CN108048075A - 一种基于聚集诱导效应的钙离子荧光探针及其制备方法和用途 - Google Patents

一种基于聚集诱导效应的钙离子荧光探针及其制备方法和用途 Download PDF

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CN108048075A
CN108048075A CN201711037336.5A CN201711037336A CN108048075A CN 108048075 A CN108048075 A CN 108048075A CN 201711037336 A CN201711037336 A CN 201711037336A CN 108048075 A CN108048075 A CN 108048075A
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李剑利
张继东
厍梦尧
刘萍
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Abstract

本发明提出了一种可溶性的对Ca2+表现出高选择性荧光检测且不受其它金属离子干扰的结构式(I)所示的四苯乙烯基荧光探针。该探针可适用pH范围较宽,水溶性好,灵敏度较高,可应用于环境和生物样品中Ca2+的选择性检测,对Ca2+相关疾病的诊断具有一定的应用前景。

Description

一种基于聚集诱导效应的钙离子荧光探针及其制备方法和 用途
技术领域
本发明涉及一种四苯乙烯基荧光探针及其合成方法和在体外和细胞中Ca2+检测方面的应用。
背景技术
功能分子荧光探针技术在表达分子间识别作用及复杂生命和环境体系方面具有非常优异的性能。近年来,随着荧光化学标记和分子探针技术的迅速发展,荧光功能分子探针以其优异的光学性能和生物相溶性已被广泛应用在生物及环境体系中分析物的检测、药物筛选及病理诊断等领域。
近年来,随着聚集诱导发光(Aggregation Induced Emission,AIE)现象的发现,越来越多的具有AIE效应的有机小分子被设计和开发。AIE效应解决了长期困扰人们的聚集荧光淬灭(ACQ)现象。四苯乙烯(TPE)是典型的具有AIE效应的荧光分子。该结构具有合成方便和容易修饰的特点而被人们所青睐。在目前报道的多种基于四苯乙烯的荧光探针中,基于AIE效应的Ag+, Cu2+, Hg2+, Zn2+, Cd2+, Al3+ 荧光探针已被广泛报到,但基于AIE效应的Ca2+荧光探针很少有报道。
发明内容
本发明的目的之一是提供一种具有AIE效应的四苯乙烯基Ca2+荧光探针。
本发明的目的之二是提供一种四苯乙烯基Ca2+荧光探针制备方法。
本发明还有一个目的是提供上述荧光探针对环境和生物体中的Ca2+检测方面的应用。
本发明的实现过程如下:
结构式(I)所示的化合物,
结构式(I)所示化合物的合成方法,包括以下步骤:
(1)将4-羟基二苯甲酮和碳酸钾加入丙酮中,再加入1-溴-2-氯乙烷混合加热回流反应,过滤、重结晶得到化合物 2;
(2)将化合物 2 和锌粉加入到冰浴的四氢呋喃中,氩气保护下加入TiCl4加热回流反应,然后过滤,滤液浓缩、分离得到化合物3;
(3)将化合物1、化合物3和K2CO3加入到DMF中,氩气保护下回流反应,经过滤、除去溶剂分离得到化合物4;
(4)将化合物 4和K2CO3溶解于体积比1:1的乙醇与水的混合溶液中回流反应后,冷却到室温,加入盐酸溶液得黄色沉淀,将沉淀加入到KOH溶液中,蒸发除去溶剂得到目标化合物。
化合物1可通过以下常规方法合成得到:
结构式(I)所示化合物在钙离子检测中的应用,具体可应用在环境和生物体中的Ca2+检测,其识别原理为:在DMSO/HEPES buffer (10 mM, 1:99 v/v) 溶液中,探针表现出弱的荧光,但向其中加入Ca2+后,Ca2+可以被吡啶-二羧酸特异性识别形成聚合物在505 nm处产生强烈的荧光发射。通过测定荧光强度的变化,达到检测Ca2+的存在和测定Ca2+浓度的目的。
本发明结构中四苯乙烯作为发光团,双齿吡啶羧酸作为识别基团,识别基团和发光基团之间采用-OCH2CH2O-基团连接。该探针在不同溶剂中对Ca2+ 的检测具有较高的选择性且不受其它金属离子的干扰,同时具有灵敏度高、水溶性好、适用pH范围宽和检测浓度范围广等优点,特别是不受电子结构排布相似的同一主族Mg2+ 的干扰,可通过荧光信号进行检测。探针的优良性能使其可用于环境和生物样品中Ca2+ 的检测,显示出较强的应用前景。
附图说明
图1为该探针在DMSO/HEPES buffer (10 mM, 1:99 v/v) 溶剂中的离子选择性荧光发射图;
图2为该探针在DMSO/HEPES buffer (10 mM, 1:99 v/v) 溶剂中的抗干扰能力荧光发射图;
图3为该探针在DMSO/HEPES buffer (10 mM, 1:99 v/v) 溶剂中荧光强度随Ca2+浓度的变化图;
图4为该探针和探针与Ca2+的加合物在DMSO/HEPES buffer (10 mM, 1:99 v/v) 溶剂中荧光发射强度随pH的变化图;
图5为该探针在DMSO/HEPES buffer (10 mM, 1:99 v/v) 溶剂中与Ca2+的配位比测定图;
图6为该探针在DMSO/HEPES buffer (10 mM, 1:99 v/v) 溶剂中加入Ca2+后的可逆循环检测图;
图7为该探针在DMSO/HEPES buffer (10 mM, 1:99 v/v) 溶剂中加入Ca2+后的可逆循环次数图;
图8为该探针和探针与CaCl2配合物的形貌图;
图9为该探针在活的A549细胞中对Ca2+ 检测的细胞成像图。
具体实施方式
实施例1:探针的合成
为了更加清楚的理解本发明,下面通过具体实施例对本发明做进一步的详细描述。4-羟基二苯甲酮 (1.98 g, 10 mmol) 和碳酸钾 (4.14 g, 30 mmol) 加入到50 mL丙酮溶液中,接着在常温下缓慢加入1-溴-2-氯乙烷 (1.43 g, 10 mmol)。混合液加热回流8 h,然后过滤,将滤液浓缩,在甲醇中重结晶得到白色固体化合物 2,产率为70%。
1H NMR (400 MHz, CDCl3), δ (ppm): 7.83 (d, J = 8.7Hz, 2H); 7.76 (d, J= 7.5Hz, 2H); 7.58 (d, 1H); 7.47 (m, J = 6.9Hz, 2H); 6.98 (d, J = 6.8Hz, 2H);4.38 (t, J = 7.5Hz, 2H); 3.69 (t, J = 7.5Hz, 2H). 13 C NMR (100 MHz, CDCl3), δ(ppm): 195.86, 162.21, 139.46, 133.07, 132.48, 130.18, 128.91, 128.63,114.46, 68.42, 29.05. ESI-MS: m/z calc’d for C15H13ClO2: [M+Na]+ 326.9996;found, 326.9994。
称取1.83 g上述方法制备的化合物2(6 mmol)和锌粉 0.78 g (12 mmol) 加入到50 mL 冰浴的四氢呋喃溶液中, 用注射器在氩气的保护下慢慢加入TiCl4 (0.7 mL, 6mmol)。混合溶液加热回流16 h,然后过滤,滤液浓缩,接着用石油醚/氯仿 4:1 柱层析分离。得到白色粉末的化合物3,产率为72%。
1H NMR (400 MHz, DMSO), δ(ppm): 7.08-7.15 (m, 6H), 6.93-6.98 (m, 4H),6.83-6.89 (m, 4H), 6.69-6.76 (m, 4H), 4.15 (m, 4H), 3.9 (m, 4H). 13 C NMR (100MHz, CDCl3), δ(ppm): 157.28, 144.37, 139.91, 137.50, 133.11, 131.61, 126.01,114.04, 67.54, 29.13. ESI-MS: m/z calc’d for C30H26Cl2O2: [M+Na]+ 511.1207,found, 511.1214。
用1.87 g 上述方法制备的化合物3(2 mmol), 2.3 g化合物1(9.6 mmol) 和5.54g K2CO3 (40 mmol) 加入到100 mL DMF中,在氩气保护下80 °C条件下过夜回流。然后过滤,旋蒸除去溶剂。用石油醚/乙酸乙酯((1:1 v/v))过柱,得到黄色固体化合物4,产率为30.6%。
1H NMR (400 MHz, DMSO), δ(ppm): 7.85 (d, 4H), 6.92-7.07 (m, 14H),6.70-6.64 (m, 4H), 4.5-4.45 (m, 2H), 4.20-4.18 (m, 2H), 4.03-3.9 (m, 4H),2.06-1.98 (m, 8H), 1.47-1.43 (m, 12H). ESI-MS: m/z calc’d for C52H50N2O12: [M+Na]+ 917.3224, found, 917.3215.
用0.9 g上述方法制备的化合物 4(1 mmol)和 1.0 g K2CO3溶解于乙醇-水(1:1)的混合溶液中,在70 °C 的条件下过夜回流,然后冷却到室温状态,接下来慢慢加入1 mL 35%的盐酸,得到黄色沉淀。然后将沉淀加入到KOH (0.28 g, 5 mmol) 溶液中。蒸发除去溶剂得到黄色的探针L (0.70 g, 0.78 mmol), 产率为23%。
1H NMR (400 MHz, CDCl3), δ(ppm): 7.85 (d, 4H), 6.92-7.08 (m, 14H),6.70-6.64 (m, 4H), 4.48-4.30 (m, 4H), 3.92 (m, 4H). Elemental analysis: C(55.23%), H (3.79%), N (2.93%) C44H34N2O12∙4K∙H2O.
实施例2:探针的离子选择性测定
以DMSO/HEPES buffer (10 mM, 1:99 v/v)为溶剂准确配置浓度为20 μM 的探针,分别与5倍当量的各种金属离子混合后的溶液,测定其在340 nm激发波长下的荧光发射光谱,测定结果如图1所示。可以看出,该探针只对Ca2+表现出明显的选择性响应,对其他离子均无明显响应,特别是对Mg2+ 没有表现出明显响应信号。
实施例3:探针的抗干扰能力测定
以DMSO/HEPES buffer (10 mM, 1:99 v/v)为溶剂准确配置浓度为20 μM探针溶液,先与5倍当量的Ca2+ 混合,再分别与5倍当量的各种干扰离子混合后的溶液,测定其在490 nm激发波长下的荧光发射光谱,测定结果如图2。其中1: Ca2+; 2: Na+; 3: K+; 4: Ag+; 5:Mg2+; 6: Al3+; 7: Cr3+; 8: Mn2+ ; 9: Fe2+; 10: Fe3+; 11: Co2+; 12: Ni2+; 13: Cu2+;14: Zn2+; 15: Cd2+; 16: Ba2+; 17: Hg2+; 18: Pb2+。可以看出,除Cu2+,Co2+,Fe2+和Fe3+ 因其顺磁性和强的配位作用引起一定程度的荧光淬灭外,该探针对Ca2+ 的测定基本不受其他共存离子的干扰。
实施例4:探针的检测范围测定
以DMSO/HEPES buffer (10 mM, 1:99 v/v)为溶剂准确配置浓度为20 μM探针溶液,分别与0-5.0当量的Ca2+ 混合后的溶液,测定其在340 nm激发波长下的荧光发射光谱,测定结果如图3所示。可以看出,该探针荧光发射强度与Ca2+浓度的增加而逐渐增强。在2 -12 μM的范围内表现出明显的线性关系,检测限为51.2 nM (图4)。
实施例5:探针的适用pH范围测定
以DMSO/HEPES buffer (10 mM, 1:99 v/v) 为溶剂分别准确配置在不同pH值下,探针浓度为20 μM的纯探针和探针与5.0当量的Ca2+ 混合的两组溶液,测定其在340 nm激发波长下的荧光发射光谱,测定结果如图5所示。可以看出,该探针适用于pH值为5-11的体系中Ca2 + 的检测。
实施例6:探针与Ca2+离子的配位比测定
以DMSO/HEPES buffer (10 mM, 1:99 v/v)为溶剂准确配置探针与Ca2+浓度之和为40μM (分别为20 µM),[Ca2+]/([Ca2+]+[探针])的比例分别为0.1-0.9的溶液,测定其在340nm激发波长下的荧光发射光谱,测定结果如图6所示。可以看出,该探针与Ca2+的配位比为1:1。
实施例7:探针对Ca2+ 的可逆性测定
以DMSO/HEPES buffer (10 mM, 1:99 v/v) 为溶剂分别准确配置浓度为20 μM的探针和1倍当量的Ca2+ 的混合溶液,然后向其中加入1.0倍当量的EDTA溶液,测定其在340 nm激发波长下的荧光发射光谱,测定结果如图7,8所示。可以看出,随着EDTA的加入,探针荧光强度逐渐减弱,当EDTA加入量为探针的1倍当量时,溶液荧光降低到和探针本身的相接近(图7),说明探针对Ca2+ 的检测具有可逆性以及探针可以循环使用。
实施例8:探针L和L + CaCl2的固体形态成像研究
通过扫描电镜 (SEM) 研究探针L和L-Ca2+配合物的形貌,研究发现,纯的探针L在固体状态形成团簇状,没有规则的形貌结构。当加入CaCl2之后,快速搅拌形成沉淀,通过SEM观察发现,L-Ca2+为纳米花状形貌。如图 9 所示。明显的形貌变化可以说明探针与Ca2+能够很好的配位结合。这种结合在一定程度上可以改变探针本身的物理性能。
实施例9:探针在活细胞中荧光成像检测Ca2+
首先,用20 μM的探针培养A549细胞30 min,用共聚焦荧光显微镜可以观察到比较微弱的荧光信号。另一组细胞先用50 μM 的Ca2+培养 30 min,接着用探针L培养30 min,在A549细胞的细胞质部分观察到明显的蓝色荧光信号。该成像实验说明探针L具有很好的细胞膜的穿透性。接着,用探针L监测细胞内Ca2+与探针L随时间结合的变化。另一组细胞先用50 μM 的Ca2+培养A549细胞,接着用探针L培养,当培养30 min 的时候,可以观察到比较弱的荧光信号。当用探针L的培养时间为60 min的时候,可以在细胞质中观察到强烈的荧光信号。实验结果说明,该探针可以作为相容性好,低毒的Ca2+荧光探针。

Claims (4)

1.结构式(I)所示的化合物,
2.权利要求1所示化合物的合成方法,其特征在于包括以下步骤:
(1)将4-羟基二苯甲酮和碳酸钾加入丙酮中,再加入1-溴-2-氯乙烷混合加热回流反应,过滤、重结晶得到化合物 2;
(2)将化合物 2 和锌粉加入到冰浴的四氢呋喃中,氩气保护下加入TiCl4加热回流反应,然后过滤,滤液浓缩、分离得到化合物3;
(3)将化合物1、化合物3和K2CO3加入到DMF中,氩气保护下回流反应,经过滤、除去溶剂分离得到化合物4;
(4)将化合物 4和K2CO3 溶解于体积比1:1的乙醇与水的混合溶液中回流反应后,冷却到室温,加入盐酸溶液得黄色沉淀,将沉淀加入到KOH溶液中,蒸发除去溶剂得到目标化合物。
3.权利要求1所示化合物在钙离子检测中的应用。
4.权利要求1所示化合物在环境和生物体中钙离子检测中的应用。
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