CN111848465B - 一种双功能荧光探针分子、制备及应用 - Google Patents
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Abstract
本发明涉及一种氟离子和氰化物检测探针的制备方法,属于荧光探针技术领域。本发明将1,3,5‑三恶烷与冰醋酸反应,并将其用DMSO/H2O重结晶;将4,4'‑二氨基二苯砜和之前所得化合物反应制备双功能荧光分子探针;将产物过滤洗涤并烘干称重,得到最终产品。该探针实现在紫外和荧光两个通道上对F‑和CN‑同时快速选择性识别,尤其是在荧光通道,加入F‑和CN‑以后不仅探针分子的荧光强度发生不同程度的淬灭而且发射峰也出现不同程度的红移,这对于区别性检测F‑和CN‑十分有效。
Description
技术领域
本发明涉及一种双功能荧光探针分子、制备及应用,特别涉及一种用于检测F-和CN-的荧光探针,属于荧光探针技术领域。
背景技术
单分子光学传感器通过溶液颜色和光谱响应的变化来选择性地检测多种阴离子,由于其在生物和化学过程中的重要作用以及学术上的挑战,其设计和合成已经得到了广泛的研究。在所有的阴离子中,特别是氰化物和氟化物,在日常生活、生化行为和广泛的工业产品中发挥着重要的作用。氰化物主要通过金银开采过程释放到环境中,但在生物学和环境中是一种毒性极强的阴离子,可引起中毒。同时,氟化物是一种生物学上至关重要的阴离子,因为它在骨质疏松症的治疗和牙科保健中发挥着既定的作用,不过,过量氟化物的存在会导致牙齿斑白、氟骨症、骨病、肝脏、甲状腺等器官的损害。因此,迫切需要一种有效的检测氰化物和氟化物的传感方法。
在过去的几十年里,大量基于各种机制的化学传感器被报道用于检测氰化物和氟化物,如与过渡金属形成阴离子络合物、激发态分子内质子转移(ESIPT)、脱质子、亲核加成反应、激元-单体开关和氢键相互作用。但是,大多数要么无法在相同的测量方法中进行鉴别,要么无法同时使用掩蔽剂进行鉴别。考虑到这一点,多功能化学传感器可以通过不同的识别机制或不同的结合位点进行多分析物检测,具有成本低、响应动态、实时检测等优点。此外,单分子化学传感器可以实现多分析物同时检测,它在“分子逻辑门”的开发中也有潜在的应用前景。
发明内容
本发明所要解决的技术问题是:提供一种同时能够检测F-和CN-的荧光探针。
本发明的目的是通过下述技术方案实现的:
一种双功能荧光探针分子,其结构式如下:
一种双功能荧光探针分子的制备,具体步骤如下:
步骤一:将约1g1,3,5-三恶烷溶解在50ml冰醋酸中,完全溶解后边搅拌边滴加3-6ml水杨醛;得到混合溶液A;
步骤二:向混合溶液A中滴加3-5滴催化剂浓硫酸;反应完全后得到溶液B;
步骤三:将溶液B后冷却,呈细流状倒入置于碎冰的烧杯中,用酒精清洗固体物质,然后干燥,得到固体;
步骤四:将约1g步骤三得到的固体与约20g 4,4'-二氨基二苯砜溶解在50ml DMF溶液中;在20-40℃温度下,滴加3-5滴催化剂浓盐酸;反应完毕,冷却至室温;以DMSO/H2O或DMF溶液对产物进行过滤、干燥、重结晶。得到荧光探针。
采用双功能荧光探针定性检测F-和CN-的方法,具体步骤如下:
步骤一、粗测:将待测溶液加入探针溶液中,观察混合溶液的颜色,含F-的溶液呈现橘黄色,含CN-的溶液无变化。
步骤二、细测:将步骤一的混合溶液放入荧光光谱仪,峰值有明显的选择性响应;
采用荧光探针定量检测F-和CN-的方法,具体步骤如下:
步骤一、用有机溶剂将光传感材料配制成C=1×10-5mol/L的荧光传感材料分散液;
步骤二、将其他负离子和F-和CN-离子分别配制成与荧光传感材料摩尔比为50的溶液;将步骤一制得的分散液分别与所述溶液混合,得到混合溶液;测定混合溶液的荧光强度值;
步骤三、配制F-和CN-与荧光传感材料摩尔比为0.5,1,2,5,10,20,30,40,50的溶液A和B;将步骤一制得的分散液分别于所述溶液A和B混合,得到混合溶液C和D;测定混合溶液C和D的荧光强度值的变化与F-和CN-浓度的对应关系(单位:10-5M)。
进一步地,检测F-的检测限为0.53μM。
进一步地,检测CN-的检测限为0.63μM。
有益效果:
本发明的一种荧光探针,分别于F-和CN-发生反应形成新的物质,从而分别影响其相应的紫外谱图和荧光谱图,并且灵敏度高,专一性好。
附图说明
图1为本发明所述的荧光探针可以从肉眼角度上区分F-和CN-
图2为本发明所述的荧光探针的荧光发射光谱随着F-含量增加的变化趋势图;
图3为本发明所述的荧光探针的荧光发射光谱随着CN-含量增加的变化趋势图。
具体实施方式
下面结合附图与实施例与附图对本发明做进一步说明。
实施例1
一种荧光探针,其结构式如下:
一种荧光探针的制备方法,具体步骤如下:
步骤一:将0.62g 1,3,5-三恶烷溶解在50ml冰醋酸中,完全溶解后边搅拌边滴加3ml水杨醛;得到混合溶液A;
步骤二:向混合溶液A中滴加3滴催化剂浓硫酸;反应完全后得到溶液B;
步骤三:将溶液B后冷却,呈细流状倒入置于碎冰的烧杯中,用酒精清洗固体物质,然后干燥,得到固体;
步骤四:将0.50g步骤三得到的固体与21.82g 4,4'-二氨基二苯砜溶解在20mlDMF溶液中;在24℃温度下,滴加3滴催化剂浓盐酸;反应完毕,冷却至室温;以DMSO/H2O溶液对产物进行过滤、干燥、重结晶。得到荧光探针。
所述的荧光探针用于对F-和CN-的荧光检测:
步骤如下:
探针分子溶液配置用分析天平准确称量2.5mg探针化合物,将其加入10mL的容量瓶中,然后将已配置好的含水DMF或者DMSO溶液加入容量瓶,待化合物完全溶解以后,定容配制成浓度为5×10-4mol/L的原始母液,再用100-1000微升的移液枪准确移取0.1mL原始母液于10mL的容量瓶中,加DMF或者DMSO溶液定容配成浓度为5×10-6mol/L的待测溶液。
检测目标化合物配置用天平准确称量F-和CN-的四丁基铵盐,将其加入10mL的容量瓶,然后将DMF或者DMSO溶液加入容量瓶,待化合物完全溶解以后,定容配制成浓度为1×10-4mol/L的原始母液,其它离子溶液(Cl-、Br-、I-、OAc-、PF6 -、HSO4 -、SO42-、ClO4 -)也按照同样方法分别配成1×10-4mol/L的原始母液。
荧光探针的荧光强度随着F-含量增加的变化,具体步骤如下:
配制一系列一定浓度的探针溶液(用pH=7.3的DMSO缓冲溶液控制整体酸度),共计20个样,依次向该溶液中加入不同当量浓度的F-溶液,使其浓度为0-40μM。加入完全后,静置反应一段时间,测试其荧光响应,结果表明,随着浓度的上升,探针的荧光强度先逐渐升高然后再保持基本不变,得到图1结果。从图中可以看出,随着F-的浓度升高,390nm和600nm处的荧光强度出现峰值,通过对340nm处探针的荧光发射强度和加入的F-的当量浓度进行非线性相关拟合,所得拟合相关常数R2高达0.9927。
荧光探针的荧光发射光谱随着CN-含量增加的变化,具体步骤如下:
配制一系列一定浓度的探针溶液(用pH=7.3的DMSO缓冲溶液控制整体酸度),共计20个样,依次向该溶液中加入不同当量浓度的CN-溶液,使其浓度为0-40μM。加入完全后,静置反应一段时间,测试其荧光响应,结果表明,随着浓度的上升,探针的荧光强度先逐渐升高然后再保持基本不变,得到图2结果。随着CN-的浓度升高,510nm处的荧光强度出现峰值。通过对340nm处探针的荧光发射强度和加入的CN-的当量浓度进行非线性相关拟合,所得拟合相关常数R2高达0.9931。
其他阴离子对F-和CN-检测的影响
从图3我们可以明显看出,探针分子及其在其它阴离子存在下在DMSO缓冲液(pH=7.3)中的荧光发射光谱图。从测试结果中不难看出,加入其它阴离子(Cl-、Br-、I-、OAc-、PF6 -、HSO4 -、SO42-、ClO4 -)以后,F-和CN-的峰值分别在390nm与510nm处,其中加入其它阴离子几乎没有使探针的荧光强度发生任何淬灭,本方法有灵敏、低成本和“一探针多用途”的优势,泛用于环境与生产中的微量F-和CN-的检测。
实施例2
一种荧光探针,其结构式如下:
一种荧光探针的制备方法,具体步骤如下:
步骤一:将0.90g1,3,5-三恶烷溶解在50ml冰醋酸中,完全溶解后边搅拌边滴加5ml水杨醛;得到混合溶液A;
步骤二:向混合溶液A中滴加5滴催化剂浓硫酸;反应完全后得到溶液B;
步骤三:将溶液B后冷却,呈细流状倒入置于碎冰的烧杯中,用酒精清洗固体物质,然后干燥,得到固体;
步骤四:将0.75步骤三得到的固体与22.32g 4,4'-二氨基二苯砜溶解在20ml DMF溶液中;在35℃温度下,滴加5滴催化剂浓盐酸;反应完毕,冷却至室温;以DMF溶液对产物进行过滤、干燥、重结晶。得到荧光探针。
所述的荧光探针用于对F-和CN-的荧光检测,同实施例1。
以上显示和描述了本发明的基本原理、主要特征和本发明的优点。本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理,在不脱离本发明精神和范围的前提下,本发明还会有各种变化和改进,这些变化和改进都落入要求保护的本发明的范围内。本发明要求保护范围由所附的权利要求书及其等同物界定。
Claims (1)
1.一种荧光探针分子用于检测F-和CN-的用途,其特征如下:
所述荧光探针分子的结构式如下:
所述荧光探针分子采用如下方法制备:
步骤一:将约1g 1,3,5-三恶烷溶解在50ml冰醋酸中,完全溶解后边搅拌边滴加3-6ml水杨醛;得到混合溶液A;
步骤二:向混合溶液A中滴加3-5滴催化剂浓硫酸;反应完全后得到溶液B;
步骤三:将溶液B冷却后,呈细流状倒入置于碎冰的烧杯中,用酒精清洗固体物质,然后干燥,得到固体;
步骤四:将约1g步骤三得到的固体与约20g 4,4'-二氨基二苯砜溶解在50ml DMF溶液中;在20-40℃温度下,滴加3-5滴催化剂浓盐酸;反应完毕,冷却至室温;以DMSO/H2O或DMF溶液对产物进行过滤、干燥、重结晶;得到荧光探针。
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