CN109336898B - 一种铁离子探针及其应用 - Google Patents
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- 229910052742 iron Inorganic materials 0.000 title claims abstract description 47
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims abstract description 50
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Abstract
本发明涉及荧光探针技术领域,具体涉及一种高灵敏度的铁离子探针及其应用。具体方案为:本发明公开了一种高灵敏度的铁离子探针的结构式,还公开了在检测Fe3+上的应用,能够在Fe3+浓度为3mmol/L时,Fe3+的最低检测限为0.32μM,并与Fe3+进行络合反应。本发明合成的铁离子探针,合成过程简单,原料易得,反应条件简单,操作简单,产率高,在多种常见金属离子中,对Fe3+具有高度选择性,不受其他常见离子的干扰,对Fe3+的结合属于反应型识别,具有不可逆性;利用该目标探针可对Fe3+进行裸眼检测,无需借助任何设备。而且,对Fe3+检测的时间短,具有更高的灵敏度。
Description
技术领域
本发明涉及荧光探针技术领域,具体涉及一种铁离子探针及其应用。
背景技术
铁是人体必要的微量元素之一,约占人体体重的0.006%,同时也是生物体中最重要的过渡金属离子,是许多酶促反应的辅助因子,为血红素提供携氧能力,并在细胞的新陈代谢等诸多生理过程中发挥着至关重要的作用。同时Fe元素是组成肌红蛋白、血红蛋白等多种酶的最主要成分。人体内铁的来源一方面是从食物中摄入,另一方面是红细胞释放。如果体内缺铁,则影响肌红白蛋等的合成并表现出相应的病例特征,如免疫力、抗感染力降低,身体调节体温的能力减弱,神经紊乱等疾病。另外,生活中频发的缺铁症状是缺铁性贫血。因此对铁离子的检测显得十分重要。
目前铁离子的传统检测方法有:原子吸收分光光度法(AAS),电感耦合等离子体原子发射光谱法(ICP-AES)和电化学分析法等。但上述方法需要借助昂贵的仪器和专业的检测人员,不适合大批量检测和实时检测。荧光探针检测方法技术因具有灵敏度好、成本低和易于操作等优点而成为研究热点。因此,本发明提供了一种新的具有铁离子探针,能够检测Fe3+。
发明内容
本发明的目的是提供一种铁离子探针及其应用。
为实现上述发明目的,本发明所采用的技术方案是:
本发明提供一种铁离子探针,所述铁离子探针具有如下结构式:
优选的,所述铁离子探针由以下步骤制备:
(1)将2~5g罗丹明6G溶于100~200mL无水乙醇中,得罗丹明6G溶液;将乙二胺与无水乙醇混合均匀,得乙二胺溶液,将所述乙二胺溶液滴入到所述罗丹明6G溶液中,在室温搅拌下,18~22min内滴完;
(2)将步骤(1)得到的混合溶液进行加热回流,回流温度为110~130℃,回流时间为10~15h,回流速度为1滴/秒,然后用展开剂点板确定反应终点,当反应到达终点后,停止回流;
(3)回流结束后,控制温度79~81℃,蒸馏回收乙醇;在常温下搅拌溶液2~4h,直至有淡黄色固体析出,再进行抽滤、洗涤、干燥,即得淡黄色产物LDMO;
(4)将所述LDMO溶于10~50mL的无水乙醇中,加入邻香兰素,加热回流,回流温度为100~120℃,回流时间为6~10h,用展开剂点板确定反应是否结束,当反应结束后停止回流,将溶液冷却至室温,此时溶液中有黄色固体析出,将黄色固体洗涤、重结晶,即得到目标产物。
优选的,步骤(1)中,所述乙二胺和无水乙醇的体积比为1:5。
优选的,步骤(2)和步骤(4)中,所述展开剂为石油醚和乙酸乙酯按体积比为1:1的混合溶液。
优选的,步骤(4)中,所述LDMO与邻香兰素的摩尔比为1:1。
本发明还提供了一种铁离子探针在检测Fe3+上的应用。
优选的,所述铁离子探针在Fe3+浓度为3mmol/L时,对Fe3+的最低检测限为0.32μM。
优选的,所述铁离子探针与Fe3+按1:1络合反应。
本发明中罗丹明6G的合成路线为:
本发明中中间体LDMO的合成路线为:
本发明目标探针的合成路线为:
本发明具有以下有益效果:
本发明用罗丹明6G、乙二胺和邻香兰素为原料合成了铁离子探针,合成过程简单,原料易得,反应条件简单,操作简单,产率高,在多种常见金属离子中,对Fe3+具有高度选择性,不受其他常见离子的干扰,对Fe3+的结合属于反应型识别,具有不可逆性;利用该目标探针可对Fe3+进行裸眼检测,无需借助任何设备。而且,对Fe3+检测的时间短,具有更高的灵敏度,能检测Fe3+浓度为3mmol/L的水体,对Fe3+最低检测限为0.32μM。
附图说明
图1为本发明铁离子探针的结构式;
图2为本发明铁离子探针核磁共振氢谱图;
图3为加入不同金属离子的铁离子探针的紫外吸收光谱图;
图4为Fe3+与其他金属离子的紫外吸收光谱图;
图5为在含有铁离子探针的Fe3+溶液中加入EDTA前后的紫外吸收光谱图;
图6为Fe3+与铁离子探针的Job’s-plot曲线;
图7为Fe3+浓度变化与铁离子探针作用的紫外吸收光谱图;
图8为Fe3+在530nm处最大吸收的线性回归方程;
具体实施方式
下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
若未特别指明,实施举例中所用的技术手段为本领域技术人员所熟知的常规手段。
实施例1铁离子探针的制备
(1)罗丹明6G的合成:
a、将5.0000g 3-乙基氨基-4-甲基苯酚、15.0000g邻苯二甲酸酐和4.8000g氯化锌置于研钵中研磨,研磨均匀后倒入茄型烧瓶中(茄型***大小根据使用需要进行常规选择),对烧瓶进行加热,保持温度在165℃,缓慢搅拌反应1h,使混合物逐渐熔融,且颜色变深,此时需要小心搅拌,随着反应的进行,稠度逐渐变小,随后又逐渐变大,反应物呈现金属光泽的棕***;然后减压抽真空,5~10min后去除瓶塞,直至瓶内无苯酐升华;
b、将步骤a得到的混合物溶于120mL的N,N-二甲基甲酰胺(DMF)中,然后缓慢滴入1200mL 5%的氯化钠水溶液,在60℃下剧烈搅拌30min,然后趁热抽滤,滤饼用水洗1~2次,滤饼呈***,然后在60℃下真空干燥,得到茄紫色粉末;
c、将步骤b得到的茄紫色粉末进行柱层析,先用乙酸乙酯洗脱,然后用二氯甲烷洗脱,得到***粉末,***粉末有10.5226g,产率为77%。将该***粉末10.0000g与300mL无水乙醇和10mL浓硫酸进行酯化反应,反应后的溶液倒入600mL 5%的氯化钠水溶液中,在40℃下充分搅拌0.5h后抽滤,并用乙醇进行重结晶,得到最终产物罗丹明6G,紫色晶体,有10.2556g,产率85%。
(2)罗丹明6G衍生物中间体LDMO的合成
a、称取2.0038g罗丹明6G于250mL茄型烧瓶中,加入150mL无水乙醇,常温搅拌10min,使其完全溶解,此时溶液呈棕色。取4mL乙二胺与20mL无水乙醇于锥形瓶中混合均匀后,滴入到含有罗丹明6G的溶液中,在室温搅拌下20min滴完;
b、将步骤a得到的混合溶液进行油浴加热回流,回流温度为120℃,回流时间为12h,回流速度为1滴/秒,此时溶液颜色逐渐变浅,呈黄色;然后用石油醚/乙酸乙酯=1:1作为展开剂,点板确定反应终点,当反应到达终点后,停止回流;
c、回流结束后,控制温度为80℃,蒸馏回收乙醇100mL,此时溶液颜色加深,呈黄橙色;然后在常温下搅拌溶液3h,直至有淡黄色固体析出,再用循环水式真空泵进行抽滤,收集滤饼,用无水乙醇将滤饼洗涤2~3次后,将洗涤后的固体置于真空干燥箱中干燥,得到淡黄色产物LDMO 1.5514g,产率为81%。
(3)中间体LDMO合成目标探针
a、将0.5010g中间体LDMO于50mL茄型烧瓶中,加入20mL无水乙醇中,常温搅拌20min,使其完全溶解,此时溶液呈黄色;然后加入0.1510g邻香兰素(黄色固体,有奶香味),此时溶液颜色加深,中间体LDMO与邻香兰素的摩尔比为1:1;
b、将步骤a得到的混合溶液进行油浴加热回流,回流温度为110℃,回流时间为8h,随着反应的进行,溶液颜色进一步加深,呈黄棕色;然后用石油醚/乙酸乙酯=1:1作为展开剂,点板确定反应已结束,当反应结束后停止回流,并将溶液冷却至室温,此时溶液中伴有黄色固体析出,用胶头滴管吸取残余的溶液,固体用无水乙醇洗涤1~2次,然后用无水乙醇进行重结晶,重结晶的步骤为:将固体加入到无水乙醇中,在70℃下加热回流溶液,使固体在短时间内完全溶解(如若固体无法完全溶解则通过滤纸进行自然过滤,得到澄清透明的溶液),溶解之后将溶液转移至100mL小烧杯中,用保鲜膜封好,在保鲜膜上留几个小孔(对小孔的数量并没有要求,根据需要进行设置即可),置于通风橱等待晶体析出,即得到目标产物黄色针状固体0.3959g,产率61%。
需要说明的是:本发明中的罗丹明6G可直接采用市售的罗丹明6G,也可采用本发明的方法进行制备,现配现用。
本实施例制备的铁离子探针的结构式为:
对上述制备的目标产物黄色针状固体进行结构检测,采用核磁共振仪对黄色针状固体进行表征,其核磁共振氢谱图如图2所示,从目标产物的核磁共振氢谱图可知:1H NMR(60MHz,CDCl3):δ8.07(s,1H),7.94(m,1H),7.47(m,2H),7.17(m,1H),6.84(d,3H),6.42(s,2H),6.28(d,2H),3.92(s,3H),3.27(m,9H),1.92(d,6H),1.37(t,6H),得知目标产物中氢的种类有18种,峰面积表示各个种类的氢的数目。
结果表明:制备的目标产物黄色针状固体的结构与设计的结构相符。
实施例2铁离子探针的离子响应和选择性
用移液枪分别往15支7mL的离心管中加入2940μL乙腈水溶液(水和乙腈的体积比为1:4)和30μL铁离子探针溶液(称取88mg实施例1制备的目标产物加入到50mL容量瓶中,用乙腈溶解,并用乙腈定容),然后再向14支离心管中分别加入60μL配置好的3mmol/L金属离子溶液,每种金属离子溶液对应一个离心管,其中一支不含探针溶液的乙腈水溶液作为空白样,并用标签纸进行标记;其中14种金属离子分别为Ag+、Al3+、Ba2+、Ca2+、Co2+、Cu2+、Fe3+、Hg+、K+、Mn+、Na+、Ni+、Pb+、Zn2+。
当加入Fe3+溶液时,发现离心管里溶液颜色由淡黄色变成无色,且逐渐变成红色,等待一段时间后,Al3+也出现了浅红色,加入Fe3+的乙腈水溶液的颜色比Al3+的深,而加入其他金属离子溶液并未使离心管中探针溶液发生明显的变化,说明该铁离子探针对Fe3+和Al3 +均有不同程度的响应。
再用紫外分光光度计检测除空白样外的其余14支离心管中溶液的紫外吸收情况,设定波长为300~600nm,结果如图3所示,发现只有加入的Fe3+溶液在530nm处有非常明显的紫外吸收。
结果显示:图3中,只有Fe3+和Al3+在530nm处有较为明显的紫外吸收,并且Fe3+的吸光度高于Al3+的吸光度,而其他离子无明显吸收。因此,可认为含有铁离子探针的乙腈水溶液与Fe3+发生了化学反应,而其他的金属离子不与铁离子探针发生反应,说明本发明的铁离子探针对Fe3+具有很好的选择性。
由于Fe3+对探针响应时间快,Al3+对探针响应时间慢,因此,以Fe3+作为主要检测的离子。
实施例3铁离子探针的干扰性
本实施例对Fe3+是否对其他金属离子的响应产生干扰进行离子干扰性检测,用移液枪往实施例2中除空白样外的其余14支离心管中分别加入60μL的Fe3+溶液,然后摇匀。加入Fe3+溶液后,14支离心管的颜色均变为红色,说明其他金属离子溶液对本发明的铁离子探针不产生影响。
然后用紫外分光光度计检测这14支离心管中溶液的紫外吸收情况,波长设定在300~600nm,结果如图4所示。结果显示:当加入Fe3+溶液后,所有14支离心管内的溶液在530nm处均出现了明显的紫外吸收峰,吸光度发生了变化,其中Fe3+的吸光度明显高于其他金属离子和Fe3+的吸光度,说明其他金属离子对Fe3+与铁离子探针乙腈水溶液的响应不产生干扰。
实施例4络合机理分析
根据实施例2认为的含有铁离子探针的乙腈水溶液与Fe3+发生了化学反应,为此对该化学反应进行进一步的研究。往实施例2中已经变红的含有铁离子探针的溶液中加入配好的3mmol/L的EDTA溶液,此时溶液颜色由红色变为淡黄色,对加入EDTA前和加入EDTA后的溶液进行紫外可见光分析,其紫外吸收光谱图如图5所示,从图中可以看出加入EDTA前的溶液在波长530nm处有明显的峰,此时溶液颜色为红色,并且有明显的荧光;当加入3mmol/L的EDTA溶液后,溶液变为淡黄色,再进行紫外吸收的检测,明显的看出在波长530nm处并没有出现吸收。由此得出:本发明的铁离子探针与Fe3+是通过络合反应而出现的颜色变化,反应机理如下:
实施例5Job's-Plot测定
取12根离心管,其中1根离心管用移液枪介入3mL的乙腈水溶液(水和乙腈的体积比为1:4)作为参照,再用移液枪分别向其余11根离心管中加入2900μL的乙腈水溶液,然后加入铁离子探针溶液(该溶液从实施例2制备好的溶液中移取)和Fe3+溶液,并保持铁离子探针溶液和Fe3+溶液的体积和为100μL,其中Fe3+溶液的体积以10μL为一个梯度,从0μL到100μL递增,即铁离子探针溶液的体积从100μL至0μL递减,最后将上述12根离心管内的溶液用紫外分光光度计进行检测,检测结果如图6所示。从图中可以看出,本发明的铁离子探针与Fe3+是按1:1络合反应的。
实施例6灵敏度分析
取14根离心管,其中1根离心管用移液枪介入3mL的乙腈水溶液(水和乙腈的体积比为1:4)作为参照,另外13根离心管用移液枪分别加入30μL的铁离子探针溶液(该溶液从实施例2制备好的溶液中移取),然后以10μL为梯度,加入Fe3+溶液,Fe3+溶液的体积从0到120μL递增,为保证离心管内的溶液的总体积为3mL,乙腈水溶液的体积由2970μL到2850μL递减,并贴上标签进行标号,最后将上述14根离心管内的溶液用紫外分光光度计进行检测,并在530nm处对Fe3+进行线性回归方程分析,结果如图7和图8所示,从图7中可以看出,随着Fe3+溶液浓度的增大,吸光度增大,在波长530nm处的紫外吸收也越来越强。从图8中可以看出,在40~120nm的波长范围内吸光度和Fe3+溶液的浓度成线性关系,线性方程是:Y=0.00474x-0.17524,r=0.9864。根据最低检测公式:LOD=3σ/k,其中k是斜率,σ是测量值与空白样的标准偏差,最后计算得出该铁离子探针的乙腈水溶液对Fe3+的最低检测限度0.32μM,即0.01792mg/L,这数值小于国家饮用水规定的最低限度(GB5749-2006,生活饮用水卫生标准,Fe3+最低限度0.3mg/L),对检测生态环境中Fe3+含量具有很大的实际意义。
以上所述的实施例仅是对本发明的优选方式进行描述,并非对本发明的范围进行限定,在不脱离本发明设计精神的前提下,本领域普通技术人员对本发明的技术方案做出的各种变形和改进,均应落入本发明权利要求书确定的保护范围内。
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