CN106083816B - 一种极酸性的咔唑类pH荧光探针及其制备方法和应用 - Google Patents

一种极酸性的咔唑类pH荧光探针及其制备方法和应用 Download PDF

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CN106083816B
CN106083816B CN201610528234.2A CN201610528234A CN106083816B CN 106083816 B CN106083816 B CN 106083816B CN 201610528234 A CN201610528234 A CN 201610528234A CN 106083816 B CN106083816 B CN 106083816B
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钞建宾
王会娟
宋凯伦
张永斌
李志清
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Abstract

本发明公开了一种极酸性的咔唑类pH荧光探针及其制备方法和应用。该荧光探针是3‑(9‑丁基咔唑‑3‑氰乙烯基)吡啶。其制备方法：将咔唑、溴丁烷溶解于DMSO/KOH混合溶液中，搅拌加热，生成9‑丁基咔唑；以DMF为溶剂，POCl3与9‑丁基咔唑反应，得到3‑甲酰基‑9‑丁基咔唑；然后将得到的3‑甲酰基‑9‑丁基咔唑与3‑吡啶基乙腈在甲醇中混合，加入叔丁醇钾，抽滤，干燥，得黄色固体产品即可。该探针具有较低的pKa值，对H+显示了高的灵敏性、选择性及稳定性好，并且检测过程简便、快速，检测结果准确等优点。此外，通过结合激光共聚焦扫描显微技术，该新型荧光探针可以用于极度酸性环境中生物样品pH变化的检测。

Description

一种极酸性的咔唑类pH荧光探针及其制备方法和应用
技术领域
本发明涉及荧光探针，具体属于一种极酸性的咔唑类pH荧光探针及其制备方法，以及该探针用于极度酸性环境中生物样品的pH变化的检测。
背景技术
细胞内的pH在参与细胞活动中起着必不可少的作用，比如：细胞循环调控、细胞的生长和凋亡、离子转运、酶活性、钙调控、肌肉收缩和多用耐药性等方面。
pH异常会导致细胞功能紊乱甚至严重者会引发诸如炎症、癌症、阿尔茨海默症等疾病。因此，对pH值的动态变化进行灵敏、准确的实时监测能够为分子水平上研究细胞的生理和毒理过程提供重要的信息。
相较于微电极、NMR、和紫外吸收光谱法等众多的pH检测方法中，荧光光谱检测技术具有快速实时响应、分辨率高、灵敏度高、操作简便、非破坏性等优点，且基于荧光探针与氢离子作用引起的荧光信号变化的传感、荧光显微成像的荧光光谱法显示出独特的时间和空间上的优势，结合激光共聚焦显微镜，荧光成像技术成为分子水平上进行实时原位监测细胞内pH的重要手段。然而，现在文献中报道了许多性能优异的pH荧光探针大多数适用于弱酸条件(pH 4.0-5.5)和近中性条件(pH 6.8-7.4)下pH值的检测，而测定极度酸性环境(pH<4.0)的荧光探针的报道非常少。因此，这就迫切需要计和合成具有合成简单、灵敏度高、选择性好、检出限低、光稳定性好的pH荧光探针应用于极度酸性环境中生物样品的pH变化的检测。
发明内容
本发明的目的之一是提供一种能在极酸性条件下测定pH的咔唑类荧光探针。目的之二是提供该探针的制备方法，该制备工艺简单，成本低廉。目的之三是提供该探针的用途，即应用于极度酸性环境中生物样品pH变化的检测。该探针具有pH快速响应、灵敏度高、选择性和光稳定性好，并且具有大的Stokes位移，能够有效减小激发和生物样品自身荧光的干扰的优点。
本发明提供了一种极酸性的咔唑类pH荧光探针，其是3-(9-丁基咔唑-3-氰乙烯基)吡啶(BILE)，结构式为：
本发明提供的一种极酸性咔唑类pH荧光探针的制备方法，包括如下步骤：
(1)将咔唑、溴丁烷按等摩尔比溶解于DMSO/KOH混合溶液中，并且将温度加热至60-90℃不断搅拌，反应生成9-丁基咔唑；
(2)以DMF为溶剂，POCl3与9-丁基咔唑按摩尔比3-5∶1反应，反应温度为60-90℃，反应时间8-12h，得到3-甲酰基-9-丁基咔唑；
(3)将等摩尔的3-甲酰基-9-丁基咔唑与3-吡啶基乙腈在50℃的甲醇中混合后，加入叔丁醇钾在室温搅拌5h，反应完成后，抽滤、干燥，得黄色固体产品即可。
其合成路线如下：
本发明提供了一种快速响应pH的荧光检测方法，其特征在于，步骤为：
(1)用DMSO体系配制1.0mM的BILE荧光探针储备液；
(2)将2.0mL水以及20.0μL BILE荧光探针储备液加入荧光比色皿中，在荧光分光光度仪上检测，随着待测样的加入，502nm处的荧光强度逐渐减弱；
(3)以pH为横坐标，502nm处荧光强度F为纵坐标绘制图并进行Sigmoidal拟合，求得pKa＝2.93；通过线性拟合得到BILE最佳线性响应范围为pH2.63-3.28，回归方程为：F＝2495.42×pH-6316.28，线性系数为R2＝0.9926。
稳定性实验证明BILE荧光探针对pH的测定具有良好的光稳定性。
经实验验证，常见金属阳离子不干扰体系对pH的测定。
本探针通过荧光共聚焦显微镜成像技术，证明了可用于生物样品(例如：大肠杆菌)内极度酸性pH变化的检测。
与现有极度酸性pH荧光探针相比，本发明合成的咔唑类pH荧光探针具有以下优点：1、本发明的荧光探针合成步骤简单，成本低廉。2、该探针具有较低的pKa值，可以应用于极度酸性条件下生物样品的pH变化的检测。3、对H+响应具有灵明度高和选择性好，不受常见金属离子的干扰并且具有大的Stokes位移，能够有效减小激发和生物样品自身荧光的干扰。4、检测手段简单，只需要借助荧光光谱仪。
附图说明
图1实施例2荧光探针BILE随pH变化的紫外吸收光谱图
图2实施例3荧光探针BILE随pH变化的荧光滴定图
图3实施例3荧光探针BILE对pH响应的工作曲线
图4实施例4荧光探针BILE对常见金属离子的响应情况
图5实施例5大肠杆菌(E.coli)成像图
具体实施方式
实施例1极酸性的咔唑类pH荧光探针的制备
(1)9-丁基咔唑的合成
在装有磁力搅拌装置、温度计和回流冷凝管的100mL三颈烧瓶中加入8.35g(0.050mol)咔唑和60mL的二甲基亚砜，搅拌使其溶解后，迅速加入3.0g(0.054mol)氢氧化钾，加热至90℃，搅拌下反应至固体全溶，继续反应30min，冷却，装上恒压滴液漏斗，待反应液冷却至38℃以下缓慢滴加5.5mL(0.051mol)溴丁烷。保持90℃下继续搅拌反应5h。反应完成后趁热倾入于二倍体积的冰水中，静置过夜，有白色沉淀析出。抽滤，用水洗涤滤饼3次，除去无机物和二甲基亚砜，干燥得粗产物。所得粗产物用无水乙醇重结晶，得白色针状晶体6.7g，产率为59.8％。
(2)3-甲酰基-9-丁基咔唑的合成
将2.23g(0.010mol)9-丁基咔唑在磁力搅拌下溶于7.7mL DMF(0.10mol)中，冰水浴下将4.9mL(0.05mol)三氯氧磷滴加进去，升温到90℃反应10h，冷却到50℃左右将反应液倒入2倍体积的碎冰中(预先加入50mL三氯甲烷)，搅拌，分液，继续用50mL三氯甲烷萃取两次(每次50mL)，合并有机层，水洗有机层一次，加入适量无水硫酸镁干燥过夜，滤掉干燥剂后，浓缩有机层到10mL，柱层析分离进行梯度洗脱(先V乙酸乙酯:V石油醚＝1:8，后V乙酸乙酯:V石油醚＝1:4)，得产品0.78g，产率31.1％。
(3)荧光探针BILE的合成
将0.75g(3mmol)3-甲酰基-9-丁基咔唑和0.32mL(3mmol)3-吡啶基乙腈溶解在20mL干燥的50℃左右的甲醇中，加入0.5g(4.5mmol)叔丁醇钾。反应混合物于室温下搅拌5h时，反应完成后，抽滤，用少量甲醇洗涤滤饼两次溶剂，干燥，得黄色固体产品0.57g，产率54.3％。
探针BILE用1H NMR表征，结果如下：
1HNMR(600MHz,DMSO-d6,δ/ppm):δ9.00(m,1H),8.77(s,1H),8.62(d,J＝4.7Hz,1H),8.29(s,1H),8.20(d,J＝8.6Hz,1H),8.15(m,2H),7.81(d,J＝8.7Hz,1H),7.69(d,J＝8.2Hz,1H),7.54(m,2H),7.30(m,1H),4.46(t,J＝7.0Hz,2H),1.79(m,2H),1.32(m,2H),0.89(t,J＝7.4Hz,3H).
13C NMR(600MHz,DMSO-d6,δ/ppm):δ149.76,146.95,146.06,141.93,141.15,133.32,131.09,127.25,127.09,124.83,124.41,123.27,122.72,122.40,120.76,120.36,118.83,110.53,110.46,103.27,42.79,31.17,20.23.
实施例2荧光探针BILE随pH变化的紫外吸收光谱图
在2.0mL体系中加入20.0μL荧光探针BILE储备液,并且用HCl进行调节pH值，并记录其紫外吸收光谱(图1)。随着pH值的降低，在298nm和391nm处的紫外吸收均下降。
实施例3荧光探针BILE随pH变化的荧光滴定图
在2.0mL水的体系中加入20.0μL荧光探针BILE储备液，用HCl调节体系的pH值，在荧光分光光度仪上检测，随着pH值的降低，502nm处的荧光强度逐渐减弱。仪器参数:激发波长和发射波长的狭缝宽度分别为5.0nm、5.0nm，电压为600V，荧光探针溶液的最大激发波长为：λex为380nm和最大发射波长为λem 502nm。利用502nm处的荧光强度F对pH值作图，并利用Sigmoidal进行拟合，求得pKa＝2.93；通过线性拟合得到BILE最佳线性响应范围为pH2.63-3.28，回归方程为：F＝2495.42×pH-6316.28，线性系数为R2＝0.9926。(见图2、图3)
实施例4荧光探针BILE对常见金属离子的响应情况
将实施例1中的探针浓度保持在10.0μM，考察该探针在常见金属离子存在下，对H+的选择性。图4所示，分别在不同pH(pH 7.20,2.82)条件下，探针对金属离子几乎没有响应，证明了对H+具有很高的选择性。图4中物质的顺序和浓度依次为:1.空白；2.K+(150mM)；3.Na+(150mM)；4.Ca2+(150mM)；5.Zn2+(0.2mM)；6.Mg2+(2.0mM)；7.Fe2+(0.2mM)；8.Al3+(0.2mM)；9.Pb2+(0.2mM)；10.Mn2+(0.2mM)；11.Co2+(0.2mM)；12.Cr3+(0.2mM)；13.Hg2+(0.2mM)；14.Bi2+(0.2mM)；15.Fe3+(0.2mM)；16.Ni2+(0.2mM)；17.Cu2+(0.2mM).
实施例5荧光探针BILE在大肠杆菌(E.coli)的成像实验
将接种好的大肠杆菌(E.coli)与实施例1的探针分别在pH 7.20，3.03和1.50的条件下于摇床中共同孵育2h，在激光共聚焦显微镜下观察。固定激发波长为405nm，收集发射波段为绿色通道(410-513nm)。当pH＝7.20时，大肠杆菌呈现明亮的绿色。当pH＝3.03时，绿色显著变暗。当pH值降低至极酸性1.50时，大肠杆菌内的绿色荧光几乎淬灭(见图5)。

Claims (4)

1.一种咔唑类pH荧光探针(BLIE)，特征在于，其结构式为：
2.如权利要求1所述的一种咔唑类pH荧光探针的制备方法，其特征在于，包括如下步骤：
(1)将咔唑、溴丁烷按等摩尔比溶解于DMSO/KOH混合溶液中，并加热至60-90℃，搅拌，反应生成9-丁基咔唑；
(2)以DMF为溶剂，POCl3与9-丁基咔唑按摩尔比3-5∶1反应，反应温度为60-90℃，反应时间8-12h，得到3-甲酰基-9-丁基咔唑；
(3)将等摩尔的3-甲酰基-9-丁基咔唑与3-吡啶基乙腈在50℃的甲醇中混合后，加入叔丁醇钾在室温搅拌5h，反应完成后，抽滤、干燥，得黄色固体产品即可。
3.一种快速响应pH的荧光检测方法，其特征在于，步骤为：
(1)用DMSO配制1mM的如权利要求1所述的BLIE荧光探针储备液；
(2)将2.0mL水以及20.0μL BLIE荧光探针储备液加入荧光比色皿中，在荧光分光光度仪上检测，随着待测样的加入，502nm处的荧光强度逐渐减弱；
(3)以pH为横坐标，502nm处荧光强度F为纵坐标绘制图并进行Sigmoidal拟合，求得pKa＝2.93；通过线性拟合得到BLIE最佳线性响应范围为pH 2.63-3.28，回归方程为：F＝2495.42×pH-6316.28，线性相关系数为R2＝0.9926。
4.如权利要求1所述的一种咔唑类pH荧光探针用于极度酸性环境中生物样品pH检测，所述极度酸性的酸性范围为pH 2.63-3.28。
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