CN109053709B - 一种用于检测Al3+的荧光探针及试剂盒 - Google Patents
一种用于检测Al3+的荧光探针及试剂盒 Download PDFInfo
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Abstract
Description
技术领域
本发明属于荧光探针合成技术领域,涉及一种具有激发态分子内质子转移性质的Al3+荧光探针的合成,以及对溶液中Al3+的快速检测的应用。
背景技术
铝元素是地壳中含量仅次于氧和硅,居第三位,也是地壳中最丰富的金属元素。它广泛存在于自然水与大多数植物体内,可以通过食物和水进入人体体内。一个人平均日摄取Al3+的含量为3-10mg,而过度摄取Al3+可能会导致一些疾病,如胃肠道疾病、损害肝和肾功能、干扰钙代谢、帕金森综合症、阿尔茨海默综合症等。鉴于Al3+与人体疾病有着密切的关系,因此,对于Al3+的检测越来越引起化学与生物学工作者的研究兴趣。
与其他传统方法相比,人们越来越对荧光分析法产生兴趣,主要是由于荧光分析法具有更高的灵敏度、相对简便的仪器、更短的响应时间和实时监测等优点。近年来,一些Al3+荧光探针已经被陆续报道,但只有为数不多的ESIPT型Al3+荧光探针被报道。另外一方面,目前已报道的一些Al3+荧光探针的选择性不好,如不能很好的区分三价离子(Al3+、Cr3+和Fe3+)。本专利提供的方法可高效、灵敏的实现对Al3+的荧光检测,且简单易操作、成本低。本发明设计合成的这类黄酮染料衍生物具有结构简单,且易于合成的特点。
发明内容
本发明的目的在于提供一种用于检测Al3+的荧光探针及试剂盒,本发明的有益效果是本发明的荧光探针在甲醇溶液中,对水溶液中的Al3+有较好的荧光选择性、较高的灵敏度及较强的抗其他待测离子干扰的能力。
本发明所采用的技术方案是2-位为噻吩基团,荧光探针的分子结构式为:
其中R=-H,-CH3,-OCH3,-Cl,-Br。
进一步,荧光探针的工作液的浓度为10-5mol/L,溶剂为甲醇、乙醇或二甲基亚砜。
进一步,用所述荧光探针配置黄酮类衍生物探针试剂,在菌种瓶中放入10-4 mol/L至10-5mol/L范围内的探针试剂和一定浓度的待测试样,充分摇匀,并静置2min;最后在手提紫外灯的激发下,仔细观察所有菌种瓶中溶液的颜色,与铝离子浓度标准比色卡对照。
一种用于检测Al3+的荧光探针及试剂盒,试剂盒包括荧光探针和溶剂,其中荧光探针的分子结构式为:
其中R=-H,-CH3,-OCH3,-Cl,-Br;荧光探针的工作液的浓度为10-5mol/L,溶剂为甲醇、乙醇或二甲基亚砜。
附图说明
图1为探针的甲醇溶液对不同浓度Al3+(水溶液)的荧光发射图;
图2为I462nm/I542nm的比值与Al3+浓度所作出的校正曲线;
图3为探针(10μM)对Al3+(50μM)和其他不同离子(100μM)的荧光响应图;
图4为在Al3+(50μM)存在的条件下,探针(10μM)对其他离子(100μM) 的响应的荧光强度(I462nm)柱状图;
图5为探针与Al3+的Job-plot曲线(控制探针与Al3+的总浓度为50μM)。
具体实施方式
下面结合具体实施方式对本发明进行详细说明。
本发明Al3+离子针对性检测的探针结构式如下:
通式(Ⅰ)中R=-H,-CH3,-OCH3,-Cl,-Br。所述荧光探针的工作液的浓度为10-5mol/L,溶剂为甲醇、乙醇或二甲基亚砜。专用检测试剂盒,包含通式(Ⅰ)所示化合物和溶剂。
测定Al3+离子含量的方法,包括如下步骤:
(1)制作标准曲线:
以360nm作为激发波长,测定一系列不同浓度的Al3+离子标准品的溶液在 462nm和542nm处的荧光强度,计算二者的比值,即I462nm/I542nm。以Al3+离子的浓度c为横坐标,荧光强度的比值I462nm/I542nm为纵坐标,绘制标准曲线;
(2)检测待测样品中Al3+离子的含量:
将所述步骤(1)所述Al3+离子标准品替换为待测样品,按照所述步骤(1) 所述方法检测所述待测样品在发射波长为462nm和542nm处的荧光强度,计算二者的比值,即I462nm/I542nm。将所述I462nm/I542nm的比值代入所述步骤(1)所得标准曲线,进而得到所述待测样品中Al3+离子的含量。
所述Al3+离子的标准储备溶液中,溶剂为水。
本发明提供的Al3+离子检测试剂盒,具有以下特点:
(1)包含黄酮类衍生物(通式(Ⅰ))的试剂盒为无色透明,青色荧光(手提紫外灯的激发下);而与Al3+离子反应后则可显示近无色,并且发出强烈的蓝绿色荧光(手提紫外灯的激发下)。
(2)反应速度快,数秒钟内即可显色。
(3)灵敏度高,Al3+离子浓度在≥5μM时,即可在手提紫外灯的激发下,用肉眼观察到明显的蓝绿色荧光。
(4)该显色反应仅在Al3+离子存在的条件下发生,其他常见的阳离子(包括Fe3+、Cr3 +)、阴离子、活性氧等物种基本不产生干扰。
本发明的探针试剂可针对涉及“环食药”案件中的Al3+离子进行检测,其具有操作简便,成本低,快速高效灵敏等优点,易于推广和应用。包含本发明荧光探针的试剂盒是一种性能优良、使用方便的Al3+离子检测设备,会成为公安一线部门办案的得力工具。为公安相关业务部门提供一例能够实现涉及“药食环”案件中 Al3+的快速检测的荧光探针与专用检测试剂盒,为打击该类违法犯罪提供技术支撑。
实施例1
Al3+离子浓度标准比色卡的配置方法如以下步骤所示。
(1)将菌种瓶清洗干净备用。
(2)由于实验的需要,预先配好不同浓度的Al3+离子,浓度由大到小,在菌种瓶上贴好标签纸。
(3)往配好的探针溶液(10-4mol/L至10-5mol/L)中滴加不同量的Al3+离子,并用手提紫外灯激发,仔细观察溶液的颜色,发现随着滴入的Al3+离子浓度逐渐增大,溶液的蓝绿色荧光逐渐增强,从而得到Al3+离子浓度标准比色卡。
实施例2
本发明的探针对Al3+离子有很好的选择性。
(1)预先将所要使用容量瓶洗干净(超声处理),容量瓶洗净烘干待用,将黄酮类染料与甲醇在容量瓶中配成浓度为10-3mol/L的母液,并用甲醇稀释成浓度为10-4mol/L至10- 5mol/L的溶液。
(2)金属离子溶液的配制:称取相应的无机盐,在水溶液中配制成实验所需要的浓度。密封保存好待用。
(3)将配好的探针溶液装入10个2mL菌种瓶中(菌种瓶是预先清洗干净的),往菌种瓶中逐一滴加配好的离子(如Al3+、Na+、Li+、K+、Mn2+、Mg2+、 Zn2+、Cu2+、Pb2+、Hg2+、Ni2+、Co2+、Cd2+、Sr2+、Cr3+、Fe3+、NO3 -、H2PO4 -、 Cl-、Br-、I-、ClO-),滴加完毕后摇晃均匀,仔细观察所有菌种瓶中溶液的颜色,与Al3+离子浓度标准比色卡比较,发现滴有Al3+离子的菌种瓶中溶液在手提紫外灯的激发下呈现出明显的蓝绿色荧光(图1为探针的甲醇溶液对不同浓度Al3+ (水溶液)的荧光发射图(Al3+最终浓度为1,2,3,4,5,10,12,14,16,18,20,30,50, 60,70,80,90,100,120,140,160,180和200μM)),而滴有其它离子溶液中在紫外灯的激发下,看不出明显的变化(除了Zn2+、Cd2+、Mg2+有些许的影响)(图 2为I462nm/I542nm的比值与Al3+浓度所作出的校正曲线)。
实施例3
式(Ⅰ)所示化合物用于各种干扰物种反应的荧光发射光谱
如图3所示,加入5当量的Al3+促使探针(式(Ⅰ))甲醇溶液体系在462nm 处发生了明显的荧光增强现象,而当加入10当量的其他离子时,在462nm处的荧光变化不大。但这里需要说明的是Zn2+、Cd2+和Mg2+在482nm处波长下有较弱的荧光增强。另外,值得一提的是该例探针对Fe3+、Cr3+几乎没有响应,从这一点来说,本体系所设计合成的探针要优于文献上一些已经报道的Al3+荧光探针 (它们并不能很好的区分三价离子),这也体现了本发明的优点。
在离子竞争性实验中,只有H2PO4 -会使溶液体系的荧光发生猝灭。从这一点而言,探针(通式(Ⅰ))是一个高选择性的Al3+荧光探针,可用于混合离子体系中Al3+的识别(图4)(图4为在Al3+(50μM)存在的条件下,探针(10μM) 对其他离子(100μM)的响应的荧光强度(I462nm)柱状图(0.blank;1.Na+;2.Li+; 3.K+;4.Mn2+;5.Mg2+;6.Zn2+;7.Cu2+;8.Pb2+;9.Hg2+;10.Ni2+;11.Co2+;12.Cd2+; 13.Sr2+;14.Cr3+;15.Fe3+;16.NO3 -;17.H2PO4 -;18.Cl-;19.Br-;20.I-;21.ClO-.))。
实施例4
式(Ⅰ)所示化合物对Al3+配位比的研究
固定探针与Al3+的总浓度为50μM,同时调节Al3+所占的比例(0.1-0.8)。以荧光强度对Al3+的浓度百分比作图得到图5,从图可以得到n=2,即探针与Al3+的结合比为1:2。
以上所述仅是对本发明的较佳实施方式而已,并非对本发明作任何形式上的限制,凡是依据本发明的技术实质对以上实施方式所做的任何简单修改,等同变化与修饰,均属于本发明技术方案的范围内。
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