CN102128825B - All-solid state optical pesticide residue detecting device - Google Patents
All-solid state optical pesticide residue detecting device Download PDFInfo
- Publication number
- CN102128825B CN102128825B CN 201010034287 CN201010034287A CN102128825B CN 102128825 B CN102128825 B CN 102128825B CN 201010034287 CN201010034287 CN 201010034287 CN 201010034287 A CN201010034287 A CN 201010034287A CN 102128825 B CN102128825 B CN 102128825B
- Authority
- CN
- China
- Prior art keywords
- solid state
- sensitive chip
- pallet
- agricultural chemicals
- chip
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 230000003287 optical effect Effects 0.000 title claims abstract description 45
- 239000007787 solid Substances 0.000 title claims abstract description 45
- 239000000447 pesticide residue Substances 0.000 title claims abstract description 22
- 238000001514 detection method Methods 0.000 claims abstract description 49
- 239000000575 pesticide Substances 0.000 claims abstract description 48
- 238000012545 processing Methods 0.000 claims abstract description 26
- 239000003905 agrochemical Substances 0.000 claims description 66
- 239000012528 membrane Substances 0.000 claims description 44
- 239000000243 solution Substances 0.000 claims description 28
- 239000000523 sample Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000007639 printing Methods 0.000 claims description 16
- 238000012360 testing method Methods 0.000 claims description 16
- 102100032404 Cholinesterase Human genes 0.000 claims description 15
- 101710083761 Cholinesterase Proteins 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 230000002209 hydrophobic effect Effects 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 102100033639 Acetylcholinesterase Human genes 0.000 claims description 11
- 108010022752 Acetylcholinesterase Proteins 0.000 claims description 11
- 229940022698 acetylcholinesterase Drugs 0.000 claims description 11
- 229920003023 plastic Polymers 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 239000004033 plastic Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 239000013074 reference sample Substances 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000008363 phosphate buffer Substances 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- MEYZYGMYMLNUHJ-UHFFFAOYSA-N tunicamycin Natural products CC(C)CCCCCCCCCC=CC(=O)NC1C(O)C(O)C(CC(O)C2OC(C(O)C2O)N3C=CC(=O)NC3=O)OC1OC4OC(CO)C(O)C(O)C4NC(=O)C MEYZYGMYMLNUHJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000005259 measurement Methods 0.000 claims description 6
- 239000004065 semiconductor Substances 0.000 claims description 6
- 238000013016 damping Methods 0.000 claims description 4
- 239000005357 flat glass Substances 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 4
- 230000002572 peristaltic effect Effects 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 239000006096 absorbing agent Substances 0.000 claims description 2
- 239000002985 plastic film Substances 0.000 claims description 2
- 150000003376 silicon Chemical class 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000002835 absorbance Methods 0.000 description 12
- 102000004190 Enzymes Human genes 0.000 description 7
- 108090000790 Enzymes Proteins 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 229940088598 enzyme Drugs 0.000 description 7
- 230000000694 effects Effects 0.000 description 4
- 229960001952 metrifonate Drugs 0.000 description 4
- NFACJZMKEDPNKN-UHFFFAOYSA-N trichlorfon Chemical compound COP(=O)(OC)C(O)C(Cl)(Cl)Cl NFACJZMKEDPNKN-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 235000013399 edible fruits Nutrition 0.000 description 3
- 239000012088 reference solution Substances 0.000 description 3
- 235000013311 vegetables Nutrition 0.000 description 3
- 102000003914 Cholinesterases Human genes 0.000 description 2
- 108090000322 Cholinesterases Proteins 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000011095 buffer preparation Methods 0.000 description 2
- 229940048961 cholinesterase Drugs 0.000 description 2
- 239000012916 chromogenic reagent Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- NHMCKQVQOCESFN-UHFFFAOYSA-N 2,3-dinitro-4-sulfobenzoic acid Chemical compound S(=O)(=O)(O)C1=C(C(=C(C(=O)O)C=C1)[N+](=O)[O-])[N+](=O)[O-] NHMCKQVQOCESFN-UHFFFAOYSA-N 0.000 description 1
- KIUMMUBSPKGMOY-UHFFFAOYSA-N 3,3'-Dithiobis(6-nitrobenzoic acid) Chemical compound C1=C([N+]([O-])=O)C(C(=O)O)=CC(SSC=2C=C(C(=CC=2)[N+]([O-])=O)C(O)=O)=C1 KIUMMUBSPKGMOY-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- HUGQNTGOVJKASF-UHFFFAOYSA-M [SH-].[I+] Chemical compound [SH-].[I+] HUGQNTGOVJKASF-UHFFFAOYSA-M 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000002210 biocatalytic effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000152 carbamate pesticide Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000005911 diet Nutrition 0.000 description 1
- 230000037213 diet Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003987 organophosphate pesticide Substances 0.000 description 1
- 230000000361 pesticidal effect Effects 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000005373 porous glass Substances 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 230000000192 social effect Effects 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Images
Abstract
The invention discloses an all-solid state optical pesticide residue detecting device, relating to the detection technology. The device comprises at least one detecting unit and at least one signal processing chip, wherein the detecting unit comprises a light source, a tray, a pesticide-sensitive chip and a photodetector, the photodetector is electrically connected with the signal processing chip, and the output terminal of the signal processing chip is electrically connected with follow-up equipment; and the device can be assembled into a single-channel or multichannel optical detecting device. The detecting device disclosed by the invention has the advantages of simple structure, small volume, low cost, convenience for use, reliability and sensitivity, short determination time, easiness for storing the sensitive chip, and convenience for carrying, and is applicable to rapid field quantitative detection on pesticide residue in agricultural products in the places such as a home, an emporium and a farmer market.
Description
Technical field
The present invention relates to the detection technique field, is a kind of all-solid state optical pesticide residue detecting device, can carry out on-the-spot rapid and accurate determination to contained agricultural chemicals in remains of pesticide in the crops and the water body.
Background technology
China is large agricultural country, and the production of agricultural chemicals and use are very extensively general in China, and especially highly toxic organophosphorus and carbamate chemicals for agriculture are the agricultural chemicals of at present production of China and use amount maximum.The large tracts of land of agricultural chemicals is used and is abused, society is upper in addition lacks agricultural chemicals Site Detection means and the supervision that causes is not in place fast and effectively, so that the phenomenon that remains of pesticide exceeds standard in the agricultural product such as China vegetables, fruit is quite serious, also caused the pollution of agricultural chemicals to China's surface water and groundwater simultaneously.On the other hand, along with improving constantly of China's living standards of the people, people more and more pay close attention to the safe diet problem.In the case, research and development can be carried out on-the-spot method and the instrument that quick and precisely detects to pesticide residue on agricultural product and the contained agricultural chemicals of water body and has very important social effect and practical value.
At present, China mainly uses vapor-phase chromatography, liquid phase chromatography and gas chromatography-mass spectrum to be used in conjunction method contained agricultural chemicals in remains of pesticide and the water body in the agricultural product such as vegetables, fruit is detected.Although these large-scale instruments are highly sensitive, testing result exists instrument expensive accurately and reliably, complicated operation, and sample needs pre-treatment, and testing cost is high, and detection time is long, is not suitable for the shortcomings such as field quick detection.In order to satisfy the great demand to the organophosphorus field quick detection, based on organophosphorus and carbamate chemicals for agriculture agricultural chemicals quick measuring card and tacheometer that the distinctive inhibiting effect of cholinesterase biocatalytic reaction develops were come out one after another in China more in recent years.These quick measuring cards and tacheometer all adopt the colorimetric test mode, and only quick measuring card is based on the visual colorimetric of carrying out of bore hole, and precision is not high, and accuracy is relatively poor; And tacheometer is based on the mensuration to solution absorption spectrum, and accuracy and measuring accuracy are higher than quick measuring card.But quick measuring card is allowed at normal temperatures long period preservation, is easy to carry, and is easy to use, do not need on-the-spot preparation to detect required various solution.This is because cholinesterase can at room temperature keep the activity of long period after being fixed, and the biology enzyme that is in the solution at room temperature loses activity easily.Therefore need in use to use a plurality of containers based on the spectrometric agricultural chemicals tacheometer of solution absorption, plurality of reagents, the multiple solution that on-the-spot preparation test needs, thus so that the test formality is loaded down with trivial details, measuring process is consuming time.
Summary of the invention
The object of the present invention is to provide a kind of all-solid state optical pesticide residue detecting device, can carry out on-the-spot Simple fast to contained agricultural chemicals in remains of pesticide in the agricultural product and the water body and accurately detect.This structure of the detecting device is simple, volume is little, and cost is low, is easy to carry, and is highly sensitive, easy to use, solved agricultural chemicals tacheometer test formality loaded down with trivial details shortcoming consuming time in the market and the sensitivity of agricultural chemicals quick measuring card is low, the problem of poor accuracy.
For achieving the above object, technical solution of the present invention is:
A kind of all-solid state optical pesticide residue detecting device comprises a detecting unit, and a signal processing chip consists of the single channel pick-up unit; Its detecting unit comprises a light source, a photo-detector, an agricultural chemicals sensitive chip, a pallet; One agricultural chemicals sensitive chip level places in the pallet of bottom printing opacity, one light source is arranged on pallet one side, and the light positive that light source sends is penetrated in the tray bottom, and a photo-detector is arranged on the opposite side of pallet, coaxial relative with light source, be used for receiving the light signal that sees through tray bottom and sensitive chip;
Detecting unit is electrically connected with signal processing chip, and namely the photo-detector output terminal of detecting unit links to each other with the signal processing chip input end, and the signal processing chip output terminal is electrically connected on follow-up equipment.
Described all-solid state optical pesticide detection device, its when detecting unit be a plurality of, consist of multi-channel testing device, and signal processing chip is when being one, the photo-detector output terminal of each detecting unit links to each other with a signal processing chip input end respectively altogether; Or signal processing chip is when being a plurality of, and the photo-detector output terminal of each detecting unit links to each other with a signal processing chip input end respectively;
The signal processing chip output terminal is electrically connected on follow-up equipment.
Described all-solid state optical pesticide detection device, its described agricultural chemicals sensitive chip comprises multilayer printing opacity porous membrane, overlapped being connected of multilayer printing opacity diaphragm;
The printing opacity porous membrane is hydrophilic microporous filter membrane or filter paper, or hydrophobic micropore filter membrane or filter paper, or transparent plastic film.
Described all-solid state optical pesticide detection device, its described agricultural chemicals sensitive chip, during for the trilamellar membrane chip architecture: the superiors are the hydrophilic porous diaphragm of ground floor, it is lower to the hydrophobic porous diaphragm of the second layer, is down the 3rd layer of hydrophilic porous diaphragm; Be filled with in the micropore of ground floor porous membrane can with acetylcholinesterase or the butyrylcholine esterase of organophosphorus and carbamate chemicals for agriculture reaction; Be filled with substrate and developer in the micropore of the 3rd layer of porous membrane; Or developer is in acetylcholinesterase or butyrylcholine esterase are filled in the porous membrane of ground floor.
Described all-solid state optical pesticide detection device, its described agricultural chemicals sensitive chip, when being four tunic chip architectures: the superiors are the hydrophilic porous diaphragm of ground floor, it is lower to the hydrophobic porous diaphragm of the second layer, is the 3rd layer of hydrophilic porous diaphragm again under it; Be down the 4th layer of hydrophilic porous diaphragm; Be filled with in the micropore of ground floor porous membrane can with acetylcholinesterase or the butyrylcholine esterase of organophosphorus and carbamate chemicals for agriculture reaction; Be filled with substrate in the micropore of the 3rd layer of porous membrane; Be filled with developer in the micropore of the 4th layer of porous membrane.
Described all-solid state optical pesticide detection device, its described agricultural chemicals sensitive chip, each layer porous membrane is of similar shape, and the area of the hydrophobic diaphragm of the second layer wherein is more than or equal to the area of the hydrophilic porous diaphragm of other arbitrary layers;
Multilayer printing opacity diaphragm is connected with web member each other.
Described all-solid state optical pesticide detection device, its described web member is staple.
Described all-solid state optical pesticide detection device, its described pallet comprises a clear plate glass and an opaque-plastic plate, and a through hole is arranged on the plastic plate, clear plate glass covers and sealing is fixed in the through hole below;
The thickness of opaque-plastic plate is tray depth, and tray depth is greater than sensitive chip thickness, and through-hole diameter is tray bottom surface, and tray bottom surface is greater than the sensitive chip diameter.
Described all-solid state optical pesticide detection device, its described opaque-plastic plate, thickness≤7mm, through-hole diameter≤14mm.
Described all-solid state optical pesticide detection device, its described light source is light emitting diode or semiconductor laser, the emission wavelength of light emitting diode or semiconductor laser is positioned at the Absorber Bandwidth scope after the agricultural chemicals sensitive chip is met the water variable color; Light activated silicon photoelectric diode or the silicon photocell of photo-detector for light source is sent.
A kind of detection method of described all-solid state optical pesticide detection device, it adopts Comparison Method, comprise: a) with the all-solid state optical pesticide detection device respectively to aqueous sample to be analyzed and reference sample detection once, two results that relatively record under the uniform temp condition are to obtain the pesticide concentration in the aqueous solution to be analyzed; Or b) with the all-solid state optical pesticide detection device aqueous sample to be analyzed is detected once, the result who records is made comparisons with the normal data database data of making in advance, to obtain the pesticide concentration in the aqueous solution to be analyzed.
Described detection method, its described reference sample is for pure water, deionized water or prepare the used damping fluid of aqueous sample to be analyzed.
Described detection method, its described damping fluid is phosphate buffer: use 0.1mol/LKH
2PO
4With 0.1mol/L Na
2HPO
412H
2The phosphate buffer of the 0.1mol/L pH=8 of O aqueous solution preparation 500ml
Described detection method, its described a) kind Comparison Method comprises step:
(1) at first, the agricultural chemicals sensitive chip is lain in a horizontal plane in the pallet, and make include acetylcholinesterase or butyrylcholine esterase the ground floor porous membrane up;
(2) utilize syringe or pipettor or peristaltic pump to draw aqueous sample to be analyzed, drip the ground floor upper surface at sensitive chip, make the ground floor porous membrane fully moistening, and keep each layer porous membrane below the second layer hydrophobic membrane not contact sample;
(3) with the while in (2) step, open light source, photo-detector, the enabling signal process chip from dripping aqueous sample to be analyzed, is measured transmitted intensity over time;
(4) behind certain hour, in pallet, add again aqueous sample to be analyzed and flood whole sensitive chip;
(5) continue to measure transmitted intensity, and the data of record measurement result;
(6) measure complete after, used agricultural chemicals sensitive chip is taken out from pallet, and removes the interior solution of pallet, pallet is cleaned dries;
(7) then, again get a slice agricultural chemicals sensitive chip and put into the pallet that cleaned, repeating (1) to (5) under the uniform temp condition goes on foot, but in going on foot, (2), (3) add the reference sample, test in the situation of reference sample transmitted intensity over time, and the record measurement result data;
(8) measurement result with (5) step and (7) step compares, thereby obtains the pesticide concentration in the aqueous sample to be analyzed.
Described detection method, the certain hour of its described (4) in the step is≤10 minutes.
The invention has the advantages that: described all-solid state optical pesticide detection device is simple in structure, make easily, volume is little, cost is low, easy to use, be convenient to deposit and carry, accurately reliable, highly sensitive, test duration is short, amount of samples is few, has overcome the loaded down with trivial details shortcoming consuming time of agricultural chemicals tacheometer test process in the market and the sensitivity of agricultural chemicals quick measuring card is low, the problem of low precision, be suitable for the places such as family, market, the market of farm produce to agricultural product in remains of pesticide carry out on-the-spot Quantitative detection.
Description of drawings
Fig. 1 is the structural representation of single channel all-solid state optical pesticide detection device of the present invention;
Fig. 2 is the structural representation of hyperchannel all-solid state optical pesticide detection device of the present invention;
Fig. 3 utilizes over time curve synoptic diagram of absorbance that single channel all-solid state optical pesticide detection device shown in Figure 1 records respectively under three kinds of metrifonate pesticide concentrations.
Embodiment
The purpose, technical solutions and advantages of the present invention are more clear to be understood in order to make, below in conjunction with specific embodiment, and with reference to accompanying drawing the present invention is described in more detail.
The present invention is by being filled with all solid state agricultural chemicals sensitive chip of different biochemical reagents in the multilayer printing opacity diaphragm micropores that form and different diaphragms as core take one, dispose an agricultural chemicals sensitive chip pallet, the light source that can launch quasi-monochromatic light, the single channel all-solid state optical pesticide detection device of a photo-detector and a signal processing chip composition that links to each other with photo-detector.Use a plurality of agricultural chemicals sensitive chips, a plurality of sensitive chip pallets, a plurality of light sources and a plurality of photo-detector, and a signal processing chip that links to each other with a plurality of detectors can form corresponding hyperchannel all-solid state optical pesticide detection device.
Fig. 1 is the structural representation of single channel all-solid state optical pesticide detection device of the present invention, and Fig. 2 is the structural representation of hyperchannel all-solid state optical pesticide detection device of the present invention.Wherein, 1 is light source, and 2 is the agricultural chemicals sensitive chip that is comprised of multilayer printing opacity diaphragm, and 3 is agricultural chemicals sensitive chip pallet, and 4 is photo-detector, and 5 is signal processing chip.Light emitting diode or semiconductor laser are arranged on the below of pallet 3 as light source 1, light directive pallet 3 bottoms that light source 1 sends, silicon photoelectric diode or silicon photocell are arranged on the pallet relative with light source 3 opposite sides as photo-detector 4, are used for receiving the light signal that sees through pallet 3 bottoms and sensitive chip 2.The signal processing chip 5 that the electric signal input that photo-detector 4 produces links to each other with detector 4, the electric signal of 5 pairs of inputs of signal processing chip is processed.
In the structure of pick-up unit of the present invention, light source 1 and photo-detector 4 can switches, be the top that described light emitting diode or semiconductor laser are arranged on pallet 3, and silicon photoelectric diode or silicon photocell are arranged on the below of the pallet 3 relative with light source 1.
Agricultural chemicals sensitive chip 2 is by three layers or four layers of overlapping connecting and composing of printing opacity diaphragm.The agricultural chemicals sensitive chip 2 that is comprised of the trilamellar membrane sheet comprises: the superiors' diaphragm is hydrophilic porous diaphragm, be filled with in its micropore can with acetylcholinesterase or the butyrylcholine esterase of organophosphorus and carbamate chemicals for agriculture reaction, second layer diaphragm is that teflon membrane filter etc. has hydrophobic diaphragm, the trilamellar membrane sheet also is hydrophilic porous diaphragm, is filled with substrate and developer in its micropore.Developer can not be filled in the trilamellar membrane sheet yet, and in acetylcholinesterase or butyrylcholine esterase are filled in the superiors' porous membrane.In being filled into separately the micropore of the hydrophilic porous diaphragm of one deck, developer as the 4th tunic sheet, just constituted the agricultural chemicals sensitive chip 2 that is formed by four tunic sheets with other trilamellar membrane sheets.
The hydrophilic porous diaphragm of each layer that forms agricultural chemicals sensitive chip 2 is filled when surveying the required biochemical reagents of agricultural chemicals, at first disposes the aqueous solution of corresponding reagent, and it is natural drying to be placed on shading place after then adopting dipping-pulling method that porous membrane is soaked in solution.Perhaps, utilize syringe or pipettor that a certain amount of reagent solution is dripped and make diaphragm by fully moistening at hydrophilic porous diaphragm, it is natural drying then to be placed on shading place.After each tunic sheet is by finish-drying, superposes successively and link together and form agricultural chemicals sensitive chip 2.The agricultural chemicals sensitive chip 2 for preparing is by Vacuum Package, and then at room temperature shading is preserved.
Agricultural chemicals sensitive chip 2 is positioned horizontally in the pallet 3, and make be filled with acetylcholinesterase or butyrylcholine esterase porous membrane up.Utilize syringe or pipettor or peristaltic pump to draw a certain amount of aqueous sample to be analyzed, then dripping upper surface at sensitive chip 2 makes the hydrophilic porous diaphragm of the superiors fully moistening but hydrophilic porous diaphragm below making does not contact water, after placing certain hour (a few minutes), in pallet, add again quantitative aqueous solution to be analyzed and flood whole sensitive chip 2, place again afterwards certain hour (a few minutes).From agricultural chemicals sensitive chip 2 be placed on pallet 3 interior, open light source 1 irradiation pallet 3 and sensitive chip 2, start photo-detector 4 continuous coverages and also record the transmission light intensity.Measure complete after, used agricultural chemicals sensitive chip 2 is taken out from pallet 3, and remove solution in the pallet 3, pallet 3 inside surfaces are cleaned dry, then new agricultural chemicals sensitive chip 2 is put into the pallet 3 that cleaned, transmitted intensity is over time in the situation of reference sample by the test of top step.Two results that record more under the same conditions, thus pesticide concentration in the aqueous solution to be analyzed obtained; Perhaps the result who records in the situation about existing in aqueous solution to be analyzed is made comparisons with the normal data database data of making in advance, thereby obtain pesticide concentration in the aqueous solution to be analyzed.
Embodiment:
Preparation process and detection running program are as follows before the detection of all-solid state optical pesticide residue detecting device of the present invention:
1. it is for subsequent use to be formulated as follows reagent:
(1) phosphate buffer: use 0.1mol/L KH
2PO
4With 0.1mol/L Na
2HPO
412H
2The phosphate buffer of the 0.1mol/L pH=8 of O aqueous solution preparation 500ml.
(2) enzyme solutions: contain 0.75mg/ml butyrylcholine esterase solution with the phosphate buffer preparation.
(3) substrate solution: prepare the 10mmol/L iodine bisulfide for BuCh solution with deionized water.
(4) chromogenic reagent solution: contain 5mmol/L two sulfo-dinitrobenzoic acid (DTNB) solution with the phosphate buffer preparation.
(5) pesticidal solutions to be analyzed: first with the metrifonate standard solution of deionized water preparation 250mg/L, then be diluted to the solution of variable concentrations (0.1mg/L-5mg/L) with deionized water.
2. the preparation of agricultural chemicals sensitive chip 2:
Prepared agricultural chemicals sensitive chip is by four layers of overlapping connecting to form of printing opacity diaphragm in this example.The superiors diaphragms is selected diameter 13mm, and the hydrophilic porous glass fibre disk of thickness 1mm takes out that to be placed on shading place natural drying after adopting dipping-pulling method that this porous disk is soaked in above-mentioned enzyme solutions.Second layer hydrophobic membrane adopts and the onesize polyethylene film of the superiors' enzyme membrane sheet.The trilamellar membrane sheet is hydrophilic porous filter paper, and its size is also identical with the enzyme membrane sheet, fills substrate in the micropore.Get the above-mentioned substrate solution of 20 μ L with pipettor and drip on the porous filter paper surface, it is natural drying then to be placed on shading place.The 4th tunic sheet also uses the hydrophilic porous filter paper onesize with the enzyme membrane sheet, fills developer in the micropore.Get the above-mentioned chromogenic reagent solution of 20 μ L with pipettor and drip on the porous filter paper surface, it is natural drying to be placed on equally shading place.Behind each tunic sheet finish-drying, successively stack and connect and form the agricultural chemicals sensitive chip with staple, Vacuum Package then, at room temperature shading is preserved.
3. the preparation of agricultural chemicals sensitive chip pallet 3:
Be the black plastic plate of the 7mm through hole that to make a call to a diameter be 14mm at thickness, then use the one side sealing of a clear plate glass and black plastic plate bonding, and the openings on the black plastic plate face is hidden by glass plate, make thus agricultural chemicals sensitive chip pallet 3.During use agricultural chemicals sensitive chip 2 is lain in a horizontal plane in hole inner pallet 3 tops, be arranged on pallet 3 belows, the photo-detector 4 that is arranged on pallet 3 tops behind the light transmission glass plate that sends over against the light source 1 of through hole and the chip 2 receives.
4. operation steps:
Present embodiment uses single channel all-solid state optical pesticide detection device shown in Figure 1, and wherein light source 1 employing wavelength is the light emitting diode of 410 ± 5nm, and photo-detector 4 adopts silicon photoelectric diodes.
(1) reference solution test: reference solution is actual in the present embodiment is deionized water, and described agricultural chemicals sensitive chip 2 lies in a horizontal plane in the pallet 3, and the fritted glass fiber disk that makes the filling butyrylcholine esterase up.Use first pipettor to draw 120 μ L deionized waters, drip the upper surface at sensitive chip 2, place after 5 minutes, at pallet 3 interior adding 300 μ L deionized waters, placed again afterwards 10 minutes again.Be placed on pallet 3 interior beginning continuous coverages and record the transmission light intensity from agricultural chemicals sensitive chip 2.
(2) solution testing to be analyzed: above-mentioned used agricultural chemicals sensitive chip 2 is taken out from pallet 3, and remove solution in the pallet 3, pallet 3 inside surfaces are cleaned dry, then new agricultural chemicals sensitive chip 2 is put into the pallet 3 that cleaned, be changed in the metrifonate solution situation of variable concentrations transmitted intensity at deionized water by top-operation step test over time.
(3) absorbance contrast: calculate over time absorbance over time according to the transmitted intensity that records, then the absorbance change curve of solution to be analyzed and reference solution more under the same conditions.Absorbance
I wherein
tBe t transmitted intensity constantly, I
dBias light intensity when closing light source, I
0Transmitted intensity when adding solution to be analyzed for the second time.
Fig. 3 utilizes over time curve of absorbance that single channel all-solid state optical pesticide detection device shown in Figure 1 records respectively under three kinds of metrifonate pesticide concentrations.If do not have organophosphorus and carbamate pesticide residue, when namely pesticide concentration is 0mg/L, the hydrolysis of butyrylcholine esterase catalytic substrate, its product and developer reaction, produce rapidly yellow substance, at the 412nm place maximum absorption band is arranged, therefore the generation absorbance along with yellow substance increases fast; If contain remains of pesticide in the test sample, when being 0.1mg/L such as pesticide concentration, the activity of butyrylcholine esterase can be suppressed, thereby the formation speed of yellow substance slows down, the slope of measured absorbance change curve reduces, and its absorbance numerical value also reduces within the same time; If during the residues of pesticides severe overweight, when being 5mg/L such as pesticide concentration, the activity of enzyme is almost suppressed fully, and measured absorbance obviously slows down over time, also reduces at same time internal absorbance numerical value, as shown in Figure 3.Therefore the absorbance that sample solution is recorded over time curve is made comparisons with the normal data database data of making in advance, can know namely whether residues of pesticides exceed standard and the size of residual concentration.
All-solid state optical pesticide residue detecting device of the present invention, use the agricultural chemicals sensitive chip that is filled with different biochemical reagents in a kind of diaphragm micropore that be comprised of multilayer printing opacity diaphragm and different, chromogenic reaction in various degree can occur in this sensitive chip when meeting the aqueous solution that contains agricultural chemicals.This sensitive chip is met steeping in water for reconstitution and is given birth to change color, and when containing organophosphorus and carbamate chemicals for agriculture in the water change color with suppressed.
All-solid state optical pesticide residue detecting device of the present invention, highly sensitive, accurately and reliably, simple to operate, easy to carry and store, be suitable for contained agricultural chemicals in remains of pesticide in the agricultural product and the water body is carried out field quick detection.Be suitable for the places such as family, market, the market of farm produce to agricultural product such as vegetables, fruit in remains of pesticide carry out on-the-spot Quantitative detection.
All-solid state optical pesticide residue detecting device of the present invention has kept the high advantage of agricultural chemicals tacheometer accuracy of detection and agricultural chemicals quick measuring card and has allowed at normal temperatures long-time the preservation and advantage easy to use, their shortcoming of having given up.Known to our investigation, all-solid state optical pesticide residue detecting device of the present invention has not yet to see newspaper.
Claims (13)
1. an all-solid state optical pesticide residue detecting device comprises a detecting unit, and a signal processing chip consists of the single channel pick-up unit; It is characterized in that detecting unit comprises a light source, a photo-detector, an agricultural chemicals sensitive chip, a pallet; One agricultural chemicals sensitive chip level places in the pallet of bottom printing opacity, one light source is arranged on pallet one side, and the light positive that light source sends is penetrated in the tray bottom, and a photo-detector is arranged on the opposite side of pallet, coaxial relative with light source, be used for receiving the light signal that sees through tray bottom and sensitive chip;
Detecting unit is electrically connected with signal processing chip, and namely the photo-detector output terminal of detecting unit links to each other with the signal processing chip input end, and the signal processing chip output terminal is electrically connected on follow-up equipment;
Wherein, described agricultural chemicals sensitive chip comprises multilayer printing opacity diaphragm, overlapped being connected of multilayer printing opacity diaphragm;
Described agricultural chemicals sensitive chip, during for the trilamellar membrane chip architecture: the superiors are the hydrophilic porous diaphragm of ground floor, it is lower to second layer hydrophobic membrane, is down the 3rd layer of hydrophilic porous diaphragm; Be filled with in the micropore of ground floor porous membrane can with acetylcholinesterase or the butyrylcholine esterase of organophosphorus and carbamate chemicals for agriculture reaction; Be filled with substrate and developer in the micropore of the 3rd layer of porous membrane; Or developer is in acetylcholinesterase or butyrylcholine esterase are filled in the porous membrane of ground floor;
Described agricultural chemicals sensitive chip, when being four tunic chip architectures: the superiors are the hydrophilic porous diaphragm of ground floor, it is lower to be the 3rd layer of hydrophilic porous diaphragm under it for second layer hydrophobic membrane again, is down the 4th layer of hydrophilic porous diaphragm; Be filled with in the micropore of ground floor porous membrane can with acetylcholinesterase or the butyrylcholine esterase of organophosphorus and carbamate chemicals for agriculture reaction; Be filled with substrate in the micropore of the 3rd layer of porous membrane; Be filled with developer in the micropore of the 4th layer of porous membrane.
2. all-solid state optical pesticide residue detecting device as claimed in claim 1, it is characterized in that, when detecting unit is a plurality of, consist of multi-channel testing device, and signal processing chip is when being one, and the photo-detector output terminal of each detecting unit links to each other with a signal processing chip input end respectively altogether; Or signal processing chip is when being a plurality of, and the photo-detector output terminal of each detecting unit links to each other with a signal processing chip input end respectively;
The signal processing chip output terminal is electrically connected on follow-up equipment.
3. all-solid state optical pesticide residue detecting device as claimed in claim 1 is characterized in that, described printing opacity diaphragm is hydrophilic microporous filter membrane or filter paper, or hydrophobic micropore filter membrane or filter paper, or transparent plastic film.
4. such as claim 1 or 3 described all-solid state optical pesticide residue detecting devices, it is characterized in that, described agricultural chemicals sensitive chip, each layer printing opacity diaphragm is of similar shape, and the area of the hydrophobic diaphragm of the second layer wherein is more than or equal to the area of the hydrophilic porous diaphragm of other arbitrary layers;
Multilayer printing opacity diaphragm is connected with web member each other.
5. all-solid state optical pesticide residue detecting device as claimed in claim 4 is characterized in that, described web member is staple.
6. all-solid state optical pesticide residue detecting device as claimed in claim 1 is characterized in that, described pallet comprises a light-passing board and light tight plate, and a through hole is arranged on the light tight plate, and light-passing board covers and sealing is fixed in the through hole below;
Light-passing board is clear plate glass or transparent plate plastics, and light tight plate is opaque-plastic plate or sheet metal;
The thickness of light tight plate is tray depth, and tray depth is greater than sensitive chip thickness, and through-hole diameter is the diameter of tray bottom surface, and the diameter of tray bottom surface is greater than the sensitive chip diameter.
7. all-solid state optical pesticide residue detecting device as claimed in claim 6 is characterized in that, described light tight plate, thickness≤7mm, through-hole diameter≤14mm.
8. all-solid state optical pesticide residue detecting device as claimed in claim 1, it is characterized in that, described light source is light emitting diode or semiconductor laser, and the emission wavelength of light emitting diode or semiconductor laser is positioned at the Absorber Bandwidth scope after the agricultural chemicals sensitive chip is met the water variable color; Light activated silicon photoelectric diode or the silicon photocell of photo-detector for light source is sent.
9. the detection method of an all-solid state optical pesticide residue detecting device as claimed in claim 1, it is characterized in that, adopt Comparison Method, comprise: a) with the all-solid state optical pesticide detection device respectively to aqueous sample to be analyzed and reference sample detection once, two results that relatively record under the uniform temp condition are to obtain the pesticide concentration in the aqueous solution to be analyzed; Or b) with the all-solid state optical pesticide detection device aqueous sample to be analyzed is detected once, the result who records is made comparisons with the normal data database data of making in advance, to obtain the pesticide concentration in the aqueous solution to be analyzed.
10. detection method as claimed in claim 9 is characterized in that, described reference sample is for pure water, deionized water or prepare the used damping fluid of aqueous sample to be analyzed.
11. detection method as claimed in claim 10 is characterized in that, described damping fluid is phosphate buffer: use 0.1mol/L KH
2PO
4With 0.1mol/L Na
2HPO
412H
2The phosphate buffer of the 0.1mol/L pH=8 of O aqueous solution preparation 500ml.
12. detection method as claimed in claim 9 is characterized in that, described a) kind Comparison Method comprises step:
(1) at first, the agricultural chemicals sensitive chip is lain in a horizontal plane in the pallet, and make include acetylcholinesterase or butyrylcholine esterase the ground floor porous membrane up;
(2) utilize syringe or pipettor or peristaltic pump to draw aqueous sample to be measured, drip the ground floor upper surface at sensitive chip, make the ground floor porous membrane fully moistening, and keep each layer porous membrane below the second layer hydrophobic membrane not contact sample;
(3) with the while in (2) step, open light source, photo-detector, the enabling signal process chip from dripping aqueous sample to be analyzed, is measured transmitted intensity over time;
(4) behind certain hour, in pallet, add again aqueous sample to be analyzed and flood whole sensitive chip;
(5) continue to measure transmitted intensity, and the data of record measurement result;
(6) measure complete after, used agricultural chemicals sensitive chip is taken out from pallet, and removes the interior solution of pallet, pallet is cleaned dries;
(7) then, again get a slice agricultural chemicals sensitive chip and put into the pallet that cleaned, repeating (1) to (5) under the uniform temp condition goes on foot, but in going on foot, (2), (3) add the reference sample, test in the situation of reference sample transmitted intensity over time, and the record measurement result data;
(8) measurement result with (5) step and (7) step compares, thereby obtains the pesticide concentration in the aqueous sample to be analyzed.
13. detection method as claimed in claim 12 is characterized in that, the certain hour in described (4) step is≤10 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010034287 CN102128825B (en) | 2010-01-20 | 2010-01-20 | All-solid state optical pesticide residue detecting device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010034287 CN102128825B (en) | 2010-01-20 | 2010-01-20 | All-solid state optical pesticide residue detecting device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102128825A CN102128825A (en) | 2011-07-20 |
| CN102128825B true CN102128825B (en) | 2013-05-29 |
Family
ID=44266995
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010034287 Expired - Fee Related CN102128825B (en) | 2010-01-20 | 2010-01-20 | All-solid state optical pesticide residue detecting device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102128825B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104181112A (en) * | 2013-05-21 | 2014-12-03 | 浙江托普仪器有限公司 | Sixteen-channel pesticide residue rapid detector |
| CN103472019B (en) * | 2013-09-30 | 2015-12-23 | 重庆大学 | The residual spectrum method for quick of agriculture |
| CN103808948A (en) * | 2014-03-12 | 2014-05-21 | 杭州霆科生物科技有限公司 | Micro-fluidic chip system and method for pesticide residue field detection |
| CN107941991B (en) * | 2017-10-31 | 2019-12-03 | 重庆双丰化工有限公司 | A kind of detection method for pesticide |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3992158A (en) * | 1973-08-16 | 1976-11-16 | Eastman Kodak Company | Integral analytical element |
| CN1595104A (en) * | 2004-07-02 | 2005-03-16 | 江阴市凡能环保仪器科技有限公司 | Detecting optical generator with multiple channel double linear array construction |
| CN2687662Y (en) * | 2004-02-25 | 2005-03-23 | 吉林大学 | Portable pollutant detecting instrument |
| CN2731441Y (en) * | 2004-07-04 | 2005-10-05 | 华中科技大学 | Multi-channel hand-held food securing detector |
-
2010
- 2010-01-20 CN CN 201010034287 patent/CN102128825B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3992158A (en) * | 1973-08-16 | 1976-11-16 | Eastman Kodak Company | Integral analytical element |
| CN2687662Y (en) * | 2004-02-25 | 2005-03-23 | 吉林大学 | Portable pollutant detecting instrument |
| CN1595104A (en) * | 2004-07-02 | 2005-03-16 | 江阴市凡能环保仪器科技有限公司 | Detecting optical generator with multiple channel double linear array construction |
| CN2731441Y (en) * | 2004-07-04 | 2005-10-05 | 华中科技大学 | Multi-channel hand-held food securing detector |
Non-Patent Citations (4)
| Title |
|---|
| 固相微萃取2气相色谱/质谱(SPME2GC/MS)联用分析海水中痕量有机磷农药;王凌 等;《环境化学》;20060131;第25卷(第1期);全文 * |
| 张乔 等.有机磷农药多残留检测方法及其应用.《环境科学》.1988,第9卷(第1期), |
| 有机磷农药多残留检测方法及其应用;张乔 等;《环境科学》;19880229;第9卷(第1期);全文 * |
| 王凌 等.固相微萃取2气相色谱/质谱(SPME2GC/MS)联用分析海水中痕量有机磷农药.《环境化学》.2006,第25卷(第1期), |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102128825A (en) | 2011-07-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5288646A (en) | Method of photometric in vitro determination of the content of an analyte in a sample of whole blood | |
| CN103091262B (en) | Miniaturized optical device for detecting ammonia nitrogen in water and detecting method | |
| CN202216956U (en) | Organic phosphorus pesticide multi-residue gold-labeled rapid test card | |
| SE445146B (en) | PROCEDURE, DEVICE AND AUTOMATED SYSTEM TO DETERMINE HEMATOCRIT IN A BLOOD BLOOD TEST | |
| CN102128825B (en) | All-solid state optical pesticide residue detecting device | |
| US20020173040A1 (en) | Chemically-resistant sensor devices, and systems and methods for using same | |
| CN109358043B (en) | Method for rapidly detecting pesticide residues by using organic solvent extraction sample | |
| Pénicaud et al. | Oxygen quantification methods and application to the determination of oxygen diffusion and solubility coefficients in food | |
| CN101627304A (en) | Electrochemical biosensor measuring system | |
| CN105115911A (en) | Water quality detecting method and micro-fluidic chip special for water quality detecting method | |
| Andreou et al. | Novel fiber-optic biosensor based on immobilized glutathione S-transferase and sol–gel entrapped bromcresol green for the determination of atrazine | |
| CN102928389B (en) | Device for quickly detecting impregnation amount in real time and using method thereof | |
| CN112033929B (en) | In-situ detection device and detection method for content of water and fertilizer in crop cultivation medium | |
| CN103674856B (en) | Microchannel based on scanner uni colorimetric analysis is used for residues of organophosphate pesticides fast determining method | |
| Schaffar et al. | Chemically mediated fiberoptic biosensors | |
| US6455320B1 (en) | Solar cell sensors, process for their manufacture and their use | |
| CN109596560A (en) | A kind of integrated infrared gas sensor of multichannel | |
| CN108254348A (en) | A kind of the pH responsive types fluorescent optical sensor and construction method of high-throughput detection active microorganism | |
| CN201788153U (en) | Pesticide residue detector integrated with micro electronic balance | |
| CN102384971A (en) | Spittle alcoholicity test strip and production method thereof | |
| Saari | Trends in fiber optic sensor development | |
| Faura et al. | Transmittance measurements on paper soaked with deep eutectic solvents | |
| CN1560601A (en) | Portable investigating instrument for food and environment pollutant and its application | |
| CN202210072U (en) | Organophosphorus pesticide detector | |
| CN102281814A (en) | System and method for analyzing a body fluid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130529 |