CN1297151A - Method and special instrument for in-situ detection of organophosphorus agricultural chemical - Google Patents
Method and special instrument for in-situ detection of organophosphorus agricultural chemical Download PDFInfo
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- CN1297151A CN1297151A CN 99126615 CN99126615A CN1297151A CN 1297151 A CN1297151 A CN 1297151A CN 99126615 CN99126615 CN 99126615 CN 99126615 A CN99126615 A CN 99126615A CN 1297151 A CN1297151 A CN 1297151A
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- organophosphorus pesticide
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- enzyme electrode
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Abstract
A method for in-situ detecting agricultural organophosphorus chemical includes adding solid oxidant to specimen, reaction for 4-6 min, adding solid reducer, inserting enzyme electrode, reaction for 10-30 min, washing the enzyme electrode, detecting the enzyme electrode with a special instrument and reading data. Said instrument is composed of voltage stabilizing unit, signal converting module unit, display control unit and data acquisition and CPU unit. Its advantages are convenient operation and high speed.
Description
The present invention relates to the detection method and the instrumentation thereof of the detection method and the instrumentation thereof, particularly organophosphorus pesticide of organic phosphorus compound.
Organophosphorus pesticide is current the most widely used crops pesticide, its residual big hidden danger that becomes harm humans health in crop products, the situation that organophosphorus pesticide causes people, animal to be poisoned takes place often, quick on-the-spot detection the to them is the research emphasis in food hygiene science field always, and has the important clinical diagnostic value.
The laboratory detection means of organophosphorus pesticide thing is chromatography, chromatograph-mass spectrometer coupling method and spectral method, though these method sensitivity are higher, but instrument complexity, costliness, complex operation, often need processing procedure in early stage such as liquid-liquid extraction or leaching, thereby be difficult to on-the-spot the use, can not satisfy the needs of fast detecting.
Biosensor technology combines easy microminiaturized, integrated, the intelligentized characteristics of high specific, high sensitivity, rapid reaction and the electronic circuit of biological respinse, is comparatively desirable on-the-spot detection technique.Yet because organophosphorus pesticide poorly water-soluble, chaff interference is many in the actual sample, need sample to be extracted with organic solvents such as acetone, chloroforms, and be that the layman is difficult to grasp to using and extracting operation of organic solvent, limited biosensor technology to organophosphorus pesticide and the on-the-spot use that detects of toxic agent.In addition, because organophosphorus pesticide is slow to the cholinesterase effect, the sensor response is insensitive, needs organophosphorus pesticide is carried out activation processing.Activating reagent commonly used is bromine water or bromine vapor, however because the toxicity of bromine water, the flowability of instability and liquid, give instrument storage, carry, use and cause trouble, further limited the practicability of such sensor.The existing route of measuring is:
Actual sample
↓
Organic solvent extraction such as acetone, chloroform
↓
Dry up organic solvent
↓
Residue is water-soluble
↓
The activation of dropping bromine water
↓
Add Na
2S
2O
3Remove excessive bromine water Deng reductive agent
↓
Insert enzyme sensor
↓
Add zymolyte
↓
Measure
The method that the purpose of this invention is to provide a kind of field quick detection organophosphorus pesticide.
For achieving the above object, the present invention takes following design proposal: a kind of method that detects organophosphorus pesticide consists essentially of following steps:
(1) solid oxidizer of adding q.s in sample reacted 4-6 minute;
(2) in above-mentioned reactant liquor, add the solid reductant that is enough to make the excess oxidant reduction that adds in the above-mentioned steps, vibrate;
(3) insert enzyme electrode, reacted 10-30 minute;
(4) cleaning of enzyme electrode;
(5) with detector of the present invention enzyme electrode is measured reading of data.
Another object of the present invention provides a kind of instrumentation of realizing above-mentioned field quick detection organophosphorus pesticide.
This purpose of the present invention is achieved in that a kind of instrument that detects organophosphorus pesticide and toxic agent, this instrument comprises constant voltage adjustment module unit, signal conversion processes modular unit, indicative control unit, data acquisition and cpu central processing unit unit four parts, wherein said constant voltage adjustment module unit comprises constant pressure source and amplifier follower amplifier, and its output resistance is zero; Described signal conversion processes modular unit comprises the element that little current signal is converted to the relevant voltage signal after filtering and program control amplification, analog signal conversion is become corresponding digital signal and carry out the hardware and software of digital Filtering Processing; Described indicative control unit comprises four bit serial displays, and described data acquisition and cpu central processing unit unit comprise one-off programming single chip microcomputer and numerical evaluation and Control Software.
For more convenient use, also include sound equipment control section and failure diagnosis unit in the instrument of the present invention.
Using detection method of the present invention, can be detected object with surface water, vegetable juice, fruit syrup or gastric juice former state directly, after enzyme electrode and the testing sample effect, the cleaning of enzyme electrode, measure enzyme electrode surface residual enzyme vigor, both avoided the sample extraction process, got rid of the impurity interference again; The solid medicine hypochlorite that take cheapness, is easy to get is activating reagent, realized organophosphorus pesticide in the sample entirely in chemical activation, greatly simplified sample reactivation process.Whole mensuration process does not need with an organic solvent, and is simple to operate, and the user of service does not need special training just can operate.Because avoided the use of organic solvent and liquid, apparatus is Miniaturized, even can make hand held detector in hand held, can detect at any time at the scene, save time, convenient.
The enzyme immobilization method of stifling glutaraldehyde steam of the present invention has realized that the mass of electrode strip surface enzyme fixes, thereby obtain disposable use enzyme electrode, avoided the taskworkization of sensor probe, improved the reappearance of made enzyme electrode greatly, and making the normal temperature storage life-span be no more than trimestral enzyme sensor can place more than 1 year at normal temperature, refrigerator is placed more than 3 years, high conformity, stability is high.
Special detector volume of the present invention is little, low in energy consumption, be quick on the draw and cost lower.
The invention will be further described below in conjunction with accompanying drawing.
Fig. 1 is the front view (FV) of detector of the present invention
Fig. 2 is the outboard profile of detector of the present invention
Fig. 3 is the circuit diagram of detector of the present invention
Fig. 4 is the hardware elementary diagram of detector of the present invention
Fig. 5 is the operation block diagram of detector of the present invention
As shown in Figure 1 and Figure 2, detector of the present invention can be made into the palm machine of cuboid (also can make other shape), and there is display screen 1 in the front of fuselage, TEST button 2, and STEP button 3, POWER button 4, there is the jack 5 of enzyme electrode the side of fuselage.
As shown in Figure 3, Figure 4, detector of the present invention is shown and the sound equipment control module that by constant voltage regulon, signal conversion processes modular unit failure diagnosis unit, data acquisition and cpu central processing unit unit five parts are formed.The constant voltage adjustment module comprises constant pressure source and amplifier follower amplifier, its design feature is that output resistance is zero, operating voltage does not change with the increase and decrease of instrument working current, the electric current of sensor output by the signal conversion processes module with its linearization and after filtering, convert voltage signal to, this voltage signal by data disaply moudle with serial input and 4 demonstrations of line output; The signal conversion processes modular unit comprises the I/V conversion and amplifies, filter function, conversion of signals is become voltage signal, also has anti-tampering filter function, its design feature is that input resistance is zero, be that subsequent conditioning circuit is under the prerequisite that does not influence the working sensor condition, can not only extract the working current of sensor, simultaneously under CPU control, again can be according to the output current size of sensor, automatically regulate conversion proportion, make transformation result that the highest data acquisition resolution be arranged: demonstration and sound equipment control module comprise four bit serial displays and the hummer that drives by width modulation, the sound equipment control module comprises the multiple pulse width modulation mode of output key sound, the modulation system of output function false alarm sound, the modulation system of output results suggest sound is outside the data disaply moudle decapacitation display result, also double as human-machine operation guiding, user-friendly, sound equipment has been realized button sound under programmed control, the operating mistake chimes of doom, the result exports the output of several alternative sounds signals such as prompting sound; Failure diagnosis unit comprises function for monitoring such as sensor signal is unusual, contact is unusual, operating voltage is unusual, its supplementary module conveniently designs for instrument assembling, debugging, maintenance, by adding some ancillary hardware circuit, give CPU with the main information feedback of other each functional module, be convenient to the working condition that CPU understands and control each parts; Cpu central processing unit is the comprehensive management module of above-mentioned several modules, has adopted the one-off programming single chip microcomputer, and this one-chip CPU is integrated multiple functions such as RAM, ROM, A/D, PWM, house dog in a chip.
The using method of this detector is started shooting as shown in Figure 5, and CPU carries out self check, if normally then show 8888, further other hardware of diagnosis normally then shows RED1, presses feeler switch, survey the blank value of distilled water, show RED2 on the screen, the electrode of insert behind sample effect, handling is pressed feeler switch, show RUN2, show test results then; If there has been blank value in the detector, the electrode of then directly insert behind sample effect, handling is pressed the STEP key, tests, and selects then RUN2, shows test results.
Embodiment 1: the on-site measurement organophosphorus pesticide, and its step is as follows:
1, gets by the sample of side (surface water, vegetable juice, fruit syrup, gastric juice etc.);
2, in above-mentioned sample, add the solid sodium hypochlorite (calcium hypochlorite, magnesium hypochlorite also can) of q.s, reacted 5 minutes, make the abundant oxidation of sample;
3, in above-mentioned reactant liquor, add solid sulfur sodium thiosulfate (Na
2S
2O
3), vibrate to Na
2S
2O
3Dissolving approximately needed about 1 minute, made the excess oxidant reduction;
4, inserted the cholinesterase electrode reaction 20 minutes;
5, take out above-mentioned enzyme electrode and clean (being generally 3 times), to remove surface remaining agricultural chemicals and pollutant with clean water;
6, with detector of the present invention enzyme electrode is measured reading of data.
In the above-described embodiments, the method for production of cholinesterase electrode is that screen printing technique is made basal electrode, and glutaraldehyde cross-linking method immobilized enzyme (see Anal, chim, Acta, 1999,382:277-282).Use said method, can also make other enzyme electrode, as glucose electrode, lactic acid electrode, blood lead electrode, uric acid electrode etc.
The principle of method of the present invention institute foundation is: with enzyme, particularly cholinesterase is made the biological identification molecule of organophosphorus pesticide, toxic agent, makes the substrate of enzyme with acetylthiocholine, and enzyme hydrolysis is created in electrode surface generation electrochemical oxidation.Method of the present invention is used very extensive, and organophosphorus pesticide is measured as all available this method such as DDVP, parathion, thimet, Rogor, malathion, acephatemet, Azodrin, carbofuran, Entex, orthene.
Claims (9)
1, a kind of on-the-spot method that detects organophosphorus pesticide is characterized in that: consist essentially of following steps:
(1) solid oxidizer of adding q.s in sample reacted 4-6 minute;
(2) in above-mentioned reactant liquor, add the solid reductant that is enough to make the excess oxidant reduction that adds in the above-mentioned steps, vibrate;
(3) insert enzyme electrode, reacted 10-30 minute;
(4) cleaning of enzyme electrode;
(5) with detector of the present invention enzyme electrode is measured reading of data.
2, a kind of on-the-spot method that detects organophosphorus pesticide according to claim 1, it is characterized in that: the enzyme electrode that inserts in described (3) step, its method for making fixes the enzyme on electrode strip surface then at first making the enzyme electrode bar with screen printing technique with the stifling fixation of glutaraldehyde steam.
3, a kind of on-the-spot method that detects organophosphorus pesticide according to claim 2, it is characterized in that: described enzyme electrode bar is the cholinesterase electrode strip.
4, according to claim 1 or 2 or 3 described a kind of on-the-spot methods that detect organophosphorus pesticide, it is characterized in that: the described oxygenant that adds in sample is the hypochlorite solid reagent, sodium hypochlorite preferably wherein, calcium hypochlorite or magnesium hypochlorite, most preferred is sodium hypochlorite.
5, according to claim 1 or 2 or 3 described a kind of on-the-spot methods that detect organophosphorus pesticide, it is characterized in that: the described reductive agent that adds in reactant liquor is a sodium thiosulfate.
6, a kind of on-the-spot method that detects organophosphorus pesticide according to claim 4, it is characterized in that: the described reductive agent that adds in reactant liquor is a sodium thiosulfate.
7, a kind of instrument that detects organophosphorus pesticide, it is characterized in that: this instrument comprises constant voltage adjustment module unit, signal conversion processes modular unit, indicative control unit, data acquisition and cpu central processing unit unit four parts, wherein said constant voltage adjustment module unit comprises constant pressure source and amplifier follower amplifier, and its output resistance is zero; Described signal conversion processes modular unit comprises the element that little current signal is converted to the relevant voltage signal after filtering and program control amplification, analog signal conversion is become corresponding digital signal and carry out the hardware and software of digital Filtering Processing; Described indicative control unit comprises four bit serial displays, and described data acquisition and cpu central processing unit unit comprise one-off programming single chip microcomputer and numerical evaluation and Control Software.
8, a kind of instrument that detects organophosphorus pesticide according to claim 7, it is characterized in that: described indicative control unit also comprises the sound equipment control section, it comprises the width modulation type of drive of output key sound, the width modulation type of drive of output function false alarm sound, the width modulation type of drive of output results suggest sound.
9, a kind of instrument that detects organophosphorus pesticide according to claim 8 is characterized in that: described instrument also comprises the failure diagnosis unit with function for monitoring such as sensor signal are unusual, contact is unusual, operating voltage is unusual.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB991266153A CN1138140C (en) | 1999-12-22 | 1999-12-22 | Method and special instrument for in-situ detection of organophosphorus agricultural chemical |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB991266153A CN1138140C (en) | 1999-12-22 | 1999-12-22 | Method and special instrument for in-situ detection of organophosphorus agricultural chemical |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1297151A true CN1297151A (en) | 2001-05-30 |
| CN1138140C CN1138140C (en) | 2004-02-11 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB991266153A Expired - Fee Related CN1138140C (en) | 1999-12-22 | 1999-12-22 | Method and special instrument for in-situ detection of organophosphorus agricultural chemical |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102103122A (en) * | 2011-01-26 | 2011-06-22 | 山东理工大学 | Rapid detector and detection method for electrochemical pesticide residue |
| CN103675057A (en) * | 2013-11-29 | 2014-03-26 | 中国广州分析测试中心 | Biosensor for organophosphorus pesticide rapid detection and detecting method thereof |
| CN105548299A (en) * | 2015-12-28 | 2016-05-04 | 扬州工业职业技术学院 | Method for rapidly detecting acetochlor residues in soil and detection device |
| CN106841346A (en) * | 2016-12-22 | 2017-06-13 | 山东理工大学 | A kind of palm aflatoxin fast detector based on Internet of Things |
| CN109342537A (en) * | 2018-12-13 | 2019-02-15 | 上海大学 | A method of utilizing 430 stainless steel tow electrode detection vegetable pesticide residues |
| CN112630286A (en) * | 2020-12-14 | 2021-04-09 | 山东理工大学 | Multi-channel potentiostat circuit for electrochemical detection of organophosphorus pesticide and detection method |
-
1999
- 1999-12-22 CN CNB991266153A patent/CN1138140C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102103122A (en) * | 2011-01-26 | 2011-06-22 | 山东理工大学 | Rapid detector and detection method for electrochemical pesticide residue |
| CN102103122B (en) * | 2011-01-26 | 2014-03-12 | 山东理工大学 | Rapid detector and detection method for electrochemical pesticide residue |
| CN103675057A (en) * | 2013-11-29 | 2014-03-26 | 中国广州分析测试中心 | Biosensor for organophosphorus pesticide rapid detection and detecting method thereof |
| CN105548299A (en) * | 2015-12-28 | 2016-05-04 | 扬州工业职业技术学院 | Method for rapidly detecting acetochlor residues in soil and detection device |
| CN105548299B (en) * | 2015-12-28 | 2018-03-27 | 扬州工业职业技术学院 | A kind of method and detection means of quick detection acetochlor in soil residual |
| CN106841346A (en) * | 2016-12-22 | 2017-06-13 | 山东理工大学 | A kind of palm aflatoxin fast detector based on Internet of Things |
| CN109342537A (en) * | 2018-12-13 | 2019-02-15 | 上海大学 | A method of utilizing 430 stainless steel tow electrode detection vegetable pesticide residues |
| CN109342537B (en) * | 2018-12-13 | 2020-12-15 | 上海大学 | Method for detecting bifenthrin residue in vegetable by using 430 stainless steel wire bundle electrode |
| CN112630286A (en) * | 2020-12-14 | 2021-04-09 | 山东理工大学 | Multi-channel potentiostat circuit for electrochemical detection of organophosphorus pesticide and detection method |
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| Publication number | Publication date |
|---|---|
| CN1138140C (en) | 2004-02-11 |
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