CN109796962B - 一种具有大斯托克位移检测次氯酸的比值型荧光探针 - Google Patents
一种具有大斯托克位移检测次氯酸的比值型荧光探针 Download PDFInfo
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Abstract
Description
技术领域
本发明属于化学分析检测技术领域,具体涉及一种具有大斯托克位移识别次氯酸的比值型荧光探针及其应用。
背景技术
次氯酸(HClO)作为典型的活性氧(ROS)物质在生理和病理过程中都起着重要的作用。在人体内不同的活性氧通过不同的生理途径生成,而次氯酸的产生是由过氧化氢和氯离子通过酶髓过氧化物酶(MPO)催化反应产生。适量的次氯酸有助于生物体对细菌的破坏,但是过量的次氯酸对人的伤害是非常大,导致很多疾病,例如心血管病,关节炎,动脉硬化,癌症等等。所以,在生物体内监测次氯酸的浓度变化是必不可少的。可用于选择性检测的次氯酸的方法有很多,如比色法,碘量滴定法,库仑法,化学发光法等等。但是这些方法步骤比较繁琐,而且很多方法必须在有机介质或有机/水介质中进行,限制了其在生物方面的应用。与上述方法相比,荧光探针却是一种比较理想的检测手段,因为它具有检测方便,响应时间快,灵敏度高,检测限低,对细胞损害小等优点。
发明内容
本发明目的之一是开发一种具有长波长大斯托克斯位移的黄酮染料;目的之二是提供一种灵敏度高、选择性好,抗干扰能力强,比值型,能够对体外或者活细胞内的次氯酸进行快速监测或者细胞成像的荧光探针,其结构如下FPT:
其合成路线为:
具体合成方法:(a)将氢氧化钾(25mg,0.45mmol)加入到5mL无水乙醇中,再加入PTZ(56mg,0.2mmol)和2-羟基苯乙酮(47mg,0.35mmol),在65℃下反应7小时后,将反应液旋干后通过柱层析纯化得深红色固体(18.0mg,产率22.5%)。b,将化合物1(115mg,0.29mmol)溶解在15mL乙醇中,加入3mL的氢氧化钠溶液(0.5M),而后逐滴加入100μL的30%的过氧化氢溶液,在70℃下反应3h后,把反应体系倒入20mL的冰水中,调节pH至2~3,用二氯甲烷萃取得到橙色有机相,用无水硫酸钠干燥,旋干柱层析得到橙色固体(50mg,产率41.7%)。
本发明的探针的机理如下:
探针FPT在次氯酸(HClO)存在下,分子中的硫醚键会被氧化成亚砜,而探针FPT本身的红色荧光(最大发射波长586nm)会蓝移到FPT-O的绿色荧光(最大发射波长524nm)。从而达到特异性检测次氯酸。
本发明的荧光探针具有比值荧光发射,其与次氯酸(HClO)作用前发射橙红色荧光在586nm处,作用后荧光发生蓝移发射峰在524nm处。
附图说明
图1为本发明的荧光探针(10.0×10-6mol/L)在pH为7.4的HEPES缓冲溶液(20.0mM,1.0mM CTAB)中,与不同浓度的次氯酸响应后(HClO)紫外吸收变化图,横坐标为波长,纵坐标分别为吸收强度。
图2为本发明的荧光探针(10.0×10-6mol/L)在pH为7.4的HEPES缓冲溶液(20.0mM,1.0mM CTAB)中,与不同浓度的次氯酸响应后荧光光谱变化图,横坐标为波长,纵坐标分别为荧光强度。
图3为本发明的荧光探针(10.0×10-6mol/L)在pH为7.4的HEPES缓冲溶液(20.0mM,1.0mM CTAB)中,随着加入次氯酸(HClO)的量的荧光强度比值变化散点图,横坐标为次氯酸(HClO)浓度,纵坐标为荧光强度比值。
图4为本发明的荧光探针(10.0×10-6mol/L)在pH为7.4的HEPES缓冲溶液(20.0mM,1.0mM CTAB)中,加入次氯酸(HClO)的量与荧光强度比值变化的线性关系,横坐标为次氯酸浓度,纵坐标为荧光强度比值。
图5为本发明的荧光探针(10.0×10-6mol/L)在存在和不存在次氯(HClO)时在不同pH值的体系中荧光强度比值变化,横坐标为pH值,纵坐标为荧光强度比值。
图6为本发明的荧光探针(10.0×10-6mol/L)在pH为7.4的HEPES缓冲溶液(20.0mM,1.0mM CTAB)中,存在次氯酸(HClO)和其他物质时的荧光发射情况,横坐标为波长,纵坐标为荧光强度。
图7为本发明的荧光探针(10.0×10-6mol/L)在pH为7.4的HEPES缓冲溶液(20.0mM,1.0mM CTAB)中,加入8倍当量次氯酸(HClO)后,荧光强度比值随着时间的变化图,横坐标为时间,纵坐标为荧光强度比值。
图8为本发明的荧光探针(10.0×10-6mol/L)在pH为7.4的HEPES缓冲溶液(20.0mM,1.0mM CTAB)中存在(1)PBS,(2)ClO-,(3)1O2,(4)H2O2,(5)O2 -,(6)NO-,(7)-OH,(8)ONOO-,(9)ROO-,(10)TBHP,(11)Hcy,(12)Cys,(13)GSH,(14)SH-,(15)HSO3 -,(16)S2O3 2-,(17)SO4 2-,(18)Br-,(19)I-,(20)K+,(21)Na+,(22)Fe3+.等不同物质时选择性的条形图,纵坐标为I524/I586强度的变化。
图9为本发明的荧光探针细胞适用性的毒性研究实验,横坐标为探针浓度,纵坐标为细胞存活率。
图10为本发明的荧光探针斑马鱼内检测次氯酸(HClO)。
具体实施实例
实施例1:探针分子的合成化合物1的合成
取氢氧化钾(25mg,0.45mmol)于10mL的圆底烧瓶中,再加入5mL无水乙醇,在搅拌下加入PTZ(56mg,0.2mmol)和2-羟基苯乙酮(47mg,0.35mmol),在65℃下反应7小时后,直接将反应液用旋转蒸发仪旋干后,通过硅胶柱层析纯化即得18mg化合物1为深红色固体,产率为22.5%。
1H NMR(400MHz,CDCl3)δH 12.92(s,1H),7.92(d,J=7.7Hz,1H),7.85(d,J=14.3Hz,1H),7.52–7.43(m,3H),7.38(d,J=5.9Hz,1H),7.13(d,J=7.2Hz,2H),7.02(d,J=8.3Hz,1H),6.94(t,J=7.5Hz,1H),6.84(d,J=7.1Hz,3H),4.04(s,2H),1.85–1.73(m,2H),1.48(dd,J=14.8,7.4Hz,2H),0.97(t,J=7.3Hz,3H)。
13C NMR(400MHz,CDCl3)δC 163.5,147.8,144.5,143.9,136.2,129.5,129.3,128.8,127.5,126.7,125.1,123.7,123.1,120.1,118.8,118.6,117.5,115.7,115.2,47.4,28.8,20.1,13.8。
FPT的合成
将化合物1(115mg,0.29mmol)置于25mL的圆底烧瓶中,加入15mL乙醇溶解,再加入3mL的氢氧化钠溶液(0.5M),而后逐滴加入100μL的30%的过氧化氢溶液,在70℃下反应3h后,把反应体系倒入20mL的冰水中,调节溶液pH至2~3,用二氯甲烷(30mL×3次)萃取得到橙色有机相,用无水硫酸钠干燥,用旋转蒸发仪将溶液旋干后,通过硅胶柱层析纯化即得50mg产物FPT为橙色固体,产率为41.7%。
1H NMR(400MHz,CDCl3)δH 8.23(d,J=7.8Hz,1H),8.11(d,J=8.2Hz,1H),8.00(s,1H),7.68(t,J=7.7Hz,1H),7.57(d,J=8.4Hz,1H),7.40(t,J=7.4Hz,1H),7.14(d,J=6.9Hz,2H),7.03–6.92(m,3H),6.89(d,J=7.8Hz,1H),3.91(s,2H),1.83(dt,J=14.4,7.2Hz,2H),1.49(dd,J=14.9,7.4Hz,2H),0.97(t,J=7.3Hz,3H)。
13C NMR(400MHz,CDCl3)δC 155.2,144.5,137.7,133.5,127.2,125.9,125.6,124.5,123.7,122.8,121.0,118.0,115.6,114.7,47.3,29.7,28.8,20.1,13.8。
实施例2:本发明的荧光探针的应用
荧光探针(10.0×10-6mol/L)在pH为7.4的HEPES缓冲溶液(20.0mM,含1.0mM CTAB)中加入PBS,1O2,H2O2,O2 -,NO-,-OH,ONOO-,ROO-,TBHP,Hcy,Cys,GSH,SH-,HSO3 -,S2O3 2-,SO4 2-,Br-,I-,K+,Na+,Fe3+后没有引起探针本身发射峰的明显变化,而加入次氯酸(HClO)后,则引起了荧光变化,说明该探针具有优良的选择性。且该探针够快速的检测次氯酸(HClO),表现出了一个快的响应速率,而细胞毒性实验,斑马鱼中成像实验说明探针具有好的生物适用前景。
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