CN105606607B - 一种阳离子型有机铱(iii)配合物的比色型汞离子探针的制备方法及应用 - Google Patents
一种阳离子型有机铱(iii)配合物的比色型汞离子探针的制备方法及应用 Download PDFInfo
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Classifications
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- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
Abstract
本发明涉及一种比色型汞离子探针的制备方法和用途,该汞离子比色探针是一种含罗丹明基团的阳离子型有机铱(III)配合物,该比色探针操作便捷高效,只需要简单的制样处理既可现场检测,可以进行水相、泥土、生物等中的汞离子的定性、定量检测,在环境科学、分析化学等领域有着重要的应用价值。
Description
技术领域
本发明涉及汞离子定量检测技术领域,具体涉及一种阳离子型有机铱()配合物的比色型汞离子探针及其制备方法,以及在汞离子作用下该探针产生比色响应;进而达到检测的要求。
背景技术
汞广泛应用于工业、电子或电器产品、高温温度计中。在自然界的循环过程中很容易通过很多种方式富集并在在人体中累积,并且人体无法通过自身的代谢排出汞与汞离子。汞是一种具有很强生理毒性的重金属元素,具有神经毒性、肾脏毒性、免疫毒性、生殖毒性和其他的毒副作用。因此对汞的监测显得尤为重要。常规检测汞离子的方法有紫外分分光度法、高效液相色谱法、原子吸收/发射光谱法级冷原子荧光光谱法等;这些方法能够很好的检测出汞离子,但存在操作复杂,仪器昂贵、需要复杂的前期准备工作等缺点。由此可见,需要寻找一种能够现场实时检测汞离子的方法。
发明内容
本发明的目的旨在提供一种能够与汞离子特异结合的阳离子型有机铱()配合物用于汞离子检测。能够通过肉眼观察并且可以用紫外分光光度计定量分析,将在现场检测汞离子中有较好的应用前景。
本发明提供的阳离子型有机铱()配合物汞离子探针属于比色型小分子探针;定性检测是可以现场通过视觉判断且不需要借助其他仪器,定量检测时需要借助紫外分光光度计测定其标准曲线,然后分析汞离子浓度。该探针不需要在纯有机溶剂中进行,并且只需对待测样品进行简单的制样处理,具有操作方便、价格低廉、可以现场检测等优点。
为了实现上述目的,本发明所述的阳离子型有机铱()配合物对汞离子的定性定量检测,包括以下步骤:
阳离子型有机铱()配合物的合成
化合物1的制备:称取5.00 g(25.3 mmol)一水合邻菲啰啉和5.00 g(89.3 mmol)氢氧化钾于水中,加热至沸腾,搅拌下将13.00 g(82.3 mmol)高锰酸钾热的水溶液(150 mL水,70 ~ 80 °C)滴入。滴加完毕后,继续沸腾下搅拌10分钟,趁热过滤。虑液呈橘红色,冷却后用氯仿萃取三次,合并有机相,无水硫酸镁干燥,过滤,最后减压蒸除溶剂。丙酮重结晶,得淡黄色针状晶体产物,产率23.5 %(1.08 g)。
罗丹明B酰肼的制备:
将2.00 g 罗丹明B溶解在30 mL 乙醇溶液中,过量的水合肼1.80 mL加入到上述体系中,反应体系在80 下回流至粉红色消失。待反应结束后冷却至室温,倒入水中用乙酸乙酯萃取,合并有机相,无水硫酸钠干燥,过滤,最后减压蒸除溶剂。得淡粉色固体产物,产率86 %(1.83 g)。
化合物3的制备:
将0.36 g (1.99 mmol)化合物1,0.91 g(1.99 mmol)罗丹明B 酰肼,1.41 g(10mmol)五氧化二磷和20 mL甲醇的混合物加热回流30分钟。将反应物冷却至室温,倒入水中用二氯甲烷萃取,合并有机相,无水硫酸钠干燥,过滤,最后减压蒸除溶剂。得黄色固体产物3,产率76 %(0.94 g)。
化合物4的制备:
将1.6 g(1.3 mmol)化合物3和0.52 g(1.3 mmol)劳森试剂溶解于干燥的甲苯溶液中,将混合液在通有氩气的条件下回流4小时。将反应物冷却至室温,倒入水中用二氯甲烷萃取,合并有机相,无水硫酸钠干燥,过滤,最后减压蒸除溶剂。得棕黑色固体产物4,产率73 %(2.21g)。
铱的二聚物的制备:
将2.33 g(15 mmol)2-苯基吡啶和2.64 g(7.5 mmol)三水合三氯化铱加入到2-乙氧基乙醇/去离子水(体积比,3:1)的混合溶液中,然后在氩气气氛中加热24小时,得到的黄绿色固体产物,产率86 %(3.46 g),进行干燥之后可以直接用于下一步合成。
阳离子铱配合物的制备:
将铱(III)二聚物0.26 g(0.24 mmol),化合物4 0.30 g(0.48 mmol)的混合物加入到30 mL乙二醇中于150 ℃和氩气气氛下反应16小时。冷却至室温后加入10 mL 0.6mol/L 的六氟磷酸铵产生大量絮状沉淀。过滤,水洗,干燥得粗产物。进一步用硅胶柱提纯,淋洗液为二氯甲烷/乙腈(体积比,10:1)。红褐色固体产物,产率60.0 %(0.5 g)。
合成路线
附图说明
图1为本发明的比色探针的核磁共振图谱。
图2为本发明的比色探针的质谱图。
图3为各种金属离子对本发明的比色探针吸光度变化的干扰性对比数据图,加入后的其他金属离子的浓度均为1.0×10-4 mol/L,汞离子浓度为5.0×10-6 mol/L。
图4为本发明的比色探针的选择性示意图。
图5为不同汞离子浓度时,本发明的比色探针的紫外吸收光谱变化图。
图6为本发明的比色探针随汞离子浓度变化的吸光度变化值对应的拟合曲线。
具体实施方式
下面结合附图及具体实施例对本发明进一步详细说明
实施例1
本发明的比色探针的制备方法,包括以下步骤:
(1)化合物1的合成
称取5.00 g(25.3 mmol)一水合邻菲啰啉和5.00 g(89.3 mmol)氢氧化钾于水中,加热至沸腾,搅拌下将13.00 g (82.3 mmol) 高锰酸钾热的水溶液(150 mL水,70 ~ 80°C)滴入。滴加完毕后,继续沸腾下搅拌10分钟,趁热过滤。虑液呈橘红色,冷却后用氯仿萃取三次,合并有机相,用无水硫酸镁干燥,过滤,最后减压蒸除溶剂。丙酮重结晶,得淡黄色针状晶体产物,产率23.5 %(1.08 g)。
核磁共振化学位移值:1H NMR (400 MHz,CDCl3,ppm), δ:8.81 (m,2H,ArH),8.01(m,2H,ArH), 7.36 (m,2H,ArH)。
(2)罗丹明B酰肼的合成
将2.00 g罗丹明B溶解在30 mL乙醇溶液中,过量的水合肼1.80 mL加入到上述体系中,反应体系在80 ℃下回流至粉红色消失。待反应结束后冷却至室温,倒入水中用乙酸乙酯萃取,合并有机相,无水硫酸钠干燥,过滤,最后减压蒸除溶剂。得淡粉色固体产物,产率86 %(1.83 g)。
核磁共振化学位移值:1H NMR(400 MHz,CDCl3,ppm),δ:7.93(m,1H,ArH), 7.45(m,2H,ArH), 7.11(m,1H,ArH), 6.46(d,2H,xanthene-H),6.42(d,2H,xanthene-H),6.29(dd,2H,xanthene-H),3.61(s,2H,NH2),3.34(q,8H,NCH2CH3),1.17(t,12H,NCH2CH3)。
(3)化合物3的合成
将0.36 g(1.99 mmol)化合物1,0.91 g(1.99 mmol)罗丹明B酰肼,1.41 g(10mmol)五氧化二磷和20 mL甲醇的混合物加热回流30分钟。将反应物冷却至室温,倒入水中用二氯甲烷萃取,合并有机相,无水硫酸钠干燥,过滤,最后减压蒸除溶剂。得黄色固体产物,产率76 %(0.94 g)。
核磁共振化学位移值:1H NMR(400 MHz,CDCl3,ppm), δ: 8.63 (m,2H,ArH),8.03(d,1H,ArH),7.81(d,1H,ArH),7.71(d,1H,ArH),7.58(m,2H,ArH),7.27(m,2H,ArH),7.16(m,1H,ArH),6.59(d,2H,xanthene-H),6.41(d,2H,xanthene-H),6.29(dd,2H,xanthene-H),3.33(q,8H,NCH2CH3),1.15(t,12H,NCH2CH3)。
(4)化合物4的合成
将1.6 g(1.3 mmol)化合物3和0.52 g(1.3 mmol)劳森试剂溶解于干燥的甲苯溶液中,将混合液在通有氩气的条件下回流4小时。将反应物冷却至室温,倒入水中用二氯甲烷萃取,合并有机相,无水硫酸钠干燥,过滤,最后减压蒸除溶剂。得棕黑色固体产物,产率73%(2.21g)。
核磁共振化学位移值:1H NMR (400 MHz,CDCl3,ppm),δ: 8.63(m,2H,ArH),8.03(d,1H,ArH),7.81(d,1H,ArH),7.71(d,1H,ArH),7.58(m,2H,ArH),7.27(m,2H,ArH),7.16(m,1H,ArH),6.59(d,2H,xanthene-H),6.41(d,2H,xanthene-H),6.29 (dd,2H,xanthene-H),3.33(q,8H,NCH2CH3),1.15(t,12H,NCH2CH3)。
5)铱的二聚物的制备:
将2.33 g(15 mmol)2-苯基吡啶和2.64 g(7.5 mmol)三水合三氯化铱加入到2-乙氧基乙醇/去离子水(体积比,3:1)的混合溶液中,然后在氩气气氛中加热24小时,得到的黄绿色固体产物,产率86 %(3.46 g)进行干燥之后可以直接用于下一步合成。
(6)阳离子铱配合物的合成:
将铱(III)二聚物0.26 g(0.24 mmol),化合物3 0.30 g(0.48 mmol)的混合物加入到30 mL乙二醇中于150 °C和氩气气氛下反应16小时。冷却至室温后加入10 mL 0.6mol/L的六氟磷酸铵产生大量絮状沉淀。过滤,水洗,干燥得粗产物。进一步用硅胶柱提纯,淋洗液为二氯甲烷/乙腈(体积比,10:1)。红褐色固体产物,产率60.0 %(0.5 g)。
核磁共振化学位移值如图1所示:1H NMR(400 MHz,CDCl3,ppm),δ: 9.06(q,1H,ArH),8.25(q,1H,ArH),7.91(t,1H,ArH),7.72-7.79(m,5H,ArH),7.63-7.69(m,4H,ArH),7.51-7.60(m,2H,ArH),7.45(q,1H,ArH),7.17(d,1H,ArH),7.09-7.13(m,1H,ArH),6.99-7.05(q,3H,ArH),6.88-6.94(q,2H,ArH),6.72(t,2H,ArH),6.37(d,2H,ArH),6.26-6.32(m,4H,ArH),3.31(q,8H,NCH2CH3),1.13(t,12H,NCH2CH3)。
本发明比色探针的用途
实施例2
(1)本发明探针溶液的配制
称取0.0321 g(0.025 mmol)阳离子铱配合物,用DMF定容至100 mL,得到2.5×10-4 mol/L探针溶液。
(2)本发明探针的离子选择性测试
取0.1 mL的其他金属离子溶液(Na+、Ni2+、Al3+、Pb2+、Co2+、Ba2+、K+、Mn2+、Zn2+、Li+、Cr3+、Fe2+、Mg2+、Fe3+、Ca2+、Ag+、Cu2+)和汞离子溶液加入到24.4 mL PBS缓冲溶液中(50 mMpH=6.0)。其他金属离子浓度为2.5×10-2 mol/L,汞离子浓度为1.25×10-3 mol/L,然后加入0.5 mL上述探针溶液。滴加后摇晃均匀,静置半小时,仔细观察颜色,并且分别测定其吸光度变化值,得紫外吸收光谱变化图,如图2所示,其颜色变化如图3所示,测试结果表明:本发明的比色探针选择性好,其他离子没有明显影响。
(3)不同汞离子浓度下,本发明探针的吸光度测试
取0.1 mL的汞离子溶液加入到24.4 mL PBS缓冲溶液中(50 mM pH=6.0)。汞离子溶液浓度分别为1.25×10-4 mol/L,2.5×10-4 mol/L,3.75×10-4 mol/L,5×10-4 mol/L,6.25×10-4 mol/L,7.5×10-4 mol/L,8.75×10-4 mol/L,1×10-3 mol/L,1.125×10-3 mol/L,1.25×10-3 mol/L,1.5×10-3 mol/L,1.75×10-3 mol/L,2×10-3 mol/L,2.25×10-3mol/L,2.5×10-3 mol/L。然后加入0.5 mL上述探针溶液,滴加后摇晃均匀,静置半小时,分别测定其吸光度变化值,得紫外吸收光谱变化图,如图4所示,其568 nm处吸光度变化值对应的拟合曲线如图5所示。测试结果表明:本发明的探针与汞离子时1:1的结合比例,当汞离子较少的时候,吸光度随汞离子浓度增加而增强,呈线性关系。也说明了在该比色探针与汞离子摩尔比为0~1之间时,能够很好的检测汞离子,该范围即为该比色探针的检测区间。
Claims (3)
1.一种用于检测水相介质内汞离子的阳离子型有机铱(III)配合物比色探针,其结构式如式I所示:
(式I)。
2.一种用于检测水相介质内汞离子的阳离子型有机铱(III)配合物比色探针的合成路线和方法,具体包括以下步骤:
(1)称取一定量的一水合邻菲啰啉和氢氧化钾于水中,加热至沸腾,搅拌下将高锰酸钾热的水溶液滴入;滴加完毕后,继续沸腾下搅拌10分钟,趁热过滤;虑液呈橘红色,冷却后用氯仿萃取三次,合并有机相,无水硫酸镁干燥,过滤,最后减压蒸除溶剂;丙酮重结晶,得化合物1;
(2)将一定量的罗丹明B 溶解在乙醇溶液中,将过量的水合肼加入到上述溶液中,然后在80 ℃下回流至粉红色消失;待反应结束后冷却至室温,倒入水中用乙酸乙酯萃取,合并有机相,无水硫酸钠干燥,过滤,最后减压蒸除溶剂;得罗丹明B酰肼;
(3)将化合物1,罗丹明B酰肼,五氧化二磷和甲醇的混合物加热回流30分钟;将反应物冷却至室温,倒入水中用二氯甲烷萃取,合并有机相,无水硫酸钠干燥,过滤,最后减压蒸除溶剂;得黄色固体产物3;
(4)将化合物3和劳森试剂溶解于干燥的甲苯溶液中,将混合液在通有氩气的条件下回流4小时;将反应物冷却至室温,倒入水中用二氯甲烷萃取,合并有机相,无水硫酸钠干燥,过滤,最后减压蒸除溶剂;得化合物4;
(5)将铱(III)二聚物和化合物4的混合物加入到乙二醇中于150 ℃和氩气气氛下反应16小时;冷却至室温后加入的六氟磷酸铵产生大量絮状沉淀;过滤,水洗,干燥得粗产物;进一步用硅胶柱提纯;得阳离子铱配合物探针;
阳离子铱配合物的比色汞离子探针的制备方法所述步骤(1)中,一水合邻菲罗啉与氢氧化钾的摩尔比为1:3.5,所述高锰酸钾的水溶液浓度为0.55 mol/L;
阳离子铱配合物的比色汞离子探针的制备方法所述步骤(2)中,罗丹明B的无水乙醇溶液浓度为0.14 mol/L,罗丹明B与水合肼摩尔比为1:2.5~3.5;
阳离子铱配合物的比色汞离子探针的制备方法所述步骤(3)中,化合物1与罗丹明B酰肼的摩尔比为1:1,罗丹明B酰肼与五氧化二磷摩尔比为1:5,罗丹明B酰肼的无水甲醇溶液浓度为0.1 mol/L;
阳离子铱配合物的比色汞离子探针的制备方法所述步骤(4)中,化合物3与劳森试剂的摩尔比为1:1;
阳离子铱配合物的比色汞离子探针的制备方法所述步骤(5)中,铱的二聚物与化合物4的摩尔比为1:2,铱的二聚物的乙二醇溶液浓度为0.008 mol/L。
3.权利要求1所述的阳离子型有机铱(III)配合物比色汞离子探针在水相介质中对汞离子的比色检测应用。
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