CN107219218B - 一种简单灵敏的二价镍离子比色检测方法 - Google Patents
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- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
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- NMWONDKHBZEDMY-UHFFFAOYSA-H [Au](Cl)(Cl)Cl.C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-].[Na+].[Na+].[Na+] Chemical compound [Au](Cl)(Cl)Cl.C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-].[Na+].[Na+].[Na+] NMWONDKHBZEDMY-UHFFFAOYSA-H 0.000 description 1
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Abstract
本发明公开了一种简单灵敏的二价镍离子比色检测方法。该方法利用低浓度邻菲罗啉可有效介导金纳米颗粒凝集,导致反应溶液发生由红变蓝的颜色改变反应。而少量的Ni2+即能高效、特异地与邻菲罗啉生成邻菲罗啉‑Ni2+配合物,从而抑制上述溶液的变色反应。金纳米颗粒凝集导致反应溶液发生颜色改变的程度反比于样本中Ni2+浓度。因此,通过肉眼观察反应溶液的颜色变化即可实现Ni2+的简单灵敏定性或半定量检测。若借助光度计则可进一步实现目标金属离子分析物的准确定量检测。本发明方法能够直接推广应用于医学诊断、环境监测、食品安全等诸多领域里各类型样本中Ni2+分析物的简单、经济、快速、灵敏、特异的分析检测。
Description
技术领域
本发明属于纳米化学传感技术领域,具体涉及一种简单灵敏的二价镍离子比色检测方法。
背景技术
二价镍离子(Ni2+)属于过渡族元素,是人体必需的生命元素之一,可以激活人体中的各种酶,参与新陈代谢。然而,Ni2+具有中等毒性,人体大剂量吸收或者长期接触会引发严重疾病,如皮肤疾病、肺部感染、恶性肿瘤等。我国生活饮用水标准规定水中Ni2+限值为0.02mg/L。为保障人类健康和其他生物的生命安全,对食物、水和环境中的痕量Ni2+进行灵敏检测意义重大。现有的Ni2+检测技术主要包括有分光光度法、原子吸收法、原子发射光谱法、等离子体质谱法、电化学分析法和液相色谱法等。然而,这些方法要么操作步骤繁琐费时,不能用于现场分析和即时检验(Point-of-Care Testing),要么检测灵敏度有限。
发明内容
本发明的目的是针对现有技术的不足,提供一种简单灵敏的二价镍离子比色检测方法。
本发明的思路:含有N原子的低浓度邻菲罗啉可通过N-Au反应介导金纳米颗粒发生凝集,导致反应溶液发生由红变蓝的颜色改变反应。而少量的Ni2+即能通过与N原子配位,高效、特异地与邻菲罗啉分子生成邻菲罗啉-Ni2+配合物,从而抑制上述溶液变色反应。金纳米颗粒凝集导致反应溶液发生颜色改变的程度反比于样本中Ni2+浓度。因此,通过肉眼观察反应溶液的颜色变化即可实现Ni2+的简单灵敏定性或半定量检测。若借助紫外可见分光光度计则可进一步实现目标金属离子分析物的准确定量检测。
具体步骤为:
步骤一,将Ni2+样本溶液与邻菲罗啉溶液混合,生成邻菲罗啉-Ni2+配合物,制得反应溶液。
步骤二,向步骤一制得的反应溶液中加入金纳米颗粒溶液,制得混合溶液,混合溶液中剩余的邻菲罗啉将介导金纳米颗粒凝集,金纳米颗粒的凝集程度与Ni2+样本溶液中Ni2 +的浓度呈反比,肉眼观测该混合溶液的颜色变化进行定性或半定量分析,或使用光度计进行定量分析,即实现简单灵敏的Ni2+比色检测。
所述金纳米颗粒溶液的颜色为红色。
所述光度计为台式光度计和便携式光度计中的一种。
与现有的Ni2+检测方法相比,本发明的突出优点在于:
1)整个Ni2+分析过程中的操作极为简单,未经专业技能培训的操作人员也能开展实验;2)通过协同邻菲罗啉有效介导金纳米颗粒凝集反应和Ni2+高效、特异与邻菲罗啉分子生成邻菲罗啉-Ni2+配合物反应,显著提高方法的检测灵敏度;3)仅需肉眼观测溶液颜色的改变,即可实现Ni2+的灵敏定性或半定量分析,或可通过借助便携式光度计进一步实现分析物的准确定量检测,在极大降低分析成本的同时还能用于Ni2+样本的现场分析和即时检测;4)本发明可直接推广应用于医学诊断、环境监测、食品安全等诸多领域里各类型样本中Ni2+分析物的简单、经济、快速、灵敏、特异的定性与定量检测。
附图说明
图1为本发明实施例1和实施例2中简单灵敏的二价镍离子比色检测方法的原理示意图。
图中标记:1-1—无色超纯水;1-2—邻菲罗啉;2—检测试管;3-1—无色超纯水;3-2—Ni2+;4—邻菲罗啉-Ni2+配合物;5-1—红色溶液;5-2—金纳米颗粒;6—肉眼;7—便携式分光光度计。
图2为本发明实施例1中使用简单灵敏的二价镍离子比色检测方法分别检测(A)2μM Ni2+样本溶液与(B)空白样(超纯水)所得比色结果的比较。
图3为本发明实施例2中使用简单灵敏的二价镍离子比色检测方法分析一系列含有不同浓度Ni2+的样本溶液时在730 nm处的吸收强度值(A730)与在520 nm处的吸收强度值(A520)的比值(A730/A520)和Ni2+的浓度值之间的工作曲线。
具体实施方式
以下实施例将对本发明予以进一步的说明,但并不因此而限制本发明。
实施例1:
使用简单灵敏的二价镍离子比色检测方法分别检测2 μM Ni2+样本溶液与空白样(超纯水)。
如图1所示,本实施例的具体步骤为:步骤一,在1个1.5 mL的塑料检测试管中加入150 μL 2 μM的邻菲罗啉溶液(由电阻率为18.2 MΩ·cm的超纯水配制),随后往该溶液中滴加150 μL 2 μM 的Ni2+样本溶液(由电阻率为18.2 MΩ·cm的超纯水配制的氯化镍溶液),并摇动试管使两种溶液混合均匀,生成邻菲罗啉-Ni2+配合物,制得反应溶液;步骤二,在上述反应溶液中继续加入300 μL红色金纳米颗粒溶液(粒径约13 nm,由柠檬酸钠还原氯金酸制得),并摇动试管使溶液混合均匀后,肉眼观测溶液的颜色变化。
根据相同的步骤,分析空白样,即超纯水(电阻率为18.2 MΩ·cm),并肉眼观测溶液的颜色变化。从图2可以看出,检测空白样得到的是蓝色溶液,而检测2 μM 的Ni2+分析物所得的是红色溶液。这是因为检测空白样时,含有N原子的邻菲罗啉分子可以通过N-Au反应介导金纳米颗粒发生凝集,导致反应溶液产生由红变蓝的颜色变化。而当样本中存在Ni2+时,Ni2+通过与N原子配位,高效、特异地与邻菲罗啉分子生成邻菲罗啉-Ni2+配合物产物。由于该产物不能导致金纳米颗粒发生凝集,整个反应溶液依然保持金纳米颗粒溶液的原始红色。图2中的对比实验结果表明,本发明的简单灵敏的Ni2+比色检测方法切实可行。
实施例2:
使用简单灵敏的二价镍离子比色检测方法分析浓度范围为465 nM~2 μM的Ni2+样本溶液。具体实施过程如下:
如图1所示,本实施例中每个Ni2+样本溶液分析的具体步骤为:步骤一,在1个1.5mL的塑料检测试管中加入150 μL 2 μM的邻菲罗啉溶液(由电阻率为18.2 MΩ·cm的超纯水配制),随后往该溶液中滴加150 μL 某一浓度Ni2+样本溶液(由电阻率为18.2 MΩ·cm的超纯水配制的氯化镍溶液),并摇动试管使两种溶液混合均匀,生成邻菲罗啉-Ni2+配合物,制得反应溶液;步骤二,在上述反应溶液中继续加入300 μL红色金纳米颗粒溶液(粒径约13nm,由柠檬酸钠还原氯金酸制得),并摇动试管使溶液混合均匀后,肉眼观测溶液的颜色变化,并使用便携式紫外-可见分光光度计量测该溶液在520和730 nm处的吸收强度值(A520和A730)。将所有样本这两个波长处的吸收强度值的比值(A730/A520)对Ni2+的浓度值作图(图3),即可得到Ni2+的定量测定工作曲线。
由图3可知,随着Ni2+浓度的增加,相应的A730/A520比值逐渐降低。这是因为,当样本中Ni2+浓度较大时,分析物可以高效、特异地与较多的邻菲罗啉分子生成邻菲罗啉-Ni2+配合物产物。此时,剩余的邻菲罗啉分子不足以通过N-Au反应介导金纳米颗粒发生凝集,含有较多自由分散的金纳米颗粒的相应混合溶液在730 nm处的吸收强度值,即A730值较小;而其在520 nm处的吸收强度值,即A520值则较大。此外,图3显示,新方法量测所有镍离子样本所得A730/A520比值与Ni2+浓度在浓度范围465 nM~2 μM内呈现良好的线性关系。
Claims (1)
1.一种简单灵敏的二价镍离子比色检测方法,其特征在于具体步骤为:
步骤一,将镍离子样本溶液与邻菲罗啉溶液混合,生成邻菲罗啉-Ni2+配合物,制得反应溶液;
步骤二,向步骤一制得的反应溶液中加入金纳米颗粒溶液,制得混合溶液,混合溶液中剩余的邻菲罗啉将介导金纳米颗粒凝集,金纳米颗粒的凝集程度与镍离子样本溶液中Ni2+的浓度呈反比,肉眼观测该混合溶液的颜色变化进行定性或半定量分析,或使用光度计进行定量分析,即实现简单灵敏的二价镍离子比色检测;
所述金纳米颗粒溶液的颜色为红色;
所述光度计为台式光度计和便携式光度计中的一种。
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铜、锌、钴、镍-邻菲罗啉体系中稀土元素与偶氮氯膦Ⅲ显色反应的研究;虞光禹;《分析化学》;19861231;第14卷(第9期);第646-649页 * |
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Application publication date: 20170929 Assignee: Guilin Qiyun New Materials Co.,Ltd. Assignor: GUILIN University OF TECHNOLOGY Contract record no.: X2023980044906 Denomination of invention: A simple and sensitive colorimetric detection method for divalent nickel ions Granted publication date: 20191126 License type: Common License Record date: 20231101 |