CN101942086A - Preparation and application of melamine molecular imprinting electrochemical sensor - Google Patents
Preparation and application of melamine molecular imprinting electrochemical sensor Download PDFInfo
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- CN101942086A CN101942086A CN 201010289714 CN201010289714A CN101942086A CN 101942086 A CN101942086 A CN 101942086A CN 201010289714 CN201010289714 CN 201010289714 CN 201010289714 A CN201010289714 A CN 201010289714A CN 101942086 A CN101942086 A CN 101942086A
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Abstract
The invention relates to a molecular imprinting electrochemical sensor, which is used for determining melamine in liquid milk and belongs to the technical field of food safety detection. The melamine in the liquid milk is taken as an object of study, and a molecularly imprinted polymer is prepared by electropolymerization on a gold electrode by using the cyclic voltammetry method. The invention constructs a new method for selectively detecting the melamine by taking mixed solution of equimolar hydroxyphenol and o-aminophenol as functional monomers, taking the melamine as template molecules and taking K3Fe(CN)6 as a probe between an imprinting electrode and base solution. The reaction conditions are respectively as follows: the monomer/template mass ratio is 0.55/1, the pH value is 5.5, and the temperature is 30 DEG C. The molecularly imprinted polymer imprinted polymer thin film which leaves template molecular configuration holes is prepared by using methanol solution to carry out ultrasonic elution for 6min and removing the template molecules from the electrode. The detection is carried out through the differential pulse method, and the linear range is 0.50-7.50mg/kg. The response time is 10 seconds. The molecular imprinting electrochemical sensor can be used for detecting an actual liquid milk sample without pretreatment, the selectivity is good, and the recovery rate of adding standard is 87.5-109%.
Description
Technical field
The present invention relates to a kind of electrochemical method electropolymerization on gold electrode that utilizes and prepare molecule marking material, this new membrane material has the feature recognition performance to trimeric cyanamide.Belong to the technical field of utilizing the electrochemical production type material to be used for food safety detection.
Background technology
(Melamine is a kind of triazines nitrogen heterocyclic ring organic compound MAM) to trimeric cyanamide, is often used as industrial chemicals.Because the nitrogen content of trimeric cyanamide is up to 66.63%, Protein content is " Kjeldahl determination (the Kjeldahl method) " that adopts food service industry current in the milk and measure at present, the method of promptly passing through to measure the content of nitrogen-atoms in the food and calculating indirectly, protein and other nitrogenous substancess such as trimeric cyanamide can't be distinguished, thereby can't judge correctly whether content in food is up to standard.Trimeric cyanamide is difficult for being had renal toxicity and carcinogenesis by organism metabolism." Sanlu milk powder " incident in 2008 has caused the whole nation even the interior attention to interpolation trimeric cyanamide in the emulsion milk-product of world wide, therefore trimeric cyanamide in the milk powder is carried out rapid detection research and has very important significance.At present, among the GB GB/T22388-2008 in raw dairy and the milk-product trimeric cyanamide detection method have three kinds: high performance liquid chromatography, liquid chromatography-mass spectrography/mass spectroscopy and GC-MS(gas chromatography-mass spectrography).The detection thresold of this method is low and measuring result is accurate, but because apparatus expensive, the restriction of sample pre-treatments complexity etc. and unsuitable penetration and promotion.
Electropolymerization prepares the molecular imprinting sensor sensing film and has certain report.Present electricity consumption polymerization prepares the melamine molecular engram film sensors and yet there are no report.With the existing bibliographical information of trimeric cyanamide in separation of molecular imprinting method and the mensuration milk preparation.
Analytica Chimica Acta 576 in 2006 rolls up 67 pages of the 1st phases and has reported with the trimeric cyanamide to be template molecule, and methacrylic acid is a function monomer, and ethylene glycol dimethacrylate is a linking agent, has prepared trimeric cyanamide ion selective electrode film.This membrane electrode is 5.0 * 10
-6-1.0 * 10
-2The mol/L scope shows and can this spy respond protonated trimeric cyanamide, and electrode response 16 seconds kept stable in two months.
Analyze 687 pages of 28 the 6th phases of volume of test journal in 2009 and reported the isolating method of trimeric cyanamide in a kind of preparation of melamine molecular engram polymer and the milk preparation.Adopt molecular imprinting, with the trimeric cyanamide is template molecule, methacrylic acid is a function monomer, ethylene glycol dimethacrylate is a linking agent, synthesized and trimeric cyanamide had the better selectivity molecularly imprinted polymer can be from milk preparations such as milk powder, pure milk optionally separates, the enrichment trimeric cyanamide, and removed the complex matrices in the milk preparation effectively.
Chemistry circular in 2010 the 6th phase 545 pages of preparations of having reported the melamine molecular engram integral post.Be template molecule with the trimeric cyanamide in the research, methacrylic acid is a function monomer, Ethylene glycol dimethacrylate is a linking agent, situ aggregation method has prepared has the very molecular engram integral column of strong selectivity recognition capability to MAM, this trace integral post is as solid-phase extraction column, the MAM in the online or off-line selective enrichment sample.
The present invention is to be function monomer with equimolar Resorcinol and o-aminophenol, is template molecule with the trimeric cyanamide, has made up the molecular imprinting electrochemical sensor that trimeric cyanamide is had single-minded selectivity characteristic, and with K
3Fe (CN)
6Be the probe between trace electrode and end liquid, realized melamine detection in the liquid towards milk.
Summary of the invention:
1. the preparation of molecular imprinting sensor sensing film
Gold electrode is a working electrode, and equimolar Resorcinol and o-aminophenol are function monomer, with the high chloro acid dissolution of 0.05moL/L, regulates pH value 4.5-6.5 with sodium hydroxide or the potassium hydroxide of 0.1moL/L, adds trimeric cyanamide in proportion.With the cyclic voltammetry current potential is-0.2～1.2V, and starting time is 10 seconds scope interscan 25-35 circles, and sweep velocity is 50mv/s.The nitrogen protection of electropolymerization process.Polymeric membrane is deposited on the surface of electrode, spends methanol solution and carries out ultrasonic wash-out 5-10min, and template molecule is removed from electrode, makes the molecular imprinting polymer imprinted polymer film that leaves template molecule configuration hole.
In the electropolymerization scanning process, template and monomer effect are at gold electrode surfaces voltolisation synthetic molecules blotting membrane.In the starting stage, electrode surface and K
3Fe (CN)
6Contact, so current-responsive is arranged, and then the formation of electropolymerization film has hindered K
3Fe (CN)
6With contacting of electrode, so K
3Fe (CN)
6Just there is not the peak current response at electrode surface.
In the forming process of melamine molecular engram film, equimolar Resorcinol and o-aminophenol monomer and the effect of template trimeric cyanamide, mode by electropolymerization, and then at the nonconducting electropolymerization film of electrode surface formation one deck, wash-out template molecule then, formation has the hole in specific identification site, in order to detect melamine molecule.Phenolic hydroxyl group on the monomer, can with amino generation hydrogen bond and the ionic linkage effect on the trimeric cyanamide.And the amino on the trimeric cyanamide is good hydrogen bond donor, and the C=N on the monomer is a hydrogen bond receptor, and ionic linkage or hydrogen bond action can take place.Molecular engram film has the recognition reaction in three-dimensional hole, K to the template molecule trimeric cyanamide
3Fe (CN)
6Molecule diffuses to sensor surface by the hole, and electrochemical reaction takes place.The electropolymerization film is not destroyed in order to prove in the elution process, the wash-out rear electrode is carried out abundant trace in containing the solution of trimeric cyanamide after, detecting electrode can be seen K to the differential pulse response of indicator again
3Fe (CN)
6The oxidation peak of molecule obviously reduces again, illustrates that the trace electrode pair trimeric cyanamide of preparation has reasonable trace ability.
The material of electrode pair ad hoc structure has recognition performance, and the mensuration of actual sample is not needed pre-treatment.Electrode response time was less than 10 seconds.Use and keep stable in 30 times.
2. experiment material and device
Trimeric cyanamide (purity＞99%, AG), Resorcinol (purity＞99%, AG), o-aminophenol (purity＞99%, AG), the Tripotassium iron hexacyanide (purity＞99.5%, AG), perchloric acid (purity＞72%, AG), sodium hydroxide (purity＞99%, AG), methyl alcohol (purity＞99.5%, AG) nitrogen (purity＞99.999%).
The pre-treatment of gold electrode: before the electropolymerization, gold electrode elder generation is at the Al of 0.3 μ m
2O
3Polish on the powder,, use rare HNO then successively until slick minute surface occurring
3(volume ratio is 1: 1), methyl alcohol, the distilled water supersound washing, each 5 minutes, take out electrode, stand-by.
Experimental technique adopts three electrode devicies: the microsphere transmitter is a working electrode, and platinum electrode is a counter electrode, and saturated calomel electrode is a reference electrode.Assembling liquid is prepared by institute feed nitrogen, the logical nitrogen time is 5 minutes, carries out electropolymerization then on the basis of continuing feeding nitrogen, carries out wash-out afterwards, detects.At ambient temperature, the trace electrode is immersed in 5.0mmol/LK
3Fe (CN)
6In the solution, when background current reach stable after, add trimeric cyanamide standardized solution or actual testing sample.Adopt cyclic voltammetry that the molecular imprinting transmitter is carried out electrochemical Characterization.With the differential impulse method molecular imprinting effect of trimeric cyanamide trace transmitter is carried out quantitative Analysis.
3. the application of molecular imprinting trimeric cyanamide transmitter
The trace electrode pair different concns trimeric cyanamide that utilization prepares detects.Reaction conditions is respectively, and monomer/template quality ratio is 0.54/1, and the pH value is 5.5, and temperature is 30 ℃, nitrogen protection.Spend methanol solution and carry out ultrasonic wash-out 6min, template molecule is removed from electrode, make the molecular imprinting polymer imprinted polymer film that leaves template molecule configuration hole.Carry out differential pulse scanning at the 5.00mmol/L potassium ferricyanide solution, the variation of record peak current.Melamine concentration linear in the 0.5-7.5mg/L scope; Coefficient R
2=0.996.Be limited to 0.5mg/L under measuring.Detect the trimeric cyanamide (n=5) of same concentrations, calculation result shows that relative standard deviation is respectively 6.45-6.13%.Recovery of standard addition is 87.5-109%.
Embodiment:
(diameter=0.8cm) is at the Al of 0.3 μ m for gold electrode
2O
3Polish on the powder, until slick minute surface occurring.Use rare HNO successively
3(volume ratio is 1: 1), methyl alcohol, deionized water supersound washing 5min..Take out electrode, stand-by.
Deng mole Resorcinol and o-aminophenol is the high chloro acid dissolution of function monomer (Resorcinol is got 0.0555g, and o-aminophenol is got 0.0550g) with 0.05moL/L, and the NaOH adjusting pH value 5.5 with 0.10moL/L adds trimeric cyanamide 0.20g.With the cyclic voltammetry current potential is-0.2～1.2V, and starting time is 10 seconds scope interscan 30 circles, and sweep velocity is 50mv/s.Polymeric membrane is deposited on the surface of electrode, carries out ultrasonic wash-out 6min. with methyl alcohol, and template molecule is removed from electrode, makes the molecular imprinting polymer imprinted polymer film that leaves template molecule configuration hole.Nitrogen protection in the electropolymerization process.
Actual liquid state milk sample detection process adds a certain amount of K for getting 20mL liquid state milk sample
3Fe (CN)
6Solid, making its strength of solution is 5.0mmol/L.With the molecular imprinting electrode is working electrode, and platinum electrode is a counter electrode, and saturated calomel electrode is a reference electrode.Differential impulse method scanning samples, the time of response is less than 10 seconds, and writes down its current value, horizontal survey three times.Content according to trimeric cyanamide in the standard working curve calculation sample.Embodiment 1, example 2, example 3, example 4, example 5 see Table 1.Each sample electrode ultrasonic wash-out 6min. in methanol solution that measured.
Melamine detection result in the table 2 liquid state milk sample
Accuracy for the confirmatory experiment method, do mark-on and reclaim experiment, in sample, add the trimeric cyanamide standard specimen, using the same method, (the molecular imprinting electrode is a working electrode in detection, platinum electrode is a counter electrode, saturated calomel electrode is a reference electrode), and write down current value, according to the content of trimeric cyanamide in the standard working curve calculation sample.Calculate recovery of standard addition simultaneously.Embodiment 1, example 2, example 3, example 4, example 5 see Table 2.
Table 2 recovery of standard addition experimental result
Claims (5)
1. one kind is utilized electrochemical production melamine molecular engram electropolymerization chemical sensor.Gold electrode is a working electrode, and the Resorcinol of a certain amount of mol ratio and o-aminophenol are function monomer, uses a certain amount of high chloro acid dissolution, regulates pH value 4.5～6.5 with sodium hydroxide or the potassium hydroxide of 0.1moL/L, adds trimeric cyanamide in proportion.With the cyclic voltammetry current potential is-0.2～1.2V, and starting time is scope interscan in 10 seconds 25～35 circles, and sweep velocity is 50mv/s.The nitrogen protection of electropolymerization process.Polymeric membrane is deposited on the surface of electrode, carries out ultrasonic wash-out 5～10min with methanol solution, and template molecule is removed from electrode, makes the molecular imprinting polymer imprinted polymer film that leaves template molecule configuration hole.
2. a kind of melamine molecular engram electropolymerization chemical sensor preparation method according to claim 1, its mol ratio of function monomer of the Resorcinol of the described a certain amount of mol ratio of its feature and o-aminophenol are a kind of in 1: 1～1: 1.5.
3. a kind of melamine molecular engram electropolymerization chemical sensor preparation method according to claim 1, a certain amount of perchloric acid of the described usefulness of its feature is a kind of among 0.05～0.15moL/L.
4. a kind of melamine molecular engram electropolymerization chemical sensor preparation method according to claim 1, the described trimeric cyanamide that adds in proportion of its feature is that function monomer/template quality ratio is 0.55/1.
5. the melamine molecular engram electropolymerization chemical sensor with claim 1 preparation is applied to actual liquid state milk sample detection, and the material of electrode pair ad hoc structure has recognition performance, and the mensuration of actual sample is not needed pre-treatment.Electrode response time was less than 10 seconds.Use and keep stable in 30 times.
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Cited By (7)
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| CN102393411A (en) * | 2011-10-19 | 2012-03-28 | 西安医学院 | Preparation method of electrochemical sensor for detecting molecular imprinting of organophosphorus pesticide residue |
| CN103866367A (en) * | 2014-03-31 | 2014-06-18 | 福建师范大学 | Preparation method and application of tri-(2, 3-dibromopropyl) isocyanurate sensor |
| CN104267087A (en) * | 2014-10-29 | 2015-01-07 | 安徽师范大学 | Electrochemical biosensor as well as preparation method and application thereof |
| CN104597092A (en) * | 2014-10-28 | 2015-05-06 | 肇庆学院 | Preparation method of dicyandiamide molecular imprinting polymer membrane electrode |
| CN104764775A (en) * | 2015-02-26 | 2015-07-08 | 河北科技大学 | Method for preparation of triazole molecularly imprinted electrochemical sensor based on electropolymerized OPD/OAP composite membrane and application thereof |
| CN105548151A (en) * | 2015-12-14 | 2016-05-04 | 江南大学 | Novel method for detection of codeine based on ionic iridium complex electrochemiluminescence and molecular imprinting recognition |
| CN110208219A (en) * | 2018-02-28 | 2019-09-06 | 北京大学 | A kind of surface phasmon optical fiber probe and preparation method thereof based on electrochemical polymerization molecular imprinting technology |
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| US6924322B2 (en) * | 2003-03-18 | 2005-08-02 | The Regents Of The University Of California | Thio-,amine-,nitro-,and macrocyclic containing organic aerogels & xerogels |
| CN101559352A (en) * | 2009-05-15 | 2009-10-21 | 华南农业大学 | Molecularly imprinted polymers (MIPs) for inspecting melamine and preparation method thereof |
| CN101560277A (en) * | 2009-06-03 | 2009-10-21 | 中国农业科学院农业质量标准与检测技术研究所 | Melamine molecular engram polymer and method for preparing same |
| CN101706469A (en) * | 2009-01-09 | 2010-05-12 | 烟台海岸带可持续发展研究所 | Method and device for detecting tripolycyanamide |
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| US6924322B2 (en) * | 2003-03-18 | 2005-08-02 | The Regents Of The University Of California | Thio-,amine-,nitro-,and macrocyclic containing organic aerogels & xerogels |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102393411A (en) * | 2011-10-19 | 2012-03-28 | 西安医学院 | Preparation method of electrochemical sensor for detecting molecular imprinting of organophosphorus pesticide residue |
| CN103866367A (en) * | 2014-03-31 | 2014-06-18 | 福建师范大学 | Preparation method and application of tri-(2, 3-dibromopropyl) isocyanurate sensor |
| CN104597092A (en) * | 2014-10-28 | 2015-05-06 | 肇庆学院 | Preparation method of dicyandiamide molecular imprinting polymer membrane electrode |
| CN104597092B (en) * | 2014-10-28 | 2017-02-15 | 肇庆学院 | Preparation method of dicyandiamide molecular imprinting polymer membrane electrode |
| CN104267087A (en) * | 2014-10-29 | 2015-01-07 | 安徽师范大学 | Electrochemical biosensor as well as preparation method and application thereof |
| CN104764775A (en) * | 2015-02-26 | 2015-07-08 | 河北科技大学 | Method for preparation of triazole molecularly imprinted electrochemical sensor based on electropolymerized OPD/OAP composite membrane and application thereof |
| CN104764775B (en) * | 2015-02-26 | 2020-01-03 | 河北科技大学 | Method for preparing triazole molecularly imprinted electrochemical sensor based on electropolymerized OPD/OAP composite membrane and application thereof |
| CN105548151A (en) * | 2015-12-14 | 2016-05-04 | 江南大学 | Novel method for detection of codeine based on ionic iridium complex electrochemiluminescence and molecular imprinting recognition |
| CN105548151B (en) * | 2015-12-14 | 2019-02-12 | 江南大学 | Based on ionic type iridium complex electrogenerated chemiluminescence-electropolymerization molecular engram recognition detection codeine novel method |
| CN110208219A (en) * | 2018-02-28 | 2019-09-06 | 北京大学 | A kind of surface phasmon optical fiber probe and preparation method thereof based on electrochemical polymerization molecular imprinting technology |
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