CN103344693B - Sensing chip method for detecting nitrite - Google Patents
Sensing chip method for detecting nitrite Download PDFInfo
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- CN103344693B CN103344693B CN201310293741.9A CN201310293741A CN103344693B CN 103344693 B CN103344693 B CN 103344693B CN 201310293741 A CN201310293741 A CN 201310293741A CN 103344693 B CN103344693 B CN 103344693B
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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 detecting nitrite, belong to chemical/biological field of sensing technologies, be applicable to food safety detection.
Background technology
Nitrite is extensively present in environment, food, beverage.In food industry, nitrite Chang Zuowei adjuvant, has certain Antimicrobial preservative effect.Nitrite and amine substance can generate carcinogen N-nitrosamine.Due to the toxicity that it is potential, therefore no matter the detection of content of nitrite is all have important meaning in environmental science or field of public health.Spectrophotometric method, chromatography is had in recent years, electrochemical method etc. to the assay method of nitrite.In these methods, electrochemical method because it is highly sensitive, low with cost easily and fast, be widely used in measuring nitrite.Due to NO
2 -bare electrode has very high overpotential, is very easily subject to the interference of readily oxidizable substance, in order to improve mensuration sensitivity, can electrode face finish be suitable for eelctro-catalyst reduce operating potential.About NO
2 -the modified electrode measured 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 Nanotubes/Chitosan modified glassy 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, gadolinium oxide-titania composite nanometer particle assembling is modified to golden film substrate surface, is formed a kind of sensing chip detecting nitrite by electrostatic adsorption by the present invention.This sensing chip makes simple, with low cost, easy to use, is better than Conventional electrochemical modified electrode, can be used for the quick detection of Trace Nitrite in food, in the fields such as agricultural food product, biomedicine and environmental monitoring, 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 nitrite simple, 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 detecting nitrite, it is characterized in that: this sensing chip comprises the golden film substrate that a gadolinium oxide-titania composite nanometer particle 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 gadolinium oxide-titania composite nanometer particle layer after chemical cleaning process, thus forms the sensing chip detecting nitrite.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 assemble that to modify the thickness of gadolinium oxide-titania composite nanometer particle layer be 20-400nm.
In the Design & preparation of sensing chip, with other method unlike, the present invention proposes a kind of preparation method of simple gadolinium oxide-titania composite nanometer particle, namely get appropriate gadolinium oxide and add nitration acid heat dissolving, form colourless transparent solution, add appropriate absolute ethyl alcohol and tetrabutyl titanate under stirring, form A liquid; Then dropwise add the finely dispersed B liquid mixed by absolute ethyl alcohol, glacial acetic acid, hydrogen peroxide and PEG400, with dilute nitric acid solution adjust ph to 1-5, continue to keep stirring 10-60 minutes, obtain a uniform and stable colloidal sol; Ageing 2-48 hours, obtains gadolinium oxide-titania composite nanometer particle sol solution, i.e. C liquid.And, the preparation key of this sensing chip is also the assembling method of modifying of gadolinium oxide-titania composite nanometer particle layer, namely first the golden membranous layer surface redistilled water of sensing chip gold film substrate is cleaned, each 1-10 minutes of ultrasonic cleaning in absolute ethyl alcohol, redistilled water successively, takes out and naturally dries under room temperature; Get that gadolinium oxide-titania composite nanometer particle sol solution (C liquid) is dissolved in appropriate redistilled water; ultrasonic disperse 1-10 hours; get 2-40 microlitres and be evenly coated on golden membranous layer on the surface; dry under infrared lamp; form the composite nanometer particle layer of Gadolinium oxide nanoparticles and titania nanoparticles mixing; 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 used time does not preserve in refrigerator 4 ° of C sealings.
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 Conventional electrochemical modified electrode, can be used for the quick detection of Trace Nitrite in food, in the fields such as agricultural food product, biomedicine and environmental monitoring, 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 nitrite.
Accompanying drawing 2 is the cross-sectional view of the sensing chip gold film substrate detecting nitrite.
In accompanying drawing 1, the golden film substrate that 1. gadolinium oxide-titania composite nanometer particle 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. gadolinium oxides-titania composite nanometer particle layer, 17. titania nanoparticles, 18. Gadolinium oxide nanoparticles.
Embodiment
embodiment 1
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, 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 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 0.021g gadolinium oxide and add the dissolving of 0.5mL nitration acid heat, obtain 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 mixed B liquid by 10mL absolute ethyl alcohol, 2mL glacial acetic acid, 2mL hydrogen peroxide and 4mL PEG400, regulated solution ph=3.0 with dilute nitric acid solution, continue to keep stirring 40 minutes, obtain a uniform and stable colloidal sol; Ageing 18 hours, obtains gadolinium oxide-titania composite nanometer particle sol solution, i.e. C liquid.
And, the preparation key of this sensing chip is also the assembling method of modifying of gadolinium oxide-titania composite nanometer particle layer 16, namely first the golden membranous layer 15 surface redistilled water of sensing chip gold film substrate 1 is cleaned, each 2 minutes of ultrasonic cleaning in absolute ethyl alcohol, redistilled water successively, takes out and naturally dries under room temperature; Get that gadolinium oxide-titania composite nanometer particle sol solution (C liquid) is dissolved in appropriate redistilled water, concentration is 0.75mg/mL, ultrasonic disperse 1.5 hours, get 20 microlitres and be evenly coated on golden membranous layer 15 on the surface, dry under infrared lamp, form the composite nanometer particle layer 16 of Gadolinium oxide nanoparticles 18 and titania nanoparticles 17 mixing, the effect of Ti-O-Gd key is formed between two kinds of nano particles, namely obtain the sensing chip that gadolinium oxide-titania composite nanometer particle is modified, the used time does not preserve in refrigerator 4 ° of C sealings.
embodiment 2
The detection of nitrite:
Adopt Conventional electrochemical three-electrode system: the sensing chip that gadolinium oxide-titania composite nanometer particle layer 16 is modified said method assembling modified is working electrode, platinum filament is to electrode, silver/silver chloride (saturated potassium chloride) electrode is as contrast electrode, carry out 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 within the scope of mol/L, 1.2 × 10 are reached to the Monitoring lower-cut of nitrite
-7mol/L.
embodiment 3
The reappearance of sensing chip:
Be working electrode by the sensing chip that 9 gadolinium oxides-titania composite nanometer particle layer 16 is modified assembling modification as stated above, platinum filament is to electrode, silver/silver chloride (saturated potassium chloride) electrode as contrast electrode, respectively to 1.0 × 10
-5mol/L and 2.0 × 10
-6the nitrite solution sample of mol/L carries out cyclic voltammetry, can find out, after carrying out 9 mensuration continuously, the RSD of peak current is respectively 1.8% and 3.1%, 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 gadolinium oxide-titania composite nanometer particle layer 16 is modified assembling modification as stated above, platinum filament is to electrode, silver/silver chloride (saturated potassium chloride) electrode, as contrast electrode, has investigated Common Cations and negative ion respectively to NO
2 -the impact measured, can find out: work as NO
2 -concentration is 2.0 × 10
-4mol/L, containing 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 on mensuration without impact, show that the selectivity of this sensing chip detection method is good.
embodiment 5
The mensuration of ham sausage sample nitrite:
Be working electrode by the sensing chip that gadolinium oxide-titania composite nanometer particle layer 16 is modified assembling modification as stated above, platinum filament is to electrode, silver/silver chloride (saturated potassium chloride) electrode is as contrast electrode, the mark-on having investigated four kinds of ham sausage sample nitrites respectively detects, the recovery, between 95.9 ~ 103.2%, illustrates that the method recovery is good; And contrast with standard spectrophotometric method, 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 actual sample nitrite.
Claims (7)
1. one kind is detected the sensing chip of 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, 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 assembled in its surface again and is modified gadolinium oxide-titania composite nanometer particle (16) after chemical cleaning process; The preparation method of described gadolinium oxide-titania composite nanometer particle, gets appropriate gadolinium oxide and adds nitration acid heat dissolving, form colourless transparent solution, add appropriate absolute ethyl alcohol and tetrabutyl titanate under stirring, form A liquid; Then dropwise add the finely dispersed B liquid mixed by absolute ethyl alcohol, glacial acetic acid, hydrogen peroxide and PEG400, regulate pH value to 1-5 with dilute nitric acid solution, continue to keep stirring 10-60 minutes, obtain a uniform and stable colloidal sol; Ageing 2-48 hours, obtains gadolinium oxide-titania composite nanometer particle sol solution, i.e. C liquid.
2. according to the sensing chip described in claim 1, it is characterized in that: the shape of described golden film substrate (1) is square, and its length of side is 6-12mm.
3. according to the sensing chip described in claim 1, it 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 described in claim 1, 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, and the thickness of Titanium rete (13) is 20-80nm, and the thickness of signal bronze rete (14) is 80-380nm.
5. according to the sensing chip described in claim 1, 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.
6., according to the sensing chip described in claim 1, it is characterized in that: golden membranous layer (15) after chemical cleaning process, in its surface assemble that to modify the thickness of gadolinium oxide-titania composite nanometer particle layer (16) be 20-400nm.
7. according to the sensing chip described in claim 1, it is characterized in that the assembling method of modifying of gadolinium oxide-titania composite nanometer particle layer (16), namely first golden membranous layer (15) the surface redistilled water of sensing chip gold film substrate (1) is cleaned, each 1-10 minutes of ultrasonic cleaning in absolute ethyl alcohol, redistilled water successively, takes out and naturally dries under room temperature; Get that gadolinium oxide-titania composite nanometer particle sol solution (C liquid) is dissolved in appropriate redistilled water, ultrasonic disperse 1-10 hours, get 2-40 microlitres and be evenly coated on golden membranous layer (15) on the surface, dry under infrared lamp, obtain the sensing chip that gadolinium oxide-titania composite nanometer particle is modified, the used time does not preserve in the sealing of 4 DEG C, refrigerator.
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| CN202614627U (en) * | 2012-07-02 | 2012-12-19 | 长沙理工大学 | Quartz crystal microbalance sensor based on titanium base three-layer metal films |
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Non-Patent Citations (5)
| Title |
|---|
| Contaminants: Part A》.2012,第29卷(第12期), * |
| M.-L.Zhang et al.A simple gold plate electrode modified with Gd-doped TiO2 nanoparticles used for determination of trace nitrite in cured food.《Food Additives & * |
| TiO2 /Gd2O3 纳米粉体的制备、表征及光催化活性;姜洪泉 等;《无机化学学报》;20060131;第22卷(第1期);第73-78页 * |
| 制备不同稀土掺杂的纳米氧化钛光催化剂及其光催化活性;周武艺 等;《硅酸盐学报》;20041031;第32卷(第10期);第1203-1208页 * |
| 纳米复合 Y2O3/ TiO2 的制备、表征及其光催化性能研究;李芳柏 等;《中国稀土学报》;20010630;第19卷(第3期);第225-228页 * |
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