CN110396405A - 一种基于异喹啉的比率型氟离子检测探针及其制备方法和应用 - Google Patents
一种基于异喹啉的比率型氟离子检测探针及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开一种基于异喹啉的比率型氟离子检测探针及其制备方法和应用。该荧光探针结构如式I所示,其以邻炔基醛为原料,经与苄胺衍生物反应而成。本发明的探针光学性能稳定,对氟离子检测灵敏度高,检测下限低,检测限为3.79nM,响应范围为0.2‑10μM。选择性好,对氯离子、溴离子、碘酸根离子、高碘酸根离子、硝酸根离子、亚硝酸根离子、醋酸根离子、碳酸根离子、硫酸根离子、亚硫酸根离子阴离子没有响应。且合成简单,条件温和,收率高。本发明的荧光分子探针在生物化学与环境化学,特别是水中氟离子的检测等领域具有实际的应用价值。
Description
技术领域
本发明涉及的是化学分析检测技术领域,具体涉及基于异喹啉的比率型氟离子检测探针及其制备方法和应用。
背景技术
阴离子是维持生物生命活动的重要元素,设计、合成新的阴离子荧光检测探针是化学分析学科的一个重要研究领域。氟离子被认为是牙齿和人体生长所必需的微量元素,它可以保护牙齿和预防骨质疏松。过量与不足均有可能导致某些疾病,过量的摄取含氟化合物会引起严重的疾病,如氟中毒、尿结石、肿瘤、器官病变、氟骨症等。美国环保署对健康饮用水中的最大氟离子浓度的要求是4ppm(211μM),因此,发展高灵敏、高选择性的氟离子识别与检测方法具有重要的意义。
传统的氟离子检测方法有分光光度法、氟离子选择性电极、离子色谱、高效液相色谱和荧光分析法。荧光化学传感器因其高灵敏度、高选择性、低成本、易检测等优点而成为现代检测氟化物的重要方法。氟离子对硅具有特别的亲和力,氟硅键也是最强的化学键之一,这些特性使得分析化学家们利用氟硅键的特征化学反应设计荧光探针检测识别氟离子。这类探针在检测氟离子的过程中,不易受到其它阴阳离子的干扰,专一性很好。传统的荧光传感器大多数是依靠荧光强度变化来识别检测氟离子,而大多数的荧光探针都是单一波长的,容易受到外界以及背景信号的干扰,从而影响检测结果的准确性。
发明内容
针对上述技术问题,本发明提供一种基于异喹啉的比率型氟离子检测探针及其制备方法和应用。
本发明的技术方案为:
一种基于异喹啉的比率型氟离子检测探针,具有式(I)所示的结构:
其中R1、R2、R3为甲基、乙基、叔丁基、或苯基,R4为二甲氨基、二乙氨基、甲氧基。
上述的基于异喹啉的比率型氟离子检测探针的制备方法,包括如下步骤:
将化合物1和邻炔基醛化合物2溶于溶剂中,所述化合物1和2的物质的量之比为1~3∶1,并加入路易斯催化剂,一定温度条件下搅拌3~36小时,反应完毕后加入饱和食盐水,然后用氯仿进行萃取,无水硫酸钠干燥1~2小时,过滤除去硫酸钠固体,溶液减压旋蒸,粗产物柱层析得到黄色固体荧光探针化合物I,即式(I)所示的氟离子检测探针。
以上各化合物均以反应式中各化合物下面序号加以区分。
进一步地,化合物1和2的物质的量之比优选为1∶1。
进一步地,合成步骤中,所述的溶剂优选无水乙醇。
进一步地,合成步骤中,所述的路易斯酸优选硝酸银。
进一步地,合成步骤中,R1、R2优选苯基,R3优选叔丁基,R4优选甲氧基。
上述的氟离子检测探针应用于氟离子检测的方法,包括如下步骤:
1)配制分散有荧光探针化合物I的乙腈-水混合溶液;
2)确定荧光探针分子的检测限;
3)绘制并计算溶液中氟离子的浓度;
4)确定荧光探针对阴离子的选择性。
检测原理如下所示:
本发明中荧光探针对氟离子的识别检测基于氧化消除反应机理。荧光探针与氟离子作用前,分子的荧光发射在522nm左右;当有氟离子存在时,探针分子的硅氧键被氟离子切断,同时酚羟基上马上被氧化发生消除反应转变为异喹啉化合物3。两种化合物由于共轭结构不一样,具有各自的最大发射波长。因此,可以根据探针分子荧光强度的变化识别和定量检测氟离子。
更具体的检测方法如下:
1)配制荧光探针化合物I浓度为0.1mmol/L的90%乙腈-水(即V(乙腈)/V(水)=90/10)混合溶液,得到荧光探针分子的水分散溶液;
2)取一系列1-3mL的荧光探针分子的水分散溶液,分别加入10-30μL不同浓度的氟离子(0,0.2,0.4,0.6,0.8,1.0,2.0,3.0,4.0,5.0,6.0,7.0,8.0,9.0,10),放置5~30分钟后,分别测量并计算出398与522nm处的荧光强度比值,根据荧光强度比值与氟离子浓度的关系制作工作曲线;
3)取一系列1-3mL的荧光探针分子的水分散溶液,分别加入10-30μL浓度为10-2的Cl-,Br-,IO3 -,IO4 -,NO3 -,NO2 -,Ac-,CO3 2-,SO4 2-,SO3 2-的水溶液,放置5~30分钟后,分别测量并记录398与522nm处的荧光强度,由此验证探针分子对氟离子的选择性。
本发明的有益效果在于:
(1)本发明提供的荧光探针分子对氟离子的识别不仅灵敏,而且专一性强,是一种比率型荧光探针,受仪器及环境因素的影响较小。
(2)本发明提供的荧光探针分子适用于含氟水溶液。
(3)本发明提供的荧光探针分子对氟离子的检测限低,可以达到纳摩尔级。
附图说明
图1为本发明实施例4制备的比率荧光探针分子的水分散溶液,加入不同浓度氟离子后的荧光光谱图,自上而下的曲线代表浓度逐渐降低的探针溶液。
图2为本发明实施例5,350nm激发光激发下,分别加入20μL的Cl-,Br-,IO3 -,IO4 -,NO3 -,NO2 -,Ac-,CO3 2-,SO4 2-,SO3 2-的水溶液,30min后的荧光强度。
其中,图1至图2中,横坐标表示波长(wavelength),纵坐标表示强度(intensity)。
具体实施方式
以下通过具体实施例对本发明做进一步地详细说明,但不应将此理解为本发明上述主题的范围仅限于以下的实施例。凡基于本发明上述内容所实现的技术均属于本发明的范围。
本发明所用仪器与试剂:
核磁共振仪:Bruker AV-II 500MHz NMR,TMS为内标,CDCl3为溶剂;红外光谱仪:TFS-40型,KBr压片。
所用试剂均为市售化学纯或分析纯。
实施例1
本发明荧光探针的合成
本发明荧光探针的制备途径如下:
将化合物1a和邻炔基醛化合物2a溶于1,2-二氯乙烷中,所述化合物1a和2a的物质的量之比为1∶1,并加入硝酸银,80度条件下搅拌12小时,反应完毕后加入饱和食盐水,然后用氯仿进行萃取,无水硫酸钠干燥1小时,过滤除去硫酸钠固体,溶液减压旋蒸,粗产物柱层析得到黄色固体荧光探针化合物Ia,即式(I)所示的氟离子检测探针,产率66%。
Ia,黄色固体,IR(KBr)cm-13441,2927,2853,2048,2025,1704,1635,1506,1383,1256,1179,1110,1028,916,826,703,572.1H NMR(500MHz,CDCl3)δ10.675(s,1H),8.580(d,J=7.5Hz,1H),7.999(t,J=7.5Hz,1H),7.936(d,J=8.0Hz,1H),7.880(s,1H),7.804(t,J=7.5Hz,1H),7.572(d,J=7.5Hz,4H),7.342(t,J=7.5Hz,2H),7.272(t,J=7.5Hz,4H),7.123(d,J=8.0Hz,2H),6.842(d,J=8.0Hz,2H),6.563(d,J=8.5Hz,2H),6.510(d,J=8.0Hz,2H),5.809(s,2H),3.766(s,3H),0.975(s,9H).13C NMR(125MHz,CDCl3)δ161.3,156.3,152.9,145.9,137.7,137.4,135.4,132.4,131.7,131.3,131.1,130.1,129.7,127.8,127.4,126.6,125.8,123.9,120.3,114.6,62.0,55.6,26.4,19.4.
实施例2
将化合物1b和邻炔基醛化合物2b溶于溶剂中,所述化合物1b和2b的物质的量之比为1∶1,并加入三氟甲磺酸银,70度条件下搅拌10小时,反应完毕后加入饱和食盐水,然后用氯仿进行萃取,无水硫酸钠干燥1小时,过滤除去硫酸钠固体,溶液减压旋蒸,粗产物柱层析得到黄色固体荧光探针化合物Ib,即式(I)所示的氟离子检测探针,产率50%。
实施例3
将化合物1c和邻炔基醛化合物2b溶于溶剂中,所述化合物1c和2b的物质的量之比为1∶1,并加入碘化亚铜,70度条件下搅拌10小时,反应完毕后加入饱和食盐水,然后用氯仿进行萃取,无水硫酸钠干燥1小时,过滤除去硫酸钠固体,溶液减压旋蒸,粗产物柱层析得到黄色固体荧光探针化合物Ic,即式(I)所示的氟离子检测探针,产率50%。
实施例4
比率荧光探针分子工作曲线
取2mL配制好的比率荧光探针分子Ia的水分散溶液,加入20μL不同浓度(0,0.2,0.4,0.6,0.8,1.0,2.0,3.0,4.0,5.0,6.0,7.0,8.0,9.0,10μM)的氟化钠水溶液,放置30min后,荧光光谱仪分别记录398与522nm处荧光强度的变化。以荧光强度为纵坐标,氟离子浓度为横坐标作图,拟合得到比率荧光探针分子的工作曲线。本实施例中比率荧光探针对氟离子浓度的测定,其在350nm激发光激发下,荧光强度随氟离子浓度变化的关系图如图1所示。
实施例5
荧光探针分子阴离子选择性测定
取2mL实施例2中配制好的比率荧光探针分子Ia的水分散溶液,加入20μL浓度为0.01M的Cl-,Br-,IO3 -,IO4 -,NO3 -,NO2 -,Ac-,CO3 2-,SO4 2-,SO3 2-水溶液,放置30min后,荧光光谱仪分别记录398与522nm处荧光强度的变化。实验结果表明,除了氟离子以外,其它粒子没有引起荧光的明显变化,说明本发明的探针分子具有很好的选择性。本实施例中荧光探针分子选择性测定,其在350nm激发光激发下,荧光强度随氟离子浓度变化的关系图如图2所示。
Claims (7)
1.一种基于异喹啉的比率型氟离子检测探针,其特征在于,具有式(I)所示的结构:
其中R1、R2、R3为甲基、乙基、叔丁基、或苯基,R4为二甲氨基、二乙氨基、甲氧基。
2.权利要求1所述的基于异喹啉的比率型氟离子检测探针的制备方法,其特征在于,包括如下步骤:
将化合物1和邻炔基醛化合物2溶于溶剂中,所述化合物1和2的物质的量之比为1~3∶1,并加入路易斯酸催化剂,加热条件下搅拌3~36小时,反应完毕后加入饱和食盐水,然后用氯仿进行萃取,无水硫酸钠干燥1~2小时,过滤除去硫酸钠固体,溶液减压旋蒸,粗产物柱层析得到黄色固体荧光探针化合物I,即式(I)所示的氟离子检测探针。
3.根据权利要求1所述的基于异喹啉的比率型氟离子检测探针的制备方法,其特征在于,化合物1和2的物质的量之比为1∶1。
4.根据权利要求1所述的基于异喹啉比率型氟离子检测探针的制备方法,其特征在于,所述的溶剂为无水甲醇、乙醇、1,2-二氯乙烷。
5.根据权利要求1所述的基于异喹啉的比率型氟离子检测探针的制备方法,其特征在于,所述的路易斯酸为三氟醋酸银,三氟甲磺酸银,硝酸银,碘化亚铜,氯化亚钴,碘单质,氯化碘。
6.权利要求1所述的氟离子检测探针在氟离子检测中的应用。
7.根据权利要求7所述的氟离子检测探针在氟离子检测中的应用,其特征在于,包括如下步骤:
配制荧光探针化合物I的乙腈-水混合溶液,浓度为100μmol/L,制成标准溶剂,然后用制成的标准溶剂配制成氟离子浓度分别为0,0.2,0.4,0.6,0.8,1.0,2.0,3.0,4.0,5.0,6.0,7.0,8.0,9.0,10μmol/L的氟离子标准溶液,放置5~30分钟后,在激发波长350nm,发射波长398与522nm处分别测定不同氟离子浓度时的荧光强度,做成标准曲线,拟合确定荧光强度与氟离子浓度的函数关系,然后据此测定待测溶液的氟离子浓度。
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