CN114736331B - Preparation method of nanocellulose-stabilized Pickering emulsion olaquindox imprinting microsphere - Google Patents
Preparation method of nanocellulose-stabilized Pickering emulsion olaquindox imprinting microsphere Download PDFInfo
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- TURHTASYUMWZCC-UHFFFAOYSA-N Olaquindox [BAN:INN] Chemical compound C1=CC=C2N([O-])C(C)=C(C(=O)NCCO)[N+](=O)C2=C1 TURHTASYUMWZCC-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 229950010210 olaquindox Drugs 0.000 title claims abstract description 73
- 239000004005 microsphere Substances 0.000 title claims abstract description 58
- 239000000839 emulsion Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 23
- 229920001046 Nanocellulose Polymers 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 8
- 239000003999 initiator Substances 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 29
- 229920000642 polymer Polymers 0.000 claims description 16
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- 238000001291 vacuum drying Methods 0.000 claims description 12
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 10
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 10
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 10
- 239000003480 eluent Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000012719 thermal polymerization Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000010828 elution Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 28
- 238000001514 detection method Methods 0.000 abstract description 7
- 235000013305 food Nutrition 0.000 abstract description 7
- 229920002678 cellulose Polymers 0.000 abstract description 4
- 239000001913 cellulose Substances 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 30
- 239000003921 oil Substances 0.000 description 15
- 229960000583 acetic acid Drugs 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- 241001465754 Metazoa Species 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- -1 disodium hydrogen phosphate-ethyl acetate Chemical compound 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 241000238557 Decapoda Species 0.000 description 3
- 235000015278 beef Nutrition 0.000 description 3
- 235000013601 eggs Nutrition 0.000 description 3
- 239000002207 metabolite Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- BJPNADFNSANIPF-UHFFFAOYSA-N 3-methylquinoxaline-2-carboxylic acid Chemical compound C1=CC=C2N=C(C(O)=O)C(C)=NC2=C1 BJPNADFNSANIPF-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 239000004098 Tetracycline Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003640 drug residue Substances 0.000 description 1
- 238000000835 electrochemical detection Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001917 fluorescence detection Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000007952 growth promoter Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000000589 high-performance liquid chromatography-mass spectrometry Methods 0.000 description 1
- 239000003547 immunosorbent Substances 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000002470 solid-phase micro-extraction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229960002180 tetracycline Drugs 0.000 description 1
- 229930101283 tetracycline Natural products 0.000 description 1
- 235000019364 tetracycline Nutrition 0.000 description 1
- 150000003522 tetracyclines Chemical class 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28019—Spherical, ellipsoidal or cylindrical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/042—Elimination of an organic solid phase
- C08J2201/0424—Elimination of an organic solid phase containing halogen, nitrogen, sulphur or phosphorus atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2335/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
- C08J2335/02—Characterised by the use of homopolymers or copolymers of esters
Abstract
The invention relates to a preparation method of a nano-cellulose stable Pickering emulsion olaquindox imprinting microsphere, which aims to improve the adsorption rate and the recycling property of the existing olaquindox imprinting microsphere to a target object by improving the surface hole structure of the existing olaquindox imprinting microsphere. The method comprises the following steps: (1) Preparing deionized water with dispersed nanocellulose; (2) Preparing an oil phase in which template molecules, functional monomers, a cross-linking agent and an initiator are dissolved; (3) Emulsion is formed, and olaquindox imprinting Microsphere (MIP) is prepared. The olaquindox imprinting microsphere prepared by the invention has rich pore structures, has a high adsorption rate to a target object, is excellent in reusability, can meet the requirement of rapid detection of food safety, and has huge application potential.
Description
Technical Field
The invention belongs to the technical field of preparation of high molecular specificity adsorption materials, and particularly relates to a novel Pickering emulsion molecular imprinting polymerization method and a preparation method of nanocellulose-stabilized olaquindox imprinting microspheres based on the polymerization method.
Background
Olaquindox (OLA) is an antibacterial growth promoter, which not only can promote protein assimilation and increase feed conversion rate, so that animal growth is accelerated, but also has stronger antibacterial effect, and European countries can be used as feed additives for animal production as early as 20 th century 70. Recent researches show that the olaquindox drug has obvious accumulation toxicity, and long-term eating of food with the drug residue can cause cancer, teratogenesis or mutation. China prohibits the olaquindox drug from being used in the livestock and poultry production process in 2019.
Currently, the olaquindox detection method includes an enzyme-linked immunosorbent method, a high performance liquid chromatography, an electrochemical detection method, a fluorescence detection method, a high performance liquid chromatography-mass spectrometry method and the like. The complex food sample matrix has great influence on the sensitivity of the detection method, the accuracy and stability of the detection result, and the extraction, purification and enrichment of olaquindox and metabolites thereof in food are key sample pretreatment steps before detection. The sample pretreatment method comprises a solid phase extraction method, a matrix dispersion solid phase extraction method, a solid phase microextraction method and the like. The efficiency of the sample pretreatment method mainly depends on the adsorption performance of the adsorption material in the extraction device, and the adsorption material with the characteristics of good selectivity, high adsorption rate and the like is the basis for improving the analysis performance of the olaquindox residue detection method in food.
The molecular imprinting technology is a simple and effective method for synthesizing the high molecular adsorption material, and has the remarkable advantages of excellent selectivity, physical and chemical stability, reusability and the like. The Pickering emulsion imprinting polymerization method uses solid particles to replace an emulsifier as a stabilizer, so that the consumption of an organic solvent is reduced, and the damage to the environment is reduced. Compared with the traditional emulsion polymerization method, the polymer prepared by the Pickering emulsion imprinting polymerization method has more uniform particle size and better dispersibility. The prior art is to prepare a imprinted polymer by taking silicon dioxide as a solid stabilizer; and preparing the tetracycline imprinted microsphere by taking the biochar as a solid stabilizer. At present, a uniform microsphere structure is obtained by using a imprinted polymer with silicon dioxide, biochar and the like as a solid stabilizer, but the quantity and the structure of holes for preparing the imprinted microsphere still need to be improved, which influences the adsorption performance of the imprinted microsphere on a target object.
Disclosure of Invention
Object of the Invention
Aiming at the defects of small hole number, low adsorption rate and the like of a imprinting adsorption material synthesized by the existing Pickering emulsion polymerization molecular imprinting technology, the invention provides a preparation method of a Pickering emulsion olaquindox imprinting microsphere based on stable nanocellulose.
Technical proposal
The preparation method of the nanocellulose-stabilized Pickering emulsion olaquindox imprinting microsphere comprises the following preparation processes:
(1) Dispersing 1.5-3.0 mg of nano cellulose in 1mL of deionized water to obtain a water phase;
(2) Dissolving template molecule olaquindox, functional monomer methacrylic acid, cross-linking agent ethylene glycol dimethacrylate and initiator azodiisobutyronitrile into toluene to be used as an oil phase; the mol ratio of the olaquindox, the methacrylic acid and the ethylene glycol dimethacrylate is 1: 3-7: 6-9; the mass molar ratio of the azodiisobutyronitrile to the olaquindox is 35-45 mg:1mmoL;
(3) Adding the oil phase obtained in the step (2) into the water phase obtained in the step (1), and homogenizing in a homogenizer at 14000-16000 rpm to prepare the Pickering emulsion.
(4) Placing the Pickering emulsion prepared in the step (3) in a water bath kettle at 60-80 ℃ for thermal polymerization for 16-20 h, washing the polymer with deionized water for 3-4 times after the polymerization reaction is finished, vacuum drying the obtained polymer at 50 ℃, removing template molecules by using a methanol/acetic acid mixed solution as eluent through a Soxhlet extractor, and vacuum drying at 50 ℃ to obtain the olaquindox imprinting microsphere.
In the step (1), the length-diameter ratio of the nanocellulose is 18-19.
In the step (2), the molar mass volume ratio of the template molecule olaquindox to the pore-forming agent toluene is 1mmol:400 to 600 mu L.
In the step (3), the oil phase obtained in the step (2) is added into the water phase obtained in the step (1), and the volume ratio of the oil phase to the water phase is 1: 4-6.
The method is characterized in that: in the step (4), the volume ratio of methanol to acetic acid is 7-8: 2-3; the elution time is 72-80 h.
Advantages and effects
The preparation method of the nano-cellulose stable Pickering emulsion olaquindox imprinting microsphere mainly improves the pore structure and the number of the olaquindox imprinting microsphere surface, so that the target can be adsorbed rapidly, and the preparation method has the advantages of simple synthesis, low cost and high product yield; the adopted stabilizer nanocellulose has wide material selection range, and is green and has no environmental pollution; the olaquindox molecularly imprinted microsphere prepared by the method has large specific surface area, quick and stable adsorption, is suitable for being used as a filling material of a solid phase extraction column to be applied to sample pretreatment in a process of accurately and efficiently purifying and enriching olaquindox and metabolite residues thereof in animal-derived foods and feeds, and has a huge application prospect.
Drawings
FIG. 1 (a) is a olaquindox imprinting microsphere scanning electron microscope image, and (b) is a olaquindox non-imprinting microsphere scanning electron microscope image;
FIG. 2 is an isothermal adsorption curve of olaquindox blotting (MIP) and non-blotting microspheres (NIP) to olaquindox;
FIG. 3 is a graph showing the adsorption kinetics of olaquindox to olaquindox for both olaquindox-imprinted (MIP) and non-imprinted (NIP) microspheres;
FIG. 4 shows adsorption capacity of olaquindox-imprinted microspheres with different regeneration times.
Detailed Description
The invention is described in detail below with reference to the attached drawings:
the invention relates to a preparation method of a nano-cellulose stable Pickering emulsion olaquindox imprinted microsphere, which comprises the steps of dispersing nano-cellulose in deionized water to serve as a water phase, dissolving template molecule olaquindox, functional monomer methacrylic acid, cross-linking agent ethylene glycol dimethacrylate and initiator azodiisobutyronitrile in toluene to serve as an oil phase, homogenizing at a high speed to obtain stable emulsion, and then heating to prepare olaquindox imprinted polymer. In the invention, the nano cellulose is only used as an emulsion stabilizer and does not participate in polymerization reaction, and the nano cellulose can be eluted from the polymer along with the template molecules in the process of eluting the template molecules, so that the hole structure of the imprinting microsphere is increased, and the adsorption rate and stability of the imprinting microsphere to a target object are improved.
The invention relates to a preparation method of a nanocellulose-stabilized Pickering emulsion olaquindox imprinting microsphere, which comprises the following preparation steps:
(1) Dispersing 1.5-3.0 mg of nano cellulose in 1mL of deionized water to obtain a water phase;
(2) Dissolving template molecule olaquindox, functional monomer methacrylic acid, cross-linking agent ethylene glycol dimethacrylate and initiator azodiisobutyronitrile into toluene to be used as an oil phase; the mol ratio of the olaquindox, the methacrylic acid and the ethylene glycol dimethacrylate is 1: 3-7: 6-9; the mass molar ratio of the azodiisobutyronitrile to the olaquindox is 35-45 mg:1mmoL;
(3) Adding the oil phase obtained in the step (2) into the water phase obtained in the step (1), and homogenizing in a homogenizer at 14000-16000 rpm to prepare the Pickering emulsion.
(4) Placing the Pickering emulsion prepared in the step (3) in a water bath kettle at 60-80 ℃ for thermal polymerization for 16-20 h, washing the polymer with deionized water for 3-4 times after the polymerization reaction is finished, vacuum drying the obtained polymer at 50 ℃, removing template molecules by using a methanol/acetic acid mixed solution as eluent through a Soxhlet extractor, and vacuum drying at 50 ℃ to obtain the olaquindox imprinting microsphere.
In the step (1), the length-diameter ratio of the nanocellulose is 18-19.
In the step (2), the molar mass volume ratio of the template molecule olaquindox to the pore-forming agent toluene is 1mmol:400 to 600 mu L.
In the step (3), the oil phase obtained in the step (2) is added into the water phase obtained in the step (1), and the volume ratio of the oil phase to the water phase is 1: 4-6.
In the step (4), the volume ratio of the methanol to the acetic acid is 7-8: 2-3; the elution time is 72-80 h.
The invention will be further illustrated with reference to specific examples.
Example 1
The invention relates to a preparation method of a nanocellulose-stabilized Pickering emulsion olaquindox imprinting microsphere, which comprises the following preparation steps:
(1) Dispersing nanocellulose with the length-diameter ratio of 18 of 1.5 and mg in 1mL of deionized water to obtain a water phase;
(2) 1mmol of template molecule olaquindox, 3mmol of functional monomer methacrylic acid, 6mmol of cross-linking agent ethylene glycol dimethacrylate and 35 mg initiator azodiisobutyronitrile are dissolved in 400 mu L of toluene to be used as an oil phase;
(3) Adding 1mL of the oil phase obtained in the step (2) into the water phase obtained in the step (1) of 4 mL, and homogenizing in a homogenizer at 14000 rpm to prepare Pickering emulsion;
(4) Placing the pickering emulsion prepared in the step (3) in a water bath kettle at 60 ℃ for thermal polymerization of 16 h, washing the emulsion with deionized water for 3 times after the polymerization reaction is finished, and vacuum drying the obtained polymer at 50 ℃, wherein the volume ratio of methanol to acetic acid is 7: and 3, removing template molecules from the mixed solution serving as eluent by a Soxhlet extractor, and performing vacuum drying at 50 ℃ for 72 hours to obtain the olaquindox imprinting microsphere.
Example 2
The invention relates to a preparation method of a nanocellulose-stabilized Pickering emulsion olaquindox imprinting microsphere, which comprises the following preparation steps:
(1) Dispersing nanocellulose with the length-diameter ratio of 2.5 and mg of 18.5 in 1mL of deionized water to obtain a water phase;
(2) 1mmol of template molecule olaquindox, 4 mmol of functional monomer methacrylic acid, 8 mmol of cross-linking agent ethylene glycol dimethacrylate and 40mg initiator azodiisobutyronitrile are dissolved in 500 mu L of toluene to be used as an oil phase;
(3) Adding 1mL of the oil phase obtained in the step (2) into the water phase obtained in the step (1) of 5 mL, and homogenizing in a homogenizer at 15000 rpm to prepare Pickering emulsion;
(4) Placing the pickering emulsion prepared in the step (3) in a water bath kettle at 70 ℃ for thermal polymerization of 18 h, washing with deionized water for 3 times after the polymerization reaction is finished, vacuum drying the obtained polymer at 50 ℃, and then carrying out vacuum polymerization on the polymer at a methanol/acetic acid volume ratio of 7: and 3, removing template molecules from the mixed solution serving as eluent by a Soxhlet extractor, and performing vacuum drying at 50 ℃ for 78 hours to obtain the olaquindox imprinting microsphere.
Example 3
The invention relates to a preparation method of a nanocellulose-stabilized Pickering emulsion olaquindox imprinting microsphere, which comprises the following preparation steps:
(1) Dispersing nanocellulose with the length-diameter ratio of 3.0 mg being 19 in 1mL of deionized water to obtain a water phase;
(2) 1mmol of template molecule olaquindox, 7 mmol of functional monomer methacrylic acid, 9 mmol of cross-linking agent ethylene glycol dimethacrylate and 45mg initiator azodiisobutyronitrile are dissolved in 600 mu L of toluene to be used as an oil phase;
(3) Adding 1mL of the oil phase obtained in the step (2) into the water phase obtained in the step (1) of 6 mL, and homogenizing in a homogenizer at 16000 rpm to prepare Pickering emulsion;
(4) Placing the pickering emulsion prepared in the step (3) in a water bath kettle at 80 ℃ for thermal polymerization of 20 h, washing with deionized water for 3 times after the polymerization reaction is finished, vacuum drying the obtained polymer at 50 ℃, and then carrying out vacuum polymerization on the polymer at a methanol/acetic acid volume ratio of 8: and 2, removing template molecules from the mixed solution serving as eluent by a Soxhlet extractor, and performing vacuum drying at 50 ℃ for 80 hours to obtain the olaquindox imprinting microsphere.
As can be seen from FIG. 1, the surface of the olaquindox imprinting microsphere has rich hole structures, which is beneficial to improving the adsorption rate of the imprinting microsphere to the target.
The following example 4: preparation of non-imprinted microspheres (NIP): the conditions were the same as in example 1, but no olaquindox as a template molecule was added.
Example 4:
7mL of Olaquindox (OLA) solution with initial concentrations of 5mg/L,10mg/L,20mg/L,30mg/L,40mg/L,60mg/L,80mg/L,100mg/L,120mg/L and a 25 mL volumetric flask were taken, and then 10mg of olaquindox-imprinted Microspheres (MIP) and non-imprinted microspheres (NIP) prepared in example 1 and example 4 were added, respectively, and adsorbed by shaking on a shaker at room temperature at 120 r/min for 4 h. After the end of the time period, the clear solution was collected after passing through a 0.45 μm filter, the unadsorbed olaquindox concentration was measured by ultraviolet-visible spectrophotometry, and the adsorption capacity was calculated from the result. As a result, FIG. 2 shows isothermal adsorption curves of MIP and NIP, and FIG. 2 shows that the adsorption capacities of MIP and NIP increased with the increase of the initial concentration, and that the adsorption capacity of MIP to olaquindox was 4.52 mg/g and the maximum adsorption capacity of NIP was 2.05 mg/g at a concentration of 100 mg/L. The adsorption capacity of MIP to olaquindox is obviously higher than that of NIP to olaquindox, which shows that the synthesized MIP has specific selective property to olaquindox.
Example 5:
7 parts of 10mg MIP were added to a methanol solution containing 20mg/L of olaquindox at a concentration of 10mL, respectively, and then the 7 parts of the mixture were shaken on a horizontal shaker at a rotation speed of 120 r/min for 5 min, 10 min, 20 min, 40 min, 60 min, 80 min, 120 min at room temperature. After the shaking time was completed, the clear solution was collected through a 0.45 μm filter membrane, and the concentration of the non-adsorbed olaquindox was measured by ultraviolet-visible spectrophotometry, and the adsorption capacity was calculated from the result. As shown in FIG. 3, the prepared MIP has a fast adsorption rate to the target olaquindox, and can reach adsorption equilibrium within 60 min at the experimental concentration.
Example 6:
the specific cases of applying the olaquindox molecularly imprinted microspheres of example 1 to determine olaquindox residues in beef, shrimp, and eggs are as follows:
weighing 5g of beef, shrimp and egg samples, adding 10mL of 0.1mol/L disodium hydrogen phosphate-ethyl acetate (V: V; 9:1) extracting solution, mixing uniformly, performing ultrasonic treatment for 20 min at the ultrasonic power and temperature of 400W and 40 ℃, then performing centrifugation for 10 min at 4000 r/min, and taking supernatant. This operation was repeated twice, and the two supernatants were combined. The combined supernatants were dried with nitrogen at 40 ℃, redissolved in 10mL aqueous methanol, and subjected to liquid chromatography after solid phase extraction.
The method of solid phase extraction is as follows:
100mg of the imprinted microspheres obtained in example 1A were loaded into a polytetrafluoroethylene column, the polytetrafluoroethylene column was activated with 6 mL methanol/water (60:40; v/v), a standard sample was prepared with methanol solution, and 10mL was loaded. Thereafter, elution was performed with 2 mL methanol/glacial acetic acid (80:20; v/v) followed by liquid chromatography, and the polytetrafluoroethylene column was regenerated with methanol/water (60:40; v/v) for reuse.
As can be seen from fig. 4, the prepared MIP has no effect on the adsorption capacity after 5 times of repeated use.
Conclusion: the adsorption material is used as a solid-phase extraction adsorbent to adsorb olaquindox and metabolites thereof in beef, shrimp and eggs, and the standard recovery rate of 3-methyl-quinoxaline-2-carboxylic acid of the olaquindox and the olaquindox metabolites is 82.17% -97.64%, the relative standard deviation is 3.73% -5.01%, and the enrichment factor is 15-20 times through HPLC detection. The olaquindox imprinting microsphere prepared by the invention can be used for detecting olaquindox residues in animal-derived foods.
The above embodiments are merely preferred embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (3)
1. The preparation method of the nanocellulose-stabilized Pickering emulsion olaquindox imprinting microsphere is characterized by comprising the following steps of:
the method comprises the following steps:
(1) Dispersing 1.5-3.0 mg of nano cellulose in 1mL of deionized water to obtain a water phase;
(2) Dissolving template molecule olaquindox, functional monomer methacrylic acid, cross-linking agent ethylene glycol dimethacrylate and initiator azodiisobutyronitrile into toluene to be used as an oil phase; the mol ratio of the olaquindox, the methacrylic acid and the ethylene glycol dimethacrylate is 1: 3-7: 6-9; the mass molar ratio of the azodiisobutyronitrile to the olaquindox is 35-45 mg:1mmoL;
(3) Adding the oil phase obtained in the step (2) into the water phase obtained in the step (1), and homogenizing in a homogenizer at 14000-16000 rpm to prepare Pickering emulsion;
(4) Placing the Pickering emulsion prepared in the step (3) in a water bath kettle at 60-80 ℃ for thermal polymerization for 16-20 h, washing the polymer with deionized water for 3-4 times after the polymerization reaction is finished, vacuum drying the obtained polymer at 50 ℃, removing template molecules by using a methanol/acetic acid mixed solution as eluent through a Soxhlet extractor, and vacuum drying at 50 ℃ to obtain olaquindox imprinted microspheres;
in the step (1), the length-diameter ratio of the nanocellulose is 18-19;
in the step (3), the oil phase obtained in the step (2) is added into the water phase obtained in the step (1), and the volume ratio of the oil phase to the water phase is 1: 4-6.
2. The method for preparing nanocellulose-stabilized pickering emulsion olaquindox imprinting microspheres, as claimed in claim 1, wherein the method comprises the following steps: in the step (2), the molar mass volume ratio of the template molecule olaquindox to the pore-forming agent toluene is 1mmol:400 to 600 mu L.
3. The method for preparing nanocellulose-stabilized pickering emulsion olaquindox imprinting microspheres, as claimed in claim 1, wherein the method comprises the following steps: in the step (4), the volume ratio of methanol to acetic acid is 7-8: 2-3; the elution time is 72-80 h.
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