CN108359446B - 一种用于检测Fe3+的有机荧光传感探针及制备方法、使用方法和应用 - Google Patents
一种用于检测Fe3+的有机荧光传感探针及制备方法、使用方法和应用 Download PDFInfo
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Abstract
一种用于检测Fe3+的有机荧光传感探针,其制备方法包括以下步骤:将油性荧光传感材料与甲酸混合,40℃‑90℃回流1小时,得到保护好基团的原料探针分子;将原料探针分子与三卤苯酚混合,55℃‑110℃催化剂下回流24个小时,得到有机荧光传感探针,本有机荧光传感探针水溶性好,生物相容性好,保留了有机荧光探针材料专一性强,灵敏度高的优点,大大的提升了铁离子检测下限,检查范围广,检测下限处于世界领先水平。
Description
技术领域
本发明涉及Fe3+离子检测领域,尤其涉及一种用于检测Fe3+的有机荧光传感探针及制备方法、使用方法和应用。
背景技术
Fe3+离子广泛分布于天然水、蔬菜、水果、作物和动物体中。生物在新陈代谢的过程中,Fe3+离子参与着许多非常重要的生化过程,然而,生物体本身摄入过多或过少的Fe3+离子会产生不良的反应。科学发展的过程中投入了巨大的努力对于定性或定量的Fe3+离子测定,伴随着传感技术的发展已经开发和应用了多种方法,包括原子吸收、色谱法、电化学法、流动注射法和荧光传感材料,均可应用于Fe3+离子检测,但是这些方法不仅检测成本高昂,检测程序复杂,时间慢,并且选择性大大不如有机荧光离子检测法。
有机荧光离子检测法是一项重要的技术,检测Fe3+离子具有时间短、高效率、灵敏度高、便于检测的优点。但是大部分的有机探针分子是在油相合成的,并且分子整体疏水,水溶性差一直是有机荧光离子检测方法无法突破的现状,目前世界最低检测下限为2pmol/ml。
因此尚需要一种水溶性好、毒性低,同时还兼备有机荧光检测试剂优点的离子探针材料。
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,提供一种水溶性好,生物相容性好的有机荧光传感探针材料,保留了有机荧光探针材料专一性强,灵敏度高的优点,大大的提升了铁离子检测下限,检查范围广,检测下限处于世界领先水平的一种用于检测Fe3+的有机荧光传感探针及制备方法、使用方法和应用。
为实现本发明提供以下技术方案:
一种用于检测Fe3+的有机荧光传感探针的制备方法,其制备方法包括以下步骤:
(1)将油性荧光传感材料与甲酸混合,40℃-90℃回流1小时,得到保护好基团的原料探针分子;
(2)将原料探针分子与三卤苯酚混合,55℃-110 ℃催化剂下回流24个小时,得到有机荧光传感探针。
作为优选,所述步骤(1)中油性荧光传感材料为香豆素母体,所述油性荧光传感材料与甲酸的摩尔比为1:3~1:10,温度最优选为60℃。
作为优选,所述步骤(2)的具体过程为:将0.3mmol-1.5mmol原料探针分子与0.1mmol-0.5mmol的三卤苯酚混合,55℃-110℃催化剂下回流24个小时,所述三卤苯酚为三溴苯酚、三氯苯酚或三碘苯酚中的一种,所述催化剂为碘化亚铜,温度最优选为75℃。
一种用于检测Fe3+的有机荧光传感探针的使用方法,包括以下步骤:
(1)将制备好的有机荧光传感探针材料配成1umol/ml的标准液;
(2)将配好的标准液100ul,水100ul和PBS缓冲溶液100ul混合,得到混合液;
(3)将混合液进行超声处理后,投加不同浓度的Fe3+离子标准液100ul;
(4)针对不同浓度的Fe3+离子标准液依次进行光谱分析,最终绘制成检测限图。
一种用于检测Fe3+的有机荧光传感探针的应用,用于检测Fe3+的浓度,检测范围为6umol/ml-50pmol/ml,理论检测下限为5pmol/ml,还用于荧光标记和裸眼可视方面的应用。
本发明的有益之处:第一,水溶性好,生物相容性好的有机荧光传感探针材料,保留了有机荧光探针材料专一性强,灵敏度高的优点;第二,大大的提升了铁离子检测下限,检查范围广,本发明大大提升了Fe3+的检测下限,由目前世界最低检测下限为2pmol/ml提升到5pmol/ml,处于世界领先水平;第三,合成方法简单易行。
附图说明
图1为本发明提供的有机荧光传感探针的结构。
图2为该有机荧光传感探针的吸收光谱随铁离子浓度变化图。
图3为该有机荧光传感探针的发射光谱,以及该产品检测线图。
图4为该有机荧光传感探针选择性的图。
图5为该有机荧光传感探针的质谱图。
图6为该有机荧光传感探针的红外光谱。
图7为固体核磁1H NMR(400MHz)δ8.2461,6.5133,3.1935,2.1733,0.7211。
图8为一组该有机荧光探针的生物毒性的测试(MTT法)。
图9为该有机荧光传感探针在癌细胞中的细胞成像实验荧光变化。
图10为用96孔板做了一组紫外灯下裸眼可视的检测图。
图11为该有机荧光传感探针自然光可视化检测的应用图。
具体实施方式
实施例1:
一种用于检测Fe3+的有机荧光传感探针的制备方法,其制备方法包括以下步骤:
(1)将油性荧光传感材料与甲酸混合,40℃-90℃回流1小时,得到保护好基团的原料探针分子;所述油性荧光传感材料为香豆素母体,所述油性荧光传感材料与甲酸的摩尔比为1:3,温度最优选为60℃。
(2)将原料探针分子与三卤苯酚混合,55℃-110 ℃催化剂下回流24个小时,得到有机荧光传感探针,具体过程为:将0.3mmol-1.5mmol原料探针分子与0.1mmol-0.5mmol的三卤苯酚混合,55℃-110℃催化剂下回流24个小时,所述三卤苯酚为三溴苯酚、三氯苯酚或三碘苯酚中的一种,所述催化剂为碘化亚铜,温度最优选为75℃。
一种用于检测Fe3+的有机荧光传感探针的使用方法,包括以下步骤:
(1)将制备好的有机荧光传感探针材料配成1umol/ml的标准液;
(2)将配好的标准液100ul,水100ul和PBS缓冲溶液100ul混合,得到混合液;
(3)将混合液进行超声处理后,投加不同浓度的Fe3+离子标准液100ul;
(4)针对不同浓度的Fe3+离子标准液依次进行光谱分析,最终绘制成检测限图。参考图3,图3中取1umol/ml 1ml荧光分子,1ml(PH=7.4)PBS缓冲溶液,1ml 浓度范围6umol/ml-50pmol/ml Fe(NO3)3 配成待测液,测出发射光谱随Fe3+离子浓度变化图,绘制检测线图并计算检测下限。
一种用于检测Fe3+的有机荧光传感探针的应用,用于检测Fe3+的浓度,检测范围为6umol/ml-50pmol/ml,理论检测下限为5pmol/ml,还用于荧光标记和裸眼可视方面的应用。
图4为该有机荧光传感探针选择性的图。研究内容主要包括对材料选择性的测试,通过对该有机荧光传感探针的性能测试,体现出该有机荧光传感探针只对Fe3+离子有荧光猝灭的现象。具体的操作过程如下:配置1umol/ml 1ml荧光材料、1ml(PH=7.4)PBS缓冲溶液、1mmol/ml 不同种金属离子溶液(Na+、 K+、 Zn2+、Ca2+、Fe2+、Fe3+、Sn2+、Cu2+、Ba2+、Mn2+、Ni2+、Co2+)混合后通过对其发射光谱强度的变化绘制出选择性图。
图5为该有机荧光传感探针的质谱图,可以反映该材料的摩尔质量为1078g/mol。
图6为该有机荧光传感探针的红外光谱,图中可以看出:a,1604.7cm-17处有一个较强的吸收峰为苯环的吸收峰;b,1265.30cm-1处较强吸收峰为苯酚的吸收峰;c,1203.58cm-1的较尖强峰说明存在联苯醚的吸收峰。
图7为固体核磁1H NMR(400MHz)δ8.2461,6.5133,3.1935,2.1733,0.7211。
图8为一组该有机荧光传感探针的生物毒性的测试(MTT法),可以看出该材料具备非常好的生物相容性。
图9为该有机荧光传感探针在癌细胞中的细胞成像实验,具体步骤:MCF-7细胞与荧光材料共同孵育4个小时,去除多余的有机荧光传感探针,加入100ulPBS,800ul细胞培养液,100ul(1-4um/ml)的Fe3+混合后置于共聚焦显微镜下观察荧光变化。
图10用96孔板做了一组紫外灯下裸眼可视的检测,测试范围为0.2-5um/ml,检测下限为3.8um/ml,做了一组对比图,鱼身为3.6um/ml的Fe3+与有机荧光传感探针的混合物,周围为3.8um/mlFe3+的与有机荧光传感探针的混合物。
图11,为该有机荧光传感探针自然光可视化检测的应用,具体操作:100ul(1nmol/ml-4um/ml)Fe3+与100ul 1umol/ml荧光材料混合后加入500ul的比色皿中拿到太阳光下裸眼观察颜色变化。
实施例2:
重复实施例1,其不同之处在于,第一步中香豆素母体和甲酸混合的回流温度为70oC,结果依然得到了实施例1的物质,并且具备其所有的性质。
实施例3
重复实施例1,其不同之处在于,第二步中与三卤苯酚的回流温度为100oC,结果依然得到了实施例1的物质,并且具备其所有的性质。
实施例4
重复实施例1,其不同之处在于,第二步中增加了三卤苯酚的量,使其同原料探针分子的摩尔比达到10:1,结果依然得到了实施例1的物质,并且具备其所有的性质。
本发明并不局限于上述具体实施方式所涉及的一种用于检测Fe3+的有机荧光传感探针及制备方法、使用方法和应用,熟悉本技术领域的人员还可据此做出多种变化,但任何与本发明等同或相类似的变化都应涵盖在本发明权利要求的范围内。
Claims (6)
2.一种如权利要求1所述的用于检测Fe3+的有机荧光传感探针的制备方法,其特征在于:
其制备方法包括以下步骤:
将油性荧光传感材料与甲酸混合,40℃-90℃回流1小时,得到保护好基团的原料探针分子;
将原料探针分子与三卤苯酚混合,55℃-110℃催化剂下回流24个小时,得到有机荧光传感探针。
3.根据权利要求2所述的一种用于检测Fe3+的有机荧光传感探针的制备方法,其特征在于:所述步骤(1)中油性荧光传感材料为香豆素母体,所述油性荧光传感材料与甲酸的摩尔比为1:3~1:10。
4.根据权利要求2所述的一种用于检测Fe3+的有机荧光传感探针的制备方法,其特征在于:所述步骤(2)的具体过程为:将0.3mmol-1.5mmol原料探针分子与0.1mmol-0.5mmol的三卤苯酚混合,55℃-110℃催化剂下回流24个小时,所述三卤苯酚为三溴苯酚、三氯苯酚或三碘苯酚中的一种,所述催化剂为碘化亚铜。
5.一种用于检测Fe3+的有机荧光传感探针的使用方法,其特征在于:包括以下步骤:
(1)将制备好的有机荧光传感探针材料配成1umol/ml的标准液;
(2)将配好的标准液100ul,水100ul和PBS缓冲溶液100ul混合,得到混合液;
(3)将混合液进行超声处理后,投加不同浓度的Fe3+离子标准液100ul;
(4)针对不同浓度的Fe3+离子标准液依次进行光谱分析,最终绘制成检测限图。
6.一种用于检测Fe3+的有机荧光传感探针的应用,其特征在于:用于检测Fe3+的浓度,检测范围为6umol/ml-50pmol/ml,用于荧光标记和裸眼可视方面的应用。
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