CN112326644A - 基于Sip-Me/DMPS可逆反应的重金属离子指示剂及应用 - Google Patents
基于Sip-Me/DMPS可逆反应的重金属离子指示剂及应用 Download PDFInfo
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Abstract
本发明提供了一种基于Sip‑Me/DMPS可逆反应的重金属离子指示剂及应用,将硅吡罗红和2,3‑二巯基丙磺酸钠按照体积比为1:2混合室温反应,反应后以硅吡罗红为荧光团,二巯基为识别位点检测重金属离子。同时将吸收有硅吡罗红和2,3‑二巯基丙磺酸钠溶液的吸水弹作为指示剂,硅吡罗红和2,3‑二巯基丙磺酸钠反应使得荧光猝灭,再与重金属离子反应,形成配合物脱去二巯基丁二酸,从而使体系荧光恢复,进而能够检测汞离子,锌离子,镍离子,镉离子,铜离子和钴离子,六种重金属离子的存在。
Description
技术领域
本发明涉及重金属离子反应策略设计领域,具体涉及一种基于Sip-Me/DMPS可逆反应的重金属离子指示剂及应用。
背景技术
重金属离子不仅受到科学化学家、生物学家和环境科学家的高度关注,而且越来越受到公众的关注。尽管某些重金属离子在生命系统中起着重要作用,但它们毒性很大,并可能导致严重的环境和健康问题。例如,汞是毒性最高的重金属之一。它是生物的非必需有害元素。通常,汞为液态,在常温下可能会蒸发。如果土壤中的汞含量过高,则会使植物中的汞富集。植物产生毒性作用,如果它们通过食物链进入人体,会对人体功能产生有害影响,包括增加严重脑损伤,肾脏问题,免疫功能障碍和人体运动障碍的风险。锌是人体微量元素之一,但是,摄入过多的锌会导致急性锌中毒,并伴有胃肠道症状,例如呕吐和腹泻;吸入工厂锌雾可能有低烧和感冒样症状;慢性锌中毒可能有贫血的其他症状;动物实验可引起肝肾功能和免疫功能受损。同样的,镍是人体必需的生活元素,在人体中的含量极少。通常,成年人体内含有约10mg的镍,血液中的正常浓度为0.11μg的镍。在激素的作用和生物大分子的结构稳定性以及新陈代谢过程中,都涉及镍。但是,当与人体接触时,镍离子可通过毛孔和皮脂腺渗入皮肤。进入体内,引起皮肤刺激和炎症、瘙痒、丘疹或丘疹性水疱性皮炎和湿疹的临床表现,并伴有苔藓样变。一旦出现过敏症状,镍过敏就会无限期地持续下去。电子元件中常用的材料铜,同样会给人体带来伤害,当大量重金属铜残留在体内时,很容易给人体的内部器官增加负担,尤其是肝脏和胆囊。当这两个器官出现问题时,体内的新陈代谢将紊乱并发生肝硬化。钴是水中常见的污染物之一,当水中的钴离子浓度超过标准浓度时,会引起许多严重的健康问题,例如低血压,瘫痪,腹泻和骨骼缺损。它还会引起活细胞的基因突变。此外,放射性钴(例如60钴)也是重要的核污染物。与汞类似,镉(Cd)是对人体有害的元素。它在自然界中以复合状态存在,其含量非常低。镉污染环境后,镉会富集在生物体内,并通过食物链进入人体,从而引起慢性中毒。进入人体的镉在体内形成镉硫蛋白,通过血液到达全身,并选择性地积累在肾脏和肝脏中,损害肾小管,引起糖尿病,蛋白尿和氨基酸尿等症状,并增加尿钙和尿酸的排泄。慢性镉中毒主要影响肾脏。最典型的例子是疼痛疾病,这是日本著名的公共疾病。
目前常用的检测重金属离子的方法有,电感耦合等离子体发射光谱法(ICP-OES),荧光和比色传感器,表面增强拉曼光谱,比率计传感器,光电化学传感器,微机电传感器等方法。其中,荧光和比色传感器方法由于方便、快速、经济得到了广泛的应用。但是,目前大多数用于重金属离子检测的荧光小分子探针会生成不溶性的硫化物,不能排除体外,还有可能生成脂溶性的金属络合物,更容易进入细胞并分布到体内各处,造成更大毒性。而少数用于检测并解毒的探针,又由于其合成的复杂性,以及检测的单一性而不能够得到实际的应用。因此,设计一种快速对多种重金属离子进行检测和解毒的荧光策略的发明对环境和生命体是有巨大的实际应用价值。
发明内容
本发明提出了一种指示剂及硅吡罗红(Sip-Me)和2,3-二巯基丙磺酸钠(DMPS)可逆反应在检测重金属离子中的应用,解决了目前检测重金属的探针合成复杂,检测单一的问题。
实现本发明的技术方案是:
硅吡罗红和2,3-二巯基丙磺酸钠可逆反应在检测重金属离子中的应用,将硅吡罗红和2,3-二巯基丙磺酸钠按照体积比为1:2混合室温反应,反应后以硅吡罗红为荧光团,二巯基为识别位点检测重金属离子。
所述反应液使得荧光猝灭,之后加入重金属离子反应,体系荧光恢复。
所述重金属离子为汞离子,锌离子,镍离子,镉离子,铜离子和钴离子。
具体过程如下:
(1)配制pH =7.4、10 mM的PBS缓冲溶液;
(2)将硅吡罗红用乙腈溶解,配制2 mM的硅吡罗红储存液;配制4 mM的2,3-二巯基丙磺酸钠;
(3)向比色皿中加入2 mL的PBS缓冲溶液后,加入5 µL浓度为2 mM的硅吡罗红储存液,再加入5 µL 2,3-二巯基丙磺酸钠,进行荧光光谱测试;
(4)向2 mL的PBS缓冲体系中,加入5 µL硅吡罗红储存液和2,3-二巯基丙磺酸钠,分别加入不同浓度汞离子、锌离子、镍离子、镉离子、铜离子和钴离子,以625 nm光激发,进行荧光光谱测定。
所述步骤(3)中荧光强度减弱,步骤(4)中加入重金属离子后,荧光强度增加。
上述应用具体包括:
分别测试硅吡罗红和2,3-二巯基丙磺酸钠混合液加入重金属离子前后的紫外可见光谱和荧光光谱的变化,荧光的发射波长为652 nm;观察荧光图谱变化及其加入重金属汞离子,锌离子,镍离子,镉离子,铜离子和钴离子前后荧光的变化。
荧光光谱的变化为:以625 nm光激发时,逐渐加入不同浓度的汞离子,锌离子,镍离子,镉离子,铜离子和钴离子在652 nm处的荧光逐渐增强,并在某一浓度时达到最大值且保持不变。
反应机理如下:
本发明还可以利用上述可逆反应,制备一种检测重金属离子的指示剂,所述指示剂为吸收硅吡罗红和2,3-二巯基丙磺酸钠溶液的吸水弹。
将吸水弹加入到硅吡罗红溶液中,吸水弹吸水变成蓝色,显示红色荧光,之后加入2,3-二巯基丙磺酸钠溶液,吸水弹变成无色,,红色荧光淬灭,无色吸水弹置于含有重金属离子的水样中,无色吸水弹再次变蓝。
利用该颜色变化检测水中是否具有重金属离子。
将吸水弹加入到硅吡罗红和2,3-二巯基丙磺酸钠的混合溶液中,红色荧光淬灭,之后将吸水弹置于含有重金属离子的水样中,吸水弹变为蓝色,并恢复红色荧光。
本发明的有益效果是:
(1)以硅吡罗红为基本结构作为荧光基团,具有光稳定性好、量子产率高,硅吡罗红发射波长较长,能够广泛的应用到生物体内等;
(2)硅吡罗红具有较低的pKa值,对羟基阴离子的亲电活性增强。同时,又由于巯基比羟基表现出更强的亲核性,它的荧光可以更容易被硫醇淬灭;
(3)本发明中的策略设计简单,能快速检测环境和生物体内的汞离子,锌离子,镍离子,镉离子,铜离子和钴离子,灵敏度高,反应迅速,不引入新的污染物,并且可对检测出来的重金属离子直接进行脱毒处理,保护产生有毒有害的物质。这实际检测重金属离子提供了一个快速安全有效的方法;
(4)本发明还可以利用该可逆反应,制备一种重金属离子指示剂,利用硅吡罗红和2,3-二巯基丙磺酸钠溶液的吸水弹的颜色变化,能够直观的看出,水样中是否含有重金属离子。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。
图1是在PBS缓冲(10 mM,pH = 7.4)体系中,5 µM硅吡罗红和10 µM 2,3-二巯基丙磺酸钠反应后混合液的荧光光谱图。
图2是在PBS缓冲(10 mM,pH = 7.4)体系中,含5 µM硅吡罗红和10 µM2,3-二巯基丙磺酸钠的检测液与不同浓度汞离子(0-15 µM)反应的荧光光谱图。
图3是在PBS缓冲(10 mM,pH = 7.4)体系中,含5 µM硅吡罗红和10 µM2,3-二巯基丙磺酸钠的检测液与不同浓度锌离子(0-15 µM)反应的荧光光谱图。
图4是在PBS缓冲(10 mM,pH = 7.4)体系中,含5 µM硅吡罗红和10 µM 2,3-二巯基丙磺酸钠的检测液与不同浓度镍离子(0-15 µM)反应的荧光光谱图。
图5是在PBS缓冲(10 mM,pH = 7.4)体系中,含5 µM硅吡罗红和10 µM 2,3-二巯基丙磺酸钠的检测液与不同浓度镉离子(0-15 µM)反应的荧光光谱图。
图6是在PBS缓冲(10 mM,pH = 7.4)体系中,含5 µM硅吡罗红和10 µM 2,3-二巯基丙磺酸钠的检测液与不同浓度铜离子(0-15 µM)反应的荧光光谱图。
图7是在PBS缓冲(10 mM,pH = 7.4)体系中,含5 µM硅吡罗红和10 µM 2,3-二巯基丙磺酸钠的检测液与不同浓度钴离子(0-15 µM)反应的荧光光谱图。
图8是在PBS缓冲(10 mM,pH = 7.4)体系中。含5 µM硅吡罗红和10 µM 2,3-二巯基丙磺酸钠的检测液与浓度范围在(0-15mM)的汞离子反应时,在652 nm处的荧光强度与汞离子浓度的变化趋势图。
图9是在PBS缓冲(10 mM,pH = 7.4)体系中。含5 µM硅吡罗红和10 µM 2,3-二巯基丙磺酸钠的检测液探针与浓度范围在(0-15mM)的锌离子反应时,在652 nm处的荧光强度与汞离子浓度的变化趋势图。
图10是在PBS缓冲(10 mM,pH = 7.4)体系中。含5 µM硅吡罗红和10 µM 2,3-二巯基丙磺酸钠的检测液与浓度范围在(0-15mM)的镍离子反应时,在652 nm处的荧光强度与汞离子浓度的变化趋势图。
图11是在PBS缓冲(10 mM,pH = 7.4)体系中。含5 µM硅吡罗红和10 µM 2,3-二巯基丙磺酸钠的检测液与浓度范围在(0-15mM)的镉离子反应时,在652 nm处的荧光强度与汞离子浓度的变化趋势图。
图12是在PBS缓冲(10 mM,pH = 7.4)体系中。含5 µM硅吡罗红和10 µM 2,3-二巯基丙磺酸钠的检测液与浓度范围在(0-15mM)的铜离子反应时,在652 nm处的荧光强度与汞离子浓度的变化趋势图。
图13是在PBS缓冲(10 mM,pH = 7.4)体系中。含5 µM硅吡罗红和10 µM 2,3-二巯基丙磺酸钠的检测液与浓度范围在(0-15mM)的钴离子反应时,在652 nm处的荧光强度与汞离子浓度的变化趋势图。
图14是在PBS缓冲(10 mM,pH = 7.4)体系中。含5 µM硅吡罗红和10 µM 2,3-二巯基丙磺酸钠的检测液与浓度范围在(0-6 µM)的汞离子反应时,在652 nm处的荧光强度的对数与汞离子浓度的线性关系图。
图15是在PBS缓冲(10 mM,pH = 7.4)体系中。含5 µM硅吡罗红和10 µM 2,3-二巯基丙磺酸钠的检测液与浓度范围在(0-10 µM)的锌离子反应时,在652 nm处的荧光强度的对数与锌离子浓度的线性关系图。
图16是在PBS缓冲(10 mM,pH = 7.4)体系中。含5 µM硅吡罗红和10 µM 2,3-二巯基丙磺酸钠的检测液与浓度范围在(0-5 µM)的镍离子反应时,在652 nm处的荧光强度的对数与镍离子浓度的线性关系图。
图17是在PBS缓冲(10 mM,pH = 7.4)体系中。含5 µM硅吡罗红和10 µM 2,3-二巯基丙磺酸钠的检测液与浓度范围在(0-7 µM)的镉离子反应时,在652 nm处的荧光强度的对数与镉离子浓度的线性关系图。
图18是在PBS缓冲(10 mM,pH = 7.4)体系中。含5 µM硅吡罗红和10 µM 2,3-二巯基丙磺酸钠的检测液与浓度范围在(0-3 µM)的铜离子反应时,在652 nm处的荧光强度的对数与铜离子浓度的线性关系图。
图19是在PBS缓冲(10 mM,pH = 7.4)体系中。含5 µM硅吡罗红和10 µM 2,3-二巯基丙磺酸钠的检测液与浓度范围在(0-4 µM)的钴离子反应时,在652 nm处的荧光强度的对数与钴离子浓度的线性关系图。
图20是用MTT比色法,评估在单独检测液,单独汞离子,以及汞离子和探针的混合物中HL-7702细胞的细胞活性程度。
图21是含有硅吡罗红、硅吡罗红+DMPS以及硅吡罗红+DMPS+Hg2+的吸水弹的颜色以及荧光变化。
图22是不同重金属离子的吸水弹的荧光变化。
图23为不同浓度汞离子水样对吸水弹的荧光变化图。
具体实施方式
下面将结合本发明实施例,对本发明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付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。
1.硅吡罗红和2,3-二巯基丙磺酸钠反应的荧光强度变化。
配制pH =7.4的PBS (10 mM)缓冲溶液;称取硅吡罗红,用乙腈溶解,准确配制2 mM的探针储存液;配制4 mM的2,3-二巯基丙磺酸钠。向比色皿中加入2 mL的PBS缓冲溶液后,加入5 µL浓度为2 mM的硅吡罗红储存液,再加入5 µL 2,3-二巯基丙磺酸钠,进行荧光光谱测试。如图1所示,该探针发射波长为652 nm,加入2,3-二巯基丙磺酸钠荧光强度减弱。
2.与汞离子,锌离子,镍离子,镉离子,铜离子和钴离子反应的荧光强度变化。
配制pH =7.4的PBS (10 mM)缓冲溶液;配制检测液,准确配制含2 mM硅吡罗红和4mM 2,3-二巯基丙磺酸钠的检测液;分别配制2 mM的汞离子,锌离子,镍离子,镉离子,铜离子和钴离子。向比色皿中加入2 mL的PBS缓冲溶液后,加入5 µL浓度为2 mM的探针储存液,再加入10 µL 汞离子,锌离子,镍离子,镉离子,铜离子和钴离子,进行荧光光谱测试。如图2-7所示,该探针发射波长为652nm,加入上述重金属离子后荧光光谱曲线逐渐上升。
3. 探针与汞离子,锌离子,镍离子,镉离子,铜离子和钴离子反应的荧光强度随重金属离子浓度的变化。
向2 mL的PBS缓冲(10 mM,pH=7.4)体系中,加入5 µL浓度为含2 mM硅吡罗红和4mM 2,3-二巯基丙磺酸钠的检测液,再分别加入不同浓度汞离子,锌离子,镍离子,镉离子,铜离子和钴离子(0-15 µM),以625 nm光激发,进行荧光光谱测定。随着重金属离子浓度的增加,荧光强度逐渐增加。如图8-13所示。对荧光强度与重金属离子的浓度进行线性拟合,发现汞离子浓度范围为0-6 µM,锌离子浓度范围为0-10 µM,镍离子浓度范围为0-5 µM,镉离子浓度范围为0-7 µM,铜离子浓度范围为0-3 µM,钴离子浓度范围为0-4 µM时,荧光强度的对数与浓度呈现很好的线性关系,如图14-19所示,具有很高的灵敏度,可以应用于环境和生物体内中汞离子,锌离子,镍离子,镉离子,铜离子和钴离子的检测。
4.探针对汞离子的解毒检测。
将7702细胞接种于透明96孔板中,在37℃、5% CO2、饱和湿度的细胞培养箱中培养24 h,在细胞中孵育于不同浓度(25、50、100 μM)的检测液, 单独的汞离子(50、100、200 μM),以及汞离子和检测液的混合物,在汞离子和检测液混合物的情况下,7702细胞先用汞离子孵育1 h紧随其后用检测液治疗24 h,用MTT比色的方法评估细胞活性。如图20所示。
5. 指示剂
用作玩具的吸水弹用来从水样中提取重金属离子,本发明所用吸水弹为市面上常见的吸水弹,将珠子添加到Sip(硅吡罗红)的水溶液中时,珠子吸收水并变成蓝色,显示红色荧光。加入DMPS后,其变为无色,并且红色荧光被淬灭。将无色珠粒放入含有汞离子的水样中后,珠粒再次变蓝,并恢复了红色荧光(图21)。同样的效果也适用于铜,锌,镍,钴和镉离子(图22下面一排为红色)。以汞离子为例,将珠子添加到不同浓度的汞离子的水样中,红色荧光也得以恢复(图23下面一排为红色)。珠粒通过分散剂水将Sip,Sip-DMPS和重金属离子吸收到珠粒中,这使探针充当指示剂,指示水样品中含有重金属离子。珠粒充当从水样品中提取重金属离子的载体。该策略提供了一种有前景的净化水环境的方法。
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.Sip-Me/DMPS可逆反应在检测重金属离子中的应用,其特征在于:将硅吡罗红和2,3-二巯基丙磺酸钠按照体积比为1:2混合室温反应,反应后以硅吡罗红为荧光团,二巯基为识别位点检测重金属离子。
2.根据权利要求1所述的应用,其特征在于,所述反应液使得荧光猝灭,之后加入重金属离子反应,体系荧光恢复。
3.根据权利要求1所述的应用,其特征在于:所述重金属离子为汞离子、锌离子、镍离子、镉离子、铜离子或钴离子。
4.根据权利要求1所述的应用,其特征在于,具体过程如下:
(1)配制pH =7.4、10 mM的PBS缓冲溶液;
(2)将硅吡罗红用乙腈溶解,配制2 mM的硅吡罗红储存液;配制4 mM的2,3-二巯基丙磺酸钠;
(3)向比色皿中加入2 mL的PBS缓冲溶液后,加入5 µL浓度为2 mM的硅吡罗红储存液,再加入5 µL 2,3-二巯基丙磺酸钠,进行荧光光谱测试;
(4)向2 mL的PBS缓冲体系中,加入5 µL硅吡罗红储存液和2,3-二巯基丙磺酸钠,分别加入不同浓度汞离子、锌离子、镍离子、镉离子、铜离子和钴离子,以625 nm光激发,进行荧光光谱测定。
5.根据权利要求4所述的应用,其特征在于:所述步骤(3)中荧光强度减弱,步骤(4)中加入重金属离子后,荧光强度增加。
7.一种基于Sip-Me/DMPS可逆反应的检测重金属离子指示剂,其特征在于:所述指示剂为含有权利要求1所述的硅吡罗红和2,3-二巯基丙磺酸钠溶液的吸水弹,利用可逆反应检测重金属离子。
8.根据权利要求7所述的指示剂,其特征在于,将吸水弹加入到硅吡罗红溶液中,吸水弹吸水变成蓝色,之后加入2,3-二巯基丙磺酸钠溶液,吸水弹变成无色,无色吸水弹置于含有重金属离子的水样中,无色吸水弹再次变蓝。
9.根据权利要求7所述的指示剂,其特征在于:吸水弹变成蓝色后,显示红色荧光,变为无色后,红色荧光淬灭。
10.根据权利要求7或8所述的指示剂,其特征在于:将吸水弹加入到硅吡罗红和2,3-二巯基丙磺酸钠的混合溶液中,红色荧光淬灭,之后将吸水弹置于含有重金属离子的水样中,吸水弹变为蓝色,并恢复红色荧光。
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