CN117050019A - 一种亚锡离子荧光探针及其合成方法 - Google Patents
一种亚锡离子荧光探针及其合成方法 Download PDFInfo
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Abstract
本发明公开一种亚锡离子荧光探针,其结构式为:本发明还公开一种亚锡离子荧光探针的合成方法,包括以下步骤:S1、将2‑(4‑氨基苯基)‑5‑氨基苯并咪唑溶解于无水乙醇中,室温搅拌1h,得到预混液;S2、往步骤S1中预混液中滴加乙二醛,并将溶液在室温下搅拌1h,生成黄褐色沉淀;S3、将黄褐色沉淀进行过滤,再用无水乙醇对黄褐色沉淀进行洗涤,最后在室温下使其风干。本发明荧光探针对Sm2+能灵敏的识别,且抗其他金属离子的干扰。
Description
技术领域
本发明涉及离子检测领域,尤其涉及一种亚锡离子荧光探针及其合成方法。
背景技术
锡是人体不能缺乏的微量元素之一,是维持人生生理健康的必要条件。虽然简单的无机锡离子是无毒的,但是自然界中的细菌及微生物能将无机锡转化为高水溶性、高毒性的有机锡,在生物体内富集进入食物链,严重危害人类的健康。有机锡化物会危害生物体的中央神经系统,抑制胸腺及淋巴系统。作为人体正常生理活动所不可缺少的微量元素之一,在人的生长发育过程中亚锡离子的意义十分重大。大量充分的证据表明,亚锡离子能够有效限制癌细胞的产生,同时,它还能够刺激核酸和蛋白质的生物合成,从而提高细胞的新陈代谢能力。亚锡离子的作用不仅仅局限于此,它还可以调节神经系统,促进神经元的发育,保护神经细胞不受损害,从而改善人们的记忆力和思维能力。此外,亚锡离子还参与组成多种酶以及黄素酶的生物反应,从而达到增强人体内环境的稳定性的效果。亚锡离子的缺乏可能会导致生长不良和听力丧失,但亚锡离子(Sn 2+)过多积累造成对锌离子代谢干扰,会影响呼吸道和消化系统。而且亚锡离子是一种有毒物质,可在人体和动物组织中积累,过高浓度的亚锡离子甚至能阻碍人体的新陈代谢,不利于人体健康。亚锡离子可以对皮肤产生刺激作用,接触后会引起红肿和疼痛等不适症状。亚锡离子会通过呼吸道进入人体,导致呼吸道刺激和喉咙灼热感,严重的可能导致气管炎和支气管炎等呼吸系统疾病。人体大量接触或摄入亚锡离子会引起中毒,同时表现为恶心、腹泻、呕吐、头疼等症状,并可能导致肾肝功能损害。亚锡离子还可能对神经系统产生不良影响,引起失眠、头晕、记忆力降低等症状。因此,在环境和生物系统中,选择一种可靠和灵敏的分析方法,来识别和检测亚锡离子的存在显得格外重要。
目前,常用的检测亚锡离子的方法为原子发射光谱法、电化学法等,但这些方法存在成本高,操作方法复杂等缺陷。随着荧光探针相关研究的不断深入,荧光探针以响应敏捷、灵敏度高、准确性好、成本低廉等优点弥补了传统方法诸多不足,越来越受到诸多研究者的青睐。近年来,人们将主体-客体识别的相关原理和概念应用到重金属离子识别和检测的研究中,设计并合成了大量高灵敏度、高选择性的荧光金属离子探针,且取得了较好的应用效果。但相对其他金属离子探针,有关亚锡离子荧光探针文献报道相对较少,亚锡离子广泛存在于我们生活中,因此要寻求一个高效便利的方法实现对亚锡离子的检测。因此,亟需一种可定向检测的亚锡离子荧光探针。
发明内容
为了克服现有技术的不足,本发明的目的在于提供一种可定向检测的亚锡离子荧光探针。
本发明的目的采用以下技术方案实现:
一种亚锡离子荧光探针,其结构式为:
优选的,Sn2+为亚锡离子荧光探针的24~100eq。
本发明还提供一种亚锡离子荧光探针的合成方法,包括以下步骤:
S1、将2-(4-氨基苯基)-5-氨基苯并咪唑溶解于无水乙醇中,室温搅拌1h,得到预混液;
S2、往步骤S1中预混液中滴加乙二醛,并将溶液在室温下搅拌1h,生成黄褐色沉淀,反应方程式为:
S3、将黄褐色沉淀进行过滤,再用无水乙醇对黄褐色沉淀进行洗涤,最后在室温下使其风干。
优选的,乙二醇为质量分数40%的乙二醛。
优选的,2-(4-氨基苯基)-5-氨基苯并咪唑与乙二醛的物质的量之比为0.05:0.0199。
优选的,0.05mol 2-(4-氨基苯基)-5-氨基苯并咪唑溶解于200mL无水乙醇中。
与现有技术中的亚锡离子荧光探针相比,本发明亚锡离子荧光探针具有以下优点:
苯并咪唑中苯环的存在,使配体的共轭性增加,为π-π堆积等超分子作用的形成提供了可能,也有利于提高超分子配位聚合物的稳定性,苯并咪唑环的C=N原子与亚锡离子结合,形成稳定的金属络合物,使荧光探针对Sm2+能灵敏的识别,且抗其他金属离子的干扰。
附图说明
图1为本发明荧光探针的红光光谱图。
图2为本发明荧光探针的核磁共振氢谱图。
图3为日光下加入不同金属离子时荧光探针溶液的颜色变化图。
图4为紫外光加入不同金属离子时荧光探针溶液的颜色变化图。
图5为加入不同金属离子后荧光探针溶液的紫外-可见吸收光谱。
图6为加入不同金属离子后荧光探针溶液的荧光发射图。
图7为日光下加入不同浓度Sn2+时荧光探针溶液颜色变化图。
图8为紫外光下加入不同浓度Sn2+时荧光探针溶液颜色变化图。
图9为其它金属离子和Sn2+共存时荧光探针溶液的荧光强度。
具体实施方式
为使本发明解决的技术问题、采用的技术方案和达到的技术效果更加清楚,下面将对本发明实施方式的技术方案作进一步的详细描述。
本发明具体实施方式中的亚锡离子荧光探针的合成方法,包括以下步骤:
S1、将0.05mol 2-(4-氨基苯基)-5-氨基苯并咪唑溶解于200mL无水乙醇中,室温搅拌1h,得到预混液;
S2、往步骤S1中预混液中滴加0.0199mol 40%的乙二醛,并将溶液在室温下搅拌1h,生成黄褐色沉淀,反应方程式为:
S3、将黄褐色沉淀进行过滤,再用无水乙醇对黄褐色沉淀进行洗涤,最后在室温下使其风干。
采用KBr压片的方法对合成的荧光探针进行了红外光谱分析测试。如图1所示,其中σ=3422cm-1为N-H键的伸缩振动峰;σ=σ=3422cm-1、σ=3422cm-1为苯环骨架的伸缩振动;σ=802cm-1、669cm-1、518cm-1为芳环上C-H键面内弯曲振动。
以DMSO-d6为溶剂,以四甲基硅烷为内标,采用BrukerAvance600核磁共振波谱仪表征荧光探针结构,其核磁氢谱如图2所示。其中δ=12.56ppm,为苯并咪唑环的N-H质子信号;δ=8.5ppm,为HC═N上的与碳相连的氢原子;δ=6.66-7.77ppm,为HC═N上苯环上的多重质子氢信号;δ=5.28ppm,为与苯环相连的氨基(—NH2—)上的四个氢。
一、荧光探针的定向识别检测
用电子天平称取0.00235g荧光探针,并在500mL容量瓶中,用N-甲基吡咯烷酮(NMP)作为溶剂,配制成1.0×10-5mol·L-1的荧光探针溶液,使用的阳离子溶液为Ca2+、Co 2 +、Cu+、Cu2+、Fe3+、La3+、Li+、Mg2+、Mn2+、Ni2+、Sn2+、Zn2+溶液,根据所用试剂的相对分子量,用电子天平称取一定量的固体样品:无水氯化钙(0.0555g)、乙酸钴(0.0885g)、氯化亚铜(0.0495g)、无水硫酸铜(0.0798g)、乙酸铁(0.0955g)、乙酸镧(0.1580g)、氯化锂(0.0302g)、无水硫酸镁(0.0602g)、乙酸锰(0.0865g)、氯化镍(0.0648g)、无水氯化亚锡(Ⅱ)(0.0948g)及无水醋酸锌(0.0917g),分别用去离子水定容在500mL容量瓶中,配制成1.0×10-3mol·L-1的金属离子溶液。
a)、可视化检测
准备若干个4mL的透明玻璃样品瓶,然后用移液枪吸取2.0mL的荧光探针溶液于每一个样品瓶中备用。接着分别向样品瓶中滴入配制好的1.0mL(50eq,eq为当量)不同的金属离子溶液,其中一组不加入任何金属离子溶液,作为空白对照组,分别在试剂瓶上标记所加入阳离子。盖上样品瓶盖后,将其充分摇晃均匀并静置,静置时间为15分钟。接着,分别在正常日光和紫外分析仪下观察加入不同的金属离子溶液颜色的变化,以判断荧光探针对金属离子的选择性。在紫外分析仪下观察时,可以发现,在两种不同光的照射下,荧光探针溶液只有加入Sn2+时发生了明显的颜色变化。如图3所示,在正常日光照射下,荧光探针溶液颜色发生改变,从黄色变为白色。如图4所示,在紫外灯的照射下,加入Sn2+后荧光探针溶液发出了蓝绿色的荧光;除了Sn2+离子以外,其余金属离子的加入并没有使荧光探针溶液发生比较明显的颜色变化。
b)、紫外光谱分析
先用无水乙醇溶液清洗石英比色皿,待充分干燥后,向比色皿内滴入N-甲基吡咯烷酮(NMP)溶液,接着将其放入紫外线分光光度仪内,并接通测试软件,以进行扫描基线。基线扫描完毕后,将其中一个比色皿取出并洗净,在完全晾干后,往其中倒入混合好的待测溶液,然后继续扫描280nm-800nm波长范围内的分析液的紫外吸收光谱,以确定波长范围,再进行进一步的实验测试。往4mL的透明玻璃样品瓶分别滴入2.0mL的荧光探针溶液和1.0mLCa2+、Co 2+、Cu+、Cu2+、Fe3+、La3+、Li+、Mg2+、Mn2+、Ni2+、Sn2+、Zn2+离子溶液,溶解反应均匀静置后待测,静置时间为15分钟。最后,将石英比色皿洗净后,用擦镜纸擦干,依次滴入荧光探针溶液与不同金属离子的反应溶液,并在波长范围280-600nm内测定其吸光度。
紫外吸收光谱如图5所示,荧光探针在346nm处产生吸收峰,再向荧光探针反应溶液中加入对应各种测试的金属离子1.0mL后,荧光探针在346nm处的高能量带的吸光度发生改变。尤其是当向荧光探针中滴加Sn2+离子后,Sn2+可以引起紫外-可见吸收光谱的明显变化,使吸光度明显增大,说明在荧光探针的的C═N原子可能与亚锡离子结合,形成稳定的金属络合物。
c)、荧光光谱分析
固定激发光的波长为350nm,激发带带宽为3.0nm,发射带带宽为5.0nm,激发波长定为335.5nm,并于365.5~640.5nm范围内测试荧光探针加入不同金属离子后探针溶液的荧光发射光谱。然后往4mL的透明玻璃样品瓶中分别滴入2.5mL的荧光探针溶液和1.0mLCa2+、Co 2+、Cu+、Cu2+、Fe3+、La3+、Li+、Mg2+、Mn2+、Ni2+、Sn2+、Zn2+离子溶液,溶解反应均匀后静置待测,静置时间为15分钟。将荧光比色皿充分洗净后,用擦镜纸擦干,依次滴入荧光探针溶液(1.0×10-5mol·L-1)与不同金属离子(1.0×10-3mol·L-1)的反应溶液,在激发波长为335.5nm,激发带带宽为3.0nm,发射带带宽为5.0nm条件下,测定其荧光强度。
结果如图6所示,荧光探针在389nm处荧光强度最高。当向荧光探针中滴加Sn2+后,荧光探针在389nm处的荧光强度大大增加,并伴随明显的红移(Δλ=14nm)。同时,在加入Sn2+后,403nm处的荧光强度明显地增强。在其他金属离子和Sn2+离子中,Sn2+的紫外-可见吸收更明显。加入其他金属离子时,在环境光下几乎没有颜色变化,在紫外光照射下也没有明显的荧光效果。因此,本发明荧光探针可以有效地识别Sn2+。
二、Sn2+离子的浓度滴定实验
a)、可视化实验
用移液枪向其中加入2.5mL的配制好的1.0×10-5mol·L-1的荧光探针溶液,再用微量进样器吸取Sn2+溶液加入透明玻璃样品瓶中,加入的Sn2+浓度梯度为0~100eq。待溶液充分混合均匀后观察瓶内颜色变化现象,结果如图7和图8所示,Sn2+浓度越来越大,玻璃瓶中荧光探针反应溶液颜色由黄色逐渐变无色,颜色随浓度梯度变浅。随着加入的Sn2+的浓度越来越大,玻璃瓶中荧光探针反应溶液颜色由暗蓝色逐渐变为明亮的蓝绿色荧光,且荧光随浓度梯度变得更明亮,当量大于20eq时,荧光效果便于观察。
三、离子竞争实验
用电子天平称取0.00235g合成的荧光探针,并在500mL容量瓶中,用N-甲基吡咯烷酮(NMP)作为溶剂,配制成1.0×10-5mol·L-1的荧光探针溶液。
测试溶液即荧光探针溶液,用于本实验接下来的各种测试项目。首先测量荧光探针在加入Sn2+溶液后的荧光强度(对照组),接着在控制相同变量的情况下,在多种竞争性金属离子(包括Ca2+、Co2+、Cu+、Cu2+、Fe3+、La3+、Li+、Mg2+、Mn2+、Ni2+、Sn2+、Zn2+)(1.0×10-5mol·L-3,100eq)的存在下离子探针溶液荧光强度的变化,结果如图9所示,其他竞争性金属对Sn2 +的检测没有明显的干扰,荧光探针溶液的荧光强度没有受到太大的影响,足以用于定向识别和检测Sn2+。
四、苯并咪唑环的C=N
将本发明的荧光探针换为用N-甲基吡咯烷酮(NMP)作为溶剂,配制浓度1.0×10-5mol·L-1;加入Sn2+浓度为分别50eq、100eq,均没有明显的荧光现象,由此可见,本发明荧光探针的苯并咪唑环的C=N是导致特异性荧光现象的重要因素。
上述实施方式仅为本发明的部分优选实施方式,不能以此来限定本发明保护的范围,本领域的技术人员在本发明的基础上所做的任何非实质性的变化及替换均属于本发明所要求保护的范围。
Claims (6)
1.一种亚锡离子荧光探针,其特征在于,其结构式为:
2.根据权利要求1所述的亚锡离子荧光探针,其特征在于,所述Sn2+为亚锡离子荧光探针的24~100eq。
3.一种如权利要求1所述亚锡离子荧光探针的合成方法,其特征在于,包括以下步骤:
S1、将2-(4-氨基苯基)-5-氨基苯并咪唑溶解于无水乙醇中,室温搅拌1h,得到预混液;
S2、往步骤S1中所述预混液中滴加乙二醛,并将溶液在室温下搅拌1h,生成黄褐色沉淀,反应方程式为:
S3、将所述黄褐色沉淀进行过滤,再用无水乙醇对黄褐色沉淀进行洗涤,最后在室温下使其风干。
4.根据权利要求3所述亚锡离子荧光探针的合成方法,其特征在于,所述乙二醇为质量分数40%的乙二醛。
5.根据权利要求4所述亚锡离子荧光探针的合成方法,其特征在于,所述2-(4-氨基苯基)-5-氨基苯并咪唑与乙二醛的物质的量之比为0.05:0.0199。
6.根据权利要求5所述亚锡离子荧光探针的合成方法,其特征在于,0.05mol所述2-(4-氨基苯基)-5-氨基苯并咪唑溶解于200mL无水乙醇中。
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CN105907387A (zh) * | 2016-04-22 | 2016-08-31 | 东华大学 | 一种利用罗丹明类荧光探针检测亚锡离子的方法 |
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