CN110283213B - 可检测亚硫酸氢根和汞离子的比色探针及合成方法与应用 - Google Patents
可检测亚硫酸氢根和汞离子的比色探针及合成方法与应用 Download PDFInfo
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Abstract
本发明公开了一种可连续检测亚硫酸氢根和汞离子的比色探针及合成方法与应用。该比色探针经2‑卤吡啶、5‑醛基‑2‑噻吩硼酸、[Ru(cycme)Cl2]2、2,2’‑联吡啶以及3‑乙基‑2,3‑二氢‑1,1,2‑三甲基‑1H‑苯并[e]吲哚六氟磷酸盐依次反应制备得到。既可分别又可连续检测水溶液中的HSO3 ‑和Hg2+,尤其是在与HSO3 ‑作用以后,原位对Hg2+的检测效果更明显。本发明的比色探针灵敏度高,选择性好。
Description
技术领域
本发明属于分析检测技术领域,特别涉及一种可检测亚硫酸氢根和汞离子的比色探针及合成方法与应用。
背景技术
亚硫酸氢盐在人类的生活中具有普遍广泛的应用,常作为添加剂用于食品和药物的生产,但过量摄入亚硫酸氢盐也可能会对身体造成一些危害,例如腹泻、低血压、引发哮喘和过敏反应,因此对于亚硫酸氢根离子的检测非常重要。当前,常见的亚硫酸氢根离子的检测方法有色谱法、毛细管电泳法、化学发光法、酶分析法和光谱法等。
汞离子作为一种常见的环境污染物,由于非生物降解性与生物积累性,当其进入人体后,会对中枢神经***,消化***造成不可逆损害。随着人们对身体健康和环境保护的重视,设计合成出对这些离子具有高选择性、高灵敏度的化学传感器,对于环境监测、疾病防治等方面都有着重要的意义。当前,常见汞离子检测手段有原子吸收/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)等。
相比于基于有机小分子构筑的光化学传感器,金属配合物构筑的光化学传感器因其Stokes位移大、激发能量低、稳定性好、易实现比色识别等优势,近年来得到迅猛发展。并且其作为传感器优异的表现得益于其良好可调的磷光发射性质。尽管借助磷光/荧光发射变化检测小分子及离子在灵敏度方面具有一定的优势,但基于直观颜色变化的比色传感器则在操作上更为简单,甚至不需要借助于仪器,在实际应用中颇为方便。一个优良的比色传感器需在可见光区具有很好的吸收,其中环金属钌配合物因Ru-C的形成,其MLCT态吸收位于可见光区,且通过配体调节,极易将功能团引入并与特定离子作用,从而引起可见光区的光谱变化,实现肉眼可见的变化。因此,关于环金属钌配合物用于检测离子的工作引起了人们的注意。但这些配合物只能在特定的溶剂或水溶液中单一的识别某种特定的离子。
发明内容
本发明所要解决的一个技术问题是提供一种可检测亚硫酸氢根和汞离子的比色探针,该比色探针具有同时识别金属离子Hg2+和阴离子HSO3 -的能力,对水中Hg2+和HSO3 -均具有较好的选择性,并且在配合物中加入HSO3 -后,对汞离子可形成肉眼可见的颜色变化,从而使测试方法简化。
本发明所要解决的第二个技术问题是提供上述比色探针的制备方法。
本发明所要解决的第三个技术问题是提供上述比色探针的应用。
为了解决上述第一个技术问题,本发明采用以下技术方案:
一种可检测亚硫酸氢根和汞离子的比色探针,该比色探针具有如下的化学结构式:
为解决上述第二个技术问题,本发明设计的合成路线包括如下的步骤(反应结构式中仅以某一具体的物质作为代表,例如2-卤吡啶以2-溴吡啶为代表):
1)制备5-(2-吡啶基)噻吩甲醛,即化合物1;
向反应装置中依次加入2-卤吡啶、有机溶剂和碳酸。惰性气氛下充分搅拌后,加入5-醛基-2-噻吩硼酸及Pd(PPh3)4于90~100℃下回流20~24h后,停止反应。提纯得浅黄色的5-(2-吡啶基)噻吩甲醛固体。
2)制备含醛基的金属钌配合物,即化合物2;
向反应装置中依次加入5-(2-吡啶基)噻吩甲醛、KPF6、乙腈。通入氩气或氮气以赶走反应装置中的氧气后,加入[Ru(cycme)Cl2]2,混合液于50~60℃下搅拌回流12~18h后冷却至室温。除去溶剂,得橙红色固体。然后加入2,2’-联吡啶、甲醇,60~80℃下在惰性气氛下回流反应8~14h。提纯得黑色的含醛基的金属钌配合物固体。
3)制备目标比色探针,即金属钌配合物I;
向反应装置中依次加入3-乙基-2,3-二氢-1,1,2-三甲基-1H-苯并[e]吲哚六氟磷酸盐、含醛基的金属钌配合物和乙醇,在70~85℃且避光条件下反应8~14小时,溶液颜色由红色变为红褐色,经提纯得红褐色固体。
优选地,所述步骤1)中,2-卤吡啶为2-溴吡啶或2-氯吡啶。
优选地,所述步骤1)中,有机溶剂为乙二醇二甲醚或四氢呋喃。
优选地,所述步骤1)中,按物质的量比,2-卤吡啶、5-醛基-2-噻吩硼酸和碳酸盐、Pd(PPh3)4为(2.5~3.0):(2.5~3.0):1:(0.05~0.1)。
优选地,所述步骤2)中,按物质的量比,[Ru(cycme)Cl2]2、5-(2-吡啶基)噻吩甲醛和2,2’-联吡啶为1:(1.2~1.6):(2.5~4)。
优选地,所述步骤3)中,按物质的量,含醛基的金属钌配合物与3-乙基-2,3-二氢-1,1,2-三甲基-1H-苯并[e]吲哚六氟磷酸盐为1:1~1.5。
为解决上述第三个技术问题,本发明将上述比色探针用于分别检测水溶液中的亚硫酸氢根和汞离子。
为解决上述第三个技术问题,本发明还将上述比色探针用于连续检测水溶液中的亚硫酸氢根和汞离子。
本发明的比色探针与现有技术相比具有以下有益效果:
第一,本发明的比色探针利用苯并[e]吲哚结构达到识别HSO3 -的目的;同时也可以利用噻吩基团与Hg2+的配位作用,达到识别Hg2+的目的,尤其是在与HSO3 -作用以后,原位对Hg2+的检测更明显,即可连续识别Hg2+和HSO3 -。
第二,本发明的比色探针检测光/化学稳定性好、灵敏度高,选择性好。
第三,本发明的比色探针在水中溶解性较好。
附图说明
图1为本发明中间产物的氢谱图。
图2为本发明比色探针的氢谱图。
图3为本发明比色探针在不同当量HSO3 -滴定下吸光度的变化。
图4为本发明比色探针在不同当量HSO3 -滴定下得到的检测线LOD。
图5为本发明比色探针在不同阴离子干扰下,HSO3 -对其吸光度的影响。
图6为本发明比色探针在不同当量Hg2+滴定下吸光度的变化。
图7为本发明比色探针在不同当量Hg2+滴定下得到的检测线LOD。
图8为本发明比色探针在不同阳离子干扰下,Hg2+对其吸光度的影响。
图9为本发明比色探针在加入HSO3 -后原位检测不同当量Hg2+下吸光度的变化。
图10为本发明比色探针在加入HSO3 -后原位检测不同当量Hg2+得到的检测线LOD。
图11为本发明比色探针加入HSO3 -后原位检测在不同金属离子下的吸光度的变化。
图12为本发明比色探针在加入HSO3 -后原位检测Hg2+肉眼可见的比色图。
具体实施方式
以下结合附图和具体实施例对本发明进一步详细说明。
实施例一 本发明的比色探针的制备:
(1)5-(2-吡啶基)噻吩甲醛的合成
向100mL三口烧瓶中依次加入2-溴吡啶(0.51g,3.2mmol)、乙二醇二甲醚(15mL)和碳酸钾(5mL,0.8mmol)。氩气保护下充分搅拌后,加入5-醛基-2-噻吩硼酸(0.52g,3.3mmol)及Pd(PPh3)4(0.19g,0.16mmol)于100℃下回流24h后,停止反应。加入水(10mL),用二氯甲烷萃取3次后旋干得棕色油状物。以二氯甲烷/石油醚(v/v,1/1)为展开剂柱层析得浅黄色固体0.17g,产率28%。
核磁共振化学位移:1H NMR(400MHz,CDCl3)δ:9.94(s,1H),8.66~8.63(m,1H),7.80~7.72(m,3H),7.70(d,J=4.0Hz,1H),7.31~7.27(m,1H).
(2)化合物2的合成
向100mL三口烧瓶中依次加入5-(2-吡啶基)噻吩甲醛(0.15g,0.78mmol)、KPF6(0.2937g,1.60mmol)、乙腈(12mL)。通入氩气10min后,加入[Ru(cycme)Cl2]2(0.3g,0.5mmol),混合液于55℃下搅拌回流16h后冷却至室温。旋蒸除去溶剂,得橙红色固体。继续向上述反应瓶中加入2,2’-联吡啶(0.25g,1.57mmoll)、甲醇(12mL),通入氩气,于70℃下回流反应12h。停止反应,旋干。以二氯甲烷/乙腈(v/v,10/1)为展开剂柱层析黑色固体0.27g,产率58%。
核磁共振化学位移:1H NMR(400MHz,CD3CN)δ(ppm):9.80(s,1H),8.48(d,J=8.2Hz,1H),8.41(d,J=8.2Hz,1H),8.35(t,J=7.7Hz,2H),8.07~7.97(m,2H),7.93~7.77(m,7H),7.71(t,J=7.8Hz,1H),7.55(d,J=5.7Hz,1H),7.45(t,J=7.4Hz,1H),7.28(m,J=6.5Hz,3H),7.12(s,1H),6.94(t,J=6.5Hz,1H);13C NMR(101MHz,CD3CN),δ(ppm):184.12,162.22,157.66,157.17,156.87,155.54,154.71,151.06,150.98,150.61,149.42,146.21,143.84,136.62,136.32,135.34,134.49,134.30,127.08,126.53,126.51,126.39,126.26,123.44,123.29,123.05,122.93,122.17,119.69,117.27;MS(Maldi-TOF,CHCA)m/z:Calculated for602.06([M-PF6]+),Found:601.98.
(3)目标产物化合物I的合成
向50mL三口烧瓶中依次加入苯并吲哚六氟磷酸盐(0.06g,0.15mmol),含醛基的金属钌配合物(0.09g,0.12mmol),乙醇(10mL),在80℃下反应12小时,且对反应装置进行避光处理,溶液颜色由红色变为红褐色。以乙腈/甲醇/饱和KPF6以及水为展开剂柱层析得红褐色固体0.053g,产率40%。
核磁共振化学位移:1H NMR(400MHz,Methanol-d4)δ8.74–8.49(m,5H),8.36(d,J=8.5Hz,1H),8.25–8.17(m,2H),8.17–8.06(m,2H),8.02–7.84(m,8H),7.78(q,J=7.9Hz,2H),7.72–7.60(m,2H),7.54(dd,J=7.4,5.7Hz,1H),7.38(dp,J=5.6,1.6Hz,4H),7.16(d,J=15.6Hz,1H),7.03(dd,J=7.4,5.7Hz,1H),4.70(d,J=7.4Hz,2H),2.02(dd,J=19.4,1.2Hz,6H),1.61(t,J=7.2Hz,3H).
实施例二 本发明比色探针的应用:
(1)比色探针溶液的配置
称取0.0022g(0.002mmol)目标金属钌配合物,用HEPES缓冲溶液定容至100mL,得到2×10-5M的比色探针溶液。
(2)不同当量HSO3 -下,本发明探针的吸光度测试
取用HEPES缓冲溶剂配制的2×10-5M的比色探针溶液3mL,然后分别向其中加入0-200μM的亚硫酸氢根离子(本领域的技术人员公知,加入0-200μM的亚硫酸氢根离子,并不意味着实际实验时需要加入所有满足0-200μM区间的亚硫酸氢根离子,这既不可能也不必要,而是分布在该区间足以反映相关规律的一组数据,步骤(4)和(6)相关范围亦同此解释),待平衡后,用紫外分光光度计测试其在波长为500nm处吸光度的变化。测试结果见图3、4。该比色探针在波长为500nm的吸光度随亚硫酸氢根离子量的增加而降低。
(3)不同阴离子干扰下,HSO3 -对其吸光度的影响
在配置的该比色探针溶液中加入浓度均为1mM的不同的阴离子Cl-、Br-、I-、ClO4 -、SO4 2-、NO3 -、H2PO4 -、CO3 2-、HCO3 -、Ac-、HS-,以及在此基础上继续加入40μM的HSO3 -,待平衡后,用紫外分光光度计测试其在波长为500nm处吸光度的变化。测试结果见图5。从图5可以看出,该比色探针对亚硫酸氢根离子有较好的选择性。
(4)不同当量Hg2+下,本发明探针的吸光度测试
取用HEPES缓冲溶剂配制的2×10-5M的比色探针溶液3mL,然后分别向其中加入0-600μM的汞离子,待平衡后,用紫外分光光度计测试其在波长为500nm处吸光度的变化。测试结果见图6、7。该比色探针的在波长为500nm吸光度随汞离子量的增加而降低。
(5)在不同阳离子干扰下,Hg2+对其吸光度的影响
在配置的该比色探针溶液中加入浓度均为2mM的不同的阳离子Cu2+、Pb2+、Cr2+、Co2 +、Ni2+、Sr2+、Ag+、Mn2+、Ca2+、Mg2+、Ba2+、Na+,以及继续在此基础上加入0.5mM的Hg2+,待平衡后,用紫外分光光度计测试其在波长为500nm处吸光度的变化。测试结果见图8。从图8可以看出,该比色探针对汞离子有较好的选择性,仅大量的Ag+会产生一定的干扰。
(6)在加入定量的HSO3 -的探针溶液中,本发明原位检测不同当量Hg2+下吸光度的变化。
取3mL该比色探针溶液和20uL2×10-3M亚硫酸氢根离子于试管中,然后加入0-20μM的Hg2+,待平衡后,用紫外分光光度计测试其在波长为500nm处吸光度的变化。测试结果见图9、10。从图9、10可以看出,该比色探针能连续检测亚硫酸氢根离子和汞离子。
(7)在加入定量的HSO3 -的探针溶液中,本发明原位检测不同金属离子对其吸光度的影响。
取3mL该比色探针溶液和20μL 2×10-3M亚硫酸氢根离子溶液于试管中,各种阳离子浓度为2.5×10-2M,然后分别加入20当量的金属离子,待平衡后,用紫外分光光度计测试其在波长为500nm处吸光度的变化。测试结果见图11。从图11可以看出,该比色探针在加入阴离子亚硫酸氢根离子后,对汞离子金属离子仍具有选择性,仅大量银离子会产生一定作用。
(8)在加入HSO3 -后原位检测Hg2+肉眼可见的比色图。
组一:取2mL该比色探针溶液和20μL 2×10-3M亚硫酸氢根离子于试管中,然后加入1-30当量浓度为1×10-2M的汞离子溶液(即首先加入1当量,进行检测分析,然后在该体系中再加入1当量,再检测分析,直至在该体系中加入30当量浓度为1×10-2M的汞离子溶液),混匀。组二:取2mL该比色探针溶液于试管中,然后直接加入30当量浓度为1×10-2M的汞离子溶液,混匀。两组均放置1小时(对于组一来说,每增加1当量浓度为1×10-2M的汞离子溶液就放置1小时)。结果见图12(图中仅示出加入1当量浓度为1×10-2M的汞离子溶液和30当量浓度为1×10-2M的汞离子溶液的比色图)。
本发明的比色探针HEPES缓冲溶液体系中加入适量亚硫酸氢根离子后,整个体系由橘红色变为浅粉红色,这时仍可以对不同浓度的汞离子进行检测,上述组一中汞离子浓度达到在每次加入1当量的汞离子溶液时,体系颜色逐渐变深,颜色变化肉眼可查,累计至30当量时,可发现颜色由仅加入亚硫酸氢根离子未加入汞离子时的浅粉红色变为棕红色,而组二直接在本发明的比色探针HEPES缓冲溶液体系中加入30当量汞离子时,颜色则由最初的橘红色亦变为红棕色,该红棕色和组一的红棕色基本一样且都与最初的橘红色比较接近,但肉眼可查其与最初的橘红色的区别。
另外,发明人亦按照组一的方法在本发明的比色探针HEPES缓冲溶液体系中每次加入1当量的浓度为1×10-2M的汞离子溶液进行实验,发现,在每次加入汞离子溶液时,体系颜色变化不明显,肉眼不可查,仅因累计加至30当量时才发生肉眼可见的变化,同样变成了与橘红色接近的红棕色。
Claims (8)
2.权利要求1所述比色探针的制备方法,其特征在于:该方法包括如下步骤:
1)制备5-(2-吡啶基)噻吩甲醛;
向反应装置中依次加入2-卤吡啶、有机溶剂和碳酸盐;惰性气氛下充分搅拌后,加入5-醛基-2-噻吩硼酸及Pd(PPh3)4于90~100℃下回流20~24h后,停止反应;经提纯得浅黄色的5-(2-吡啶基)噻吩甲醛固体;
2)制备含醛基的金属钌配合物;
向反应装置中依次加入5-(2-吡啶基)噻吩甲醛、KPF6、乙腈;通入氩气或氮气以赶走反应装置中的氧气后,加入[Ru(cycme)Cl2]2,混合液于50~60℃下搅拌回流12~18h后冷却至室温,除去溶剂,得橙红色固体;然后加入2,2’-联吡啶、甲醇,在惰性气氛下于60~80℃回流反应8~14h;提纯得黑色的含醛基的金属钌配合物固体;
3)制备目标比色探针即金属钌配合物;
向反应装置中依次加入3-乙基-1,1,2-三甲基-1H-苯并[e]吲哚六氟磷酸盐、含醛基的金属钌配合物和乙醇,在70~85℃且避光条件下反应8~14小时,溶液颜色由红色变为红褐色,经提纯得红褐色固体。
3.根据权利要求2所述的比色探针的制备方法,其特征在于:
所述步骤1)中,2-卤吡啶为2-溴吡啶或2-氯吡啶。
4.根据权利要求2或3所述的比色探针的制备方法,其特征在于:
所述步骤1)中,有机溶剂为乙二醇二甲醚或四氢呋喃。
5.根据权利要求2或3所述的比色探针的制备方法,其特征在于:
所述步骤1)中,按物质的量比,2-卤吡啶、5-醛基-2-噻吩硼酸和碳酸盐、Pd(PPh3)4为(2.5~3.0):(2.5~3.0):1:(0.05~0.1)。
6.根据权利要求2或3所述的比色探针的制备方法,其特征在于:
所述步骤2)中,按物质的量比,[Ru(cycme)Cl2]2、5-(2-吡啶基)噻吩甲醛和2,2’-联吡啶为1:(1.2~1.6):(2.5~4)。
7.根据权利要求2或3所述的比色探针的制备方法,其特征在于:所述步骤3)中,按物质的量,含醛基的金属钌配合物与3-乙基-1,1,2-三甲基-1H-苯并[e]吲哚六氟磷酸盐为1:1~1.5。
8.权利要求1所述的比色探针在制备连续检测亚硫酸氢根和汞离子的探针中的应用。
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CN106496197A (zh) * | 2016-10-27 | 2017-03-15 | 湖南师范大学 | 一种荧光增强型快速检测亚硫酸氢根离子或亚硫酸根离子荧光分子探针的合成和应用 |
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CN103275698A (zh) * | 2013-05-31 | 2013-09-04 | 太原理工大学 | 一种比率型亚硫酸氢根离子荧光探针及制备方法 |
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Non-Patent Citations (4)
Title |
---|
Benzo[e]indolium derivatives in aqueous solutions: Reaction with bisulfite and successive interaction with Cu2+ and Hg2+;Rongqing Zeng等;《Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy》;20180526;324-332页 * |
功能型环金属钌配合物的设计合成及其在比色传感器中的应用;苏显龙;《中南民族大学硕士学位论文》;20180119;全文 * |
离子识别型环金属钌配合物的合成及性质研究;谢超异;《中国优秀硕士学位论文全文数据库-工程科技Ⅰ辑》;20190815;第二章至第四章 * |
谢超异.离子识别型环金属钌配合物的合成及性质研究.《中国优秀硕士学位论文全文数据库-工程科技Ⅰ辑》.2019, * |
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