CN107266627B - A kind of the core-shell type molecularly imprinted polymer and preparation method of recognizable erythrosine - Google Patents
A kind of the core-shell type molecularly imprinted polymer and preparation method of recognizable erythrosine Download PDFInfo
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- CN107266627B CN107266627B CN201710406530.XA CN201710406530A CN107266627B CN 107266627 B CN107266627 B CN 107266627B CN 201710406530 A CN201710406530 A CN 201710406530A CN 107266627 B CN107266627 B CN 107266627B
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- erythrosine
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- silicon dioxide
- methanol
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- 239000004174 erythrosine Substances 0.000 title claims abstract description 51
- 235000012732 erythrosine Nutrition 0.000 title claims abstract description 51
- 229940011411 erythrosine Drugs 0.000 title claims abstract description 51
- IINNWAYUJNWZRM-UHFFFAOYSA-L erythrosin B Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(I)C(=O)C(I)=C2OC2=C(I)C([O-])=C(I)C=C21 IINNWAYUJNWZRM-UHFFFAOYSA-L 0.000 title claims abstract description 50
- 229920000344 molecularly imprinted polymer Polymers 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000011258 core-shell material Substances 0.000 title claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 37
- 229920000642 polymer Polymers 0.000 claims abstract description 31
- 238000005576 amination reaction Methods 0.000 claims abstract description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 60
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 239000004005 microsphere Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 235000012239 silicon dioxide Nutrition 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000003431 cross linking reagent Substances 0.000 claims description 12
- 238000002604 ultrasonography Methods 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000010828 elution Methods 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 8
- 239000012498 ultrapure water Substances 0.000 claims description 8
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 7
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical group FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 7
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- 239000000908 ammonium hydroxide Substances 0.000 claims description 6
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical group C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 claims description 5
- 238000003760 magnetic stirring Methods 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- -1 last eluted template Substances 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000002045 lasting effect Effects 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 13
- 238000005516 engineering process Methods 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 7
- 239000000049 pigment Substances 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 5
- 235000002864 food coloring agent Nutrition 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000004540 process dynamic Methods 0.000 abstract description 2
- 238000002336 sorption--desorption measurement Methods 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 8
- 238000001514 detection method Methods 0.000 description 7
- 239000006228 supernatant Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 235000013305 food Nutrition 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 244000299461 Theobroma cacao Species 0.000 description 5
- 235000015203 fruit juice Nutrition 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 235000013361 beverage Nutrition 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 3
- 239000005695 Ammonium acetate Substances 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 229940043376 ammonium acetate Drugs 0.000 description 3
- 235000019257 ammonium acetate Nutrition 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 235000019219 chocolate Nutrition 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 238000000944 Soxhlet extraction Methods 0.000 description 2
- 235000009470 Theobroma cacao Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000576 food coloring agent Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000002798 spectrophotometry method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 235000010894 Artemisia argyi Nutrition 0.000 description 1
- 238000007445 Chromatographic isolation Methods 0.000 description 1
- 241000792859 Enema Species 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 101150026858 VP30 gene Proteins 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 229920006221 acetate fiber Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 235000013334 alcoholic beverage Nutrition 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 244000030166 artemisia Species 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000003592 biomimetic effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 235000020992 canned meat Nutrition 0.000 description 1
- 238000005251 capillar electrophoresis Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229940126678 chinese medicines Drugs 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 239000007920 enema Substances 0.000 description 1
- 229940095399 enema Drugs 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 235000015094 jam Nutrition 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
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- 210000003296 saliva Anatomy 0.000 description 1
- 235000015067 sauces Nutrition 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000005406 washing 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
- B01D15/38—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving specific interaction not covered by one or more of groups B01D15/265 and B01D15/30 - B01D15/36, e.g. affinity, ligand exchange or chiral chromatography
- B01D15/3852—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving specific interaction not covered by one or more of groups B01D15/265 and B01D15/30 - B01D15/36, e.g. affinity, ligand exchange or chiral chromatography using imprinted phases or molecular recognition
-
- 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
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
-
- 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
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
- C08K7/18—Solid spheres inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- 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
- C08J2333/00—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/08—Homopolymers or copolymers of acrylic acid esters
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- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Analytical Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention is the core-shell type molecularly imprinted polymer and preparation method of a kind of recognizable erythrosine, belong to function of molecular engram field of material technology, specifically a kind of polymer material based on molecular imprinting technology preparation to synthetic food color erythrosine with special identification function, the silica that the present invention is modified using amination is core, using erythrosine pigment molecular as template, one layer of imprinted layer is wrapped up on its surface.Its advantage is that imprinted sites are in polymer surfaces, template is easy to elute from polymer, overcome adsorption/desorption process dynamics slowly and quality transfer the shortcomings that, specific recognition fast and accurately can be carried out to erythrosine, and simplified operation step of the present invention, the usage amount of solvent is reduced, the rate of recovery is improved.
Description
Technical field
It is that a kind of prepared based on molecular imprinting technology is closed to artificial the invention belongs to function of molecular engram field of material technology
There is the polymer material of special identification function at pigment erythrosine, can with the specific recognition of erythrosine with separate.
Background technique
Erythrosine is as a kind of synthetic food color, and due to its strong coloring force, stability is good, low in cost, is usually used in eating
It is aesthetic to improve its in product.For most of artificial fabricated food colorants, it is not intended as a kind of nutriment, it cannot
It is absorbed by the body, and it is prepared often using benzene, toluene as raw material, through a series of sulfonation, nitration reaction, and in the synthesis process
The heavy metals such as arsenic and lead may be infiltrated, if abused it, huge threat is come to the health care belt of consumer.China is to food
Colorant, which has, explicitly uses standard and limitation.Currently, according to GB 2760-2014 " national food safety standard food additives
Use standard " regulation, allow using the food of erythrosine to be following several: fruit jelly class, cocoa products, chocolate and chocolate system
Color make-up, composite flavouring, fruit juice on product (including substitute of cocoa fat chocolate and product) and candy, sauce and jam product, cake
Beverage, soda, flavor beverage (only limiting fruit-flavored beverage), assembled alcoholic drinks are 0.05g/kg using limitation；Fried-in-oil nuts and seed
Class, dilated food are 0.025g/kg using limitation；Meat enema class, canned meat class are 0.015g/kg using limitation；Decorative fruit
Vegetable is 0.1 g/kg using limitation.
Currently, being mainly high performance liquid chromatography, ultraviolet spectrophotometer method, chromatography-matter for the detection method of pigment
Spectrum combination, capillary electrophoresis and thin-layered chromatography etc..In order to reduce the influence of food substrate, the pre-treatment of sample is to subsequent
Instrument precision detection plays a crucial role.Erythrosine belongs to more special one in several common food colors
Kind, the Silon of the extraction for erythrosine, common national regulations is adsorbed to this and is not suitable for, and liquid-liquid extraction consumption
Reagent is larger, and step is cumbersome, causes working efficiency low, and most of extractant has certain toxicity, long-time service pair
Health and environment will cause certain injury.Furthermore Solid Phase Extraction is also a kind of more common pre-treating method, including magnetic solid phase
Extraction, dispersive solid-phase extraction, micro- Solid Phase Extraction and the micro- Solid Phase Extraction of dispersion are widely used in multi-residue analysis, have simplified detection
Step, has saved a large amount of solvent, but Solid Phase Extraction lacks selectivity for the extraction of pigment, the substance similar for structure without
Method separation, and existing solid phase extraction method is not high to the rate of recovery of erythrosine at present.Therefore, the new method of one kind is explored for red
The red detection of moss has great significance.
Molecular imprinting technology (Molecular Imprinting Technique, MIT) is a kind of imitative antibody technique, is referred to
The technology for preparing the imprinted polymer that can be mutually distinguishable on three-dimensional space on particular combination site with template molecule, is one
Kind can be used to simulate the identification function of natural materials, prepare the manual method with specific selectivity imprinted polymer.Molecule
The basic principle of engram technology is specific function monomer to be selected, under the action of initiator using target molecule as template molecule
It is condensed together under specific initiation conditions by the effect of crosslinking agent, then washing away template molecule with eluant, eluent can obtain
To the polymer on three-dimensional space with specific structure and recognition site.Compared with antibody, enzyme, biomolecule, molecular engram
The intrinsic feature that polymer is shown has following: the preparation of imprinted polymer is comparatively simple and economical；Polymer is shown
The stability of good physics and chemistry；The binding characteristic of its template will not be lost under extreme electrochemical conditions.In recent years,
The preparation of MIPs makes great progress, and has developed the preparation method of multiple polymers, as bulk polymerization, precipitating are poly-
Conjunction, suspension polymerisation, surface aggregate etc. prepare various polymer.The pattern of common polymer mainly have it is block-like,
Rodlike, spherical, molecular engram film and molecularly imprinted polymer nano material be such as: nano particle, nanotube, nano wire.
Molecular imprinting technology is applied in fields such as chromatographic isolation, enzyme simulation, drug chiral separation and biomimetic sensors,
While in terms of the enrichment of analytes in low concentration, reaction process balance the control and combinatorial chemical library shifted
Certain progress is obtained.Due to molecularly imprinted polymer advantage and characteristic, if be used as a kind of adsorbent apply to it is red
In the detection of moss haematochrome, the rate of recovery of erythrosine can be greatly improved, and there is presently no polymerize about erythrosine molecular engram
The related article of object has the meaning of research.
Summary of the invention
The purpose of the invention is to overcome the shortcomings of existing methods (complex for operation step, a large amount of reagents of consumption, the rate of recovery
It is low), provide it is a kind of can the hud typed molecular blotting polymer microsphere of specific recognition erythrosine preparation method, it be using point
Sub- engram technology prepares the functional material of imitative antibody molecule recognition performance, and simplified operation step reduces the use of solvent
Amount improves the rate of recovery.
In order to achieve the object of the present invention, the present inventor by a large number of experiments study and persistent exploration, be finally obtained as
Lower technical solution:
First using silicon dioxide microsphere as carrier, amination modification is carried out on its surface, by amination after the completion of amination
Kernel of the silica as polymerization reaction.Template and function monomer are carried out to be incubated at room temperature and then formed and is intended to polymerize
Object.Then polymer, crosslinking agent and initiator is intended to be added in the reaction dissolvent containing amination silicon dioxide microsphere kernel
Second step polymerization reaction is carried out, so that silicon dioxide microsphere surface forms the molecular engram outer shell of layer.Finally
After the template of polymer surfaces is removed using eluant, eluent, it will leave template molecule in the molecular engram thin layer of microsphere surface
Imprinted cavity, for being identified mutually with template molecule, it is specific the preparation method is as follows:
(1) preparation of activated silica microballoon: silicon dioxide microsphere is weighed in flask, NaOH is added, is placed on magnetic force
30 min are corroded in stirring at room temperature on blender, and then with ultrapure water elution, the silica being base treated uses Hcl 90 again
Flow back 8 h under the conditions of DEG C, is eluted to neutrality with ultrapure water after reflux, dry, the concentration difference of the sodium hydroxide, hydrochloric acid
For 0.25moL/L, 2moL/L.
(2) preparation of amination silicon dioxide microsphere: the silicon dioxide microsphere of activation is placed in flask, and first is added
Benzene adds silane coupling agent, and 15 min of ultrasound, in 90 DEG C of 12 h of reflux, methanol washes away unreacted silane after reflux
Coupling agent filters resulting amination silicon dioxide granule, and dry, spare, wherein silane coupling agent accounts for the 5% of volume of toluene,
The silane coupling agent is 3- aminopropyl triethoxysilane (APTES),.
(3) it is intended to the preparation of polymer: accurately weighing erythrosine and be dissolved in the mixture of methanol, water, and function list is added
Body, at room temperature stirring be incubated for 2 h, the function monomer be 4-vinylpyridine (4-VP), methanol, water mixture in methanol,
The volume ratio of water is 4:1.
(4) preparation method of erythrosine molecularly imprinted polymer: amination is sequentially added in the reactant of step (3)
Silicon dioxide microsphere, crosslinking agent, initiator, ultrasound mix, and upper end installs threeway glass tube additional after magnetic agitation 10min at room temperature,
It is passed through nitrogen 30-60min, to remove oxygen；And the closed container equipped with reaction solution is placed on magnetic stirring apparatus, persistently stir
It mixes, oil bath heating at 60-70 DEG C, reaction is drawn off afterwards for 24 hours, and the polymer generated after reaction is taken out with G1 sand core funnel
Filter, to filter off little particle.Then eluted template is carried out with the mode of the methanol Soxhlet extraction containing 10% ammonium hydroxide, used for the last time
Methanol elution, washes away the ammonium hydroxide in polymer, and polymer is dry, can be collected into molecularly imprinted polymer, the crosslinking
Agent is ethylene glycol dimethacrylate (EGDMA), and the initiator is azo such as azodiisobutyronitrile (AIBN), function
Monomer, crosslinking agent molar ratio are 1:5, the percentage by volume 2% of function monomer, crosslinking agent in the reaction system.
It can obtain having the core-shell type molecularly imprinted polymer of specific recognition function micro- erythrosine using this method
Ball can be used as a kind of adsorbent material, and erythrosine in food is identified and adsorbed.
Compared with prior art, advantages of the present invention are as follows: the present invention uses surface molecule print technology, is modified with amination
Silica be core, using erythrosine pigment molecular as template, its surface wrap up one layer of imprinted layer.Its advantage are as follows: trace
In polymer surfaces, template is easy to elute from polymer in site；Overcome adsorption/desorption process dynamics slowly and
The shortcomings that quality is transferred the possession of.The basic principle of its adsorpting pigment is by the electrostatic interaction phase between erythrosine and 4-vinylpridine
The hud typed imprinted polymer of mutually identification, preparation fast and accurately can carry out specific recognition to erythrosine.
Attached drawing and its explanation:
The synthetic route of the hud typed erythrosine molecular blotting polymer microsphere of Fig. 1 and its schematic diagram that erythrosine is identified.
Fig. 2 tests the infrared figure of silica obtained, amination silica, non-imprinted polymer microballoon (NIP)
Spectrogram.
Adsorption dynamics adsorption kinetics figure of Fig. 3 .MIP/NIP microballoon to template molecule erythrosine.
Isothermal adsorption performance map of Fig. 4 .MIP/NIP microballoon to template molecule erythrosine.
Fig. 5 .MIP/ Silon marked graph.A indicates absorption stoste, and b indicates color of the stoste through Silon adsorption recovery
Element, c indicate that stoste adsorbs recycled pigment through MIP, the concentration for scheming erythrosine in centrifuge tube in a is from left to right respectively as follows: 0,
1,5,10 μ g/mL, schemes b and figure c is corresponding with figure a.
Specific embodiment
The following is specific embodiments of the present invention, and technical scheme of the present invention is further described, but of the invention
Protection scope be not limited to these examples.It is all to be included in this hair without departing substantially from the change of present inventive concept or equivalent substitute
Within bright protection scope.
(1) instrument and reagent
(1) apparatus
C-MAG HS7 magnetic stirring apparatus (German IKA company)；(city of Kunshan's ultrasonic instrument has KQ5200 ultrasonic cleaner
Limit company)；AL104 precise electronic assay balance (Mei Tele-support benefit Instrument Ltd.)；7230 full-automatic novel of ZRD-
Drying box (Shanghai ZHICHENG Anaiytical Instrument Manufacturing Co., Ltd.)；UV-Lambda 35 is ultraviolet-visible spectrophotometer (platinum Chinese mugwort
Er Mo company)；VP30 vacuum filtration pump (Beijing LabTech instrument company)；2000 Fourier's infrared scanner of FT-IR；Electricity
Hot thermostatic water bath (the upper macro experimental facilities Co., Ltd of Nereid)；TGL-16G desk centrifuge (Anting Scientific Instrument Factory, Shanghai's system
It makes)；3000 high performance liquid chromatograph of Ultimate.
(2) reagent
Ethylene glycol dimethacrylate (EGDMA), erythrosine (analyzing pure, Aladdin)；4-vinylpridine, methanol,
Ammonium hydroxide, Silon (analyzing pure, Chinese medicines group chemical reagent)；Azodiisobutyronitrile (AIBN) (98%, source leaf biology)；0.45
μm water system filter membrane (acetate fiber；Upper Haixing County Asia scavenging material factory)；0.45 μm of organic phase filter membrane (nylon66 fiber；Saliva is grand)；0.22 μ
M water system syringe needle filter (polyether sulfone, rub fast scientific equipment Co., Ltd in Shanghai)；0.22 μm of hydrophobic phase syringe needle filter (polytetrafluoroethyl-ne
Alkene；Rub fast scientific equipment Co., Ltd in Shanghai)；Sodium hydroxide (analyzes pure, Sinopharm Chemical Reagent Co., Ltd.)；Hydrochloric acid
(analysis is pure, and break a seal chemical reagent work, Dong great Chemical Co., Ltd.)；3- aminopropyl triethoxysilane (Aladdin)；Toluene (analysis is pure,
Shanghai Ling Feng chemical reagent Co., Ltd).
(2) experimental procedure
Example 1: silica surface amination modification
1g solid sodium hydroxide is accurately weighed, 100mL ultrapure water is added to dissolve, is configured to the hydrogen-oxygen that concentration is 0.25 moL/L
Change sodium water solution；It is accurate to measure 6.18mL hydrochloric acid, the dilution of 93.82mL ultrapure water is added, is configured to the hydrochloric acid that concentration is 2moL/L
Aqueous solution.
(1) activation of silica: 10g silicon dioxide microsphere is accurately weighed in the round-bottomed flask of 250mL, is added 100
ML NaOH(0.25 moL/L), 30 min of stirring corrosion at room temperature are placed on magnetic stirring apparatus, then with ultrapure water elution；Quilt
Alkali-treated silica is flowed back 8 h again with the Hcl of 100 mL, 2 moL/L under the conditions of 90 DEG C, with ultrapure after reflux
Water elution is dry to neutrality.
(2) silica surface amination: silica that 10 g were activated is weighed in the round-bottomed flask of 250 mL, is added
The toluene for entering 100 mL, adds the 3- aminopropyl triethoxysilane (APTES) of 5 mL, and 15 min of ultrasound flow back at 90 DEG C
12 h, methanol washes away unreacted APTES after reflux, and the amidized silicon dioxide granule of preparation is filtered, dry, standby
With.
Example 2: the preparation of erythrosine molecularly imprinted polymer and non-molecularly imprinted polymer
Accurately weigh erythrosine 0.2375mmoL and be dissolved in 50 mL methanol: water=4:1(v/v) in, and by functive 4-VP
(0.95mmoL) is added in solution, and stirring is incubated for 2 h at room temperature, then sequentially adds the silica (1 that surface modification is crossed
G), crosslinking agent EGDMA(4.75mmoL), initiator A IBN(0.014 g), ultrasound mix, be then charged into round-bottomed flask, room temperature
Upper end installs threeway glass tube additional after lower magnetic agitation 10min, nitrogen (60min) is passed through, to remove oxygen.
Closed container equipped with above-mentioned reaction solution is placed on magnetic stirring apparatus, appropriate revolving speed is adjusted and persistently stirs, 70
Oil bath heating at DEG C, reaction are drawn off afterwards for 24 hours, and polymerization occurs for reaction solution to prepare erythrosine molecularly imprinted polymer
(MIP), the balloon apparatus in reaction process using tee tube remains the nitrogen environment of closed container, polymerize after reaction
Object is filtered with G1 sand core funnel, to filter off little particle, is then eluted with the mode of the methanol Soxhlet extraction containing 10% ammonium hydroxide
Template is eluted with methanol for the last time, washes away the ammonium hydroxide in polymer.Polymer is dry, collect MIP.Non- imprinted polymer
(NIP) preparation is in addition to being not added template, and other steps are as MIP.
Silica, amination silica and NIP are characterized by infrared spectrometer, it is as a result as shown in Fig. 2, right
Than the silica of non-amination modification, it can be seen that amination silica is in 1500 cm in figure-1With 685 cm-1Place has
Peak occurs, this is because amination silica is in 1500 cm-1Left and right at C-N key and in 685 cm-1The Si-C key at place
Caused by stretching vibration, illustrate silica it is amido modified up.Compare the infrared figure of amination silica and NIP
Spectrum finds NIP in 1700 cm-1There is peak at left and right, and amination silica does not have, this is because the flexible vibration of C=O in crosslinking agent
Movable property life, illustrate successfully to have wrapped up one layer of shell outside amination silica.
Example 3: the adsorption kinetic data
7.2mg erythrosine solid sample is accurately weighed, is dissolved in 12mL ultrapure water, ultrasound mixes, and being configured to concentration is
The erythrosine aqueous solution of 600 μ g/mL.10 4mL centrifuge tubes and marking serial numbers are taken, then weigh the MIP that 10mg is prepared respectively
Microballoon and NIP microsphere solid are placed wherein, each 5 pipe of two kinds of microballoons.It is 600 μ g/mL that 1mL concentration is added into each centrifuge tube
Erythrosine aqueous solution, ultrasound mix, then standing adsorption at room temperature.It is sampled when adsorption time is 5,15,30,45,60 min,
Centrifuging and taking supernatant surveys its light absorption value at 533nm with spectrophotometry instrument (Uv-vis), passes through (1) formula meter
Its adsorbance (Q) is calculated, observes its adsorbance with the changing rule of adsorption time.
Wherein, Q is adsorbance (μ g/mg)；C0For the concentration (μ g/mL) for adsorbing preceding erythrosine solution；C is red moss after absorption
The concentration (μ g/mL) of red solution；V is adsorption liquid volume (mL)；M is the quality (mg) of polymer.With adsorption time (t) for horizontal seat
Mark, adsorbance (Q) are ordinate mapping, study adsorbance (Q) with the variation relation of adsorption time.As a result as shown in figure 3, MIP
Reach adsorption equilibrium in 15min with NIP.
Example 4: adsorption isotherm experiment
8mg erythrosine solid sample is accurately weighed, is dissolved in 8mL deionization pure water, ultrasound mixes, and is configured to 1mg/mL
Erythrosine aqueous solution.8 4mL centrifuge tubes and marking serial numbers are taken, being configured to concentration is respectively 50 μ g/mL, 100 μ g/mL, 150 μ
Each 3mL of erythrosine aqueous solution of g/mL, 200 μ g/mL, 250 μ g/mL, 350 μ g/mL, 600 μ g/mL, 800 μ g/mL.
Then it weighs respectively in the MIP microballoon and NIP microsphere solid placement 4mL centrifuge tube that 10mg is prepared, two kinds of microballoons
Each 8 pipe, and the concentration for marking upper 50-800 μ g/mL different on each centrifuge tube, are successively added into each centrifuge tube according to label
1mL concentration is the erythrosine aqueous solution of 50-800 μ g/mL, and after ultrasound mixes, microballoon concentration is 10 mg/mL, stands inhale at room temperature
Attached 20min.It after the completion of absorption, is centrifuged (15 min, 12000 r/min), takes supernatant, surveyed with spectrophotometry instrument
Determine light absorption value of the erythrosine unadsorbed in solution at 533 nm.Erythrosine absorption front and back is calculated according to the variation of light absorption value
Then the variation of concentration calculates the adsorbance for obtaining polymer by formula.As a result as shown in figure 4, the saturation of MIP is adsorbed
Amount is about 29 μ g/mg.
Example 5: actual sample recovery testu
" NongFuGuoYuan fruit juice " beverage of the yellow without any synthetic food color is chosen as experimental subjects, in fruit juice sample
Different amounts of erythrosine is added in product, spiked levels are prepared are as follows: 0,1,5,10 μ g/mL.
20 mg imprinted polymers (MIP) and each 4 parts of Silon are accurately weighed respectively in the centrifuge tube of 4 mL, then
The erythrosine juice solution of 2 mL various concentrations is added, at room temperature 20 min of standing adsorption.After the completion of standing adsorption, centrifugation
(12000 r/min, 15 min) remove supernatant, retain the substance in centrifuge tube.
Substance in centrifuge tube is done into two kinds of processing, one is the elution that 2 mL are added in first removal of impurities in each centrifuge tube
Liquid (V Water:V Formic acid:V Methanol=4:2:4), ultrasound elution, be centrifuged (12000 r/min, 15 min), remove supernatant, then with eluant, eluent into
Row template removal.Another method is direct progress template removal, the process that centre does not elute is added 2 in centrifuge tube
The ammoniated methanol solution of mL 10% carries out template removal, and ultrasound is centrifuged (12000 r/min, 15 min), takes supernatant.
Obtained supernatant is crossed to 0.22 μm of organic system syringe needle filter, then will supernatant place water-bath in steam to
200 μ L or so add methanol to redissolve, and cross the hydrophobic system's syringe needle filter of 0.22 μm of polytetrafluoroethylene (PTFE), are then analyzed with HPLC, count
Calculate its rate of recovery.As a result as shown in table 1 and table two and Fig. 5, it is higher than without the MIP rate of recovery of rinsing step and contains rinsing step
The rate of recovery, and the rate of recovery of MIP is higher than Silon, 85% or more.The above is the result shows that erythrosine molecular engram
Polymer can be used for being selectively adsorbing and separating for erythrosine in food samples, and does not need rinsing step in the process and saved greatly
The organic solvent of amount, can be as a kind of potential Solid Phase Extraction adsorbent material.
HPLC analysis condition:
Ultraviolet device detection, Detection wavelength: 254nm.
Mobile phase: methanol: ammonium acetate solution (pH=4,0.02moL/L).
Gradient elution: methanol: 20%-35%, 3%/min；35%-98%, 9%/min；98% continues 6min.
Flow velocity: 1mL/min.
Ammonium acetate solution configuration: 1.54g ammonium acetate solid sample is accurately weighed, water is added to be dissolved to 1000mL, ultrasound makes it
Sufficiently dissolution crosses 0.45 μm of organic filter membrane of water system with acetic acid tune pH to 4.
The rate of recovery and accuracy of 1 erythrosine of table in mark-on fruit juice
Note: including rinsing step during the experiment.
The rate of recovery and accuracy of 2 erythrosine of table in mark-on fruit juice
Claims (1)
1. a kind of preparation method of the core-shell type molecularly imprinted polymer of recognizable erythrosine, which is characterized in that this method includes
Following steps:
(1) preparation of activated silica microballoon: silicon dioxide microsphere is weighed in flask, NaOH is added, is placed on magnetic agitation
30 min are corroded in stirring at room temperature on device, and then with ultrapure water elution, the silica being base treated uses HCL in 90 DEG C of items again
Flow back 8 h under part, is eluted to neutrality with ultrapure water after reflux, dry；
(2) preparation of amination silicon dioxide microsphere: the silicon dioxide microsphere of activation is placed in flask, and toluene is added, then
Silane coupling agent is added, 15 min of ultrasound, in 90 DEG C of 12 h of reflux, methanol washes away unreacted silane coupled after reflux
Resulting amination silicon dioxide granule is filtered in agent, and dry, spare, wherein silane coupling agent accounts for the 5% of volume of toluene, described
Silane coupling agent be 3- aminopropyl triethoxysilane；
(3) preparation method of erythrosine molecularly imprinted polymer: weighing erythrosine and be dissolved in the mixture of methanol, water, and adds
Enter function monomer, stirring is incubated for 2 h at room temperature, then sequentially adds amination silicon dioxide microsphere, crosslinking agent, initiator, surpasses
Sound mixes, and upper end installs threeway glass tube additional after magnetic agitation 10min at room temperature, is passed through nitrogen 30-60min, and will be equipped with anti-
The closed container of liquid is answered to be placed on magnetic stirring apparatus, lasting to stir, oil bath heating at 60-70 DEG C, reaction is taken afterwards for 24 hours
Out, the polymer generated after reaction filters, and to filter off little particle, last eluted template, ammonium hydroxide are dry by polymer, i.e.,
Collect molecularly imprinted polymer；
The function monomer is 4-vinylpyridine (4-VP)；
The crosslinking agent is ethylene glycol dimethacrylate (EGDMA)；
The initiator is azodiisobutyronitrile (AIBN)；
Wherein function monomer, crosslinking agent molar ratio are 1:5, the percentage by volume 2% of function monomer, crosslinking agent in the reaction system；
The methanol, water mixture in methanol, water volume ratio be 4:1.
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| Title |
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| "A New Core@Shell Silica-Coated Magnetic Molecular Imprinted Nanoparticles for Selective Detection of Sunset Yellow in Food Samples";Majid Arvand1 et al.;《Food Anal. Methods》;20170130;第2595页左栏第1-6段 |
| "Electrochemical sensor based on gold nanoparticles fabricated molecularly imprinted polymer film at chitosan–platinum nanoparticles/graphene–gold nanoparticles double nanocomposites modified electrode for detection of erythromycin";Wenjing Lian et al.;《Biosensors and Bioelectronics》;20120524;全文 |
| Jixiang Wang et al.."Optical Detection of λ‑Cyhalothrin by Core−Shell Fluorescent Molecularly Imprinted Polymers in Chinese Spirits".《Journal of Agricultural and Food Chemistry》.2015, |
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