CN102072895A - Electrogenerated chemiluminescence sensor with quantum dot modified nano porous carbon paste electrode for testing trace antibiotic residue - Google Patents
Electrogenerated chemiluminescence sensor with quantum dot modified nano porous carbon paste electrode for testing trace antibiotic residue Download PDFInfo
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Abstract
The present invention discloses a preparation method of an electrogenerated chemiluminescence sensor with a quantum dot modified nano porous carbon paste electrode for detecting trace antibiotic residues. The preparation method for the carbon paste electrode comprises the following steps: synthesizing nanoporous gold and quantum dot solution according to the existing method; modifying light-emitting quantum dots into the surface and the porous channels of the nanoporous gold material layer by layer by adopting the layer-by-layer self-assembly modification technology; doping the modified nanoporous gold material into graphite powder. The method for detecting the trace antibiotic residues comprises the following steps: connecting the modified carbon paste electrode with an electrogenerated chemiluminescence instrument, and detecting the trace antibiotic residues in dairy and meat products. The sensor has high sensitivity and a high detection speed, and one basic detection process can be completed within only 2-5 minutes. Moreover, the sensor has a low cost, and is economical and practical. The instrument is easy to operate and can automatically record and analyze experimental results, the effect of subjective factors is avoided, and good repeatability is achieved.
Description
Technical field
The present invention relates to antibiotic residue detection technique field, a kind of preparation that detects the high-sensitive electrogenerated chemiluminescence sensor of trace antibiotic residue of more specifically saying so the invention still further relates to the method that adopts the antibiotic residue in described electrogenerated chemiluminescence sensor breast, the meat products.
Background technology
Microbiotic also claims antibiotic, and microbiotic is the material that is produced in life process by bacterium, fungi or other microorganisms, also can make similar substance (microbiotic that is called synthetic) by chemical semi-synthesis method.Mainly comprise Tetracyclines, macrolides, chloromycetin, beta-lactam, aminoglycosides, lincomycin class, antifungal antibiotic and antitumor antibiotics etc.Microbiotic has low concentration can inhibition or the effect of kill bacteria, conveyor screw, chlamydial pathogenic microorganisms.From the fifties in last century, microbiotic as additive for farm animal feed since, guarantee animal health, promote growth, save feed and the aspects effect of boosting productivity remarkable.Also bring simultaneously the problem of antibiotic residues in animal-derived food, used microbiotic can cause the livestock and poultry immunity of organisms to descend for a long time.A large amount of microbiotic can be distributed to each histoorgan with blood circulation after it is ingested body, the immunocompetence of animal body is just weakened gradually, and the humans and animals chronic disease increases.
Because antibiotic residue has above potential threat, many national strictnesses are forbidden microbiotic such as chloromycetin are used for food animal (particularly laying hen and milk cow), U.S.'s strict regulations does not allow to use chloromycetin in home poultry raising, the poultry of selling must be cooked the detection of residual chloromycetin, and same China Ministry of Agriculture has forbidden using chloromycetin in the property animal of food source.But microbiotic such as chloromycetin are cheap, and a lot of breeding enterprises are in order to pursue bigger interests, the illegal microbiotic that adds in animal feed.Therefore the high selectivity of antibiotic residue is quick and precisely detected and have crucial social effect.
Set up the method for a kind of high sensitivity and specific fast detecting antibiotic residue, just become current this research field and need one of problem of solution badly.The detection method of present existing antibiotic residue mainly comprises immunoassay, UV-VIS spectrophotometry, fluorescence method, high performance liquid chromatography and chemoluminescence method etc., and is not enough but these detections or screening method exist:
1. immunoassay has advantage highly sensitive, that selectivity is good, but immunoreagent costs an arm and a leg, and detects the cost height, and then has limited the application of immunoassay in antibiotic residue detects.
2. UV-VIS spectrophotometry and fluorescence method method are simple, cheap with it, the range of linearity is wide, but its sensitivity and selectivity are not high, so used concentration is limited in 10
-6Therefore level is using UV detecting device mensuration antibiotic residue sample generally will just can reach requirement through concentrating.
3. high performance liquid chromatography is the residual method of using always of detection of antibiotics, and these two kinds of method sensitivity are higher, also can solve the certain selectivity problem, but these two kinds of methods, it is more loaded down with trivial details to operate, and analytic process length consuming time can not satisfy present high-throughout detection demand.
4. chemoluminescence method is the new method that development in recent years is got up, in antibiotic residue detects, certain application is arranged also, its sensitivity is very high, amount of samples also seldom, can realize automation equipment with the coupling of flow injection technology, but the poor selectivity of method can not solve the interference problem of coexisting substances, thereby has just brought the result that coexisting substances disturbs in the testing result into.
5. above several method is for the detection and the analysis of antibiotic residue, generally all exist detect the cost height, as a result false positive, testing process complexity, detect single, reagent dosage big, be unsuitable for field quick detection, coexisting substances disturbs shortcomings such as big, therefore can not satisfy the needs of actual detected.
Summary of the invention
The technical problem to be solved in the present invention provided a kind of highly sensitive, detection speed is fast, reagent dosage is few, detects the quantum dot decorated nanometer porous gold carbon paste electrode electrogenerated chemiluminescence sensor of trace antibiotic residue.
In order to solve the problems of the technologies described above, the present invention realizes by following measure: a kind of preparation method who detects the quantum dot decorated nanometer porous gold carbon paste electrode electrogenerated chemiluminescence sensor of trace antibiotic residue, and it may further comprise the steps:
(1) prepares nanoporous gold copper-base alloy and luminescent quantum dot solution according to existing method;
(2) luminescent quantum dot is modified in the duct of nano-porous gold;
(3) according to the preparation method of carbon paste electrode, nano-porous gold and graphite that luminescent quantum dot is modified are mixed and made into carbon paste electrode, make the electrogenerated chemiluminescence sensor;
(4) the electrogenerated chemiluminescence sensor of making is detected antibiotic residue in conjunction with the electrogenerated chemiluminescence instrument.
The preparation of luminescent quantum dot decorated nanometer porous gold of the present invention and carbon paste electrode may further comprise the steps:
(1) nano-porous gold surface hydroxylation: at first use deionized water, acetone and ethanol ultrasonic cleaning, dry up with high purity nitrogen afterwards, 10-30min in the NaOH solution of immersion 4%, washed with de-ionized water then, 120 ℃ dry 1-3 hour down, make to generate uniform hydroxyl in nanoporous gold surface and the duct.
(2) nano-porous gold that will modify hydroxyl advances to be immersed in 10-30min in the toluene solution of triamido propyl trimethoxy silicane (APS), and with the toluene flushing, nitrogen dries up then;
(3) nano-porous gold that (2) are obtained is immersed in 5-10min in the mercaptoacetic acid (TGA), the flushing of secondary water;
(4) nano-porous gold that (3) are obtained is immersed in that 5-10min forms a quantum dot layer in the luminescent quantum dot solution;
(5) repeat the quantum dot number of plies that above (2) (3) (4) process can obtain needs;
(6) carbon paste electrode preparation: (mass ratio is 2-4: 1) to take by weighing a certain amount of dag and whiteruss, the careful grinding of agate mortar mixes it, pack in the glass tube of diameter 4mm, with the copper rod is lead, packing at the head end of glass bar is mixed with the carbon paste of the nano-porous gold of having modified quantum dot, obtains the carbon paste electrode of quantum dot decorated nanometer porous gold;
(7) with the carbon paste electrode dried for preparing 24 hours.
The present invention is further comprising the steps of:
Carbon paste electrode assembled layers electrogenerated chemiluminescence sensor with preparation is connected on the electrogenerated chemiluminescence instrument and measures.
Of the present invention is CdTe quantum dot solution, CdSe quantum dot solution.
Electrogenerated chemiluminescence instrument of the present invention is the auspicious MPI-B type multiparameter portable injection chemiluminescence analyser advanced in years in Xi'an.
A kind of preparation method who detects the high-sensitive quantum dot decorated nanometer porous gold carbon paste electrode electrogenerated chemiluminescence sensor of trace antibiotic residue in breast, the meat products, it is characterized in that comprising the steps: that the quantum dot decorated nanometer porous gold carbon paste electrode electrogenerated chemiluminescence sensor utmost point that will make as stated above cooperates the electrogenerated chemiluminescence instrument, to the antibiotic residue of trace in breast, the meat products carry out highly sensitive, detect fast.
Beneficial effect of the present invention:
1. the method for luminescent quantum dot with self assembly is modified in the surface and duct of nano-porous gold layer by layer, this method of modifying can well solve the shortcoming that simple in the past adsorption method quantum dot is taken away by solution easily with quantum dot and the firm combination of nano-porous gold.
2. nano-porous gold has very big specific surface area, quantum dot is modified in this big specific surface area material compares with the common planar electrode, the surface area of the electrode of Zeng Daing greatly, and then increased the adsorbance of quantum dot on electrode, can make the sensor luminous signal of making stronger.
3. the nano-porous gold used of the present invention is the fabulous material of a kind of electric conductivity, and the adding of nano-porous gold can improve the conductance of carbon paste electrode, increases the utilization ratio of electric signal.
4. the electrogenerated chemiluminescence sensor that the bigger serface of combining nano porous gold of the present invention and good electrical conductivity are prepared, improved Sensitivity of Analytical Method, detectability can reach below the ng level, detection speed is fast, the detection of finishing a sample only needs 2-5min, finishes the detection of a large amount of samples again in the short time.
4. the required amount of reagent of the resulting quantum dot decorated nanometer of the present invention porous gold carbon paste electrode electrogenerated chemiluminescence sensor is few, and cost is low, and is economical and practical, and carbon paste electrode can batch making.
5. resulting quantum dot decorated nanometer porous gold carbon paste electrode sensor and the coupling of electrogenerated chemiluminescence instrument detect the antibiotic residue of trace in breast, the meat products, instrumentation is simply quick, reaction and result finish automatically, write down and analyze by instrument, avoided the influence of subjective factor, and guarantee that good repeatability is arranged, be convenient to on-the-spot the detection.
Embodiment
Embodiment 1 (Tetracyclines is as tetracycline)
A kind of residual quantum dot decorated nanometer porous gold carbon paste electrode electrogenerated chemiluminescence transducer production method of trace tetracycline that detects may further comprise the steps:
(1) according to synthesizing nano-porous gold copper-base alloy of existing method and luminescent quantum dot solution;
(2) nano-porous gold surface hydroxylation: at first use deionized water, acetone and ethanol ultrasonic cleaning, dry up with high purity nitrogen afterwards, 20min in the NaOH solution of immersion 4%, washed with de-ionized water then, 120 ℃ dry 1.5 hours down, make to generate uniform hydroxyl in nanoporous gold surface and the duct;
(3) nano-porous gold that will modify hydroxyl advances to be immersed in 5min in the toluene solution of triamido propyl trimethoxy silicane (APS), and with the toluene flushing, nitrogen dries up then;
(4) nano-porous gold that (3) are obtained is immersed in 7min in the mercaptoacetic acid (TGA), the flushing of secondary water;
(5) nano-porous gold that (4) are obtained is immersed in that 7min forms a quantum dot layer in the luminescent quantum dot solution;
(6) repeat above (3) (4) (5) process 4 times, 4 layers of quantum dot that can obtain modifying;
(7) carbon paste electrode preparation: take by weighing a certain amount of dag and whiteruss (mass ratio is 3.5: 1), the careful grinding of agate mortar mixes it, pack in the glass tube of diameter 4mm, with the copper rod is lead, packing at the head end of glass bar is mixed with the carbon paste of the nano-porous gold of having modified quantum dot, obtains the carbon paste electrode of quantum dot decorated nanometer porous gold;
(8) with the carbon paste electrode dried for preparing 24 hours;
The quantum dot decorated nanometer porous gold carbon paste electrode that (9) will make is as stated above made the electrogenerated chemiluminescence sensor in conjunction with the electrogenerated chemiluminescence instrument.
Detect the residual quantum dot decorated nanometer porous gold carbon paste electrode electrogenerated chemiluminescence sensor cooperation electrogenerated chemiluminescence instrument of trace tetracycline with making, the residual detection of tetracycline to trace in dairy products and the meat products the results are shown in Table 1.Utilize existing fluorometry to detect, the results are shown in Table 1 the trace tetracycline is residual in dairy products and the meat products..
Table 1 quantum dot decorated nanometer of the present invention porous gold carbon paste electrode electrogenerated chemiluminescence sensor and fluorescence method detect effect comparison to tetracycline
The result is as can be seen from table 1: quantum dot decorated nanometer porous of the present invention gold carbon paste electrode electrogenerated chemiluminescence sensor compare with existing fluorescence method have the wideer range of linearity, higher sensitivity and lower detectability.
Embodiment 2 (macrolides is as erythromycin)
A kind of residual quantum dot decorated nanometer porous gold carbon paste electrode electrogenerated chemiluminescence transducer production method of trace erythromycin that detects may further comprise the steps:
(1) according to synthesizing nano-porous gold copper-base alloy of existing method and luminescent quantum dot solution;
(2) nano-porous gold surface hydroxylation: at first use deionized water, acetone and ethanol ultrasonic cleaning, dry up with high purity nitrogen afterwards, 30min in the NaOH solution of immersion 4%, washed with de-ionized water then, 120 ℃ dry 1 hour down, make to generate uniform hydroxyl in nanoporous gold surface and the duct;
(3) nano-porous gold that will modify hydroxyl advances to be immersed in 10min in the toluene solution of triamido propyl trimethoxy silicane (APS), and with the toluene flushing, nitrogen dries up then;
(4) nano-porous gold that (3) are obtained is immersed in 5min in the mercaptoacetic acid (TGA), the flushing of secondary water;
(5) nano-porous gold that (4) are obtained is immersed in that 10min forms a quantum dot layer in the luminescent quantum dot solution;
(6) repeat above (3) (4) (5) process 3 times, 3 layers of quantum dot that can obtain modifying;
(7) carbon paste electrode preparation: take by weighing a certain amount of dag and whiteruss (mass ratio is 3: 1), the careful grinding of agate mortar mixes it, pack in the glass tube of diameter 4mm, with the copper rod is lead, packing at the head end of glass bar is mixed with the carbon paste of the nano-porous gold of having modified quantum dot, obtains the carbon paste electrode of quantum dot decorated nanometer porous gold;
(8) with the carbon paste electrode dried for preparing 24 hours;
The quantum dot decorated nanometer porous gold carbon paste electrode that (9) will make is as stated above made the electrogenerated chemiluminescence sensor in conjunction with the electrogenerated chemiluminescence instrument.
Detect the residual quantum dot decorated nanometer porous gold carbon paste electrode electrogenerated chemiluminescence sensor cooperation electrogenerated chemiluminescence instrument of trace erythromycin with making, the residual detection of erythromycin to trace in dairy products and the meat products the results are shown in Table 2.Utilize existing fluorometry to detect, the results are shown in Table 2 trace erythromycin is residual in dairy products and the meat products..
Table 2 quantum dot decorated nanometer of the present invention porous gold carbon paste electrode electrogenerated chemiluminescence sensor and fluorescence method detect effect comparison to erythromycin
The result is as can be seen from table 1: quantum dot decorated nanometer porous of the present invention gold carbon paste electrode electrogenerated chemiluminescence sensor compare with existing fluorescence method have the wideer range of linearity, higher sensitivity and lower detectability.
Embodiment 3 (chloromycetin is as chloromycetin)
A kind of residual quantum dot decorated nanometer porous gold carbon paste electrode electrogenerated chemiluminescence transducer production method of trace amount chloramphenicol that detects may further comprise the steps:
(1) according to synthesizing nano-porous gold copper-base alloy of existing method and luminescent quantum dot solution;
(2) nano-porous gold surface hydroxylation: at first use deionized water, acetone and ethanol ultrasonic cleaning, dry up with high purity nitrogen afterwards, 25min in the NaOH solution of immersion 4%, washed with de-ionized water then, 120 ℃ dry 2 hours down, make to generate uniform hydroxyl in nanoporous gold surface and the duct;
(3) nano-porous gold that will modify hydroxyl advances to be immersed in 8min in the toluene solution of diamido propyl trimethoxy silicane (APS), and with the toluene flushing, nitrogen dries up then;
(4) nano-porous gold that (3) are obtained is immersed in 5min in the mercaptoacetic acid (TGA), the flushing of secondary water;
(5) nano-porous gold that (4) are obtained is immersed in that 8min forms a quantum dot layer in the luminescent quantum dot solution;
(6) repeat above (3) (4) (5) process 3 times, 3 layers of quantum dot that can obtain modifying;
(7) carbon paste electrode preparation: take by weighing a certain amount of dag and whiteruss (mass ratio is 4: 1), the careful grinding of agate mortar mixes it, pack in the glass tube of diameter 4mm, with the copper rod is lead, packing at the head end of glass bar is mixed with the carbon paste of the nano-porous gold of having modified quantum dot, obtains the carbon paste electrode of quantum dot decorated nanometer porous gold;
(8) with the carbon paste electrode dried for preparing 24 hours;
The quantum dot decorated nanometer porous gold carbon paste electrode that (9) will make is as stated above made the electrogenerated chemiluminescence sensor in conjunction with the electrogenerated chemiluminescence instrument.
Will make detect the residual quantum dot decorated nanometer porous gold carbon paste electrode electrogenerated chemiluminescence sensor of trace amount chloramphenicol and cooperate the electrogenerated chemiluminescence instrument, the residual chloromycetin of trace in dairy products and the meat products will be detected, the results are shown in Table 3.Utilize existing fluorometry to detect, the results are shown in Table 3 trace amount chloramphenicol is residual in dairy products and the meat products..
Table 3 quantum dot decorated nanometer of the present invention porous gold carbon paste electrode electrogenerated chemiluminescence sensor and high performance liquid chromatography detect effect comparison to chloromycetin
The result is as can be seen from table 3: quantum dot decorated nanometer porous of the present invention gold carbon paste electrode electrogenerated chemiluminescence sensor compare with existing high performance liquid chromatography have the wideer range of linearity, higher sensitivity and lower detectability.
Embodiment 4 (beta-lactam is as the Amoxicillin)
A kind of residual quantum dot decorated nanometer porous gold carbon paste electrode electrogenerated chemiluminescence transducer production method in trace Amoxicillin that detects may further comprise the steps:
(1) according to synthesizing nano-porous gold copper-base alloy of existing method and luminescent quantum dot solution;
(2) nano-porous gold surface hydroxylation: at first use deionized water, acetone and ethanol ultrasonic cleaning, dry up with high purity nitrogen afterwards, 30min in the NaOH solution of immersion 4%, washed with de-ionized water then, 120 ℃ dry 1 hour down, make to generate uniform hydroxyl in nanoporous gold surface and the duct;
(3) nano-porous gold that will modify hydroxyl advances to be immersed in 10min in the toluene solution of triamido propyl trimethoxy silicane (APS), and with the toluene flushing, nitrogen dries up then;
(4) nano-porous gold that (3) are obtained is immersed in 6min in the mercaptoacetic acid (TGA), the flushing of secondary water;
(5) nano-porous gold that (4) are obtained is immersed in that 8min forms a quantum dot layer in the luminescent quantum dot solution;
(6) repeat above (3) (4) (5) process 5 times, 5 layers of quantum dot that can obtain modifying;
(7) carbon paste electrode preparation: take by weighing a certain amount of dag and whiteruss (mass ratio is 3: 1), the careful grinding of agate mortar mixes it, pack in the glass tube of diameter 4mm, with the copper rod is lead, packing at the head end of glass bar is mixed with the carbon paste of the nano-porous gold of having modified quantum dot, obtains the carbon paste electrode of quantum dot decorated nanometer porous gold;
(8) with the carbon paste electrode dried for preparing 24 hours;
The quantum dot decorated nanometer porous gold carbon paste electrode that (9) will make is as stated above made the electrogenerated chemiluminescence sensor in conjunction with the electrogenerated chemiluminescence instrument.
Detect the residual quantum dot decorated nanometer porous gold carbon paste electrode electrogenerated chemiluminescence sensor cooperation electrogenerated chemiluminescence instrument in trace Amoxicillin with making, the residual detection of Ah not two woodss to trace in dairy products and the meat products the results are shown in Table 4.Utilize existing fluorometry to detect, the results are shown in Table 4 the trace Amoxicillin is residual in dairy products and the meat products..
Table 4 quantum dot decorated nanometer of the present invention porous gold carbon paste electrode electrogenerated chemiluminescence sensor and chemoluminescence method detect effect comparison to the Amoxicillin
The result is as can be seen from table 4: quantum dot decorated nanometer porous of the present invention gold carbon paste electrode electrogenerated chemiluminescence sensor compare with existing chemoluminescence method have the wideer range of linearity, higher sensitivity and lower detectability.
Claims (6)
1. the preparation method of a quantum dot decorated nanometer porous gold carbon paste electrode electrogenerated chemiluminescence sensor that detects the trace antibiotic residue is characterized in that may further comprise the steps:
1.1 prepare quantum dot solution and nanoporous gold copper-base alloy according to existing method;
1.2 the self-assembled modified layer by layer technology of luminescent quantum dot utilization is modified in the surface and duct of nanoporous gold copper-base alloy;
1.3 according to the preparation method of carbon paste electrode, the nano-porous gold that quantum dot is modified is made into carbon paste electrode, further makes the electrogenerated chemiluminescence sensor;
1.4 the nano-porous gold carbon paste electrode electrogenerated chemiluminescence sensor that quantum dot of the present invention is modified carries out the detection of actual sample in conjunction with the electrogenerated chemiluminescence instrument.
2. according to the described transducer production method of claim 1, it is characterized in that may further comprise the steps with the preparation of quantum dot decorated nanometer porous gold and carbon paste electrode:
2.1 nano-porous gold surface hydroxylation: at first use deionized water, acetone and ethanol ultrasonic cleaning, dry up with high purity nitrogen afterwards, 10-30min in the NaOH solution of immersion 4%, washed with de-ionized water then, 120 ℃ dry 1-3 hour down, make to generate uniform hydroxyl in nanoporous gold surface and the duct;
2.2 will modify 10-30min in the toluene solution that the nano-porous gold of hydroxyl advances to be immersed in triamido propyl trimethoxy silicane (APS), with the toluene flushing, nitrogen dries up then;
2.3 2.2 nano-porous golds that obtain are immersed in 5-10min in the mercaptoacetic acid (TGA), the flushing of secondary water;
5-10min forms a quantum dot layer in the luminescent quantum dot solution 2.4 2.3 nano-porous golds that obtain are immersed in;
2.5 repeat the quantum dot number of plies that above 2.2,2.3,2.4 processes can obtain needs;
2.6 the carbon paste electrode preparation: (mass ratio is 2-4: 1) to take by weighing a certain amount of dag and whiteruss, the careful grinding of agate mortar mixes it, pack in the glass tube of diameter 4mm, with the copper rod is lead, packing at the head end of glass bar is mixed with the carbon paste of the nano-porous gold of having modified quantum dot, obtains the carbon paste electrode of quantum dot decorated nanometer porous gold;
2.7 with the carbon paste electrode dried for preparing 24 hours;
3. transducer production method according to claim 2 is characterized in that the gold nano-material that will be modified with quantum dot is used to make carbon paste electrode, and designs the electrogenerated chemiluminescence sensor.
4. according to the described electrode preparation method of claim 2, it is characterized in that quantum dot is modified in the surface and duct of nano-porous gold.
5. electrode preparation method according to claim 4 is characterized in that: the number of plies that quantum dot is modified in nanoporous gold surface and duct.
6. the preparation and the application process of a quantum dot decorated nanometer porous gold carbon paste electrode electrogenerated chemiluminescence sensor that detects the trace antibiotic residue, it is characterized in that comprising the steps: the described sensor of the present invention of claim 2 is cooperated the electrogenerated chemiluminescence instrument, be used for the antibiotic residue of dairy products and meat products trace is detected.
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| CN103091302A (en) * | 2012-12-27 | 2013-05-08 | 济南大学 | Preparation of ECL (electro chemical luminescence) DNA (Deoxyribose Nucleic Acid) sensor based on 3D paper chip, and application of sensor to simultaneous detection on Hg<2+> and Ag<+> |
| CN103558256A (en) * | 2013-11-19 | 2014-02-05 | 山东理工大学 | Antibiotic multi-residue detection method based on array type sensor |
| CN106398697A (en) * | 2015-07-28 | 2017-02-15 | 上海师范大学 | Method for changing fluorescence color of quantum dots |
| CN108459062A (en) * | 2017-09-01 | 2018-08-28 | 湖南工程学院 | Nano cupric oxide modified electrode and the method for replacing meter Sha Xing with modified electrode analysis |
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| CN103091302A (en) * | 2012-12-27 | 2013-05-08 | 济南大学 | Preparation of ECL (electro chemical luminescence) DNA (Deoxyribose Nucleic Acid) sensor based on 3D paper chip, and application of sensor to simultaneous detection on Hg<2+> and Ag<+> |
| CN103558256A (en) * | 2013-11-19 | 2014-02-05 | 山东理工大学 | Antibiotic multi-residue detection method based on array type sensor |
| CN103558256B (en) * | 2013-11-19 | 2015-06-24 | 山东理工大学 | Antibiotic multi-residue detection method based on array type sensor |
| CN106398697A (en) * | 2015-07-28 | 2017-02-15 | 上海师范大学 | Method for changing fluorescence color of quantum dots |
| CN106398697B (en) * | 2015-07-28 | 2018-10-30 | 上海师范大学 | A method of changing quantum dot iridescent |
| CN108459062A (en) * | 2017-09-01 | 2018-08-28 | 湖南工程学院 | Nano cupric oxide modified electrode and the method for replacing meter Sha Xing with modified electrode analysis |
| CN108459062B (en) * | 2017-09-01 | 2020-06-26 | 湖南工程学院 | Nano copper oxide modified electrode and method for analyzing tilmicosin by using modified electrode |
| CN109060778A (en) * | 2018-07-13 | 2018-12-21 | 天津理工大学 | A method of the electrochemical luminescence based on graphene quantum dot detects butylated hydroxy anisole |
| CN113138183A (en) * | 2021-04-30 | 2021-07-20 | 南京师范大学 | Detection method of amoxicillin based on graphite alkyne quantum dot fluorescence quenching effect |
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