CN116903892A - Multicolor dye composite polymer microsphere, preparation method and application thereof - Google Patents
Multicolor dye composite polymer microsphere, preparation method and application thereof Download PDFInfo
- Publication number
- CN116903892A CN116903892A CN202311177307.4A CN202311177307A CN116903892A CN 116903892 A CN116903892 A CN 116903892A CN 202311177307 A CN202311177307 A CN 202311177307A CN 116903892 A CN116903892 A CN 116903892A
- Authority
- CN
- China
- Prior art keywords
- reactive
- monomer
- polymer microsphere
- dye
- composite polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004005 microsphere Substances 0.000 title claims abstract description 124
- 229920000642 polymer Polymers 0.000 title claims abstract description 117
- 239000002131 composite material Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 66
- 238000001514 detection method Methods 0.000 claims abstract description 28
- 230000000975 bioactive effect Effects 0.000 claims abstract description 15
- 238000005576 amination reaction Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 29
- 239000011259 mixed solution Substances 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 238000005406 washing Methods 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000003999 initiator Substances 0.000 claims description 18
- 239000006228 supernatant Substances 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000006116 polymerization reaction Methods 0.000 claims description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 15
- 239000006185 dispersion Substances 0.000 claims description 15
- -1 benzamide peroxide Chemical class 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- GXBYFVGCMPJVJX-UHFFFAOYSA-N Epoxybutene Chemical compound C=CC1CO1 GXBYFVGCMPJVJX-UHFFFAOYSA-N 0.000 claims description 12
- KXDAEFPNCMNJSK-UHFFFAOYSA-N benzene carboxamide Natural products NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 claims description 12
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 12
- 239000002798 polar solvent Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 10
- 229920002873 Polyethylenimine Polymers 0.000 claims description 10
- 239000007853 buffer solution Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- 238000005119 centrifugation Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000003760 magnetic stirring Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- TUXJTJITXCHUEL-UHFFFAOYSA-N disperse red 11 Chemical compound C1=CC=C2C(=O)C3=C(N)C(OC)=CC(N)=C3C(=O)C2=C1 TUXJTJITXCHUEL-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 8
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 7
- KHAVLLBUVKBTBG-UHFFFAOYSA-N caproleic acid Natural products OC(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-N 0.000 claims description 7
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- 229960002703 undecylenic acid Drugs 0.000 claims description 7
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 6
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- 229940014800 succinic anhydride Drugs 0.000 claims description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 4
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 claims description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 4
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005642 Oleic acid Substances 0.000 claims description 4
- OVSNDJXCFPSPDZ-UHFFFAOYSA-N Reactive red 120 Chemical compound OS(=O)(=O)C1=CC2=CC(S(O)(=O)=O)=CC(NC=3N=C(NC=4C=CC(NC=5N=C(NC=6C7=C(O)C(N=NC=8C(=CC=CC=8)S(O)(=O)=O)=C(C=C7C=C(C=6)S(O)(=O)=O)S(O)(=O)=O)N=C(Cl)N=5)=CC=4)N=C(Cl)N=3)=C2C(O)=C1N=NC1=CC=CC=C1S(O)(=O)=O OVSNDJXCFPSPDZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000000862 absorption spectrum Methods 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- XWZDJOJCYUSIEY-UHFFFAOYSA-L disodium 5-[(4,6-dichloro-1,3,5-triazin-2-yl)amino]-4-hydroxy-3-phenyldiazenylnaphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].Oc1c(N=Nc2ccccc2)c(cc2cc(cc(Nc3nc(Cl)nc(Cl)n3)c12)S([O-])(=O)=O)S([O-])(=O)=O XWZDJOJCYUSIEY-UHFFFAOYSA-L 0.000 claims description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 4
- 230000031700 light absorption Effects 0.000 claims description 4
- KJPUOJVUFLEJRP-UHFFFAOYSA-N n-[(4,6-dichloro-1,3,5-triazin-2-yl)methyl]-6-(naphthalen-2-yldiazenyl)naphthalen-2-amine Chemical compound ClC1=NC(Cl)=NC(CNC=2C=C3C=CC(=CC3=CC=2)N=NC=2C=C3C=CC=CC3=CC=2)=N1 KJPUOJVUFLEJRP-UHFFFAOYSA-N 0.000 claims description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 4
- WXQMFIJLJLLQIS-UHFFFAOYSA-N reactive blue 21 Chemical compound [Cu+2].C1=CC(S(=O)(=O)CCO)=CC=C1NS(=O)(=O)C1=CC=C2C([N-]3)=NC(C=4C5=CC=C(C=4)S(O)(=O)=O)=NC5=NC(C=4C5=CC=C(C=4)S(O)(=O)=O)=NC5=NC([N-]4)=C(C=C(C=C5)S(O)(=O)=O)C5=C4N=C3C2=C1 WXQMFIJLJLLQIS-UHFFFAOYSA-N 0.000 claims description 4
- HFIYIRIMGZMCPC-YOLJWEMLSA-J remazole black-GR Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]S(=O)(=O)C1=CC2=CC(S([O-])(=O)=O)=C(\N=N\C=3C=CC(=CC=3)S(=O)(=O)CCOS([O-])(=O)=O)C(O)=C2C(N)=C1\N=N\C1=CC=C(S(=O)(=O)CCOS([O-])(=O)=O)C=C1 HFIYIRIMGZMCPC-YOLJWEMLSA-J 0.000 claims description 4
- 229940047670 sodium acrylate Drugs 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 4
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 claims description 4
- JGIGXKSJLSQJGQ-UHFFFAOYSA-K trisodium 5-[[4-chloro-6-(N-methylanilino)-1,3,5-triazin-2-yl]amino]-4-hydroxy-3-[(2-sulfonatophenyl)diazenyl]naphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].[Na+].CN(c1ccccc1)c1nc(Cl)nc(Nc2cc(cc3cc(c(N=Nc4ccccc4S([O-])(=O)=O)c(O)c23)S([O-])(=O)=O)S([O-])(=O)=O)n1 JGIGXKSJLSQJGQ-UHFFFAOYSA-K 0.000 claims description 4
- ZUCXUTRTSQLRCV-UHFFFAOYSA-K trisodium;1-amino-4-[3-[[4-chloro-6-(3-sulfonatoanilino)-1,3,5-triazin-2-yl]amino]-2,4,6-trimethyl-5-sulfonatoanilino]-9,10-dioxoanthracene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].CC1=C(S([O-])(=O)=O)C(C)=C(NC=2C=3C(=O)C4=CC=CC=C4C(=O)C=3C(N)=C(C=2)S([O-])(=O)=O)C(C)=C1NC(N=1)=NC(Cl)=NC=1NC1=CC=CC(S([O-])(=O)=O)=C1 ZUCXUTRTSQLRCV-UHFFFAOYSA-K 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 238000007306 functionalization reaction Methods 0.000 claims description 2
- BGRKEFKKVGRFIH-UHFFFAOYSA-N oxiran-2-ylmethyl pent-3-enoate Chemical compound CC=CCC(=O)OCC1CO1 BGRKEFKKVGRFIH-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 4
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 239000003086 colorant Substances 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 71
- 238000012360 testing method Methods 0.000 description 21
- 241000711573 Coronaviridae Species 0.000 description 15
- 239000000427 antigen Substances 0.000 description 15
- 102000036639 antigens Human genes 0.000 description 15
- 108091007433 antigens Proteins 0.000 description 15
- 238000002835 absorbance Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000004043 dyeing Methods 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000000020 Nitrocellulose Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005562 fading Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 238000003317 immunochromatography Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 229920001220 nitrocellulos Polymers 0.000 description 3
- WPPDXAHGCGPUPK-UHFFFAOYSA-N red 2 Chemical compound C1=CC=CC=C1C(C1=CC=CC=C11)=C(C=2C=3C4=CC=C5C6=CC=C7C8=C(C=9C=CC=CC=9)C9=CC=CC=C9C(C=9C=CC=CC=9)=C8C8=CC=C(C6=C87)C(C=35)=CC=2)C4=C1C1=CC=CC=C1 WPPDXAHGCGPUPK-UHFFFAOYSA-N 0.000 description 3
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 238000003908 quality control method Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 241000220317 Rosa Species 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000003018 immunoassay Methods 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/126—Polymer particles coated by polymer, e.g. core shell structures
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/34—Material containing ester groups
- D06P3/348—Material containing ester groups using reactive dyes
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
- G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
- G01N33/53—Immunoassay; Biospecific binding assay; Materials therefor
- G01N33/543—Immunoassay; Biospecific binding assay; Materials therefor with an insoluble carrier for immobilising immunochemicals
- G01N33/54366—Apparatus specially adapted for solid-phase testing
- G01N33/54386—Analytical elements
- G01N33/54387—Immunochromatographic test strips
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
- G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
- G01N33/53—Immunoassay; Biospecific binding assay; Materials therefor
- G01N33/569—Immunoassay; Biospecific binding assay; Materials therefor for microorganisms, e.g. protozoa, bacteria, viruses
- G01N33/56983—Viruses
-
- 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
- C08J2333/14—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 halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
-
- 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
- C08J2433/00—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
- C08J2433/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- 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
- C08J2435/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Immunology (AREA)
- Chemical & Material Sciences (AREA)
- Hematology (AREA)
- Molecular Biology (AREA)
- Urology & Nephrology (AREA)
- Biomedical Technology (AREA)
- Medicinal Chemistry (AREA)
- Biochemistry (AREA)
- Biotechnology (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Food Science & Technology (AREA)
- Microbiology (AREA)
- Virology (AREA)
- Pathology (AREA)
- General Physics & Mathematics (AREA)
- Textile Engineering (AREA)
- Cell Biology (AREA)
- General Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Tropical Medicine & Parasitology (AREA)
- Crystallography & Structural Chemistry (AREA)
Abstract
The application discloses a multicolor dye composite polymer microsphere, which is formed by bonding dye monomers and bioactive monomers on the surface of a polymer; the preparation method mainly comprises the following steps: step a, preparing polymer microspheres; step b, functionalizing the surface groups of the polymer microspheres; step c, amination of the surface of the polymer microsphere. The application utilizes the active functional group of the polymer and the double bond hung on the microsphere surface to prepare the multi-color polymer dye composite functional microsphere, has the characteristics of simple preparation method, high dye content, high fixation rate, good monodispersity, multiple colors and adjustability, and the like, and can be applied to biological detection to realize the purposes of high sensitivity and rapid detection in real time.
Description
Technical Field
The application relates to the field of high molecular compounds, in particular to a multicolor dye composite polymer microsphere, a preparation method and application thereof.
Background
Immunoassay techniques typically use nanoparticles, typically colloidal gold or dye polymer composite microspheres, as detection reagents.
Compared with colloidal gold, the synthesis of conventional multicolor dye polymer composite microspheres is very complex, and is mostly prepared by a two-step method: first, polymer microspheres are synthesized, and then the polymer microspheres are mixed with dye through swelling, so that multicolor dye polymer composite microspheres are prepared.
However, when the dye polymer composite microsphere is used as a detection reagent, on a detected carrier, such as a test strip for realizing rapid diagnosis, the dye can leak into a buffer solution in the LM-protein coupling process, so that the judgment of a detection result is affected. In addition, the latex microspheres are easy to generate dye leakage after long-time storage, so that the long-term storage stability of the biological detection test strip product is unqualified, and the color depth and the detection sensitivity of the test strip in detection application can be reduced.
Disclosure of Invention
Aiming at the defects of the prior art, the novel polymer microsphere is synthesized, and the multicolor dye polymer composite microsphere with high dye uptake and high fixation rate can be synthesized by means of microsphere amination and covalent bond combination reactive dye dyeing. The application provides a new polymer microsphere, double bonds suspended on the surface of the polymer microsphere modify biological active groups, nucleophilic substitution is carried out between the polymer with active functional groups and dye, thus preparing the multi-color polymer dye composite microsphere, the dye and the microsphere are chemically bonded, the bonding force is firmer, the problem of dye leakage is overcome, and the application is very suitable for preparing biological detection reagents which can be stably stored for a long time.
Specifically, the multicolor dye composite polymer microsphere provided by the application is formed by bonding dye monomers and bioactive monomers on the surface of a polymer; wherein the polymer is poly-1-epoxy-4-methyl-1, 3-pentenoic acid-2, 3-epoxypropyl ester; the multicolor dye composite polymer microsphere has the structural formula:
wherein M represents a bonded dye monomer; n=5 to 20.
The technical proposal is that: the particle size of the multicolor dye composite polymer microsphere is 300-1000 nm; the average molecular weight of the polymer is 2000-10000, the content of dye monomer is 7.62-11.55wt%, and the content of bioactive monomer is 3.22-4.76wt%.
The technical proposal is that: the dye monomer is a functional monomer dye with a specific visible light absorption spectrum: at least one of oil red o, disperse red 120, disperse red 153, reactive red 2, reactive red 5, reactive red 24, reactive red 3B-ase:Sub>A, reactive red 120, reactive red 180, reactive blue 13, reactive turquoise blue KN-G, reactive blue 49, reactive blue 72, reactive blue 140, reactive blue KN-R, reactive black 14, reactive black 5, reactive black KN-B, reactive super black KNN-B, reactive green 19, reactive yellow X-R; the bioactive monomer is at least one of methacrylic acid, sodium methacrylate, acrylic acid, sodium acrylate, maleic anhydride, mercaptopropionic acid, succinic anhydride, crotonic acid, undecylenic acid and oleic acid.
In another aspect, the present application also provides a method for preparing a multicolor dye composite polymer microsphere, comprising the following preparation steps:
(1) Preparing polymer microspheres: stirring a proper amount of monomer glycidyl methacrylate, monomer epoxybutene, a stabilizer and a solvent at 15-20 ℃ to obtain a mixed solution; stirring and heating the obtained mixed solution to 60-80 ℃ under the protection of nitrogen or argon, adding an initiator solution for polymerization reaction, wherein the content of the initiator accounts for 0.1-0.4 wt% of the total weight of the mixed solution; centrifugally washing for 3-5 times to obtain polymer microspheres;
(2) Functionalization of the surface groups of the polymer microspheres: mixing the polymer microsphere prepared in the step (1), the bioactive functional monomer and the initiator solution at 60-80 ℃ under magnetic stirring of 500-800 r/min for polymerization reaction for 2-5 h, and centrifugally washing for 3-5 times, wherein the content of the initiator accounts for 0.1-0.4 wt% of the total weight of the mixed solution;
(3) Amination of the surface of the polymer microsphere: adding the product obtained in the step (2) into an initiator solution, adding a proper amount of polyamino monomer modified with double bonds at the reaction temperature of 50-95 ℃, wherein the content of the initiator accounts for 0.1-0.4 wt% of the total weight of the mixed solution, reacting for 2-5 h to obtain amino modified polymer microspheres, and centrifugally washing for 3-5 times;
(4) Adding dye with a certain proportion into the product of the step (3), and continuing the bonding reaction for 2-5 h by using the polar solvent mixed solution; wherein the dye content accounts for 8-12 wt% of the total weight of the mixed solution;
(5) And (3) centrifuging the reaction solution obtained in the step (4), discarding the supernatant, adding a solvent, performing ultrasonic dispersion, repeating for a plurality of times until the supernatant is colorless, transparent and clear after centrifugation, and drying in a vacuum oven at 60 ℃ to obtain the multicolor dye composite polymer microsphere.
The technical proposal is that: the molar mass ratio of the monomer glycidyl methacrylate to the monomer epoxybutene in the step (1) is 1:1, the concentration of the monomer glycidyl methacrylate and the monomer epoxybutene in the mixed solution is 5-20wt%; the stabilizer is polyvinyl alcohol; the concentration of the stabilizer is 1-4wt%.
The technical proposal is that: the bioactive monomer in the step (2) is at least one selected from methacrylic acid, sodium methacrylate, acrylic acid, sodium acrylate, maleic anhydride, mercaptopropionic acid, succinic anhydride, crotonic acid, undecylenic acid and oleic acid, and the mass ratio of the polymer microsphere to the bioactive functional monomer is 20-30: 1.
the technical proposal is that: the polyamino monomer in the step (3) is at least one selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine with average molecular weight of 600, polyethyleneimine with average molecular weight of 3000 and polyethyleneimine with average molecular weight of 7000; the polyamino monomer modified with double bonds is obtained by reacting the polyamino monomer with the monomer containing double bonds, the monomer modified with double bonds is at least one selected from acrylic acid, methacrylic acid, undecylenic acid and crotonic acid, and the molar ratio of the polyamino monomer modified with double bonds to the bioactive functional monomer is 1:1.
the technical proposal is that: the technical proposal is that: the dye monomer in the step (4) is a functional monomer dye with a specific visible light absorption spectrum: oil red o, disperse red 120, disperse red 153, reactive red 2, reactive red 5, reactive red 24, reactive red 3B-ase:Sub>A, reactive red 120, reactive red 180, reactive blue 13, reactive turquoise blue KN-G, reactive blue 49, reactive blue 72, reactive blue 140, reactive blue KN-R, reactive black 14, reactive black 5, reactive black KN-B, reactive super black KNN-B, reactive green 19, reactive yellow X-R.
The technical proposal is that: the solvent in all the steps is one of methanol, ethanol, water and acetone, and the addition amount of the solvent is 200-250 ml; the initiator solution in all the steps is formed by dissolving a certain amount of initiator in a small amount of solvent and mixing; the initiator is at least one selected from benzamide peroxide, ammonium persulfate, potassium persulfate, azobisisobutyronitrile and azobisisobutyrimidine hydrochloride; the polar solvent is prepared from a solvent and a buffer solution, wherein the buffer solution is one of sodium carbonate and sodium bicarbonate buffer solution, the concentration of the buffer solution is 0.1mol/L, and the pH value of the polar solvent is=9-10.5.
Furthermore, the application also provides a preparation method of the multicolor dye composite polymer microsphere dispersion liquid, wherein the multicolor dye composite polymer microsphere is dispersed in a polar solvent, wherein the content of the multicolor dye composite polymer microsphere is 1-10wt%, and the content of the polar solvent is 90-99wt%.
The application also provides application of the multicolor dye composite polymer microsphere dispersion liquid in biological detection.
The application has the beneficial effects that:
1. firstly, using dye and polymer with active functional group to make nucleophilic substitution reaction to obtain polymer microsphere, then using microsphere surface to hang double bond to further modify biological active group to obtain multi-colour dye composite polymer microsphere, finally using multi-colour dye composite polymer microsphere to obtain dispersion liquid for biological detection.
2. The multicolor dye composite polymer microsphere provided by the application has the characteristics of simple preparation method, high dye content, high fixation rate, good monodispersity, multicolor adjustability and the like, and can realize the purposes of high sensitivity and rapid detection in real time when being used for biological detection.
3. The multicolor dye composite polymer microsphere provided by the application has the advantages that the dye and the microsphere are chemically bonded, and the bonding force is firmer, so that the dye is not easy to fall off from the microsphere and is not easy to leak, the dye leakage is not easy to occur after long-time storage, and the color signals of the dye and the microsphere are not reduced. Solves the problems of low dye-uptake and decolorization in the practical application process of the multicolor dye composite polymer microsphere.
Drawings
FIG. 1 is a structural formula of a multicolor dye composite polymer microsphere of the present application;
FIG. 2 is a scanning electron microscope image of the multicolor dye composite polymer microsphere according to the embodiment of the application, wherein (a), (b) and (c) are respectively the scanning electron microscope images of the multicolor dye composite polymer microsphere according to the embodiments 1, 5 and 6 of the application;
FIG. 3 is a schematic structural diagram of a colloidal gold-type novel coronavirus antigen lateral flow immunochromatographic test strip;
FIG. 4 is a schematic diagram of the detection result of a novel coronavirus antigen lateral flow immunochromatographic test strip;
FIG. 5 is a graph showing absorbance of polymer microsphere (labeled dye) of example 1 of the present application after treatment in soda bath at 95℃and concentration of 3g/l for 10 minutes;
FIG. 6 is an absorbance curve after the dispersion prepared by the microspheres of examples 1 and 2 was left for 1 year in example 7 of the present application.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions in the embodiments of the present application are clearly and completely described, and it is obvious that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
The embodiment and the application example of the application improve the content ratio and the fixation rate of the dye in the microsphere by providing the multicolor polymer dye composite functionalized microsphere dispersion liquid, the preparation method and the application thereof, and the prepared multicolor polymer dye composite functionalized microsphere dispersion liquid has the advantages of high real-time sensitivity and rapid detection when being used for biological detection.
In order to better understand the above technical solutions, the following detailed description will refer to the accompanying drawings and specific embodiments.
Example 1
(1) 14.215g of monomer glycidyl methacrylate, 7.009g of monomer epoxybutene, 4.8g of polyvinyl alcohol and 120ml of ethanol are stirred for 1h at 20 ℃ to obtain a mixed solution; magnetically stirring the obtained mixed solution at 800 r/min under the protection of nitrogen or argon, heating to 80 ℃, adding 0.14g of benzamide peroxide for polymerization reaction, and centrifugally washing for 3-5 times to obtain polymer microspheres;
(2) Mixing the prepared polymer microsphere, 1.0g methacrylic acid, 0.14g benzamide peroxide and 120ml ethanol at 80 ℃ under magnetic stirring at 800 r/min for polymerization reaction for 5h, and centrifugally washing for 3-5 times;
(3) Adding the product obtained in the step (2) into 0.14g of benzamide peroxide and 120ml of ethanol solution, adding 70g of acrylic acid modified polyethyleneimine at the reaction temperature of 95 ℃, reacting for 5 hours to obtain amino modified polymer microspheres, and centrifugally washing for 3-5 times;
(4) Adding 16.8g of active red 2, 0.636g of sodium carbonate and 120ml of ethanol into the product of the step (3) to continue the bonding reaction for 5 hours;
(5) Centrifuging the reaction solution obtained in the step (4), discarding the supernatant, adding ethanol, performing ultrasonic dispersion, and repeating for a plurality of times until the supernatant is colorless, transparent and clear after centrifugation, and the liquid is rose; and (3) drying in a vacuum oven at 60 ℃ to obtain the multicolor dye composite polymer microsphere, wherein the result is shown in figure 1, and the scanning electron microscope diagram is shown in figure 2 (a).
Example 2
(1) 14.215g of monomer glycidyl methacrylate, 7.009g of monomer epoxybutene, 1.25g of polyvinyl alcohol and 50ml of deionized water are stirred for 0.5h at 20 ℃ to obtain a mixed solution; magnetically stirring the obtained mixed solution at 700 r/min under the protection of nitrogen or argon, heating to 70 ℃, adding 0.14g of benzamide peroxide for polymerization reaction, and centrifugally washing for 3-5 times to obtain polymer microspheres;
(2) Mixing the prepared polymer microsphere, 0.8g maleic anhydride, 0.175g ammonium persulfate and 50ml deionized water at 70 ℃ under magnetic stirring at 700 r/min for polymerization reaction for 4 hours, and centrifugally washing for 3-5 times;
(3) Adding the product obtained in the step (2) into a solution of 0.175g of ammonium persulfate and 50ml of deionized water, adding 57g of methacrylic acid modified polyethyleneimine at the reaction temperature of 90 ℃, reacting for 4 hours to obtain amino modified polymer microspheres, and centrifugally washing for 3-5 times;
(4) Adding 7g of active green 19, 0.265g of sodium carbonate and 50ml of deionized water into the product of the step (3) to continue the bonding reaction for 4 hours;
(5) Centrifuging the reaction solution obtained in the step (4), discarding the supernatant, adding ethanol, performing ultrasonic dispersion, and repeating for a plurality of times until the supernatant is colorless, transparent and clear after centrifugation, and the liquid is green; and (5) drying in a vacuum oven at 60 ℃ to obtain the multicolor dye composite polymer microsphere.
Example 3
(1) 14.215g of monomer glycidyl methacrylate, 7.009g of monomer epoxybutene, 0.2g of polyvinyl alcohol and 20ml of acetone are stirred for 1h at 20 ℃ to obtain a mixed solution; heating the obtained mixed solution to 60 ℃ under the protection of nitrogen or argon under the magnetic stirring of 600 r/min, adding 0.16g of azodiisobutyronitrile for polymerization reaction, and centrifugally washing for 3-5 times to obtain polymer microspheres;
(2) Mixing the prepared polymer microsphere, 0.67g of succinic anhydride and 0.16g of azodiisobutyronitrile, 50ml of deionized water at 60 ℃ under magnetic stirring at 600 r/min for polymerization reaction for 3h, and centrifugally washing for 3-5 times;
(3) Adding the product obtained in the step (2) into 0.16g of azodiisobutyronitrile and 20ml of acetone solution, adding 20g of undecylenic acid modified ethylenediamine at the reaction temperature of 60 ℃, reacting for 3 hours to obtain amino modified polymer microspheres, and centrifugally washing for 3-5 times;
(4) Adding 3.2g of active yellow X-R, 0.084g of sodium bicarbonate and 20ml of acetone into the product of the step (3) to continue the bonding reaction for 3 hours;
(5) Centrifuging the reaction solution obtained in the step (4), discarding the supernatant, adding ethanol, performing ultrasonic dispersion, and repeating for a plurality of times until the supernatant is colorless, transparent and clear after centrifugation, and the liquid is yellow; and (5) drying in a vacuum oven at 60 ℃ to obtain the multicolor dye composite polymer microsphere.
Example 4
(1) 14.215g of monomeric glycidyl methacrylate, 7.009g of monomeric epoxybutene, 0.6g of polyvinyl alcohol and 115ml of methanol are stirred at 20 ℃ for 0.5h to obtain a mixed solution; magnetically stirring the obtained mixed solution at 500 r/min under the protection of nitrogen or argon, heating to 75 ℃, adding 0.405g of potassium persulfate for polymerization reaction, and centrifugally washing for 3-5 times to obtain polymer microspheres;
(2) Mixing the prepared polymer microsphere, 1.4g of crotonic acid, 0.405g of potassium persulfate and 115ml of methanol at 75 ℃ under 500 r/min magnetic stirring for polymerization reaction for 4h, and centrifugally washing for 3-5 times;
(3) Adding the product obtained in the step (2) into 0.405g of potassium persulfate and 115ml of methanol solution, adding 65g of crotonic acid modified ethylenediamine at the reaction temperature of 75 ℃, reacting for 4 hours to obtain amino modified polymer microspheres, and centrifugally washing for 3-5 times;
(4) 13.5g of active blue 49, 0.483g of sodium bicarbonate and 115ml of methanol are added into the product of the step (3) to continue the bonding reaction for 4 hours;
(5) Centrifuging the reaction solution obtained in the step (4), discarding the supernatant, adding ethanol, performing ultrasonic dispersion, and repeating for a plurality of times until the supernatant is colorless, transparent and clear after centrifugation, and the liquid is blue; and (5) drying in a vacuum oven at 60 ℃ to obtain the multicolor dye composite polymer microsphere.
Example 5
(1) 28.43g of monomer glycidyl methacrylate, 14.018g of monomer epoxybutene, 4.8g of polyvinyl alcohol and 120ml of ethanol are stirred at 20 ℃ for 1 hour to obtain a mixed solution; magnetically stirring the obtained mixed solution at 800 r/min under the protection of nitrogen or argon, heating to 80 ℃, adding 0.14g of benzamide peroxide for polymerization reaction, and centrifugally washing for 3-5 times to obtain polymer microspheres;
(2) Mixing the prepared polymer microsphere, 1.0g methacrylic acid, 0.14g benzamide peroxide and 120ml ethanol at 80 ℃ under magnetic stirring at 800 r/min for polymerization reaction for 5h, and centrifugally washing for 3-5 times;
(3) Adding the product obtained in the step (2) into 0.14g of benzamide peroxide and 120ml of ethanol solution, adding 70g of acrylic acid modified polyethyleneimine at the reaction temperature of 95 ℃, reacting for 5 hours to obtain amino modified polymer microspheres, and centrifugally washing for 3-5 times;
(4) Adding 16.8g of active red 2, 0.636g of sodium carbonate and 120ml of ethanol into the product of the step (3) to continue the bonding reaction for 5 hours;
(5) And (3) centrifuging the reaction solution obtained in the step (4), discarding the supernatant, adding ethanol, performing ultrasonic dispersion, repeating for a plurality of times until the supernatant is colorless, transparent and clear after centrifugation, and drying in a vacuum oven at 60 ℃ to obtain the multicolor dye composite polymer microsphere, wherein a scanning electron microscope image of the multicolor dye composite polymer microsphere is shown in (b) of fig. 2.
Example 6
(1) 42.625g of monomer glycidyl methacrylate, 21.027g of monomer epoxybutene, 4.8g of polyvinyl alcohol and 120ml of ethanol are stirred at 20 ℃ for 1 hour to obtain a mixed solution; magnetically stirring the obtained mixed solution at 800 r/min under the protection of nitrogen or argon, heating to 80 ℃, adding 0.14g of benzamide peroxide for polymerization reaction, and centrifugally washing for 3-5 times to obtain polymer microspheres;
(2) Mixing the prepared polymer microsphere, 1.0g methacrylic acid, 0.14g benzamide peroxide and 120ml ethanol at 80 ℃ under magnetic stirring at 800 r/min for polymerization reaction for 5h, and centrifugally washing for 3-5 times;
(3) Adding the product obtained in the step (2) into 0.14g of benzamide peroxide and 120ml of ethanol solution, adding 70g of acrylic acid modified polyethyleneimine at the reaction temperature of 95 ℃, reacting for 5 hours to obtain amino modified polymer microspheres, and centrifugally washing for 3-5 times;
(4) Adding 16.8g of active red 2, 0.636g of sodium carbonate and 120ml of ethanol into the product of the step (3) to continue the bonding reaction for 5 hours;
(5) And (3) centrifuging the reaction solution obtained in the step (4), discarding the supernatant, adding ethanol, performing ultrasonic dispersion, repeating for a plurality of times until the supernatant is colorless, transparent and clear after centrifugation, and drying in a vacuum oven at 60 ℃ to obtain the multicolor dye composite polymer microsphere, wherein a scanning electron microscope image of the multicolor dye composite polymer microsphere is shown in (c) in fig. 2.
Example 7
The color-losing rate is defined as the ratio of the maximum peak value of absorbance of the upper residual liquid obtained after microsphere dispersion liquid is subjected to microsphere centrifugal separation treatment to the absorbance of pure dye dispersion liquid with the same nominal content as the microsphere. Thus, the dye uptake can be defined by the following relationship: the sum of the dye-uptake and the fading rate is 1.
The polymer microsphere of example 1 is boiled in 3g/l sodium carbonate solution for 10 minutes at 95 ℃, the absorbance of the supernatant after centrifugation is tested and is shown as the absorbance curve of the dye in figure 5, the dye curve which is consistent with the content of the microsphere is prepared as a standard line, and the fading rate of the microsphere is calculated by the Billbert law. As a result, the polymer microsphere of example 1 had a 20.4% fading rate and a 79.6% dyeing rate, indicating that the microsphere had a good dyeing effect.
The absorbance of the supernatant of the polymer microsphere dispersion solutions of examples 1 and 2 after being left for 1 year was measured and almost zero as shown in fig. 6, and it was confirmed that the effect of dyeing the microspheres was stable.
In addition, the application of the multicolor dye composite polymer microsphere is as follows:
example 8
Dispersing the multicolor dye composite polymer microsphere obtained in the examples 1-6 in a polar solvent to form multicolor dye composite polymer microsphere dispersion, wherein the content of the multicolor dye composite polymer microsphere is 1-10wt% and the content of the polar solvent is 90-99wt%.
Example 9
Preparing a novel coronavirus antigen current-measuring immunochromatography test strip:
labeling the multicolor dye composite polymer microsphere dispersion obtained in the embodiment 7 of the application onto the antibody of the novel coronavirus, and expressing the concentration of the labeled antibody by using the absorbance value (OD) of λmax;
loading the labeled antibody onto a gold marking machine, uniformly spraying the labeled antibody with a certain OD value onto a polyester film (a labeled pad 202), and putting the polyester film into a 37-DEG oven for baking for 8 hours after spraying; cutting into proper size, placing into aluminum foil bag equipped with drier, and storing at room temperature;
diluting the new coronavirus antigen to a proper concentration, spotting the new coronavirus antigen to the corresponding detection line 201 (T line) position on the nitrocellulose membrane 207 by a spot film spotting machine, adding the corresponding antigen (used for detecting whether the detection card is effective) to the corresponding quality control line 200 (C line) position on the nitrocellulose membrane 207, and drying at 37 ℃ for 12 hours;
sample pad 208- -glass fiber is treated by buffer solution and surface activity, and dried for 10 hours at 37 ℃ for standby;
the novel coronavirus antigen flow-measuring immunochromatography test strip is assembled according to a sample pad 208, a marking pad 202, a nitrocellulose membrane 207, a water absorbing pad 204 and a large card 205, and is shown in figure 3;
and preparing a small molecule solution with corresponding concentration, adding the small molecule solution to the sample adding area 203 of the sample pad 208, and reading results of the result quality control line 200 and the detection line 201 in the reaction area 206 after 5 minutes.
Application example 1
The multicolor dye composite polymer microsphere prepared by the method of the embodiment 8 is added into the novel coronavirus antigen current-measuring immunochromatography test strip prepared by the embodiment 9 for testing.
Application example 2
Example 5 multicolor dye composite polymer microspheres were tested by adding the dispersion prepared in example 8 to the novel coronavirus antigen lateral flow immunochromatographic test strip prepared in example 9.
Application example 3
Example 6 multicolor dye composite polymer microspheres were tested by adding the dispersion prepared in example 8 to the novel coronavirus antigen lateral flow immunochromatographic test strip prepared in example 9.
As shown in fig. 4, fig. 4 (a) includes: an indication of the detection result of the detection plate 110 provided with an outsourced novel coronavirus antigen lateral flow immunochromatographic test strip (An Xu biotechnology Co., ltd., hangzhou) and an indication of the application result of the detection plate 120 provided with the novel coronavirus antigen lateral flow immunochromatographic test strip prepared in application example 1 of the present application and an indication of the application result of the detection plate 130 provided with the novel coronavirus antigen lateral flow immunochromatographic test strip prepared in application example 2 of the present application; all the test strips are tested simultaneously in the same environment, and it can be obviously observed that the test strips in application examples 1 and 2 can display test results faster and more clearly; (b) comprising: a detection result of a detection plate 140 provided with a purchased novel coronavirus antigen lateral flow immunochromatographic test strip (An Xu Biotechnology Co., ltd.) and a detection result of a detection plate 150 provided with a novel coronavirus antigen lateral flow immunochromatographic test strip prepared in application example 3 of the present application; similarly, the test is performed simultaneously under the same environment, and the application example 3 of the application can also display the test result faster and more clearly.
Claims (10)
1. A multicolor dye composite polymer microsphere, which is characterized in that the multicolor dye composite polymer microsphere is formed by bonding dye monomers and bioactive monomers on the surface of a polymer; wherein the polymer is poly-1-epoxy-4-methyl-1, 3-pentenoic acid-2, 3-epoxypropyl ester; the multicolor dye composite polymer microsphere has the structural formula:
，
wherein M represents a bonded dye monomer; n=5 to 20.
2. The multicolor dye composite polymer microsphere according to claim 1, wherein the particle size of the multicolor dye composite polymer microsphere is 300-1000 nm; the average molecular weight of the polymer is 2000-10000, the content of dye monomer is 7.62-11.55wt%, and the content of bioactive monomer is 3.22-4.76wt%.
3. The multicolor dye composite polymer microsphere according to claim 1 or 2, wherein the dye monomer is a functional monomer dye with specific visible light absorption spectrum: at least one of oil red o, disperse red 120, disperse red 153, reactive red 2, reactive red 5, reactive red 24, reactive red 3B-ase:Sub>A, reactive red 120, reactive red 180, reactive blue 13, reactive turquoise blue KN-G, reactive blue 49, reactive blue 72, reactive blue 140, reactive blue KN-R, reactive black 14, reactive black 5, reactive black KN-B, reactive super black KNN-B, reactive green 19, reactive yellow X-R; the bioactive monomer is at least one of methacrylic acid, sodium methacrylate, acrylic acid, sodium acrylate, maleic anhydride, mercaptopropionic acid, succinic anhydride, crotonic acid, undecylenic acid and oleic acid.
4. A method for preparing a multicolour dye composite polymer microsphere according to any one of claims 1 to 3, comprising the following steps:
(1) Preparing polymer microspheres: stirring a proper amount of monomer glycidyl methacrylate, monomer epoxybutene, a stabilizer and a solvent at 15-20 ℃ to obtain a mixed solution; stirring and heating the obtained mixed solution to 60-80 ℃ under the protection of nitrogen or argon, adding an initiator solution for polymerization reaction, wherein the content of the initiator accounts for 0.1-0.4 wt% of the total weight of the mixed solution; centrifugally washing for 3-5 times to obtain polymer microspheres;
(2) Functionalization of the surface groups of the polymer microspheres: mixing the polymer microsphere prepared in the step (1), the bioactive functional monomer and the initiator solution at 60-80 ℃ under magnetic stirring of 500-800 r/min for polymerization reaction for 2-5 h, and centrifugally washing for 3-5 times, wherein the content of the initiator accounts for 0.1-0.4 wt% of the total weight of the mixed solution;
(3) Amination of the surface of the polymer microsphere: adding the product obtained in the step (2) into an initiator solution, adding a proper amount of polyamino monomer modified with double bonds at the reaction temperature of 50-95 ℃, wherein the content of the initiator accounts for 0.1-0.4 wt% of the total weight of the mixed solution, reacting for 2-5 h to obtain amino modified polymer microspheres, and centrifugally washing for 3-5 times;
(4) Adding dye with a certain proportion into the product of the step (3), and continuing the bonding reaction for 2-5 h by using the polar solvent mixed solution; wherein the dye content accounts for 8-12 wt% of the total weight of the mixed solution;
(5) And (3) centrifuging the reaction solution obtained in the step (4), discarding the supernatant, adding a solvent, performing ultrasonic dispersion, repeating for a plurality of times until the supernatant is colorless, transparent and clear after centrifugation, and drying in a vacuum oven at 60 ℃ to obtain the multicolor dye composite polymer microsphere.
5. The method for preparing the multicolor dye composite polymer microsphere according to claim 4, wherein the molar mass ratio of the monomer glycidyl methacrylate to the monomer epoxybutene in the step (1) is 1:1, the concentration of the monomer glycidyl methacrylate and the monomer epoxybutene in the mixed solution is 5-20wt%; the stabilizer is polyvinyl alcohol; the concentration of the stabilizer is 1-4wt%.
6. The method for preparing the multicolor dye composite polymer microsphere according to claim 4, wherein the bioactive monomer in the step (2) is selected from at least one of methacrylic acid, sodium methacrylate, acrylic acid, sodium acrylate, maleic anhydride, mercaptopropionic acid, succinic anhydride, crotonic acid, undecylenic acid and oleic acid, and the mass fraction ratio of the polymer microsphere to the bioactive functional monomer is 20-30: 1, a step of; the polyamino monomer in the step (3) is at least one selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine with average molecular weight of 600, polyethyleneimine with average molecular weight of 3000 and polyethyleneimine with average molecular weight of 7000; the polyamino monomer modified with double bonds is obtained by reacting the polyamino monomer with the monomer containing double bonds, the monomer modified with double bonds is at least one selected from acrylic acid, methacrylic acid, undecylenic acid and crotonic acid, and the molar ratio of the polyamino monomer modified with double bonds to the bioactive functional monomer is 1:1.
7. the method for preparing the multicolor dye composite polymer microsphere according to claim 4, wherein the dye monomer in the step (4) is a functional monomer dye with a specific visible light absorption spectrum: oil red o, disperse red 120, disperse red 153, reactive red 2, reactive red 5, reactive red 24, reactive red 3B-ase:Sub>A, reactive red 120, reactive red 180, reactive blue 13, reactive turquoise blue KN-G, reactive blue 49, reactive blue 72, reactive blue 140, reactive blue KN-R, reactive black 14, reactive black 5, reactive black KN-B, reactive super black KNN-B, reactive green 19, reactive yellow X-R.
8. The method for preparing the multicolor dye composite polymer microsphere according to any one of claims 4 to 7, wherein the solvent in all steps is one of methanol, ethanol, water and acetone, and the addition amount of the solvent is 200 to 250ml; the initiator solution in all the steps is formed by dissolving a certain amount of initiator in a small amount of solvent and mixing; the initiator is at least one selected from benzamide peroxide, ammonium persulfate, potassium persulfate, azobisisobutyronitrile and azobisisobutyrimidine hydrochloride; the polar solvent is prepared from a solvent and a buffer solution, wherein the buffer solution is one of sodium carbonate and sodium bicarbonate buffer solution, the concentration of the buffer solution is 0.1mol/L, and the pH value of the polar solvent is=9-10.5.
9. A method for preparing a multicolor dye composite polymer microsphere dispersion liquid, which is characterized in that the multicolor dye composite polymer microsphere as defined in any one of claims 1-8 is dispersed in a polar solvent, wherein the content of the multicolor dye composite polymer microsphere is 1-10wt% and the content of the polar solvent is 90-99wt%.
10. Use of a multicolour dye composite polymer microsphere dispersion prepared according to claim 9 in biological detection.
Priority Applications (1)
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