CN103344683A - Sensing chip method for detecting mercury ions - Google Patents
Sensing chip method for detecting mercury ions Download PDFInfo
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- CN103344683A CN103344683A CN201310293771XA CN201310293771A CN103344683A CN 103344683 A CN103344683 A CN 103344683A CN 201310293771X A CN201310293771X A CN 201310293771XA CN 201310293771 A CN201310293771 A CN 201310293771A CN 103344683 A CN103344683 A CN 103344683A
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- sensing chip
- rete
- undecanoic acid
- gold
- membrane layer
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Abstract
The invention discloses a sensing chip for detecting mercury ions. The sensing chip comprises a metal substrate (1) modified by a 11-sulfydryl hendecanoic acid membrane layer (16), wherein one corner of a gold layer of the metal substrate (1) is connected with a metal wire conductor (2) wrapped by a plastic insulation layer (3), and the connection part is wrapped and sealed by using expoxy resin glue (4); and the metal substrate (1) is formed by gradually sputtering and depositing a SiO2 membrane layer (12), a metal titanium membrane layer (13), a copper-tin alloy membrane layer (14) and a gold membrane layer (15) on a polished silicon nitride substrate (11), the gold membrane layer (15) is subjected to chemical cleaning treatment, and then a modification 11-sulfydryl hendecanoic acid membrane layer (16) is assembled on the surface of the gold membrane layer (15), thus the sensing chip for detecting the mercury ions is manufactured. The sensing chip is simple in manufacturing, low in cost and convenient to use and can be used for rapidly detecting trace amounts of mercury ions in environments.
Description
Technical field
The present invention relates to a kind of sensing chip that detects mercury ion, belong to the chemical/biological field of sensing technologies, be applicable to that Environmental security detects.
Background technology
Mercury pollution is a global problem, because its severe toxicity and biological accumulation, it has received increasing concern.Dimercurion (Hg
2+) be the most stable inorganic mercury, be present in the natural water body Hg
2+Even micro-concentrations also can toxigenicity, it can be accumulated in vivo, by food chain transport in human body, and the Trace Mercury of accumulation can't be drained by self metabolism in the human body, to directly cause heart, liver, thyroid disease, cause nerve problems, chronic mercury poisoning, even the formation of initiation malignant tumour.Secondly, the ecological methylate methyl mercury of the microorganism of mercury ion also is a kind of strong toxin, can be delivered in the tissue of fish and marine mammal by food chain, is converted into the organic mercury of severe toxicity.Therefore, can quick and precisely analyze the content of beary metal in the medium such as water body in the living environment, for improve the human existence quality, the environment of preserving our planet has very important meaning.
The method that detects metal mercury ions has a lot, as atomic spectroscopy, inductively coupled plasma atomic emission spectrum (ICP-AES method), spectrophotometric method, high performance liquid chromatography, inductively coupled plasma mass spectrometry (ICPMS), chemoluminescence method and fluorometry etc.Yet these methods often need expensive exact instrument, complicated sample preparation flow and skilled operating personnel, can not or inconvenience carry out fast detecting out of doors.For this reason, the present invention modifies golden film substrate surface by the unimolecule self-assembling method with the assembling of 11-sulfydryl undecanoic acid, forms a kind of sensing chip that detects mercury ion.This sensing chip is made simple, with low cost, easy to use, is better than traditional instrument analytical method, can be used for the fast detecting of Trace Mercury ion in the environment, has very important application prospect in fields such as environmental monitoring, agricultural food product and biomedicine.
Summary of the invention
Technical matters to be solved by this invention provides a kind of sensing chip of making the detection mercury ion simple, that cost is low, can be used for Environmental security and detects.
In order to achieve the above object, the technical solution used in the present invention is: a kind of sensing chip that detects mercury ion, it is characterized in that: this sensing chip comprises the golden film substrate that a 11-sulfydryl undecanoic acid rete is modified, one jiao on the gold layer of this gold film substrate is connected junction epoxide-resin glue environmental sealing with the tinsel lead that is surrounded by plastic insulating layer outward; Described golden film substrate is sputtering sedimentation SiO progressively on the silicon nitride substrate of polishing
2Rete, Titanium rete, signal bronze rete, golden membranous layer, golden membranous layer are assembled in its surface after chemical cleaning is handled again and are modified 11-sulfydryl undecanoic acid rete, thereby constitute the sensing chip that detects mercury ion.Wherein, described golden film substrate be shaped as square, its length of side is 6 ~ 12mm, the material of tinsel lead is copper wire, aluminium wire or filamentary silver.And, the SiO of sputtering sedimentation progressively on the silicon nitride substrate of polishing
2The thickness of rete is 80 ~ 380nm, and the thickness of Titanium rete is 20 ~ 80nm, and the thickness of signal bronze rete is 80 ~ 380nm.Especially, the signal bronze rete is after polishing, and the thickness of institute's deposited gold rete is 120 ~ 400nm in its surface; Golden membranous layer is after chemical cleaning is handled, and assembling the amount of modifying 11-sulfydryl undecanoic acid rete in its surface is 5 ~ 50 μ g.
Aspect the design and preparation of sensing chip, different with other method is, the present invention proposes a kind of assembling method of modifying of simple 11-sulfydryl undecanoic acid rete, namely earlier the golden membranous layer surface of sensing chip gold film substrate is cleaned with redistilled water, successively at redistilled water, ultrasonic cleaning is each 1 ~ 10 minute in the absolute ethyl alcohol, take out in the 11-sulfydryl undecanoic acid/ethanolic solution that immerses 1.0 ~ 100mmol/L then, self assembly is 2 ~ 48 hours in 4 ℃ of refrigerators, take out dry, get the sensing chip that 11-sulfydryl undecanoic acid rete is modified, the time spent does not place deionized water to preserve in 4 ° of C refrigerators sealings.
The invention has the beneficial effects as follows, this nano-gold film electrode is made simple, with low cost, easy to use, and golden film flatness height, easily carry out finishing, versatility is very strong, be better than traditional instrument analytical method, the fast detecting that can be used for Trace Mercury ion in the environment has very important application prospect in fields such as environmental monitoring, agricultural food product and biomedicine.
Description of drawings
The present invention is further described below in conjunction with accompanying drawing.
Accompanying drawing 1 is the planar structure synoptic diagram that detects the sensing chip of mercury ion.
Accompanying drawing 2 is the cross-sectional view of golden film substrate that detect the sensing chip of mercury ion.
In the accompanying drawing 1, the 1. golden film substrate modified of 11-sulfydryl undecanoic acid rete, 2. tinsel lead, 3. plastic insulating layer, 4. epoxide-resin glue.
In the accompanying drawing 2,11. silicon nitride substrates, 12. SiO
2Rete, 13. Titanium retes, 14. signal bronze retes, 15. golden membranous layers, 16. 11-sulfydryl undecanoic acid retes, 17. 11-sulfydryl undecanoic acid molecules.
Embodiment
Embodiment 1
The assembling preparation of sensing chip:
As shown in Figure 1, detect the sensing chip of mercury ion, this sensing chip comprises the golden film substrate 1 that a 11-sulfydryl undecanoic acid rete 16 is modified, one jiao on the gold layer of this gold film substrate 1 is connected junction usefulness epoxide-resin glue 4 environmental sealings with the tinsel that is surrounded by plastic insulating layer 3 outward such as copper wire lead 2.Used epoxide-resin glue 4 links to each other one jiao on the gold layer of golden film substrate 1 with copper wire lead 2 sealed envelope, with assurance favorable conductive, conduction.
As shown in Figure 2, for golden film substrate 1, it is shaped as square, and the selection length of side is 6mm, is the SiO of sputtering sedimentation 300nm progressively on the silicon nitride substrate 11 of polishing
2The Titanium rete 13 of rete 12,50nm, the signal bronze rete 14 of 180nm; Signal bronze rete 14 golden membranous layer 15 of sputtering sedimentation 150nm in its surface again after polishing; Golden membranous layer 15 is after chemical cleaning is handled, and 11-sulfydryl undecanoic acid rete 16 is modified in assembling in its surface, and its quality is 22 μ g.
It should be noted that the assembling method of modifying of 11-sulfydryl undecanoic acid rete 16, namely earlier golden membranous layer 15 surfaces of sensing chip gold film substrate 1 are cleaned with redistilled water, successively in redistilled water, absolute ethyl alcohol ultrasonic cleaning each 3 minutes, take out in the 11-sulfydryl undecanoic acid/ethanolic solution that immerses 10mmol/L then, self assembly is 24 hours in 4 ℃ of refrigerators, take out dry, get the sensing chip that 11-sulfydryl undecanoic acid rete 16 is modified, the time spent does not place deionized water to preserve in 4 ° of C refrigerators sealings.
The detection of mercury ion:
Adopt conventional electrochemical primary cells test macro: the sensing chip that the 11-sulfydryl undecanoic acid rete 16 of said method assembling modification is modified is working electrode, saturated calomel electrode is as contrast electrode, carry out the electrochemical potential test, the potential response value of this sensing chip electrode and the concentration of mercury ion are 1.0 * 10
-8~ 1.0 * 10
-4Linear in the mol/L scope, the detection lower limit of mercury ion is reached 5.6 * 10
-9Mol/L.
The reappearance of sensing chip:
The sensing chip that 10 11-sulfydryl undecanoic acid retes 16 of assembling modification are as stated above modified is working electrode, and saturated calomel electrode is as contrast electrode, respectively to 1.0 * 10
-5Mol/L and 1.0 * 10
-4The mercury ion solution example of mol/L carries out electrochemical potential test, and as can be seen, after carrying out continuously measuring for 10 times, relative standard deviation is respectively 0.52% and 0.34%, shows the favorable reproducibility of this sensing chip detection method.
The selectivity of sensing chip:
The sensing chip that the 11-sulfydryl undecanoic acid rete 16 of assembling modification is as stated above modified is working electrode, and saturated calomel electrode has been investigated the influence that common kation is measured mercury ion respectively as contrast electrode, finds except Cu
2+, Fe
2+Two metal ion species have outside the less interference, Na
+, K
+, Mg
2+, Ba
2+, Ca
2+, Zn
2+, Sn
2+, Pb
2+, Ag
+, Bi
3+, Al
3+, Fe
3+And Ni
2+ Interference Deng 14 metal ion species is not obvious, shows that the selectivity of this sensing chip detection method is good.
Embodiment 5
The mensuration of mercury ion in the environmental wastewater sample:
The sensing chip that the 11-sulfydryl undecanoic acid rete 16 of assembling modification is as stated above modified is working electrode, saturated calomel electrode is as contrast electrode, the mark-on of having investigated mercury ion in four kinds of wastewater samples respectively detects, and the recovery illustrates that this method recovery is good between 97.5 ~ 104.2%; And with standard spectrophotometric method contrast, the measurement result of sample is relatively more consistent, meets the requirement of quantitative test, illustrates that this sensing chip can be applicable to the detection of mercury ion in the real wastewater samples.
Claims (8)
1. sensing chip that detects mercury ion, it is characterized in that: this sensing chip comprises the golden film substrate (1) that a 11-sulfydryl undecanoic acid rete (16) is modified, one jiao on the gold layer of this gold film substrate (1) is connected junction usefulness epoxide-resin glue (4) environmental sealing with the tinsel lead (2) that is surrounded by plastic insulating layer (3) outward.
2. sensing chip according to claim 1 is characterized in that: described golden film substrate (1) is sputtering sedimentation SiO progressively on the silicon nitride substrate (11) of polishing
2Rete (12), Titanium rete (13), signal bronze rete (14), golden membranous layer (15), golden membranous layer (15) are assembled in its surface after chemical cleaning is handled again and are modified 11-sulfydryl undecanoic acid rete (16).
3. sensing chip according to claim 1 is characterized in that: described golden film substrate (1) be shaped as square, its length of side is 6 ~ 12mm.
4. sensing chip according to claim 1, it is characterized in that: the material of described tinsel lead (2) is copper wire, aluminium wire or filamentary silver.
5. sensing chip according to claim 2 is characterized in that: the SiO of sputtering sedimentation progressively on the silicon nitride substrate (11) of polishing
2The thickness of rete (12) is 80 ~ 380nm, and the thickness of Titanium rete (13) is 20-80nm, and the thickness of signal bronze rete (14) is 80 ~ 380nm.
6. sensing chip according to claim 2, it is characterized in that: signal bronze rete (14) is after polishing, and the thickness of institute's deposited gold rete (15) is 120 ~ 400nm in its surface.
7. sensing chip according to claim 2 is characterized in that: golden membranous layer (15) is after chemical cleaning is handled, and the amount of assembling modification 11-sulfydryl undecanoic acid rete (16) in its surface is 5 ~ 50 μ g.
8. sensing chip according to claim 2, the assembling method of modifying that it is characterized in that 11-sulfydryl undecanoic acid rete (16), namely earlier golden membranous layer (15) surface of sensing chip gold film substrate (1) is cleaned with redistilled water, successively at redistilled water, ultrasonic cleaning is each 1 ~ 10 minute in the absolute ethyl alcohol, take out in the 11-sulfydryl undecanoic acid/ethanolic solution that immerses 1.0 ~ 100mmol/L then, self assembly is 2 ~ 48 hours in 4 ℃ of refrigerators, take out dry, get the sensing chip that 11-sulfydryl undecanoic acid rete (16) is modified, the time spent does not place deionized water to preserve in 4 ° of C refrigerators sealings.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103760205A (en) * | 2014-02-26 | 2014-04-30 | 长沙理工大学 | Method for dithiothreitol membrane mercury ion selective electrode |
| CN103776886A (en) * | 2014-02-26 | 2014-05-07 | 长沙理工大学 | Preparation method of mercury ion selective electrode |
| CN103776887A (en) * | 2014-02-26 | 2014-05-07 | 长沙理工大学 | Preparation method of self-assembled film mercury ion selective electrode |
| CN103776882A (en) * | 2014-02-26 | 2014-05-07 | 长沙理工大学 | Silicon nitride-based nano gold film electrode method |
| CN103792273A (en) * | 2014-02-26 | 2014-05-14 | 长沙理工大学 | Nano gold membrane electrode based on borosilicate |
| CN111948163A (en) * | 2019-05-17 | 2020-11-17 | 安徽伊尔思环境科技有限公司 | Waste water detection sensing chip and system thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20060092751A (en) * | 2005-02-19 | 2006-08-23 | 이종협 | Chip for the detection of heavy metal using surface plasmon resonance measurements |
| CN201831878U (en) * | 2010-09-02 | 2011-05-18 | 深圳安维森实业有限公司 | Medical body-temperature probe |
| CN203337596U (en) * | 2013-07-15 | 2013-12-11 | 长沙理工大学 | Sensing chip for detecting mercury ions |
-
2013
- 2013-07-15 CN CN201310293771.XA patent/CN103344683B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20060092751A (en) * | 2005-02-19 | 2006-08-23 | 이종협 | Chip for the detection of heavy metal using surface plasmon resonance measurements |
| CN201831878U (en) * | 2010-09-02 | 2011-05-18 | 深圳安维森实业有限公司 | Medical body-temperature probe |
| CN203337596U (en) * | 2013-07-15 | 2013-12-11 | 长沙理工大学 | Sensing chip for detecting mercury ions |
Non-Patent Citations (2)
| Title |
|---|
| ANTJE WIDMANN ET AL: "Mercury Detection in Seawater Using a Mercaptoacetic Acid Modified Gold Microwire Electrode", 《ELECTROANALYSIS》, vol. 17, no. 10, 27 January 2005 (2005-01-27) * |
| 张慢乐: "纳米材料修饰电极的制备及用于食品中亚硝酸根检测的应用研究", 《中国优秀硕士学位论文全文数据库（工程科技Ⅰ辑）》, no. 9, 15 September 2012 (2012-09-15) * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103760205A (en) * | 2014-02-26 | 2014-04-30 | 长沙理工大学 | Method for dithiothreitol membrane mercury ion selective electrode |
| CN103776886A (en) * | 2014-02-26 | 2014-05-07 | 长沙理工大学 | Preparation method of mercury ion selective electrode |
| CN103776887A (en) * | 2014-02-26 | 2014-05-07 | 长沙理工大学 | Preparation method of self-assembled film mercury ion selective electrode |
| CN103776882A (en) * | 2014-02-26 | 2014-05-07 | 长沙理工大学 | Silicon nitride-based nano gold film electrode method |
| CN103792273A (en) * | 2014-02-26 | 2014-05-14 | 长沙理工大学 | Nano gold membrane electrode based on borosilicate |
| CN103776886B (en) * | 2014-02-26 | 2016-01-20 | 长沙理工大学 | A kind of mercury ion choice electrode method |
| CN103776882B (en) * | 2014-02-26 | 2016-01-20 | 长沙理工大学 | A kind of Nanometer scale Au film electrode based on silicon nitride |
| CN103792273B (en) * | 2014-02-26 | 2016-02-17 | 长沙理工大学 | A kind of Nanometer scale Au film electrode based on borosilicate |
| CN103760205B (en) * | 2014-02-26 | 2016-04-13 | 长沙理工大学 | Method for dithiothreitol membrane mercury ion selective electrode |
| CN103776887B (en) * | 2014-02-26 | 2016-05-04 | 长沙理工大学 | A kind of self-assembled film mercury ion is selected electrode method |
| CN111948163A (en) * | 2019-05-17 | 2020-11-17 | 安徽伊尔思环境科技有限公司 | Waste water detection sensing chip and system thereof |
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| Publication number | Publication date |
|---|---|
| CN103344683B (en) | 2015-11-11 |
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