CN110156821A - 一种BODIPY类酸性pH响应的近红外荧光探针及其制备方法 - Google Patents
一种BODIPY类酸性pH响应的近红外荧光探针及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种BODIPY类酸性pH响应的近红外荧光探针及其制备方法，其化学结构式如式(I)所示，该荧光探针通过2，6‑二乙炔基噻吩BODIPY衍生物与对二甲氨基苯甲醛的缩合反应制备。本发明所述的荧光探针化合物制备过程简单、反应条件温和、纯化步骤简便，且在很窄的酸性pH范围(pH＝1.7‑3.5)表现出较高的灵敏度。该探针在结合H+前后颜色变化明显，可裸眼识别，可通过溶液的颜色变化定性判断环境的pH值，是一种较好的可视化pH荧光探针。该荧光探针在化学反应、环境监测、生态保护等方面对酸度的检测具有潜在应用价值。
Description
技术领域
本发明属于有机合成技术领域，涉及一种BODIPY类酸性pH响应的近红外荧光探针及其制备方法。
背景技术
氟硼二吡咯(Dipyrrom ethene Boron Difluoride，简称BODIPY)荧光物质是一类新兴的染料，具有斯托克斯位移较小、稳定性好、对酸碱不敏感、荧光量子产率较高(甚至在水中，都通常接近100％)、荧光激发和发射峰较窄，且都在可见光区(λ≥500nm)在许多有机溶剂中的溶解性较高等优点。并且可以通过对BODIPY中心骨架结构加以修饰，得到一系列具有高荧光量子产率，近红外吸收的BODIPY衍生物。
在环境分析、化学反应过程控制、生物医学等方面中，pH值的测定具有十分重要的意义。物质的物化性质及其在水溶液中的反应性能、生命体系中的许多生理过程都与其所处环境的pH值密切相关。目前，pH测定方法主要有指示剂法、pH试纸法、玻璃电极法、光学传感器法等。pH试纸的需要肉眼观测，主观性太强导致测量准确性较差。电极法虽然可以准确测量，但受到电化学干扰，易损伤，难以用于细胞方面的检测使用局限性大。相比于其他pH的测定方法，使用荧光探针法进行pH检测具有灵敏度高、选择性好等优点。尽管基于分子的荧光探针可以准确测量不同环境下pH值，但由于在强酸条件下探针分子的变质或荧光猝灭等限制，大多数荧光探针无法在强酸条件下进行探针。且绝大多数pH荧光分子探针检测范围宽，这就降低了探针的灵敏度，对于强酸性低pH范围内(pH＜4)的荧光探针鲜有报道。另外，近红外荧光探针的最大吸收波长和发射波长为600～900nm，可避免背景干扰。因此，近红外荧光检测在生物样品分析中有明显的优越性。因此，设计并合成能够在强酸条件下精确测量pH值的近红外荧光探针，尤其是比率型探针，对于环境、化学及生物研究具有重要的学术价值和实际应用意义。
发明内容
发明目的：针对现有技术中存在的不足，本发明的目的是提供一种BODIPY类酸性pH响应的近红外荧光探针及其制备方法。
技术方案：为了实现上述发明目的，本发明采用的技术方案为：
本发明涉及的一种BODIPY类酸性pH响应的近红外荧光探针的结构如下：
本发明涉及的一种BODIPY类酸性pH响应的近红外荧光探针合成路线为：
本发明涉及的一种BODIPY类酸性pH响应的近红外荧光探针的制备过程包括以下步骤：
步骤1：在氩气保护下，将式(II)2，6-二碘代BODIPY衍生物、式(III)所示2-乙炔噻吩、CuI溶于干燥四氢呋喃与N，N-二异丙基乙胺，后迅速加入四(三苯基膦)钯，缓慢升温至60℃反应10～14小时，反应结束后减压除去有机溶剂，残余物经硅胶柱层析分离提纯得到式(VI)所示的2，6-二乙炔噻吩基BODIPY衍生物；
步骤2：在无水条件下，在配备有Dean-Stark装置的圆底烧瓶中加入式(IV)所示的2，6-二乙炔噻吩基BODIPY衍生物、式(V)所示的对二甲氨基苯甲醛和对甲苯磺酸，然后溶于甲苯，并加入少量哌啶，混合物加热到140℃回流，TLC检测反应原料点消失，反应结束后减压除去有机溶剂，残余物经硅胶柱层析分离提纯得到式(I)所示的BODIPY类酸性pH响应的近红外荧光探针。；
上述反应步骤1中催化剂四(三苯基膦)钯、碘化亚铜用量与2，6-二碘代BODIPY衍生物(II)的物质的量之比为1∶1∶10；
上述反应步骤2中，式(IV)所示的2，6-二乙炔噻吩基BODIPY衍生物与式(V)所示的对二甲氨基苯甲醛物质的量之比为1∶4；
上述反应步骤2中，加入的甲苯与哌啶的体积分别为25mL和2mL。
本发明的有益效果
与现有技术相比，本发明中一种BODIPY类酸性pH响应的近红外荧光探针的制备方法所具有的优点有：本发明所述的荧光探针(1)制备条件温和，步骤简单，对氧气不敏感；(2)在近红外区(＞650am)具有窄的吸收峰和发射峰、高的摩尔吸光系数。(3)在很窄的酸性pH范围有极高的灵敏度，对不同pH值时溶液颜色变化非常明显，颜色由咖啡色变为绿色，是一种较好的可视化pH荧光探针，有良好的潜在应用前景。
附图说明
图1为不同pH值下，探针I(浓度为1×10-5mol/L)的紫外-可见吸收光谱图；
图2为不同pH值下，探针I(浓度为1×10-5mol/L)的荧光发射光谱图；
图3为将探针加入到pH＝3.5溶液(左)和pH＝1.7(右)，日光灯照射下拍摄的荧光图像；
图4为探针的核磁共振氢谱；
具体实施方式
下面结合具体实例对本发明作进一步地解释，具体实施事例并不对本发明作任何限定。
实施例1
氮气保护下，将2，6-二碘代BODIPY衍生物(II)(309mg，0.50mmol)、Pd(PPh3)4(58mg，0.05mmol)、CuI(10mg，0.05mmol)溶于四氢呋喃和N，N-二异丙基乙胺，加入2-乙炔噻吩(III)。混合物加热至60℃并搅拌过夜。冷却，二氯甲烷稀释，水洗，二氯甲烷提取，无水硫酸钠干燥，减压蒸干，硅胶柱层析，洗脱剂为(石油醚∶CH2Cl2＝7∶3)，得到深棕色固体(IV)(155.70mg，54％)。1H NMR(600MHz，CDCl3，ppm)，δ7.30-7.29(m，2H)，7.24-7.23(m，2H)，7.02-7.01(m，4H)，2.73(s，6H)，2.39(s，3H)，2.12(s，6H)，1.54(s，6H)，Esi-MS：calcd forC34H29BF2N2S2：578.18336，found：578.18994(M+).
实施例2
圆底烧瓶中配备有分水器，将2，6-二乙炔噻吩基BODIPY衍生物(IV)(28.93mg，0.05mmol)，对二甲氨基苯甲醛(29.92mg，0.20mmol)和对甲苯磺酸(20mg)溶于25mL甲苯和2mL哌啶，混合物加热到140℃回流。将反应物浓缩，硅胶柱层析，洗脱剂为(石油醚∶CH2Cl2＝2∶8)，得到咖啡色固体(I)(15.97mg，38％)。1H NMR：(600MHz，CDCl3，ppm)，δ8.35(d，J＝16.20Hz，2H)，7.68(d，J＝16.20Hz，2H)，7.61(t，J＝9.00Hz，4H)，7.30-7.29(m，2H)，7.24-23(m，2H)，7.03-02(m 2H)，6.98(s，2H)，6.74(d，J＝9.00Hz，4H)，3.05(s，12H)，2.37(s，3H)，2.12(s，6H)，1.54(s，6H).Esi-MS：calcd for C52H47BF2N2S2：840.33036，found：840.33380(M+).
Claims (8)
1.一种BODIPY类酸性pH响应的近红外荧光探针，其特征在于，其化学结构式如式(I)所示：
2.一种如专利要求1所述的式(I)所示的BODIPY类酸性pH响应的近红外荧光探针的制备方法，其特征在于，所述的制备方法为：2-乙炔噻吩与2，6-二碘代BODIPY衍生物在钯催化剂作用下得到2，6-二乙炔噻吩基BODIPY衍生物；然后2，6-二乙炔噻吩基BODIPY衍生物与对二甲氨基苯甲醛发生Knoevenagel缩合反应得到如式(I)所示的BODIPY类酸性pH响应的近红外荧光探针。
3.如专利要求2所述的制备方法，其特征在于，所述制备方法包括以下步骤：
步骤1：在氩气保护下，将2，6-二碘代BODIPY衍生物、2-乙炔噻吩、CuI溶于干燥四氢呋喃与N，N-二异丙基乙胺，后迅速加入四(三苯基膦)钯，缓慢升温至60℃反应10～14小时，反应结束后减压除去有机溶剂，残余物经硅胶柱层析分离提纯得到2，6-二乙炔噻吩基BODIPY衍生物；
步骤2：在无水条件下，在配备有Dean-Stark装置的圆底烧瓶中加入2，6-二乙炔噻吩基BODIPY衍生物、对二甲氨基苯甲醛和对甲苯磺酸，然后用甲苯溶解，并加入少量哌啶，混合物加热到140℃回流，反应10～14小时，反应结束后减压除去有机溶剂，残余物经硅胶柱层析分离提纯得到式(I)所示的BODIPY类酸性pH响应的近红外荧光探针化合物。
4.一种如权利要求3所述的制备方法，其特征在所述步骤1中催化剂四(三苯基膦)钯、碘化亚铜用量与2，6-二碘代BODIPY衍生物的物质的量之比为0.05∶0.05∶1。
5.一种如权利要求3所述的制备方法，其特征在所述步骤2中，2，6-二乙炔噻吩基BODIPY衍生物与对二甲氨基苯甲醛物质的量之比为1∶4。
6.一种如权利要求1所述近红外荧光探针的用途，其特征在于，采用荧光法，荧光分子探针在溶液中对pH有荧光强度效应，用于溶液中pH检测分析。
7.一种如权利要求1所述荧光探针的用途，其特征在于：适用于酸性环境，且在强酸(pH＝1.7-3.5)时效果明显。
8.一种如权利要求5所述的pH荧光探针的应用，其最大吸收波长及发射波长均大于650nm。
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