CN105542745A - 一种检测汞离子的分子探针及其合成方法和应用 - Google Patents
一种检测汞离子的分子探针及其合成方法和应用 Download PDFInfo
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- 239000003068 molecular probe Substances 0.000 title claims abstract description 29
- 238000001308 synthesis method Methods 0.000 title claims abstract 3
- 239000000523 sample Substances 0.000 claims abstract description 26
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000001514 detection method Methods 0.000 claims abstract description 17
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 15
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- 125000000217 alkyl group Chemical group 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
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- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 description 2
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Abstract
本发明公开了一种检测汞离子的分子探针及其合成方法和应用，属于化学分析检测技术领域。该探针由联吡啶衍物及异硫氰根与金属钌中心原子经过配位反应得到。该探针结构通式如下：其中n为具为0至18的整数，磷酸烷基连接联吡啶环的4、5、4′、5′位。该探针分子对汞离子的选择性和灵敏度高，响应速度快，响应范围为0.1–25μmol·L-1，检测限为0.015μmol·L-1。该探针可用于水体、土壤以及生物体内汞离子的检测。
Description
技术领域
本发明属于化学分析检测技术领域，具体涉及一种裸眼及比色法检测汞离子的分子探针及其制备方法和在检测汞离子方面的应用。
背景技术
汞离子(Hg2+)是一种高毒性的重金属离子。汞能导致一系列的严重病症的产生，包括脑损伤、肾功能衰竭、认知与运动障碍等。工业中产生的含汞排放物在自然界中会被各种动植物吸收，并产生剧毒性的甲基汞在食物链中富集。如果被人摄入后，甲基汞能通过人血脑屏障，然后直接作用于我们的中枢神经系统，对人体造成巨大的伤害。所以开发高灵敏、高选择检测汞离子的方法对环境保护是非常必要的。
传统的检测汞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以及气相色谱法等。但这些方法一般都涉及复杂繁琐的样品处理过程、昂贵的精密仪器而且需要较专业的操作。而基于光学分子探针的比色法在检测汞离子中具有样品处理简洁、成本低廉及操作简便快速等优点，近年来得到了发展与利用。
汞离子具有较强的嗜硫特性，能与含有孤对电子的硫原子发生结合或反应。比如联吡啶钌染料(如常见的N3，N719等)具有强的可见区吸收和优良的光伏性能，已作为敏化剂广泛应用于DSSCs中。联吡啶钌染料的吸收光谱特点也使其成为了一种潜在的有效比色法检测探针(PalomaresE.,VilarR.,DurrantJ.R.,Chem.Commun.,2004,40,362；HaoY.,XiongD.,WangL.,etal.,Talanta,2013,115,253.)。另外，目前报导的汞离子分子探针在还存在水溶性不好的缺点。基于此，设计一种以选用异硫氰根作为汞离子的识别基团，联吡啶钌作为生色团的水溶性比色法分子探针为目前实际应用所急需。
发明内容
对于上述情况，本发明的目的是提供一种高选择性和高灵敏度且水溶性好、性能稳定的新型汞离子分子探针；另一目的在于提供该探针的合成方法及其检测方法。
为实现本发明目的，本发明技术方案如下：
所述检测汞离子的分子探针，结构通式如下：
其中n为0至18的整数，磷酸烷基连接联吡啶环的4、4′或5、5′位。优选：n为1至3的整数，磷酸烷基联接联吡啶环的4、4′或5、5′位。
进一步优选为：
其合成方法具体如下：
将官能团化的联吡啶与三氯化钌在有机溶剂中回流反应，生成二氯二(二联吡啶)合钌衍生物，然后将得到的二氯二(二联吡啶)合钌衍生物与异硫氰化物在极性溶剂中回流反应，加入丙酮或乙醚沉淀产物，将沉淀与强酸回流反应，减压蒸馏除去溶剂后分离纯化得到探针分子化合物。
所述官能团化的联吡啶的结构如为：
其中：R1、R2各自独立选自H或1至18个碳原子的烷基链中的任一种，n为0至18的整数，磷酸烷基联接联吡啶环的4、4′或5、5′位。优选：R1、R2各自独立为H或1至3个碳原子的烷基链中的任一种，n为0至3的整数，磷酸烷基联接联吡啶环的4、4′或5、5′位。更优选：R1、R2各自独立为H，n为1，磷酸烷基联接联吡啶环的4、4′位。
有机溶剂为溴苯、邻二氯苯、N,N-二甲基甲酰胺或N-甲基吡咯烷酮。
异硫氰化物为异硫氰化钾或异硫氰化钠。
极性溶剂为甲醇、乙醇、四氢呋喃、水中的一种或几种。
强酸为盐酸、氢溴酸、氢碘酸、硫酸或磷酸中的一种或几种。
上述方法中优选强酸回流反应时的质量浓度不低于20％。
上述方法中官能团化的联吡啶与三氯化钌在有机溶剂中的回流反应时间优选1-24h。
上述方法中二氯二(二联吡啶)合钌衍生物与异硫氰化物的回流反应时间优选2-24h。
上述方法中强酸回流反应优选2-24h。
上述方法反应流程如下：
其中：R1、R2各自选自H或1至18个碳原子的烷基链中的任一种，n为0至18的整数，磷酸烷基连接联吡啶环的4、4或′5、5′位。
更进一步优选如下：
将2,2'-联吡啶-4,4'-二甲磷酸二乙酯与三氯化钌在N,N-二甲基甲酰胺中回流反应，生成中间产物二氯双(N,N’-2,2’-联吡啶-4,4’-二(甲基磷酸二乙酯))钌；然后将该产物与异硫氰化钾置于乙醇和水混合溶剂(1/1,v/v)中回流反应，加入丙酮沉淀产物，将沉淀与浓度为6mol·L-1的盐酸水溶液回流反应，分离纯化后得到探针分子化合物二异氰酸基双(N,N’-2,2’-联吡啶-4,4’-二(甲基磷酸))钌。反应流程如下：
利用该分子探针对水体、土壤或生物体系中汞离子进行定性和定量测定。
本发明原理在于：该探针的生色团为联吡啶钌的配合物，对汞离子的响应基团为异硫氰根。当加入汞离子时，汞离子与探针分子中的异硫氰基的硫离子配位结合，改变了探针分子原来的配体至金属电荷转移历程，从而使反应溶液呈现出从黄到红的显著颜色变化。可以很好地实现裸眼检测和比色法对汞离子的检测。
采用裸眼检测和比色法检测时，将该分子探针溶解于水缓冲体系溶液中，室温下便可以对汞离子进行测试。经测试将该分子探针对汞离子的检测浓度为0.1–25μmol·L-1，检测限为0.015μmol·L-1。
本发明分子探针具有如下特点和优点：具有良好的稳定性和光学性质，反应前最大吸收波长为514nm，呈现黄色；随着汞离子的加入，探针分子在514nm处的最大吸收值逐渐下降，同时在476nm处出现一个逐渐增强的新吸收峰，吸收光谱红移约为40nm，溶液的颜色由黄色变为红色。光学性能稳定，灵敏度较高，水溶性好，对汞离子识别能力强，响应速度较快，响应范围为0.1–25.0μmol·L-1，检测限低(0.015μM)，因此该类型探针可用于水体、土壤以及生物体系中汞离子的检测。并且本发明所述的探针分子原料易得，合成产率较高，达到67％以上。
附图说明
图1为本发明合成的分子探针的核磁共振氢谱；
图2为本发明50μmol·L-1分子探针在加入不同汞离子浓度后紫外吸收光谱图，从上至下加入的汞离子浓度分别为0、0.1、0.2、0.5、1、2、5、10、15、20、25、30、35、40、45、50μmol·L-1，溶液体系为10mMHEPES(pH7.4)的水溶液，横坐标为波长，纵坐标为吸光度；
图3为汞离子的浓度标准曲线图，即本发明分子探针50μmol·L-1，反应前后在514nm处紫外吸收的变化值和汞离子浓度的线性关系；横坐标为汞离子的浓度，纵坐标为紫外值的变化；
图4为本发明探针对汞离子选择性；即50μM本发明分子探针，加入100μmol·L-1不同阳离子(Ag+、Cd2+、Co2+、Cr3+、Cu2+、Fe2+、K+、Mg2+、Mn2+、Na+、Ni2+、Pd2+、Zn2+)后，514nm处紫外吸收的变化值；横坐标为测试的干扰离子，纵坐标为吸光度。
图5为本发明探针的稳定性实验；50μM本发明分子探针在514nm处紫外吸收值随时间的变化值；横坐标为测试时间，纵坐标为吸光度值，溶液体系为10mMHEPES(pH7.4)的水溶液。
具体实施方式
以下实施例用于说明本发明，但不用来限制本发明的范围。
实施例1：分子探针的合成
(1)取2,2'-联吡啶-4,4'-二甲磷酸二乙酯0.228g(0.5mmol)、三氯化钌62mg(0.30mmol)于10mLDMF中,，通入氮气，10min后，在遮光条件下加热回流反应6h。待反应结束后，溶液冷却至室温，加入二氯甲烷50mL，将沉淀过滤并用二氯甲烷洗涤3次。所得固体以丙酮:甲醇＝1:1的混合溶剂为洗脱剂过硅胶柱。得到红黑色固体二氯双(N,N’-2,2’-联吡啶-4,4’-二(甲基磷酸二乙酯))钌。取上述固体100mg(0.092mmol)与KSCN(85mg,0.87mmol)混合溶于水(5mL)和乙醇(5mL)的混合溶液中。氮气保护下，遮光回流反应8h。加入丙酮沉淀产物，过滤并用丙酮洗涤沉淀。将沉淀溶于10mL含有6mol·L-1HCl的水溶液，氮气保护下，遮光回流反应12h。反应结束后，旋转蒸发掉溶剂，固体溶于少量水，以水为洗脱剂过葡聚糖凝胶色谱柱(SephadexLH20)，得到黄色粉末固体(56mg，产率67％)。结构式如下：
1HNMR(500MHz,D2O)δ9.19(t,J＝5.8Hz,2H),8.39(s,2H),8.24(d,J＝10.0Hz,2H),7.74–7.69(m,2H),7.60–7.54(m,2H),7.01(d,J＝5.8Hz,2H),3.20(d,J＝20.1Hz,4H),2.95(d,J＝20.0Hz,4H).MS[ESI]:m/z,calcdfor[M-NCS]+847.94；found847.96.
实施例2：探针对汞离子的裸眼和比色法检测
将上述制得的分子探针溶解于10mMHEPES(pH7.4)的水溶液中，配制成50μmol·L-1的探针溶液。探针分子具有良好的水溶性，可在纯水体系中进行检测，无需加入其它有机溶剂辅助溶解。在3mL的比色皿中加入2mL配制的50μmol·L-1的探针溶液，然后分别加入不同浓度的Hg2+(氯化汞)后均匀混合，测试其紫外光谱，结果如图2所示。以溶液在514nm处吸收的变化值对Hg2+浓度作图，Hg2+浓度在0.1–25.0μmol·L-1范围内时，两者之间呈现良好的线性关系(图3)，能实现该浓度范围内Hg2+的定量检测，而且溶液的颜色发生显著变化，也适用于裸眼检测。并且此探针不受其它一些常见阳离子的影响，如：Ag+、Cd2+、Co2+、Cr3+、Cu2+、Fe2+、K+、Mg2+、Mn2+、Na+、Ni2+、Pd2+、Zn2+。在上述干扰离子存在的条件下，探针对含汞离子仍具有良好的选择性和灵敏度(图4)。该探针还具有良好的稳定性，在缓冲溶液中能存放三个月，其光谱性质仍未发生改变(图5)。
Claims (7)
1.一种检测汞离子的分子探针，其特征在于，结构通式如下：
其中n为具为0至18的整数，磷酸烷基连接联吡啶环的4、4′或5、5′位。
2.如权利要求1所述的检测汞离子的分子探针，其特征在于，n为1至3的整数，磷酸烷基连接联吡啶环的4、4′或5、5′位。
3.如权利要求1所述的检测汞离子的分子探针，其特征在于，n为1，磷酸烷基连接联吡啶环的4、4′位。
4.合成如权利要求1所述的检测汞离子分子探针的方法，其特征在于，通过如下方法实现：
将结构如下的官能团化联吡啶与三氯化钌在有机溶剂中回流反应，生成二氯二(二联吡啶)合钌衍生物，然后将得到的二氯二(二联吡啶)合钌衍生物与异硫氰化物在极性溶剂中回流反应，加入丙酮或乙醚沉淀产物，将沉淀与强酸回流反应，减压蒸馏除去溶剂后分离纯化得到探针分子化合物；
其中：R1、R2各自选自H或1至18个碳原子的烷基链中的任一种，n为0至18的整数，磷酸烷基连接联吡啶环的4、4′或5、5′位；
有机溶剂为溴苯、邻二氯苯、N,N-二甲基甲酰胺或N-甲基吡咯烷酮；异硫氰化物为异硫氰化钾或异硫氰化钠；
极性溶剂为甲醇、乙醇、四氢呋喃、水中的一种或几种；
强酸为盐酸、氢溴酸、氢碘酸、硫酸或磷酸中的一种或几种。
5.如权利要求4所述的检测汞离子分子探针的合成方法，其特征在于，官能团化联吡啶取代基选：R1、R2各自独立为H，n为1，磷酸烷基联接联吡啶环的4、4′位。
6.如权利要求1-3其中之一所述的检测汞离子分子探针的应用，其特征在于，利用该分子探针对水体、土壤或生物体系中汞离子进行定性或定量测定。
7.根据权利要求6所述的检测汞离子分子探针的应用，其特征在于，将分子探针溶解于水相缓冲溶液中，采用比色法检测或裸眼对汞离子进行检测。
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