CN104237333B - A kind of many hydrogen bonds electrochemical sensor and preparation method thereof and the application in melamine detects - Google Patents
A kind of many hydrogen bonds electrochemical sensor and preparation method thereof and the application in melamine detects Download PDFInfo
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Abstract
The present invention relates to a kind of many hydrogen bonds electrochemical sensor and preparation method thereof and the application in melamine detects, at SiO2For nano grain surface, 3-aminopropyl triethoxysilane, pentanedial decoration access function monomer 6-semicarbazides pyrimidine, using melamine as template molecule, make molecular engram core-shell nano particle with methacrylic acid, initator and crosslinking agent polymerisation; The suspension of reduced form graphene oxide is become to dressing agent with the DMF solution mixing system of ionic liquid, get this dressing agent modified glassy carbon electrode, then molecular engram core-shell nano particle is made into suspension, drip and be coated onto the electrode surface obtaining above and make sensor. Molecularly imprinted polymer of the present invention has very high selective, Graphene and ionic liquid combine use, also improved the electrochemical signals of sensor in the present invention, thereby auxiliary three hydrogen bond molecular imprintings better play a role, and realize higher sensitivity and accuracy.
Description
Technical field
The present invention relates to a class based on many hydrogen bonds electrochemical sensor, particularly a kind of many hydrogen bonds electrochemical sensor and preparation thereofMethod and the application in melamine detects.
Background technology
Many hydrogen bonds are a kind of significant active forces in molecular engram system. Template molecule and function monomer are by many hydrogenKey generates based on the binding site of ligand-optionally and in molecular engram system, carries out the knowledge of target molecule by this active forceNot. The research synthetic and application of the molecularly imprinted polymer based on many interaction of hydrogen bond has been seen in report, in these researchIn, using 2 – (trifluoromethyl) acrylic acid and diaminopyridine derivatives as function monomer, contain with thymidine, uracil etc.The compound of pyrimidine bases, as target molecule, is prepared molecularly imprinted polymer by forming many hydrogen bonds between the two, thereby realThe detection of existing pyrimidine derivatives. Melamine (Melamine), is again 2,4,6-triamido-1,3,5-triazines, is a kind of important nitrogenHeterocyclic organic compounds. It is a kind of important industrial chemicals originally, is usually used in manufacturing melmac, with food, feedIndustry is not theed least concerned, but 2004 and occur in several of the U.S. in March, 2007 and cause pet poisoning by contaminated feed for petDead event and occur in Chinese Sanlu baby milk powder contamination accident in September, 2008, but makes them closely contactTogether. Melamine belongs to difficult metabolite, if entered in humans and animals body, can cause to some extent kidney failure or deadDie. Melamine can also cause calculus, thereby brings out bladder and disease in the urological system. Therefore, strictly control making of melaminePay close attention to being more and more subject to people. The method of early stage industrial detection melamine is gravimetric method and potentiometric titration, these methodsPre-treatment to sample and detection limit all do not reach the requirement that country is detected melamine in food, and meanwhile, these methods are consuming timeLong, experimental procedure is loaded down with trivial details, has limited its utilization.
Based on above consideration, the present invention necessarily revises traditional three hydrogen bond mechanism, and Fan Qi road and going exchanges traditional three hydrogen bondsThe role of middle function monomer and template molecule, taking uracil derivative as function monomer, taking compound in triazine class (in the present invention asMelamine) be template molecule, set up a kind of molecular engram polymerization of the novel melamine specific recognition based on many hydrogen bondsThing, and under the mixture of reduced form Graphene and ionic liquid auxiliary, build electrochemical sensor and carry out the inspection of melamineSurvey.
Summary of the invention
The invention provides a kind of many hydrogen bonds electrochemical sensor and preparation method thereof, and its answering in melamine detects is providedWith. This sensor can enter to catch and enrichment to melamine in food rapidly, and reaches the object of detection, and synthetic method is simple,Experimental implementation is easy, and has higher selective and precision.
The technical scheme that the present invention takes is:
A preparation method for many hydrogen bonds electrochemical sensor, comprises the steps:
(1) mixed solution of silester TEOS and ethanol is joined rapidly in the mixed liquor of ammoniacal liquor and water, stir lower reaction2～3 hours, filter and obtain monodispersed SiO2Nano particle;
(2) SiO step (1) being obtained2Nanoparticulate dispersed, in dry toluene, and adds 3-aminopropyl-triethoxy siliconAlkane (APTES) adds hot reflux 10-12 hour, uses ethanol wash products, and product is re-dispersed in ethanol, addsGlutaraldehyde stirs 5-12 hour, afterwards products therefrom is cleaned and is distributed in methyl alcohol; Take 6-semicarbazides pyrimidine, use dimethylSulfoxide heating for dissolving, joins in the methyl alcohol dispersion liquid of above-mentioned product, then adds appropriate methyl alcohol, stirs half an hour, then in bottleAdd sodium borohydride, continue to stir 8-12 hour, carry out the modification of 6-semicarbazides pyrimidine function monomer;
(3) by the nanoparticulate dispersed of gained access function monomer in step (2) in acetonitrile, and add melamine conductTemplate molecule, methacrylic acid, initator and crosslinking agent, carry out polymerisation according to two step temperature-raising methods:: first at 50 DEG C～55 DEG CReact 3～6 hours, then 60 DEG C～70 DEG C reactions 18～24 hours, and at 85 DEG C～90 DEG C aging 6～8 hours, obtain threePoly cyanamid three hydrogen bond molecular engram core-shell nano particles;
(4) prepare reduced form graphene oxide;
(5) by the aqueous suspension of reduced form Graphene and ionic liquid 1-butyl-3-methyl imidazolium tetrafluoroborate ([BMIm] BF4)DMF solution mixing system become dressing agent, get this dressing agent and drip and be coated onto glass-carbon electrode surface to uniform fold and modify and be dried;
(6) get the DMF suspension of the melamine three hydrogen bond molecular engram core-shell nano particles that step (3) makes, drip and be coated withThe electrode surface obtaining to step (5) is to uniform fold, dry.
The silester that step in above-mentioned preparation method (1) is described and the volume ratio of ethanol are 5-6:4-5, preferably 5.4:4.6.The mol ratio of ammoniacal liquor and water is 0.5～2:3～10, and the proportion of TEOS and ammoniacal liquor is 5～6:0.5～2.
SiO in step (2)2The usage ratio of nano particle and toluene is 0.3:50, g:mL; SiO2Nano particle and 3-aminopropylThe usage ratio of triethoxysilane, glutaraldehyde, 6-semicarbazides pyrimidine is 0.1～0.3:4.0～7.0:0.5～1.0:0.168, g:mL:mL:g.Ethanol, dimethyl sulfoxide (DMSO), methyl alcohol, sodium borohydride and SiO2The additional proportion of nano particle is 50:20:30:0.5:0.3,mL:mL:mL:g：g。
Nano particle and acetonitrile, melamine, methacrylic acid, initator and the crosslinking agent of access function monomer in step (3)Usage ratio be 0.1～0.5:50～100:10～30:0.2～0.4:10～20:1.0～3.5, g:mL:mg:mL:mg:mL. Described initiationAgent is azodiisobutyronitrile, and described crosslinking agent is ethylene glycol dimethacrylate.
The preparation of the reduced form graphene oxide described in above-mentioned steps (4) adopts conventional method, and method for optimizing is: take 0.75Gram graphite powder adds in there-necked flask, adds 90 milliliters of concentrated sulfuric acids and 10 milliliters of phosphoric acid, about stirring at normal temperature half an hour, thenSlowly add 4.5 grams of potassium permanganate, in adition process, be warming up to 50 DEG C, react afterwards 12 hours, stop heating, continueStirring is cooled to room temperature, and sample is poured in 40 milliliters of frozen water, adds in advance 300 microlitre hydrogen peroxide, solution face in frozen waterLook becomes khaki, and ice melts gradually, then drip a small amount of hydrogen peroxide with dropper, until react completely. Finally carry out fromThe heart cleans. And dry in vacuum drying chamber. The graphene oxide obtaining is made into the suspension of 0.5 mg/ml, with5.0 milliliters of above-mentioned suspensions react 12 hours with 4.0 milligrams of polyvinylpyrrolidones at 50 DEG C, are cooled to room temperature and add afterwardsThe hydrazine of 3.5 microlitres, 40.0 microlitre ammoniacal liquor react and within 1 hour, obtain reduced form graphene oxide at 95 DEG C.
Aqueous suspension concentration range 0.5～1.0 mg/ml of the reduced form graphene oxide described in above-mentioned steps (5), ionic liquidDimethyl formamide DMF solution concentration scope 2.0～5.0 microlitre/milliliters of body; The aqueous suspension of reduced form graphene oxide with fromThe dimethyl formamide DMF liquor capacity of sub-liquid is than being 1:1.
In step (6), the concentration range of the DMF suspension of melamine three hydrogen bond molecular engram core-shell nano particles is 2～3 millisGrams per milliliter.
Many hydrogen bonds electrochemical sensor that said method obtains.
Above-mentioned electrochemical sensor is the application in melamine in detection food samples.
Electrochemical sensor application process in melamine in detection food is: prepared electrochemical sensor is dipped in to preparationIn good food samples, adsorb 30 minutes, use afterwards deionized water rinsing electrode, then utilize three-electrode system, at PBSIn cushioning liquid, carry out the content detection of melamine with cyclic voltammetry. After one-time detection, electrode is repeatedly circulated and sweptRetouch, until the signal of signal when not adsorbing template molecule is suitable, now can think the template molecule on molecularly imprinted polymerTotal overall reaction is fallen, and after clear water rinses, electrode is reusable.
Technical essential of the present invention has following four aspects: 1) molecularly imprinted polymer is with SiO2For kernel, at SiO2Nano particleSurface is modified layer by layer, and on keyed jointing, required function monomer is also finally realized the trace of template molecule; 2) function monomer and templateMolecule by three Hydrogenbonds, is realized specific identification, is the absorption of melamine and the detection basis that theorizes; 3) electrodeModification adopt cladding process, first drip the DMF mixed liquor of graphitization alkene and ionic liquid, after treating nature volatile dry, then generalThe DMF solution of molecularly imprinted polymer drips and is coated onto electrode surface, drying for standby under room temperature; 4) after modified electrode is measured, carry outReusable after processing.
Outstanding characteristic of the present invention is: 1) in the present invention, and by function monomer and mould in three traditional hydrogen bond molecular engram systemsThe role swap of plate molecule, by the function monomer in traditional system, in the present invention as template molecule, and in traditional systemTemplate molecule is used as function monomer in body series; 2) Graphene and ionic liquid have synergy, can improve electrodeElectric conductivity, makes detection method sensitiveer; 3) the present invention have very high selective, only for melamine and triazines chemical combinationThing has specific binding, so in the very strong food inspection of specific aim, have good selective enrichment suction-operated, reaches foodThe detection of melamine in product.
Advantage of the present invention is, due in the present invention by template molecule and function monomer in traditional three hydrogen bond molecular engram systemsRole exchange, has opened up a kind of synthetic method of novel compound in triazine class molecularly imprinted polymer and has built this compoundsElectrochemical sensor, realized high selectivity and the high-sensitivity detection of melamine in food and feeds etc. The present invention is firstThis synthetic theory of inferior proposition, to utilizing further expanding that material scope that molecular imprinting detects carries out, provides threeThe new detection method of piperazine class material. Graphene and ionic liquid combine use, also improved the electrification of sensor in the present inventionLearn signal, thereby auxiliary three hydrogen bond molecular imprintings better play a role, and realize higher sensitivity and accuracy. MoleculeThe physical and chemical stability of imprinted polymer makes it in recycling process, have good reappearance and stability, increases thisBright range of application and frequency in practical process. The present invention is simple to operate, performance is efficient, and whole process environment close friend, is expected toIn the testing mechanisms such as each food and feeds, realize extensive use.
Brief description of the drawings
Fig. 1. three hydrogen bond structure mechanism schematic diagrames in the present invention.
Fig. 2. synthetic SiO2Nano particle pattern SEM photo.
Fig. 3. be modified with the SiO of APTES2SEM photo after the external GA of nano particle.
Fig. 4. melamine molecular engram core-shell nano granule-morphology SEM photo.
Fig. 5. non-imprinted polymer pattern SEM photo.
Fig. 6. electrochemical sensor builds schematic diagram.
Fig. 7. the CV curve of different modifying electrode.
Detailed description of the invention
Further illustrate below in conjunction with embodiment.
Embodiment 1:
The mixed liquor of the ethanol of the TEOS that contains 5.4 milliliters and 4.6 milliliters is joined to the ammoniacal liquor and 5 that contains 1 mol/L to rubYou/liter the mixed liquor of water in, under mechanical agitation, react 2 hours, obtain monodispersed SiO2Nano particle. As shown in Figure 2.Carry out on this basis the synthetic of melamine molecular engram core-shell nano particle: by the SiO obtaining2Nano particle takes 0.3 gramBe distributed in dry toluene, and add 7 milliliters of 3-aminopropyl triethoxysilanes (APTES) to add hot reflux 12 hours,By ethanol wash products 3 times, product is re-dispersed in 50 milliliters of ethanol, add 1 milliliter of glutaraldehyde to stir 12 hours,Further modify (products therefrom pattern as shown in Figure 3), afterwards products therefrom is cleaned and is distributed in methyl alcohol, take 0.168Gram 6-semicarbazides pyrimidine, by 20 milliliters of dimethyl sulfoxide (DMSO) heating for dissolving, joins in above-mentioned flask, adds appropriate methyl alcohol, stirsHalf an hour, then add a spoon sodium borohydride in bottle, continue to stir 12 hours, carry out 6-semicarbazides pyrimidine and carry out function monomerModification, by nanoparticulate dispersed to the 50 milliliter acetonitrile of gained access function monomer, and add 30 milligrams of melamines to doFor template molecule, 0.4 milliliter of methacrylic acid, 20 milligrams of AIBN as initator and 3.5 milliliters of EGDMA as crosslinking agent,Carry out polymerisation according to two step temperature-raising methods: first 50 DEG C of reactions 6 hours, then 60 DEG C of reactions 24 hours, and at 85 DEG CLower aging 6 hours, obtain melamine three hydrogen bond molecular engram core-shell nano particles. Its pattern as shown in Figure 4. According to identicalMethod in the situation that not adding template molecule, synthetic non-imprinted polymer is to make pattern and Performance Ratio. Products therefrom patternAs shown in Figure 5.
Being prepared as of reduced form graphene oxide: take 0.75 gram of graphite powder and add in there-necked flask, add 90 milliliters of concentrated sulfuric acidsWith 10 milliliters of phosphoric acid, about stirring at normal temperature half an hour, then slowly add 4.5 grams of potassium permanganate, in adition process, be warming up to50 DEG C, react afterwards 12 hours, stop heating, continue stirring and be cooled to room temperature, sample is poured in 40 milliliters of frozen water,In frozen water, add in advance 300 microlitre hydrogen peroxide, solution colour becomes khaki, and ice melts gradually, is then dripping with dropperA small amount of hydrogen peroxide, until react completely. Finally carry out eccentric cleaning. And dry in vacuum drying chamber. By what obtainGraphene oxide is made into the suspension of 0.5 mg/ml, exists with 5.0 milliliters of above-mentioned suspensions and 4.0 milligrams of polyvinylpyrrolidonesAt 50 DEG C, react 12 hours, be cooled to the hydrazine that room temperature adds 3.5 microlitres afterwards, 40.0 microlitre ammoniacal liquor react 1 at 95 DEG CHour obtain reduced form graphene oxide.
By the DMF of 5.0 microlitre/milliliter ionic liquids of the reduced form Graphene suspension of 0.5 milliliter of 1 mg/ml and 0.5 milliliterSolution mixing system becomes dressing agent, gets this dressing agent of 4.0 microlitres and drips and be coated onto glass-carbon electrode surface and modify and be dried; By what makeMelamine three hydrogen bond molecular engram core-shell nano particle DMF suspensions, this is suspended drop and is coated onto to get 6 microlitre 2 mg/mlThe electrode surface that above-mentioned modification obtains, dry, make electrochemical sensor.
Embodiment 2:
By the mixed liquor that contains 6.0 milliliters of TEOS and 4.0 milliliters of ethanol join the ammoniacal liquor that contains 0.7 mol/L and 4 moles/In the mixed liquor of the water rising, under mechanical agitation, react 2 hours, obtain monodispersed SiO2Nano particle. Enter on this basisSynthetic (actual conditions and the materials amount) of row melamine molecular engram core-shell nano particle: take 0.127 gram of 6-semicarbazides phoneticPyridine, by 20 milliliters of dimethyl sulfoxide (DMSO) heating for dissolving, joins in flask as function monomer, then in flask, adds 50 millisRise acetonitrile, and add 10 milligrams of melamines as template molecule, 0.4 milliliter of methacrylic acid, 20 milligrams of AIBN as drawingSend out agent and 3.5 milliliters of EGDMA as crosslinking agent, carry out polymerisation according to two step temperature-raising methods: first 55 DEG C of reactions 4 hours,Again 70 DEG C of reactions 18 hours, and at 90 DEG C aging 8 hours, melamine three hydrogen bond molecular engram core-shell nanos obtainedGrain.
Being prepared as of reduced form graphene oxide: take 0.5 gram of graphite powder and add in there-necked flask, add 85 milliliters of concentrated sulfuric acids and15 milliliters of phosphoric acid, about stirring at normal temperature half an hour, then slowly add 5.0 grams of potassium permanganate, are warming up to 50 DEG C in adition process,React afterwards 12 hours, stop heating, continue stirring and be cooled to room temperature, sample is poured in 40 milliliters of frozen water, in frozen waterAdd in advance 500 microlitre hydrogen peroxide, solution colour becomes khaki, and ice melts gradually, is then dripping a small amount of mistake with dropperHydrogen oxide, until react completely. Finally carry out eccentric cleaning. And dry in vacuum drying chamber. By the oxidation stone obtainingChina ink alkene is made into the suspension of 0.5 mg/ml, with 5.0 milliliters of above-mentioned suspensions and 4.0 milligrams of polyvinylpyrrolidones at 50 DEG CLower reaction 12 hours, is cooled to the hydrazine that room temperature adds 3.5 microlitres afterwards, and 40.0 microlitre ammoniacal liquor react 1 hour at 95 DEG CObtain reduced form graphene oxide.
By 5.0 microlitre/milliliter ionic liquid 1-fourths of the reduced form Graphene suspension of 0.5 milliliter of 1 mg/ml and 0.5 milliliterBase-3-methylimidazole hexafluorophosphate ([BMIm] PF6) DMF solution mixing system become dressing agent, get this dressing agent of 6.0 microlitresDrip and be coated onto glass-carbon electrode surface and modify and be dried; By the melamine making three hydrogen bond molecular engram core-shell nano particle DMFSuspension, this is suspended drop and is coated onto the electrode surface that above-mentioned modification obtains to get 8.0 microlitre 2 mg/ml, dry, makes electrificationLearn sensor.
Embodiment 3:
Described silester and the volume ratio of ethanol are 5～6:4～5, preferably 5.4:4.6.
The mol ratio of ammoniacal liquor and water is 0.5～2:3～10, and the volume ratio of TEOS and ammoniacal liquor is 5～6:0.5～2.
The mixed liquor of the ethanol of the TEOS that contains 5.0 milliliters and 5.0 milliliters is joined to the ammoniacal liquor and 3.0 that contains 0.5 mol/LIn the mixed liquor of the water of mol/L, under mechanical agitation, react 2 hours, obtain monodispersed SiO2Nano particle.
Obtain monodispersed SiO2Nano particle. Carry out on this basis the synthetic of melamine molecular engram core-shell nano particle:Take 0.254 gram of 6-semicarbazides pyrimidine, by 20 milliliters of dimethyl sulfoxide (DMSO) heating for dissolving, join in flask as function monomer,Then in flask, add 50 milliliters of acetonitriles, and add 20 milligrams of melamines as template molecule, 0.5 milliliter of methacrylic acid,20 milligrams of AIBN as crosslinking agent, carry out polymerisation according to two step temperature-raising methods as initator and 7.0 milliliters of EGDMA:First 55 DEG C of reactions 5 hours, then 65 DEG C of reactions 24 hours, and at 85 DEG C aging 6 hours, melamine three obtainedHydrogen bond molecular engram core-shell nano particle.
Being prepared as of reduced form graphene oxide: the mixture of 1 gram of graphite powder and 50 grams of sodium chloride is ground 10 minutes with mortar.Sodium chloride water-soluble and filter remove. Graphite powder after grinding is joined in 23 milliliters of concentrated sulfuric acids, and stir 12 hours, itAfter temperature is controlled to 20 DEG C, 6 grams of potassium permanganate are joined in above-mentioned solution, and 40 DEG C stir 30 minutes, afterwardsAt 90 DEG C, stir 90 minutes, then add 46 milliliters of ultra-pure waters, temperature is increased to large 105 DEG C, heat 25 minutes. FinallyAdd the hydrogen peroxide of 140 milliliters of ultra-pure waters and 10 milliliter 30%, after reaction finishes, with 5% hydrochloric acid solution cleaning, then useUltra-pure water cleans. And dry in vacuum drying chamber. The graphene oxide obtaining is made into the suspension of 0.5 mg/ml,At 50 DEG C, react 12 hours with 4.0 milligrams of polyvinylpyrrolidones with 5.0 milliliters of above-mentioned suspensions, after being cooled to room temperatureAdd the hydrazine of 3.5 microlitres, 40.0 microlitre ammoniacal liquor react and within 1 hour, obtain reduced form graphene oxide at 95 DEG C.
By 5.0 microlitre/milliliter ionic liquid 1-third of the reduced form Graphene suspension of 0.5 milliliter of 1 mg/ml and 0.5 milliliterItrile group-3-methyl imidazolium tetrafluoroborate ([PMIm] BF4) DMF solution mixing system become dressing agent, get this modification of 5.0 microlitresAgent is dripped and is coated onto glass-carbon electrode surface and modifies and be dried; By the melamine making three hydrogen bond molecular engram core-shell nano particlesDMF suspension, this is suspended drop and is coated onto the electrode surface that above-mentioned modification obtains to get 10.0 microlitre 2 mg/ml, dry, systemObtain electrochemical sensor.
Performance test:
Prepare respectively different electrode modification agent: the 1. DMF solution of ionic liquid; 2. graphene oxide and ionic liquid DMFMixed liquor; 3. the mixed liquor of reduced form graphene aqueous solution and DMF; 4. the DMF of reduced form Graphene and ionic liquid mixesLiquid; 5. the DMF suspension of the melamine molecular engram polymer of 2 mg/ml. 1.～4. as dressing agent I, 5. conductDressing agent II. The modification of electrode is: the dressing agent I of getting 4 microlitres is dripped and is coated onto glass-carbon electrode surface, after drying at room temperature, gets 6Microlitre dressing agent II continues to drip and is coated in electrode surface, to be dried after, obtain various modified electrodes. As shown in Figure 6.
Only by dressing agent II, electrode is modified, after being dried, is dipped in the food samples preparing, adsorb 30 minutes,Use afterwards deionized water rinsing electrode, then utilize three-electrode system, in PBS cushioning liquid, investigating with cyclic voltammetry shouldThe absorption of electrode pair melamine and detection effect. As shown in Figure 7a.
With 1. modified electrode surface of dressing agent, to be dried after, then electrode is further modified by dressing agent II, dry after,Be dipped in the food samples preparing, adsorbed 30 minutes, used afterwards deionized water rinsing electrode, then utilized three electrodesSystem, in PBS cushioning liquid, investigates the absorption of this electrode pair melamine and detects effect and study simultaneously with cyclic voltammetryThe effect of ionic liquid in this process. As shown in Figure 7b.
With 2. modified glassy carbon electrode surface first of dressing agent, after drying at room temperature, then electrode is further modified by dressing agent II,After dry, be dipped in the food samples preparing, adsorbed 30 minutes, used afterwards deionized water rinsing electrode, then profitWith three-electrode system, in PBS cushioning liquid, investigate the absorption of this electrode pair melamine and detect effect with cyclic voltammetry,Observe the effect to electrode process of graphene oxide and ionic liquid simultaneously. As shown in Figure 7 c.
With 3. modified glassy carbon electrode surface first of dressing agent, after drying at room temperature, then electrode is further modified by dressing agent II,After dry, be dipped in the food samples preparing, adsorbed 30 minutes, used afterwards deionized water rinsing electrode, then profitWith three-electrode system, in PBS cushioning liquid, investigate the absorption of this electrode pair melamine and detect effect with cyclic voltammetry,Investigate the humidification of reduced form graphene oxide to electric conductivity in electrode process simultaneously. As shown in Fig. 7 d.
With 4. modified glassy carbon electrode surface first of dressing agent, after drying at room temperature, then electrode is further modified by dressing agent II,After dry, be dipped in the food samples preparing, adsorbed 30 minutes, used afterwards deionized water rinsing electrode, then profitWith three-electrode system, in PBS cushioning liquid, investigate the absorption of this electrode pair melamine and detect effect with cyclic voltammetry,Reduced form graphene oxide and chemiluminescence and this modification of ionic liquid to electric conductivity in inspecting electrode course of reaction simultaneouslyInteraction between layer and molecularly imprinted polymer. As shown in Fig. 7 e.
Claims (9)
1. a preparation method for the electrochemical sensor of hydrogen bond more than, is characterized in that, comprises the steps:
(1) mixed solution of silester TEOS and ethanol is joined rapidly in the mixed liquor of ammoniacal liquor and water, stir lower reaction2～3 hours, filter and obtain monodispersed SiO2Nano particle;
(2) SiO step (1) being obtained2Nanoparticulate dispersed, in dry toluene, and adds 3-aminopropyl-triethoxy siliconAlkane adds hot reflux 10-12 hour, uses ethanol wash products, and product is re-dispersed in ethanol, adds glutaraldehyde to stir 5-12Hour, afterwards products therefrom is cleaned and is distributed in methyl alcohol; Take 6-semicarbazides pyrimidine, use dimethyl sulfoxide (DMSO) heating for dissolving,Join in the methyl alcohol dispersion liquid of above-mentioned product, then add appropriate methyl alcohol, stir half an hour, then add sodium borohydride in bottle,Continue to stir 8-12 hour, carry out the modification of 6-semicarbazides pyrimidine function monomer;
(3) by the nanoparticulate dispersed of gained access function monomer in step (2) in acetonitrile, and add melamine conductTemplate molecule, methacrylic acid, initator and crosslinking agent, carry out polymerisation according to two step temperature-raising methods: first at 50 DEG C～55 DEG CReact 3～6 hours, then 60 DEG C～70 DEG C reactions 18～24 hours, and at 85 DEG C～90 DEG C aging 6～8 hours, melamine obtainedAmine three hydrogen bond molecular engram core-shell nano particles; (4) prepare reduced form graphene oxide;
(5) by the DMF solution of the aqueous suspension of reduced form Graphene and ionic liquid 1-butyl-3-methyl imidazolium tetrafluoroborateBe mixed and made into dressing agent, get this dressing agent and drip and be coated onto glass-carbon electrode surface to uniform fold and modify and be dried;
(6) get the DMF suspension of the melamine three hydrogen bond molecular engram core-shell nano particles that step (3) makes, drip and be coated ontoThe electrode surface that step (5) obtains is to uniform fold, dry.
2. the preparation method of a kind of many hydrogen bonds electrochemical sensor according to claim 1, is characterized in that, step (1) instituteThe silester of stating and the volume ratio of ethanol are 5-6:4-5, and the mol ratio of ammoniacal liquor and water is 0.5～2:3～10, TEOS and ammoniacal liquorRatio is 5～6:0.5～2.
3. the preparation method of a kind of many hydrogen bonds electrochemical sensor according to claim 1, is characterized in that, in step (2)SiO2The usage ratio of nano particle and toluene is 0.3:50, g:mL; SiO2Nano particle and 3-aminopropyl triethoxysilane, pentaThe usage ratio of dialdehyde, 6-semicarbazides pyrimidine is 0.1～0.3:4.0～7.0:0.5～1.0:0.168, g:mL:mL:g.
4. the preparation method of a kind of many hydrogen bonds electrochemical sensor according to claim 1, is characterized in that, in step (3)The usage ratio of the nano particle of access function monomer and acetonitrile, melamine, methacrylic acid, initator and crosslinking agent is0.1～0.5:50～100:10～30:0.2～0.4:10～20:1.0～3.5，g:mL:mg:mL:mg:mL。
5. the preparation method of a kind of many hydrogen bonds electrochemical sensor according to claim 1, is characterized in that, step (3) instituteThe initator of stating is azodiisobutyronitrile, and described crosslinking agent is ethylene glycol dimethacrylate.
6. the preparation method of a kind of many hydrogen bonds electrochemical sensor according to claim 1, is characterized in that, step (5)Aqueous suspension concentration range 0.5～1.0 mg/ml of described reduced form graphene oxide, the dimethyl formamide of ionic liquidDMF solution concentration scope 2.0～5.0 microlitre/milliliters; The aqueous suspension of reduced form graphene oxide and the dimethyl of ionic liquidFormamide DMF liquor capacity is than being 1:1.
7. the preparation method of a kind of many hydrogen bonds electrochemical sensor according to claim 1, is characterized in that, step (6)The concentration range of the DMF suspension of middle melamine three hydrogen bond molecular engram core-shell nano particles is 2～3 mg/ml.
8. many hydrogen bonds electrochemical sensor that the method described in claim 1-7 any one makes.
9. many hydrogen bonds electrochemical sensor claimed in claim 8 is the application in melamine in detection food samples.
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| EP2426487A1 (en) * | 2010-09-03 | 2012-03-07 | The Provost Fellows And Scholars Of The College Of The Holy and Undivided Trinity Of Queen Elizabeth Near Dublin | Nano-carbon sensor and method of making a sensor |
| WO2012028825A1 (en) * | 2010-09-01 | 2012-03-08 | Universite Paris Diderot-Paris 7 | Ultra-thin films of molecularly imprinted polymers confined to the surface of a substrate |
| CN103698373A (en) * | 2013-12-23 | 2014-04-02 | 济南大学 | Preparation method of molecular-imprinting electrochemical sensor for detecting 2,6-butylated hydroxytoluene and application thereof |
| CN103868966A (en) * | 2014-03-21 | 2014-06-18 | 上海出入境检验检疫局工业品与原材料检测技术中心 | Molecularly-imprinted polymer-graphene composite material modified electrode as well as preparation method and application thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012028825A1 (en) * | 2010-09-01 | 2012-03-08 | Universite Paris Diderot-Paris 7 | Ultra-thin films of molecularly imprinted polymers confined to the surface of a substrate |
| EP2426487A1 (en) * | 2010-09-03 | 2012-03-07 | The Provost Fellows And Scholars Of The College Of The Holy and Undivided Trinity Of Queen Elizabeth Near Dublin | Nano-carbon sensor and method of making a sensor |
| CN103698373A (en) * | 2013-12-23 | 2014-04-02 | 济南大学 | Preparation method of molecular-imprinting electrochemical sensor for detecting 2,6-butylated hydroxytoluene and application thereof |
| CN103868966A (en) * | 2014-03-21 | 2014-06-18 | 上海出入境检验检疫局工业品与原材料检测技术中心 | Molecularly-imprinted polymer-graphene composite material modified electrode as well as preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| Electrochemical determination of methyl parathion using a molecularly imprinted polymer–ionic liquid–graphene composite film coated electrode;Lijuan Zhao 等;《Sensors and Actuators B》;20121011;第818-824页 * |
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