CN113072710B - Gas response type resonance photon molecular imprinting sensor and preparation method thereof - Google Patents
Gas response type resonance photon molecular imprinting sensor and preparation method thereof Download PDFInfo
- Publication number
- CN113072710B CN113072710B CN202110331937.7A CN202110331937A CN113072710B CN 113072710 B CN113072710 B CN 113072710B CN 202110331937 A CN202110331937 A CN 202110331937A CN 113072710 B CN113072710 B CN 113072710B
- Authority
- CN
- China
- Prior art keywords
- carrier
- carbon
- silicon dioxide
- molecular imprinting
- methanol
- 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.)
- Active
Links
- 230000004044 response Effects 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 69
- 241000700605 Viruses Species 0.000 claims abstract description 58
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000000178 monomer Substances 0.000 claims abstract description 31
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 19
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 96
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 76
- 239000007789 gas Substances 0.000 claims description 58
- 239000000377 silicon dioxide Substances 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 34
- 239000011701 zinc Substances 0.000 claims description 34
- 235000012239 silicon dioxide Nutrition 0.000 claims description 33
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 31
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical group [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 31
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 28
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 27
- 229910052725 zinc Inorganic materials 0.000 claims description 24
- 230000003287 optical effect Effects 0.000 claims description 23
- 230000008569 process Effects 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 239000003999 initiator Substances 0.000 claims description 19
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 18
- 239000003431 cross linking reagent Substances 0.000 claims description 18
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 16
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 16
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 15
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 15
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 15
- 239000003153 chemical reaction reagent Substances 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical group CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 13
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000002444 silanisation Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims description 10
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 230000005587 bubbling Effects 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 238000012673 precipitation polymerization Methods 0.000 claims description 7
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 230000000977 initiatory effect Effects 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- -1 comonomer Substances 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 10
- 230000000638 stimulation Effects 0.000 abstract description 9
- 238000009825 accumulation Methods 0.000 abstract description 5
- 239000002245 particle Substances 0.000 description 31
- 239000000463 material Substances 0.000 description 21
- 238000001179 sorption measurement Methods 0.000 description 20
- 238000001514 detection method Methods 0.000 description 16
- 229910004298 SiO 2 Inorganic materials 0.000 description 15
- 229920000344 molecularly imprinted polymer Polymers 0.000 description 14
- 239000000047 product Substances 0.000 description 9
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 8
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 7
- 238000001209 resonance light scattering Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 241000700721 Hepatitis B virus Species 0.000 description 5
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000012876 carrier material Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000002860 competitive effect Effects 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000006884 silylation reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 3
- 239000013177 MIL-101 Substances 0.000 description 2
- 239000013132 MOF-5 Substances 0.000 description 2
- 239000013207 UiO-66 Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000012421 spiking Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- 230000003612 virological effect Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 1
- 206010002820 Antisocial behaviour Diseases 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 208000025721 COVID-19 Diseases 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000027455 binding Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000003759 clinical diagnosis Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000010460 detection of virus Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 210000005260 human cell Anatomy 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- JBFYUZGYRGXSFL-UHFFFAOYSA-N imidazolide Chemical compound C1=C[N-]C=N1 JBFYUZGYRGXSFL-UHFFFAOYSA-N 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000009871 nonspecific binding Effects 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000008055 phosphate buffer solution Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000001262 western blot Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
-
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- 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
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- 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
- B01J20/28002—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 physical properties
- B01J20/28009—Magnetic properties
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention discloses a gas response type resonance photon molecular imprinting sensor and a preparation method thereof, wherein the gas response type resonance photon molecular imprinting sensor comprises a carrier and an imprinting polymer, wherein the imprinting polymer is connected to the carrier; the imprinted polymer is formed by CO 2 The response functional monomer and the comonomer are polymerized, and the imprinted polymer is connected with a target virus template. The carbon dioxide response type imprinted polymer not only improves the specific recognition capability of the sensor on the target virus template, but also effectively avoids the unresponsiveness caused by the accumulation of substances generated by stimulation compared with imprinted polymers of other chemical stimulation modes.
Description
Technical Field
The invention relates to the field of analytical chemistry detection, and mainly relates to a gas response type resonance optical molecular imprinting sensor and a preparation method thereof.
Background
Recently, a novel form of coronary viral pneumoniaThe outbreak of (COVID-19) has raised increasing interest in viral assays. Due to the complex surface conformation and large size of the virus [ Alkordi, H., EL-Khamisy S.F., biosens Bioelectron, 2017,92:349-356 ].]The design and synthesis of receptors for which recognition is a continuing challenge. With the proposal of surface molecular imprinting technology, molecular imprinting technology has been rapidly developed in the field of virus detection in recent years. Nevertheless, the application of this technology in virus detection still has some defects, and needs to be solved urgently. Currently, Molecularly Imprinted Polymers (MIPs) with stimulus response are widely concerned due to their special molecular recognition capabilities, and the types of current stimulus-responsive molecularly imprinted polymers mainly include pH-responsive, temperature-responsive, light-responsive, and solvent-responsive types [ Zhang y., Qin b., Zhang b., anal. chim. Acta, 2020,1096, 193-flac 202. Liu y., Hu x., Liu, z., chem. eng. j., 2017,328,11-24. Xie x., Hua q., Ke r., Zhen x., Bu y., Wang s., chem. eng. j.,2019,371, 130-flac 137. Cui y., z., He., Xu y., Su y., Ding l., Li y.]. And CO 2 / N 2 The responsive material is for the macromolecular biological template, and other responsive materials are milder in stimulation to the template compared with light response, temperature response and solvent response, so that the template is prevented from being denatured and inactivated in the response process, and the gas response is relatively cleaner. On the other hand, compared with a pH response material, the gas response type polymer avoids the phenomenon that accumulation of acid or alkali causes no response, and excessive salt accumulation is not beneficial to the biological activity of the template. Therefore, the application of the gas response molecule recognition material in the virus molecular imprinting has great prospect. However, at present, gas responsive polymers are mostly used for western blotting and never used for virus molecular blotting.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a gas-responsive resonant photonic molecular imprinting sensor and a method for preparing the same, and aims to provide a novel imprinting sensor for specific recognition and detection of viruses.
The technical scheme of the invention is as follows:
a gas response type resonance photon molecular imprinting sensor comprises a carrier and an imprinting polymer, wherein the imprinting polymer is connected to the carrier; the imprinted polymer is formed by CO 2 The response functional monomer and the comonomer are polymerized, and the imprinted polymer is connected with a target virus template.
The gas response type resonance photon molecular imprinting sensor is characterized in that the imprinting polymer takes dimethylaminoethyl methacrylate as CO 2 And initiating polymerization by using a response functional monomer, taking acrylamide as a comonomer, taking a target virus template as a template molecule and N, N-methylene bisacrylamide as a cross-linking agent through an initiator to form the imprinted polymer connected with the target virus template.
The gas response type resonance photon molecular imprinting sensor is characterized in that the initiator adopts the combination of ammonium persulfate and sodium bisulfite or the combination of potassium persulfate and sodium bisulfite; the carrier is ZIF-8 or SiO 2 、 Fe 3 O 4 MIL-101, MOF-5 or UiO-66.
The gas response type resonance photon molecular imprinting sensor is characterized in that the surface of the carrier is coated with a silicon dioxide layer, carbon-carbon double bonds are grafted on the silicon dioxide layer, and the imprinting polymer is connected to the carrier through the carbon-carbon double bonds.
A preparation method of the gas response type resonance photon molecular imprinting sensor comprises the following steps:
adding carrier and CO 2 And (3) carrying out precipitation polymerization reaction on a response functional monomer, a comonomer, a cross-linking agent, an initiator and a target virus template at low temperature to obtain the gas response type resonance photo-molecular imprinting sensor.
The preparation method of the gas response type resonance photon molecular imprinting sensor comprises the steps of adding the carrier and CO 2 The process of performing precipitation polymerization reaction in response to functional monomer, comonomer, cross-linking agent, initiator and target virus template, comprising the steps of:
adding a carrier, a comonomer and a crosslinking agent, and introducing argon to remove oxygen;
adding CO treated with carbon dioxide 2 Responding the aqueous solution of the functional monomer and the target virus template, and performing dispersion treatment;
adding an initiator in a carbon dioxide atmosphere, and carrying out polymerization reaction for 10-30 hours at the temperature of 0-5 ℃;
adding 10-70 mu L of target virus template into every 100mg of vector;
the CO is 2 The response functional monomer is dimethylaminoethyl methacrylate, and 7.86-31.42 mg of CO is added into each 50 mu L of target virus template 2 A response functional monomer;
the comonomer is acrylamide and CO 2 The molar ratio range of the response functional monomer to the comonomer is 1: 3-9;
the cross-linking agent is N, N-methylene bisacrylamide and CO 2 The mass ratio of the sum of the response functional monomer and the comonomer to the cross-linking agent is 1-3: 1;
the initiator adopts the combination of ammonium persulfate and sodium bisulfite or the combination of potassium persulfate and sodium bisulfite; the mass ratio of the N, N-methylene-bisacrylamide to the ammonium persulfate or the potassium persulfate is 1-5: 1; the mass ratio of ammonium persulfate or potassium persulfate to sodium bisulfite is 5-20: 1;
the carbon dioxide treatment process is a carbon dioxide bubbling treatment.
In the present invention, the dispersion treatment is preferably ultrasonic dispersion treatment.
The preparation method of the gas response type resonance optical molecular imprinting sensor comprises the following steps of when the carrier is ZIF-8:
respectively dissolving a zinc source compound and 2-methylimidazole in methanol, quickly introducing the solution of the latter into the solution of the former, stirring at room temperature for 8-20 hours, centrifuging the obtained product, washing with methanol, and drying;
wherein the mass ratio of the zinc source compound to the 2-methylimidazole is 1: 1-4;
the zinc source compound is Zn (NO) 3 ) 2 ·6H 2 O、Zn(NO 3 ) 2 ·H 2 O、ZnCl 2 、Zn(CH 3 COO) 2 ·2H 2 O or ZnBr 2 ；
13 to 68mL of methanol may be added per 1mg of the zinc source compound, and 6 to 31mL of methanol may be added per 1mg of 2-methylimidazole.
The preparation method of the gas response type resonance optical molecular imprinting sensor comprises the step of preparing a zinc source compound Zn (NO) 3 ) 2 ·6H 2 O，Zn(NO 3 ) 2 ·6H 2 The mass ratio of O to 2-methylimidazole is 1: 2.2;
33.67mL of methanol was added per 1mg of the zinc source compound; 15.24mL of methanol was added per 1mg of 2-methylimidazole.
The preparation method of the gas response type resonance optical molecular imprinting sensor comprises the following steps of, when the carrier is ZIF-8:
coating silicon dioxide on the surface of the carrier;
modifying carbon-carbon double bonds on the carrier coated with the silicon dioxide;
the process for coating the surface of the carrier with the silicon dioxide comprises the following steps:
adding a carrier, a solvent and deionized water, and performing dispersion treatment; under the condition of stirring, adding a catalyst, dripping a silanization reagent, and reacting for 8-15 hours at room temperature; centrifuging to collect the product, washing with deionized water and ethanol for several times, and drying;
the process for modifying the carbon-carbon double bond on the carrier coated with the silicon dioxide comprises the following steps:
dissolving the carrier coated with the silicon dioxide in a solvent, dispersing, introducing nitrogen, slowly dropwise adding a compound providing carbon-carbon double bonds, reacting at 80-100 ℃ for 20-30 hours, washing with methanol for several times, and vacuum drying.
The preparation method of the gas response type resonance photon molecular imprinting sensor comprises the step of adding 0.2g of carrier to 0.2g of carrier in the process of coating silicon dioxide on the surface of the carrierAdding 100-180 mL of a solvent, wherein the solvent is absolute ethyl alcohol, methanol or isopropanol, and the volume ratio range of deionized water to the solvent is 1: 4-10; the carrier and the silanization reagent are added in a ratio of 1-5 mL per 0.2g of carrier, and the silanization reagent is tetraethyl orthosilicate; the volume ratio of the silanization reagent to the catalyst is 3: 5-10, the catalyst is NH 3 ·H 2 O；
In the process of modifying the carbon-carbon double bond on the carrier coated with the silicon dioxide, the proportion of the carrier coated with the silicon dioxide to the compound providing the carbon-carbon double bond is that 0.5-5 mL of the compound providing the carbon-carbon double bond is added to every 500mg of the carrier coated with the silicon dioxide, and the compound providing the carbon-carbon double bond is 3-methacryloxypropyl trimethoxysilane; the proportion of the carrier coated with the silicon dioxide to the solvent is that 20-100 mL of the solvent is added into every 500mg of the carrier coated with the silicon dioxide, and the solvent is toluene, absolute methanol or absolute ethanol.
Has the advantages that: in the gas response type resonance photon molecular imprinting sensor provided by the invention, the carbon dioxide response type imprinting polymer not only improves the specific recognition capability of the sensor on a target virus template, but also effectively avoids the irresponsibility caused by the accumulation of substances generated by stimulation compared with imprinting polymers in other chemical stimulation modes. The invention provides theoretical support for the application of molecular imprinting technology in virus clinical diagnosis, and has important application prospect.
Drawings
Fig. 1 is a flow chart of the construction of a gas response type resonance optical molecular imprinting sensor in embodiment 1 of the present invention.
FIG. 2 is a resonance light scattering intensity spectrum of MIP of the imprinted polymer particles in example 1 of the present invention.
FIG. 3 is a resonance light scattering spectrum of MIP-adsorbed HBV by imprinted polymer particles in example 1 of the present invention.
Fig. 4 is a verification of the feasibility of the gas response type resonance optical molecular imprinting sensor for virus detection in embodiment 2 of the present invention.
FIG. 5 shows the preparation of the functional monomer dimethylaminoethyl methacrylate in example 3 of the present inventionIn CO 2 And N 2 1H-NMR under the conditions.
FIG. 6 shows MIP and ZIF-8@ SiO in example 3 of the present invention 2 @ C = change in potential of the C material at different times of carbon dioxide treatment.
FIG. 7 shows adsorption and desorption of MIP and NIP in CO in example 3 of the present invention 2 And N 2 Resonance light changes at three cycles of bubbling.
FIG. 8 is an IR spectrum of ZIF-8(a), NIP (b), MIP (c), MIP + V (d) in example 3 of the present invention.
FIG. 9 shows ZIF-8(a), ZIF-8@ SiO in example 3 of the present invention 2 (b) XRD patterns of MIP (c) and NIP (d).
FIG. 10 is a ZIF (A), ZIF-8@ SiO solid, example 3 of the present invention 2 (B) Mip (c) and nip (d) particles.
FIG. 11 is a ZIF (A), ZIF-8@ SiO solid, example 3 of the present invention 2 (B)、ZIF-8@SiO 2 @ C = C (C), mip (d), and nip (e) the contact angle of the particles.
FIG. 12 is a view showing ZIF, ZIF-8@ SiO in example 3 of the present invention 2 、 ZIF-8@SiO 2 @ C = C, MIP and the potential diagram of HBV (HBV stands for MIP adsorption HBV) particles.
FIG. 13 is a graph showing the response and detection of the gas responsive resonant photonic molecular imprinting sensor to HBV concentrations in example 4 of the present invention.
FIG. 14 is a diagram showing the selective absorption of different viruses by the gas-responsive resonance optical molecular imprinting sensor in example 4 of the present invention.
FIG. 15 is a diagram showing competitive adsorption of different viruses by the gas-responsive resonance optical molecular imprinting sensor in example 4 of the present invention.
Fig. 16 is a diagram showing the reproducibility of the gas response type resonance optical molecular imprinting sensor in example 4 of the present invention.
Fig. 17 is a stability chart of the gas response type resonance optical molecular imprinting sensor in embodiment 4 of the present invention.
FIG. 18 is a diagram of a gas responsive resonance optical molecular imprinting sensor for spiking recovery of HBV in example 4 of the present invention.
Detailed Description
The invention provides a gas response type resonance photon molecular imprinting sensor and a preparation method thereof, and the invention is further explained in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the present invention provides examples of various specific processes and materials, but one of ordinary skill in the art may recognize applications of other processes and/or uses of other materials.
The invention provides a gas response type resonance photon molecular imprinting sensor, which comprises a carrier and an imprinting polymer, wherein the imprinting polymer is connected to the carrier; the imprinted polymer takes dimethylaminoethyl methacrylate as CO 2 The response functional monomer is polymerized by acrylamide comonomer, and the imprinted polymer is also connected with a target virus template.
In the invention, the imprinted polymer is specifically prepared by taking dimethylaminoethyl methacrylate as CO 2 The imprinted polymer connected with the target virus template is formed by initiating polymerization through an initiator by using a response functional monomer, an acrylamide comonomer, the target virus template as a template molecule and N, N-methylene bisacrylamide as a cross-linking agent. Dimethylaminoethyl methacrylate can cause gas response in CO 2 Amino positive ions can be formed under the atmosphere to be combined with the template through electrostatic interaction, and N is introduced 2 Can convert CO into 2 Removing the recovery potential; and the acrylamide monomer has no gas responsiveness, but the addition of the acrylamide monomer can improve the recognition specificity of the imprinted polymer. Preferably, the molar ratio of dimethylaminoethyl methacrylate to acrylamide is in the range of 1: 3 to 9, wherein the optimal molar ratio in the range is 1: and 7, obtaining the best imprinting effect.
In the invention, the gas response type functional monomer is used in the virus molecular imprinting for the first time by regulating CO 2 And N 2 Can realize reversible adsorption and desorption of the imprinted polymer on the template virus, can reversibly recognize and remove the virus, reduces the nonspecific binding of imprinted particles, and can be constructed into a novel imprinted particleThe resonant sensor of (3) is used for the detection of a target virus. The gas response type resonance photon molecular imprinting sensor not only improves the specific recognition capability of the sensor on the template virus, but also effectively avoids the phenomenon that substances generated by stimulation are accumulated to cause non-response compared with imprinting polymers of other chemical stimulation modes.
Preferably, the initiator is Ammonium Persulfate (APS) and sodium bisulfite (NaHSO) 3 ) Or a combination of potassium persulfate and sodium bisulfite. The combination is used as an initiator to initiate at low temperature, namely CO in a reaction system is avoided 2 Overflow due to high temperature initiation, and low temperature initiation can also protect template denaturation.
In the scheme of the embodiment of the invention, the carrier can be ZIF-8 or SiO 2 、 Fe 3 O 4 MIL-101, MOF-5 or UiO-66, etc. Preferably, the carrier may be ZIF-8. The ZIF-8 material belongs to a zeolite imidazole framework of a porous crystalline coordination polymer, has good chemical stability and flexibility and has wide application prospect, while the ZIF-8 has a rhombic dodecahedral structure, and has the characteristics of low density, large specific surface area, uniform cavity structure, easy surface modification and the like [ Chen, B]The molecular imprinting carrier material is an ideal molecular imprinting carrier material and can provide more accessible and effective imprinting sites for the imprinted polymer.
Further, the surface of the carrier is modified by a silanization reagent and grafted with carbon-carbon double bonds, namely, the surface of the carrier is coated with a silicon dioxide layer, the carbon-carbon double bonds are grafted on the silicon dioxide layer, and the imprinted polymer is connected to the carrier through the carbon-carbon double bonds. The surface modified carrier can lead the imprinted polymer to be more stably, effectively and more connected on the carrier.
The target virus template is not particularly limited, the gas response type resonance optical molecular imprinting sensor has universality, and the embodiment of the invention takes the HBV virus as an example for illustration.
The invention also provides a preparation method of the gas response type resonance photon molecular imprinting sensor, which comprises the following steps:
adding carrier and CO 2 And carrying out precipitation polymerization reaction on the response functional monomer, the comonomer, the cross-linking agent, the initiator and the target virus template to obtain the gas response type resonance optical molecular imprinting sensor.
Specifically, the carrier and CO are added 2 The process of performing precipitation polymerization reaction in response to functional monomer, comonomer, cross-linking agent, initiator and target virus template, comprising the steps of:
adding a carrier, a comonomer and a crosslinking agent, and introducing argon to remove oxygen;
adding CO treated with carbon dioxide 2 Responding the aqueous solution of the functional monomer and the target virus template, and performing dispersion treatment;
adding an initiator in a carbon dioxide atmosphere, and carrying out polymerization reaction for 10-30 hours at the temperature of 0-5 ℃;
and (3) sequentially washing with methanol/acetic acid (9: 1, v/v) and ultrapure water for several times until the ultraviolet absorption of the target virus template molecule cannot be detected in the supernatant, thus obtaining the gas response type resonance photonic molecular imprinting sensor (MIP).
Adding 10-70 mu L of target virus template into each 100mg of carrier;
the CO is 2 The response functional monomer is dimethylaminoethyl methacrylate, and 7.86-31.42 mg of CO is added into each 50 mu L of target virus template 2 A response functional monomer;
the comonomer is acrylamide and CO 2 The molar ratio range of the response functional monomer to the comonomer is 1: 3-9;
the cross-linking agent is N, N-methylene-bisacrylamide and CO 2 The mass ratio range of the sum of the response functional monomer and the comonomer to the cross-linking agent is 1-3: 1;
the initiator adopts the combination of ammonium persulfate and sodium bisulfite or the combination of potassium persulfate and sodium bisulfite; the mass ratio range of the N, N-methylene bisacrylamide to the ammonium persulfate or the potassium persulfate is 1-5: 1; the mass ratio of ammonium persulfate or potassium persulfate to sodium bisulfite is 5-20: 1.
the carbon dioxide bubbling treatment is carried out for 20-40 min. The bubbling of carbon dioxide is carried out in advance to remove oxygen in water, and the system is first put under carbon dioxide atmosphere to supply carbonic acid during the reaction.
In the embodiment of the invention, ZIF-8 is preferably used as a carrier, and the carrier can be prepared by the following preparation method:
respectively dissolving a zinc source compound and 2-methylimidazole in methanol, quickly introducing the solution of the latter into the solution of the former, stirring at room temperature for 8-20 hours, centrifuging the obtained product, washing with methanol for several times, and drying for later use.
Wherein the mass ratio between the zinc source compound and the 2-methylimidazole can be 1: 1 to 4. The zinc source compound may be Zn (NO) 3 ) 2 ·6H 2 O、Zn(NO 3 ) 2 ·H 2 O、ZnCl 2 、Zn(CH 3 COO) 2 ·2H 2 O or ZnBr 2 And so on. In an embodiment of the present invention, the zinc source compound may be Zn (NO) 3 ) 2 ·6H 2 O，Zn(NO 3 ) 2 ·6H 2 The mass ratio of O to 2-methylimidazole is 1: 1.5 to 4, preferably 1: 2.2, higher yields can be obtained with this optimum ratio.
13 to 68mL of methanol may be added per 1mg of the zinc source compound, and preferably 33.67mL of methanol may be added per 1mg of the zinc source compound. 6-31 mL of methanol can be added to 1mg of 2-methylimidazole, and preferably 15.24mL of methanol can be added to 1mg of 2-methylimidazole, and the proportion can be adopted to obtain a product with uniform dispersion.
In an embodiment of the present invention, when the vector is ZIF-8, the vector may be modified as follows. When the carrier is made of other materials, the following modification treatment or other modification treatment can be adopted to facilitate the carrier to be combined with the imprinted polymer, and when the carrier is made of other materials, the following raw materials, dosage ratios and the like can be adjusted as appropriate.
Specifically, when the carrier is ZIF-8, the modification treatment process comprises the following steps:
coating silicon dioxide on the surface of the carrier;
modifying carbon-carbon double bonds on the carrier coated with the silicon dioxide.
In an embodiment of the present invention, the process for coating silica on the surface of a carrier includes the following steps:
adding a carrier, a solvent and deionized water, and performing dispersion treatment;
under the condition of stirring, adding a catalyst, dripping a silanization reagent, and reacting for 8-15 hours at room temperature;
and centrifuging to collect the product, washing with deionized water and ethanol for several times respectively, and drying for later use.
Wherein the proportion of the carrier to the solvent is that 100-180 mL of solvent is added to every 0.2g of carrier, and the solvent can be absolute ethyl alcohol, methanol or isopropanol and the like. The volume ratio range of the deionized water to the solvent is 1: 4 to 10.
The ratio of the carrier to the silylation reagent is that 1-5 mL of the silylation reagent is added to every 0.2g of the carrier, and the silylation reagent can be tetraethyl orthosilicate (TEOS).
The volume ratio of the silanization reagent to the catalyst is 3: 5 to 10, the catalyst can be NH 3 ·H 2 O。
In an embodiment of the present invention, the process of modifying a carbon-carbon double bond on a silica-coated carrier includes the following steps:
dissolving the carrier coated with the silicon dioxide in a solvent, dispersing, introducing nitrogen, slowly and dropwise adding a compound for providing carbon-carbon double bonds, reacting at 80-100 ℃ for 20-30 hours, washing with methanol for several times, and drying in vacuum for later use.
Wherein the proportion of the carrier coated with the silicon dioxide to the compound providing the carbon-carbon double bond is that 0.5-5 mL of the compound providing the carbon-carbon double bond is added to every 500mg of the carrier coated with the silicon dioxide, and the compound providing the carbon-carbon double bond can be 3-Methacryloxypropyltrimethoxysilane (MPS).
The ratio of the silica-coated carrier to the solvent is 20-100 mL of the solvent per 500mg of the silica-coated carrier, and the solvent may be toluene, absolute methanol, absolute ethanol or the like, but is preferably toluene because the yield is higher when the solvent is toluene.
The invention also provides a detection method of the gas response type resonance photon molecular imprinting sensor, which comprises the following steps:
taking a proper amount of the gas response type resonance optical molecular imprinting sensor into a buffer solution, adding a test sample, and oscillating and adsorbing under an optimized adsorption condition; taking 1mL of the mixture in a cuvette, synchronously scanning by using an MFS phosphorescence/luminescence spectrophotometer, wherein the scanning range is 220.0-700.0 nm, the width of an excitation slit and an emission slit is 3 nm, and recording the resonance light scattering intensity at 470 nm. Wherein, the optimized adsorption conditions are as follows: the adsorption time was 30min and the adsorption temperature was 25 ℃.
The gas response type resonance photon molecular imprinting sensor has the following beneficial effects:
(1) the gas response type functional monomer is used for virus molecular imprinting for the first time, so that the specific recognition capability of the sensor on the template virus is improved, and the phenomenon that substances generated by stimulation cannot respond due to accumulation is effectively avoided compared with imprinting polymers of other chemical stimulation modes. While regulating CO 2 And N 2 Can realize reversible adsorption and desorption of the imprinted polymer to the template virus.
(2) The zeolite imidazole ester material combines the advantages of metal organic framework materials and zeolite, has large specific surface area and can provide more binding sites; and the surface is easy to modify, thus being more beneficial to storage and long-term use.
(3) The experimental result shows that the virus molecule resonance optical track sensor has good selectivity on target molecules, the track factor is as high as 6.7, the linear range is wider, and the detection limit reaches 9.1 pM; the imprinted polymer can be recovered and recycled. (4) The virus molecularly imprinted polymer adopts CO 2 In response, twoThe carbon oxide has biocompatibility, and is one of important metabolites naturally produced in human cells, so that the gas response type molecular recognition material has great potential in biological related applications.
The present invention is further illustrated by the following specific examples.
Example 1: preparation of gas response type resonance photon molecular imprinting sensor based on zeolite imidazole ester material
As shown in fig. 1, the method comprises the following steps:
(1) preparation of zeolite imidazolate material ZIF-8:
1.485 g of Zn (NO) 3 ) 2 ·6H 2 O and 3.28 g of 2-methylimidazole are dissolved in 50 mL of methanol respectively, then the latter solution is poured into the former solution quickly, stirred at room temperature for 12 hours, the obtained product is centrifuged and washed three times with methanol, and the obtained product is dried overnight in a vacuum drying oven at 60 ℃ for later use.
（2）ZIF-8@SiO 2 Preparation of particles:
0.2g of ZIF-8 particles was placed in a 250 mL round bottom flask, and 140 mL of absolute ethanol and 20 mL of deionized water were added. Mixing with ultrasound for 15 min to disperse uniformly. Under mechanical stirring, 8mL NH was added 3 ·H 2 O, then 3 mL TEOS is slowly dropped, reacted for 12 h at room temperature, collected by centrifugation at 8000 rpm, and washed three times with deionized water and ethanol, respectively, and dried overnight in a vacuum oven at 50 ℃ for use.
（3）ZIF-8@ SiO 2 Preparation of @ C = C particles:
weighing 500mg of ZIF-8@ SiO 2 Dissolving in 50 mL toluene, ultrasonically stirring and mixing for 15 min, introducing nitrogen, slowly dropwise adding 2 mL 3-Methacryloxypropyltrimethoxysilane (MPS), reacting at 90 ℃ for 24 h, washing with methanol for three times, and vacuum drying at 25 ℃ for 12 h for later use.
(4) Preparation of imprinted polymer particles (MIPs) and non-imprinted polymer particles (NIPs):
firstly, weighing 100mg of ZIF-8@ SiO prepared in the above way 2 @ C = C nanoparticles,acrylamide (59.7 mg, 0.84 mmol), N, N-Methylenebisacrylamide (MBA) (30.84 mg, 0.2 mmol) in a 50 mL three-necked flask, argon was first passed through to remove oxygen. 10mL of carbon dioxide treated aqueous solution (CO) containing dimethylaminoethyl methacrylate (18.86 mg, 0.12 mmol) and 50 μ L of HBV template virus 2 Bubbling for 30 min) was poured into a three-necked flask via a constant pressure funnel. After ultrasonic stirring for 30min, 11.41 mg of Ammonium Persulfate (APS) and 1.14 mg of NaHSO were injected under carbon dioxide atmosphere 3 Initiating precipitation polymerization, and polymerizing for 24 h at 0 deg.C. After the reaction is finished, repeatedly washing with methanol/acetic acid (9: 1, v/v) and ultrapure water for 3 times until no template molecule ultraviolet absorption can be detected in the supernatant, and obtaining the HBV imprinted polymer particles (MIP), namely the gas response type resonance light molecularly imprinted sensor. For reference, non-imprinted polymers (NIP) were obtained using the same synthetic procedure except that no template HBV was added.
(5) In the following examples, the detection method of the gas response type resonance photon molecular imprinting sensor is as follows:
and (3) taking the MIP in a PBS buffer solution (20 mM, pH = 7.2) to obtain the MIP with the concentration of 200 ng/mL, adding a proper amount of HBV virus, and oscillating and adsorbing under the optimized adsorption condition. Then, 1mL of the mixture was placed in a cuvette and scanned synchronously with MFS phosphorescence/luminescence spectrophotometer over a range of 220.0-700.0 nm, with excitation and emission slit widths of 3 nm, and the resonance light scattering intensity at 470 nm was recorded. Wherein, the optimized conditions are as follows: the adsorption time is 30min, and the adsorption temperature is 25 ℃.
The resonance light scattering intensity of the test imprinted polymer particle MIPs is shown in fig. 2.
The resonance light scattering intensity of MIP of the imprinted polymer particles to adsorb HBV is shown in fig. 3.
Example 2: feasibility verification of virus detection by MIP resonance optical sensor
In order to verify the applicability of the present invention, the present embodiment verifies the construction principle of the gas response type resonance optical molecular imprinting sensor.
As shown in fig. 2, the magnitude ratio of the resonant light intensity at 470 nm is:
HBV+ MIPs> MIPs; HBV+ NIPs> NIPs；
wherein HBV + MIPs are hepatitis B virus adsorbed by the imprinted polymer particles (MIP) obtained in the step (4) of the embodiment 1; MIPs are imprinted polymer particles (MIPs) of the product of step (4) of example 1; HBV + NIPs are hepatitis B virus adsorbed by non-imprinted polymer (NIP) which is a product obtained in the step (4) of example 1; the NIPs are non-imprinted polymers (NIPs) obtained in step (4) of example 1. The dosage and adsorption conditions of HBV + MIPs and HBV + NIPs are the same.
As can be seen from the results of fig. 4, the imprinted polymer particles (MIPs) according to the present invention adsorb HBV particles well and have excellent selectivity compared to NIP, and it is also known that the resonance light scattering intensity varies significantly by the variation of particle size.
Example 3: characterization of the Properties, morphology and Structure of imprinted Polymer particles (MIP) and intermediates
To verify the CO of imprinted polymer particles (MIPs) 2 Response Properties, dimethylaminoethyl methacrylate CO was studied by nuclear magnetic hydrogen spectroscopy in this example 2 The response behavior is shown in FIG. 5, in which graph A is the nuclear magnetic hydrogen spectrum of dimethylaminoethyl methacrylate and graph B is the CO introduction 2 Nuclear magnetic hydrogen spectrum of the post-methacrylic acid dimethylamino ethyl ester, wherein the C picture is the introduction of N 2 Nuclear magnetic hydrogen spectrum of the latter dimethylaminoethyl methacrylate (DMAEMA). Observations can find CO incorporation 2 Thereafter, the protons of the methyl (d) and of the methylene function (c) are transferred to the lower field at 2.03 and 2.46-2.49 ppm, and N is introduced 2 Returning to the original position, these observations indicate that the tertiary amino group of DMAEMA can be reacted with CO 2 Under treatment, CO is introduced 2 The bicarbonate produced by dissolution in the aqueous solution reacts, resulting in protonation and the formation of a charged state. The reverse process is by inert N 2 To be realized. The principle is shown as the following formula:
also by comparing imprinted polymer particles (MIP) with ZIF-8@ SiO 2 @ C = C at CO 2 And N 2 The potential change in the atmosphere was observed to increase the potential of the carbon dioxide MIP and decrease the potential after the introduction of nitrogen as shown in FIG. 6, further confirming that the polymer has CO 2 -N 2 The response performance of (c). By using N alternately for MIP, NIP as shown in FIG. 7 2 And CO 2 Bubbling for three cycles, and performing adsorption and desorption on 1nM HBV, which shows that the molecular imprinting sensor can realize reversible response identification on target virus HBV gas.
All the prepared materials are characterized by structure, morphology and properties by utilizing a Fourier transform infrared spectrometer, an X-ray diffractometer, a scanning electron microscope, a contact angle and a potential.
FIG. 8 is the infrared spectra of various materials, (a), (b), (c) and (d) corresponding to ZIF-8 carrier material, NIP, MIP + V (imprinted polymer particle MIP adsorbing hepatitis B virus HBV), respectively. 2925. 1590, 1143 and 997 cm -1 C-H, C = N and C-N oscillations, 417cm, in the imidazole ring corresponding to ZIF-8, respectively -1 The nearby peaks are characteristic peaks of Zn-N, found in 1085 and 467 cm for the other three particles -1 Two new peaks appear, which are caused by the stretching vibration of Si-O-Si and the bending vibration of Si-O, and the absorption wavelengths of the two new peaks are close, which indicates that the surface structures of the two new peaks are similar, and the structure of the imprinted polymer is not influenced by the addition of the virus.
FIG. 9 is an X-ray diffraction chart showing that (a), (b), (c) and (d) correspond to the ZIF-8 carrier material, ZIF-8@ SiO, respectively 2 Particles, MIP, NIP. As can be seen from the figure, the main characteristic peaks of ZIF-8 all appear between 2 theta 2 DEG and 50 DEG, and the crystal structure is good. The strength of the peak is weakened after the silica layer is coated, but some characteristic peaks of ZIF-8 exist, the strength of the peak is obviously weakened after the imprinting, and the characteristic peak of ZIF-8 disappears, which proves that the imprinted polymer is successfully synthesized.
FIG. 10 is ZIF-8(A), ZIF-8@ SiO 2 (B) Imprinted polymers MIP (C)And scanning electron micrographs of non-imprinted polymer nip (d). As can be seen from the graph (A), ZIF-8 particles had good dispersibility and smooth surface, a regular dodecahedral structure in shape, and an average size ranging from 80 to 100 nm. Coated SiO 2 As shown in the graph (B), the particle size was about 180 nm, and the dodecahedral morphology was observed, but the adhesiveness was severe. Panel (C) shows that after blotting, the particles range in size from 200 to 250 nm. Thus, the print layer is at least 20 nm thick. In addition, both the imprinted polymer MIP and the non-imprinted polymer NIP were relatively poorly dispersible compared to ZIF-8 particles, which was caused by agglomeration of the particles after polymerization on the surface thereof. These results all indicate that the gas response type resonance photon molecular imprinting sensor was successfully prepared in example 1.
FIG. 11 is ZIF-8(A), ZIF-8@ SiO 2 （B），ZIF-8@SiO 2 The contact angles of @ C = C (C), imprinted polymer mip (d) and non-imprinted polymer nip (e), from which the hydrophilicity of the respective materials can be seen. From the graph (C), it can be seen that the hydrophobic property of the material after grafting the double bond is enhanced, and it can be proved that the double bond is successfully grafted to ZIF-8@ SiO 2 Of (2) is provided. After imprinting, the hydrophilicity of the imprinted polymer and the non-imprinted polymer is enhanced, further proving successful imprinting.
FIG. 12 shows the respective materials ZIF-8, ZIF-8@ SiO 2 、ZIF-8@SiO 2 Graph of potential test results for @ C = C, MIP, HBV (HBV stands for MIP-adsorbed HBV). The gas response type resonance photon molecular imprinting sensor is successfully prepared through the potential change of each material, which is also important for the property discussion of the sensor. The potential measurement of HBV proves that MIP and HBV can be combined through electrostatic action.
Example 4: application of imprinted polymer particle MIP
The experimental conditions of this example were: the dosage of MIP is 200 ng/mL, the adsorption time is 30min, and the temperature is 25 ℃.
The specific implementation scheme is as follows: HBV and MIP were taken in PBS buffer (20 mM, pH = 7.2) to give specific concentration of HBV and 200 ng/mL of MIP, respectively. Under the condition, after oscillating for 30min, the resonant light intensity IRLS is measured. (1) analysis of different concentrations of HBV by MIP resonance optical sensor according to the above experimental procedures, the result of detection analysis of different concentrations of HBV by the MIP sensor described in the present invention is shown in FIG. 13, the concentration range of HBV analysis by the prepared sensor is 0.01 nM-2.5 nM, (0.05, 0.1, 0.2, 0.3, 0.5, 1, 1.5, 2 nM in sequence), the linear concentration range is 0.05-2 nM, the detection limit is 9.1 pM, the result shows that the linear range is wide, the detection limit is low, and the overall effect is good. (2) Selective and competitive adsorption of MIP resonance photosensor on HBV this example selects HAV, RV, LV and JEV with concentration of 1.0 nM as target to examine the adsorption and detection ability of MIP on HBV. The experiment was performed according to the procedure described above, and the Δ IRLS ═ IRLS-I0 was calculated by repeating the averaging three times (I0 is the intensity of resonance light without HBV). The results of the experiment are shown in FIG. 14. It can be seen that the adsorption capacity of the MIP sensor on HAV is obviously better than that of other viruses, and the Imprinting Factors (IF) = Δ IRLS, MIP/Δ IRLS and NIP are calculated to obtain the imprinting factor of 6.7, which indicates that the selectivity is better. In order to further examine the specific adsorption capacity of the sensor of the invention on HBV, the virus is taken as a competitive substance, a binary competitive adsorption experiment is designed, the experimental result is shown in FIG. 15, other viruses are added simultaneously on the basis of adding the target virus HBV, the resonant light intensity has no obvious change, which shows that the addition of other viruses does not generate non-negligible interference on the sensor, and the sensor is an important parameter in practical application.
(3) Reproducibility and stability of MIP resonant optical sensor
The reproducibility and stability of the sensor are also important indexes, firstly, the same concentration of HBV viruses are detected by synthesizing five different batches of sensors respectively, the results are shown in FIG. 16, and the results obtained from the five experiments are basically consistent, which shows that the scheme of the invention can be repeated. With respect to the stability of the sensor, the detection effect of the sensor on HBV, which was measured for 1 week, 2 weeks, 3 weeks, and 4 weeks, is shown in FIG. 17, and although the detection effect is decreased with time, the effect is still satisfactory.
(4) Labeling recovery of HBV by MIP resonance optical sensor
The method of spiking recovery was used to evaluate the analytical ability of the previously described method on actual samples. Human serum samples (stored at 4 ℃ C.) collected from Hunan Tan university Hospital were diluted 1000-fold with a phosphate buffer solution (20 mM, pH 7.2), and HBV was added thereto at concentrations of 0.08 nM, 0.15 nM, 0.85 nM, 1.25 nM and 1.75 nM, respectively, and detected using the MIP resonance optical sensor prepared in inventive example 1. The experimental result is shown in fig. 18, the recovery rate of the standard addition is 96.98-106.5%, and the method can be used for measuring actual samples.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (8)
1. A gas response type resonance photon molecular imprinting sensor is characterized by comprising a carrier and an imprinting polymer, wherein the imprinting polymer is connected to the carrier; the imprinted polymer is formed by CO 2 The response functional monomer and the comonomer are polymerized, and the imprinted polymer is connected with a target virus template;
the imprinted polymer is CO by using dimethylaminoethyl methacrylate 2 The method comprises the following steps of (1) initiating polymerization by using a response functional monomer, acrylamide as a comonomer, a target virus template as a template molecule and N, N-methylene-bisacrylamide as a cross-linking agent through an initiator to form an imprinted polymer connected with the target virus template;
the carrier is ZIF-8;
the surface of the carrier is coated with a silicon dioxide layer, carbon-carbon double bonds are grafted on the silicon dioxide layer, and the imprinted polymer is connected to the carrier through the carbon-carbon double bonds.
2. The gas response type resonance photon molecular imprinting sensor according to claim 1, wherein the initiator employs a combination of ammonium persulfate and sodium bisulfite, or a combination of potassium persulfate and sodium bisulfite.
3. A method for preparing a gas response type resonance optical molecular imprinting sensor according to any one of claims 1 to 2, comprising the steps of:
adding carrier and CO 2 Carrying out precipitation polymerization reaction on a response functional monomer, a comonomer, a cross-linking agent, an initiator and a target virus template at low temperature to obtain the gas response type resonance optical molecular imprinting sensor;
the addition of carrier, CO 2 The process of performing precipitation polymerization reaction in response to functional monomer, comonomer, cross-linking agent, initiator and target virus template, comprising the steps of:
adding a carrier, a comonomer and a crosslinking agent, and introducing argon to remove oxygen;
adding CO treated with carbon dioxide 2 Responding the aqueous solution of the functional monomer and the target virus template, and performing dispersion treatment;
adding an initiator in a carbon dioxide atmosphere, and carrying out polymerization reaction for 10-30 hours at the temperature of 0-5 ℃;
adding 10-70 mu L of target virus template into every 100mg of vector;
the CO is 2 The response functional monomer is dimethylaminoethyl methacrylate, and 7.86-31.42 mg of CO is added into each 50 mu L of target virus template 2 A response functional monomer;
the comonomer is acrylamide and CO 2 The molar ratio range of the response functional monomer to the comonomer is 1: 3-9;
the cross-linking agent is N, N-methylene bisacrylamide and CO 2 The mass ratio range of the sum of the response functional monomer and the comonomer to the cross-linking agent is 1-3: 1;
the carbon dioxide treatment process is a carbon dioxide bubbling treatment.
4. The method for producing a gas responsive resonance photon molecular imprinting sensor according to claim 3, wherein the initiator is a combination of ammonium persulfate and sodium bisulfite, or a combination of potassium persulfate and sodium bisulfite; the mass ratio range of the N, N-methylene bisacrylamide to the ammonium persulfate or the potassium persulfate is 1-5: 1; the mass ratio of ammonium persulfate or potassium persulfate to sodium bisulfite is 5-20: 1.
5. the method for preparing a gas-responsive resonance photonic molecular imprinting sensor according to claim 3, wherein the carrier is prepared by the following steps:
respectively dissolving a zinc source compound and 2-methylimidazole in methanol, quickly introducing the solution of the latter into the solution of the former, stirring at room temperature for 8-20 hours, centrifuging the obtained product, washing with methanol, and drying;
wherein the mass ratio of the zinc source compound to the 2-methylimidazole is 1: 1-4;
the zinc source compound is Zn (NO) 3 ) 2 ·6H 2 O、Zn(NO 3 ) 2 ·H 2 O、ZnCl 2 、Zn(CH 3 COO) 2 ·2H 2 O or ZnBr 2 ；
13 to 68mL of methanol may be added per 1mg of the zinc source compound, and 6 to 31mL of methanol may be added per 1mg of 2-methylimidazole.
6. The method for preparing a gas responsive resonance photon molecular imprinting sensor according to claim 5, wherein the zinc source compound is Zn (NO) 3 ) 2 ·6H 2 O，Zn(NO 3 ) 2 ·6H 2 The mass ratio of O to 2-methylimidazole is 1: 2.2;
33.67mL of methanol was added per 1mg of the zinc source compound; 15.24mL of methanol was added per 1mg of 2-methylimidazole.
7. The method for preparing a gas-responsive resonance photonic molecular imprinting sensor according to claim 3, wherein the carrier is modified by the following process:
coating silicon dioxide on the surface of the carrier;
modifying carbon-carbon double bonds on the carrier coated with the silicon dioxide;
the process for coating the surface of the carrier with the silicon dioxide comprises the following steps:
adding a carrier, a solvent and deionized water, and performing dispersion treatment; under the condition of stirring, adding a catalyst, dripping a silanization reagent, and reacting for 8-15 hours at room temperature; centrifuging to collect the product, washing with deionized water and ethanol for several times, and drying;
the process for modifying carbon-carbon double bonds on a carrier coated with silicon dioxide comprises the following steps:
dissolving the carrier coated with the silicon dioxide in a solvent, dispersing, introducing nitrogen, slowly dropwise adding a compound providing carbon-carbon double bonds, reacting at 80-100 ℃ for 20-30 hours, washing with methanol for several times, and vacuum drying.
8. The method for preparing the gas response type resonance photon molecular imprinting sensor according to claim 7, wherein in the process of coating the silicon dioxide on the surface of the carrier, 100-180 mL of solvent is added to 0.2g of carrier, the solvent is absolute ethyl alcohol, methanol or isopropanol, and the volume ratio range of deionized water to the solvent is 1: 4-10; the carrier and the silanization reagent are added in a ratio of 1-5 mL per 0.2g of carrier, and the silanization reagent is tetraethyl orthosilicate; the volume ratio of the silanization reagent to the catalyst is 3: 5 to 10, the catalyst is NH 3 ·H 2 O；
In the process of modifying the carbon-carbon double bond on the carrier coated with the silicon dioxide, the proportion of the carrier coated with the silicon dioxide to the compound providing the carbon-carbon double bond is that 0.5-5 mL of the compound providing the carbon-carbon double bond is added to every 500mg of the carrier coated with the silicon dioxide, and the compound providing the carbon-carbon double bond is 3-methacryloxypropyl trimethoxysilane; the ratio of the carrier coated with the silicon dioxide to the solvent is that 20-100 mL of the solvent is added to every 500mg of the carrier coated with the silicon dioxide, and the solvent is toluene, anhydrous methanol or anhydrous ethanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110331937.7A CN113072710B (en) | 2021-03-29 | 2021-03-29 | Gas response type resonance photon molecular imprinting sensor and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110331937.7A CN113072710B (en) | 2021-03-29 | 2021-03-29 | Gas response type resonance photon molecular imprinting sensor and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113072710A CN113072710A (en) | 2021-07-06 |
| CN113072710B true CN113072710B (en) | 2022-09-09 |
Family
ID=76611339
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110331937.7A Active CN113072710B (en) | 2021-03-29 | 2021-03-29 | Gas response type resonance photon molecular imprinting sensor and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113072710B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113774108A (en) * | 2021-07-27 | 2021-12-10 | 罗义 | Method for enriching and detecting infectious new coronavirus by selectively adsorbing spike glycoprotein |
| CN114797799B (en) * | 2022-04-15 | 2023-08-01 | 东北电力大学 | Preparation method of MOFs-based lithium ion imprinting composite nanofiber membrane |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0511116D0 (en) * | 2005-06-01 | 2005-07-06 | Univ Cranfield | Preparation of soluble and collodial imprinted polymers by living polymerization |
| CN105107482A (en) * | 2015-09-11 | 2015-12-02 | 中国农业科学院农业质量标准与检测技术研究所 | Preparation method for molecular imprinting material and molecular imprinting material prepared through preparation method |
| CN106883346B (en) * | 2017-02-03 | 2019-04-12 | 西安交通大学 | A kind of preparation method of dexamethasone magnetic molecularly imprinted polymer |
| CN109632730B (en) * | 2018-11-22 | 2022-04-01 | 湘潭大学 | Preparation and application of intelligent virus molecular imprinting resonance optical sensor based on metal organic framework |
| CN110702647A (en) * | 2019-09-02 | 2020-01-17 | 湘潭大学 | Construction and application of novel fluorescent imprinting sensor based on magnetic Metal Organic Framework (MOF) |
| CN110736725B (en) * | 2019-09-30 | 2022-04-01 | 湘潭大学 | Preparation method and application of molecularly imprinted fluorescent sensor for simultaneously and visually detecting two viruses |
| CN110918073A (en) * | 2019-11-22 | 2020-03-27 | 山东农业大学 | Preparation method and application of magnetic MOF-based bisphenol A molecularly imprinted high-selectivity nanocomposite |
-
2021
- 2021-03-29 CN CN202110331937.7A patent/CN113072710B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113072710A (en) | 2021-07-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113072710B (en) | Gas response type resonance photon molecular imprinting sensor and preparation method thereof | |
| Yang et al. | A novel fluorescence molecularly imprinted sensor for Japanese encephalitis virus detection based on metal organic frameworks and passivation-enhanced selectivity | |
| Li et al. | Novel composites of multifunctional Fe 3 O 4@ Au nanofibers for highly efficient glycoprotein imprinting | |
| Khumsap et al. | Epitope-imprinted polymers: applications in protein recognition and separation | |
| CN109632730B (en) | Preparation and application of intelligent virus molecular imprinting resonance optical sensor based on metal organic framework | |
| Li et al. | Surface molecularly imprinted polymers-based electrochemical sensor for bovine hemoglobin recognition | |
| Liu et al. | A new type of raspberry-like polymer composite sub-microspheres with tunable gold nanoparticles coverage and their enhanced catalytic properties | |
| CN113072711B (en) | Magnetic and photon-based dual-response virus molecularly imprinted sensor and construction method thereof | |
| CN111678897B (en) | Preparation method and application of molecular imprinting ratio type fluorescence sensor for detecting HBV | |
| CN110736725B (en) | Preparation method and application of molecularly imprinted fluorescent sensor for simultaneously and visually detecting two viruses | |
| Prai-In et al. | Azlactone functionalization of magnetic nanoparticles using ATRP and their bioconjugation | |
| Duan et al. | Bioreceptor multi-walled carbon nanotubes@ Fe 3 O 4@ SiO 2–surface molecular imprinted polymer in an ultrasensitive chemiluminescent biosensor for bovine hemoglobin | |
| Amiri et al. | Application of ratiometric fluorescence sensor-based microwave-assisted synthesized CdTe quantum dots and mesoporous structured epitope-imprinted polymers for highly efficient determination of tyrosine phosphopeptide | |
| Tan et al. | Development of surface imprinted core–shell nanoparticles and their application in a solid-phase dispersion extraction matrix for methyl parathion | |
| CN110702647A (en) | Construction and application of novel fluorescent imprinting sensor based on magnetic Metal Organic Framework (MOF) | |
| Wang et al. | A mild and safe gas-responsive molecularly imprinted sensor for highly specific recognition of hepatitis B virus | |
| CN111484629B (en) | MOFs type molecularly imprinted polymer, preparation method thereof and fluorescent detection method for pesticide residues | |
| CN109738401B (en) | Preparation and application of novel virus molecular imprinting fluorescence sensor | |
| CN110189882B (en) | Carbon dioxide gas stimulus response magnetic nano material with western blot and preparation method thereof | |
| CN112300347A (en) | Preparation method and application of magnetic ferroferric oxide nanoparticle-based photoresponse imprinted material | |
| CN111171071A (en) | N, O type multidentate functional monomer, preparation method thereof and application thereof in ion imprinting material | |
| Ndizeye et al. | Hierarchical polymeric architectures through molecular imprinting in liquid crystalline environments | |
| CN113332964B (en) | Magnetic graft particles Fe 3 O 4 @SiO 2 Preparation method of (E) -PAM (polyacrylamide) and application thereof in amlodipine adsorption separation | |
| Shah et al. | Highly improved adsorption selectivity of L-phenylalanine imprinted polymeric submicron/nanoscale beads prepared by modified suspension polymerization | |
| Zhang et al. | Chitosan nanoparticle carrier based on surface molecularly imprinted polymers for the recognition and separation of proteins |
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 | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240109 Address after: 411100 west suburb of Xiangtan City, Hunan Province Patentee after: XIANGTAN University Address before: 528300 Residential Committee of Beijiao Community, Beijiao Town, Shunde District, Foshan City, Guangdong Province, China. Part of the first floor area of Building B, Guangdong Shunde Military Civilian Integration Innovation and Entrepreneurship Industrial Park, No. 1 Huanzhen East Road South, and rooms B213, B213A, B215-B219, and B225-227 on the second floor of Building B Patentee before: Green Intelligent Manufacturing Research Institute Xiangtan University Foshan Patentee before: XIANGTAN University |