CN103344693A - Sensing chip method for detecting nitrite - Google Patents
Sensing chip method for detecting nitrite Download PDFInfo
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- CN103344693A CN103344693A CN2013102937419A CN201310293741A CN103344693A CN 103344693 A CN103344693 A CN 103344693A CN 2013102937419 A CN2013102937419 A CN 2013102937419A CN 201310293741 A CN201310293741 A CN 201310293741A CN 103344693 A CN103344693 A CN 103344693A
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Abstract
The invention discloses a sensing chip for detecting nitrite. The sensing chip comprises a metal substrate (1) modified by gadolinium oxide-titanium dioxide composite nanometer particles, 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 gadolinium oxide-titanium dioxide composite nanometer particle layer (16) is assembled on the surface of the gold membrane layer (15), thus the sensing chip for detecting nitrite 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 nitrite in food.
Description
Technical field
The present invention relates to a kind of sensing chip that detects nitrite, belong to the chemical/biological field of sensing technologies, be applicable to food safety detection.
Background technology
Nitrite extensively is present in environment, food, the beverage.In food industry, nitrite Chang Zuowei adjuvant has certain antibiotic antisepsis.Nitrite and amine substance can generate carcinogen N-nitrosamine.Because its potential toxicity, so the detection of content of nitrite no matter is in environmental science or all there is important meaning in the public health field.Assay method to nitrite has spectrophotometric method, chromatography, electrochemical method etc. in recent years.In these methods, electrochemical method is widely used in measuring nitrite because it is highly sensitive, low with cost easily and fast.Because NO
2 -At bare electrode very high overpotential is arranged, very easily is subjected to the interference of readily oxidizable substance, in order to improve mensuration sensitivity, can electrode face finish suitable eelctro-catalyst reduce operating potential.About NO
2 -The modified electrode of measuring has more report, as CuPtCl
6Modified glassy carbon electrode, carbon nano tube modified glass-carbon electrode, polypyrrole nano line modified electrode, decorated by nano-gold electrode, copper nano-particle/carbon nano-tube/chitosan-modified glass-carbon electrode etc., and adopt the modified electrode of gadolinium oxide-titania composite nanometer particle to yet there are no reported in literature.For this reason, the present invention modifies gadolinium oxide-titania composite nanometer particle assembling on golden film substrate surface, forms a kind of sensing chip that detects nitrite by electrostatic adsorption.This sensing chip is made simple, with low cost, easy to use, is better than the traditional electrical chemically modified electrode, can be used for the fast detecting of micro-nitrite in the food, has very important application prospect in fields such as agricultural food product, biomedicine and environmental monitoring.
Summary of the invention
Technical matters to be solved by this invention provides a kind of sensing chip of making the detection nitrite simple, that cost is low, can be used for food safety detection.
In order to achieve the above object, the technical solution used in the present invention is: a kind of sensing chip that detects nitrite, it is characterized in that: this sensing chip comprises the golden film substrate that a gadolinium oxide-titania composite nanometer particle 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 gadolinium oxide-titania composite nanometer particle layer, thereby constitute the sensing chip that detects nitrite.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 thickness of modifying gadolinium oxide-titania composite nanometer particle layer in its surface is 20-400nm.
Aspect the design and preparation of sensing chip, different with other method is, the present invention proposes the preparation method of a kind of simple oxidation gadolinium-titania composite nanometer particle, namely get an amount of gadolinium oxide and add the nitric acid heating for dissolving, form colourless transparent solution, stir and add an amount of absolute ethyl alcohol and tetrabutyl titanate down, formation A liquid; Dropwise add the finely dispersed B liquid that is mixed by absolute ethyl alcohol, glacial acetic acid, hydrogen peroxide and PEG400 then, regulate pH value to 1-5 with dilute nitric acid solution, continue to keep stirring 10-60 minutes, get a uniform and stable colloidal sol; Ageing 2-48 hours gets gadolinium oxide-titania composite nanometer particle sol solution, i.e. C liquid.And, the preparation key of this sensing chip also is the assembling method of modifying of gadolinium oxide-titania composite nanometer particle layer, namely earlier the golden membranous layer surface of sensing chip gold film substrate is cleaned with redistilled water, successively in absolute ethyl alcohol, redistilled water ultrasonic cleaning each 1-10 minutes, take out under room temperature and dry naturally; Getting gadolinium oxide-titania composite nanometer particle sol solution (C liquid) is dissolved in an amount of redistilled water; ultrasonic dispersion 1-10 hours; getting 2-40 microlitres evenly is coated on the golden membranous layer surface; dry under infrared lamp; form the composite nanometer particle layer that gadolinium oxide nano particle and titania nanoparticles mix; form the effect of Ti-O-Gd key between two kinds of nano particles, namely obtain the sensing chip that gadolinium oxide-titania composite nanometer particle is modified, the time spent preserves in 4 ° of C sealings of refrigerator.
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 the traditional electrical chemically modified electrode, the fast detecting that can be used for micro-nitrite in the food has very important application prospect in fields such as agricultural food product, biomedicine and environmental monitoring.
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 nitrite.
Accompanying drawing 2 is the cross-sectional view that detect the sensing chip gold film substrate of nitrite.
In the accompanying drawing 1, the 1. golden film substrate modified of gadolinium oxide-titania composite nanometer particle, 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. gadolinium oxides-titania composite nanometer particle layer, 17. titania nanoparticles, 18. gadolinium oxide nano particles.
Embodiment
The assembling preparation of sensing chip:
As shown in Figure 1, detect the sensing chip of nitrite, this sensing chip comprises the golden film substrate 1 that a gadolinium oxide-titania composite nanometer particle 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 gadolinium oxide-titania composite nanometer particle layer 16 is modified in assembling in its surface, and its thickness is 120nm.
It should be noted that the preparation method of gadolinium oxide-titania composite nanometer particle, namely get the 0.021g gadolinium oxide and add 0.5mL nitric acid heating for dissolving, get colourless transparent solution; At the uniform velocity stir, add 20mL absolute ethyl alcohol and 12mL tetrabutyl titanate, form A liquid; Continue to stir, dropwise add and finely dispersedly mix B liquid by 10mL absolute ethyl alcohol, 2mL glacial acetic acid, 2mL hydrogen peroxide and 4mL PEG400, with dilute nitric acid solution regulator solution pH value=3.0, continue to keep stirring 40 minutes, get a uniform and stable colloidal sol; Ageing 18 hours gets gadolinium oxide-titania composite nanometer particle sol solution, i.e. C liquid.
And, the preparation key of this sensing chip also is the assembling method of modifying of gadolinium oxide-titania composite nanometer particle layer 16, namely earlier golden membranous layer 15 surfaces of sensing chip gold film substrate 1 are cleaned with redistilled water, successively in absolute ethyl alcohol, redistilled water ultrasonic cleaning each 2 minutes, take out under room temperature and dry naturally; Getting gadolinium oxide-titania composite nanometer particle sol solution (C liquid) is dissolved in an amount of redistilled water, concentration is 0.75mg/mL, ultrasonic dispersion 1.5 hours, getting 20 microlitres evenly is coated on golden membranous layer 15 surfaces, dry under infrared lamp, form the composite nanometer particle layer 16 that gadolinium oxide nano particle 18 and titania nanoparticles 17 mix, form the effect of Ti-O-Gd key between two kinds of nano particles, namely obtain the sensing chip that gadolinium oxide-titania composite nanometer particle is modified, the time spent does not preserve in 4 ° of C sealings of refrigerator.
The detection of nitrite:
Adopt conventional galvanochemistry three-electrode system: the sensing chip that gadolinium oxide-titania composite nanometer particle layer 16 is modified that the said method assembling is modified is working electrode, platinum filament is to electrode, silver/silver chloride (saturated potassium chloride) electrode is as contrast electrode, carry out the cyclic voltammetry experiment test, the current-responsive value of this sensing chip electrode and the concentration of nitrite are 2.0 * 10
-7～2.0 * 10
-4Linear in the mol/L scope, the detection lower limit of nitrite is reached 1.2 * 10
-7Mol/L.
The reappearance of sensing chip:
The sensing chip that 9 gadolinium oxides-titania composite nanometer particle layer 16 is modified that assembling is as stated above modified is working electrode, and platinum filament is to electrode, and silver/silver chloride (saturated potassium chloride) electrode is as contrast electrode, respectively to 1.0 * 10
-5Mol/L and 2.0 * 10
-6The nitrite solution sample of mol/L carries out cyclic voltammetric test, and as can be seen, after carrying out continuously measuring for 9 times, the RSD of peak current is respectively 1.8% and 3.1%, shows the favorable reproducibility of this sensing chip detection method.
The selectivity of sensing chip:
The sensing chip that gadolinium oxide-titania composite nanometer particle layer 16 is modified that assembling is as stated above modified is working electrode, platinum filament is to electrode, silver/silver chloride (saturated potassium chloride) electrode has been investigated common kation and negative ion respectively to NO as contrast electrode
2 -The influence of measuring, as can be seen: work as NO
2 -Concentration is 2.0 * 10
-4Mol/L contains the K of 100 times of concentration
+, Na
+, Ca
2+, Mg
2+, Ni
2+, Zn
2+, SO
4 2-, CO
3 2-, NO
3 -, OAc
-, Cl
-, citrate, glucose, Sodium Benzoate do not have influence to measuring, and shows that the selectivity of this sensing chip detection method is good.
Embodiment 5
The mensuration of nitrite in the ham sausage sample:
The sensing chip that gadolinium oxide-titania composite nanometer particle layer 16 is modified that assembling is as stated above modified is working electrode, platinum filament is to electrode, silver/silver chloride (saturated potassium chloride) electrode is as contrast electrode, the mark-on of having investigated nitrite in four kinds of ham sausage samples respectively detects, the recovery illustrates that this method recovery is good between 95.9 ~ 103.2%; And with standard spectrophotometric method contrast, the measuring accuracy of sample is identical, meets the requirement of quantitative test, illustrates that this sensing chip can be applicable to the detection of nitrite in the actual sample.
Claims (9)
1. sensing chip that detects nitrite, it is characterized in that: this sensing chip comprises the golden film substrate (1) that a gadolinium oxide-titania composite nanometer particle 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 gadolinium oxide-titania composite nanometer particle layer (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 thickness of assembling modification gadolinium oxide-titania composite nanometer particle layer (16) in its surface is 20-400nm.
8. sensing chip according to claim 2, the preparation method who it is characterized in that gadolinium oxide-titania composite nanometer particle namely gets an amount of gadolinium oxide and adds the nitric acid heating for dissolving, forms colourless transparent solution, stir and add an amount of absolute ethyl alcohol and tetrabutyl titanate down, formation A liquid; Dropwise add the finely dispersed B liquid that is mixed by absolute ethyl alcohol, glacial acetic acid, hydrogen peroxide and PEG400 then, regulate pH value to 1-5 with dilute nitric acid solution, continue to keep stirring 10-60 minutes, get a uniform and stable colloidal sol; Ageing 2-48 hours gets gadolinium oxide-titania composite nanometer particle sol solution, i.e. C liquid.
9. sensing chip according to claim 2, the assembling method of modifying that it is characterized in that gadolinium oxide-titania composite nanometer particle layer (16), namely earlier golden membranous layer (15) surface of sensing chip gold film substrate (1) is cleaned with redistilled water, successively in absolute ethyl alcohol, redistilled water ultrasonic cleaning each 1-10 minutes, take out under room temperature and dry naturally; Getting gadolinium oxide-titania composite nanometer particle sol solution (C liquid) is dissolved in an amount of redistilled water, ultrasonic dispersion 1-10 hours, getting 2-40 microlitres evenly is coated on golden membranous layer (15) surface, dry under infrared lamp, get the sensing chip that gadolinium oxide-titania composite nanometer particle is modified, the time spent preserves in 4 ° of C sealings of refrigerator.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103776882A (en) * | 2014-02-26 | 2014-05-07 | 长沙理工大学 | Silicon nitride-based nano gold film electrode method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103776882A (en) * | 2014-02-26 | 2014-05-07 | 长沙理工大学 | Silicon nitride-based nano gold film 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 |
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