CN104132934A - Preparation for molecularly-imprinted electroluminescent paper chip for detecting multiple sample pesticide residues - Google Patents
Preparation for molecularly-imprinted electroluminescent paper chip for detecting multiple sample pesticide residues Download PDFInfo
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Abstract
The invention discloses a preparation for a molecularly-imprinted electroluminescent paper chip for detecting multiple sample pesticide residues. The preparation method of the sensing paper chip comprises the following steps: preparing an MIPs sol of a pesticide residue molecule; preparing a tridimensional graphene gold nanometer composite material; preparing a g-C3N4 quantum dot; and utilizing an electrode modification technology to modify the electrode surface of the sensing paper chip with the tridimensional graphene gold nanometer composite material, the g-C3N4 quantum dot and the MIPs sol. A method for detecting multiple sample pesticide residues comprises the following steps: connecting the modified sensing paper chip to an electrochemical workstation, and cooperating with a chemiluminescence apparatus to detect pesticide residues in a sample extraction solution. The prepared paper chip is strong in electrode specificity and high in sensitivity, and has the sensitivity up to nanometer gram grade. A detection process only takes 3-5 min, and the cost is low. The electrode detection method for pesticide residues is simple and rapid in operation, and reactions and results are automatically finished and recorded by an instrument.
Description
Technical field
The present invention relates to the Detection Technologies of Pesticide Residues field, more specifically say the preparation of the refill sheet of a kind of molecular engram electroluminescence Multi-example detection simultaneously residues of pesticides, the invention still further relates to the method that adopts described electroluminescence sensing chip to detect the pesticide residue in fruit, vegetables.
Background technology
In recent years, along with the raising of quality of life, food-safety problem is more and more subject to everybody attention.Yet along with agrotechnical development, agricultural chemicals is more and more used in the production of fruit and vegetable.The potential prestige evil that residues of pesticides in food form environmental and human health impacts is subject to everybody attention gradually, and Pesticide Residues, to cause human body Case Report acute or slow poisoning also of common occurrence, has caused people's extensive concern.
Because people never decay to the attention rate of Pesticide Residues, the method for various detection residues of pesticides is also all arisen at the historic moment.At present more to the detection method of residues of pesticides, mainly contain chemical method, chromatography, enzyme process, immunization and microbiological method etc.But more or less all there are some shortcomings in these detections or screening technique.
1. chemical method detection residues of pesticides are to be widely used in the method that agricultural chemicals organophosphorus detects, but the shortcoming of the method is in Near The Critical Point change color not clearly, responsive mainly for several organophosphorus pesticides.Be subject to the interference of some reducing substanceses;
2. chromatography mainly comprises vapor-phase chromatography, high performance liquid chromatography and chromatograph-MS.Vapor-phase chromatography, is that persticide residue detects for the detection of volatility agricultural chemicals, and high performance liquid chromatography is for being difficult for the detection of gasification or the labile agricultural chemicals that is heated.The two is all the conventional method of Detecting Pesticide, although highly sensitive, the shortcoming such as exist pre-treatment relative complex, the sense cycle of sample long, program is complicated, required reagent is various.Chromatograph-MS method remolding sensitivity is higher, but instrument is expensive, operation more complicated;
3. although enzyme reagent method cost is relatively low, testing process step is more, and process is more loaded down with trivial details, is unfavorable for rapid detection;
Although immunization high specificity, highly sensitive but exist equally pre-treatment relative complex, the sense cycle of sample long, the shortcoming such as program is complicated, required reagent is various;
5. microbial method has that cost is low, the advantage such as save time, but general only for screening experiment;
For the determination and analysis of residues of pesticides, all there is some problems and shortcoming and limit its application in actual sample detects in above several method.
Summary of the invention
The technical problem to be solved in the present invention be to provide a kind ofly have that sample preparation is simple, detection speed is fast, cost is low, polycomponent detects the molecular engram electroluminescence sensing refill sheet of residues of pesticides when the feature such as highly sensitive, high specificity preparation and detection method.
In order to solve the problems of the technologies described above, the present invention realizes by following measures: a kind of Multi-example detects the preparation method of the molecular engram electroluminescence refill sheet of residues of pesticides, and its feature comprises the following steps:
(1) prepare fan fold paper chip: first with wax printer, on A4 paper, print the wax pattern as accompanying drawing 1, and the A4 paper with wax pattern is put in panel heater or baking oven, at 60-150 ℃, heat 0.5-2 min, wax is melted and soak into the thickness of whole paper, form hydrophobic region; Adopt the method for screen printing electrode, at hydrophilic region printing carbon working electrode and the Ag/AgCl contrast electrode (as accompanying drawing 2) of not printing wax of the A4 paper of handling well;
(2) select can from the function monomer of different residues of pesticides Synthesis of Molecular Imprinting Polymers (molecularly imprinted polymer is called for short MIPs);
(3) by certain mol proportion, the template molecule of remains of pesticide, function monomer, crosslinking chemical, pore-foaming agent, initiating agent are mixed, make MIPs colloidal sol;
(4) prepare 3D-Graphene-nm of gold compound substance;
(5) prepare g-C
3n
4quantum dot;
(6) utilize and independently fill layer by layer surface modification technology, by Graphene-nm of gold compound substance and g-C
3n
4and MIPs Sol-Modified is on electrode surface, makes molecular engram electroluminescence sensor.
The mol ratio of pesticide residue template molecule of the present invention, function monomer, crosslinking chemical, pore-foaming agent, initiating agent is: 0.1 ~ 1:1:0.5 ~ 3:35 ~ 60:0.05 ~ 0.25.
Of the present invention by Graphene-nm of gold compound substance, g-C
3n
4and molecularly imprinted polymer (MIPs) modification comprises the following steps to the surface of printing electrode:
(1) by printing electrode with agate hammer 2 min that carefully polish on the refill sheet of preparation;
(2) prepare graphene oxide:
2 g Graphenes are joined in the ice-water bath of 2 g sodium nitrate and 40 mL 98% concentrated sulphuric acids to magnetic stirring 20 min.Under beating action, add 6 g potassium permanganate, and under room temperature environment, stir 1 h.In above-mentioned solution, add 180 mL ultrapure waters, in 95 ℃ of 15 min that reflux.After being cooled to room temperature, with ultrapure water, dilute, and add the H of 30 mL 30%
2o
2, now solution becomes tawny.By the solution suction filtration obtaining, and extremely neutral with ultrapure water washing, product is dried in 60 ℃ of vacuum drying ovens;
(3) prepare 3D-Graphene-nm of gold compound substance:
By 10 mL, 0.5 mg L
-1graphene oxide, 200 μ L, 1%, w/w gold chloride and ultrasonic mixing 1 h of 600 μ L polyglycol, be then heated to 180 ℃ of 12 h.Above-mentioned reactant is cooled to after room temperature, with ultrapure water, cleans, finally will after the product freeze drying obtaining, obtain 3D-Graphene-nm of gold compound substance, and soluble in water;
(4) prepare g-C
3n
4: 0.095 g guanidine hydrochloride and 0.048 g EDTA join in 10 mL ultrapure waters, by stirring, solution homogeneous are clarified, and then mixed liquor are placed in to 5 min in micro-wave oven.Then by above-mentioned solution by the centrifugal accessory substance of removing larger particles, the precipitation that obtains brown is g-C
3n
4;
(5) the paper working electrode surface of step (1) being processed drips through the synthetic 3D-Graphene-nm of gold compound substance solution 10 μ L of step (3) and dries;
(6) by the g-C of preparation
3n
4through ultrasonic processing 10-30 min, obtain the g-C disperseing
3n
4solution;
(7) to the middle electrode of processing of step (5), drip the g-C processing through step (6)
3n
4solution also dries;
(8) to the working electrode surface drying in step (7), drip respectively the MIPs solution of preparation, then by eluant, eluent wash-out 20-30 min, at room temperature dry 5-10 min for working electrode.
The present invention is further comprising the steps of:
After being placed to 24 h, uses by Multi-example detection molecules trace electroluminescence sensor.
Eluant, eluent of the present invention is acetonitrile, methyl alcohol-acetic acid, water or acetonitrile-acetic acid.
Chemiluminescent analyzer of the present invention is the auspicious IFFM-E type Flow Injection Analysis/Chemiluminescence instrument advanced in years in Xi'an.
Function monomer of the present invention is Methacrylamide (MAM), acrylic acid (AA), methacrylic acid (MAA), adjacent nitrogen base thiophenol or 4-vinylpridine (4-VP); Described crosslinking chemical is ethylene glycol dimethacrylate (EGDMA) Ethylene glycol dimethacrylate (EDMA); Described initiating agent is azoisobutyronitrile (ABIN); Described pore-foaming agent is chloroform, methyl alcohol.
A kind of Multi-example detects the preparation method of the residual molecular engram electroluminescence refill sheet of agriculture, its feature comprises the steps: that the molecular engram electroluminescence sensing refill sheet making according to above-mentioned any one method coordinates electrogenerated chemiluminescence instrument, carries out high sensitivity, detects fast a plurality of sample pesticide residues in fruit, vegetables.
useful achievement of the present invention
1. Multi-example detects a preparation method for the residual molecular engram electroluminescence refill sheet of agriculture, utilizes paper electrode to replace traditional electrode, has reduced the cost that pesticide residue detects.
2. the synergistic effect of three-dimensional grapheme-nm of gold compound substance is incorporated in the middle of the preparation of electrode, makes the electrode of the molecularly imprinted polymer modification of preparation there is higher sensitivity and wider detectability scope.
3. surface modification technology is applied in the middle of the preparation of the electrode that molecularly imprinted polymer modifies, makes the molecular engram electroluminescence sensing chip of nano-synergistic there is controllability, improved sensitivity and the accuracy of electrode.
4. the resulting a kind of Multi-example of the present invention detects the residual molecular engram electroluminescence paper chip sensor of agriculture, can realize high specific, high sensitivity, low cost, the fast detecting of sample Pesticide Residues.
5. the molecular engram electroluminescence paper chip sensor high specificity of the detection residues of pesticides of gained of the present invention; Highly sensitive, can reach ng level; Detection speed is fast, completes the time that a basic testing process only needs 3-5min, can realize at short notice the high flux screening of a large amount of samples; Reagent dosage is few, and detecting a sample only needs tens microlitre reagent; Cost is low, detects a sample and only needs several sharing money.
6. Multi-example detects a preparation method for the residual molecular engram electroluminescence refill sheet of agriculture, simple to operate, and reaction and result complete and record automatically by instrument, have avoided the impact of subjective factor, and have had good repeatability, are convenient to Site Detection.
Accompanying drawing explanation
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Accompanying drawing 1 is the A4 paper printing hydrophobic pattern of waxing.
Accompanying drawing 2 prints multi-channel electrode (different component can be detected in working electrode region, also can detect same composition) on paper.
Embodiment
case study on implementation 1(detection of Rogor)
Multi-example detects a preparation method for the residual molecular engram electroluminescence refill sheet of agriculture, comprises the following steps:
(1) prepare fan fold paper chip: first with wax printer, on A4 paper, print the wax pattern as accompanying drawing 1, and by with wax pattern A4 paper be put in panel heater or baking oven, at 60-150 ℃, heat 0.5-2 min, wax is melted and soak into the thickness of whole paper, form hydrophobic region; Adopt the method for screen printing electrode, the hydrophilic region printing carbon working electrode of not printing wax of the A4 paper of handling well (accompanying drawing 2 a), to electrode (accompanying drawing 2 b) and Ag/AgCl contrast electrode (accompanying drawing 2c);
(2) select to synthesize with Rogor the function monomer methacrylic acid (MAA) of MIPs;
(3) by the template molecule Rogor of remains of pesticide, function monomer methacrylic acid (MAA), crosslinking chemical ethylene glycol dimethacrylate (EGDMA), pore-foaming agent methyl alcohol, initiating agent azoisobutyronitrile (ABIN) in molar ratio for 0.1:1:5:45:0.05 mixes, make Rogor MIPs colloidal sol;
(4) prepare 3D-Graphene-nm of gold compound substance: by 10 mL, 0.5 mg L
-1graphene oxide, 200 μ L, 1%, w/w gold chloride and ultrasonic mixing 1 h of 600 μ L polyglycol, be then heated to 180 ℃ of 12 h.Above-mentioned reactant is cooled to after room temperature, with ultrapure water, cleans, finally will after the product freeze drying obtaining, obtain 3D-Graphene-nm of gold compound substance, and soluble in water;
(5) prepare g-C
3n
4quantum dot: 0.095 g guanidine hydrochloride and 0.048 g EDTA join in 10 mL ultrapure waters, by stirring, solution homogeneous are clarified, is then placed in mixed liquor 5 min in micro-wave oven.Then by above-mentioned solution by the centrifugal accessory substance of removing larger particles, the precipitation that obtains brown is g-C
3n
4quantum dot;
(6) by printing electrode with agate hammer 2 min that carefully polish on the refill sheet of preparation;
(7) the paper working electrode surface of step (6) being processed drips through the synthetic 3D-Graphene-nm of gold compound substance solution 10 μ L of step (4) and dries;
(8) by the g-C of preparation
3n
4through ultrasonic processing 10-30 min, obtain the g-C disperseing
3n
4solution;
(9) to the middle electrode of processing of step (7), drip the g-C processing through step (8)
3n
4solution also dries;
(10) to the working electrode surface drying in step (9), drip respectively the MIPs solution of preparation, then by eluant, eluent wash-out 20-30 min, at room temperature dry 5-10 min for working electrode.Detecting Rogor molecular engram electroluminescence sensor prepares complete;
The molecular engram electroluminescence sensor of the detection Rogor making is coordinated and chemiluminescent analyzer, the Rogor of fruit, Residues in Vegetables is carried out high sensitivity, detected fast, the lowest detection of Rogor is limited to 4.2 * 10
-12mol/L.
case study on implementation 2(detection of parathion)
Multi-example detects a preparation method for the residual molecular engram electroluminescence refill sheet of agriculture, comprises the following steps:
(1) prepare fan fold paper chip: first with wax printer, on A4 paper, print the wax pattern as accompanying drawing 1, and by with wax pattern A4 paper be put in panel heater or baking oven, at 60-150 ℃, heat 0.5-2 min, wax is melted and soak into the thickness of whole paper, form hydrophobic region; Adopt the method for screen printing electrode, the hydrophilic region printing carbon working electrode of not printing wax of the A4 paper of handling well (accompanying drawing 2 a), to electrode (accompanying drawing 2 b) and Ag/AgCl contrast electrode (accompanying drawing 2c);
(2) select to synthesize with parathion the adjacent nitrogen base of the function monomer thiophenol of MIPs;
(3) by the adjacent nitrogen base of template molecule parathion, function monomer thiophenol, crosslinking chemical Ethylene glycol dimethacrylate (EDMA), pore-foaming agent methyl alcohol, initiating agent azoisobutyronitrile (ABIN) in molar ratio for 0.1:1:2:45:0.15 mixes, make parathion MIPs colloidal sol;
(4) prepare 3D-Graphene-nm of gold compound substance: by 10 mL, 0.5 mg L
-1graphene oxide, 200 μ L, 1%, w/w gold chloride and ultrasonic mixing 1 h of 600 μ L polyglycol, be then heated to 180 ℃ of 12 h.Above-mentioned reactant is cooled to after room temperature, with ultrapure water, cleans, finally will after the product freeze drying obtaining, obtain 3D-Graphene-nm of gold compound substance, and soluble in water;
(5) prepare g-C
3n
4: 0.095 g guanidine hydrochloride and 0.048 g EDTA join in 10 mL ultrapure waters, by stirring, solution homogeneous are clarified, and then mixed liquor are placed in to 5 min in micro-wave oven.Then by above-mentioned solution by the centrifugal accessory substance of removing larger particles, the precipitation that obtains brown is g-C
3n
4;
(6) by printing electrode with agate hammer 2 min that carefully polish on the refill sheet of preparation;
(7) the paper electrode surface of step (6) being processed drips through the synthetic 3D-Graphene-nm of gold compound substance solution 10 μ L of step (4) and dries;
(8) by the g-C of preparation
3n
4through ultrasonic processing 10-30 min, obtain the g-C disperseing
3n
4solution;
(9) to the middle electrode of processing of step (7), drip the g-C processing through step (8)
3n
4solution also dries;
(10) to the working electrode surface drying in step (9), drip respectively the MIPs solution of preparation, then by eluant, eluent wash-out 20-30 min, at room temperature dry 5-10 min for working electrode.Detecting parathion molecular engram electroluminescence sensor prepares complete;
The molecular engram electroluminescence sensor of the detection parathion making is coordinated and chemiluminescent analyzer, the parathion of fruit, Residues in Vegetables is carried out high sensitivity, detected fast, detect and be limited to 2.6 * 10
-12mol/L.
Claims (8)
1. Multi-example detects a preparation for the molecular engram electroluminescence refill sheet of residues of pesticides, and its feature comprises the following steps:
(1.1) prepare fan fold paper chip: first with wax printer, on A4 paper, print the wax pattern as accompanying drawing 1, and by with wax pattern A4 paper be put in panel heater or baking oven, at 60-150 ℃, heat 0.5-2 min, wax is melted and soak into the thickness of whole paper, form hydrophobic region; Adopt the method for screen printing electrode, at hydrophilic region printing carbon working electrode and the Ag/AgCl contrast electrode (as accompanying drawing 2) of not printing wax of the A4 paper of handling well;
(1.2) select to be combined into from different pesticide residues the molecule imprinted polymer function monomer of (molecularly imprinted polymer is called for short MIPs);
(1.3) by certain mol proportion, the template molecule of remains of pesticide, function monomer, crosslinking chemical, pore-foaming agent, initiating agent are mixed and make MIPs colloidal sol;
(1.4) prepare 3D-Graphene-nm of gold compound substance;
(1.5) prepare g-C
3n
4quantum dot;
(1.6) utilize and independently fill layer by layer surface modification technology, by Graphene-nm of gold compound substance and g-C
3n
4and MIPs Sol-Modified is on electrode surface, makes molecular engram electroluminescence sensor;
The mol ratio of the template molecule of pesticide residue of the present invention, function monomer, crosslinking chemical, pore-foaming agent, initiating agent is: 0.1 ~ 1:1:0.5 ~ 3:35 ~ 60:0.05 ~ 0.25.
2. of the present invention by Graphene-nm of gold compound substance, g-C
3n
4and molecularly imprinted polymer (MIPs) modification comprises the following steps to the surface of printing electrode:
(2.1) by printing electrode with agate hammer 2 min that carefully polish on the refill sheet of preparation;
(2.2) prepare graphene oxide:
2 g Graphenes are joined in the ice-water bath of the concentrated sulphuric acid of 2 g sodium nitrate and 40 mL 98% to magnetic stirring 20 min; Under beating action, add 6 g potassium permanganate, and under room temperature environment, stir 1 h, in above-mentioned solution, add 180 mL ultrapure waters, in 95 ℃ of 15 min that reflux; After being cooled to room temperature, with ultrapure water, dilute, and add the H of 30 mL 30%
2o
2, now solution becomes tawny; By the solution suction filtration obtaining, and extremely neutral with ultrapure water washing, product is dried in 60 ℃ of vacuum drying ovens;
(2.3) prepare 3D-Graphene-nm of gold compound substance:
By 10 mL, 0.5 mg L
-1graphene oxide, 200 μ L, 1%, w/w gold chloride and ultrasonic mixing 1 h of 600 μ L polyglycol, be then heated to 180 ℃ of 12 h; Above-mentioned reactant is cooled to after room temperature, with ultrapure water, cleans, finally will after the product freeze drying obtaining, obtain 3D-Graphene-nm of gold compound substance, and soluble in water;
(2.4) prepare g-C
3n
4: 0.095 g guanidine hydrochloride and 0.048 g EDTA join in 10mL ultrapure water, by stirring, solution homogeneous are clarified, and then mixed liquor are placed in to 5 min in micro-wave oven; Then by above-mentioned solution by the centrifugal accessory substance of removing larger particles, the precipitation that obtains brown is g-C
3n
4;
(2.5) the paper electrode surface of step (2.1) being processed drips through the synthetic 3D-Graphene-nm of gold compound substance solution 10 μ L of step (2.3) and dries;
(2.6) by the g-C of preparation
3n
4through ultrasonic processing 10-30 min, obtain the g-C disperseing
3n
4solution;
(2.7) to the middle electrode of processing of step (2.5), drip the g-C processing through step (2.6)
3n
4solution also dries;
(2.8) to the working electrode surface drying in step (2.7), drip respectively the MIPs solution of preparation, then by eluant, eluent wash-out 20-30 min, at room temperature dry 5-10 min for working electrode;
(2.9) coordinate electrochemical workstation and chemiluminescent analyzer to detect residues of pesticides molecule after placing 24 h the electroluminescence molecular engram sensor of preparation in step 2.8.
3. according to the molecular engram electroluminescence sensor one of claim 1-2 Suo Shu, it is characterized in that: the preparation process of described 3D-Graphene-nm of gold compound substance: by 10 mL, 0.5 mg L
-1graphene oxide, 200 μ L, 1%, w/w gold chloride and ultrasonic mixing 1 h of 600 μ L polyglycol, be then heated to 180 ℃ of 12 h; Above-mentioned reactant is cooled to after room temperature, with ultrapure water, cleans, finally will after the product freeze drying obtaining, obtain 3D-Graphene-nm of gold compound substance, and soluble in water.
4. according to the molecular engram electroluminescence sensor one of claim 1-3 Suo Shu, it is characterized in that: described g-C
3n
4the preparation process of quantum dot is: 0.095 g guanidine hydrochloride and 0.048 g EDTA are joined in 10 mL ultrapure waters, by stirring, solution homogeneous is clarified, then mixed liquor is placed in to 5 min in micro-wave oven; Then by above-mentioned solution by the centrifugal accessory substance of removing larger particles, the precipitation that obtains brown is g-C
3n
4quantum dot.
5. according to the molecular engram electroluminescence sensor described in any one in claim 1-4, it is characterized in that: described function monomer is Methacrylamide (MAM), acrylic acid (AA), methacrylic acid (MAA), adjacent nitrogen base thiophenol or 4-vinylpridine (4-VP); Described crosslinking chemical is ethylene glycol dimethacrylate (EGDMA), Ethylene glycol dimethacrylate (EDMA); Described initiating agent is azoisobutyronitrile (ABIN); Described pore-foaming agent is chloroform, methyl alcohol.
6. according to the molecular engram electroluminescence sensor described in any one in claim 1-5, it is characterized in that: the mol ratio of described pesticide residue template molecule, function monomer, crosslinking chemical, pore-foaming agent, initiating agent is: 0.1 ~ 1:1:0.5 ~ 3:35 ~ 60:0.05 ~ 0.25.
7. according to the molecular engram electroluminescence sensor described in any one in claim 1-6, it is characterized in that: described eluant, eluent is acetonitrile, methyl alcohol-acetic acid, water or acetonitrile-acetic acid.
8. according to the molecular engram electroluminescence sensor described in any one in claim 1-7, it is characterized in that: described chemiluminescent analyzer is the auspicious IFFM-E type Flow Injection Analysis/Chemiluminescence instrument advanced in years in Xi'an.
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