CN103336039B - A kind of sensing chip method detecting mercury ion based on Cys - Google Patents
A kind of sensing chip method detecting mercury ion based on Cys Download PDFInfo
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- CN103336039B CN103336039B CN201310293772.4A CN201310293772A CN103336039B CN 103336039 B CN103336039 B CN 103336039B CN 201310293772 A CN201310293772 A CN 201310293772A CN 103336039 B CN103336039 B CN 103336039B
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Abstract
The invention discloses a kind of sensing chip detecting mercury ion based on Cys, this sensing chip comprises the golden film substrate (1) that a Cys 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), crome metal rete (13), cupronickel rete (14), golden membranous layer (15), golden membranous layer (15) is assembling modification Cys rete (16) in its surface again after chemical cleaning process, thus forms the sensing chip detecting mercury ion based on Cys.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 based on Cys, 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, Cys assembling is modified golden film substrate surface by unimolecule self-assembling method by the present invention, forms a kind of sensing chip detecting mercury ion based on Cys.The making of this sensing chip is simple, with low cost, easy to use, sensitivity is very high, 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.
Summary of the invention
Technical matters to be solved by this invention is to provide and a kind ofly makes simple, that cost the is low sensing chip detecting mercury ion based on Cys, 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 based on Cys, it is characterized in that: this sensing chip comprises the golden film substrate that a Cys 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, crome metal rete, cupronickel rete, golden membranous layer, golden membranous layer is assembled in its surface again and is modified Cys rete after chemical cleaning process, thus forms the sensing chip detecting mercury ion based on Cys.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 crome metal rete is 20 ~ 60nm, and the thickness of cupronickel rete is 80 ~ 380nm.Especially, cupronickel 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 Cys rete be 5 ~ 60 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 Cys 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 Cys/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 Cys 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, sensitivity is very high, 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 based on Cys.
Accompanying drawing 2 is the cross-sectional view of the golden film substrate detecting the sensing chip of mercury ion based on Cys.
In accompanying drawing 1, the golden film substrate that 1.L-halfcystine 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. crome metal retes, 14. cupronickel retes, 15. golden membranous layers, 16.L-halfcystine rete, 17.L-cysteine molecule.
Embodiment
embodiment 1
The assembling preparation of sensing chip:
As shown in Figure 1, the sensing chip of mercury ion is detected based on Cys, this sensing chip comprises the golden film substrate 1 that a Cys 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 crome metal rete 13 of rete 12,50nm, the cupronickel rete 14 of 180nm; The golden membranous layer 15 of cupronickel rete 14 sputtering sedimentation 150nm in its surface again after polishing; Golden membranous layer 15 is after chemical cleaning process, and Cys rete 16 is modified in assembling in its surface, and its quality is 27 μ g.
It should be noted that the assembling method of modifying of Cys 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 Cys/ethanolic solution immersing 20mmol/L, self assembly 24 hours in 4 DEG C of refrigerators, take out dry, obtain the sensing chip that Cys rete 16 is modified, the used time is not placed in deionized water in 4 ° of C refrigerator sealing preservations.
embodiment 2
The detection of mercury ion:
Adopt Conventional electrochemical primary element test macro: the sensing chip modified by the Cys 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
-9~ 1.0 × 10
-5linear within the scope of mol/L, 3.4 × 10 are reached to the Monitoring lower-cut of mercury ion
-10mol/L.
embodiment 3
The reappearance of sensing chip:
The sensing chip modified by 10 the Cys retes 16 assembling modification is as stated above working electrode, saturated calomel electrode as contrast electrode, respectively to 2.0 × 10
-6mol/L and 1.0 × 10
-5the 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 0.54% and 0.51%, shows the favorable reproducibility of this sensing chip detection method.
embodiment 4
The selectivity of sensing chip:
Be working electrode by the sensing chip that the Cys rete 16 assembling modification is as stated above modified, saturated calomel electrode, as contrast electrode, has investigated the impact that Common Cations measures mercury ion respectively, finds K
+, Ca
2+, Na
+, Mg
2+, Ba
2+, Cu
2+, Fe
2+, Ag
+, Zn
2+, Bi
3+, Co
2+, Sr
2+, Mn
2+, NH
4 +interference Deng 16 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:
Be working electrode by the sensing chip that the Cys rete 16 assembling modification is as stated above modified, saturated calomel electrode is as contrast electrode, the mark-on having investigated mercury ion in eight water samples respectively detects, and the recovery, between 97.9 ~ 104.8%, illustrates that the method recovery is good; And contrast with standard dithizone spectrophotometry, 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 (5)
1. one kind is detected the sensing chip of mercury ion based on Cys, it is characterized in that: this sensing chip comprises the golden film substrate (1) that a Cys 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 Cys rete (16) in its surface again after chemical cleaning process;
The assembling method of modifying of described Cys 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 Cys/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 Cys rete (16) is modified, the used time is not placed in deionized water in 4 DEG C of refrigerators sealing preservations;
Golden membranous layer (15) after chemical cleaning process, its surface institute assemble modification Cys rete (16) amount be 5 ~ 60 μ g.
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. according to the sensing chip in claim 1-3 described in any one, it 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 ~ 60nm, 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.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105675676B (en) * | 2016-01-22 | 2018-04-13 | 湖南大学 | Electrochemical DNA biosensor for detecting mercury ion or cysteine and its preparation method and application |
| CN107643228B (en) * | 2017-08-31 | 2021-04-27 | 中国船舶重工集团公司第七一九研究所 | Preparation method of chip for measuring mercury vapor and use method of sensor |
| CN109115846B (en) * | 2018-08-28 | 2023-09-08 | 长沙理工大学 | Detection method and sensor of L-cystine based on 3-mercaptopropionic acid modified gate gold electrode |
| CN113637468B (en) * | 2021-08-11 | 2023-12-26 | 淮北师范大学 | Difunctional fluorescent film for detecting mercury ions and glutathione, preparation and application |
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| CN201831878U (en) * | 2010-09-02 | 2011-05-18 | 深圳安维森实业有限公司 | Medical body-temperature probe |
| CN203337597U (en) * | 2013-07-15 | 2013-12-11 | 长沙理工大学 | Sensing chip used for detecting mercury ions and based on L-cysteine |
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| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN201831878U (en) * | 2010-09-02 | 2011-05-18 | 深圳安维森实业有限公司 | Medical body-temperature probe |
| CN203337597U (en) * | 2013-07-15 | 2013-12-11 | 长沙理工大学 | Sensing chip used for detecting mercury ions and based on L-cysteine |
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| Title |
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| 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 * |
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