CN109608483A - 一种含硼氮配位键的有机小分子及其制备方法和对氟离子的传感应用 - Google Patents
一种含硼氮配位键的有机小分子及其制备方法和对氟离子的传感应用 Download PDFInfo
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Abstract
本发明公开了一种含硼氮配位键的有机小分子及其制备方法和对氟离子的传感应用，属于荧光化合物的制备及其荧光探针制备技术领域。本发明利用2‑(3‑溴苯并噻吩)‑2’‑苯并噻唑与正丁基锂反应生成锂试剂，再与三苯基硼反应制备了含硼氮配位键的小分子。经实验验证，本发明制备的含硼氮(BN)配位键的小分子成功实现对氟离子的选择性识别。本发明的含硼氮(BN)配位键荧光化合物的制备方法操作简便、反应条件温和所制备的荧光探针具有光化学稳定、选择性好等特点。
Description
技术领域
本发明属于荧光化合物的制备及其荧光探针制备技术领域，具体涉及一种含硼氮配位键的有机小分子及其制备方法和对氟离子的传感应用。
背景技术
有机光电子学是跨化学、物理、材料及信息的一门新型交叉学科，近年来倍受学术界与工业界的广泛关注。迄今为止，有机电致发光二极管(OLED)、有机场效应晶体管(OFET)、有机光伏电池(OPV)及有机传感器等众多有机光电器件已经展现出无机非金属器件无法比拟的优势。
近年来，氟离子对人类的影响日益加剧，因为在我们的日常生活中已经避免不了与氟离子的接触，如我们每天清洁用的药膏，包括维他命在内的好多药品及饮用水中都含有大量的氟离子，这直接危害到人类的健康，如人体蓄存过量致氟中毒后牙齿变黄、变黑、腿呈X型或O型、躬腰驼背或者手臂只能弯不能伸等，中毒轻者造成氟斑牙，重者出现氟骨症，甚至完全丧失劳动和生活自理能力。氟中毒一旦患上即永远成疾，药物只能减缓病情加重。所以对氟离子的检测至关重要，在众多氟离子的检测中使氟离子形成氢键作用为最常见的一种方法，这种方法选择性好，灵敏度高，越来越受到大家的关注。虽说在众多氟离子检测的受体可以在水相中高选择性，高灵敏度检测，但是在众多有机溶剂中检测氟离子上述探针收到一定的局限，基于此，利用路易斯酸类化合物则受到大家的关注。
因为硼固有的路易斯酸性可作为氟离子很好的受体材料。但在众多含硼化合物中，因为硼的高的反芳香性对水氧极为敏感，制备稳定的硼化合物则非常必要，常用稳定硼的方法则是引入比较大的基团来增加空间位阻，但合成过程充满挑战。大量实验证明，当硼被硼氮键取代后不仅能增加其稳定性，并且呈现出很好的光电性质，已被应用于有机光电器件中。
从全碳体系到其它杂原子的引入，所制备的有机共轭杂环芳烃，无论从材料本身性质还是所制备器件的性能都有了大幅度的提升。如将硼氮(BN)引入共轭体系后其光电性能明显改变。Liu研究小组不仅首次合成了1,2-二氢-1,2-硼氮杂苯，并对其进行了全面的表征。随后，一系列的1,2-硼氮杂苯的衍生物也相继报道。基于硼氮的有机光电器件最近也有报道，北京大学裴坚研究小组报道了基于硼氮杂苯的场效应晶体管，而且器件具有很高的电子迁移率(0.23cm2V-1s-1)。
可以看出，含硼氮(BN)的共轭体系有优异的性能和巨大的发展前景，但是已报道的众多氟离子探针材料荧光发光效率不高，对氟离子响应值较低及在众多阴离子中对氟离子的选择性也不好。实现对硼氮(BN)化合物高效、简易的设计合成还是存在很多的困难。
发明内容
为了克服上述现有技术的缺点，本发明的目的在于提供一种具有高荧光量子产率的含硼氮配位键的小分子及其制备方法和对氟离子的传感应用。
为了达到上述目的，本发明采用以下技术方案予以实现：
本发明的目的之一在于公开了一种含硼氮配位键的有机小分子，该含硼氮配位键的有机小分子的结构如下式：
本发明的目的之二在于公开了上述的含硼氮配位键的有机小分子的制备方法，其特征在于，包括以下步骤：
1)在氩气保护下，将化合物1溶于绝对无水THF中，于-78℃下滴加正丁基锂，滴加完毕后保持1h，制得溶液A；
所述化合物1结构如下式：
2)将三苯基硼溶于绝对无水THF中，在氩气保护下，逐渐滴加于上述溶液A中，然后升温至室温，继续搅拌反应12h，减压除去溶剂，经硅胶层析柱分离纯化得黄色固体，即为具有高荧光量子产率的硼氮配位键小分子。
优选地，正丁基锂与化合物1的摩尔比为1：1；化合物1与三苯基硼的摩尔比为1：1.1。
优选地，步骤2)中，硅胶层析柱分离条件为乙酸乙酯：石油醚＝1:5。
本发明的目的之三在于公开了采用上述含硼氮配位键的有机小分子制备荧光探针的方法，其特征在于，包括以下步骤：
1)将具有高荧光量子产率的硼氮配位键小分子溶解于四氢呋喃中，制备成1×10- 3M的储备液；
2)按照每50μL储备液加入4950μL四氢呋喃的用量，向储备液中加入四氢呋喃，然后于室温放置2h，制得荧光探针。
本发明的目的之四在于公开了采用上述的制备荧光探针的方法制得的荧光探针。
本发明的目的之五在于公开了上述的荧光探针作为氟离子检测试剂的应用。
与现有技术相比，本发明具有以下有益效果：
本发明利用2-(3-溴苯并噻吩)-2’-苯并噻唑与正丁基锂反应生成锂试剂，再与三苯基硼反应制备了含硼氮配位键的小分子。经实验验证，本发明制备的含硼氮配位键的小分子成功应用于对氟离子的反应型选择性识别。随着氟离子的不断加入，荧光发射光谱强度发生明显降低。本发明的含硼氮配位键的荧光化合物的制备方法操作简便、反应条件温，所制备的荧光探针光化学稳定，且在众多阴离子中对氟离子的选择性好，将这类含硼氮配位键荧光分子探针与商品荧光仪器联合使用可以实现对氟离子高选择性检测。
附图说明
图1为所合成化合物2对氟离子响应的紫外谱图；
图2为所合成化合物2对氟离子响应的荧光谱图；
图3为化合物2对不同阴离子响应的荧光谱图；
图4为化合物2对氟离子及BF3·Et2O响应的紫外吸收光谱；
图5为化合物2对氟离子及BF3·Et2O响应的荧光发射光谱；
图6为化合物2的核磁氢谱；
图7为化合物2的核磁碳谱。
具体实施方式
为了使本技术领域的人员更好地理解本发明方案，下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分的实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都应当属于本发明保护的范围。
需要说明的是，术语“包括”和“具有”以及他们的任何变形，意图在于覆盖不排他的包含，例如，包含了一系列步骤或单元的过程、方法、系统、产品或设备不必限于清楚地列出的那些步骤或单元，而是可包括没有清楚地列出的或对于这些过程、方法、产品或设备固有的其它步骤或单元。
下面结合附图对本发明做进一步详细描述：
1、本发明的含硼氮(BN)小分子及聚合物，可通过以下步骤来制备：
在氩气保护下，将化合物1(0.478g,1.38mmol)溶于绝对无水THF(10mL)中，于-78℃下滴加正丁基锂(0.56mL,2.5M in hexane,1.38mmol)，滴加完毕后保持1h，将三苯基硼(0.388g,1.6mmol)溶于绝对无水THF(10mL)中，在氩气保护下逐渐滴加于上述溶液中，然后升温至室温，继续搅拌反应12h，减压除去溶剂，经硅胶层析柱分离纯化得黄色固体，产率：35％。
反应式如下：
2、荧光探针的制备
1)将荧光化合物溶解在四氢呋喃中，制备成1×10-3M的储备液；
2)按每50μL储备液加入4950μL四氢呋喃，于室温放置2小时，制得荧光探针。
检测时：用1.0M四丁基氟化铵的四氢呋喃溶液，制备成1×10-3M待测氟离子的溶液。
实施例1
在氩气保护下，将化合物1(0.478g,1.38mmol)溶于绝对无水THF(10mL)中，于-78℃下滴加正丁基锂(0.56mL,2.5M in hexane,1.38mmol)，滴加完毕后保持1h，将三苯基硼(0.388g,1.6mmol)溶于绝对无水THF(10mL)中，在氩气保护下逐渐滴加于上述溶液中，然后升温至室温，继续搅拌反应12h，减压除去溶剂，经硅胶层析柱分离纯化得黄色固体，产率：35％。
所得产物的核磁氢谱如图6所示，核磁碳谱如图7所示。
为了验证本发明的效果，对实施例1中所合成的硼氮化合物对氟离子的检测进行了探索，如图所示。
其中，图1、图2为所合成化合物2的紫外可见吸收光谱图和荧光光谱，从图1紫外可见吸收光谱上可以明显的看到，随着氟离子的加入，最大吸收光谱在380nm逐渐降低，在328nm处出现明显的增强峰；同时，也从荧光光谱图2上清楚地看到在441nm处的发射峰逐渐降低，溶液颜色由微弱的发光颜色到明显的蓝色到逐渐消失。
图3分别为化合物2对不同阴离子的荧光光谱，从荧光光谱图中可以明显看出，在F-,Cl-,Br-,I-,NO3 -,ClO4 -,BF4 -,PF6 -,AcO-,H2PO4 -,SO4 2-等阴离子中，荧光发射峰441nm处只有加氟离子后荧光强度呈降低状态，而Cl-,Br-,I-,NO3 -,ClO4 -,BF4 -,PF6 -,AcO-,H2PO4 -,SO4 2-等阴离子则没有明显变化，所以制备的有机硼氮小分子2对氟离子的选择性效果非常好，可以在众多阴离子中便捷的检测到氟离子，为其能够实际应用奠定了基础。
图4为化合物2加氟离子及氟离子更强捕获剂的紫外吸收光谱，从中可以清楚的看出，化合物2加入氟离子后紫外吸收光谱从380nm蓝移到328nm处，再加氟离子更强捕获剂BF3·Et2O后380nm处的紫外吸收峰基本恢复。
图5为化合物2加氟离子及氟离子更强捕获剂的荧光发射光谱，从中可以清楚的看出，当化合物2加入氟离子后441nm处的荧光发射峰呈淬灭状态，当再加入氟离子更强捕获剂BF3·Et2O后441nm处的荧光发射峰基本恢复。
以上内容仅为说明本发明的技术思想，不能以此限定本发明的保护范围，凡是按照本发明提出的技术思想，在技术方案基础上所做的任何改动，均落入本发明权利要求书的保护范围之内。
Claims (7)
1.一种含硼氮配位键的有机小分子，其特征在于，该含硼氮配位键的有机小分子的结构如下式：
2.权利要求1所述的含硼氮配位键的有机小分子的制备方法，其特征在于，包括以下步骤：
1)在氩气保护下，将化合物1溶于绝对无水THF中，于-78℃下滴加正丁基锂，滴加完毕后保持1h，制得溶液A；
所述化合物1结构如下式：
2)将三苯基硼溶于绝对无水THF中，在氩气保护下，逐渐滴加于上述溶液A中，然后升温至室温，继续搅拌反应12h，减压除去溶剂，经硅胶层析柱分离纯化得黄色固体，即为具有高荧光量子产率的硼氮配位键小分子。
3.根据权利要求2所述的含硼氮配位键的有机小分子的制备方法，其特征在于，正丁基锂与化合物1的摩尔比为1：1；化合物1与三苯基硼的摩尔比为1：1.1。
4.根据权利要求2所述的含硼氮配位键的有机小分子的制备方法，其特征在于，步骤2)中，硅胶层析柱分离条件为乙酸乙酯：石油醚＝1:5。
5.采用权利要求1所述的含硼氮配位键的有机小分子制备荧光探针的方法，其特征在于，包括以下步骤：
1)将具有高荧光量子产率的硼氮配位键小分子溶解于四氢呋喃中，制备成1×10-3M的储备液；
2)按照每50μL储备液加入4950μL四氢呋喃的用量，向储备液中加入四氢呋喃，然后于室温放置2h，制得荧光探针。
6.采用权利要求5所述的制备荧光探针的方法制得的荧光探针。
7.权利要求6所述的荧光探针作为氟离子检测试剂的应用。
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