CN112500427A - 一种检测Fe3+的荧光探针及其制备方法和应用 - Google Patents
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Abstract
本专利公开了一种检测Fe3+的荧光探针及其制备方法和应用。本发明用对氯甲基苯甲醛,2,4‑二甲基吡咯和三氟化硼乙醚反应生成氟硼二吡咯型荧光探针分子,本发明的荧光探针分子所采用的材料制备工艺简单、易操作、原料来源充足、生产成本低、产率高以及重复性好,该分子可以与Fe3+络合,改变电荷结构从而使其荧光减弱甚至消失,根据它的这个特点可以用来检测Fe3+,并且可以用于生物成像进而检测生物细胞Fe3+,为探究Fe3+在人体生命活动中的作用提供了研究方法。
Description
技术领域
本发明属于有机荧光探针领域,尤其涉及一种检测Fe3+的荧光探针及其制备方法和应用。
背景技术
铁是地壳中重要的金属元素,其含量占第四位,也是人体内含量最高的必需微量元素,多细胞水平的生物及化学过程需要铁离子的参与,铁是维持生命的主要物质,是制造血红素和肌血球素、促进维生素B族代谢的必要物质, 参与氧的运输和贮存,在增强机体免疫功能方面起着非常重要的生理作用。铁元素参与细胞色素和其它酶的合成,参与氧的运输,但是如果人体吸收过多的铁也可能导致中毒,很可能会引起肝纤维化和肝细胞肿瘤等疾病,造成机体功能障碍。
鉴于铁离子的重要生理和病理功能,因此,开发高灵敏、高选择性检测铜离子的方法是非常必要的。传统检测铁离子的方法主要有原子吸收光谱法,原子发射光谱法,电感耦合等离子体质谱法,比色法及伏安法。但这些方法一般都耗时较长、涉及复杂繁琐的样品处理过程或需要昂贵的精密仪器等。而利用分子探针荧光法检测铁离子具有样品处理简洁、成本低廉及操作简便快速等优点,近年来得到了快速发展与利用。
荧光探针技术因为自身诸多的优点诸如便于检测、易操作等,在许多领域中都得到了广泛的应用,特别是离子检测领域。常见的荧光探针作用机理有:光诱导电子转移(PET),分子内电荷转移(ICT)、荧光共振能量转移(FRET)、跨键能量转移(TBET)、激发态分子内质子转移(ESIPT)、聚集荧光增强(AIEE)、电子能量转移(EET)等。基于上述情况,研究能用于铁离子检测的新型的探针具有重要意义。
BODIPY类荧光染料对光的感应度很高,优点主要有 (1)具有较高的荧光量子产率,有些甚至接近于1.0。(2)摩尔吸光系数一般大于80000 cm-1· M-1。(3)对酸碱不敏感,不易受环境、溶液pH的影响,对溶液极性不敏感。(4)具有相对较好的光稳定性。(5)荧光光谱半峰宽较窄,使得作为荧光标识的时候灵敏度非常高。(6)激发波长在可见光区,而且其结构比较容易修饰。基于以上优点,BODIPY类染料被广泛的应用于细胞染色标记、各种金属离子的检测。
发明内容
针对现有技术的缺陷,本发明提供一种检测Fe3+的荧光探针及其制备方法和应用。
本发明提供一种能够特异性检测Fe3+的荧光探针,本发明的荧光探针分子以氟硼二吡咯为发光团,引入对氯甲基苯为金属配体,通过其荧光强度随Fe3+浓度而变化,可制成特异性检测Fe3+的荧光探针。
为实现上述及其他目的,本发明提供如下技术方案:
本发明第一方面,一种检测Fe3+的荧光探针,并且作为荧光探针的化合物结构如下所示:
本发明提供BODIPY环为发光团用于检测Fe3+的荧光探针,所述探针包含BODIPY发光团和对氯甲基苯,并且,对氯甲基苯为金属离子络合体。
本发明第二方面,荧光探针化合物的制备方法,包括如下步骤:
无水无氧条件下,将对氯甲基苯甲醛与2,4-二甲基吡咯在过量二氯甲烷中溶解搅拌均匀,加入三氟乙酸反应2-4小时,加入2,3-二氯-5,6-二氰基苯琨(DDQ),搅拌1-2小时,加入三乙胺反应1-2小时,加入三氟化硼乙醚反应2-4小时,
其中,对氯甲基苯甲醛、2,4-二甲基吡咯、三氟乙酸、2,3-二氯-5,6-二氰基苯琨(DDQ)、三乙胺、三氟化硼乙醚的摩尔比为1:1.5-2.5:1.5-2.5:2-3:5-15:5-15;
然后,加水、萃取、分液、干燥、抽滤、旋蒸、提纯后即得到荧光探针的化合物。
本发明第三方面,本发明制备的荧光探针分子在Fe3+检测的领域应用,具体地,采用荧光光谱检测手段探针分子对Fe3+的识别具有专一性,并且随着Fe3+浓度的变化,探针荧光强度也有变化。
本发明具体描述如下:将荧光探针分子配成10-6 M的溶液,向探针分子溶液中定量加入配制好的Fe3+溶液,以371 nm光激发,监测到其荧光光谱的变化,随着Fe3+浓度逐渐增大,荧光强度逐渐减弱,很好的监测了金属离子的浓度,即表明本发明的探针对Fe3+有很好的灵敏度。
本发明的荧光探针分子作为金属离子探针具有如下突出的技术优势:
1、本发明通过对氯甲基苯与铁离子络合,在对氯甲基苯对位引入BODIPY荧光团,当铁离子含量改变时,其荧光强度随之改变,由此可从荧光强度计算出溶液中铁离子的含量。
2、还可利用“裸眼”检测,本发明的荧光探针分子基于PET机理,随着铁离子含量增加,荧光强度降低,在紫外等条件下可用“裸眼”检测。
附图说明
附图用来提供对本发明技术方案的进一步理解,并且构成说明书的一部分,与本申请的具体实施方式一起用于解释本发明的技术方案,并不构成对本发明技术方案的限制。
图1为本发明制备荧光型金属离子探针的反应路线。
图2为本发明合成的分子探针的核磁共振氢谱。
图3为本发明2μM荧光探针在加入不同浓度Fe3+后荧光发射光谱图, Fe3+浓度分别为0、20、40、60、80、100、120、140、160、180、200、220、240μM,溶液体系为乙腈和水的混合溶液,横坐标为波长,纵坐标为荧光强度。
图4为本发明铁离子的浓度标准曲线图,即2μM分子探针,反应前后在512nm处荧光发射强度和铁离子浓度的线性关系;横坐标为铁离子的浓度,纵坐标为荧光强度,并计算出它的检出限。
图5为本发明荧光探针对Fe3+的选择性;即2μM本发明探针,加入400μM不同离子(Fe3+、Na+、K+、Li+、Mg2+、Al3+、Ba2+、Ca2+、Zn2+、Hg2+、Cd2+、Ni2+、Co2+、Cr2+、Cu2+、Pb2+)后,荧光光谱图的变化。
图6为本发明荧光探针对Fe3+的选择性;即2μM本发明探针,加入400μM不同离子(Fe3+、Na+、K+、Li+、Mg2+、Al3+、Ba2+、Ca2+、Zn2+、Hg2+、Cd2+、Ni2+、Co2+、Cr2+、Cu2+、Pb2+)后,在512nm处荧光发射强度的变化;横坐标为空白和测试的干扰离子,纵坐标为荧光强度。
图7为本发明铁离子荧光探针检测铁离子,适用于裸眼检测。即配制的2μM的本发明探针,加入(Fe3+、Na+、K+、Li+、Mg2+、Al3+、Ba2+、Ca2+、Zn2+、Hg2+、Cd2+、Ni2+、Co2+、Cr2+、Cu2+、Pb2 +)后,第一个是未加入离子的空白荧光探针溶液,第二个是加入铁离子的荧光探针溶液,其他的依次分别是加入了其他金属离子的荧光探针溶液,均为在紫外光照射下的图像。
图8为本发明荧光探针的抗干扰性,即2μM本发明探针,分别加入400μM不同离子(Na+、K+、Li+、Mg2+、Al3+、Ba2+、Ca2+、Zn2+、Hg2+、Cd2+、Ni2+、Co2+、Cr2+、Cu2+、Pb2+),再分别在荧光探针溶液和加入不同离子的荧光探针溶液中加入200μM的Fe3+后,在512 nm处荧光发射强度的变化;横坐标为空白和测试的干扰离子,纵坐标为荧光强度。
图9为本发明铁离子荧光探针用分子荧光光谱法检测工业废水的标准曲线图,横坐标是铁离子浓度,纵坐标是荧光强度。图表征出工业废水中Fe3+的浓度。
具体实施方式
下面将参照附图对本发明进行更详细的描述,其中表示了本发明的优选实施例,应该理解本领域技术人员可以修改在此描述的本发明而仍然实现本发明的有益效果。因此,下列描述应当被理解为对于本领域技术人员的广泛知道,而并不作为对本发明的限制。
为使本发明的目的、特征更明显易懂,下面结合附图对本发明的具体实施方式作进一步的说明。需要说明的是,附图均采用非常简化的形式且均使用非精准的比率,仅用于方便、清晰地辅助说明本发明实施例的目的。
实施例1:荧光探针的合成
本发明的检测Fe3+的BODIPY型荧光探针按下述方法合成:
在无水无氧条件下,将0.6798g对氯甲基苯甲醛与0.7ml 2,4-二甲基吡咯按在二氯甲烷中溶解搅拌均匀,加入0.15ml三氟乙酸反应三小时,得到中间产物,后加入1.98g 2,3-二氯-5,6-二氰基苯琨(DDQ),搅拌一小时, 加入10ml三乙胺反应一小时,加10ml的三氟化硼乙醚反应三小时。加50ml水开始萃取,分液取有机相,加入5g无水硫酸钠干燥,抽滤,旋蒸,柱层析分离(洗脱剂为石油醚/乙酸乙酯=3/1的混合溶液)得到产物红色固体105mg(收率:68%),如图2所示,确认制备出下设化合物。产物结构式如下:
1H NMR (400 MHz, CDCl3) δ 7.56, 7.55, 7.54, 7.54, 7.32, 7.32, 7.30,7.30, 7.28, 7.27, 6.07, 6.01, 5.32, 4.68, 4.35, 4.33, 4.31, 2.58, 2.56, 2.27,1.74, 1.72, 1.63, 1.49, 1.48, 1.48, 1.46, 1.45, 1.45, 1.44, 1.43, 1.40, 1.36,1.31, 1.28, 1.25, 1.00, 0.99, 0.97, 0.92, 0.90, 0.89, 0.89, 0.10, 0.02.
实施例2:探针对铁离子的荧光检测
将上述制得荧光探针溶解于水与乙腈的混合溶液中,配制成2μM的探针溶液在比色皿中加入2mL配制的2μM本发明探针溶液,然后分别加入不同浓度的Fe3+后均匀混合,测试其荧光光谱,发现荧光强度随Fe3+的浓度增加而降低,结果如图3所示,表明本发明的荧光探针的荧光强度随Fe3+的浓度增加而降低。
以溶液在512nm处荧光发射强度对Fe3+的浓度作图,Fe3+浓度在0–120μM范围内时,两者之间呈现良好的线性关系(图4),表明本发明的探针能实现该浓度范围内Fe3+的定量检测。
为检测本发明荧光探针对Fe3+的专一性,向荧光探针溶液中加入其他金属离子如Na+、K+、Li+、Mg2+、Al3+、Ba2+、Ca2+、Zn2+、Hg2+、Cd2+、Ni2+、Co2+、Cr2+、Cu2+、Pb2+。如图5、6所示,图5中峰值最高的是空白的荧光探针溶液,其余稍低的是加入金属离子的荧光探针溶液,峰值最低的是加入铁离子的荧光探针溶液。图6中的1是空白探针溶液的荧光强度,2是加入铁离子的荧光探针溶液荧光强度,3-17分别是按照上述离子顺序依次加入了其他离子的荧光探针溶液荧光强度。
图5、6表明加入其他离子的荧光溶液的荧光强度与空白荧光探针溶液的荧光强度相近,而加入铁离子的荧光探针溶液的荧光强度明显降低,证明本发明的探针对Fe3+仍具有良好的选择性和灵敏度。
向配制的2μM的本发明探针溶液中加入Blank、Fe3+、Na+、K+、Li+、Mg2+、Al3+、Ba2+、Ca2 +、Zn2+、Hg2+、Cd2+、Ni2+、Co2+、Cr2+、Cu2+、Pb2+后,如图7所示,其中,图7中各荧光瓶自左至右按照上述离子顺序摆放,可发现加入Fe3+的溶液(左2)由黄绿色变为黄色,在紫外灯下可发现加入Fe3+的溶液没有荧光,而其他溶液有荧光。需要说明的是由于专利的说明书附图要求为无色彩,图7中Fe3+的溶液无荧光,灰度黑白处理后显示深暗色,其他离子显示的荧光色彩灰度黑白处理后显示灰白色。
以上显示本发明的荧光探针随着铁离子浓度的增加荧光强度越来越低,说明本发明的荧光探针具有良好的响应,灵敏度高,选择性好,且抗干扰强,能实现对铁离子的定性、定量检测。
实施例3:探针的抗干扰性测试
分别向配制的2μM的本发明探针溶液中分别加入400μM的不同离子Na+、K+、Li+、Mg2+、Al3+、Ba2+、Ca2+、Zn2+、Hg2+、Cd2+、Ni2+、Co2+、Cr2+、Cu2+、Pb2+后,再分别在荧光探针溶液和加入不同离子的荧光探针溶液中加入200μM的Fe3+后,在512 nm处荧光发射强度的变化;横坐标为空白和测试的干扰离子,纵坐标为荧光强度。
如图8所示,向荧光探针加入Fe3+与向荧光探针加入其他金属离子后再加入Fe3+的荧光强度减弱程度相近,表明本发明荧光探针具有优异的抗干扰性,可以在存在其他金属离子的情况下用来检测铁离子。
实施例4:探针对工业废水中铁离子的荧光检测
在比色皿中加入2mL配制的2μM本发明探针溶液,然后分别加入不同浓度的Fe3+后均匀混合,测试其荧光光谱,以溶液在512nm处荧光发射强度对Fe3+的浓度作图,绘制标准曲线,向荧光探针中加入废水,根据荧光强度求出工业废水中Fe3+的浓度如图9所示,工业废水中Fe3+的浓度为2.43mM,计算加标回收率为117.8%。表明本发明的荧光探针能够对工业废水中铁离子进行有效的荧光检测。
以上具体实施方式的实例说明能够制备出本发明的荧光探针,而且,本发明的荧光探针能够随着Fe3+浓度荧光强度变化,可以有效监测金属离子的浓度。本发明荧光探针的关键在于所述探针包含BODIPY发光团和对氯甲基苯,对氯甲基苯对位引入BODIPY荧光团。进一步的,对氯甲基苯能够与铁离子络合,当铁离子含量改变时,其荧光强度随之改变,由此可从荧光强度计算出溶液中铁离子的含量。因此,将本发明将荧光探针分子配成10-6 M的溶液,向探针分子溶液中定量加入配制好的Fe3+溶液,以371 nm光激发即能够监测到其荧光光谱的变化,而且,随着Fe3+浓度逐渐增大,荧光强度逐渐减弱,很好的监测了金属离子的浓度,表明本发明的探针对Fe3+有很好的灵敏度。
以上详细描述了本发明的优选实施方式,但是,本发明并不限于上述实施方式中的具体细节,在本发明的技术构思范围内,可以对本发明的技术方案进行多种等同变换,这些等同变换均属于本发明的保护范围。另外需要说明的是,在上述具体实施方式中所描述的各个具体技术特征,在不矛盾的情况下,可以通过任何合适的方式进行组合。为了避免不必要的重复,本发明对各种可能的组合方式不再另行说明。此外,本发明的各种不同的实施方式之间也可以进行任意组合,只要其不违背本发明的思想,其同样应当视为本发明所公开的内容。
Claims (3)
2.一种荧光探针化合物的制备方法,其特征在于,包括如下步骤:
无水无氧条件下,将对氯甲基苯甲醛与2,4-二甲基吡咯在过量二氯甲烷中溶解搅拌均匀,加入三氟乙酸反应2-4小时,加入2,3-二氯-5,6-二氰基苯琨(DDQ),搅拌1-2小时,加入三乙胺反应1-2小时,加入三氟化硼乙醚反应2-4小时,
其中,对氯甲基苯甲醛、2,4-二甲基吡咯、三氟乙酸、2,3-二氯-5,6-二氰基苯琨(DDQ)、三乙胺、三氟化硼乙醚的摩尔比为1:1.5-2.5:1.5-2.5:2-3:5-15:5-15;
然后,经加水、萃取、分液、干燥、抽滤、旋蒸、提纯后即得到荧光探针的化合物。
3.权利要求2所述方法制备的荧光探针化合物作为荧光探针在Fe3+检测中的应用。
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