CN113025313A - 吗啉-吡啶-部花菁衍生物作为硫化氢荧光探针的应用 - Google Patents

吗啉-吡啶-部花菁衍生物作为硫化氢荧光探针的应用 Download PDF

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CN113025313A
CN113025313A CN202110346841.8A CN202110346841A CN113025313A CN 113025313 A CN113025313 A CN 113025313A CN 202110346841 A CN202110346841 A CN 202110346841A CN 113025313 A CN113025313 A CN 113025313A
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pyridine
morpholine
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hydrogen sulfide
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韩学锋
吴伟娜
郭芳芳
宋雨飞
刘爽爽
王元
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Henan University of Technology
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Abstract

本发明提供了一种吗啉‑吡啶‑部花菁衍生物荧光探针作为硫化氢荧光探针的应用，所述吗啉‑吡啶‑部花菁衍生物的化学结构式如下：
Figure DEST_PATH_IMAGE002
本发明的吗啉‑吡啶‑部花菁衍生物荧光探针在生理条件下能选择性的与硫化氢作用，溶液荧光颜色由绿色变成橙黄色，呈现典型的比率荧光信号，特别是作为荧光探针在细胞溶酶体中硫化氢的方便检测的应用。

Description

吗啉-吡啶-部花菁衍生物作为硫化氢荧光探针的应用
技术领域
本发明属于有机合成领域，具体涉及吗啉-吡啶-部花菁衍生物及其制备方法和应用。
背景技术
硫化氢（H2S）是一种有名的无色，剧毒的酸性气体，H2S既是一种活性硫（RSS），也是一种还原剂。因此，生物体内的H2S水平的失衡会对机体造成伤害，引起阿尔茨海默病、胃黏膜损伤、中风、糖尿病、唐氏综合征、肝硬化及癌症等多种疾病。此外，H2S在神经、呼吸、胃肠道和内分泌系统的调节中也发挥重要作用，即使是低浓度的外源性硫化氢也会影响眼睛以及呼吸和中枢神经系统。因此，能够准确、快速、可靠检测H2S浓度变化是非常必要的。
近年来，荧光分子探针技术由于具有灵敏度高、操作简单、成本低等特点，已经成为检测重要金属离子，阴离子和小分子的重要手段。但现有绝大多数硫化氢荧光探针需要有机助溶剂（>10%），无法在纯水相中实现硫化氢的识别，限制了其进一步实际应用。而且当今对溶酶体靶向定位的硫化氢荧光探针的报道并不多。
有鉴于此，特提出本发明。
发明内容
针对现有技术中存在的问题，本发明考虑到部花菁衍生物优异的光化学和光物理特性，以含吡啶的部花菁衍生物为荧光探针，并引进吗啉环作为溶酶体的定位基团，合成了一种高灵敏度、高选择性的硫化氢荧光探针。该探针能应用于纯水体系中硫化氢的测定，并具有溶酶体靶向功能，能应用于溶酶体内硫化氢浓度的检测。
本发明的主要目的在于提供一种吗啉-吡啶-部花菁衍生物荧光探针在作为硫化氢荧光探针方面的应用，特别是在作为检测HeLa活细胞溶酶体内硫化氢的荧光探针中的应用。本发明的吗啉-吡啶-部花菁衍生物硫化氢荧光探针可用于纯水体系和细胞溶酶体内针对硫化氢的灵敏度高、选择性好的吗啉-吡啶-部花菁衍生物荧光探针；本发明还提供了该荧光探针的制备方法。
为实现上述目的，本发明采用以下技术方案：
一种吗啉-吡啶-部花菁衍生物作为硫化氢荧光探针在细胞溶酶体荧光成像中的应用，所述吗啉-吡啶-部花菁衍生物具有如下结构式：
Figure 748760DEST_PATH_IMAGE001
。
本发明还提供了一种吗啉-吡啶-部花菁衍生物荧光探针的制备方法，具体制备方法如下：
S1：将4-[2-(6-羟基-2-萘基)-乙烯基]-1-[2-(4-吗啉基乙基)]-吡啶溴盐和2,4-二硝基氟苯溶解于乙腈中；
S2：将S1所得溶液加入无水碳酸钾，然后在室温下搅拌反应3-4h；
S3：将S2所得溶液旋蒸，将所得固体残渣用乙酸乙酯清洗，再用乙醇重结晶，得到所述吗啉-吡啶-部花菁衍生物荧光探针。
更进一步地，步骤S2中，4-[2-(6-羟基-2-萘基)-乙烯基]-1-[2-(4-吗啉基乙基)]-吡啶溴盐和无水碳酸钾的摩尔比为1:2。
更进一步地，步骤S1中加入的4-[2-(6-羟基-2-萘基)-乙烯基]-1-[2-(4-吗啉基乙基)]-吡啶溴盐和2,4-二硝基氟苯的摩尔比为1:1.2。
更进一步地，吗啉-吡啶-部花菁衍生物的具体制备方法为，将4.41 g, 4-[2-(6-羟基-2-萘基)-乙烯基]-1-[2-(4-吗啉基乙基)]-吡啶溴盐（10 mmol）和2.23 g 2，4-二硝基氟苯（12 mmol）溶于0.2L乙腈中，再加入2.77 g无水碳酸钾（20 mmol），室温下搅拌反应3-4h，反应结束将反应液旋蒸，所得固体用乙酸乙酯清洗，再用无水乙醇重结晶，得到所述吗啉-吡啶-部花菁衍生物。
与现有技术相比，本发明的优点和积极效果在于：本发明的吗啉-吡啶-部花菁衍生物硫化氢荧光探针可用于纯水体系和细胞溶酶体内硫化氢的高灵敏度高选择性荧光检测。本发明通过缩合反应制备吗啉-吡啶-部花菁衍生物荧光探针，原料易得，合成和后处理方法简单。在多种常见阴离子及氨基酸中，只对HS−（硫化氢源）表现出较高的荧光识别性能。探针工作环境中无需任何有机溶剂助溶，非常有利于应用于生物体系，具有广泛的潜在应用价值。
附图说明
图1为本发明实施例1制得的吗啉-吡啶-部花菁衍生物荧光探针的1H NMR谱图；
图2为本发明实施例1制得的吗啉-吡啶-部花菁衍生物荧光探针的13C NMR谱图；
图3为本发明实施例1制得的吗啉-吡啶-部花菁衍生物荧光探针的质谱谱图；
图4为本发明实施例1制得的吗啉-吡啶-部花菁衍生物荧光探针(1×10-5 mol／L)的HEPES缓冲溶液(0.05 mol／L，pH = 5)分别加入3×10-5 mol／L阴离子(OAc−、Br−、Cl−、ClO−、I−、F−、PPi、H2PO4 −、HPO4 −、PO4 3−、HS−、HSO3 −、HSO4 −、SO4 2−、S2O3 2−、S2−和SO3 2−)或氨基酸 (Ala、Hcy、Cys)的荧光光谱图（a）和F580/F520荧光强度比值图（b），激发波长为370 nm。
图5为本发明实施例1制得的吗啉-吡啶-部花菁衍生物荧光探针(1×10-5 mol／L)的HEPES缓冲溶液(0.05 mol／L，pH = 5)滴定不同浓度HS−的荧光光谱图, 插图为F580/F520荧光强度比随HS-浓度的线性变化趋势图（激发波长为370 nm）；
图6为在HeLa细胞中，吗啉-吡啶-部花菁衍生物荧光探针与商用溶酶体定位染料LysoTracker Blue共染荧光成像图；HeLa细胞用1×10-5 mol／L 荧光探针和LysoTrackerRed共同培育30分钟后，使用Olympus FV500-IX70激光共聚焦显微镜进行荧光成像。
其中：a为蓝色通道荧光成像图；b为绿色通道荧光成像图；c为蓝色通道和绿色通道叠加后的图片；d为蓝色通道和绿色通道强度相关图；e为贯穿单个HeLa细胞区域蓝色通道和绿色通道强度分布叠加图。
图7为在HeLa细胞中，HeLa细胞用1×10-5 mol／L的上述实施例1制得的吗啉-吡啶-部花菁衍生物荧光探针在37℃下培育30分钟，并将其分成两组，一组加入HS−（5×10-5 mol/L）后再培育30分钟，另一组加入硝普钠（1×10-2 mol/L）后再培育30分钟，获得在HeLa细胞的荧光成像图，使用Olympus FV500-IX70激光共聚焦显微镜进行荧光成像。
其中：a为上述荧光探针绿色通道荧光成像图；b为上述荧光探针红色通道荧光成像图；c为上述荧光探针绿色通道和红色通道荧光图叠加后的图片；d为上述荧光探针亮场图；e为绿色通道、红色通道和亮场图叠加后的图片；f为上述荧光探针+HS−绿色通道荧光成像图；g为上述荧光探针+HS−红色通道荧光成像图；h为上述荧光探针+HS−绿色通道和红色通道荧光图叠加后的图片；i为上述荧光探针+HS−亮场图；j为上述荧光探针+HS−绿色通道、红色通道和亮场图叠加后的图片；k为上述荧光探针+硝普钠绿色通道荧光成像图；l为上述荧光探针+硝普钠红色通道荧光成像图；m为上述荧光探针+硝普钠绿色通道和红色通道荧光图叠加后的图片；n为上述荧光探针+硝普钠亮场图；o为上述荧光探针+硝普钠绿色通道、红色通道和亮场图叠加后的图片。
具体实施方式
下面结合附图和具体实施例进一步详细说明本发明，但本领域技术人员将会理解，下列实施例仅用于说明本发明，而不应视为限定本发明的范围。本发明实施例采用的试剂和原料为常规市场购买得到。
实施例1
本实施例吗啉-吡啶-部花菁衍生物荧光探针的制备方法如下：
将4.41 g, 4-[2-(6-羟基-2-萘基)-乙烯基]-1-[2-(4-吗啉基乙基)]-吡啶溴盐（10 mmol）和2.23 g 2,4-二硝基氟苯（12 mmol）溶于0.2L乙腈中，再加入2.77 g无水碳酸钾（20 mmol），室温下搅拌反应3-4 h，反应结束将反应液旋蒸，所得固体用乙酸乙酯清洗，再用无水乙醇重结晶，得到所述吗啉-吡啶-部花菁衍生物荧光探针。目标产物的产率为67%。
采用核磁共振仪对制得的吗啉-吡啶-部花菁衍生物进行核磁共振分析，结果如下：
1H NMR (400 MHz, D2O), δ (ppm): 8.97 (s, 5H), 8.49 (d, J = 9.1 Hz,2H), 8.25 (dd, J = 32.4, 16.0 Hz, 9H), 8.05 (s, 4H), 7.85 (s, 2H), 7.73 (d, J= 16.3 Hz, 2H), 7.55 (d, J = 8.8 Hz, 2H), 7.36 (d, J = 9.2 Hz, 2H), 4.66 (s,4H), 3.53 (s, 8H), 2.84 (s, 4H), 2.47 (s, 8H). 具体核磁共振氢图谱见图1；
13C NMR (400 MHz, DMSO-d 6 ) δ: 154.94, 153.29, 153.16, 145.28, 142.35,140.95, 140.26, 135.13, 133.49, 132.22, 131.38, 130.20, 130.09, 128.98,125.38, 124.52, 123.87, 122.45, 121.12, 120.78, 117.07, 66.68, 58.01, 56.86,53.31. 具体核磁共振碳图谱见图2；
质谱ESI-MS: m/z = 527.1859 for [M-Br]+。具体质谱谱图见图3。
实施例2
吗啉-吡啶-部花菁衍生物对HS−的光学性质测定
将上述实施例1制得的吗啉-吡啶-部花菁衍生物作为荧光探针在HEPES缓冲溶液(0.05 mol/L，pH = 5)中配制成摩尔浓度为1×10-5 mol/L的溶液，分别在含摩尔浓度为3×10-5 mol／L阴离子(OAc−、Br−、Cl−、ClO−、I−、F−、PPi、H2PO4 −、HPO4 −、PO4 3−、HS−、HSO3 −、HSO4 −、SO4 2 −、S2O3 2−、S2−和SO3 2−)或氨基酸 (Ala、Hcy、Cys) 的溶液中加入等量的上述荧光探针溶液，采用荧光光谱仪进行分析（激发波长为370 nm），所得荧光光谱图见图4。通过图4可以看出，本发明制得的吗啉-吡啶-部花菁衍生物作为探针只对HS−具有明显响应，荧光信号变化可用于HS-的快速鉴别，而其它离子无变化。
通过图5的滴定光谱计算可以得到HS−检出限为0.81 nM，荧光光谱的线性检测范围为0-6.0 μM，因此本发明制得的吗啉-吡啶-部花菁衍生物可用于HS−的荧光定量检测。
实施例3
吗啉-吡啶-部花菁衍生物荧光探针在细胞内HS−的检测实验
HeLa细胞用1×10-5 mol／L的上述实施例1制得的吗啉-吡啶-部花菁衍生物荧光探针和商用溶酶体定位染料LysoTracker Blue在37℃下共同培育30分钟，获得在HeLa细胞的荧光成像图，具体如图6所示，其中：其中：a为蓝色通道荧光成像图；b为绿色通道荧光成像图；c为蓝色通道和绿色通道叠加后的图片；d为蓝色通道和绿色通道强度相关图；f为贯穿单个HeLa区域蓝色通道和绿色通道强度分布叠加图。从图6可以看出HeLa细胞中探针绿色通道荧光和LysoTracker Blue蓝色通道荧光基本吻合，重叠系数为0.86。故本发明实施例1制得的吗啉-吡啶-部花菁衍生物荧光探针可以靶向细胞溶酶体。
HeLa细胞用1×10-5 mol／L的上述实施例1制得的吗啉-吡啶-部花菁衍生物荧光探针在37℃下培育30分钟，并将其分成两组，一组加入HS−（5×10-5 mol/L）后再培育30分钟，另一组加入硝普钠（1×10-4 mol/L）后再培育30分钟，获得在HeLa细胞的荧光成像图，具体如图7所示，其中a为上述荧光探针绿色通道荧光成像图；b为上述荧光探针红色通道荧光成像图；c为上述荧光探针绿色通道和红色通道荧光图叠加后的图片；d为上述荧光探针亮场图；e为绿色通道、红色通道和亮场图叠加后的图片；f为上述荧光探针+HS−绿色通道荧光成像图；g为上述荧光探针+HS−红色通道荧光成像图；h为上述荧光探针+HS−绿色通道和红色通道荧光图叠加后的图片；i为上述荧光探针+HS−亮场图；j为上述荧光探针+HS−绿色通道、红色通道和亮场图叠加后的图片；k为上述荧光探针+硝普钠绿色通道荧光成像图；l为上述荧光探针+硝普钠红色通道荧光成像图；m为上述荧光探针+硝普钠绿色通道和红色通道荧光图叠加后的图片；n为上述荧光探针+硝普钠亮场图；o为上述荧光探针+硝普钠绿色通道、红色通道和亮场图叠加后的图片。HeLa细胞中加入吗啉-吡啶-部花菁衍生物荧光探针后绿色通道荧光强，红色通道荧光弱；再加入HS−后绿色通道荧光强度基本不变，而红色通道荧光增强，说明探针可以检测细胞外源性硫化氢。硝普钠作为细胞内源性硫化氢生成刺激剂，与探针共染的细胞成像现象和加HS−的现象一致，说明探针可以检测细胞内源性硫化氢。故本发明实施例1制得的吗啉-吡啶-部花菁衍生物可用于细胞内源性和外源性中HS−的定性检测。
以上所述实施例仅是为充分说明本发明而所举的较佳的实施例，其保护范围不限于此。本技术领域的技术人员在本发明基础上所作的等同替代或变换，均在本发明的保护范围之内，本发明的保护范围以权利要求书为准。

Claims (5)

1.吗啉-吡啶-部花菁衍生物作为硫化氢荧光探针的应用，其特征在于：所述吗啉-吡啶-部花菁衍生物作为硫化氢荧光探针在细胞溶酶体荧光成像中的应用；所述吗啉-吡啶-部花菁衍生物具有如下结构式：
Figure DEST_PATH_IMAGE001
。
2.根据权利要求1所述的应用，其特征在于，所述吗啉-吡啶-部花菁衍生物的制备方法，包括如下步骤：
S1：将4-[2-(6-羟基-2-萘基)-乙烯基]-1-[2-(4-吗啉基乙基)]-吡啶溴盐和2,4-二硝基氟苯溶解于乙腈中；
S2：将S1所得溶液加入无水碳酸钾，然后在室温下搅拌反应3-4h；
S3：将S2所得溶液旋蒸，将所得固体残渣用乙酸乙酯清洗，再用乙醇重结晶，得到所述吗啉-吡啶-部花菁衍生物荧光探针。
3.根据权利要求2所述的应用，其特征在于：所述步骤S1中加入的4-[2-(6-羟基-2-萘基)-乙烯基]-1-[2-(4-吗啉基乙基)]-吡啶溴盐和2,4-二硝基氟苯的摩尔比为1:1.2。
4.根据权利要求2所述的应用，其特征在于：所述步骤S2中，4-[2-(6-羟基-2-萘基)-乙烯基]-1-[2-(4-吗啉基乙基)]-吡啶溴盐和无水碳酸钾的摩尔比为1:1.2。
5.根据权利要求2所述的应用，其特征在于所述吗啉-吡啶-部花菁衍生物的制备方法如下：将4.41 g 4-[2-(6-羟基-2-萘基)-乙烯基]-1-[2-(4-吗啉基乙基)]-吡啶溴盐和2.23 g 2,4-二硝基氟苯溶于0.2 L乙腈中，再加入2.77 g无水碳酸钾，常温下搅拌反应3-4h，TLC追踪反应结束后，旋蒸，所得固体用乙酸乙酯清洗，再用乙醇重结晶，得到所述吗啉-吡啶-部花菁衍生物。
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