CN107807160A - A kind of 3 MCPD of detection molecular engram transducer production method - Google Patents
A kind of 3 MCPD of detection molecular engram transducer production method Download PDFInfo
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- CN107807160A CN107807160A CN201710813166.9A CN201710813166A CN107807160A CN 107807160 A CN107807160 A CN 107807160A CN 201710813166 A CN201710813166 A CN 201710813166A CN 107807160 A CN107807160 A CN 107807160A
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Abstract
A kind of 3 MCPD of detection provided by the invention molecular engram transducer production method, including：Using 3 MCPD as template molecule, hybrid material is obtained using sol-gal process based on carbon-based core-shell structured nanomaterials, synthesizes to obtain polymer with reference to acrylic ester cross-linking agent and azo-initiator；The glassy carbon electrode surface to after handling is modified after the polymer is removed into 3 MCPD using spin-coating method, obtains molecular engram sensor.The present invention is by using surface molecule print technology, imprinted polymer material is prepared based on 3 MCPD and carbon-based core-shell structured nanomaterials, its imprinted sites is located at the top layer of carbon-based core-shell structured nanomaterials, improve the identification response speed of target molecule, reduce non-specific adsorption, there is the selectivity of height to identification target molecule simultaneously, and the molecular engram sensor has Stability Analysis of Structures, high mechanical strength, easily obtains the advantages of certain physical property, cost are low and reusable.
Description
Technical field
The present invention relates to molecular engram sensor technical field, is printed more particularly, to the molecule of detection 3-MCPD a kind of
Mark transducer production method.
Background technology
Chloropropyl alcohol be glycerine hydroxyl by chlorine substitute caused by a kind of compound, its molecular formula is：CH3CH(OH)
CH2Cl, including monochloro propane diols：3- chlorine-1,2-propylene glycols (abbreviation 3- chloropropyl alcohols, 3-MCPD), the chloro- 1,3-PD (2- of 2-
MCPD)；Double chloropropyl alcohols：1,3- bis- chloro- 2- propyl alcohol (1,3-DCP), 2,3- bis- trimethylewne chlorohydrin 3-s (2,3-DCP).In chloropropyl alcohol series
In compound, the main component of contaminated food products is 3-MCPD, and submember is 1,3-DCP, and the content ratio of the two is 20: 1.3-
MCPD be water white transparency liquid, water-soluble, ethanol, ether.Relative molecular weight is 94.54, and relative density is 1.132, boiling
Point is 160-162 DEG C.
Chloropropyl alcohol is widely present in cereal, meat products, dairy products, bakery product, cooks food, curing food, edible oil, soup
In the numerous food such as material and drinking water.Because chloropropyl alcohol belongs to non-genotoxic carcinogenic substance, kidney body can be caused to increase than increase, renal tubule
Raw and denaturation, and sperm quantity can be reduced, weaken spermatozoon activity and survival rate, therefore by food additives joint specialist committee member
Meeting (JECFA) is classified as evaluation of priorities project.
Systems in Certain Developed Countries has also formulated 3- accordingly while Related product management intensity is increased in the world at present
MCPD's uses limit standard, but standard and disunity.U.S.'s food chemicals regulation ((FCC) regulation, sour hydrolyzing plant egg
3-MCPD content should be less than 1mg/kg in white, and 3-DCP is less than 0.05mg/kg；The baste of China's 21 mouthfuls of promulgations July in 2002
Provide that 3-MCPD contents are no more than 1mg/kg in the 8-2000 standards of SB 1033；Recently, European Food Science committee ((SCF)
Provided with FAO (Food and Agriculture Organization of the United Nation)/World Health Organization (JECFA), the free 3-MCPD that human body can be born daily is to greatest extent
The intake of 2 μ g/kg body weights.3-MCPD problems just cause the attention of various countries science personage recent years in polished fat,
Limitation for 3-MCPD contents in polished fat does not refer to also at present.
Although 3-MCPD chemical constitution is relatively easy, due to the missing of chromophore, higher boiling and low molecule amount
These features so that sensitive analysis is carried out to it becomes difficult, is not suitable for using the fluoroscopic examination of high performance liquid chromatography one or ultraviolet
Detection method.At present, 3-MCPD detection method mainly have gas-chromatography (GC) analytic approach, gas chromatography-mass spectrography (GC-MS),
Gas chromatography tandem mass spectrometry method (GC-MS-MS), capillary electrophoresis technique (HPCE).But these traditional detection techniques need
Complicated sample pre-treatments and derivatization, during operating cost, cost is high, background noise is big, reduces sensitivity and the standard of detection
Exactness.Therefore, a kind of quick, sensitive new detecting method of foundation is needed badly.
The content of the invention
The present invention provides the molecule print of detection 3-MCPD for overcoming above mentioned problem or partly solving the above problems a kind of
Mark transducer production method.
According to a kind of detection 3-MCPD molecular engram transducer production method provided by the invention, including：With 3-MCPD
For template molecule, hybrid material is obtained using sol-gel process based on carbon-based core-shell structured nanomaterials, with reference to esters of acrylic acid
Crosslinking agent and azo-initiator synthesize to obtain polymer；Modification is extremely located after the polymer is removed into 3-MCPD using spin-coating method
Glassy carbon electrode surface after reason, obtain molecular engram sensor.
Wherein, the principle of molecular imprinting technology is：Can shape when template molecule (microsphere) contacts with polymer monomer
Into multiple action point, it will be memorized by this effect of polymerization process, after template molecule removes, with regard to shape in polymer
Into the hole with multiple action point to match with template molecule steric configuration, such hole will to template molecule and its
Analog has selection evident characteristics.
Wherein, the advantages that carbon-based core-shell structured nanomaterials are due to carbon material preferably acidproof, corrosion resistance and electric conductivity,
It can protect nuclear particle that physical and chemical changes do not occur when it is as shell, and prevent nuclear particle from continuing to grow up and reuniting
Deng, or even the excellent properties of carbon-coating can also be given to wrapped particle.And stratum nucleare can with monodisperse particles, nano wire,
The metal of the shape such as nanometer sheet and aggregate, metal oxide, metal salt etc..
Specifically, hybrid material is obtained based on carbon-based core-shell structured nanomaterials using sol-gel process, for example, this is miscellaneous
Change material is the carbon-based core-shell structured nanomaterials of silica.Then using the hybrid material as molecular engram carrier, with 3-MCPD
For template molecule, with reference to acrylic ester cross-linking agent and azo-initiator, polymer is obtained.The mould in the polymer is removed again
Plate molecule, that is, the 3-MCPD molecules in the polymer are removed, obtain molecularly imprinted polymer.Spin-coating method is finally used by the molecule
Imprinted polymer is modified to the glassy carbon electrode surface through processing, you can obtains molecular engram sensor.
In embodiments of the present invention, by using surface molecule print technology, received based on 3-MCPD and carbon-based core shell structure
Rice material prepares imprinted polymer material, and its imprinted sites is located at the top layer of carbon-based core-shell structured nanomaterials, improves target
The identification response speed of molecule, non-specific adsorption is reduced, while there is the selectivity of height to identification target molecule, and this point
Sub- trace sensor has Stability Analysis of Structures, high mechanical strength, and it is low and reusable easily to obtain certain physical property, cost
Advantage.
It is described to be obtained based on carbon-based core-shell structured nanomaterials using sol-gel process on the basis of above-described embodiment
The step of hybrid material, includes：The carbon-based core-shell structured nanomaterials are added in ethanol solution, ultrasound makes the ethanol molten
Liquid disperses；Ethanol solution after being dispersed with stirring, and phenmethylol and ammoniacal liquor are sequentially added, obtain carbon-based core-shell structured nanomaterials
Suspension；Tetraethoxysilane and ethanol are added dropwise in the suspension, the hydridization is obtained with alcohol flushing after stirring
Material.
Specifically, first, will when being based on carbon-based core-shell structured nanomaterials acquisition hybrid material using sol-gel process
A certain amount of carbon-based core-shell structured nanomaterials are added in ethanol solution, for example, adding 200.0mg's in 50mL ethanol solutions
Carbon-based core-shell structured nanomaterials, ultrasonic 30min make it that adding the ethanol solution for having carbon-based core-shell structured nanomaterials disperses.So
Afterwards, while the ethanol solution after disperseing is stirred, phenmethylol and ammoniacal liquor are sequentially added, for example, adding 10.0mL benzene first
The ammoniacal liquor that alcohol and addition mass fraction are 25%, you can obtain the suspension of carbon-based core-shell structured nanomaterials.It is carbon-based at this again
Tetraethoxysilane and ethanol is added dropwise in the suspension of core-shell structured nanomaterials, for example, adding 5.0mL tetraethoxy
The ethanol of silane and 5.0mL, and after stirring 12h, with alcohol flushing, the suspension can obtain hybrid material.
On the basis of the various embodiments described above, described synthesis the step of obtaining polymer, includes：The hybrid material is added
In the aminopropyl triethoxysilane and toluene that enter predetermined amount, and the condensing reflux preset time at 80 DEG C；With absolute ethyl alcohol pair
The hybrid material carries out centrifugation, obtains amino silane modified hybrid material；Based on the amino silane modified hydridization material
Material, 3-MCPD, acrylic ester cross-linking agent and azo-initiator, obtain the polymer.
Specifically, using hybrid material as molecular engram carrier, using 3-MCPD as template molecule, handed over reference to esters of acrylic acid
When connection agent and azo-initiator obtain polymer, first, 100mg hybrid materials are added into a certain amount of aminopropyl-triethoxy
Silane and toluene, for example, adding 0.5mL aminopropyl triethoxysilane and 48.0mL toluene, then condensed at 80 DEG C
Backflow a period of time, for example, condensing reflux 20h.Centrifugation is carried out to the hybrid material with absolute ethyl alcohol again, obtains amino silicone
Alkane is modified hybrid material, using the amino silane modified hybrid material as molecular engram carrier, using 3-MCPD as template molecule, with reference to
Acrylic ester cross-linking agent and azo-initiator, obtain polymer.
For example, in the 50mL ethanol solutions containing 1mmol/L 3-MCPD, it is amino silane modified to add 80.0mg
Hybrid material, magnetic agitation 30min carry out prepolymerization, add 950 μ L acrylic ester cross-linking agents and 20.0mg azos
Class initiator, flask mouth is sealed after being passed through nitrogen 15min, 24h is reacted under 120 DEG C of oil baths, obtains polymer.It is poly- that this is removed again
3-MCPD molecules in compound, obtain molecularly imprinted polymer.Finally using spin-coating method by the molecularly imprinted polymer modify to
Glassy carbon electrode surface through processing, you can obtain molecular engram sensor.
In embodiments of the present invention, the polymer obtained based on amino silane modified hybrid material, the molecular engram of acquisition
Sensor, there is more preferable molecular recognition performance, can quickly identify 3-MCPD.
On the basis of the various embodiments described above, the step of polymer removal 3-MCPD, is included：By the polymer
With methanol-acetic acid (volume ratio 9:1) mixed solvent carries out surname extraction, to remove 3-MCPD.
On the basis of the various embodiments described above, the processing step of the glass-carbon electrode is included：With 0.3 μm of alumina powder
After polishing the glassy carbon electrode surface, and it is cleaned by ultrasonic the glass-carbon electrode three times with deionized water repetition, and ultrasound is clear every time
The time washed is 2-3 minutes；Successively with absolute ethyl alcohol, HNO3The glass-carbon electrode is cleaned by ultrasonic again with distilled water,
And the ultrasonic cleaning time is 2-3 minutes；The glassy carbon electrode surface is polished with 0.05 μm of alumina powder again, and to glass carbon electricity
The current-responsive that pole is activated to be stablized.
Specifically, when handling glass-carbon electrode, first, after polishing the glassy carbon electrode surface with 0.3 μm of alumina powder,
It is cleaned by ultrasonic three times with deionized water, i.e. ultrasonic water bath, each 2-3 minutes.Again successively with 1：1 absolute ethyl alcohol, 1:1HNO3With
Distilled water is cleaned by ultrasonic, and finally polishes the glassy carbon electrode surface with 0.05 μm of alumina powder.Then glass-carbon electrode is existed
0.5-1mol/LH2SO4Activated with cyclic voltammetry in solution, be repeatedly scanned with -1.0V-1.0V potential ranges, until reaching
Untill stable cyclic voltammogram.Again 2.5mmol L potassium ferricyanide electrolyte in, in 0.2V-0.6V potential ranges, with
100mv/s speed carries out cyclic voltammetry scanning, and the spike potential difference in cyclic voltammogram is in below 80mV, and close to 65mV
When, the glass-carbon electrode can use.
In embodiments of the present invention, by the processing to glass-carbon electrode, activate and make its stable performance so that molecule is printed
Mark it is polymer-modified to the glass-carbon electrode when, obtained molecular engram sensor relatively rapid can identify 3-MCPD molecules.
On the basis of the various embodiments described above, the glass-carbon electrode to after handling is modified after the polymer is removed into 3-MCPD
The step of surface, includes：After the polymer is removed into 3-MCPD, molecularly imprinted polymer is obtained after drying 12h at 65 DEG C；
The molecularly imprinted polymer is added in chitosan solution, the chitosan solution ultrasonic mixing uniformly applied afterwards described in dropping to
Glassy carbon electrode surface after processing, obtain molecular engram sensor.
Specifically, when molecularly imprinted polymer modifies the glassy carbon electrode surface to processing, first, gone by polymer
After 3-MCPD, it is that can obtain molecularly imprinted polymer that 12h is dried at 65 DEG C.Then, 20.0mg molecular engram is polymerize
Thing is added in 1mL0.5% chitosan solution, and ultrasonic mixing is uniform, takes the mixed solution 5.0 μ L to apply the naked glass for dropping to and handling well
Carbon electrodes, dry can obtain molecular engram sensor at room temperature.The molecular engram sensor is placed in the anhydrous of 10mL
In ethanol polymeric solution, the absolute ethyl alcohol polymeric solution contain 0.1mmol/L to coloured glaze base aniline (p-ATP), 0.05mmol/L
3-MCPD and 50mmol/L tetrabutylammonium perchlorate (TBAP).Stirring and adsorbing 7min, glass-carbon electrode is rinsed with water, by glass carbon
Electrode is placed in blank phosphate buffer (PBS, 0.1mol/L), carries out cyclic voltammetry (CV) and differential pulse voltammetry
(DPV) detect.
On the basis of the various embodiments described above, the mass ratio of the carbon-based core-shell structured nanomaterials and the phenmethylol is
(0.16-0.24)：(8.4-12.4)；Suspension, the tetraethoxysilane and the institute of the carbon-based core-shell structured nanomaterials
The volume ratio for stating ethanol is (48-72)：(4-6)：(4-6).The volume ratio of the aminopropyl triethoxysilane and the toluene
For (0.4-0.6)：(40-60)；The mass ratio of the amino silane modified hybrid material and the azo-initiator is (64-
96)：(16-24).
On the basis of the various embodiments described above, the acrylic ester cross-linking agent include diacrylate -1,4- butanediol esters,
GDMA and butyl acrylate；The azo-initiator includes two different heptan of azodiisobutyronitrile and azo
Nitrile.
Second aspect, the present invention provide a kind of application method of detection 3-MCPD molecular engram sensor, including：It is to be measured
Sample drop is in the glassy carbon electrode surface of molecular engram sensor, stirring and adsorbing 7min at room temperature；By the molecular engram sensor
It is placed in electrolytic cell, electrolytic cell detects the 2.5mmol/L [Fe (CN) that bottom liquid is the KCl containing 0.1mol/L6]3-/4-Solution；Setting
Sweep parameter, carry out cyclic voltammetry and differential pulse voltammetry detection.
Specifically, the molecular engram obtained using above-mentioned detection 3-MCPD molecular engram transducer production method is sensed
Device, the molecular engram sensor is placed in the sample to be tested solution containing 3-MCPD, for example, molecular engram sensor is placed in
In 10mL absolute ethyl alcohol polymeric solution, the absolute ethyl alcohol polymeric solution contain 0.1mmol/L to coloured glaze base aniline (p-ATP),
0.05mmol/L 3-MCPD and 50mmol/L tetrabutylammonium perchlorate (TBAP).Stirring and adsorbing 7min, glass carbon is rinsed with water
Electrode, glass-carbon electrode is placed in the 2.5mmol/L [Fe (CN) of the KCl containing 0.1mol/L6]3-Solution or [Fe (CN)6]4-Solution
Electrolytic cell in, carry out cyclic voltammetry (CV) and differential pulse voltammetry (DPV) detect, you can detect in the sample to be tested
Contain 3-MCPD.
A kind of detection 3-MCPD provided by the invention molecular engram transducer production method, prints by using surface molecular
Mark technology, imprinted polymer material is prepared based on 3-MCPD and carbon-based core-shell structured nanomaterials, its imprinted sites is positioned at carbon-based
The top layer of core-shell structured nanomaterials, improve the identification response speed of target molecule, reduce non-specific adsorption, while to knowing
Other target molecule has the selectivity of height, and the molecular engram sensor has Stability Analysis of Structures, high mechanical strength, easily obtains one
Fixed physical property, the advantages of cost is low and reusable.
Embodiment
, below will be in the embodiment of the present invention to make the purpose, technical scheme and advantage of the embodiment of the present invention clearer
Technical scheme be explicitly described, it is clear that described embodiment is part of the embodiment of the present invention, rather than whole
Embodiment.Based on the embodiment in the present invention, those of ordinary skill in the art are obtained under the premise of creative work is not made
The every other embodiment obtained, belongs to the scope of protection of the invention.
In recent years, the international trade dispute as caused by chloropropyl alcohol class Substances Pollution takes place frequently, and European Union detects China within 1999
Chloropropyl alcohol content overproof in soy sauce is exported, so that China's Some Enterprises product is prohibited import, causes huge economic damage
Lose, and then cause the attention of domestic hygienist.
Embodiment 1
The preparation of hybrid material：First, 200.0mg carbon-based nuclear shell structure nano material is added in 50mL ethanol solutions
Material, ultrasonic 30min make it that adding the ethanol solution for having carbon-based core-shell structured nanomaterials disperses.Then, after stirring this and disperseing
Ethanol solution while, sequentially add 10.0mL phenmethylol and add mass fraction be 25% ammoniacal liquor, you can obtain carbon
The suspension of base core-shell structured nanomaterials.5.0mL is added dropwise in the suspension of the carbon-based core-shell structured nanomaterials again
Tetraethoxysilane and 5.0mL ethanol, and after stirring 12h, with alcohol flushing, the suspension can obtain hybrid material.
The preparation of polymer：80mg hybrid materials are added to 0.5mL aminopropyl triethoxysilane and 48.0mL first
Benzene, then the condensing reflux 20h at 80 DEG C.Centrifugation is carried out to the hybrid material with absolute ethyl alcohol again, obtains amino silane
Modified hybrid material.In the 50mL ethanol solutions containing 1mmol/L 3-MCPD, it is amino silane modified to add 80.0mg
Hybrid material, magnetic agitation 30min carry out prepolymerization, add 942.9 μ L acrylic ester cross-linking agents and 20.0mg is even
Nitrogen class initiator, flask mouth is sealed after being passed through nitrogen 15min, 24h is reacted under 120 DEG C of oil baths, obtains polymer.This is polymerize
Thing methanol-acetic acid (volume ratio 9:1) mixed solvent carries out surname extraction, to remove 3-MCPD.
The preparation of molecular engram sensor：After polymer is removed into 3-MCPD, it is to be divided that 12h is dried at 65 DEG C
Sub- imprinted polymer.Then, 20.0mg molecularly imprinted polymer is added in 1mL0.5% chitosan solution, ultrasonic mixing
Uniformly, take the mixed solution 5.0 μ L to apply the bare glassy carbon electrode surface for dropping to and handling well, dry can obtain molecular engram at room temperature
Sensor.
In addition to template molecule 3-MCPD is not added with, using identical method and steps, non-molecular engram sensor is made.
Molecular engram sensor and non-molecular engram sensor are respectively placed in 10mL absolute ethyl alcohol polymeric solution, should
Absolute ethyl alcohol polymeric solution contain 0.1mmol/L to coloured glaze base aniline (p-ATP), 0.05mmol/L 3-MCPD and 50mmol/L
Tetrabutylammonium perchlorate (TBAP).Stirring and adsorbing 7min, glass-carbon electrode is rinsed with water, glass-carbon electrode is placed in containing 0.1mol/L
KCl 2.5mmol/L [Fe (CN)6]3-In the electrolytic cell of solution, cyclic voltammetry (CV) and differential pulse voltammetry are carried out
(DPV) detect.
Draw using the current-responsive of molecular engram sensor be using non-molecular engram sensor current-responsive 3
Times, therefore, by the curent change for observing molecular engram sensor, you can detect to whether there is 3-MCPD in sample to be tested.
And the molecular engram sensor in the embodiment of the present invention detects that the accuracy containing 3-MCPD is 95% in sample to be tested.
Embodiment 2
The embodiment of the present invention differs only in embodiment 1, when preparing hybrid material, carbon-based core-shell structured nanomaterials
Dosage be 150mg, the dosage of phenmethylol is 8.5mL, the dosage of tetraethoxysilane is 4.5mL and the dosage of ethanol is
4.5m L.When preparing polymer, the dosage of hybrid material is 90mg, the dosage of aminopropyl triethoxysilane is 0.4mL, toluene
Dosage be 42.0mL, the dosage of azo-initiator be 15.0mg.Obtained molecular engram sensor detection 3-MCPD is just
True rate is 97%.
Embodiment 3
The embodiment of the present invention differs only in embodiment 1, when preparing hybrid material, carbon-based core-shell structured nanomaterials
Dosage be 220mg, the dosage of phenmethylol is 12.0mL, the dosage of tetraethoxysilane is 5.5mL and the dosage of ethanol is
5.5m L.When preparing polymer, the dosage of hybrid material is 70mg, the dosage of aminopropyl triethoxysilane is 0.6mL, toluene
Dosage be 58.0mL, the dosage of azo-initiator be 22.0mg.The correct of molecular engram sensor detection 3-MCPD is made
Rate is 92%.
Comparative example 1
The embodiment of the present invention is distinguished as with embodiment 1, when prepared by hybrid material, takes 300.0mg CNTs to be scattered in
In 48.0mL H20, at 40 DEG C after ultrasonic 10min, 3h is stirred, obtains solution A；5.0mL tetraethoxysilanes are taken to be scattered in 50.0mL
In ethanol, 3h is stirred, obtains solution B.Magnetic agitation 10min after solution A is mixed with B, obtained after being dried in vacuo 12h at 65 DEG C
The CNT (CNTs/SiO2) of coated with silica.120.0mg CNTs/SiO2 are dispersed in 50.0mL dry toluenes,
Then 10.0mLMAPS is added, and the 12h that flowed back at 120 DEG C, after product is washed with toluene, vacuum drying 12h is obtained at 65 DEG C
To hybrid material.Obtained molecular engram sensor detection 3-MCPD accuracy is 80%.
Comparative example 2
The embodiment of the present invention is distinguished as with embodiment 1, and when preparing polymer, the dosage of hybrid material is 120mg, ammonia third
The dosage of ethyl triethoxy silicane alkane is 0.3mL, the dosage of azo-initiator is 35mg.Molecular engram sensor detection 3- is made
MCPD accuracy is 75%.
Finally it should be noted that：The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
The present invention is described in detail with reference to the foregoing embodiments, it will be understood by those within the art that：It still may be used
To be modified to the technical scheme described in foregoing embodiments, or equivalent substitution is carried out to which part technical characteristic；
And these modification or replace, do not make appropriate technical solution essence depart from various embodiments of the present invention technical scheme spirit and
Scope.
Claims (10)
- A kind of 1. detection 3-MCPD molecular engram transducer production method, it is characterised in that including：Using 3-MCPD as template molecule, hybrid material, knot are obtained using sol-gel process based on carbon-based core-shell structured nanomaterials Close acrylic ester cross-linking agent and azo-initiator synthesizes to obtain polymer；The glassy carbon electrode surface to after handling is modified after the polymer is removed into 3-MCPD using spin-coating method, obtains molecular engram Sensor.
- 2. detection 3-MCPD according to claim 1 molecular engram transducer production method, it is characterised in that the base Include the step of carbon-based core-shell structured nanomaterials obtain hybrid material using sol-gel process：The carbon-based core-shell structured nanomaterials are added in ethanol solution, ultrasound disperses the ethanol solution；Ethanol solution after being dispersed with stirring, and phenmethylol and ammoniacal liquor are sequentially added, obtain the outstanding of carbon-based core-shell structured nanomaterials Turbid；Tetraethoxysilane and ethanol are added dropwise in the suspension of the carbon-based core-shell structured nanomaterials, second is used after stirring Alcohol rinses to obtain the hybrid material.
- 3. detection 3-MCPD according to claim 1 molecular engram transducer production method, it is characterised in that the conjunction Into including the step of obtaining polymer：In the aminopropyl triethoxysilane and toluene that the hybrid material adds predetermined amount, and condensing reflux is pre- at 80 DEG C If the time；Centrifugation is carried out to the hybrid material with absolute ethyl alcohol, obtains amino silane modified hybrid material；Based on the amino silane modified hybrid material, the 3-MCPD, the acrylic ester cross-linking agent and the azo Initiator, obtain the polymer.
- 4. detection 3-MCPD according to claim 1 molecular engram transducer production method, it is characterised in that by described in The step of polymer removal 3-MCPD, includes：By polymer methanol-acetic acid (volume ratio 9:1) mixed solvent carries out surname extraction, to remove 3-MCPD.
- 5. the molecular engram transducer production method of the detection 3-MCPD according to claim any one of 1-4, its feature exist In including to the processing step of the glass-carbon electrode：After polishing the glassy carbon electrode surface with 0.3 μm of alumina powder, and it is cleaned by ultrasonic the glass carbon with deionized water repetition Three times, and the time being cleaned by ultrasonic every time is 2-3 minutes to electrode；Successively with absolute ethyl alcohol, HNO3The glass-carbon electrode is cleaned by ultrasonic again with distilled water, and the ultrasonic cleaning time is 2-3 minutes；The glassy carbon electrode surface is polished with 0.05 μm of alumina powder again, and glass-carbon electrode is activated to obtain stabilization Current-responsive.
- 6. detection 3-MCPD according to claim 5 molecular engram transducer production method, it is characterised in that by described in The step of modifying the glassy carbon electrode surface to after handling after polymer removal 3-MCPD includes：After the polymer is removed into 3-MCPD, molecularly imprinted polymer is obtained after drying 12h at 65 DEG C；The molecularly imprinted polymer is added in chitosan solution, the chitosan solution ultrasonic mixing is uniformly applied afterwards and dropped to Glassy carbon electrode surface after the processing, obtain molecular engram sensor.
- 7. detection 3-MCPD according to claim 2 molecular engram transducer production method, it is characterised in that the carbon The mass ratio of base core-shell structured nanomaterials and the phenmethylol is (0.16-0.24)：(8.4-12.4)；The volume ratio of the suspensions of the carbon-based core-shell structured nanomaterials, the tetraethoxysilane and the ethanol is (48- 72)：(4-6)：(4-6).
- 8. detection 3-MCPD according to claim 3 molecular engram transducer production method, it is characterised in that the ammonia The volume ratio of propyl-triethoxysilicane and the toluene is (0.4-0.6)：(40-60)；The mass ratio of the amino silane modified hybrid material and the azo-initiator is (64-96)：(16-24).
- 9. the molecular engram transducer production method of the detection 3-MCPD according to claim any one of 6-8, its feature exist In the acrylic ester cross-linking agent includes diacrylate -1,4- butanediol esters, GDMA and acrylic acid Butyl ester；The azo-initiator includes azodiisobutyronitrile and ABVN.
- A kind of 10. application method of detection 3-MCPD molecular engram sensor, it is characterised in that including：Molecular engram sensor is placed in the sample to be tested solution containing 3-MCPD, at room temperature stirring and adsorbing 7min；The molecular engram sensor is placed in electrolytic cell, the detection bottom liquid of electrolytic cell is the KCl's containing 0.1mol/L 2.5mmol/L[Fe(CN)6]3-/4-Solution；Sweep parameter is set, carries out cyclic voltammetry and differential pulse voltammetry detection.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107894453A (en) * | 2017-10-25 | 2018-04-10 | 中国农业大学 | A kind of preparation method of molecular engram sensor |
| CN112697867A (en) * | 2020-12-24 | 2021-04-23 | 东北师范大学 | General detection method for amphetamine drugs based on artificial molecule recognition system |
| CN115097022A (en) * | 2022-05-30 | 2022-09-23 | 浙江万盛股份有限公司 | Method for measuring content of impurities in process of preparing dichloropropanol by glycerol method |
| CN115184422A (en) * | 2022-06-22 | 2022-10-14 | 天津科技大学 | Preparation method of molecular imprinting sensor for detecting DBP |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013250186A (en) * | 2012-06-01 | 2013-12-12 | Fuji Oil Co Ltd | Method for separating or measuring 3-mono chloropropane-1,2-diol fatty acid esters in edible oil and fat using supercritical fluid chromatography |
| CN103785476A (en) * | 2014-01-15 | 2014-05-14 | 江苏大学 | Preparation method of surface imprinting CdS compound photocatalyst based on magnetic carbon material |
| KR20150107006A (en) * | 2014-03-12 | 2015-09-23 | 광운대학교 산학협력단 | Composite of creatinine molecular imprinted polymer and biosensor using the same |
-
2017
- 2017-09-11 CN CN201710813166.9A patent/CN107807160B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013250186A (en) * | 2012-06-01 | 2013-12-12 | Fuji Oil Co Ltd | Method for separating or measuring 3-mono chloropropane-1,2-diol fatty acid esters in edible oil and fat using supercritical fluid chromatography |
| CN103785476A (en) * | 2014-01-15 | 2014-05-14 | 江苏大学 | Preparation method of surface imprinting CdS compound photocatalyst based on magnetic carbon material |
| KR20150107006A (en) * | 2014-03-12 | 2015-09-23 | 광운대학교 산학협력단 | Composite of creatinine molecular imprinted polymer and biosensor using the same |
Non-Patent Citations (4)
| Title |
|---|
| LI YUN等: "Identification of 3-chloro-1,2-propandiol using molecularly imprinted composite solid-phase extraction materials", 《ANALYTICAL AND BIOANALYTICAL CHEMISTRY》 * |
| SUN XIULAN等: "Development and application of 3-chloro-1,2-propandiol electrochemical sensor based on a polyaminothiophenol modified molecularly imprinted film", 《JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY》 * |
| ZHANG CHUNJING等: "A highly selective photoelectrochemical biosensor for uric acid based on core-shell Fe3O4@C nanoparticle and molecularly imprinted TiO2", 《BIOSENSORS AND BIOELECTRONICS》 * |
| 唐婷等: "碳纳米管/二氧化硅的表面分子印迹聚合物制备及其在芦丁电化学检测方面的应用", 《分析测试学报》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107894453A (en) * | 2017-10-25 | 2018-04-10 | 中国农业大学 | A kind of preparation method of molecular engram sensor |
| CN107894453B (en) * | 2017-10-25 | 2020-04-28 | 中国农业大学 | Preparation method of molecular imprinting sensor |
| CN112697867A (en) * | 2020-12-24 | 2021-04-23 | 东北师范大学 | General detection method for amphetamine drugs based on artificial molecule recognition system |
| CN115097022A (en) * | 2022-05-30 | 2022-09-23 | 浙江万盛股份有限公司 | Method for measuring content of impurities in process of preparing dichloropropanol by glycerol method |
| CN115184422A (en) * | 2022-06-22 | 2022-10-14 | 天津科技大学 | Preparation method of molecular imprinting sensor for detecting DBP |
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