CN112521376A - 色烯-吡啶衍生物荧光探针、制备方法及应用 - Google Patents

色烯-吡啶衍生物荧光探针、制备方法及应用 Download PDF

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CN112521376A
CN112521376A CN202011484444.9A CN202011484444A CN112521376A CN 112521376 A CN112521376 A CN 112521376A CN 202011484444 A CN202011484444 A CN 202011484444A CN 112521376 A CN112521376 A CN 112521376A
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chromene
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吴伟娜
王元
郭芳芳
宋雨飞
刘爽爽
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Henan University of Technology
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Abstract

本发明提供了一种色烯‑吡啶衍生物荧光探针、制备方法及应用，荧光探针的结构式如下：
Figure 100004_DEST_PATH_IMAGE002
。具体制备方法为，将3H‑苯并[f]色烯‑2‑甲醛和4‑甲基‑1‑(2‑吗啉‑4‑基‑乙基)‑吡啶溴化物溶于乙醇中，滴加哌啶作催化剂，80℃下回流搅拌4‑5h，冷却静置至室温，减压抽滤，所得固体用乙醇清洗得到所述色烯‑吡啶衍生物荧光探针。本发明的色烯‑吡啶衍生物荧光探针在纯水相生理条件下能选择性的与次氯酸根作用，溶液黄色褪色，同时红色荧光显著减弱，特别是作为荧光探针在细胞溶酶体内次氯酸根的方便检测的应用。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。

Description

色烯-吡啶衍生物荧光探针、制备方法及应用
技术领域
本发明涉及有机合成领域，具体涉及一种色烯-吡啶衍生物荧光探针、制备方法及应用。
背景技术
次氯酸（HClO）通常以次氯酸根（ClO−）的形式存在于生理环境中，具有杀菌作用，在机体被微生物入侵时也起到免疫作用。但是，吞噬细胞中产生的过量的HClO也会对人体产生伤害。已经有证据表明一些组织的炎症与次氯酸根有关，而且人们认为中性粒细胞释放的次氯酸根与肺部受损、类风湿性关节炎、肝缺血再灌注损伤以及肾脏疾病有关。细胞内过量的次氯酸根主要由溶酶体代谢产生，其浓度与溶酶体氧化还原平衡密切相关。在日常生活中，次氯酸也是常用的消毒剂。因此，生物样品中次氯酸根检测的选择性和敏感性工具的开发愈发显得重要。
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。但现有绝大多数次氯酸根荧光探针需要有机助溶剂（>10%），无法在纯水相环境中实现次氯酸根识别、没有对pH的工作范围进行细致的研究，限制了其进一步的实际应用，而且当今对溶酶体靶向定位的次氯酸根荧光探针的报道并不多。
发明内容
本发明提出了一种色烯-吡啶衍生物荧光探针、制备方法及应用，以含吡啶的色烯衍生物为荧光探针，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、高选择性的近红外的次氯酸根荧光探针。该探针能应用于纯水体系中次氯酸根的测定，具有溶酶体靶向功能，并能应用于溶酶体内次氯酸根浓度的检测。
实现本发明的技术方案是：
一种色烯-吡啶衍生物荧光探针，所述荧光探针的结构式如下：
Figure DEST_PATH_IMAGE002
。
所述的色烯-吡啶衍生物荧光探针的制备方法，步骤如下：
S1：将3H-苯并[f]色烯-2-甲醛和4-甲基-1-(2-吗啉-4-基-乙基)-吡啶溴化物溶解于有机溶剂中；
S2：将S1所得溶液滴加哌啶，在80℃下回流搅拌反应4-5h；
S3：将S2所得溶液冷却至室温，减压抽滤，所得固体残渣用乙醇清洗，再用乙醇重结晶，得到荧光探针。
所述步骤S1中的有机溶剂为无水乙醇。
所述步骤S1中3H-苯并[f]色烯-2-甲醛和4-甲基-1-(2-吗啉-4-基-乙基)-吡啶溴化物的摩尔比为1:（1-1.02）。
所述步骤S2中，3H-苯并[f]色烯-2-甲醛和哌啶的摩尔比为1:0.02。
更进一步地，具体制备方法为，将2.102 g 3H-苯并[f]色烯-2-甲醛（10 mmol）和2.87 g 4-甲基-1-(2-吗啉-4-基-乙基)-吡啶溴化物（10 mmol）溶于0.05L乙醇中，滴加0.017 g哌啶（0.2 mmol）作催化剂，80℃下回流搅拌4-5h，冷却静置至室温，减压抽滤，所得固体用乙醇清洗得到所述色烯-吡啶衍生物荧光探针。
所述步骤S1中3H-苯并[f]色烯-2-甲醛的结构式如下：
Figure DEST_PATH_IMAGE004
，4-甲基-1-(2-吗啉-4-基-乙基)-吡啶溴化物的结构式为：
Figure DEST_PATH_IMAGE006
。
优选地，上述制备的荧光探针作为次氯酸根荧光探针中的应用，特别是在作为检测HeLa活细胞溶酶体内次氯酸根的荧光探针中的应用。
本发明的有益效果是：本发明通过缩合反应制备色烯-吡啶衍生物荧光探针，原料易得，合成和后处理方法简单。在多种常见阴离子及活性氧物种中，对次氯酸根表现出较高的荧光识别性能。探针为近红外荧光探针，受背景干扰极小，极大提高了探针的选择性和灵敏度。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
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为本发明实施例1制得的色烯-吡啶衍生物荧光探针的1H NMR谱图；
图2为本发明实施例1制得的色烯-吡啶衍生物荧光探针的13C NMR谱图；
图3为本发明实施例1制得的色烯-吡啶衍生物荧光探针的质谱谱图；
图4为本发明实施例1制得的色烯-吡啶衍生物荧光探针(1×10-5 mol/L)的HEPES缓冲溶液(0.05 mol/L，pH = 5)分别加入5×10-5 mol/L阴离子（AcO−、Br−、Cl−、ClO−、ClO4 −、CN−、F−、H2PO4 −、HPO4 −、I−、PO4 3−、S2−、SO3 2−、PPi、HSO3 2−、SO4 2−和HSO4 2−)的紫外（a）和荧光（b）光谱图（激发波长为450 nm）；
图5为本发明实施例1制得的色烯-吡啶衍生物荧光探针(1×10-5 mol／L)的HEPES缓冲溶液 (0.05 mol/L，pH = 5)滴定不同浓度ClO−的荧光光谱图，插图为640 nm处荧光强度随次氯酸根浓度的线性变化趋势图（激发波长为450 nm）；
图6为在HeLa细胞中，色烯-吡啶衍生物荧光探针与ClO−的荧光成像图；HeLa细胞用1×10-5 mol/L 荧光探针培育30分钟后加入5×10-5 mol/L ClO−，继续培育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为上述荧光探针绿色通道荧光成像图；b为上述荧光探针明场图；c为上述荧光探针明场图和荧光图叠加后的图片；d为上述荧光探针+ ClO−绿色通道荧光成像图；e为上述荧光探针+ ClO−明场下的成像图；f为上述荧光探针ClO−明场图和荧光图叠加后的图片；
图7为在HeLa细胞中，色烯-吡啶衍生物荧光探针与商用溶酶体定位染料LysoTracker Red共染荧光成像图；HeLa细胞用1×10-5 mol/L荧光探针和LysoTracker Red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为绿色通道荧光成像图；b为红色通道荧光成像图；c为绿色通道和红色通道叠加后的图片；d为明场图；e为绿色通道、红色通道和明场叠加后的图片；f为绿色通道和红色通道强度分布叠加图。
具体实施方式
下面将结合本发明实施例，对本发明的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有付出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
本实施例色烯-吡啶衍生物荧光探针的制备方法如下：
将2.102 g 3H-苯并[f]色烯-2-甲醛（10 mmol）和2.87 g 4-甲基-1-(2-吗啉-4-基-乙基)-吡啶溴化物（10 mmol）溶于0.05L乙醇中，滴加0.017 g哌啶（0.2 mmol）作催化剂，80℃下回流搅拌4-5h，冷却静置至室温，减压抽滤，所得固体用乙醇清洗，再用乙醇重结晶得到所述色烯-吡啶衍生物荧光探针。目标产物的产率为84%。
采用核磁共振仪对制得的色烯-吡啶衍生物进行核磁共振分析，结果如下：
1H NMR (400 MHz, DMSO-d 6 ), δ (ppm): 8.87-8.89 (2H, d, Ar-H), 8.11-8.15(3H, m, Ar-H), 7.85-7.96 (4H, m, Ar-H), 7.61-7.63 (1H, t, Ar-H), 7.44-7.48(1H, t, Ar-H), 7.19-7.21 (1H, d, CH=C), 6.95-6.99 (1H, d, CH=C), 5.25 (2H, s,CH2), 4.61 (2H, s, CH2), 3.53 (4H, s, 2CH2), 2.82 (2H, s, CH2), 2.52 (4H, s,2CH2). 具体核磁共振氢图谱见图1；
13C NMR (400 MHz, DMSO-d 6 ) δ:153.60, 153.10, 145.09, 138.96, 132.16,130.19, 129.59, 129.28, 128.15, 127.51, 124.87, 123.33, 123.05, 121.73,117.79, 115.54, 66.67, 64.99, 57.97, 56.76, 53.30. 具体核磁共振碳图谱见图2；
质谱ESI-MS: m/z = 399.1884归属为[M-Br]+，具体质谱谱图见图3。
性质测定
（1）色烯-吡啶衍生物对次氯酸根的光学性质测定
将上述实施例1制得的色烯-吡啶衍生物作为荧光探针在HEPES缓冲溶液 (0.05mol/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5×10-5mol/L的阴离子（AcO−、Br−、Cl−、ClO−、ClO4 −、CN−、F−、H2PO4 −、HPO4 −、I−、PO4 3−、S2−、SO3 2−、PPi、HSO3 2−、SO4 2−和HSO4 2−）的溶液中加入等量的上述荧光探针溶液，采用紫外可见分光光度计或荧光光谱仪进行分析（激发波长为450 nm），所得紫外和荧光光谱图见图4。通过图4可以看出，本发明制得的色烯-吡啶衍生物作为探针只对次氯酸根具有明显响应，紫外信号和荧光信号均可用于次氯酸根的快速鉴别，而其它离子无变化。
通过图5的荧光滴定光谱计算可以得到ClO−检出限为1.2×10-8 mol/L，荧光光谱的线性检测范围为5.0×10-6-2.4×10-5 mol/L，因此本发明制得的色烯-吡啶衍生物可用于次氯酸根的荧光定量检测。
（2）色烯-吡啶衍生物荧光探针在细胞内次氯酸根的检测实验
HeLa细胞用1×10-5 mol/L的上述实施例1制得的色烯-吡啶衍生物荧光探针和商用溶酶体定位染料LysoTracker Red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：a为绿色通道荧光成像图；b为红色通道荧光成像图；c为绿色通道和红色通道叠加后的图片；d为明场图；e为绿色通道、红色通道和明场叠加后的图片；f为绿色通道和红色通道强度分布叠加图。HeLa细胞中探针绿色通道荧光和LysoTracker Red红色通道荧光基本吻合，重叠系数为0.92。故本发明实施例1制得的色烯-吡啶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制得的色烯-吡啶衍生物荧光探针在37℃下培育30分钟，加入ClO−（5×10-5 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为上述荧光探针明场图；c为上述荧光探针明场图和荧光图叠加后的图片；d为上述荧光探针+ ClO−绿色通道荧光成像图；e为上述荧光探针+ ClO−明场下的成像图；f为上述荧光探针ClO−明场图和荧光图叠加后的图片。HeLa细胞中加入色烯-吡啶衍生物荧光探针出现强荧光，而再加入ClO−后荧光明显减弱。故本发明实施例1制得的色烯-吡啶衍生物可用于细胞溶酶体中ClO−的定性检测。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

1.一种色烯-吡啶衍生物荧光探针，其特征在于，所述荧光探针的结构式如下：
Figure 781089DEST_PATH_IMAGE001
。
2.权利要求1所述的荧光探针在检测次氯酸根中的应用。
3.权利要求1所述的色烯-吡啶衍生物荧光探针的制备方法，其特征在于，步骤如下：
S1：将3H-苯并[f]色烯-2-甲醛和4-甲基-1-(2-吗啉-4-基-乙基)-吡啶溴化物溶解于有机溶剂中；
S2：将S1所得溶液滴加哌啶，在80℃下回流搅拌反应4-5h；
S3：将S2所得溶液冷却至室温，减压抽滤，所得固体残渣用乙醇清洗，再用乙醇重结晶，得到荧光探针。
4.根据权利要求3所述的制备方法，其特征在于：所述步骤S1中的有机溶剂为无水乙醇。
5.根据权利要求3所述的制备方法，其特征在于：所述步骤S1中3H-苯并[f]色烯-2-甲醛和4-甲基-1-(2-吗啉-4-基-乙基)-吡啶溴化物的摩尔比为1：（1-1.2）。
6.根据权利要求3所述的制备方法，其特征在于：所述步骤S2中，3H-苯并[f]色烯-2-甲醛和哌啶的摩尔比为1:0.02。
7.根据权利要求3所述的制备方法，其特征在于：所述步骤S1中3H-苯并[f]色烯-2-甲醛的结构式如下：
Figure 295247DEST_PATH_IMAGE002
，4-甲基-1-(2-吗啉-4-基-乙基)-吡啶溴化物的结构式为：
Figure 408566DEST_PATH_IMAGE003
。
8.权利要求3-7任一项所述的制备方法制备的荧光探针。
9.权利要求8所述的荧光探针作为次氯酸根荧光探针中的应用。
10.根据权利要求9所述的应用，其特征在于：所述荧光探针用于纯水体系中次氯酸根的测定，同时应用于溶酶体内次氯酸根浓度的检测。
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