CN109096317A - 一种新型生物硫醇荧光探针及其制备方法和应用 - Google Patents
一种新型生物硫醇荧光探针及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种新型生物硫醇荧光探针及其制备方法,所述新型生物硫醇荧光探针为4‑[7‑(二乙氨基)‑2,2‑二氟苯并[e][1,3,2]恶唑硼烷‑3‑基]苯基‑2,4‑二硝基苯磺酸酯。制备方法包括:(1)4‑(二乙氨基)水杨醛与对氨基苯酚发生缩合反应;(2)步骤(1)所得5‑二乙氨基‑2‑[[(4‑羟基苯基)亚胺]甲基]‑苯酚与三氟化硼乙醚溶液在碱性条件下反应;(3)步骤(2)所得4‑[7‑(二乙氨基)‑2,2‑二氟苯并[e][1,3,2]恶唑硼烷‑3‑基]苯酚与2,4‑二硝基苯磺酰氯发生磺酰化反应,得到所述新型生物硫醇荧光探针。本发明荧光探针分子对生物硫醇的检测表现出较高的选择性和灵敏度。
Description
技术领域
本发明属于分析化学技术领域,尤其涉及一种新型生物硫醇荧光探针及其制备方法和应用。
背景技术
生物体内的硫醇如半胱氨酸(Cys),谷胱甘肽(GSH),同型半胱氨酸(Hcy)在生理和病理过程中起至关重要的作用。然而,细胞内硫醇水平的改变与很多疾病密切相关。体内缺乏半胱氨酸会导致多种病症,如儿童生长缓慢,肝损伤和皮肤损伤等。谷胱甘肽(GSH)在细胞内含量在1mM到15mM之间,是细胞内最富裕的硫醇,在维持细胞的氧化还原动态平衡中起着重要作用。血液中同型半胱氨酸的浓度增加会导致维生素B12的缺失和老年痴呆症。因此,检测生物体系中硫醇具有非常重要的意义。
相比其他方法,荧光法由于具有选择性好、灵敏度高、快速简便等优点,因此,开发硫醇荧光探针越来越受到重视。
发明内容
本发明要解决的技术问题是克服现有技术的不足,提供一种选择性好、灵敏度高、快速简便的新型生物硫醇荧光探针,还相应提供该新型生物硫醇荧光探针的制备方法和应用。
为解决上述技术问题,本发明采用以下技术方案:
一种新型生物硫醇荧光探针,所述新型生物硫醇荧光探针为4-[7-(二乙氨基)-2,2-二氟苯并[e][1,3,2]恶唑硼烷-3-基]苯基-2,4-二硝基苯磺酸酯,结构式如式(1):
作为一个总的发明构思,本发明还提供一种上述的新型生物硫醇荧光探针的制备方法,包括以下步骤:
(1)4-(二乙氨基)水杨醛与对氨基苯酚发生缩合反应,得到5-二乙氨基-2-[[(4-羟基苯基)亚胺]甲基]-苯酚,结构式如式(3):
(2)步骤(1)所得的5-二乙氨基-2-[[(4-羟基苯基)亚胺]甲基]-苯酚与三氟化硼乙醚溶液在碱性条件下反应,得到4-[7-(二乙氨基)-2,2-二氟苯并[e][1,3,2]恶唑硼烷-3-基]苯酚,结构式如式(2):
(3)步骤(2)所得的4-[7-(二乙氨基)-2,2-二氟苯并[e][1,3,2]恶唑硼烷-3-基]苯酚与2,4-二硝基苯磺酰氯发生磺酰化反应,得到式(1)所示的化合物。
优选的,所述步骤(1)的具体过程为:
将4-(二乙氨基)水杨醛和对氨基苯酚溶于无水乙醇中,加热回流缩合反应10~50min,将缩合反应液冷却至室温加入石油醚,减压过滤,用石油醚淋洗,得固体产物为5-二乙氨基-2-[[(4-羟基苯基)亚胺]甲基]-苯酚。
优选的,所述4-(二乙氨基)水杨醛和对氨基苯酚的摩尔比为1∶1.1~1.5。
优选的,所述步骤(2)的具体过程为:
将5-二乙氨基-2-[[(4-羟基苯基)亚胺]甲基]-苯酚用二氯甲烷溶解,在氩气保护下,控温-5~0℃加入三氟化硼乙醚溶液和N,N-二异丙基乙胺,将反应液室温反应12~18h后,将反应液倒入饱和碳酸氢钠溶液中,用二氯甲烷萃取,合并有机相,有机相用饱和氯化钠溶液洗,无水硫酸钠干燥后,减压浓缩除去溶剂,再用二氯甲烷重结晶,过滤所得物为4-[7-(二乙氨基)-2,2-二氟苯并[e][1,3,2]恶唑硼烷-3-基]苯酚。
优选的,所述5-二乙氨基-2-[[(4-羟基苯基)亚胺]甲基]-苯酚、三氟化硼乙醚和N,N-二异丙基乙胺的摩尔比为1∶2.0~2.5:2.0~2.5。
优选的,所述步骤(3)的具体过程为:
将5-二乙氨基-2-[[(4-羟基苯基)亚胺]甲基]-苯酚、2,4-二硝基苯磺酰氯和三乙胺溶解于二氯甲烷中,在氩气保护下室温反应0.25~0.5h,反应完毕后,减压过滤,用二氯甲烷淋洗,得到式(1)所示的化合物。
优选的,所述5-二乙氨基-2-[[(4-羟基苯基)亚胺]甲基]-苯酚、2,4-二硝基苯磺酰氯和三乙胺的摩尔比为1∶1.1~1.4∶1.2~1.5。
作为一个总的发明构思,本发明还提供一种上述的新型生物硫醇荧光探针或上述的制备方法制得的新型生物硫醇荧光探针,将所述新型生物硫醇荧光探针与磷酸盐缓冲液(PBS)和二甲基亚砜(DMSO)的缓冲液混合,再加入待测溶液中,得到混合溶液,利用混合溶液的荧光变化来检测生物硫醇的存在与否。
优选的,所述待测溶液中无生物硫醇时,所述混合溶液为无荧光发射;所述待测溶液中有生物硫醇时,所述混合溶液发出蓝色荧光。
优选的,所述新型生物硫醇荧光探针检测生物硫醇的检出浓度下限分别为:半胱氨酸为44.7nM,谷胱甘肽为65.4nM,同型半胱氨酸为106.0nM。
与现有技术相比,本发明的优点在于:
1、本发明的一种新型生物硫醇荧光探针是以4-[7-(二乙氨基)-2,2-二氟苯并[e][1,3,2]恶唑硼烷-3-基]苯酚为荧光团,本发明的荧光团为首次报道。
2、本发明的一种新型生物硫醇荧光探针是以2,4-二硝基苯磺酰基为识别单元的荧光探针,实践表明,本发明的荧光探针分子在对生物硫醇进行检测时表现出了较高的选择性和灵敏度。
3、本发明的新型生物硫醇荧光探针的制备方法,只需要三步就可以完成,且后处理过程简单,适于工业化生产。
附图说明
图1为实施例1的式(1)所示的化合物(即新型生物硫醇荧光探针)的合成路线图。
图2为实施例1制备的式(3)所示的化合物的1H NMR图谱。
图3为实施例1制备的式(3)所示的化合物的13C NMR图谱。
图4为实施例1制备的式(3)所示的化合物的ESI-MS图谱。
图5为实施例1制备的式(2)所示的化合物的1H NMR图谱。
图6为实施例1制备的式(2)所示的化合物的13C NMR图谱。
图7为实施例1制备的式(2)所示的化合物的ESI-MS图谱。
图8为实施例1制备的式(1)所示的化合物的1H NMR图谱。
图9为实施例1制备的式(1)所示的化合物的13C NMR图谱。
图10为实施例1制备的式(1)所示的化合物的ESI-MS图谱。
图11为不同pH值对实施例1制备的式(1)所示的化合物和式(2)所示的化合物的荧光强度的影响((a)图)和不同pH值对实施例1制备的式(1)所示的化合物与Cys反应前后荧光强度的影响((b)图)。
图12为式(2)所示的化合物、式(1)所示的化合物与生物硫醇(Cys、GSH和Hcy)反应前后的吸收光谱((a)图)和荧光光谱图((b)图)。
图13为实施例1的式(1)所示的化合物与Cys反应的荧光光谱图;其中,(a)图为(1)所示的化合物与Cys反应后不同时间条件下荧光光谱的变化,(b)图为式(1)所示的化合物与Cys反应后在474nm处的荧光强度随时间的变化。
图14为实施例1的式(1)所示的化合物(即新型生物硫醇荧光探针)对生物硫醇检测的反应机理图。
图15为实施例1的式(1)所示的化合物分别与各种氨基酸和常见金属离子反应后在474nm处的荧光强度;
图16为实施例1的式(1)所示的化合物分别与各种氨基酸和常见金属离子反应后的荧光颜色。
图17为不同Cys浓度对实施例1的式(1)所示的化合物与Cys反应后在474nm处荧光强度的影响示意图;其中(a)图为不同Cys浓度条件下,式(1)所示的化合物与Cys反应后在474nm处荧光强度随时间的变化,(b)图为式(1)所示的化合物在474nm处的荧光强度随Cys浓度的变化。
图18为不同GSH浓度对实施例1的式(1)所示的化合物与GSH反应后在474nm处荧光强度的影响示意图;其中(a)图为不同GSH浓度条件下,式(1)所示的化合物与GSH反应后在474nm处荧光强度随时间的变化,(b)图为式(1)所示的化合物在474nm处的荧光强度随GSH浓度的变化。
图19为不同Hcy浓度对实施例1的式(1)所示的化合物与Hcy反应后在474nm处荧光强度的影响示意图;其中(a)图为不同Hcy浓度条件下,式(1)所示的化合物与Hcy反应后在474nm处荧光强度随时间的变化,(b)图为式(1)所示的化合物在472nm处的荧光强度随Hcy浓度的变化。
具体实施方式
以下结合具体优选的实施例对本发明作进一步描述,但并不因此而限制本发明的保护范围。
实施例1:
一种本发明的新型生物硫醇荧光探针,名称为4-[7-(二乙氨基)-2,2-二氟苯并[e][1,3,2]恶唑硼烷-3-基]苯基-2,4-二硝基苯磺酸酯,分子式为C23H21BF2N4O8S,结构式如式(1)所示:
上述本实施例的新型生物硫醇荧光探针的制备方法,其合成路线如图1所示,包括以下步骤:
(1)5-二乙氨基-2-[[(4-羟基苯基)亚胺]甲基]-苯酚,结构式如式(3):
反应式如式(3):
具体过程为:将4-(二乙氨基)水杨醛(1.93g,10mmol)、对氨基苯酚(1.1g,10mmol)溶于无水乙醇(50mL)中,加热回流30min,将缩合反应液冷却至室温加入石油醚,减压过滤,用石油醚淋洗,即得到5-二乙氨基-2-[[(4-羟基苯基)亚胺]甲基]-苯酚,产率为96%。
所得的5-二乙氨基-2-[[(4-羟基苯基)亚胺]甲基]-苯酚的1H NMR图谱如图2所示,1H NMR(400MHz,d6-DMSO,ppm)δ13.74(br s,1H),9.55(br s,1H),8.59(s,1H),7.27(d,J=8.8Hz,1H),7.18(d,J=8.4Hz,2H),6.82(d,J=8.8Hz,1H),6.27-6.25(m,1H),6.07(d,J=2.4Hz,1H),3.38(q,J=6.8Hz,4H),1.12(t,J=6.8Hz,6H)。
所得的5-二乙氨基-2-[[(4-羟基苯基)亚胺]甲基]-苯酚的13C NMR图谱如图3所示,13C NMR(100MHz,d6-DMSO,ppm)δ163.01,158.87,155.71,150.99,139.87,133.61,121.70,115.87,108.70,103.50,97.00,43.84,12.51。
所得的5-二乙氨基-2-[[(4-羟基苯基)亚胺]甲基]-苯酚的ESI-MS图谱如图4所示,ESI-MS m/z for C17H21N2O2 +([M+H]+):calcd:285.2,found:285.1。
(2)合成结构式如式(2)所示的4-[7-(二乙氨基)-2,2-二氟苯并[e][1,3,2]恶唑硼烷-3-基]苯酚:
反应式如式(4):
具体过程为:将步骤(1)所得的5-二乙氨基-2-[[(4-羟基苯基)亚胺]甲基]-苯酚(2.28g,8.0mmol)、三氟化硼乙醚(20mL,20mmol)和N,N-二异丙基乙胺(3.3mL,20mmol)溶解在无水二氯甲烷(50mL)中,将反应液室温反应过夜后,将反应液倒入饱和碳酸氢钠溶液中,用二氯甲烷萃取,合并有机相,有机相用饱和氯化钠溶液洗,无水硫酸钠干燥后,减压浓缩除去溶剂,再用二氯甲烷重结晶,即式(2)所示的化合物,产率为85%。
式(1)所示的化合物的1H NMR图谱如图5所示,1H NMR(400MHz,d6-DMSO,ppm)δ9.68(s,1H),8.53(s,1H),7.47(d,J=9.2Hz,1H),7.35(d,J=8.8Hz,2H),6.51-6.48(m,2H),6.14(d,J=2.4Hz,1H),3.49(q,J=6.8Hz,4H),1.16(t,J=7.2Hz,6H)。
式(1)所示的化合物的13C NMR图谱如图6所示,13C NMR(100MHz,d6-DMSO,ppm)δ160.53,158.98,156.75,155.42,134.59,134.40,124.04,115.56,106.26,96.73,44.33,12.43。
式(1)所示的化合物的ESI-MS图谱如图7所示,ESI-MS m/z for C17H20BF2N2O2 +([M+H]+):calcd:333.2,found:333.1。
(3)合成结构式如式(1)所示的4-[7-(二乙氨基)-2,2-二氟苯并[e][1,3,2]恶唑硼烷-3-基]苯基-2,4-二硝基苯磺酸酯:
反应式如式(5):
具体过程为:将步骤(2)所得的4-[7-(二乙氨基)-2,2-二氟苯并[e][1,3,2]恶唑硼烷-3-基]苯酚(332.2mg,1mmol)、2,4-二硝基苯磺酰氯(319.9mg,1.2mmol)和三乙胺(0.21mL,1.5mmol)溶解在无水二氯甲烷(20mL)中,在氩气保护下室温反应0.5h,反应完毕后,减压过滤,用二氯甲烷淋洗,即式(1)所示的化合物,产率为59%。
式(1)所示的化合物的1H NMR图谱如图8所示,1H NMR(400MHz,d6-DMSO,ppm)δ9.12(d,J=2.4Hz,1H),8.66-8.63(m,2H),8.33(d,J=8.4Hz,1H),7.62(d,J=9.2Hz,2H),7.49(d,J=9.2Hz,1H),7.34-7.32(m,2H),6.57-6.64(m,1H),6.16(d,J=2.4Hz,1H),3.52(q,J=6.8Hz,4H),1.17(t,J=6.8Hz,6H)。
式(1)所示的化合物的13C NMR图谱如图9所示,13C NMR(100MHz,d6-DMSO,ppm)δ161.05,159.84,156.23,151.47,148.07,146.92,142.34,135.06,133.49,130.90,127.52,124.72,122.78,121.10,107.03,106.47,96.64,44.50,12.43。
式(1)所示的化合物的ESI-MS图谱如图10所示,ESI-MS m/z for C23H22BF2N4O8S+([M+H]+):calcd:563.1,found:563.1。
上述本实施例制得的新型生物硫醇荧光探针的应用,将10mM PBS/DMSO体积比为1∶1,pH 7.4的缓冲溶液2mL加入比色皿中,加入本实施例制得的新型生物硫醇荧光探针混合均匀后,再加入待测溶液进行测试,该待测溶液中无生物硫醇时,混合溶液为无荧光发射;该待测溶液中有生物硫醇时,混合溶液发出蓝色荧光。
上述本实施例制得的新型生物硫醇荧光探针的应用研究:
1、pH值对式(1)所示的化合物和式(2)所示的化合物的荧光强度的影响
取实施例1合成的式(1)所示的化合物和式(2)所示的化合物溶于二甲基亚砜中,分别制成2mmol/L的储备液。当pH值不同时,在室温下以405nm为激发光测量式(1)所示的化合物和式(2)所示的化合物的荧光性质,结果如图11所示。实验结果表明,图(a)式(1)所示的化合物生理pH4.0~10.0范围内荧光性质几乎不变,式(2)所示的化合物在pH4.0~7.4范围内荧光性质几乎不变,而pH 7.4~10.0范围内荧光明显减弱;图(b)式(1)所示的化合物与Cys反应当pH 7.4时荧光最强。
2、式(2)所示的化合物和式(1)所示的化合物与生物硫醇(Cys、GSH和Hcy)反应的吸收光谱和荧光光谱研究
在最佳测试条件下,即10mM PBS,H2O/DMSO为1∶1,v/v,pH 7.4,25℃,研究式(2)所示的化合物和式(1)所示的化合物与生物硫醇反应的吸收光谱和荧光光谱性质,结果如图12所示。图12中(a)图为式(2)所示的化合物和式(1)所示的化合物与生物硫醇反应前后的吸收光谱图,(b)图为式(2)所示的化合物和式(1)所示的化合物与生物硫醇反应前后的荧光光谱图。化合物1与生物硫醇Cys反应后不同时间条件下荧光光谱的变化,如图13(a)所示;化合物1与生物硫醇Cys反应在474nm处的荧光强度随时间的变化,如图13(b)所示。实验结果证明,式(1)所示的化合物适用于生物硫醇的快速检测,原理如图14所示,生物硫醇的巯基通过亲核取代反应,使2,4-二硝基苯磺酰基从式(1)所示的化合物上脱去,使其失去淬灭作用,从而生产强荧光的4-[7-(二乙氨基)-2,2-二氟苯并[e][1,3,2]恶唑硼烷-3-基]苯酚。
3、式(1)所示的化合物对生物硫醇的选择性研究
为测试式(1)所示的化合物对生物硫醇的选择性,对式(1)所示的化合物与各种氨基酸和常见金属离子:Gly,Ser,Leu,Glu,Pro,Asn,Phe,Met,Na+,K+,Ca2+,Mg2+,Cys,GSH,Hcy,反应后在474nm处的荧光强度和荧光颜色变化进行了实验研究,结果如图15和图16所示。由图15和图16可知,式(1)所示的化合物对生物硫醇的检测具有高度的选择性。
4、式(1)所示的化合物检测生物硫醇的灵敏度研究
不同生物硫醇浓度[0-3μM(Cys),0-5μM(GSH),0-6μM(Hcy)]条件下,式(1)所示的化合物与生物硫醇反应后在474nm处荧光强度随时间的变化分别如图17(a)图(Cys),图18(a)图(GSH)和图19(a)图(Hcy)所示,式(1)所示的化合物在474nm处的荧光强度随生物硫醇浓度的变化分别如图17(b)图(Cys),图18(b)图(GSH)和图19(b)(Hcy)所示。由图17(a)图(Cys),图18(a)图(GSH)和图19(a)图(Hcy)可知,高浓度生物硫醇提供更快和更戏剧性的荧光增强。由图17(b)图(Cys),图18(b)图(GSH)和图19(b)(Hcy)可以推算出式(1)所示的化合物检测生物硫醇的检测限分别为44.7nM(Cys),65.4nM(GSH),106.0nM(Hcy)。
以上所述,仅是本申请的较佳实施例,并非对本申请做任何形式的限制,虽然本申请以较佳实施例揭示如上,然而并非用以限制本申请,任何熟悉本专业的技术人员,在不脱离本申请技术方案的范围内,利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例,均属于技术方案范围内。
Claims (10)
1.一种新型生物硫醇荧光探针,其特征在于,所述新型生物硫醇荧光探针为4-[7-(二乙氨基)-2,2-二氟苯并[e][1,3,2]恶唑硼烷-3-基]苯基-2,4-二硝基苯磺酸酯,结构式如式(1):
2.一种如权利要求1所述的新型生物硫醇荧光探针的制备方法,包括以下步骤:
(1)4-(二乙氨基)水杨醛与对氨基苯酚发生缩合反应,得到5-二乙氨基-2-[[(4-羟基苯基)亚胺]甲基]-苯酚,结构式如式(3):
(2)步骤(1)所得的5-二乙氨基-2-[[(4-羟基苯基)亚胺]甲基]-苯酚与三氟化硼乙醚溶液在碱性条件下反应,得到4-[7-(二乙氨基)-2,2-二氟苯并[e][1,3,2]恶唑硼烷-3-基]苯酚,结构式如式(2):
(3)步骤(2)所得的4-[7-(二乙氨基)-2,2-二氟苯并[e][1,3,2]恶唑硼烷-3-基]苯酚与2,4-二硝基苯磺酰氯发生磺酰化反应,得到式(1)所示的化合物。
3.根据权利要求2所述的新型生物硫醇荧光探针的制备方法,其特征在于,所述步骤(1)的具体过程为:
将4-(二乙氨基)水杨醛和对氨基苯酚溶于无水乙醇中,加热回流缩合反应10~50min,将缩合反应液冷却至室温加入石油醚,减压过滤,用石油醚淋洗,得固体产物为5-二乙氨基-2-[[(4-羟基苯基)亚胺]甲基]-苯酚。
4.根据权利要求3所述的新型生物硫醇荧光探针的制备方法,其特征在于,所述4-(二乙氨基)水杨醛和对氨基苯酚的摩尔比为1∶1.1~1.5。
5.根据权利要求2所述的新型生物硫醇荧光探针的制备方法,其特征在于,所述步骤(2)的具体过程为:
将5-二乙氨基-2-[[(4-羟基苯基)亚胺]甲基]-苯酚用二氯甲烷溶解,在氩气保护下,控温-5~0℃加入三氟化硼乙醚溶液和N,N-二异丙基乙胺,将反应液室温反应12~18h后,将反应液倒入饱和碳酸氢钠溶液中,用二氯甲烷萃取,合并有机相,有机相用饱和氯化钠溶液洗,无水硫酸钠干燥后,减压浓缩除去溶剂,再用二氯甲烷重结晶,过滤所得物为4-[7-(二乙氨基)-2,2-二氟苯并[e][1,3,2]恶唑硼烷-3-基]苯酚。
6.根据权利要求5所述的新型生物硫醇荧光探针的制备方法,其特征在于,所述5-二乙氨基-2-[[(4-羟基苯基)亚胺]甲基]-苯酚、三氟化硼乙醚和N,N-二异丙基乙胺的摩尔比为1∶2.0~2.5:2.0~2.5。
7.根据权利要求2所述的新型生物硫醇荧光探针的制备方法,其特征在于,所述步骤(3)的具体过程为:
将5-二乙氨基-2-[[(4-羟基苯基)亚胺]甲基]-苯酚、2,4-二硝基苯磺酰氯和三乙胺溶解于二氯甲烷中,在氩气保护下室温反应0.25~0.5h,反应完毕后,减压过滤,用二氯甲烷淋洗,得到式(1)所示的化合物。
8.根据权利要求7所述的新型生物硫醇荧光探针的制备方法,其特征在于,所述5-二乙氨基-2-[[(4-羟基苯基)亚胺]甲基]-苯酚、2,4-二硝基苯磺酰氯和三乙胺的摩尔比为1∶1.1~1.4∶1.2~1.5。
9.一种如权利要求1所述的新型生物硫醇荧光探针或权利要求2~8任一项所述的制备方法制得的新型生物硫醇荧光探针的应用,其特征在于,将所述新型生物硫醇荧光探针与磷酸盐缓冲液和二甲基亚砜的缓冲液混合,再加入待测溶液中,得到混合溶液,利用混合溶液的荧光变化来检测生物硫醇的存在与否。
10.根据权利要求9所述的应用,其特征在于,所述待测溶液中无生物硫醇时,所述混合溶液为无荧光发射;所述待测溶液中有生物硫醇时,所述混合溶液发出蓝色荧光。
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