CN113024595B - 1,3,5,7-四甲基环四硅氧烷基环丙沙星荧光探针及其在铁离子检测中的应用 - Google Patents
1,3,5,7-四甲基环四硅氧烷基环丙沙星荧光探针及其在铁离子检测中的应用 Download PDFInfo
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Abstract
Description
技术领域
本发明涉及荧光传感技术领域,具体涉及一种荧光探针及其在铁离子检测中的应用。
背景技术
铁是人体中不可或缺的微量元素,是血红蛋白的重要组成部分,而血红蛋白在生命体中承担着运输氧气的功能。此外,铁元素在人体中参与各种免疫系统及酶的构成。体内铁元素的缺乏会引起缺铁性贫血、细胞供养不足、人体疲劳倦怠,同时会导致人体免疫力下降。儿童时期缺铁则会影响儿童的心理活动及智力发育,并且过程不可逆。人体内铁元素过量则会导致肝脏中铁过载,引起肝纤维化及肝细胞瘤等疾病,甚至会导致机体氧化-抗氧化系统失衡,直接损伤DNA进一步诱发细胞突变。铁在自然环境中也广泛存在,各种动植物、食物、药物、土壤、江河湖泊中都含有一定的铁。基于铁污染对环境的长期性、对人体健康影响的隐蔽性等特点,做好铁的检测工作,为污染的防治和提高人的身体素质奠定基础尤为重要。
目前,对于Fe3+的检测主要包括原子吸收光谱法、发射光谱法、高效液相色谱法以及电感耦合等离子体法等,但由于这些技术普遍存在高成本、操作复杂、检测耗时长、仪器大型化等缺点,限制了其在现场检测Fe3+的应用。而荧光检测法因其操作简便、响应迅速、选择性高等优点备受关注。已报道的用于Fe3+检测的荧光小分子材料主要包括罗丹明类分子、四苯基乙烯类分子、喹啉类分子及BODIPY分子等,但是这些荧光小分子材料在检测铁离子过程中存在无法排除其他金属离子例如Zn2+的干扰缺陷,并且对Fe3+的检测限较高。
发明内容
本发明的目的在于提供一种荧光探针及其在铁离子检测中的应用。本发明提供的荧光探针灵敏性高、选择性好、毒性小,检测限低,适用于对Fe3+的特异性检测。
本发明的上述技术目的是通过以下技术方案得以实现的:
一种用于铁离子检测的1,3,5,7-四甲基环四硅氧烷基环丙沙星(D4H-HBC)荧光探针,其结构式如下:
用于铁离子检测的1,3,5,7-四甲基环四硅氧烷基环丙沙星由甲基丙烯酸羟乙基环丙沙星(HBC)与四甲基环四硅氧烷通过硅氢加成反应得到。
化合物HBC的分子结构式为:
化合物四甲基环四硅氧烷的分子结构式为:
合成具体方法为:在苯甲醚中加入1,3,5,7-四甲基环四硅氧烷与化合物HBC并置于两口瓶中,升温至80℃;加入催化剂反应8h;反应结束后减压蒸馏获得的粗产物,使用层析柱分离提纯,得到黄色固体化合物1,3,5,7-四甲基环四硅氧烷基环丙沙星。反应如下:
化合物HBC与1,3,5,7-四甲基环四硅氧烷的摩尔比为1:(2~4)。
催化剂为氯铂酸的异丙醇溶液(质量浓度为1%),氯铂酸与1,3,5,7-四甲基环四硅氧烷的摩尔比为(0.01-0.05):1。
用于铁离子检测的1,3,5,7-四甲基环四硅氧烷基环丙沙星荧光探针的使用方法,其特征在于,包括以下步骤:
(1)将1,3,5,7-四甲基环四硅氧烷基环丙沙星荧光探针溶解于乙醇中,荧光探针的浓度为1*10-4mol/L,得到荧光探针溶液;在380nm光源激发下,测定其在发射波长为521nm处的荧光强度I0;
(2)取荧光分子探针溶液2mL,向其中加入10μL的待测样品,混合均匀,得到样品溶液,在380nm光源激发下,测定样品在发射波长为521nm处的荧光强度I;
(3)当I/I0≤0.8时,则可判定样品中含有Fe3+。
本发明具有如下创新点和有益效果:
(1)本发明的荧光探针有良好的选择性和灵敏度,测试样品无需前处理;
(2)毒性很小,因此在化工、环境、生物医药等领域具有极高的应用价值。
(3)该荧光探针在识别Fe3+之后在pH值为酸性或中性范围内都能够显示荧光猝灭现象,该荧光分子探针识别响应非常迅速。
附图说明
图1为化合物D4H-HBC的核磁图。
图2为D4H-HBC荧光探针在乙醇溶液中的荧光发射光谱图。
图3为Fe3+对D4H-HBC的荧光猝灭图
图4为D4H-HBC荧光探针抗其他离子干扰图
具体实施方式
下面通过具体的实施例对本发明的技术方案做进一步详细地说明,但本发明的保护范围不仅限于这些实施例。
实施例1:
将1,3,5,7-四甲基环四硅氧烷1.208mL(5.0mmol)溶于2mL的苯甲醚中置于50mL的两口瓶中,升温至80℃;加入120μL质量分数为1%的氯铂酸-异丙醇溶液;将HBC 0.68g(1.25mmol)溶于20mL的苯甲醚中,逐滴加入至两口瓶中;在80℃反应8小时后;减压蒸馏,粗产物使用层析柱分离提纯,得到橙黄色固体,即为化合物D4H-HBC。
实施例2:
将1,3,5,7-四甲基环四硅氧烷0.604mL(2.5mmol)溶于2mL的苯甲醚中置于50mL的两口瓶中,升温至80℃;加入120μL质量分数为1%的氯铂酸-异丙醇溶液;将HBC 0.68g(1.25mmol)溶于20mL的苯甲醚中,逐滴加入至两口瓶中;在80℃反应8小时后;减压蒸馏,粗产物使用层析柱分离提纯,得到橙黄色固体,即为化合物D4H-HBC。
实施例3:
测试实施例2制备的荧光探针与不同金属离子作用后的荧光发射光谱,具体方法如下:
按荧光分子探针D4H-HBC浓度为10-4mol/L,将荧光分子探针D4H-HBC加入到乙醇溶液中,再按金属离子的浓度为5μg/mL加入金属离子,测溶液的荧光发射光谱,其中金属离子分别为Cr3+,Ag+,Co2+,Cu2+,K+,Ni2+,Cd2+,Pb2+,Ba2+,Mg2+,Al3+,Ca2+,Zn2+,Na+,Li+,Ga3+,Mn2+,这些金属均不会造成荧光猝灭,当加入Fe3+离子时,荧光强度猝灭到原来的1/7。因此,荧光分子探针D4H-HBC对Fe3+有良好的选择性和识别能力。
实施例4:
检测实施例2制备的荧光分子探针对Fe3+选择性的灵敏度,具体方法如下:
按荧光分子探针D4H-HBC浓度为10-4mol/L,将荧光分子探针D4H-HBC加入到乙醇溶液中,先后加入浓度为5μg/mL的Cr3+,Ag+,Co2+,Cu2+,K+,Ni2+,Cd2+,Pb2+,Ba2+,Mg2+,Al3+,Ca2+,Zn2+,Na+,Li+,Ga3+,Mn2+,这些混合离子一起,并不会造成荧光探针的荧光猝灭,当加入Fe3+离子时,荧光发生猝灭。因此,荧光分子探针D4H-HBC对其他金属离子有很强的抗干扰能力和对Fe3+离子良好的选择性。
Claims (8)
2.根据权利要求1所述的一种用于铁离子检测的荧光探针,其特征在于,用于铁离子检测的1,3,5,7-四甲基环四硅氧烷基环丙沙星由甲基丙烯酸羟乙基环丙沙星HBC与四甲基环四硅氧烷通过硅氢加成反应得到。
6.根据权利要求2所述一种用于铁离子检测的荧光探针,其特征在于,化合物HBC与1,3,5,7-四甲基环四硅氧烷的摩尔比为1:(2~4)。
7.根据权利要求2所述一种用于铁离子检测的荧光探针,其特征在于,催化剂为质量浓度为1%的氯铂酸的异丙醇溶液,氯铂酸与1,3,5,7-四甲基环四硅氧烷的摩尔比为(0.01-0.05):1。
8.根据权利要求1-7任意一项所述的一种用于铁离子检测的荧光探针的使用方法,其特征在于,包括以下步骤:
(1)将1,3,5,7-四甲基环四硅氧烷基环丙沙星荧光探针溶解于乙醇中,荧光探针的浓度为1*10-4mol/L,得到荧光探针溶液;在380nm光源激发下,测定其在发射波长为521nm处的荧光强度I0;
(2)取荧光分子探针溶液2mL,向其中加入10μL的待测样品,混合均匀,得到样品溶液,在380nm光源激发下,测定样品在发射波长为521nm处的荧光强度I;
(3)当I/I0≤0.8时,则可判定样品中含有Fe3+。
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