CN113234437A - 基于金属有机骨架的比率荧光探针的制备和在检测1,4-二硫苏糖醇中的应用 - Google Patents
基于金属有机骨架的比率荧光探针的制备和在检测1,4-二硫苏糖醇中的应用 Download PDFInfo
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Abstract
本发明公开了一种基于金属有机骨架的比率荧光探针的制备,是将Cu‑TCPP、ZrCl4和苯甲酸超声溶解于DMF中,于100~120℃下反应45~50h,过滤,洗涤,丙酮浸泡进行活化,过滤,真空干燥,得到具有过氧化物酶活性的金属有机骨架PCN‑224(Cu);将PCN‑224(Cu)和2‑氨基对苯二甲酸(PTA‑NH2)溶于PBS溶液中,室温下自组装反应6~8 h,即得基于金属有机骨架的比率荧光探针PTA‑NH2@PCN‑224(Cu)。该比率荧光探针可用于对1,4‑二硫苏糖醇(DTT)的识别检测,且具有良好的选择性,操作简单方便且灵敏度高;同时,该比率荧光探针为反向变化双发射比率荧光探针,可以消除环境和人为因素的干扰,减小实验误差,增加实验结论的可靠性。
Description
技术领域
本发明涉及一种基于金属有机骨架的比率荧光探针的制备方法;本发明同时涉及该比率荧光探针在检测1,4-二硫苏糖醇(DTT)中的应用。
背景技术
1,4 -二硫苏糖醇(DTT)是一种非生理合成分子,通常作为还原剂,在生物学、生物医学、生物化学等各个领域发挥着重要作用。一般情况下,低浓度的还原剂(约300 μM)可以作为一种解毒剂来保护细胞和生物。但高浓度的DTT(超过10 mM)会对某些生物分子造成氧化损伤。
DTT被认为是实验室和工业事故中的严重威胁。迄今为止,仅报道了几种用于DTT检测的分析方法,包括液相色谱法,比色测定法以及荧光测定法。其中,荧光分析法由于其工艺简单,灵敏度高,操作方便等优点而被广泛用于检测DTT。但由于复杂的合成过程、低的灵敏度和选择性,荧光方法的应用受到限制。因此,开发新型荧光材料作为DTT分析的探针仍然迫切。且现有荧光分析法多是单发射,因此,有必要开发比率荧光探针减少环境干扰和实验误差。
发明内容
本发明的目的是提供一种基于金属有机骨架的比率荧光探针的制备方法;
本发明的另一个目的是提供该比率荧光探针在检测1,4-二硫苏糖醇(DTT)中的应用。PTA-NH2@PCN-224(Cu)比率荧光探针为反向变化的双发射荧光探针,具有针对无环境干扰的自参考能力和高的灵敏度。
一、PTA-NH2@PCN-224(Cu)比率荧光探针的制备
本发明基于金属有机骨架的比率荧光探针的制备方法,包括以下步骤:
(1)将5,10,15,20-四(4-羧基苯基)卟啉与CuCl2 .2H2O溶于DMF中,于130~140℃下回流反应4~6 h,离心、洗涤、真空干燥得到Cu-TCPP。其中,所述5,10,15,20-四(4-羧基苯基)卟啉与CuCl2 .2H2O的摩尔比为1:5~1:6。
(2)将Cu-TCPP、ZrCl4和苯甲酸超声溶解于DMF中,于100~120℃下反应45~50h,过滤,洗涤,丙酮浸泡进行活化,过滤,真空干燥,得到具有过氧化物酶活性的金属有机骨架PCN-224(Cu)。其中,所述Cu-TCPP、ZrCl4和苯甲酸的质量比为1:1:50~1:2:55。
(3)将PCN-224(Cu)和2-氨基对苯二甲酸溶于PBS溶液中,室温下自组装反应6~8h,即得基于金属有机骨架的比率荧光探针PTA-NH2@PCN-224(Cu)。其中,所述PCN-224(Cu)和2-氨基对苯二甲酸的质量比为1:1;所述PBS溶液浓度为0.2 M,pH为7。
TCPP、Cu-TCPP、PCN-224和PCN-224(Cu)傅里叶变换红外光谱如图1所示。在乙醇溶液中测试,1699和1271 cm-1处的不对称振动吸收强度可以归因于TCPP中的C=O和C-OH基团。PCN-224或PCN-224(Cu)形成后,信号强度明显减弱,说明TCPP配体中含有的-COOH基团参与了与Zr4+离子的配位。在TCPP和PCN-224的检测中都发现了位于966和3427 cm-1的N-H键吸收振动峰,这一特征信号在N原子与Cu2+离子配位后无法检测到。另一个证实该金属配体键的证据为Cu-TCPP和PCN-224(Cu)在1001 cm-1的Cu-N键吸收振动峰,证明了该复合材料的成功制备。
二、PTA-NH2@PCN-224(Cu)比率荧光探针荧光检测1,4-二硫苏糖醇(DTT)
1、PTA-NH2@PCN-224(Cu)的荧光性能
将5 μL PTA-NH2@PCN-224(Cu)溶液、5 μL OPD(3 mM)、20 μL H2O2(50 mM)和PBS缓冲溶液(0.2 M,pH=7)混合(保证总体积为2mL),在常温下反应1 h,然后在390 nm的激发波长下记录荧光光谱。荧光光谱仪的狭缝宽度设定为5 nm,设置激发光波长为390 nm,测出PTA-NH2@PCN-224(Cu)荧的发射波长为432 nm和562 nm,432 nm为PTA-NH2@PCN-224(Cu)中的2-氨基对苯二甲酸(PTA-NH2)所发射的蓝色荧光峰,562 nm为具有过氧化物酶活性的PCN-224(Cu)催化氧化产物DAP发射的绿色荧光峰。具有过氧化物酶活性的PCN-224(Cu)可以催化H2O2生成羟基自由基并氧化邻苯二胺(OPD)生成2,3-二氨基吩嗪(DAP),DAP在562 nm处具有绿色荧光发射。
2、PTA-NH2@PCN-224(Cu)对DTT的特异性识别检测
将5 μL PTA-NH2@PCN-224(Cu)溶液、5 μL OPD(3 mM)、20 μL H2O2(50 mM)和PBS缓冲溶液(0.2 M,pH=7)混合(保证总体积为2mL),向PTA-NH2@PCN-224(Cu)混合液中分别加入4μL Na+、Ca2+、K+、尿素、葡萄糖、苯丙氨酸、丙氨酸、组氨酸(0.1M)和40μLDTT溶液(10mM)。在常温下反应1 h,测定荧光光谱,得到432 nm和562 nm的荧光强度F432和F562,计算荧光强度比F562/F432,结果如图2所示。发现只有DTT能够使PTA-NH2@PCN-224(Cu)混合液的荧光强度比F562/F432明显下降,其他物质的加入对PTA-NH2@PCN-224(Cu)混合液的荧光强度比F562/F432几乎没有影响,表明PTA-NH2@PCN-224(Cu)对DTT具有良好的选择性,可实现对DTT的特异性识别检测。
3、PTA-NH2@PCN-224(Cu)对DTT的检测机理
分别对PCN-224(Cu)、OPD和H2O2共存时测试了激发光谱也就是DAP的激发光谱,同时测试了PTA-NH2@PCN-224(Cu)和PTA-NH2的发射光谱(都是PTA-NH2的发射光谱),可以看到DAP的激发光谱和PTA-NH2的发射光谱很好的重叠,证明了两者满足发生荧光内滤效应的条件,结果如图3所示。
PCN-224(Cu)可以催化H2O2生成羟基自由基并氧化邻苯二胺(OPD)生成2,3-二氨基吩嗪(DAP)。PTA-NH2@PCN-224(Cu)中的2-氨基对苯二甲酸(PTA-NH2)在432 nm处具有蓝色荧光发射,DAP在562 nm处具有绿色荧光发射。DAP可通过荧光内滤效应(IFE)猝灭PTA-NH2在432 nm处的荧光。当存在DTT时,它可以与羟基自由基反应,OPD的氧化较少,DAP产生较少,减弱了荧光内滤效应,伴随着PTA-NH2的荧光强度增加(即432nm处荧光强度增强)而DAP的荧光强度下降(即562nm处荧光强度减弱),荧光强度比F562/F432下降,因此PTA-NH2@PCN-224(Cu)可实现对于DTT的特异性识别检测。
4、抗干扰性试验
将5 μL PTA-NH2@PCN-224(Cu)溶液、5 μL OPD(3 mM)、20 μL H2O2(50 mM)和PBS缓冲溶液(0.2 M,pH=7)混合(保证总体积为2mL),向PTA-NH2@PCN-224(Cu)混合液中首先加入40 μLDTT溶液(10mM),再在含有DTT的混合液中分别加入20 μLNa+、Ca2+、K+、尿素、葡萄糖、苯丙氨酸、丙氨酸、组氨酸(0.1M)。在常温下反应1 h,测定荧光光谱,得到432 nm和562 nm的荧光强度F432和F562,计算荧光强度比F562/F432,结果如图4所示。加入DTT和干扰物质后,荧光强度比F562/F432的变化可忽略不计,表明PTA-NH2@PCN-224(Cu)对DTT具有良好的选择性。
5、荧光滴定实验
将5 μL PTA-NH2@PCN-224(Cu)溶液、5 μL OPD(3 mM)、20 μL H2O2(50 mM)混合,向其中加入一系列不同浓度(0~400 μM)DTT溶液,并添加PBS溶液(0.2 M,pH为7)(保证总体积为2mL),常温下反应1 h,在390 nm的激发波长下,分别检测不同浓度DTT对探针荧光信号的影响,结果如图5所示,可以看出随着DTT浓度的增大,由于减弱了荧光内滤效应,432 nm处的荧光强度增强,而562 nm处的荧光减弱的越来越明显,并且DTT浓度与荧光强度比呈良好的线性,结果如图6所示,线性方程:F562/F432=-0.00476x+1.35896,线性范围:1-180μM,检测限:9.7 μM,其中,x为DTT的浓度。
与现有技术相比,本发明的PTA-NH2@PCN-224(Cu)比率荧光探针对DTT具有良好的选择性,操作简单方便且灵敏度高;同时,该比率荧光探针为反向变化双发射比率荧光探针,可以消除环境和人为因素的干扰,减小实验误差,增加实验结论的可靠性。
附图说明
图1是TCPP、Cu-TCPP、PCN-224和PCN-224(Cu)傅里叶变换红外光谱。
图2是PTA-NH2@PCN-224(Cu)比率荧光探针对DTT检测的选择性图。
图3是PTA-NH2的发射光谱和DAP的激发光谱。
图4是PTA-NH2@PCN-224(Cu)比率荧光探针对DTT检测的抗干扰性图。
图5是不同浓度的DTT对荧光强度比(F562/F432)的影响图。
图6是不同浓度的DTT滴定的线性关系图。
具体实施方式
实施例1 PTA-NH2@PCN-224(Cu)比率荧光探针的制备
(1)5,10,15,20-四(4-羧基苯基)卟啉(TCPP,四羧基苯基卟啉)的合成:在250mL三口圆底烧瓶中加入4-羧基苯甲醛(1.54 g,0.0103 M)和50 mL丙酸,将反应混合物加热到80℃直至4-羧基苯甲醛完全溶解。将新蒸馏的吡咯(0.7 mL,0.0103 M)加入到反应液中并将所得溶液加热140℃回流4 h,将反应混合物冷却至23℃,烧瓶置于-4℃下12h,诱导沉淀,过滤沉淀,用CH2Cl2(5×50 ml)里面加一点丙酮(10:1)洗涤,抽滤,将沉淀溶于乙醇50℃超声,旋干并真空干燥,得到紫色结晶固体TCPP。
(2)Cu-TCPP的合成:将TCPP(0.261 g,0.33 mM)与CuCl2 .2H2O(0.31 g,1.82mM)的混合物溶解于15 mL DMF中,再140℃回流5 h形成红色污泥,离心得到红色沉淀,用水洗涤3次以上,60℃真空干燥10 h得到Cu-TCPP。
(3)PCN-224(Cu)的合成:将Cu-TCPP(0.10 g)、ZrCl4(0.156 g)和苯甲酸(5.4 g)的混合物超声溶解于16 mLDMF中,将溶液转移到50 mL反应釜中,120℃反应48 h,将悬浮液过滤并分别用DMF和丙酮连续洗涤。将样品浸泡在60 mL丙酮溶液中进一步活化,其在24 h后与新鲜丙酮溶剂交换后,顷析出上层液体,将残余物过滤并在100℃下真空干燥8 h得到具有过氧化物酶活性的金属有机骨架PCN-224(Cu)。
(4)PTA-NH2@PCN-224(Cu)的合成:将PTA-NH2(1mg)和PCN-224(Cu)(1mg)溶于2 mL的PBS(0.2 M)中,一锅法室温自组装反应时间8 h,即得PTA-NH2@PCN-224(Cu)比率荧光探针。
实施例2 PTA-NH2@PCN-224(Cu)荧光检测DTT
将5 μL PTA-NH2@PCN-224(Cu)溶液、5 μL OPD(3 mM)、20 μL H2O2(50 mM)混合,向PTA-NH2@PCN-224(Cu)混合液中分别加入4μL Na+、Ca2+、K+、尿素、葡萄糖、苯丙氨酸、丙氨酸、组氨酸(0.1M)和40 μL DTT溶液(10mM),若PTA-NH2@PCN-224(Cu)混合液的荧光强度比F562/F432明显下降,说明加入的是DTT,若PTA-NH2@PCN-224(Cu)混合液的荧光强度比F562/F432没有发生明显变化,说明加入的不是DTT。
Claims (8)
1.一种基于金属有机骨架的比率荧光探针的制备方法,包括以下步骤:
(1)将5,10,15,20-四(4-羧基苯基)卟啉与CuCl2 .2H2O溶于DMF中,于130~140℃下回流反应4~6 h,离心、洗涤、真空干燥得到Cu-TCPP;
(2)将Cu-TCPP、ZrCl4和苯甲酸超声溶解于DMF中,于100~120℃下反应45~50h,过滤,洗涤,丙酮浸泡进行活化,过滤,真空干燥,得到具有过氧化物酶活性的金属有机骨架PCN-224(Cu);
(3)将PCN-224(Cu)和2-氨基对苯二甲酸溶于PBS溶液中,室温下自组装反应6~8 h,即得基于金属有机骨架的比率荧光探针PTA-NH2@PCN-224(Cu)。
2.根据权利要求1所述一种基于金属有机骨架的比率荧光探针的制备方法,其特征在于:步骤(1)中,所述5,10,15,20-四(4-羧基苯基)卟啉与CuCl2 .2H2O的摩尔比为1:5~1:6。
3.根据权利要求1所述一种基于金属有机骨架的比率荧光探针的制备方法,其特征在于:步骤(2)中,所述Cu-TCPP、ZrCl4和苯甲酸的质量比为1:1:50~1:2:55。
4.根据权利要求1所述一种基于金属有机骨架的比率荧光探针的制备方法,其特征在于:步骤(3)中,所述PCN-224(Cu)和2-氨基对苯二甲酸的质量比为1:1。
5.根据权利要求1所述一种基于金属有机骨架的比率荧光探针的制备方法,其特征在于:步骤(3)中,所述PBS溶液浓度为0.2 M,pH为7。
6.根据权利要求1所述方法制备的基于金属有机骨架的比率荧光探针在检测1,4-二硫苏糖醇中的应用。
7.根据权利要求6所述基于金属有机骨架的比率荧光探针在检测1,4-二硫苏糖醇中的应用,其特征在于:将PTA-NH2@PCN-224(Cu)溶液、邻苯二胺、H2O2和PBS缓冲溶液混合,向PTA-NH2@PCN-224(Cu)混合液中分别加入Na+、Ca2+、K+、尿素、葡萄糖、苯丙氨酸、丙氨酸、组氨酸和1,4-二硫苏糖醇溶液,只有1,4-二硫苏糖醇溶液的加入可以使PTA-NH2@PCN-224(Cu)混合液的荧光强度比F562/F432明显下降。
8.根据权利要求7所述基于金属有机骨架的比率荧光探针在检测1,4-二硫苏糖醇中的应用,其特征在于:所述PBS缓冲溶液的浓度为0.2 M,pH为7。
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