CN108456514B - 一种检测汞离子的荧光素类荧光探针及其制备方法和应用 - Google Patents
一种检测汞离子的荧光素类荧光探针及其制备方法和应用 Download PDFInfo
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Abstract
本发明涉及一种检测汞离子的荧光素类荧光探针及其制备方法和应用，荧光探针的结构式为：
制备方法包括：将荧光素溶于溶剂中，滴加水合肼反应，除去溶剂及未反应的水合肼，萃取，干燥，抽滤，旋干，得荧光素酰肼；将4‑苯基‑3‑硫代氨基脲溶于溶剂中，加入缚酸剂，在氮气保护下，滴加三聚氯氰溶液，搅拌，旋干，重结晶，干燥，得到PCF；荧光素酰肼溶于溶剂中，加入缚酸剂，氮气保护下，滴加PCF的溶液反应，冷却，过滤，旋干，分离，干燥，即得。本发明荧光素类荧光探针是通过三嗪环为桥与罗丹明酰肼反应所得，对汞离子有很好的选择性，在污水处理应用方面具有较好的使用效果；制备方法简单、收率高、成本低，应用前景良好。
Description
技术领域
本发明属于荧光探针材料及其制备和应用领域，特别涉及一种检测汞离子的荧光素类荧光探针及其制备方法和应用。
背景技术
汞离子是一种剧毒非必需元素，汞可以通过许多途径排放到环境中，例如空气、水体循环以及土壤，并继而增加人类健康被严重威胁的可能性。汞的毒性作用体现在多方面，汞进入体内后，皆被转化为二价汞离子，且以此种化学状态发挥毒性作用。在水生环境中，经过微生物的催化作用，无机汞可以转化为亲脂性的有机汞，这种转化可使汞在食物链中更易发生富集，进而由食物链进入人体后导致汞中毒。汞在体外与硫化物具有高亲和性，两者易发生化学反应生成难溶的硫化汞；汞进入生物体内后，也有类似的特性，与体内的巯基(-SH)同样具有很强的亲和性，易与其结合形成硫醇盐。在体内含巯基最多的是蛋白质，如脑的灰质部分的巯基含量最多，因此汞也就最易积存在大脑中，引起以神经损害为主的疾病。当前，常见的汞元素检测手段主要是原子吸收/发射光谱法、气相色谱法、核磁共振、X射线荧光光谱法、电感耦合等离子体-质谱、电化学方法(如阳极溶出伏安法、氧化还原电位法等)、比色法(如传统的双硫腙法)。传统的测试手段繁琐和设备昂贵而又不能进行连续的监控。在这种情况下传统的技术已经不能满足，我们迫切需要寻找其他的检测手段。在最近十几年，发现荧光探针检测法具有便捷性好，选择性、灵敏度高的优点，并且在临床生物化学、分析化学、环境方面也得到广泛应用。
申请人申请的中国专利“检测汞离子的反应型荧光素类荧光探针及其制备与应用”，在水溶液中，使用荧光光谱法，在激发波长为445nm，检测发射波长为512nm，检测汞离子的浓度在0.01-1nM的范围达到一个很好地线性，检测限为0.86nm，采用荧光探针法检测汞离子溶液，可实现对汞离子的实时和快速的检测，在环境检测方面有较好的应用前景。中国专利201310163699.9“汞离子荧光传感器及其合成方法和应用”，以罗丹明B和水合肼为原料反应生成罗丹明·酰胺，然后加入异氰酸酯反应合成汞离子的荧光传感器；中国专利201410029789.3“一种用于检测水环境中金属离子含量的有机化合物及其应用”，以N-[2-(N’N’-二(烷基巯乙基)氨基苯氧乙基]-N-烷基巯乙基-2-烷氧基苯胺作为离子络合体，适用于各种环境中金属离子浓度的连续检测，尤其对汞离子的检测。
发明内容
本发明所要解决的技术问题是提供一种检测汞离子的荧光素类荧光探针及其制备方法和应用，荧光素类荧光探针是通过三嗪环为桥与罗丹明酰肼反应所得，对汞离子有很好的选择性，在污水处理应用方面具有较好的使用效果；制备方法简单、收率高、成本低，应用前景良好。
本发明的一种检测汞离子的荧光素类荧光探针，其特征在于，所述荧光探针的结构式为：
本发明的一种检测汞离子的荧光素类荧光探针的制备方法，具体步骤为：
(1)将荧光素2-(6-羟基-3-氧代-3H-呫吨-9-基)苯甲酸溶于溶剂中，得到荧光素溶液，滴加水合肼反应，除去溶剂及未反应的水合肼，得到粗产物荧光素酰肼，萃取，干燥，抽滤，旋干，得荧光素酰肼，其中荧光素与水合肼的摩尔比为1:4-6，荧光素溶液的浓度为0.1-0.3mmol/mL；
(2)将4-苯基-3-硫代氨基脲溶于溶剂中，得到4-苯基-3-硫代氨基脲溶液，加入缚酸剂，在氮气保护下，滴加三聚氯氰溶液(约30～60min滴加完毕)，搅拌，旋干，重结晶，干燥，得到PCF，其中三聚氯氰、缚酸剂和4-苯基-3-硫代氨基脲的摩尔比为1～1.2:2～2.5:1～1.2，PCF的结构式为
(3)将步骤(1)中荧光素酰肼溶于溶剂中，得到荧光素酰肼溶液，加入缚酸剂，氮气保护下，滴加步骤(2)中PCF的溶液(溶剂为THF)反应，冷却，过滤，旋干，分离，干燥，得到荧光素类荧光探针PCFT，其中PCF、缚酸剂与荧光素酰肼的摩尔比为1～1.2:2～2.5:1～1.2，荧光素酰肼溶液的浓度为0.3-0.5mmol/mL。
所述步骤(1)中荧光素的结构为：
所述步骤(1)中溶剂为无水乙醇。
所述步骤(1)中反应温度为78～80℃，反应时间为8～9h(优选9h)。
所述步骤(1)中水合肼的规格为98～99wt％；荧光素酰肼的质量百分比浓度为98～99％。
所述步骤(1)中萃取是在二氯甲烷/水体系中进行的。
所述步骤(2)、(3)中溶剂均为无水THF；缚酸剂均为碳酸钾。
所述步骤(2)中滴加三聚氯氰溶液是在冰水浴(0～5℃)条件下进行的；三聚氯氰溶液的溶剂为THF。
所述步骤(2)中搅拌时间为3～7h(优选7h)；重结晶是用乙醇。
所述步骤(3)中反应温度为20～50℃，反应时间为10～12h。
所述步骤(3)中分离为柱层析分离，柱层析分离是用体积比为10:1的三氯甲烷和乙醇。
本发明的一种检测汞离子的荧光素类荧光探针用于溶液中汞离子的检测。
本发明荧光探针PCFT自身荧光很弱，溶于DMF溶液后与汞离子混合，产生强烈的荧光，在汞离子的条件下，经过531nm可见光激发，553nm处的荧光信号显著增强，通过记录荧光强度即可检测汞离子的浓度。所述的荧光探针的荧光强度与汞离子浓度成良好的线性关系，定量检测汞离子浓度的线性范围为0.7-10μM，检测限为141nM。
本发明荧光探针PCFT的制备路线如下：
本发明荧光探针PCFT含有荧光素内酰胺基团和硫脲基团。其机理在于：由于硫脲中C＝S双键的异构化，加入离子后，分子的刚性改变和共轭性改变对于汞离子在荧光增强的同时颜色变化，颜色改变有利于提高探针的灵敏性。内酰胺基团羰基C＝O及三聚氯氰基团中的C＝N均可提供孤对电子参与汞离子的配位。配位后探针整体共轭性增强，有利于实现高灵敏度的荧光探针。
有益效果
(1)本发明荧光素类荧光探针是通过三嗪环为桥与罗丹明酰肼反应所得，对汞离子有很好的选择性，在污水处理应用方面具有较好的使用效果；
(2)本发明制备方法简单、收率高、成本低，应用前景良好。
附图说明
图1为实施例2中荧光探针加入汞离子前后的紫外变化图谱。
图2为实施例2中荧光探针的DMSO溶液(浓度为10μM)加入汞离子溶液(浓度为10μM)后荧光激发与发射图谱。
图3为实施例3中荧光探针在DMF溶液中(浓度为10μM)对不同的金属离子(浓度为10μM)选择干扰性检测的荧光响应图。
图4为实施例4中荧光探针在DMF溶液中(浓度为10μM)对不同的金属离子(浓度为10μM)选择性检测的荧光响应图(插图为：在365nm手提式紫外灯下的荧光选择性的图)。
图5为实施例5中荧光探针PCFT荧光发射光谱与汞离子的浓度关系图(插图为：在365nm紫外灯下探针加入不同浓度汞离子后的荧光图片)。
图6为实施例6中荧光探针在DMF溶液中(浓度为10μM)对汞离子的荧光光谱响应时间图。
具体实施方式
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
实施例1
(1)将1.40g(4.0mmol)荧光素(2-(6-羟基-3-氧代-3H-呫吨-9-基)苯甲酸)溶于20mL无水乙醇中，缓慢滴加过量的水合肼1g(20mmol)，78～80℃回流反应9h，旋转蒸发除去过量的溶剂及未反应的水合肼，得到粗产物荧光素酰肼，粗产物置于二氯甲烷/水体系中萃取，无水硫酸钠干燥，抽滤，旋干，得荧光素酰肼。
(2)将0.67g(4.0mmol)4-苯基-3-硫代氨基脲，1.10g(8.0mmol)K2CO3溶于20mL无水四氢呋喃中，在冰水浴中使温度达到0-5℃，然后用10mL四氢呋喃将0.73g(4.0mmol)99％三聚氯氰溶解，缓慢滴加到三口烧瓶中，搅拌1h后，混合液在0-5℃下搅拌，继续反应6h，旋干，无水乙醇重结晶，干燥，得到产物PCF。
(3)将1.40g(4.0mmol)荧光素酰肼，1.10g(8.0mmol)K2CO3加入到10mL无水THF中，并缓慢滴加10mL无水THF溶解2.10g(4.0mmol)PCF溶液到三口烧瓶中，用滴液漏斗将2.1g(4.0mmol)PCF溶液逐滴加入，升温至45℃，氮气氛围下反应12h后，冷却，过滤，旋转蒸发出去溶剂，硅胶柱层析分离，洗脱剂为：三氯甲烷/乙醇(10:1,v/v)得到目标产物为浅黄色固体粉末PCFT，产率为60％。mp:153-154℃。FTIR(KBr):v＝3198cm-1(-OH),2925cm-1(-NH-),2046cm-1(C＝S),1696cm-1(C＝O),1613cm-1,1454cm-1(ArH),1173cm-1,1107cm-1,987cm-1(三嗪).1H NMR(600MHz,DMSO,298K,δ/ppm):δ＝4.24(s,-NH-,1H),6.43(m,ArH,2H),6.65(m,ArH,2H),7.01-7.39(m,ArH,4H),7.45(s,ArH,1H),7.52(m,ArH,4H),7.83(m,ArH,2H),9.92(s,-NH-,1H),9.98(s,-OH-,2H),10.11(s,-NH-,1H),11.17(s,-NH-,1H).13C NMR(600MHz,DMSO,298K,δ/ppm):δ＝102.93,110.20,112.75,124.37,126.58,128.38,129.14,130.23,134.20,150.21,152.42,156.06,158.95,164.05,165.89,68.73(季C),174.96(C＝S).元素分析(C30H21ClN8O4S):理论值：C,57.65％；H,3.39％；N,17.93％；实验值:C,58.90％；H,4.04％；N,16.25％.PCFT的结构式如下：
实施例2
利用实施例1中荧光探针PCFT对溶液中汞离子进行检测，具体步骤如下：配置1×10-5M的汞离子待测液，应用实施例1中合成的荧光探针检测其中的汞离子的方法，具体步骤为：
步骤1：将实施例1合成的荧光探针溶于溶剂DMF中，利用溶剂DMF在100mL容量瓶内定容，得到浓度为1.0×10-3M的探针储备液；
步骤2：将高氯酸汞溶于去离子水中，利用溶剂去离子水在100mL容量瓶内定容，得到浓度为1.0×10-2M的汞离子储备液；移取浓度为1.0×10-2M的汞离子储备液于100mL容量瓶中，利用溶剂去离子水定容，得到浓度为1.0×10-3M的汞离子储备液；移取浓度为1.0×10-3M的汞离子储备液于100mL容量瓶中，利用溶剂去离子水定容，得到浓度为1.0×10-5M的汞离子标准溶液；
步骤3：分别移取0mL、0.1mL、0.2mL、0.3mL、0.4mL、0.5mL、0.6mL、0.7mL、0.8mL、0.9mL、1mL浓度为1.0×10-5M的汞离子标准溶液加入1mL步骤1中得到的探针储备液，利用溶剂DMF在10ml容量瓶中定容，静置5min后，通过荧光光谱法，检测531nm激发波长下的荧光强度，确定荧光强度与汞离子浓度呈现良好的线性关系。
图1表明：在DMF溶液中探针分子PCFH本身在～520nm处没有吸收峰，荧光探针与汞离子络合之后，在521nm处出现新的紫外吸收峰。
图2表明：在DMF溶液中探针分子PCFH本身在～553nm处没有荧光发射峰，探针与汞离子络合之后，在553nm处出现较强的发射峰。
实施例3
做Hg2+对实施例1中PCFH荧光探针的干扰实验，对常见的金属离子Al3+、Fe3+、Pb2+、Mn2+、Ba2+、Mg2+、Zn2+、Cr3+、Sn2+、Ni2+、Ca2+、Cd2+、Co2+、Cu2+进行干扰测试。将荧光探针PCFH溶于DMF溶剂中，配成10μM荧光探针溶液，分别将Al(NO3)2、FeCl3、Pb(NO3)2、MnCl2、BaCl2、MgSO4、Zn(NO3)2、Cr(NO3)2、SnCl2、Ni(NO3)2、CdCl2、CoCl2、CaCl2、CuSO4溶于DMF溶剂中，配成10μM的Al3+、Fe3+、Pb2+、Mn2+、Ba2+、Mg2+、Zn2+、Cr3+、Sn2+、Ni2+、Ca2+、Cd2+、Co2+、Cu2+金属离子溶液，进行选择干扰性检测。具体步骤为：分别将1mL10μM荧光探针溶液与1mL 10μM的Al3+、Fe3 +、Pb2+、Mn2+、Ba2+、Mg2+、Zn2+、Cr3+、Sn2+、Ni2+、Ca2+、Cd2+、Co2+、Cu2+离子溶液混合，在激发波长为521nm的条件下，检测发射波长为553nm的荧光强度；将1mL 10μM荧光探针溶液与0.5mL10μM汞离子溶液混合后，再分别与0.5mL 10μM的Al3+、Fe3+、Pb2+、Mn2+、Ba2+、Mg2+、Zn2+、Cr3+、Sn2+、Ni2+、Ca2+、Cd2+、Co2+、Cu2+离子溶液混合，在激发波长为521nm的条件下，检测发射波长分别为553nm的荧光强度(见图3)。实验结果表明：荧光探针中其他金属离子对Hg2+对干扰较小，只有Ca2+、Cd2+、Co2+、Cu2+导致了荧光强度的减弱。
实施例4
做PCFH荧光探针对Hg2+的选择性实验，对常见的金属离子Al3+、Fe3+、Pb2+、Mn2+、Ba2 +、Mg2+、Zn2+、Cr3+、Sn2+、Ni2+、Ca2+、Cd2+、Co2+、Cu2+进行选择性测试。将荧光探针PCFH溶于DMF溶剂中，配成10μM荧光探针溶液，分别将Al(NO3)2、FeCl3、Pb(NO3)2、MnCl2、BaCl2、MgSO4、Zn(NO3)2、Cr(NO3)2、SnCl2、Ni(NO3)2、CdCl2、CoCl2、CaCl2、CuSO4、Hg(ClO4)2溶于DMF溶剂中，配成10μM的Al3+、Fe3+、Pb2+、Mn2+、Ba2+、Mg2+、Zn2+、Cr3+、Sn2+、Ni2+、Ca2+、Cd2+、Co2+、Cu2+金属离子溶液，进行选择性检测。具体步骤为：分别将1mL 10μM荧光探针溶液与1mL 10μM的Al3+、Fe3 +、Pb2+、Mn2+、Ba2+、Mg2+、Zn2+、Cr3+、Sn2+、Ni2+、Ca2+、Cd2+、Co2+、Cu2+、Hg2+离子溶液混合，之后定容到10mL，在激发波长为521nm的条件下，检测发射波长为553nm的荧光强度(见图4)。实验结果表明：荧光探针PCFH对重金属Hg2+离子具有专一的选择性。
实施例5
做Hg2+对PCFH荧光探针的滴定实验，在DMF溶液中加入不同浓度汞离子，配体荧光探针(10μM)在531nm激发波长下测量荧光强度。为了测定加入不同Hg2+浓度时探针PCFT的荧光发射图谱，固定探针的浓度(10-5M)，加入0-3equiv.的Hg2+，如图4所示，在DMF溶液中探针在531nm处激发，在最大吸收波长551nm处荧光强度很低，然而随着Hg2+浓度的增加，在551nm处发射峰的荧光强度逐渐增强，当Hg2+加入量达到1×10-7M后，荧光强度开始增强，当离子加入量达到10μM后，荧光强度达到最大值并趋于稳定。Hg2+浓度在0.7～10μM时与探针PCFT的荧光强度呈现良好的线性关系，其检出限为141nM。
实施例6
做Hg2+对PCFH荧光探针的时间响应实验，具体步骤为：荧光探针在DMF溶液中(浓度为10μM)对加入10μM的汞离子溶液在531nm激发波长下测量荧光强度，如图6所示，当时间达到22min荧光强度达到最大值并趋于稳定，表明了荧光探针对重金属Hg2+离子具有较快的时间响应。
Claims (9)
1.一种检测汞离子的荧光素类荧光探针，其特征在于，所述荧光探针的结构式为：
2.一种检测汞离子的荧光素类荧光探针的制备方法，具体步骤为：
(1)将荧光素2-(6-羟基-3-氧代-3H-呫吨-9-基)苯甲酸溶于溶剂中，得到荧光素溶液，滴加水合肼反应，除去溶剂及未反应的水合肼，萃取，干燥，抽滤，旋干，得荧光素酰肼，其中，荧光素与水合肼的摩尔比为1:4-6，荧光素溶液的浓度为0.1-0.3mmol/mL；
(2)将4-苯基-3-硫代氨基脲溶于溶剂中，得到4-苯基-3-硫代氨基脲溶液，加入缚酸剂，在氮气保护下，滴加三聚氯氰溶液，搅拌，旋干，重结晶，干燥，得到PCF，其中，三聚氯氰、缚酸剂和4-苯基-3-硫代氨基脲的摩尔比为1～1.2:2～2.5:1～1.2，4-苯基-3-硫代氨基脲溶液的浓度为0.1-0.3mmol/mL，PCF的结构式为
(3)将步骤(1)中荧光素酰肼溶于溶剂中，得到荧光素酰肼溶液，加入缚酸剂，氮气保护下，滴加步骤(2)中PCF的溶液反应，冷却，过滤，旋干，分离，干燥，得到荧光素类荧光探针PCFT，其中PCF、缚酸剂与荧光素酰肼的摩尔比为1～1.2:2～2.5:1～1.2，荧光素酰肼溶液的浓度为0.3-0.5mmol/mL。
3.按照权利要求2所述的一种检测汞离子的荧光素类荧光探针的制备方法，其特征在于，所述步骤(1)中溶剂为无水乙醇。
4.按照权利要求2所述的一种检测汞离子的荧光素类荧光探针的制备方法，其特征在于，所述步骤(1)中反应温度为78～80℃，反应时间为8～9h。
5.按照权利要求2所述的一种检测汞离子的荧光素类荧光探针的制备方法，其特征在于，所述步骤(2)、(3)中溶剂均为无水THF；缚酸剂均为碳酸钾。
6.按照权利要求2所述的一种检测汞离子的荧光素类荧光探针的制备方法，其特征在于，所述步骤(2)中滴加三聚氯氰溶液是在冰水浴条件下进行的；三聚氯氰溶液的溶剂为THF。
7.按照权利要求2所述的一种检测汞离子的荧光素类荧光探针的制备方法，其特征在于，所述步骤(2)中搅拌时间为3～7h；重结晶是用乙醇。
8.按照权利要求2所述的一种检测汞离子的荧光素类荧光探针的制备方法，其特征在于，所述步骤(3)中反应温度为20～50℃，反应时间为10～12h。
9.一种如权利要求1所述的检测汞离子的荧光素类荧光探针的应用，其特征在于，用于溶液中汞离子的检测。
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