CN103558257A - Pesticide multiresidue detector based on array sensors - Google Patents
Pesticide multiresidue detector based on array sensors Download PDFInfo
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Abstract
The invention relates to a pesticide multiresidue detector based on array sensors. The detector comprises a detection circuit, array sensors, an analog multiplexer, a power supply, buttons, a microcontroller and a display screen, wherein a detection chip generates excitation voltage which is applied to the array sensors; the analog multiplexer is used for determining which working electrode is connected and acquiring impedance response signals; different pesticide antibodies are fixed on various working electrodes of the array sensors, and after the working electrodes come into contact with actual samples, whether pesticides exceeding standard exist is determined according to change of resistance values of various sensors and the varieties of the pesticides are determined. The pesticide multiresidue detector can achieve online rapid detection of multiresidues, has the characteristics of strong practicability, convenience in carrying, high detection precision, rapidness and accuracy in detection, easiness in operation and the like and is very suitable for the places in which field rapid detection is carried out on the pesticide residues.
Description
Technical field
The present invention relates to a kind of pesticide multi-residues detector, relate in particular to a kind of instrument for detecting pesticide residue through based on array-type sensor, it has merged biology sensor detection technique and Embedded System Design method, for convenient, detect agricultural product rapidly, accurately and contain which kind of residues of pesticides and whether exceed standard.Belong to agricultural product security detection technique field.
Background technology
The pesticide variety of applying in production field now has reached kind more than 100, to agricultural, keeps good harvest volume increase to play a significant role, and it has become important a kind of means of production.Be accompanied by deeply carrying out of reform and opening-up, in some Changshu Aeras, it is very fast that the speed of development of agricultural chemicals cause becomes.Because mechanization of agriculture constantly advances, it is indispensable that the large area of agricultural chemicals is used.But the irrational use because of agricultural chemicals, has caused many environmental problems, as destroyed in farmland ecosystem etc.A large amount of uses of agricultural chemicals, when having guaranteed a large amount of stable yields of the crops such as grain, have also brought many environmental problems.In plant, soil and water, residual agricultural chemicals has two kinds of remaining forms: the first keeps original chemical constitution; The product of the second after with chemical conversion or to be biodegradable the form of product remaining.Therefore, Pesticide Residue can not be ignored.
The main method of pesticide residue analysis is gas chromatograph, liquid chromatograph, gas chromatograph-mass spectrometer, LC-MS instrument etc. at present, although these method analysis precisions are high, quantitatively accurately, but the complex pretreatment of its sample, detect the operating personnel that length consuming time, cost are high, need to be skilled in technique.The fast determining method of China's residues of pesticides is that enzyme suppresses test paper method and enzyme inhibition-spectrophotometry (the residual fast detector of agriculture), can realize the field quick detection of organophosphorus pesticide and carbamate chemicals for agriculture, has good practical value.Quick measuring card is by the change color of visual inspection card, therefore generally can only carry out observational measurement for the vegetable sample of severe overweight.The application of enzyme inhibition-spectrophotometry is also more extensive, and the residual tacheometer of domestic existing Multiple Pesticides is all based on this principle.Light splitting light ratio juris is that the variation based on absorbance detects, but in vegetable and fruit, a large amount of pigments can cause very large impact to spectrophotometric method, causes the inaccurate of testing result.And said method exists, and the recovery is low, false retrieval, undetected ratio are higher, poor repeatability, be difficult to the shortcomings such as requirement that meet low-residual and quantitatively detect.
The object of invention is for the deficiencies in the prior art, and design provides a kind of instrument for detecting pesticide residue through based on array-type sensor, have easy to carry, detect quick and precisely, simple to operate, can realize the features such as pesticide multi-residues detects simultaneously.
Its detection principle of described a kind of instrument for detecting pesticide residue through based on array-type sensor is: utilize the specific immune response between antibody and agricultural chemicals, using antibody as recognition component, adopt immobilization technology at the fixing different types of pesticide antibody of working electrode surface, by analog multichannel switch, make working electrode in array-type sensor and shared contrast electrode and electrode is connected.Which kind of agricultural chemicals is the impedance variation causing in test end liquid by sensor contain in determining sample, and according to different agricultural chemicals, produces the typical curve of impedance variation, determines the content of the agricultural chemicals in sample.
To achieve these goals, a kind of pesticide multi-residues detector based on array-type sensor provided by the invention consists of testing circuit, array-type sensor, power supply, button, microcontroller and display screen.Testing circuit is used for producing driving voltage and is applied on each immunosensor, with the line number word processing of going forward side by side of the response signal after post-sampling excitation, result is sent into microcontroller; Microcontroller and the trace routine of moving above thereof are processed again to input signal, and the operation of whole system is controlled and responded; Button is used for inputting instruction and detected parameters; Display screen is used for quantizing output and presents final testing result, is the interactive interface of user and system; Power supply is whole system power supply.
A kind of pesticide multi-residues detector concrete structure based on array-type sensor of the present invention is: pesticide multi-residues detector consists of testing circuit, array-type sensor, analog multichannel switch, power supply, button, microcontroller and display screen, wherein: testing circuit consists of feed circuit, detection chip, toggle switch, demarcation resistance, array-type sensor, analog multichannel switch.Feed circuit are connected with detection chip with microcontroller, adopt first through transformer pressure-reducing, through the method for filtering voltage regulation, obtain again+5V power supply; Chip is connected with demarcation resistance by toggle switch, according to input measurement range parameter, by toggle switch, selects corresponding demarcation resistance, with this, adjusts measurement sensitivity; Under the control of microcontroller, chip produces driving voltage and is applied on array immunosensor and collects response signal, obtains its real part and imaginary part, and outputed to microcontroller after DFT.On microcontroller, move trace routine, mould value and phase angle that mould value and phase calculation formula by the impedance real part receiving and imaginary part by impedance calculates impedance, after calibration, draw actual resistance value again, with set react before resistance value compare, obtain rate of change and contrast standard curve is reached a conclusion, deliver to display screen and show.Described display screen is connected with microcontroller, and for showing data and the window that carries out interactive operation as user, display screen adopts LED12864, and its power consumption can meet the power consumption requirement of portable set.Described button is connected with testing circuit with microcontroller, is provided with startup, starts, resets, stops key and four sensing range gears, for inputting dependent instruction and detected parameters.Described power supply is connected with feed circuit.
A kind of pesticide multi-residues detector based on array-type sensor of the present invention, detect while using, first by toggle switch, select and demarcate resistance assurance measurement sensitivity, array-type sensor is put into solution to be detected, under the control of microcontroller, chip produces driving voltage and is applied on array-type sensor and collects response signal, after DFT, obtain its real part and imaginary part, and outputed to microcontroller, through microcontroller and trace routine thereof, carrying out signal processes again, and compare with reacting front resistance value, calculate rate of change.Owing to fixing different types of pesticide antibody on the working electrode of array-type sensor, the concentration that contains which kind of agricultural chemicals and residues of pesticides in the sample that therefore has shown to detect according to the size of each sensor impedance rate of change.
For reaching above object, array-type sensor takes following technical scheme to realize: a circular electrode disk, consist of, centre bit is equipped with electrode and contrast electrode, periphery is working electrode, electrode, contrast electrode are equated with the distance of each working electrode guaranteeing, make each working electrode and the resistance value that having between electrode equated.Between working electrode and contrast electrode, add the operating voltage of 300 millivolts, what in test fluid, measure is working electrode and to the resistance value between electrode.Use analog multichannel switch to determine which working electrode connection.
A kind of pesticide multi-residues detector based on array-type sensor provided by the invention is applied to the Fast Determination of Pesticide Residue field in agricultural product, can bring great convenience for testing staff, can fully meet the requirement of residues of pesticides field quick detection.With respect to testing in the past, various testing samples must be transported to inspection center, by professional staff, in large-scale station device, carried out the outstanding feature such as that detector of the present invention has is easy to carry, detect quick and precisely, simple to operate, practical.
accompanying drawing explanation
Fig. 1 is the structured flowchart of a kind of pesticide multi-residues detector based on array-type sensor of the present invention,
Fig. 2 is feed circuit schematic diagram in the present invention,
Fig. 3 is testing circuit schematic diagram in the present invention.
Embodiment
Below in conjunction with drawings and Examples, technical scheme of the present invention is elaborated.Fig. 1 is the structured flowchart of a kind of pesticide multi-residues detector based on array-type sensor of the present invention, and the present invention consists of testing circuit, array immunosensor, analog multichannel switch, power supply, button, microcontroller and display screen.Wherein testing circuit is connected and composed by feed circuit, detection chip, toggle switch, demarcation resistance, array immunosensor.Testing circuit is used for producing driving voltage and is applied on immunosensor, with the line number word processing of going forward side by side of the response signal after post-sampling excitation, result is sent into microcontroller; Microcontroller and the trace routine of moving above thereof are processed again to input signal, and the operation of whole system is controlled and responded; Button is used for inputting instruction and detected parameters; Display screen is used for quantizing output and presents final testing result, is the interactive interface of user and system; Power supply is whole system power supply.
Described array-type sensor is comprised of a circular electrode disk, centre bit is equipped with electrode and contrast electrode, periphery is working electrode, electrode, contrast electrode is equated with the distance of each working electrode guaranteeing, makes each working electrode and the resistance value that having between electrode equated.Between working electrode and contrast electrode, add the operating voltage of 300 millivolts, what in test fluid, measure is working electrode and to the resistance value between electrode.Use analog multichannel switch to determine which working electrode connection.
Described microcontroller is selected STC89C52, loads trace routine on it.Feed circuit in testing circuit form and principle as shown in Figure 2, by transformer T1, bridge rectifier circuit BR1, electrochemical capacitor C1, C3, common capacitor C 2, C4, three terminal regulator U1 formation, its effect is the Power supply for provide+5V of whole system.In the design, the effect of electrochemical capacitor C1, C2 is filtering, simply say while being exactly the rising of electric capacity both end voltage, and capacitor charging, during lower voltage, capacitor discharge, the gradient while allowing lower voltage becomes gently, thereby plays the effect of filtering.The effect of common capacitor C 2, C4 is to prevent self-excitation, and it can absorb high frequency energizing signal to keep stable, makes circuit there is no pumping signal, thereby prevents self-excitation.The effect of three terminal regulator U1 be by output voltage stabilization on+5V, connect respectively+5V of the output and ground of U1 and ground connection.
In described testing circuit, the formation of core testing circuit as shown in Figure 3: by detection chip U3, toggle switch SW3, demarcate resistance R 1, R2, R3, R4, R5, common capacitor C 7, C8 form, its effect is produce driving voltage and be applied on immunosensor, with the line number word processing of going forward side by side of the response signal after post-sampling excitation, result is sent into microcontroller.The effect of wherein demarcating resistance R 1, R2, R3 is as external feedback resistance.Toggle switch SW3 is 4-bit DIP switch, and its effect is to select the resistance of suitable demarcation to be connected into testing circuit to prevent that response signal from surpassing the range of detection chip and guaranteeing system linearity characteristic.The effect of demarcating resistance R 4, R5 is to be connected between 15,16 pins and power supply of detection chip as pull-up resistor.The effect of capacitor C 7, C8 is used for filtering and shielding, and prevents electromagnetic interference (EMI).Detection chip U3 is a high-precision impedance measurement chip, and inside is integrated with 12, and sampling rate is up to the frequency generator of the AD converter of 1MSPS.Its effect is that the driving voltage that produces characteristic frequency encourages element under test, the response signal obtaining is sampled by ADC, and carry out discrete Fourier transform by the DSP on sheet, after Fourier transform, return to the value of real part and the imaginary values that under this output frequency, obtain, and result is sent into microcontroller.15,16 pins are connected with+5V power supply by pull-up resistor R4, R5,12,13,14 pin earths, 9,10,11 pin parallel connections are connected with+5V power supply, 4, between 5 pins by toggle switch with demarcate resistance and be connected, 5,6 be used for connecing element under test.
A kind of pesticide multi-residues detector based on array-type sensor of the present invention, concrete use procedure is as follows: before use array-type sensor working electrode surface is used the nano materials such as multi-walled carbon nano-tubes to carry out chemical modification, improve the sensitivity that sensor detects, at array immunosensor working electrode surface, fix respectively different types of antibody afterwards.Then array antibody sensor is put into refrigerator, under 4 ° of C, save backup.During use, open the power switch of pesticide multi-residues detector, array-type sensor is put into test end liquid and measure initial impedance value A1, and preserve.Immunosensor is put into the sample liquid of handling well in advance and hatch 10 minutes, then sensor is connected to detector carries out impedance measurement, obtain the resistance value A2 measuring for the second time, microcontroller is delivered to display screen and is shown.Calculate rate of change, rate of change computing formula is as follows:
Rate of change=| A1-A2|/A1
If contain agricultural chemicals in sample liquid,, containing the working electrode generation specific immune response of corresponding agricultural chemicals, cause reacted respective sensor resistance value obviously to increase.The difference of A1 and A2 is larger, and the concentration that contains certain residues of pesticides that shows to detect in solution is higher.Contrast standard curve obtains the concentration of sample Pesticide Residues, at display screen, shows.Impedance rate of change and residues of pesticides concentration relationship typical curve, can be measured and draw the different types of agricultural chemicals mark-on of many groups variable concentrations by instrument for detecting pesticide residue through.
A kind of pesticide multi-residues detector detection method operating procedure based on array-type sensor of the present invention is simple, detection time is shorter, can realize the qualitative, quantitative of residues of pesticides measures, have highly sensitive, good stability, high repeatability and other advantages, meet China's Fast Determination of Pesticide Residue technical development and internationalization requirement.
Claims (5)
1. the pesticide multi-residues detector based on array-type sensor, is characterized in that by testing circuit, array immunosensor, analog multichannel switch, microcontroller, button, display screen and electric power generating composition:
Described testing circuit consists of feed circuit, detection chip, toggle switch, demarcation resistance, array-type sensor, analog multichannel switch; Feed circuit are connected with detection chip with microcontroller, adopt first the 5V feed circuit that obtain through the method for filtering voltage regulation again through transformer pressure-reducing; Chip is connected with demarcation resistance by toggle switch, according to input measurement range parameter, by toggle switch, selects corresponding demarcation resistance, with this, adjusts measurement sensitivity; Under the control of microcontroller, chip produce driving voltage be applied to liquid generation specific immune response to be measured after immunosensor on and collect response signal, after DFT, obtain its real part and imaginary part, and outputed to microcontroller;
Described array-type sensor, by a circular electrode disk, formed, centre bit is equipped with electrode and contrast electrode, periphery is working electrode, electrode, contrast electrode are equated with the distance of each working electrode guaranteeing, make each working electrode and the resistance value that having between electrode equated, between working electrode and contrast electrode, add the operating voltage of 300 millivolts, in test end liquid, measure be working electrode with to the resistance value between electrode, use analog multichannel switch to determine which working electrode connection;
On described microcontroller, move trace routine, mould value and phase angle that mould value and phase calculation formula by the impedance real part receiving and imaginary part by impedance calculates impedance, after calibration, draw actual resistance value again, with set react before resistance value compare, draw rate of change, contrast standard curve is reached a conclusion, and delivers to display screen and shows;
Described display screen is connected with microcontroller, for showing data and the window that carries out interactive operation as user;
Described button is connected with testing circuit with microcontroller, for inputting dependent instruction and detected parameters;
Described power supply is connected with feed circuit.
2. a kind of pesticide multi-residues detector based on array-type sensor according to claim 1, is characterized in that described detection chip adopts AD5933 chip.
3. a kind of pesticide multi-residues detector based on array-type sensor according to claim 1, is characterized in that the trace routine of moving on described microcontroller.
4. a kind of pesticide multi-residues detector based on array-type sensor according to claim 1, is characterized in that described microcontroller selects STC89C52 microcontroller.
5. a kind of pesticide multi-residues detector based on array-type sensor according to claim 1, it is characterized in that described array-type sensor is immunosensor, working electrode surface is fixed different types of pesticide antibody, by analog multichannel switch, make working electrode in array-type sensor and shared contrast electrode and electrode is connected, which kind of agricultural chemicals is the impedance variation causing in test end liquid by sensor contain in determining sample, and according to the typical curve of different agricultural chemicals generation impedance variation, determine the content of the agricultural chemicals in sample.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103884764A (en) * | 2014-04-10 | 2014-06-25 | 山东理工大学 | Fast detector capable of detecting antibiotics and pesticide residue in milk simultaneously |
| CN103940854A (en) * | 2014-04-10 | 2014-07-23 | 山东理工大学 | Rapid detector capable of simultaneously detecting pesticide and heavy metal residues in fruits and vegetables |
| CN103940988A (en) * | 2014-04-10 | 2014-07-23 | 山东理工大学 | Rapid heavy metal detector based on enzyme and immune sensors |
| CN103940865A (en) * | 2014-04-10 | 2014-07-23 | 山东理工大学 | Rapid detector for beta-lactam antibiotic residue |
| CN103940868A (en) * | 2014-04-15 | 2014-07-23 | 山东理工大学 | Fast detector of pesticide residues based on enzyme immunosensor |
| CN103940987A (en) * | 2014-04-10 | 2014-07-23 | 山东理工大学 | Rapid detector for simultaneously detecting aflatoxin and pesticides in peanuts |
| CN109682858A (en) * | 2018-12-19 | 2019-04-26 | 苏州慧闻纳米科技有限公司 | A method of utilizing gas sensor real-time detection gas concentration |
| US11406056B2 (en) * | 2018-12-05 | 2022-08-09 | H2Gr0, Llc | Social farming network and control system for agricultural chemical management |
| CN114910388A (en) * | 2022-07-15 | 2022-08-16 | 北京市农林科学院智能装备技术研究中心 | Aerial pesticide application drift monitoring and early warning system and method |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103884764A (en) * | 2014-04-10 | 2014-06-25 | 山东理工大学 | Fast detector capable of detecting antibiotics and pesticide residue in milk simultaneously |
| CN103940854A (en) * | 2014-04-10 | 2014-07-23 | 山东理工大学 | Rapid detector capable of simultaneously detecting pesticide and heavy metal residues in fruits and vegetables |
| CN103940988A (en) * | 2014-04-10 | 2014-07-23 | 山东理工大学 | Rapid heavy metal detector based on enzyme and immune sensors |
| CN103940865A (en) * | 2014-04-10 | 2014-07-23 | 山东理工大学 | Rapid detector for beta-lactam antibiotic residue |
| CN103940987A (en) * | 2014-04-10 | 2014-07-23 | 山东理工大学 | Rapid detector for simultaneously detecting aflatoxin and pesticides in peanuts |
| CN103940988B (en) * | 2014-04-10 | 2015-12-09 | 山东理工大学 | A kind of heavy metal fast detector based on enzyme immunosensor and detection method thereof |
| CN103940868A (en) * | 2014-04-15 | 2014-07-23 | 山东理工大学 | Fast detector of pesticide residues based on enzyme immunosensor |
| CN103940868B (en) * | 2014-04-15 | 2016-02-24 | 山东理工大学 | A kind of rapid detector for pesticide residue based on enzyme immunosensor |
| US11406056B2 (en) * | 2018-12-05 | 2022-08-09 | H2Gr0, Llc | Social farming network and control system for agricultural chemical management |
| CN109682858A (en) * | 2018-12-19 | 2019-04-26 | 苏州慧闻纳米科技有限公司 | A method of utilizing gas sensor real-time detection gas concentration |
| CN109682858B (en) * | 2018-12-19 | 2021-09-17 | 苏州慧闻纳米科技有限公司 | Method for detecting gas concentration in real time by using gas sensor |
| CN114910388A (en) * | 2022-07-15 | 2022-08-16 | 北京市农林科学院智能装备技术研究中心 | Aerial pesticide application drift monitoring and early warning system and method |
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