的洗涤的溶剂是无水乙醇。
9.根据权利要求3所述的制备方法,其特征在于,所述步骤(2)中所述探针分子中间体与式(II)所示的氯硅烷的摩尔比为5:6。
10.根据权利要求3所述的制备方法,其特征在于,所述步骤(2)中反应结束后还包括后处理步骤,所述后处理步骤包括萃取、洗涤和柱分离步骤。
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