CN114736331A - Preparation method of Pickering emulsion olaquindox imprinted microspheres with stable nanocellulose - Google Patents
Preparation method of Pickering emulsion olaquindox imprinted microspheres with stable nanocellulose Download PDFInfo
- Publication number
- CN114736331A CN114736331A CN202210398995.6A CN202210398995A CN114736331A CN 114736331 A CN114736331 A CN 114736331A CN 202210398995 A CN202210398995 A CN 202210398995A CN 114736331 A CN114736331 A CN 114736331A
- Authority
- CN
- China
- Prior art keywords
- olaquindox
- imprinted
- pickering emulsion
- preparation
- nanocellulose
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 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 60
- 239000000839 emulsion Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229920001046 Nanocellulose Polymers 0.000 title claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 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
- 229920002678 cellulose Polymers 0.000 claims description 18
- 239000001913 cellulose Substances 0.000 claims description 18
- 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 17
- 238000000034 method Methods 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- 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 9
- 238000010828 elution Methods 0.000 claims description 8
- 238000012719 thermal polymerization Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000004088 foaming agent Substances 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 27
- 238000001514 detection method Methods 0.000 abstract description 8
- 235000013305 food Nutrition 0.000 abstract description 7
- 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
- 238000001035 drying Methods 0.000 description 6
- 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
- 239000003814 drug Substances 0.000 description 3
- 235000013601 eggs Nutrition 0.000 description 3
- 239000002207 metabolite Substances 0.000 description 3
- 238000002156 mixing Methods 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
- 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
- 239000012528 membrane 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
- 238000000746 purification 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
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 238000002965 ELISA Methods 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 239000004098 Tetracycline Substances 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
- 230000036952 cancer formation Effects 0.000 description 1
- 231100000504 carcinogenesis Toxicity 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
- 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
- 238000000265 homogenisation Methods 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement 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
- 238000012544 monitoring process Methods 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000010355 oscillation Effects 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
- 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
- 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
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
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 nanocellulose-stable Pickering emulsion olaquindox imprinted microsphere, and aims to improve the surface hole structure of the existing olaquindox imprinted microsphere and improve the adsorption rate and the reutilization property of the existing olaquindox imprinted microsphere on a target object. The invention comprises the following steps: (1) preparing deionized water phase dispersed with nano cellulose; (2) preparing an oil phase in which template molecules, functional monomers, a cross-linking agent and an initiator are dissolved; (3) emulsions were formed and olaquindox imprinted Microspheres (MIPs) were prepared. The olaquindox imprinted microspheres prepared by the invention have rich hole structures, have high adsorption rate on a target object, have excellent reusability, can meet the requirement of food safety rapid detection, and have great application potential.
Description
Technical Field
The invention belongs to the technical field of preparation of high-molecular specific adsorption materials, and particularly relates to a novel Pickering emulsion molecularly imprinted polymerization method and a preparation method of a nanocellulose-stabilized olaquindox imprinted microsphere based on the polymerization method.
Background
Olaquindox (OLA) is an antibacterial growth promoter, can promote protein assimilation, improve feed conversion rate and accelerate animal growth, has strong antibacterial effect, and is used as a feed additive for animal production in 70 th century in European countries. In recent years, research shows that the olaquindox medicine has obvious accumulative toxicity, and long-term consumption of food with residual olaquindox medicine can cause carcinogenesis, teratogenesis or mutagenesis. China forbids the olaquindox medicine to be used in the livestock and poultry production process in 2019.
At present, enzyme-linked immunosorbent assay, high performance liquid chromatography, electrochemical detection, fluorescence detection, high performance liquid chromatography-mass spectrometry and the like are adopted as the olaquindox detection method. The complex food sample matrix has great influence on the sensitivity of the detection method, the accuracy and the 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 an 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 macromolecular adsorption material, and has the remarkable advantages of excellent selectivity, physicochemical stability, reusability and the like. The Pikering emulsion imprinting polymerization method uses solid particles to replace an emulsifier as a stabilizer, so that the dosage of an organic solvent is less, and the damage to the environment is reduced. Compared with the traditional emulsion polymerization method, the polymer prepared by the Pikering emulsion imprinting polymerization method has more uniform particle size and better dispersibility. In the prior art, silicon dioxide is used as a solid stabilizer to prepare an imprinted polymer; and preparing the tetracycline imprinted microspheres by taking the biochar as a solid stabilizer. At present, the imprinting polymer taking silicon dioxide, biochar and the like as solid stabilizers obtains a uniform microsphere structure, but the number and the structure of holes for preparing the imprinting microsphere are still to be improved, so that the adsorption performance of the imprinting microsphere on a target object is influenced.
Disclosure of Invention
Object of the Invention
The invention provides a preparation method of stable Pickering emulsion olaquindox imprinted microspheres based on nanocellulose, aiming at the defects of small number of holes, low adsorption rate and the like of an imprinted adsorption material synthesized by the existing Pickering emulsion polymerization molecular imprinting technology.
Technical scheme
The preparation method of the Pickering emulsion olaquindox imprinted microsphere with stable nano-cellulose comprises the following steps:
(1) dispersing 1.5-3.0 mg of nano-cellulose in 1mL of deionized water to be used as a water phase;
(2) dissolving template molecule olaquindox, functional monomer methacrylic acid, cross-linking agent ethylene glycol dimethacrylate and initiator azobisisobutyronitrile 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 azodiisobutyronitrile to olaquindox is 35-45 mg: 1 mmoL;
(3) and (3) adding the oil phase obtained in the step (2) into the water phase obtained in the step (1), and homogenizing in a homogenizer of 14000-16000 r/min to prepare the Pickering emulsion.
(4) And (3) placing the Pickering emulsion prepared in the step (3) in a water bath kettle at the temperature of 60-80 ℃ for thermal polymerization for 16-20 h, washing the Pickering emulsion for 3-4 times by using deionized water after the polymerization reaction is finished, carrying out vacuum drying on the obtained polymer at the temperature of 50 ℃, removing template molecules by using a methanol/acetic acid mixed solution as an eluent through a Soxhlet extractor, and carrying out vacuum drying at the temperature of 50 ℃ to obtain the olaquindox imprinted microspheres.
In the step (1), the length-diameter ratio of the nano cellulose is 18-19.
In the step (2), the molar mass-to-volume ratio of the template molecule olaquindox to the pore-foaming agent toluene is 1 mmol: 400-600 μ 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 to 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 stable Pickering emulsion olaquindox imprinted microsphere with the nano-cellulose mainly improves the structure and the number of holes on the surface of the olaquindox imprinted microsphere, so that the target can be quickly adsorbed, and the preparation method has the advantages of simple synthesis, low cost and high product yield; the adopted stabilizer nano-cellulose has wide material obtaining range, is green and has no environmental pollution; the olaquindox molecularly imprinted microspheres prepared by the method have large specific surface area and quick and stable adsorption, are suitable to be used as a filling material of a solid phase extraction column to be applied to sample pretreatment in the monitoring process of olaquindox and metabolite residues thereof in accurate and efficient purification and enrichment of animal-derived food and feed, and have huge application prospects.
Drawings
FIG. 1 (a) is a scanning electron microscope image of olaquindox imprinted microspheres, and (b) is a scanning electron microscope image of olaquindox non-imprinted microspheres;
FIG. 2 is the isothermal adsorption curve of olaquindox by olaquindox blotting (MIP) and non-blotting microspheres (NIP);
FIG. 3 is the adsorption kinetics curve of olaquindox imprinted (MIP) and non-imprinted (NIP) microspheres;
FIG. 4 shows the adsorption capacity of the olaquindox imprinted microspheres for different regeneration times.
Detailed Description
The invention is described in detail below with reference to the attached drawing figures:
the invention relates to a preparation method of a stable Pickering emulsion olaquindox imprinted microsphere of nano-cellulose, which is characterized in that nano-cellulose is dispersed in deionized water as a water phase, template molecule olaquindox, functional monomer methacrylic acid, cross-linking agent ethylene glycol dimethacrylate and initiator azobisisobutyronitrile are dissolved in toluene as an oil phase, and olaquindox imprinted polymer is prepared under the heating condition after stable emulsion is obtained through high-speed homogenization. According to 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 elution process of the template molecules, so that the hole structure of the imprinted microspheres is increased, and the adsorption rate and stability of the imprinted microspheres to a target object are improved.
The invention relates to a preparation method of a stable Pickering emulsion olaquindox imprinted microsphere of nano-cellulose, which comprises the following steps:
(1) dispersing 1.5-3.0 mg of nano-cellulose in 1mL of deionized water to be used as a water phase;
(2) dissolving template molecule olaquindox, functional monomer methacrylic acid, cross-linking agent ethylene glycol dimethacrylate and initiator azobisisobutyronitrile 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: 1 mmoL;
(3) and (3) adding the oil phase obtained in the step (2) into the water phase obtained in the step (1), and homogenizing in a homogenizer of 14000-16000 r/min to prepare the Pickering emulsion.
(4) And (3) placing the Pickering emulsion prepared in the step (3) in a water bath kettle at the temperature of 60-80 ℃ for thermal polymerization for 16-20 h, washing the Pickering emulsion for 3-4 times by using deionized water after the polymerization reaction is finished, carrying out vacuum drying on the obtained polymer at the temperature of 50 ℃, removing template molecules by using a methanol/acetic acid mixed solution as an eluent through a Soxhlet extractor, and carrying out vacuum drying at the temperature of 50 ℃ to obtain the olaquindox imprinted microspheres.
In the step (1), the length-diameter ratio of the nano-cellulose is 18-19.
In the step (2), the molar mass-to-volume ratio of the template molecule olaquindox to the pore-foaming agent toluene is 1 mmol: 400-600 μ 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 to 6.
In the step (4), the volume ratio of methanol to acetic acid is 7-8: 2-3; the elution time is 72-80 h.
The present invention is further illustrated by the following specific examples.
Example 1
The invention relates to a preparation method of a stable Pickering emulsion olaquindox imprinted microsphere of nano-cellulose, which comprises the following steps:
(1) dispersing 1.5 mg of nano-cellulose with the length-diameter ratio of 18 in 1mL of deionized water to be used as 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 of initiator azobisisobutyronitrile 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 4 mL of the water phase obtained in the step (1), and homogenizing in a homogenizer of 14000 r/min to prepare a Pickering emulsion;
(4) placing the Pickering emulsion prepared in the step (3) in a water bath kettle at 60 ℃ for thermal polymerization for 16 h, washing the Pickering emulsion for 3 times by using deionized water after the polymerization reaction is finished, drying the obtained polymer in vacuum at 50 ℃, and then mixing the polymer with methanol and acetic acid in a volume ratio of 7: 3, removing template molecules from the eluent by using a Soxhlet extractor by using the mixed solution as the eluent, wherein the elution time is 72 hours, and drying in vacuum at 50 ℃ to obtain the olaquindox imprinted microspheres.
Example 2
The invention relates to a preparation method of a stable Pickering emulsion olaquindox imprinted microsphere of nano-cellulose, which comprises the following steps:
(1) dispersing 2.5 mg of nano-cellulose with the length-diameter ratio of 18.5 into 1mL of deionized water to be used as a water phase;
(2) dissolving 1mmol of template molecule olaquindox, 4 mmol of functional monomer methacrylic acid, 8 mmol of cross-linking agent ethylene glycol dimethacrylate and 40mg of initiator azobisisobutyronitrile into 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 5 mL of the water phase obtained in the step (1), and homogenizing in a homogenizer at 15000 r/min to prepare a Pickering emulsion;
(4) placing the Pickering emulsion prepared in the step (3) in a water bath kettle at 70 ℃ for thermal polymerization for 18 h, washing the Pickering emulsion for 3 times by using deionized water after the polymerization reaction is finished, drying the obtained polymer in vacuum at 50 ℃, and then mixing the polymer with methanol and acetic acid in a volume ratio of 7: 3, removing template molecules from the eluent by using a Soxhlet extractor by using the mixed solution as the eluent, wherein the elution time is 78 hours, and drying in vacuum at 50 ℃ to obtain the olaquindox imprinted microspheres.
Example 3
The invention relates to a preparation method of a stable Pickering emulsion olaquindox imprinted microsphere of nano-cellulose, which comprises the following steps:
(1) dispersing 3.0mg of nano-cellulose with the length-diameter ratio of 19 in 1mL of deionized water to be used as 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 of initiator azobisisobutyronitrile 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 6 mL of the water phase obtained in the step (1), and homogenizing in a homogenizer at 16000 r/min to prepare a Pickering emulsion;
(4) placing the Pickering emulsion prepared in the step (3) in a water bath kettle at 80 ℃ for thermal polymerization for 20h, washing the Pickering emulsion for 3 times by using deionized water after the polymerization reaction is finished, drying the obtained polymer in vacuum at 50 ℃, and then performing thermal polymerization on the polymer in a methanol/acetic acid volume ratio of 8: and 2, removing template molecules from the eluent by using a Soxhlet extractor by using the mixed solution as the eluent, wherein the elution time is 80h, and drying in vacuum at 50 ℃ to obtain the olaquindox imprinted microspheres.
As shown in figure 1, the surface of the olaquindox imprinted microsphere has abundant hole structures, which is beneficial to improving the adsorption rate of the imprinted microsphere to a target object.
Example 4 below: preparation of non-imprinted microspheres (NIP): the conditions were the same as in example 1, but the template molecule olaquindox was not added.
Example 4:
7mL of Olaquindox (OLA) solution with initial concentration of 5mg/L, 10mg/L, 20mg/L, 30mg/L, 40mg/L, 60mg/L, 80mg/L, 100mg/L, 120mg/L was taken in a 25 mL volumetric flask, then 10mg of olaquindox imprinted Microspheres (MIP) and non-imprinted microspheres (NIP) prepared in example 1 and example 4 were added, respectively, and adsorbed on a shaker at room temperature for 4 h with shaking at 120 r/min. After the time is over, the clear solution is collected after passing through a filter membrane of 0.45 mu m, the concentration of the unadsorbed olaquindox is measured by an ultraviolet-visible spectrophotometry, and the adsorption capacity is calculated according to the result. As shown in FIG. 2, FIG. 2 shows the isothermal adsorption curves of MIP and NIP, and it can be seen from FIG. 2 that the adsorption capacities of MIP and NIP increase with the increase of initial concentration, and at 100mg/L, the adsorption capacity of MIP to olaquindox is 4.52 mg/g, and the maximum adsorption capacity of NIP is 2.05 mg/g. 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 characteristics to olaquindox.
Example 5:
7 parts of 10mg MIP are added into 10mL of olaquindox methanol solution with the concentration of 20mg/L respectively, and then the 7 parts of mixture are shaken on a horizontal shaker at the rotating speed of 120 r/min for 5 min, 10 min, 20 min, 40 min, 60 min, 80 min and 120 min at room temperature. After the oscillation time is over, the clear solution is collected after passing through a filter membrane of 0.45 mu m, the concentration of the unadsorbed olaquindox is measured by an ultraviolet-visible spectrophotometry, and the adsorption capacity is calculated according to the result. The results are shown in fig. 3, and it can be known that the prepared MIP has a faster adsorption rate for the target olaquindox, and can reach adsorption equilibrium within 60 min under the experimental concentration.
Example 6:
the specific case of applying the olaquindox molecularly imprinted microspheres of example 1 to the determination of olaquindox residues in beef, shrimp and egg is 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, carrying out ultrasonic treatment for 20 min at the ultrasonic power and temperature of 400W and 40 ℃, then carrying out centrifugation for 10 min at 4000 r/min, and taking supernatant. This procedure was repeated twice and the two supernatants were combined. The combined supernatants were dried at 40 ℃ with nitrogen, redissolved with 10mL aqueous methanol, and analyzed by liquid chromatography after solid phase extraction.
The solid phase extraction method comprises the following steps:
100mg of the imprinted microspheres obtained in example 1A were loaded on a polytetrafluoroethylene column, the polytetrafluoroethylene column was activated with 6 mL of methanol/water (60: 40; v/v), a standard sample was prepared with a methanol solution, and 10mL of the sample was loaded. Thereafter, elution was performed with 2 mL of methanol/glacial acetic acid (80: 20; v/v), followed by measurement by liquid chromatography, and the polytetrafluoroethylene column was regenerated using methanol/water (60: 40; v/v) for reuse.
As can be seen from fig. 4, the MIP prepared had no effect on adsorption capacity after 5-fold reuse.
And (4) conclusion: the adsorbing material is used as a solid phase extraction adsorbent to adsorb olaquindox and metabolites thereof in beef, shrimp and eggs, and the labeling recovery rates of the olaquindox and the olaquindox metabolite 3-methyl-quinoxaline-2-carboxylic acid are 82.17% -97.64%, the relative standard deviation is 3.73% -5.01%, and the enrichment multiple is 15-20 times through HPLC detection. The olaquindox imprinted microsphere prepared in the invention can be used for olaquindox residue detection in animal-derived food.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the invention, so that any modifications, equivalents, improvements and the like, which are within the spirit and principle of the present invention, should be included in the scope of the present invention.
Claims (5)
1. The preparation method of the Pickering emulsion olaquindox imprinted microsphere with stable nanocellulose is characterized by comprising the following steps:
the method comprises the following steps:
(1) dispersing 1.5-3.0 mg of nano-cellulose in 1mL of deionized water to serve as a water phase;
(2) dissolving template molecule olaquindox, functional monomer methacrylic acid, cross-linking agent ethylene glycol dimethacrylate and initiator azobisisobutyronitrile 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: 1 mmoL;
(3) adding the oil phase obtained in the step (2) into the water phase obtained in the step (1), and homogenizing in a homogenizer of 14000-16000 r/min to prepare a Pickering emulsion;
(4) and (4) placing the Pickering emulsion prepared in the step (3) in a water bath kettle at the temperature of 60-80 ℃ for thermal polymerization for 16-20 h, washing the Pickering emulsion for 3-4 times by using deionized water after the polymerization reaction is finished, carrying out vacuum drying on the obtained polymer at the temperature of 50 ℃, removing template molecules by using a methanol/acetic acid mixed solution as an eluent through a Soxhlet extractor, and carrying out vacuum drying at the temperature of 50 ℃ to obtain the olaquindox imprinted microspheres.
2. The preparation method of the nanocellulose-stabilized Pickering emulsion Quinoethanol imprinted microsphere of claim 1, characterized in that: in the step (1), the length-diameter ratio of the nano cellulose is 18-19.
3. The preparation method of the nanocellulose-stable Pickering emulsion Quinoethanol imprinted microsphere of claim 1, characterized by: in the step (2), the molar mass-to-volume ratio of the template molecule olaquindox to the pore-foaming agent toluene is 1 mmol: 400-600 μ L.
4. The preparation method of the nanocellulose-stabilized Pickering emulsion Quinoethanol imprinted microsphere of claim 1, characterized in that: 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 to 6.
5. The preparation method of the nanocellulose-stabilized Pickering emulsion Quinoethanol imprinted microsphere of claim 1, 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210398995.6A CN114736331B (en) | 2022-04-16 | 2022-04-16 | Preparation method of nanocellulose-stabilized Pickering emulsion olaquindox imprinting microsphere |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210398995.6A CN114736331B (en) | 2022-04-16 | 2022-04-16 | Preparation method of nanocellulose-stabilized Pickering emulsion olaquindox imprinting microsphere |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114736331A true CN114736331A (en) | 2022-07-12 |
| CN114736331B CN114736331B (en) | 2023-11-14 |
Family
ID=82282657
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210398995.6A Active CN114736331B (en) | 2022-04-16 | 2022-04-16 | Preparation method of nanocellulose-stabilized Pickering emulsion olaquindox imprinting microsphere |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114736331B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104177547A (en) * | 2014-07-29 | 2014-12-03 | 江苏大学 | Method for preparing composite cellulose porous imprinting adsorbent |
| US20210213405A1 (en) * | 2019-10-31 | 2021-07-15 | Jiangnan University | Pickering emulsion stabilized by cellulose nanocrystals from ginkgo seed shells and preparation method thereof |
-
2022
- 2022-04-16 CN CN202210398995.6A patent/CN114736331B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104177547A (en) * | 2014-07-29 | 2014-12-03 | 江苏大学 | Method for preparing composite cellulose porous imprinting adsorbent |
| US20210213405A1 (en) * | 2019-10-31 | 2021-07-15 | Jiangnan University | Pickering emulsion stabilized by cellulose nanocrystals from ginkgo seed shells and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 苏立强等: "喹乙醇分子印迹聚合物的制备及其应用", 《分析试验室》, vol. 39, no. 7, pages 806 - 810 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114736331B (en) | 2023-11-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Enhanced binding capacity of boronate affinity adsorbent via surface modification of silica by combination of atom transfer radical polymerization and chain-end functionalization for high-efficiency enrichment of cis-diol molecules | |
| CN107118354B (en) | Preparation method and application of ochratoxin metal organic framework-molecular imprinting composite separation medium | |
| CN109772178B (en) | Preparation method and application of pyrimethamine molecularly imprinted composite membrane based on click chemistry double-sided loading | |
| CN110078853B (en) | Pickering emulsion and preparation of tetracycline molecular imprinting biochar composite microspheres | |
| CN108623834B (en) | Method for detecting triazine herbicide residue in agricultural products by molecular imprinting-dispersive solid-phase extraction | |
| CN106868622B (en) | Nanofiber capable of being used for detecting tetracycline and preparation and application thereof | |
| CN112337441B (en) | Phenylboronic acid-chitosan modified monolithic column and preparation method and application thereof | |
| CN114736331B (en) | Preparation method of nanocellulose-stabilized Pickering emulsion olaquindox imprinting microsphere | |
| CN114324658A (en) | Dispersive solid-phase extraction-high performance liquid chromatography combined detection method for melamine | |
| CN112110861B (en) | Carbendazim virtual template molecularly imprinted polymer and preparation method thereof | |
| CN112321763A (en) | Casidone derivative molecularly imprinted polymer and preparation method and application thereof | |
| CN117101616A (en) | Molecularly imprinted polymer adsorption material based on metal-organic framework, and preparation method and application thereof | |
| Zhang et al. | Facile one-pot preparation of chiral monoliths with a well-defined framework based on the thiol–ene click reaction for capillary liquid chromatography | |
| CN114456800B (en) | Preparation method and application of perovskite quantum dot-molecular imprinting fluorescent coding microsphere for detecting sudan red I | |
| Li et al. | Preparation and evaluation of uniform-size (-)-ephedrine-imprinted polymeric microspheres by multi-step swelling and suspension polymerization | |
| CN110452319B (en) | Preparation method and application of dendrimer functional polymer | |
| CN113234192B (en) | Double-template surface molecularly imprinted nano composite material, preparation method and application thereof | |
| CN112573612B (en) | Method for simultaneously adsorbing Sudan red I-IV by using imine covalent organic framework and application | |
| CN111892681B (en) | Preparation method and application of modified polymer microsphere adsorbent | |
| CN110885394B (en) | Triazine group modified macroporous resin and preparation method thereof | |
| CN109839452B (en) | Molecular imprinting stirring rod and preparation method and application thereof | |
| Zhang et al. | Surface molecularly imprinted polymers based on NH2-MIL-53 for selective extraction ochratoxin A in real sample | |
| CN107936176B (en) | Preparation method and application of resveratrol molecularly imprinted polymer | |
| CN110818836A (en) | Vitamin E molecularly imprinted polymer, two-step swelling preparation method and application thereof | |
| CN106397671A (en) | Preparation method of chloramphenicol molecularly imprinted polymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |