CN103558257B - 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, particularly relate to a kind of instrument for detecting pesticide residue through based on array-type sensor, whether it has merged biology sensor detection technique and Embedded System Design method, contain which kind of residues of pesticides for detecting in agricultural product conveniently, rapidly, accurately and exceed standard.Belong to agricultural product security detection technique field.
Background technology
The pesticide variety applied in present production field has reached kind more than 100, and keep good harvest volume increase to play a significant role to agricultural, it has become important a kind of means of production.Along with deeply carrying out of reform and opening-up, in some Changshu Aeras, the speed of development of agricultural chemicals cause becomes very fast.Because mechanization of agriculture constantly advances, it is indispensable that the large area of agricultural chemicals uses.But because of irrational use of agricultural chemicals, cause many environmental problems, as destroyed in farmland ecosystem etc.A large amount of uses of agricultural chemicals, while ensure that a large amount of stable yields of the crops such as grain, also bring many environmental problems.Agricultural chemicals residual in plant, soil and water has two kinds of remaining forms: the first keeps original chemical constitution; The second is with the product after chemical conversion or to be biodegradable the form of product remaining.Therefore, Pesticide Residue can not be ignored.
The main method of current pesticide residue analysis is gas chromatograph, liquid chromatograph, gas chromatograph-mass spectrometer, LC-MS instrument etc., although these method analysis precisions are high, quantitatively accurately, but the complex pretreatment of its sample, detect length consuming time, cost high, need the operating personnel that are skilled in technique.The fast determining method of China's residues of pesticides is enzyme level test paper method and enzyme level spectrophotometric method (the residual fast detector of agriculture), can realize the field quick detection of organophosphorus pesticide and carbamate chemicals for agriculture, have good practical value.Quick measuring card is changed by the color of visual inspection card, and the vegetable sample that therefore generally can only be used for severe overweight carries out observational measurement.The application of enzyme level spectrophotometric method is also relatively more extensive, and it is all based on this principle that domestic existing Multiple Pesticides remains tacheometer.Light splitting light ratio juris carries out detecting based on the change of absorbance, but pigments a large amount of in vegetable and fruit 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 meet the shortcomings such as low-residual and the requirement that quantitatively detects.
Invention object be for the deficiencies in the prior art, design a kind of instrument for detecting pesticide residue through based on array-type sensor is provided, have easy to carry, detect quick and precisely, simple to operate, the features such as pesticide multi-residues detects simultaneously can be realized.
Described its Cleaning Principle of 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 to fix different types of pesticide antibody at working electrode surface, make a working electrode in array-type sensor with the contrast electrode shared by analog multichannel switch and electrode is connected.The impedance variation caused in test end liquid by sensor is determined containing which kind of agricultural chemicals in sample, and produces the typical curve of impedance variation according to different agricultural chemicals, 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 is made up of testing circuit, array-type sensor, power supply, button, microcontroller and display screen.Testing circuit is used for producing driving voltage be applied on each immunosensor, to go forward side by side line number word processing, result is sent into microcontroller with the response signal after post-sampling excitation; Microcontroller and the trace routine run above thereof process again to input signal, and control the operation of whole system and respond; Button is used for inputting instruction and detected parameters; Display screen is used for quantizing to export presenting final testing result, is the interactive interface of user and system; Power supply is that whole system is powered.
A kind of pesticide multi-residues detector concrete structure based on array-type sensor of the present invention is: pesticide multi-residues detector is made up of testing circuit, array-type sensor, analog multichannel switch, power supply, button, microcontroller and display screen, wherein: testing circuit is made up 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+the 5V first obtained through the method for filtering voltage regulation again through transformer pressure-reducing to power; Chip is connected with demarcation resistance by toggle switch, according to input measurement range parameter, selects corresponding demarcation resistance, adjust measurement sensistivity with this by toggle switch; Under the control of the micro-controller, chip produces driving voltage and to be applied on array immunosensor and to collect response signal, obtains its real part and imaginary part, and outputted to microcontroller after DFT.Microcontroller runs trace routine, the impedance real part received and imaginary part are gone out modulus value and the phase angle of impedance by the modulus value of impedance and phase calculation formulae discovery, actual resistance value is drawn again after calibration, compare with the resistance value before the reaction of setting, obtain rate of change and contrast standard curve is reached a conclusion, deliver to display screen display.Described display screen is connected with microcontroller, and for showing data and carrying out the window of interactive operation as user, display screen adopts LED12864, and its power consumption can meet the power consumption requirements 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, when detecting use, first measurement sensistivity is ensured by the selected resistance of demarcating of toggle switch, array-type sensor is put into solution to be detected, under the control of the micro-controller, chip produces driving voltage and to be applied on array-type sensor and to collect response signal, its real part and imaginary part is obtained after DFT, and outputted to microcontroller, signal reprocessing is carried out through microcontroller and trace routine thereof, and compare with the front resistance value of reaction, calculate rate of change.Owing to fixing different types of pesticide antibody on the working electrode of array-type sensor, therefore namely indicate the concentration containing which kind of agricultural chemicals and residues of pesticides in the sample of detection according to the size of each sensor impedance rate of change.
For reaching above object, array-type sensor takes following technical scheme to realize: be made up of a circular electrode disk, centre bit is equipped with electrode and contrast electrode, periphery is working electrode, equal with the distance of each working electrode to guarantee electrode, contrast electrode, make each working electrode with to having equal resistance value between electrode.Between working electrode and contrast electrode, add the operating voltage of 300 millivolts, what measure in test fluid is working electrode and to the resistance value between electrode.Which working electrode is connected to use analog multichannel switch to determine.
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, fully can meet the requirement of residues of pesticides field quick detection for testing staff.Various testing sample must be transported to inspection center relative to testing in the past, carried out in large-scale station device by professional staff, detector of the present invention have easy to carry, detect quick and precisely, the outstanding feature such as 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 is made up 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 be applied on immunosensor, to go forward side by side line number word processing, result is sent into microcontroller with the response signal after post-sampling excitation; Microcontroller and the trace routine run above thereof process again to input signal, and control the operation of whole system and respond; Button is used for inputting instruction and detected parameters; Display screen is used for quantizing to export presenting final testing result, is the interactive interface of user and system; Power supply is that whole system is powered.
Described array-type sensor is made up of a circular electrode disk, centre bit is equipped with electrode and contrast electrode, periphery is working electrode, equal with the distance of each working electrode to guarantee electrode, contrast electrode, make each working electrode with to having equal resistance value between electrode.Between working electrode and contrast electrode, add the operating voltage of 300 millivolts, what measure in test fluid is working electrode and to the resistance value between electrode.Which working electrode is connected to use analog multichannel switch to determine.
STC89C52 selected by described microcontroller, and it loads trace routine.Feed circuit in testing circuit form and principle as shown in Figure 2, by transformer T1, bridge rectifier circuit BR1, electrochemical capacitor C1, C3, conventional capacitive C2, C4, three terminal regulator U1 is formed, and it acts on is for whole system provides the Power supply of+5V.In the design, the effect of electrochemical capacitor C1, C2 is filtering, simply say be exactly electric capacity both end voltage raise time, capacitor charging, voltage reduce time, capacitor discharge, gradient when allowing voltage reduce becomes mild, thus plays the effect of filtering.The effect of conventional capacitive C2, C4 prevents self-excitation, and high frequency energizing signal can absorb and keep stable by it, makes circuit not have pumping signal, thus prevents self-excitation.The effect of three terminal regulator U1 is by output voltage stabilization on+5V, and the output and ground of U1 connects+5V and ground connection respectively.
In described testing circuit, the formation of core testing circuit as shown in Figure 3: by detection chip U3, toggle switch SW3, demarcate resistance R1, R2, R3, R4, R5, conventional capacitive C7, C8 are formed, its effect produces driving voltage and is applied on immunosensor, to go forward side by side line number word processing with the response signal after post-sampling excitation, result is sent into microcontroller.The effect of wherein demarcating resistance R1, R2, R3 is as external feedback resistance.Toggle switch SW3 is 4-bit DIP switch, and its effect selects the resistance of suitable demarcation to be connected into testing circuit exceed the range of detection chip to prevent response signal and ensure system linearity characteristic.The effect of demarcating resistance R4, R5 is connected between 15,16 pins of detection chip and power supply as pull-up resistor.The effect of electric capacity C7, C8 is used to filtering and shields, 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 of generation characteristic frequency is to encourage element under test, the response signal obtained is sampled by ADC, and carry out discrete Fourier transform by the DSP on sheet, return the value of real part and imaginary values that obtain under this output frequency after Fourier transform, and result is sent into microcontroller.15,16 pins are connected with+5V power supply by pull-up resistor R4, R5,12,13,14 pins in parallel ground connection, 9,10,11 pins in parallel are connected with+5V power supply, 4, are connected with demarcation resistance by toggle switch between 5 pins, 5,6 are 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: used by array-type sensor working electrode surface the nano materials such as multi-walled carbon nano-tubes to carry out chemical modification before use, improve the sensitivity that sensor detects, fix different types of antibody respectively at array immunosensor working electrode surface afterwards.Then array antibody sensor is put into refrigerator, save backup under 4 ° of C.Open the power switch of pesticide multi-residues detector during use, array-type sensor is put into test end liquid and measure initial impedance value A1, and preserve.Immunosensor is put into the sample liquid hatching handled well in advance 10 minutes, then sensor is connected to detector and carries out impedance measurement, obtain the resistance value A2 that second time is measured, microcontroller is delivered to display screen display.Calculate rate of change, rate of change computing formula is as follows:
Rate of change=| A1-A2|/A1
If containing agricultural chemicals in sample liquid, then containing the working electrode generation specific immune response of corresponding agricultural chemicals, reacted respective sensor resistance value is caused obviously to increase.The difference of A1 and A2 is larger, shows that the concentration containing certain residues of pesticides detected in solution is higher.Contrast standard curve obtains the concentration of sample Pesticide Residues, shows at display screen.Impedance rate of change and residues of pesticides concentration relationship typical curve, can be drawn the different types of agricultural chemicals mark-on mensuration of many group 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, the qualitative, quantitative that can realize residues of pesticides is measured, have highly sensitive, good stability, high repeatability and other advantages, meet China's Fast Determination of Pesticide Residue technical development and internationalization requirement.
Claims (1)
1., based on a pesticide multi-residues detector for array-type sensor, it is characterized in that the described pesticide multi-residues detector based on array-type sensor is by testing circuit, array-type sensor, microcontroller, button, display screen and electric power generating composition;
Described testing circuit is made up of feed circuit, detection chip, toggle switch, demarcation resistance, analog multichannel switch, feed circuit are connected with detection chip with microcontroller, adopt first through transformer pressure-reducing again through 5V feed circuit that the method for filtering voltage regulation obtains, chip is connected with demarcation resistance by toggle switch, according to input measurement range parameter, selects corresponding demarcation resistance, adjust measurement sensistivity with this by toggle switch, under the control of the micro-controller, 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 outputted to microcontroller, described array-type sensor is immunosensor, be made up of a circular electrode disk, centre bit is equipped with electrode and contrast electrode, periphery is working electrode, to guarantee electrode, contrast electrode is equal with the distance of each working electrode, make each working electrode with to having equal resistance value between electrode, the operating voltage of 300 millivolts is added between working electrode and contrast electrode, working electrode surface fixes different types of pesticide antibody, array-type sensor puts into test end liquid, analog multichannel switch makes a working electrode in array-type sensor with the contrast electrode shared and connects electrode, testing circuit is connected with array-type sensor three electrode, measure connect working electrode and to the resistance value between electrode, which kind of agricultural chemicals is the impedance variation caused in test end liquid by sensor determined in sample containing, and the typical curve of impedance variation is produced according to different agricultural chemicals, determine the content of the agricultural chemicals in sample,
Described microcontroller runs trace routine, the impedance real part received and imaginary part are gone out modulus value and the phase angle of impedance by the modulus value of impedance and phase calculation formulae discovery, actual resistance value is drawn again after calibration, compare with the resistance value before the reaction of setting, draw rate of change, contrast standard curve is reached a conclusion, and delivers to display screen display; Described display screen is connected with microcontroller, for showing data and carrying out the window of 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., according to a kind of pesticide multi-residues detector based on array-type sensor described in claim 1, it is characterized in that described detection chip adopts AD5933 chip.
3., according to a kind of pesticide multi-residues detector based on array-type sensor described in claim 1, it is characterized in that STC89C52 microcontroller selected by described microcontroller.
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| 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 |
| CN103940987A (en) * | 2014-04-10 | 2014-07-23 | 山东理工大学 | Rapid detector for simultaneously detecting aflatoxin and pesticides in peanuts |
| CN103940865B (en) * | 2014-04-10 | 2016-01-13 | 山东理工大学 | A kind of belt-lactam antibiotics residues fast detector |
| 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 |
| 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 |
| 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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| CN201166659Y (en) * | 2008-03-20 | 2008-12-17 | 长春吉大·小天鹅仪器有限公司 | Device for rapidly detecting array type 96chunnel pesticide residue |
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