CN1699985A - Process for making nano-modification minisize electrochemical biosensor for pesticide detection - Google Patents
Process for making nano-modification minisize electrochemical biosensor for pesticide detection Download PDFInfo
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- CN1699985A CN1699985A CN 200410038067 CN200410038067A CN1699985A CN 1699985 A CN1699985 A CN 1699985A CN 200410038067 CN200410038067 CN 200410038067 CN 200410038067 A CN200410038067 A CN 200410038067A CN 1699985 A CN1699985 A CN 1699985A
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Abstract
The invention relates to a process for preparing allocate nanometer modification mini-electric chemical biology sensor used as pesticide residue measurement, which can provide a stable reference electric potential to measure pesticide residue in the vegetables, and an orgyanophosphorus pesticide detecting instrument for pesticide residue measurement.
Description
Affiliated technical field
The present invention relates to a kind of preparation method who is used for the disposable nano-modified miniature electrochemica biological sensor of Detecting Pesticide, it has provided a kind of a kind of preparation method of the disposable nano-modified miniature electrochemica biological sensor that stable reference potential can be provided, remains of pesticide in the vegetables is detected and has been used for the hand held detection of organic phosphorus pesticide instrument of Detecting Pesticide.
Background technology
Organophosphorus and carbamic acid lipid agricultural chemicals are the agricultural chemicals of the present use amount maximum of China, and wherein agricultural chemicals is to limit the quantity of to use on the vegetables and fruits crop mostly.The highly toxic pesticide that has is to forbid using on vegetable melon and fruit.But no matter how strict resignation system and management rules are, and the someone always violates the rules, pesticide abuse.Because this type of agricultural chemicals easily remains in the vegetables and fruits surface in a large number, can cause people's nerve conduction obstruction, neural paralysis and death.Therefore, carry out the fast measuring of residues of pesticides before listing, the vegetables and fruits of avoiding containing persistent pesticide because of food cause acute poisoning, ensure people health, have crucial meaning.
Pesticide residue analysis is chromatography, chromatogram-mass spectrometry method etc. in the world, but because instrument complexity, costliness, operate loaded down with trivial detailsly, often needs processing procedure in early stage such as liquid-liquid extraction or solid-liquid extraction, is difficult to on-the-spot use.Agricultural product such as vegetables, melon and fruit need fast running speed pin in order to keep fresh, and traditional instrument is difficult to or can't be guaranteed in time.Thereby need develop at normal temperatures fast survey technology at the national conditions of current China, the edible safety of the vegetables and fruits of guaranteeing immediately to go on the market.
The eighties, pesticide in vegetable Fast Detection Technique some countries abroad are widely-used.In recent years, the wholesale market of the vegetables in some provinces of China, city, vegetables production base, quality testing department also detects with rapid method, and the instrument of use has tens kinds of models, but its detection principle all adopts photoelectric colorimetry.This quasi-instrument detection sensitivity is low, and the residual toxicity that has detects the International or National lowest detectable limit standard that do not reach.Sample preparation needs ultrasonic concussion to extract, and constant temperature oven was cultivated 30 minutes for 37 ℃.Be unfavorable for on-the-spot detection and further popularize.
In recent years, along with developing rapidly of life science and all fields of environmental science, more and more receive publicity based on the Application and Development of the various biology sensors of biomaterial.It is exactly one of them that acetylcholine esterase electrochemical source of current sensor is used for organophosphorus pesticide mensuration.The detection principle of residues of pesticides toxicity: the poisoning process of simulation biosome, as object, the design reaction is measured residues of pesticides in the vegetables to the inhibition degree (toxicity) of acetylcholinesterase with the acetylcholinesterase that obtains in the responsive enzyme source.The acetyl thio choline can be under suitable current potential, oxidation reaction takes place on glass-carbon electrode, by detecting the current value under the stable state, can reflect enzymatic activity indirectly, and then the reflection agricultural chemicals is to the inhibition of enzymatic activity, under 0.1 volt of oxidizing potential, detect oxidation current and be calculated as follows the inhibiting rate of acetylcholinesterase.
Enzyme inhibition rate A (having positive correlation)=[(I with residues of pesticides
0-I)/I
0] * 100%
In the formula: I
0The enzyme electrode stable response electric current (blank electric current) that finger is not suppressed by toxic agent
I refers to by toxic agent inhibitory enzyme electrode steady-state response electric current
Existing electrode strip is two electrode systems, is difficult to guarantee the constant of current potential, is difficult to carry out the comparison between a slice, and its error is also bigger, and detection sensitivity is low.
Summary of the invention
Be difficult to keep constant mensuration current potential in order to overcome existing two electrode systems, be difficult to carry out the comparison between a slice, and error is bigger, the deficiency that detection sensitivity is low, the present invention proposes a kind of preparation method who is used for the disposable nano-modified miniature electrochemica biological sensor of Detecting Pesticide, not only volume is little for three electrodes of this method preparation, portable, and can provide stable reference potential, and, by nano composite enzyme working electrode (1), miniature silver/silver chloride (Ag/AgCl) contrast electrode (2) and electrode (3) consisted of one can provide a kind of simple, easy-to-use, not fragile and be easy to produce in batches disposable nano-modified miniature electrochemica biological sensor.
The present invention solves the scheme that its technical matters adopts:
1. the height catalytic capability that selectivity, sensitivity and nano material had of enzyme in three-electrode system in the traditional method for printing screen of China and the galvanochemistry and the living things system is combined.
2. adopt the manual plate making in the computer graphics replacement traditional silk-screened.Prepare three electrode plates;
3. the compound of decorated nanometer material and enzyme on base plate.
The invention has the beneficial effects as follows, can when adopt the electrochemical method three-electrode system to carry out the measurement of organic phosphates and carbamate chemicals for agriculture, stable reference potential be provided, and make through the electrode current constant under constant detection current potential after the pre-service.And, three electrodes of traditional dispersion are carried out microminiaturization, and become one, be easy to use.
It is the electrochemical source of current detection method of electrode that instrument adopts the acetylcholine esterase biology sensor, and directly display substrate electric current and inhibition electric current calculate inhibiting rate.Adopt carbon nanotube technology to make working electrode, improve current sensitivity, reduce the electrode internal resistance.The three electrode papery sensors that adopt screen printing technique to make, disposable use, cost is low.Current sensitivity is up to 1 * 10
-9A/V minimumly measures 1 * 10
-11The A electric current.Instrument stabilizer degree height.Time wafts＜and 1%.The corresponding instrument noise also＜1%.Instrument is a powered battery, and weight only is 250g, carries out the hand held operation.Small and exquisite, attractive in appearance, highly sensitive, easily on-the-spot test.The sample preparation program is simple, need not constant temperature culture.Instrument adopts the paster components and parts, and the design cost is low, is convenient to produce in batches.
Description of drawings
The present invention is further described below in conjunction with accompanying drawing.
Fig. 1: biosensor structure figure
Among Fig. 1: 1. working electrode, 2. pair electrode, 3. contrast electrode is 4. with instrument coupling part, 5. lead, 6. substrate, 7. nano material complex enzyme part.
Fig. 2: the theory diagram of hand held detection of organic phosphorus pesticide instrument
Among Fig. 2: 8. oxidizing potential, 9. constant potential system, 10. contrast electrode, the 11.I/V conversion, 12. amplification filtering, 13. numerals show, 14. timing controlled, 15. detecting units, 16. warnings that exceed standard, 17. electrochemical cells.
Apply the 0.1V oxidizing potential by potentiostat, on the biology sensor that contains acetylcholinesterase (three-electrode system), cause oxidation reaction, the oxidation current of generation amplifies the back by the liquid crystal digital display result through the I/V voltage transformation.
Fig. 3: hand held detection of organic phosphorus pesticide instrument sketch
Among Fig. 3: 18. power switches, 19. show selection: toggle switch is divided into SV, JV, HV, the IV fourth gear, wherein: SV is that test voltage shows; JV detects current potential demonstration is set; HV is that oxidizing potential detects; IV is that demonstration is amplified in the current/voltage conversion, 20. LCDs, 21. start buttons: pushbutton switch, the switch that control regularly begins, 22. timing indicators: glow.When pressing timing button, the bright detection of pilot lamp regularly begins, and freely extinguishes after 4.5 minutes, and the expression timing arrives, and begins to detect.Warning exceeds standard, alarm is behind the inhibiting rate that configures remains of pesticide toxicity, when the actual sample inhibiting rate that detects is lower than this setting value, its toxicity of expression of reporting to the police surpasses established standards, 23. detection potentiometer: set enzyme and suppress number percent current potential knob, 24. enlargement ratios: the switch that the voltage of I/V conversion is amplified conversion.Be divided into X0.5, X1, X2, X5 fourth gear, 25. biology sensor plug and decks: be connected with instrument for biology sensor.
The red inhibiting rate A--of Fig. 4 furans concentration logarithm lgC graph of a relation
Embodiment:
Printing process can divide several steps to carry out according to the complexity of the electrode of being printed, and the simplest three electrodes of printing with us are example, and each step all will place the baking oven heat drying more than 24 hours after printing, and just carries out next step operation.After all printing was finished, drying was 48 hours in baking oven, can use after electrode is cut out
1. the first step goes up at substrate (6) and prints conductive silver paste earlier, makes and instrument coupling part (4) and lead (5);
2. second step was printed silver-silver chloride (Ag/AgCl) layer and makes contrast electrode (3).
3. the 3rd step printed that conductive carbon paste is made working electrode (1) and to electrode (2)
4. the 4th step prepared nano material enzyme electrode (7)
5. stablize after 10 minutes after the instrument start and detect;
6. electrode is put in the buffer solution and steeped 20 minutes;
7. after washing electrode surface gently with distilled water, insert the tool interface system end, drip two at the bottom of liquid, evenly coated electrode;
8. press detector switch and begin to detect, write down the indicator current value when pilot lamp extinguishes on the instrument panel;
9. take off electrode, carefully wash electrode with distilled water after, steeped in titer to be measured 30 minutes;
10. the inhibiting rate knob on the adjusting instrument panel is set and is detected 8% of the indicator current value write down before current value is;
11. after washing electrode surface gently with distilled water, insert the tool interface system end, drip two at the bottom of liquid, evenly coated electrode;
Begin to detect 12. press detector switch, when pilot lamp extinguished on the instrument panel, if agricultural chemicals exceeds standard, instrument sent chimes of doom, if instrument is not reported to the police, illustrated that agricultural chemicals does not exceed standard.
Claims (6)
1. the preparation method of a nano-modified miniature electrochemica biological sensor and be used for the hand held detection of organic phosphorus pesticide instrument of Detecting Pesticide, form by nano composite enzyme working electrode (1), miniature silver/silver chloride (Ag/AgCl) contrast electrode (2) with to electrode (3), it is characterized in that: nano material and enzyme are compound, combine with the working electrode of film like, with miniature silver/silver chloride (Ag/AgCl) contrast electrode (2) of film like and the nano composite biology sensor to electrode (3) mutual group flakiness formula three electrode types of film like.
2. nano-modified miniature electrochemica biological sensor according to claim 1, it is characterized in that: carbon nano-tube and acetylcholinesterase are compound, form the nano-modified working electrode of film like (1) with carbon substrate;
3. nano-modified miniature electrochemica biological sensor according to claim 1, it is characterized in that: miniature silver/silver chloride (Ag/AgCl) contrast electrode (2) to film like between the electrode (3) of nano-modified working electrode of film like (1) and film like constitutes film like three electric pole type nano composite biology sensors jointly.
4. the hand held detection of organic phosphorus pesticide instrument that is used for Detecting Pesticide according to claim 1, it is characterized in that: current sensitivity is up to 1 * 10
-9A/V minimumly measures 1 * 10
-11The A electric current.
5. the hand held detection of organic phosphorus pesticide instrument that is used for Detecting Pesticide according to claim 1 is characterized in that: the degree of stability height, and time wafts＜and 1%.Corresponding instrument noise＜1%.
6. the hand held detection of organic phosphorus pesticide instrument that is used for Detecting Pesticide according to claim 1 is characterized in that: powered battery, weight only are 250g.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410038067 CN1699985A (en) | 2004-05-18 | 2004-05-18 | Process for making nano-modification minisize electrochemical biosensor for pesticide detection |
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| CN 200410038067 CN1699985A (en) | 2004-05-18 | 2004-05-18 | Process for making nano-modification minisize electrochemical biosensor for pesticide detection |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101339156B (en) * | 2008-08-19 | 2011-12-07 | 西北农林科技大学 | Pesticide residue biosensor thin layer electrode and its making process |
| CN102323301A (en) * | 2011-08-15 | 2012-01-18 | 复旦大学 | Silicon nanowire biosensor for detecting organophosphorus pesticide residue and preparation method thereof |
| CN101672814B (en) * | 2009-09-27 | 2012-11-07 | 上海大学 | Electrochemical receptor biosensor and application thereof |
| CN103018305A (en) * | 2012-12-11 | 2013-04-03 | 江苏大学 | Portable enzyme sensor based on carbon nanometer tube |
| CN103175872A (en) * | 2011-12-23 | 2013-06-26 | 长沙中生众捷生物技术有限公司 | Portable electrochemical detection test strip and preparation method thereof |
| CN103558272A (en) * | 2013-11-19 | 2014-02-05 | 山东理工大学 | Rapid detector for antibiotic residue of aptamer sensor |
| CN105911116A (en) * | 2016-05-16 | 2016-08-31 | 苏州感测通信息科技有限公司 | Paper chip for rapidly detecting organophosphorus pesticide and production method thereof |
-
2004
- 2004-05-18 CN CN 200410038067 patent/CN1699985A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101339156B (en) * | 2008-08-19 | 2011-12-07 | 西北农林科技大学 | Pesticide residue biosensor thin layer electrode and its making process |
| CN101672814B (en) * | 2009-09-27 | 2012-11-07 | 上海大学 | Electrochemical receptor biosensor and application thereof |
| CN102323301A (en) * | 2011-08-15 | 2012-01-18 | 复旦大学 | Silicon nanowire biosensor for detecting organophosphorus pesticide residue and preparation method thereof |
| CN103175872A (en) * | 2011-12-23 | 2013-06-26 | 长沙中生众捷生物技术有限公司 | Portable electrochemical detection test strip and preparation method thereof |
| CN103018305A (en) * | 2012-12-11 | 2013-04-03 | 江苏大学 | Portable enzyme sensor based on carbon nanometer tube |
| CN103558272A (en) * | 2013-11-19 | 2014-02-05 | 山东理工大学 | Rapid detector for antibiotic residue of aptamer sensor |
| CN103558272B (en) * | 2013-11-19 | 2015-07-29 | 山东理工大学 | A kind of rapid detector for antibiotic residue of aptamer sensor |
| CN105911116A (en) * | 2016-05-16 | 2016-08-31 | 苏州感测通信息科技有限公司 | Paper chip for rapidly detecting organophosphorus pesticide and production method thereof |
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