CN102375020A - Method for detecting mercury ions through gold electrode modified by polythymidine DNA - Google Patents
Method for detecting mercury ions through gold electrode modified by polythymidine DNA Download PDFInfo
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- CN102375020A CN102375020A CN2010102572721A CN201010257272A CN102375020A CN 102375020 A CN102375020 A CN 102375020A CN 2010102572721 A CN2010102572721 A CN 2010102572721A CN 201010257272 A CN201010257272 A CN 201010257272A CN 102375020 A CN102375020 A CN 102375020A
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Abstract
The invention provides a method for detecting mercury ions through a gold electrode modified by polythymidine DNA, which is characterized in that polythymidine DNA molecule is taken as a recognition element for mercury ions, the gold electrode modified by polythymidine DNA is prepared, then mercury ions in an aqueous solution is detected by the prepared gold electrode, wherein alkali base T in DNA molecule is capable of specifically binding with mercury ions to form a stable T-Hg<2+>-T structure. The intensity of an electrochemical signal is relative with the concentration of mercury ions in the solution, so that the concentration of mercury ions in the aqueous solution can be calculated. According to the invention, the method for detecting mercury ions has the advantages of no pollution on environment, good selectivity on mercury ions, eliminated interference of most metal ions, high sensitivity, simple required apparatus and low cost, and is suitable for being applicable to such humble situations as fields and the like.
Description
Technical field
The present invention relates to a kind of check and analysis method of ion concentration of mercury, particularly, is a kind of gold electrode that utilizes many thymine DNA to modify directly carries out Electrochemical Detection to the mercury ion in the WS method.
Background technology
Because the structure of DNA and performance are very sensitive to the influence of heavy metal, thereby utilize the interaction development high selectivity between DNA and the metallic ion, highly sensitive heavy metal analyzing detecting method that very big value and meaning are arranged.Gao etc. proved the guanine among the DNA can and Cu
2+Specificity combines to form stable structure, and (Y.G.Gao, M.Sriam, A.H.J.Wang, Nucleic Acid Res.21 (1993) 4093-4191) also is used for Cu
2+Detection in.Ono group reported first among the DNA base-pair C-C can and Ag
+Specificity combines to form stable C-Ag
+-C-structure (Miyake, Y.; Togashi, H.; Tashiro, M.; Yamaguchi, H.; Oda, S.; Kudo, M.; Tanaka, Y.; Kondo, Y.; Sawa, R.; Fujimoto, T.; Machinami, T.; Ono, A.J.Am.Chem.Soc.2006,128,2172-2173.).Dong group is based on C-Ag
+-C-structure has designed detection Ag
+The colorimetric bio sensor (T.Li, L.Shi, E.Wang and S.Dong, Chem.-Eur.J., 2009,15,3347-3350.).Therefore utilize biocompatibility and water-soluble all good dna molecular to detect heavy-metal pollution and received domestic and international expert's concern.
Ono group also reported first in the dna sequence dna the T-T base-pair can and Hg
2+Specificity takes place combine to form stable T-Hg
2+-T structure.Subsequently, reported both at home and abroad much based on T-Hg
2+The fluorescent optical sensor of-T structure determination mercury ion and colorimetric method (Z.D.Wang, J.H.Lee, Y.Lu, Chem.Commun., 2008,6005-6007; C.K.Chiang, C.C.Huang, C.W.Liu, H.T.Chang.Analytical Chemistry, Vol.80, No.10, May 15,2008; J.S.Lee, M.S.Han, andC.A.Mirkin.Angew.Chem.Int.Ed.2007,46,4093-4096.).Because fluoroscopic examination and ultraviolet detection all need huger, valuable detecting instrument, so these methods are not suitable for some simpler and cruder yards occasion etc. of field work in one's power.And that electrochemical measuring technique has is highly sensitive, selectivity good, easy advantage such as inexpensive and portable, and wherein to detect mercury ion be the most frequently used technology in the galvanochemistry stripping.The present invention combines many thymine DNA to the selectivity of mercury ion and simple, the highly sensitive advantage of dissolving-out technology, develop the method that Direct Electrochemistry a kind of " green ", that can not cause secondary pollution detects mercury ion in the WS.
Summary of the invention
Deficiency to existing analytical technology existence; The present invention combines many thymine DNA to the selectivity of mercury ion and simple, the highly sensitive advantage of galvanochemistry stripping detection technique; Purpose is that the gold electrode that provides a kind of many thymine DNA to modify directly detects the method for mercury ion in the WS; It adopts the recognition component of many thymine DNA as mercury ion, prepares the gold electrode that many thymine DNA are modified, and detects the mercury ion in the WS with the gold electrode that makes then.
In the Electrochemical Detection WS of the present invention in the method for mercury ion, the base T of dna molecular that is used for the recognition component of modified gold electrode can combine to form stable T-Hg with the mercury ion specificity
2+-T structure.
In the Electrochemical Detection WS of the present invention in the method for mercury ion; The preparation method of the gold electrode that said many thymine DNA is modified be utilize " Au-S " covalent bond with many thymine DNA self assembly of sulfydryl modification in gold electrode surfaces; And utilize the sulfydryl hexanol to occupy the site that gold electrode surfaces does not combine with many thymine DNA, remove because of the non-specific adsorption many thymine DNA on gold electrode surfaces that lay flat on one's back.
Method of the present invention is a specificity mercury ion probe with many thymine DNA, and mercury ion in the WS is measured in good, sensitive, easy, the quick stripping of selectivity, and the purpose of concrete invention realizes through following technical scheme:
1, the preparation of the gold electrode of many thymine DNA modifications: earlier Φ 2mm gold electrode is polished and cleans, according to the method for document (E.E.Ferapontova, T.Ruzgas, L.Gorton, Anal.Chem.2003,75,4841).To polish 0.2M HEPES (pH 7.2) the buffer solution self assembly 16 hours that good gold electrode places the many thymine DNA that contain 1 μ M sulfydryl modification then; Passivation 2 hours in the above-mentioned damping fluid that contains 1mM sulfydryl hexanol again utilizes the sulfydryl hexanol to occupy the site that gold electrode surfaces does not combine with many thymine DNA, removes because of the non-specific adsorption many thymine DNA on gold electrode surfaces that lay flat on one's back; Wash 2-3 time with 10mM HEPES damping fluid at last, and be stored in the same damping fluid for use.
2, many thymine DNA of above-mentioned preparation gold electrode of modifying and the HEPES damping fluid that contains mercury ion were cultivated 15 minutes, from solution, taken out electrode, with this gold electrode surfaces of HEPES buffer solution for cleaning; Again gold electrode is placed in the blank HEPES damping fluid, under-0.2V current potential, reduced 30 seconds; At last this modified electrode-0.2～+ 1.0V scope interscan DPV (differential pulse voltammetry), the peak current of record DPV comes the ion concentration of mercury in the calculation sample according to the peak current signal.
The method of Electrochemical Detection mercury ion of the present invention, the concentration of its mercury ion detect and are limited to 60pM.
Method according to many thymine DNA modified gold electrode Electrochemical Detection mercury ion of the present invention has the following advantages:
1. the present invention adopts many thymine DNA as detector probe, and specificity is good, can not cause second environmental pollution.
2. employing Electrochemical Detection has sensitivity, selectivity is good; Background signal is low, and sample is not had the turbidity requirement, and required instrument is simple, and low price is applicable to simple and crude occasion uses such as field.
3. the present invention has quite good detecting sensitivity, and its detectability is than low two one magnitude of permission standard of mercury ion in the potable water; Particularly, be limited to 60pM according to the detection of the method for Electrochemical Detection mercury ion of the present invention, and the detection in the potable water is limited to 10nM.。
4. the present invention is through the appropriate design dna probe, and this method can be easy to be generalized to the detection of other heavy metal ion.
Description of drawings
Fig. 1 is the stripping volt-ampere curve figure of Hg among the present invention.
Fig. 2 be of the present invention be ordinate with the oxidation voltammetric current, ion concentration of mercury is the standard working curve figure of horizontal ordinate.
Embodiment
Method below in conjunction with mercury ion in the preferred implementation of the present invention and the accompanying drawing detailed description Electrochemical Detection WS of the present invention; But the present invention does not receive the restriction of following embodiment, and all making based on thought of the present invention improved or distortion all should belong to protection scope of the present invention.
Embodiment 1:
(1) preparation of the gold electrode of many thymine DNA modifications
The fresh clean gold electrode that electrochemical treatment is crossed places many thymines oligonucleotides (PTO) solution of 1 μ M sulfydryl modification; Self assembly 16h under the room temperature takes out gold electrode, cleans with 10mM HEPES solution (pH 7.2); To remove unassembled PTO; Be placed on room temperature occupy-place 2h in the 1mM sulfydryl hexanol solution then, clean with same HEPES solution (pH 7.2), to remove unassembled sulfydryl hexanol.For preventing solution evaporation, electrode keeps sealing in whole assembling process.The electrode for preparing is the PTO/Au electrode.
(2) detection of mercury ion in the river water sample
The PTO/Au electrode for preparing is immersed in soak 15min in the 10mM HEPES solution (pH 7.2) of a series of standard water samples that contain the variable concentrations mercury ion after, with 10mM HEPES solution (pH 7.2) cleaning 2 times; With 10mM HEPES solution (pH7.2,1M NaClO
4) be supporting electrolyte, in-the electrochemical reduction 30s of 0.2V place, with Hg
2+Be reduced to Hg simple substance; Then-0.2V～+ 1.0V (vs.Ag/AgCl) carries out DPV scanning, pulse width 0.05s, recurrent interval 0.2s, increment are 0.004V, amplitude is 0.05V, promptly obtains the stripping volt-ampere curve of Hg, and is as shown in Figure 1.With the oxidation voltammetric current is ordinate, and ion concentration of mercury is a horizontal ordinate, makes standard working curve, and is as shown in Figure 2.
Adopt river as actual sample, earlier river is discolored, filter then with activated charcoal; River behind 0.22 μ m membrane filtration, again with the centrifugal 15min of 16000 commentaries on classics/min, is got supernatant as the water sample that is used to measure again.The above-mentioned river water sample of 20 μ L is added in the HEPES damping fluid, and according to the above-mentioned steps operation, its oxidation voltammetric current is-0.918 μ A, and the content that can be got mercury ion in the water sample by typical curve shown in Figure 2 is 4.61 * 10
-10MolL
-1
In the present embodiment, except that the HEPES damping fluid is to press the known technology self-control, all the other reagent are to be bought from market, and it is synthetic and purifying that wherein PTO solution is fastened marine growth technology company limited.
Claims (5)
1. the method for the Electrochemical Detection of thymine DNA modified gold electrode more than kind mercury ion; It is characterized in that; Adopt the recognition component of many thymine DNA molecule as mercury ion; Prepare the gold electrode that many thymine DNA are modified, then with the mercury ion in the gold electrode Electrochemical Detection WS that makes.
2. the method for mercury ion in the Electrochemical Detection WS described in claim 1 is characterized in that, the base T in the dna molecular of said recognition component can combine to form stable T-Hg with the mercury ion specificity
2+-T structure.
3. the method for mercury ion in the Electrochemical Detection WS described in claim 1; It is characterized in that the preparation method of the gold electrode that said many thymine DNA are modified comprises 0.2M HEPES (pH 7.2) the buffer solution self assembly 16 hours that gold electrode is placed the many thymine DNA that contain 1 μ M sulfydryl modification; Passivation 2 hours in the above-mentioned damping fluid that contains 1mM sulfydryl hexanol again.
4. the method for mercury ion in the Electrochemical Detection WS as claimed in claim 1; It is characterized in that; Gold electrode and the HEPES damping fluid that contains mercury ion to be measured that said many thymine DNA are modified were cultivated 15 minutes; Take out washing and in the HEPES of blank damping fluid in the reduction 30 seconds down of-0.2V current potential, according to-0.2～+ DPV peak current signal that the interscan of 1.0V scope is write down comes the ion concentration of mercury in the calculation sample.
5. the method for mercury ion is characterized in that in the Electrochemical Detection WS as claimed in claim 1, and the concentration of said mercury ion detects and is limited to 60pM.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102608180A (en) * | 2012-03-21 | 2012-07-25 | 上海大学 | Bioelectrochemical sensor for detecting silver ion and preparation method thereof |
| CN103105424A (en) * | 2013-01-30 | 2013-05-15 | 首都师范大学 | Electrochemical sensor for mercury ion detection, and manufacturing method and detection method thereof |
| CN104198557A (en) * | 2014-09-03 | 2014-12-10 | 大连理工大学 | Enzyme based electrochemical biosensing method applied to detection of trace mercury ions |
| CN104569085A (en) * | 2013-10-28 | 2015-04-29 | 南京大学 | High-sensitivity and high-selectivity metal mercury ion electrochemical sensor |
| CN107255669A (en) * | 2017-06-15 | 2017-10-17 | 湖南师范大学 | A kind of ppt grades of Hg2+Ampere analysis method |
| CN108107033A (en) * | 2017-11-06 | 2018-06-01 | 中山大学 | A kind of single thymidine probe and its preparation method and application |
| CN109187695A (en) * | 2016-05-31 | 2019-01-11 | 中华人民共和国南通出入境检验检疫局 | Application of the probe integrated functionality nucleic acid modified electrode in lake water water sample in lead ion detection |
| CN109470751A (en) * | 2018-09-13 | 2019-03-15 | 宁波大学 | A kind of preparation method and applications of the electrochemical sensor of binary channels output detection mercury ion |
| CN111778244A (en) * | 2020-05-29 | 2020-10-16 | 南京邮电大学 | DNA probe combined with gold nanosphere and application of DNA probe in detection of Hg based on solid-state nanopore2+In (1) |
| CN113049656A (en) * | 2021-01-25 | 2021-06-29 | 宁波大学 | Electrochemical fast-scan voltammetry method with high-order repeatability and reproducibility and analysis application thereof |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102608180A (en) * | 2012-03-21 | 2012-07-25 | 上海大学 | Bioelectrochemical sensor for detecting silver ion and preparation method thereof |
| CN102608180B (en) * | 2012-03-21 | 2014-08-13 | 上海大学 | Bioelectrochemical sensor for detecting silver ion and preparation method thereof |
| CN103105424A (en) * | 2013-01-30 | 2013-05-15 | 首都师范大学 | Electrochemical sensor for mercury ion detection, and manufacturing method and detection method thereof |
| CN103105424B (en) * | 2013-01-30 | 2015-11-18 | 首都师范大学 | A kind of electrochemical sensor for mercury ion detecting and method for making and detection method |
| CN104569085A (en) * | 2013-10-28 | 2015-04-29 | 南京大学 | High-sensitivity and high-selectivity metal mercury ion electrochemical sensor |
| CN104569085B (en) * | 2013-10-28 | 2019-04-02 | 南京大学 | The mercury metal ion electrochemical sensor of highly sensitive high selection |
| CN104198557A (en) * | 2014-09-03 | 2014-12-10 | 大连理工大学 | Enzyme based electrochemical biosensing method applied to detection of trace mercury ions |
| CN109187695A (en) * | 2016-05-31 | 2019-01-11 | 中华人民共和国南通出入境检验检疫局 | Application of the probe integrated functionality nucleic acid modified electrode in lake water water sample in lead ion detection |
| CN107255669A (en) * | 2017-06-15 | 2017-10-17 | 湖南师范大学 | A kind of ppt grades of Hg2+Ampere analysis method |
| CN108107033A (en) * | 2017-11-06 | 2018-06-01 | 中山大学 | A kind of single thymidine probe and its preparation method and application |
| CN109470751A (en) * | 2018-09-13 | 2019-03-15 | 宁波大学 | A kind of preparation method and applications of the electrochemical sensor of binary channels output detection mercury ion |
| CN109470751B (en) * | 2018-09-13 | 2020-10-30 | 宁波大学 | Preparation method and application of electrochemical sensor for detecting mercury ions through dual-channel output |
| CN111778244A (en) * | 2020-05-29 | 2020-10-16 | 南京邮电大学 | DNA probe combined with gold nanosphere and application of DNA probe in detection of Hg based on solid-state nanopore2+In (1) |
| CN111778244B (en) * | 2020-05-29 | 2023-10-27 | 南京邮电大学 | DNA probe combined with gold nanospheres and detection of Hg based on solid-state nanopores 2+ Application in (a) |
| CN113049656A (en) * | 2021-01-25 | 2021-06-29 | 宁波大学 | Electrochemical fast-scan voltammetry method with high-order repeatability and reproducibility and analysis application thereof |
| CN113049656B (en) * | 2021-01-25 | 2024-03-01 | 浙江丰能医药科技有限公司 | Electrochemical fast sweep voltammetry with high-order repeatability and reproducibility and analysis application thereof |
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Application publication date: 20120314 |