CN103344683B - A kind of sensing chip method detecting mercury ion - Google Patents
A kind of sensing chip method detecting mercury ion Download PDFInfo
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- CN103344683B CN103344683B CN201310293771.XA CN201310293771A CN103344683B CN 103344683 B CN103344683 B CN 103344683B CN 201310293771 A CN201310293771 A CN 201310293771A CN 103344683 B CN103344683 B CN 103344683B
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- rete
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- mercaptoundecanoic acid
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Abstract
The invention discloses a kind of sensing chip detecting mercury ion, this sensing chip comprises the golden film substrate (1) that a 11-Mercaptoundecanoic acid rete (16) is modified, the layer gold one jiao of this golden film substrate (1) is connected with the tinsel wire (2) being surrounded by plastic insulating layer (3) outward, junction epoxide-resin glue (4) environmental sealing; Described golden film substrate (1) is progressively sputtering sedimentation SiO on the silicon nitride board (11) of polishing
2rete (12), Titanium rete (13), signal bronze rete (14), golden membranous layer (15), golden membranous layer (15) is assembling modification 11-Mercaptoundecanoic acid rete (16) in its surface again after chemical cleaning process, thus forms the sensing chip detecting mercury ion.This sensing chip makes simple, with low cost, easy to use, can be used for the quick detection of Trace Mercury ion in environment.
Description
Technical field
The present invention relates to a kind of sensing chip detecting mercury ion, belong to chemical/biological field of sensing technologies, be applicable to Environmental security and detect.
Background technology
Mercury pollution is a global problem, and due to its severe toxicity and bioconcentration, it has received increasing concern.Dimercurion (Hg
2+) be the most stable inorganic mercury, be present in natural water body, Hg
2+even micro-concentrations also can produce toxicity, it can be accumulated in vivo, by food chain transport in human body, and the Trace Mercury of accumulation cannot be drained by own metabolism in human body, to directly cause heart, liver, thyroid disease, cause nerve problems, chronic mercury poisoning, even cause the formation of malignant tumour.Secondly, the ecological methylate methyl mercury of the microorganism of mercury ion, is also a kind of strong toxin, is delivered in the tissue of fish and marine mammal by food chain, is converted into the organic mercury of severe toxicity.Therefore, quick and precisely can analyze the content of beary metal in the media such as water body in living environment, life quality, the environment tool of preserving our planet improving the mankind is of great significance.
The method detecting 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.But these methods often need expensive exact instrument, complicated sample preparation flow process and skilled operating personnel, can not or inconvenience detect fast out of doors.For this reason, the assembling of 11-Mercaptoundecanoic acid is modified golden film substrate surface by unimolecule self-assembling method by the present invention, forms a kind of sensing chip detecting mercury ion.This sensing chip makes simple, with low cost, easy to use, is better than traditional instrument analytical method, can be used for the quick detection of Trace Mercury ion in environment, in the fields such as environmental monitoring, agricultural food product and biomedicine, have very important application prospect.
Summary of the invention
Technical matters to be solved by this invention is to provide a kind of sensing chip making the detection mercury ion simple, 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 detecting mercury ion, it is characterized in that: this sensing chip comprises the golden film substrate that a 11-Mercaptoundecanoic acid rete is modified, the layer gold one jiao of this golden film substrate is connected with the tinsel wire being surrounded by plastic insulating layer outward, junction epoxide-resin glue environmental sealing; Described golden film substrate is progressively sputtering sedimentation SiO on the silicon nitride board of polishing
2rete, Titanium rete, signal bronze rete, golden membranous layer, golden membranous layer is assembled in its surface again and is modified 11-Mercaptoundecanoic acid rete after chemical cleaning process, thus forms the sensing chip detecting mercury ion.Wherein, the shape of described golden film substrate is square, and its length of side is 6 ~ 12mm, and the material of tinsel wire is copper wire, aluminium wire or filamentary silver.And, the SiO of progressively sputtering sedimentation on the silicon nitride board 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, signal bronze rete is after polishing, and the thickness of institute's deposited gold rete is 120 ~ 400nm in its surface; Golden membranous layer after chemical cleaning process, in its surface to assemble the amount of modifying 11-Mercaptoundecanoic acid rete be 5 ~ 50 μ g.
In the Design & preparation of sensing chip, with other method unlike, the present invention proposes a kind of assembling method of modifying of simple 11-Mercaptoundecanoic acid rete, namely first the golden membranous layer surface redistilled water of sensing chip gold film substrate is cleaned, successively at redistilled water, each 1 ~ 10 minute of ultrasonic cleaning in absolute ethyl alcohol, then take out in the 11-Mercaptoundecanoic acid/ethanolic solution of immersion 1.0 ~ 100mmol/L, self assembly 2 ~ 48 hours in 4 DEG C of refrigerators, take out dry, obtain the sensing chip that 11-Mercaptoundecanoic acid rete is modified, the used time is not placed in deionized water in 4 ° of C refrigerator sealing preservations.
The invention has the beneficial effects as follows, this Nanometer scale Au film electrode makes simple, with low cost, easy to use, and golden film flatness high, easily carry out finishing, versatility is very strong, be better than traditional instrument analytical method, can be used for the quick detection of Trace Mercury ion in environment, in the fields such as environmental monitoring, agricultural food product and biomedicine, there is very important application prospect.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the present invention is further described.
Accompanying drawing 1 is the planar structure schematic diagram of the sensing chip detecting mercury ion.
Accompanying drawing 2 is cross-sectional view of the golden film substrate of the sensing chip detecting mercury ion.
In accompanying drawing 1, the golden film substrate that 1.11-Mercaptoundecanoic acid rete is modified, 2. tinsel wire, 3. plastic insulating layer, 4. epoxide-resin glue.
In accompanying drawing 2,11. silicon nitride boards, 12.SiO
2rete, 13. Titanium retes, 14. signal bronze retes, 15. golden membranous layers, 16.11-Mercaptoundecanoic acid rete, 17.11-mercapto-undecanoic acid molecule.
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-Mercaptoundecanoic acid rete 16 is modified, the layer gold one jiao of this golden film substrate 1 is connected with tinsel such as the copper wire wire 2 being surrounded by plastic insulating layer 3 outward, junction epoxide-resin glue 4 environmental sealing.The layer gold one jiao of golden film substrate 1 is connected with copper wire wire 2 sealed envelope, to ensure good conduction, conduction by epoxide-resin glue 4 used.
As shown in Figure 2, for golden film substrate 1, its shape is square, and the selection length of side is 6mm, is the SiO of progressively sputtering sedimentation 300nm on the silicon nitride board 11 of polishing
2the Titanium rete 13 of rete 12,50nm, the signal bronze rete 14 of 180nm; The golden membranous layer 15 of signal bronze rete 14 sputtering sedimentation 150nm in its surface again after polishing; Golden membranous layer 15 is after chemical cleaning process, and 11-Mercaptoundecanoic 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-Mercaptoundecanoic acid rete 16, namely first the golden membranous layer 15 surface redistilled water of sensing chip gold film substrate 1 is cleaned, each 3 minutes of ultrasonic cleaning in redistilled water, absolute ethyl alcohol successively, then take out in the 11-Mercaptoundecanoic acid/ethanolic solution immersing 10mmol/L, self assembly 24 hours in 4 DEG C of refrigerators, take out dry, obtain the sensing chip that 11-Mercaptoundecanoic acid rete 16 is modified, the used time is not placed in deionized water in 4 ° of C refrigerators sealing preservations.
embodiment 2
The detection of mercury ion:
Adopt Conventional electrochemical primary element test macro: the sensing chip modified by the 11-Mercaptoundecanoic acid rete 16 that said method assembling is modified is working electrode, saturated calomel electrode is as contrast electrode, carry out 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 within the scope of mol/L, 5.6 × 10 are reached to the Monitoring lower-cut of mercury ion
-9mol/L.
embodiment 3
The reappearance of sensing chip:
The sensing chip modified by 10 the 11-Mercaptoundecanoic acid retes 16 assembling modification is as stated above working electrode, saturated calomel electrode 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, can find out, after carrying out 10 mensuration continuously, relative standard deviation is respectively 0.52% and 0.34%, shows the favorable reproducibility of this sensing chip detection method.
embodiment 4
The selectivity of sensing chip:
The sensing chip modified by the 11-Mercaptoundecanoic acid rete 16 assembling modification is as stated above working electrode, and saturated calomel electrode, as contrast electrode, has been investigated the impact that Common Cations measures mercury ion respectively, found except Cu
2+, Fe
2+two metal ion species have outside 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 environmental wastewater sample:
The sensing chip modified by the 11-Mercaptoundecanoic acid rete 16 assembling modification is as stated above working electrode, saturated calomel electrode is as contrast electrode, the mark-on having investigated mercury ion in four kinds of wastewater samples respectively detects, and the recovery, between 97.5 ~ 104.2%, illustrates that the method recovery is good; And contrast with standard spectrophotometric method, 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 real wastewater samples.
Claims (6)
1. one kind is detected the sensing chip of mercury ion, it is characterized in that: this sensing chip comprises the golden film substrate (1) that a 11-Mercaptoundecanoic acid rete (16) is modified, the layer gold one jiao of this golden film substrate (1) is connected with the tinsel wire (2) being surrounded by plastic insulating layer (3) outward, junction epoxide-resin glue (4) environmental sealing;
Described golden film substrate (1) is progressively sputtering sedimentation SiO on the silicon nitride board (11) of polishing
2rete (12), Titanium rete (13), signal bronze rete (14), golden membranous layer (15), golden membranous layer (15) is assembling modification 11-Mercaptoundecanoic acid rete (16) in its surface again after chemical cleaning process;
The assembling method of modifying of described 11-Mercaptoundecanoic acid rete (16), namely first golden membranous layer (15) the surface redistilled water of sensing chip gold film substrate (1) is cleaned, each 1 ~ 10 minute of ultrasonic cleaning in redistilled water, absolute ethyl alcohol successively, then take out in the 11-Mercaptoundecanoic acid/ethanolic solution of immersion 1.0 ~ 100mmol/L, self assembly 24 ~ 48 hours in 4 DEG C of refrigerators, take out dry, obtain the sensing chip that 11-Mercaptoundecanoic acid rete (16) is modified, the used time is not placed in deionized water in 4 DEG C of refrigerators sealing preservations.
2. sensing chip according to claim 1, is characterized in that: the shape of described golden film substrate (1) is square, and its length of side is 6 ~ 12mm.
3. sensing chip according to claim 1, is characterized in that: the material of described tinsel wire (2) is copper wire, aluminium wire or filamentary silver.
4. sensing chip according to claim 1, is characterized in that: the SiO of progressively sputtering sedimentation on the silicon nitride board (11) of polishing
2the thickness of rete (12) is 80 ~ 380nm, the thickness of Titanium rete (13) is 20 ~ 80nm, the thickness of signal bronze rete (14) is 80 ~ 380nm.
5. sensing chip according to claim 1, 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.
6. sensing chip according to claim 1, is characterized in that: golden membranous layer (15) after chemical cleaning process, its surface institute assemble modification 11-Mercaptoundecanoic acid rete (16) amount be 5 ~ 50 μ g.
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| CN103344683B true CN103344683B (en) | 2015-11-11 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN103776886B (en) * | 2014-02-26 | 2016-01-20 | 长沙理工大学 | A kind of mercury ion choice electrode method |
| CN103760205B (en) * | 2014-02-26 | 2016-04-13 | 长沙理工大学 | Method for dithiothreitol membrane mercury ion selective electrode |
| 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 |
| 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 (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Family Cites Families (1)
| 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 |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
|---|
| Mercury Detection in Seawater Using a Mercaptoacetic Acid Modified Gold Microwire Electrode;Antje Widmann et al;《Electroanalysis》;20050127;第17卷(第10期);第826、830页 * |
| 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;张慢乐;《中国优秀硕士学位论文全文数据库（工程科技Ⅰ辑）》;20120915(第9期);第20页，图2.1（a） * |
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