CN108467475B - 一种环状聚合物及其制备方法和应用 - Google Patents
一种环状聚合物及其制备方法和应用 Download PDFInfo
- Publication number
- CN108467475B CN108467475B CN201810189654.1A CN201810189654A CN108467475B CN 108467475 B CN108467475 B CN 108467475B CN 201810189654 A CN201810189654 A CN 201810189654A CN 108467475 B CN108467475 B CN 108467475B
- Authority
- CN
- China
- Prior art keywords
- reaction
- polymer
- cyclic polymer
- solvent
- dibromo
- 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.)
- Expired - Fee Related
Links
- 229920005565 cyclic polymer Polymers 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 20
- ZOGSYJVIRUPBEA-UHFFFAOYSA-N n-methyl-2h-triazol-4-amine Chemical compound CNC1=CNN=N1 ZOGSYJVIRUPBEA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 8
- VALXCIRMSIFPFN-UHFFFAOYSA-N 2,5-dibromobenzene-1,4-diol Chemical compound OC1=CC(Br)=C(O)C=C1Br VALXCIRMSIFPFN-UHFFFAOYSA-N 0.000 claims abstract description 4
- LZPWAYBEOJRFAX-UHFFFAOYSA-N 4,4,5,5-tetramethyl-1,3,2$l^{2}-dioxaborolane Chemical compound CC1(C)O[B]OC1(C)C LZPWAYBEOJRFAX-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000004327 boric acid Substances 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 239000012043 crude product Substances 0.000 claims description 9
- -1 1, 4-bis (2-azidoethoxy) -2, 5-dibromobenzene Chemical compound 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- NPWXJWYKRFEDQH-UHFFFAOYSA-N 1,4-dibromo-2,5-bis(2-bromoethoxy)benzene Chemical compound BrC1=C(C=C(C(=C1)OCCBr)Br)OCCBr NPWXJWYKRFEDQH-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 238000004440 column chromatography Methods 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- IVDFJHOHABJVEH-UHFFFAOYSA-N HOCMe2CMe2OH Natural products CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 238000009987 spinning Methods 0.000 claims description 4
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 claims description 3
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 claims description 3
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 3
- ZRXVCYGHAUGABY-UHFFFAOYSA-N 4-bromo-n,n-bis(4-bromophenyl)aniline Chemical compound C1=CC(Br)=CC=C1N(C=1C=CC(Br)=CC=1)C1=CC=C(Br)C=C1 ZRXVCYGHAUGABY-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- RTWCHRMHGXBETA-UHFFFAOYSA-N prop-1-yn-1-amine Chemical compound CC#CN RTWCHRMHGXBETA-UHFFFAOYSA-N 0.000 claims description 3
- 235000010378 sodium ascorbate Nutrition 0.000 claims description 3
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 claims description 3
- 229960005055 sodium ascorbate Drugs 0.000 claims description 3
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 claims description 3
- FNOAMAFRNTVRTQ-UHFFFAOYSA-N C1CCCC1.CC1(OBOC1(C)C)C Chemical compound C1CCCC1.CC1(OBOC1(C)C)C FNOAMAFRNTVRTQ-UHFFFAOYSA-N 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 230000006837 decompression Effects 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 238000010791 quenching Methods 0.000 claims description 2
- 230000000171 quenching effect Effects 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 230000000855 fungicidal effect Effects 0.000 claims 1
- 239000000417 fungicide Substances 0.000 claims 1
- 238000003384 imaging method Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 32
- 238000000799 fluorescence microscopy Methods 0.000 abstract description 8
- 239000003242 anti bacterial agent Substances 0.000 abstract description 6
- 231100000135 cytotoxicity Toxicity 0.000 abstract description 3
- 230000003013 cytotoxicity Effects 0.000 abstract description 3
- UCFSYHMCKWNKAH-UHFFFAOYSA-N 4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound CC1(C)OBOC1(C)C UCFSYHMCKWNKAH-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000006069 Suzuki reaction reaction Methods 0.000 abstract 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 abstract 1
- 238000006880 cross-coupling reaction Methods 0.000 abstract 1
- 238000007257 deesterification reaction Methods 0.000 abstract 1
- 230000032050 esterification Effects 0.000 abstract 1
- 238000005886 esterification reaction Methods 0.000 abstract 1
- 230000020477 pH reduction Effects 0.000 abstract 1
- 238000005956 quaternization reaction Methods 0.000 abstract 1
- 238000006467 substitution reaction Methods 0.000 abstract 1
- DUZWQORPXCDQLI-UHFFFAOYSA-N tris(4-bromophenyl)methanamine Chemical compound BrC1=CC=C(C=C1)C(C1=CC=C(C=C1)Br)(C1=CC=C(C=C1)Br)N DUZWQORPXCDQLI-UHFFFAOYSA-N 0.000 abstract 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 17
- 241000588724 Escherichia coli Species 0.000 description 17
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 16
- 230000000844 anti-bacterial effect Effects 0.000 description 16
- 241000191967 Staphylococcus aureus Species 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 230000001954 sterilising effect Effects 0.000 description 14
- 230000001580 bacterial effect Effects 0.000 description 13
- 239000007788 liquid Substances 0.000 description 12
- 238000005286 illumination Methods 0.000 description 11
- 238000004659 sterilization and disinfection Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 9
- 238000001218 confocal laser scanning microscopy Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 229920000547 conjugated polymer Polymers 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 229940088710 antibiotic agent Drugs 0.000 description 5
- 238000003760 magnetic stirring Methods 0.000 description 5
- 239000002609 medium Substances 0.000 description 5
- XDFNWJDGWJVGGN-UHFFFAOYSA-N 2-(2,7-dichloro-3,6-dihydroxy-9h-xanthen-9-yl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1C1C2=CC(Cl)=C(O)C=C2OC2=CC(O)=C(Cl)C=C21 XDFNWJDGWJVGGN-UHFFFAOYSA-N 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 4
- 239000003899 bactericide agent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000001963 growth medium Substances 0.000 description 4
- 238000011534 incubation Methods 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 239000003642 reactive oxygen metabolite Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000012258 culturing Methods 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- 231100000956 nontoxicity Toxicity 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- VFNKZQNIXUFLBC-UHFFFAOYSA-N 2',7'-dichlorofluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC(Cl)=C(O)C=C1OC1=C2C=C(Cl)C(O)=C1 VFNKZQNIXUFLBC-UHFFFAOYSA-N 0.000 description 2
- 206010059866 Drug resistance Diseases 0.000 description 2
- 239000012880 LB liquid culture medium Substances 0.000 description 2
- 239000007832 Na2SO4 Substances 0.000 description 2
- 108010087230 Sincalide Proteins 0.000 description 2
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229960001931 ampicillin sodium Drugs 0.000 description 2
- KLOHDWPABZXLGI-YWUHCJSESA-M ampicillin sodium Chemical compound [Na+].C1([C@@H](N)C(=O)N[C@H]2[C@H]3SC([C@@H](N3C2=O)C([O-])=O)(C)C)=CC=CC=C1 KLOHDWPABZXLGI-YWUHCJSESA-M 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000010609 cell counting kit-8 assay Methods 0.000 description 2
- 230000001332 colony forming effect Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 231100000263 cytotoxicity test Toxicity 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- IZTQOLKUZKXIRV-YRVFCXMDSA-N sincalide Chemical compound C([C@@H](C(=O)N[C@@H](CCSC)C(=O)NCC(=O)N[C@@H](CC=1C2=CC=CC=C2NC=1)C(=O)N[C@@H](CCSC)C(=O)N[C@@H](CC(O)=O)C(=O)N[C@@H](CC=1C=CC=CC=1)C(N)=O)NC(=O)[C@@H](N)CC(O)=O)C1=CC=C(OS(O)(=O)=O)C=C1 IZTQOLKUZKXIRV-YRVFCXMDSA-N 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 208000035143 Bacterial infection Diseases 0.000 description 1
- 241000192125 Firmicutes Species 0.000 description 1
- 201000009906 Meningitis Diseases 0.000 description 1
- 206010034133 Pathogen resistance Diseases 0.000 description 1
- 229930182555 Penicillin Natural products 0.000 description 1
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 1
- 206010035664 Pneumonia Diseases 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- 206010040047 Sepsis Diseases 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 241000295644 Staphylococcaceae Species 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 208000022362 bacterial infectious disease Diseases 0.000 description 1
- 125000005619 boric acid group Chemical group 0.000 description 1
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003833 cell viability Effects 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000001717 pathogenic effect Effects 0.000 description 1
- 229940049954 penicillin Drugs 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 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
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/121—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from organic halides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
- C08G2261/124—Copolymers alternating
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/13—Morphological aspects
- C08G2261/134—Rod and coil building blocks
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/142—Side-chains containing oxygen
- C08G2261/1422—Side-chains containing oxygen containing OH groups
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/143—Side-chains containing nitrogen
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/18—Definition of the polymer structure conjugated
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/316—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain bridged by heteroatoms, e.g. N, P, Si or B
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/41—Organometallic coupling reactions
- C08G2261/411—Suzuki reactions
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1408—Carbocyclic compounds
- C09K2211/1425—Non-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1408—Carbocyclic compounds
- C09K2211/1433—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1441—Heterocyclic
- C09K2211/1466—Heterocyclic containing nitrogen as the only heteroatom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
本发明提供了一种环状聚合物及其制备方法和应用。制备方法：以2,5‑二溴对苯二酚为原料，经取代反应和Click交叉偶联得到1,4‑二‑[2‑(4‑甲氨基‑1,2,3‑三唑)‑乙氧基]‑2,5‑二溴苯；三‑(4‑溴苯基)甲氨经硼酸酯化得到三‑[4‑(4,4,5,5‑四甲基‑1,3,2‑二氧硼杂环戊烷)苯基]甲烷；1,4‑二‑[2‑(4‑甲氨基‑1,2,3‑三唑)‑乙氧基]‑2,5‑二溴苯和三‑[4‑(4,4,5,5‑四甲基‑1,3,2‑二氧硼杂环戊烷)苯基]甲烷通过Suzuki偶联反应和酸化脱酯及季铵化得到环状聚合物。该聚合物可作为抗菌剂应用，且对细胞毒性很小。该聚合物制备简单、反应温和、产率较高。本发明聚合物能够发射荧光，还可用于生物荧光成像。
Description
技术领域
本发明涉及聚合物，具体属于一种环状聚合物及其制备方法和作为杀菌剂应用。
背景技术
自从1928年，英国细菌学家弗莱明发现了杀死引起人体发烧的葡萄球菌的青霉素以来，抗生素作为抑制致病菌感染的方法，拯救了数以亿计的肺炎、脑膜炎、败血症等患者的生命。然而，由于抗生素被大量的乱用和滥用，细菌耐药性问题越来越严重，许多之前具有高效杀菌能力的抗生素都失去了药效。另外，抗生素对人体的副作用很大，因此急需开发新型的杀菌药物，来解决细菌耐药性的问题。
在这个方面，共轭聚合物(CPs)由于信号放大效应以及表面侧链易于修饰等特性，受到了科学家的广泛关注。许多侧链修饰有抗菌活性基团共轭聚合物被不断开发利用。此外，共轭聚合物由于大的共轭结构，在光照下可以敏化周围的氧气产生活性氧(ROS)，这一特性使其对细菌具有更强的杀伤能力。但与此同时，ROS也会对身体内的其它组织细胞产生影响，这限制了其在生物体内的应用。目前作为抗菌材料的有机共轭聚合物大多数在光照下会产生ROS，且多为长链结构。因此，得到无细胞毒性的具有较高杀菌效果的环状有机聚合物并应用于生物体杀菌是本发明的宗旨。
发明内容
本发明的目的是提供一种环状聚合物及其制备方法和应用；所述环状聚合物具有较强的杀菌活性，且对细胞没有毒性，可作为杀菌剂应用；所述制备方法操作简单、反应条件温和、产率较高。
本发明提供的一种环状聚合物，其结构式为：
其中，n＝1-3。
本发明提供的一种环状聚合物(I)的制备方法，包括如下步骤：
1)、按摩尔比为1∶10∶3.6，将2,5-二溴对苯二酚、1,2-二溴乙烷和K2CO3加入丙酮和水体积比为4∶1的混合溶剂中，加入回流反应12h，经柱色谱分离得到1,4-二溴-2,5-二(2-溴乙氧基)苯；反应式如下：
2)、按摩尔比为1∶10，将1,4-二溴-2,5-二(2-溴乙氧基)苯和NaN3加入无水DMF中，50℃下搅拌反应12h，得到1,4-二(2-叠氮基乙氧基)-2,5-二溴苯；反应式如下：
3)、在氮气保护下，按摩尔比为5∶12∶6∶2，将1,4-二(2-叠氮基乙氧基)-2,5-二溴苯、丙炔胺、CuSO4·5H2O和抗坏血酸钠加入体积比为1∶1的叔丁醇和水混合溶剂中，室温搅拌反应15h，减压旋除溶剂，用10％的氨水猝灭反应，经二氯甲烷萃取、粗产品经正己烷洗涤后得到1,4-二-[2-(4-甲氨基-1,2,3-三唑)-乙氧基]-2,5-二溴苯(II)；反应式如下：
4)、氮气保护下，按摩尔比为1∶3∶3，将三(4-溴苯基)胺、频哪醇硼酸酯和无水碳酸钾加入DMF溶剂中，再加入催化量的Pd(dppf)Cl2，加热到120℃反应过夜，反应结束，经减压旋除溶剂、二氯甲烷萃取，柱色谱分离得到三-[4-(4,4,5,5-四甲基-1,3,2-二氧硼杂环戊烷)苯基]甲烷(III)；反应式如下：
5)、在氮气保护下，按摩尔比为3∶2，将1,4-二-[2-(4-甲氨基-1,2,3-三唑)-乙氧基]-2,5-二溴苯(II)和三-[4-(4,4,5,5-四甲基-1,3,2-二氧硼杂环戊烷)苯基]甲烷(III)加入体积比为6∶25的2mol/L碳酸钾溶液和DMF混合液中，再加入催化量的Pd(PPh3)4，加热反应液至100℃反应72h，反应结束，经旋除溶剂，二氯甲烷溶解，饱和食盐水洗涤后，正己烷重结晶。所得反应产物用三氟乙酸溶解后，加入等体积的氢溴酸，室温搅拌反应1h，反应液用无水乙醚沉淀得到环状聚合物(I)；反应式如下：
其中，n＝1-3。
本发明环状聚合物对革兰氏阴性菌(大肠杆菌Top 10)和革兰氏阳性菌(金黄色葡萄球菌ATCC6358)都具有较强的杀菌活性，且对细胞没有毒性，可作为杀菌剂应用。
本发明环状聚合物能够发射荧光，可在生物荧光成像中的应用。
与现有技术相比本发明的优点和效果：
本发明得到的环状聚合物末端为季铵盐和硼酸基，能够有效吸附细菌，并将其固定在孔内，有利于杀伤细菌，且对细胞没有毒性，这将有望代替抗生素，解决细胞耐药性的难题。该环状聚合物可作为杀菌剂应用。所采用的制备方法反应操作简单，条件温和，产率较高。
附图说明
图1本发明环状聚合物(I)在DMSO中的紫外吸收和荧光发射光谱图。
图2本发明环状聚合物(I)对细胞毒性测试图。
图3本发明环状聚合物(I)产生活性氧测试图。
图4本发明环状聚合物(I)对大肠杆菌的杀菌性能测试图。
图5本发明环状聚合物(I)对金黄色葡萄球菌的杀菌性能测试图。
图6本发明环状聚合物(I)对大肠杆菌的共聚焦荧光成像图。
图7本发明环状聚合物(I)对金黄色葡萄球菌的共聚焦荧光成像图。
具体实施方式
实施例1环状聚合物(I)的制备
1)在装有磁力搅拌的50mL单口圆底烧瓶中，加入2,5-二溴对苯二酚(0.54g,2.00mmol)、1,2-二溴乙烷(1.73mL,20.0mmol)和无水K2CO3(0.995g,7.20mmol)，10mL丙酮和2.5mL水，加热至80℃反应12h。反应完成后，减压旋除有机溶剂，二氯甲烷(100mL)萃取3次，合并有机相，有机相经饱和食盐水(100mL)洗涤2次，无水Na2SO4干燥，旋除溶剂得粗产物。粗产物经柱色谱分离(展开剂:二氯甲烷/石油醚＝1/3,v/v)得到白色固体1,4-二溴-2,5-二(2-溴乙氧基)苯0.76g，产率79.2％。1H NMR(400MHz,CDCl3,ppm)δ:3.66(t,JJ＝8.0,4H),4.29(t,JJ＝8.0,4H),7.14(s,2H)；13C NMR(100MHz,CDCl3,ppm)δ:28.38,70.34,111.88,119.80,150.07；MS-ESI(m/z):481.5[M+],479.3[M+-2],483.5[M++2]。
2)在装有磁力搅拌的25mL单口圆底烧瓶中，加入1,4-二溴-2,5-二(2-溴乙氧基)苯(0.63g,1.30mmol)、NaN3(0.85g,13.0mmol)和10mL的无水DMF，加热到50℃搅拌12h。反应结束后，将反应物倒入200mL冷水中，抽滤得到白色固体1,4-二(2-叠氮基乙氧基)-2,5-二溴苯0.52g，产率98.1％。1H NMR(400MHz,CDCl3,ppm)δ:3.63(t,JJ＝6.0,4H),4.13(t,JJ＝6.0,4H),7.14(s,2H)；13C NMR(100MHz,CDCl3,ppm)δ:50.23,69.13,111.43,118.97,150.11。
3)在氮气保护下，向装有磁力搅拌的25mL三口圆底烧瓶中，加入1,4-二(2-叠氮基乙氧基)-2,5-二溴(0.41g,1.00mmol)、丙炔胺(0.15mL,2.40mmol)、CuSO4·5H2O(0.30g,1.20mmol)、抗坏血酸钠(0.079g,0.40mmol)以及叔丁醇/水(1/1,v/v)混合溶液6mL，室温搅拌15h。反应完成后，旋除有机溶剂，加入10％的氨水猝灭反应，用二氯萃取(100mL×3)萃取，合并有机相，无水硫酸钠干燥后，旋除有机溶剂得到浅黄色的固体。所得粗产物用正己烷洗涤后，得到1,4-二-[2-(4-甲氨基-1,2,3-三唑)-乙氧基]-2,5-二溴苯(II)0.31g，产率59.5％。1H NMR(400MHz,CDCl3,ppm)δ:3.31(br,4H),3.75(s,4H),4.41(s,4H),4.72(s,4H),7.35(s,2H),7.95(s,2H)；13C NMR(100MHz,CDCl3,ppm)δ:49.24,50.19,69.15,111.07,118.93,119.09,122.96,149.77。
4)氮气保护下，在装有磁力搅拌的100mL三口圆底烧瓶中，依次加入三(4-溴苯基)胺(2.00g,4.15mmol)，频哪醇硼酸酯(3.16g,12.45mmol)、无水醋酸钾(1.22g,12.45mmol)、50mL DMF和催化量的Pd(dppf)Cl2，加热至120℃搅拌反应12h。反应完成后，减压旋除大量溶剂，用100mL二氯甲烷溶解，饱和食盐水(100mL×3)洗涤，合并有机相，经无水Na2SO4干燥的粗产物。所得粗产物经柱色谱分离(二氯甲烷/石油醚＝1/2，v/v)得到三-[4-(4,4,5,5-四甲基-1,3,2-二氧硼杂环戊烷)苯基]甲烷(III)1.61g，产率62.2％。1H NMR(400MHz,CDCl3,ppm)δ:1.37(s,36H),7.11(t,JJ＝8.0,6H),7.70(d,J＝8.0,6H),7.35(s,2H),7.95(s,2H)；13C NMR(100MHz,CDCl3,ppm)δ:24.87,63.59,83.67,123.48,135.92,149.79。
5)在氮气保护下，在装有磁力搅拌的50mL三口圆底烧瓶中，依次加入1,4-二-[2-(4-甲氨基-1,2,3-三唑)-乙氧基]-2,5-二溴苯(1.53g,3.00mmol)、三-[4-(4,4,5,5-四甲基-1,3,2-二氧硼杂环戊烷)苯基]甲烷(1.25g,2.00mmol)、6.0mL K2CO3水溶液(2mol/L)、25mL DMF和催化量的Pd(PPh3)4催化剂，加热至100℃反应72h。反应完成后，旋除溶剂，用100mL二氯甲烷溶解，饱和食盐水(100mL×3)洗涤，合并有机相，旋除溶剂得到粗产物。所得粗产物用正己烷重结晶，得棕色固体0.21g。将上述所得固体加入含有1.0mL三氟乙酸的10mL圆底烧瓶中，室温搅拌1h后，再加入等量的氢溴酸，继续室温搅拌1h。将反应液直接倒入100mL冰乙醚中，离心得到棕色固体，并用冰乙醚洗涤两次，离心得到聚合物(I)0.12g。1HNMR(400MHz,d-DMSO,ppm)δ:4.15(d,4H),4.33-4.39(d,4H),4.75-4.81(m,4H),5.25-5.51(br,8H),6.86-7.02(br,6H),7.28-7.25(br,4H),8.18-8.13(br,2H),8.28-8.35(m,4H)；13CNMR(100MHz,d-DMSO,ppm)δ:39.62,51.44,72.41,99.89,102.43,111.31,112.44,115.37,119.48,120.98,122.47,125.42,130.17,133.32,135.48,138.67,139.12,146.37,149.12,150.38；Mn＝10742,Mw＝15346,PDI＝1.43。
实施例2环状聚合物(I)的紫外吸收和荧光发射性能测试
配制1.00mg/mL的聚合物(I)的DMSO溶液5mL。稀释至10倍后，准确移取2.00mL浓度为0.10mg/mL的聚合物(I)DMSO溶液至紫外样品池中，然后在HITACHI UH5300紫外吸收仪上测定，所得聚合物(I)在DMSO溶剂中的吸收峰为347nm。同样，再准确移取2.00mL的浓度为0.10mg/mL的聚合物(I)DMSO溶液至荧光样品池中，然后在HITACHI F-4600荧光仪上测定，激发和发射狭缝宽度都为5nm，激发波长为347nm，所得发射波长为449nm。归一化测试数据见图1。
实施例3环状聚合物(I)对细胞毒性测试
环状聚合物(I)对HeLa细胞的细胞毒性用CCK-8测定。将混合均匀的HeLa细胞铺在96孔板中，每孔约4000个细胞，然后在CO2培养箱中培养24h后细胞贴壁，弃去旧的培养基，加入含有不同浓度聚合物(I)的培养基。继续培养24h。然后，向每孔加入10μL浓度为5mg/mL的CCK-8溶液，再继续培养2h。将96孔板放入酶标仪中，震荡1min，测得每孔在450nm处的吸光度值。细胞活力CR的计算方法为：
CR＝A/A0×100％
其中A为聚合物(I)实验组细胞的吸光度值，A0为不加聚合物(I)对照组细胞的吸光度值。测量结果见图2。
实施例4环状聚合物(I)活性氧产生能力测试
取50μL浓度为10mmol/L的2,7-二氯荧光素二乙酸盐(DCFH)乙醇溶液，加入450μL乙醇稀释，再加入2mL浓度为0.01mol/L NaOH水溶液后室温避光活化30min。活化后加入10mL 1×PBS的溶液，混合后2,7-二氯荧光素二乙酸盐溶液的终浓度为40μmol/L。
在比色皿中加入1mL活化的DCFH(40μmol/L)溶液和52.4μL聚合物(I)(1.00mg/mL)，混合均匀后，将溶液在白光(1mW/cm2)下照射5min，每分钟记录激发波长为488nm的DCFH溶液在500-700nm的荧光发射光谱，空白组为未添加任何待测活化的DCFH溶液(40μmol/L)，在相同光照处理后用同样的方法检测其荧光发射光谱。测试结果见图3。
实施例5环状聚合物(I)对大肠杆菌的杀菌性能测试
1)大肠杆菌(Top 10)的培养
取出一支50mL离心管，吸取10mL LB液体培养基到50mL无菌离心管中，加入10μL浓度为50mg/mL氨苄西林钠和10μL大肠杆菌菌种，在温度为37℃，180rpm震荡培养6～8小时。
2)对大肠杆菌(Top 10)的杀菌率测试
将大肠杆菌在LB液体培养基中培养6～8小时，在超净台中吸取2mL菌液进行离心(7100rpm,2min)，对大肠杆菌进行沉淀，将沉淀的大肠杆菌用1×PBS洗涤后再离心沉淀，重复两次后，弃去上清液，将菌液重新悬浮于1×PBS中，调OD600为1.0。在1.5mL的离心管中，加入100μL(OD600＝1.0)的菌液和一定量的聚合物(I)(聚合物的最终浓度分别为10μg/mL、20μg/mL、30μg/mL和50μg/mL)，用无菌1×PBS缓冲液将体积补充到500μL，并在暗处37℃下孵育20min，每个浓度各两组，分别为非光照和光照组，空白组不加聚合物(I)。孵育结束后，非光照组稀释为1×104倍后吸取100μL菌液均匀涂布于90mm LB固体培养基(含50μg/mL的氨苄西林钠)上，37℃培养18h后，计数菌落形成单位。光照组在25mW/cm2的白光下照射15min。后续操作与非光照组均相同。
3)对大肠杆菌杀菌性能测试结果
在聚合物(I)浓度为30μg/mL时，暗处对大肠杆菌的杀菌率能达到93.9％，光照下杀菌率达到95.0％；浓度为50μg/mL时，暗处的杀菌率达到96.3％，光照下杀菌率达到99.6％。光照没有明显增强杀菌效果。测试结果见图4。
实施例6环状聚合物(I)对金黄色葡萄球菌的杀菌性能测试
1)金黄色葡萄球菌(ATCC6358)的培养
取出一支50mL离心管，吸取10mL NB液体培养基到50mL无菌离心管中，再加入10μL金黄色葡萄球菌(ATCC6358)的菌种，37℃下，180rpm震荡培养10h。
2)对金黄色葡萄球菌的杀菌率测试
将在NB液体培养基中培养的金黄色葡萄球菌吸取2mL菌液进行离心(7100rpm,2min)对金黄色葡萄球菌进行沉淀，将沉淀的金黄色葡萄球菌用1×PBS洗涤后离心沉淀，重复两次后，弃去上清液，将菌液重新悬浮于1×PBS中，调OD600为1.0。取100μL菌液(OD600＝1.0)和一定量的聚合物(I)(聚合物的最终浓度分别为30μg/mL、50μg/mL、100μg/mL、150μg/mL)在1.5mL离心管中作用，用无菌1×PBS缓冲溶液将体积补充到500μL，并在暗处37℃下孵育20min，每个浓度各两组，分别为非光照和光照组，空白组不加聚合物(I)。孵育结束后，非光照组稀释1×104倍后吸取100μL菌液均匀涂布于90mm NB固体培养基，37℃培养16h后计数菌落形成单位。光照组在25mW/cm2的白光下照射15min。后续操作与非光照组均相同。
3)对金黄色葡萄球菌的杀菌性能测试结果
在聚合物(I)浓度为100μg/mL时，暗处对大肠杆菌的杀菌率能达到94.4％，光照下杀菌率达到95.8％；浓度为150μg/mL时，暗处的杀菌率达到98.4％，光照下杀菌率达到98.8％。光照没有明显增强杀菌效果。测试结果见图5。
实施例7环状聚合物(I)对大肠杆菌(Top10)的荧光成像
1)大肠杆菌的培养，方法同实施案例4。
2)共聚焦显微镜(CLSM)荧光成像
将培养8h的大肠杆菌用LB培养基调OD600值为1.0。取少量菌液用LB培养基稀释1×103倍后，加入终浓度为50μg/mL的聚合物(I)。在37℃下，180rpm震荡培养6h，取10μL混液于CLSM下观察。在CLSM下可以看到明场的大肠杆菌Top10与聚合物(I)形成复合体，其中聚合物(I)的荧光位置与复合体完全重合。此外，聚合物(I)将大肠杆菌聚集在一起。荧光成像见图6。
实施例8环状聚合物(I)对金黄色葡萄球菌的荧光成像
1)大肠杆菌的培养，方法同实施案例5。
2)共聚焦显微镜(CLSM)荧光成像
将培养8h的金黄色葡萄球菌用LB培养基调OD600值为1.0。取少量菌液用LB培养基稀释1×103倍后，加入终浓度为50μg/mL的聚合物(I)。在37℃下，180rpm震荡培养6h，取10μL混液于CLSM下观察。在CLSM下可以看到明场的金黄色葡萄球菌与聚合物(I)形成复合体，其中聚合物(I)的荧光位置与复合体完全重合。此外，聚合物(I)金黄色葡萄球菌聚集在一起。荧光成像见图7。
Claims (4)
1.一种环状聚合物，其特征在于结构式为：
其中，n＝1-3。
2.如权利要求1所述的一种环状聚合物的制备方法，其特征在于包括如下步骤：
1)、按摩尔比为1∶10∶3.6，将2,5-二溴对苯二酚、1,2-二溴乙烷和K2CO3加入丙酮和水体积比为4∶1的混合溶剂中，加入回流反应12h，经柱色谱分离得到1,4-二溴-2,5-二(2-溴乙氧基)苯；
2)、按摩尔比为1∶10，将1,4-二溴-2,5-二(2-溴乙氧基)苯和NaN3加入无水DMF中，50℃下搅拌反应12h，得到1,4-二(2-叠氮基乙氧基)-2,5-二溴苯；
3)、在氮气保护下，按摩尔比为5∶12∶6∶2，将1,4-二(2-叠氮基乙氧基)-2,5-二溴苯、丙炔胺、CuSO4·5H2O和抗坏血酸钠加入体积比为1∶1的叔丁醇和水混合溶剂中，室温搅拌反应15h，减压旋除溶剂，用10％的氨水猝灭反应，经二氯甲烷萃取、粗产品经正己烷洗涤后得到1,4-二-[2-(4-甲氨基-1,2,3-三唑)-乙氧基]-2,5-二溴苯；
4)、氮气保护下，按摩尔比为1∶3∶3，将三(4-溴苯基)胺、频哪醇硼酸酯和无水碳酸钾加入DMF溶剂中，再加入催化量的Pd(dppf)Cl2，加热到120℃反应过夜，反应结束，经减压旋除溶剂、二氯甲烷萃取，柱色谱分离得到三-[4-(4,4,5,5-四甲基-1,3,2-二氧硼杂环戊烷)苯基]甲烷；
5)、在氮气保护下，按摩尔比为3∶2，将1,4-二-[2-(4-甲氨基-1,2,3-三唑)-乙氧基]-2,5-二溴苯(II)和三-[4-(4,4,5,5-四甲基-1,3,2-二氧硼杂环戊烷)苯基]甲烷(III)加入体积比为6∶25的2mol/L碳酸钾溶液和DMF混合液中，再加入催化量的Pd(PPh3)4，加热反应液至100℃反应72h，反应结束，经旋除溶剂，二氯甲烷溶解，饱和食盐水洗涤后，正己烷重结晶；所得反应产物用三氟乙酸溶解后，加入等体积的氢溴酸，室温搅拌反应1h，反应液用无水乙醚沉淀得到环状聚合物(I)。
3.如权利要求1所述的环状聚合物在制备杀菌剂中的应用。
4.如权利要求1所述的环状聚合物在生物荧光成像中的应用。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810189654.1A CN108467475B (zh) | 2018-03-08 | 2018-03-08 | 一种环状聚合物及其制备方法和应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810189654.1A CN108467475B (zh) | 2018-03-08 | 2018-03-08 | 一种环状聚合物及其制备方法和应用 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108467475A CN108467475A (zh) | 2018-08-31 |
| CN108467475B true CN108467475B (zh) | 2020-02-14 |
Family
ID=63264211
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810189654.1A Expired - Fee Related CN108467475B (zh) | 2018-03-08 | 2018-03-08 | 一种环状聚合物及其制备方法和应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108467475B (zh) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110183621B (zh) * | 2019-06-26 | 2021-06-08 | 西北师范大学 | 带有离子液体的共价有机聚合物的合成及其在染料吸附中的应用 |
| CN111067862B (zh) * | 2019-12-25 | 2021-03-30 | 山西大学 | 具有可视化诊断和治疗感染伤口的温敏水凝胶及制备方法 |
| CN111187226B (zh) * | 2020-01-15 | 2021-03-30 | 山西大学 | 一种特异性杀伤革兰氏阴性菌的化合物及制备方法和应用 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101230077A (zh) * | 2007-12-13 | 2008-07-30 | 上海交通大学 | 同手性非线性光学金属-有机硼聚合物晶体材料制备方法 |
| CN101443048A (zh) * | 2004-04-20 | 2009-05-27 | 德瑞迪克纳米科技公司 | 具有增强的扩增性和内部官能度的树枝状聚合物 |
| CN103442567A (zh) * | 2011-03-23 | 2013-12-11 | 巴斯夫欧洲公司 | 含有包含咪唑鎓基团的聚合离子型化合物的组合物 |
| WO2017049402A1 (en) * | 2015-09-22 | 2017-03-30 | Khashayar Ghandi | Multi-functional anti-microbial polymers and compositions containing same |
| CN107522664A (zh) * | 2011-10-27 | 2017-12-29 | 麻省理工学院 | 能够形成药物包封微球的在n末端上官能化的氨基酸衍生物 |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7060770B2 (en) * | 2003-05-06 | 2006-06-13 | Kerr Corporation | Metathesis-curable composition with a reaction control agent |
| US20080207822A1 (en) * | 2007-02-22 | 2008-08-28 | General Electric Company | Composition and associated method |
| WO2010144386A2 (en) * | 2009-06-08 | 2010-12-16 | University Of Massachusetts | Antimicrobial polymers |
| US9156934B2 (en) * | 2011-12-23 | 2015-10-13 | Johnson & Johnson Vision Care, Inc. | Silicone hydrogels comprising n-vinyl amides and hydroxyalkyl (meth)acrylates or (meth)acrylamides |
| WO2014164167A1 (en) * | 2013-03-12 | 2014-10-09 | Hoffman/Barrett, L.L.C. | Porphyrazine optical and dual optical/mr contrast and therapeutic agents |
-
2018
- 2018-03-08 CN CN201810189654.1A patent/CN108467475B/zh not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101443048A (zh) * | 2004-04-20 | 2009-05-27 | 德瑞迪克纳米科技公司 | 具有增强的扩增性和内部官能度的树枝状聚合物 |
| CN101230077A (zh) * | 2007-12-13 | 2008-07-30 | 上海交通大学 | 同手性非线性光学金属-有机硼聚合物晶体材料制备方法 |
| CN103442567A (zh) * | 2011-03-23 | 2013-12-11 | 巴斯夫欧洲公司 | 含有包含咪唑鎓基团的聚合离子型化合物的组合物 |
| CN107522664A (zh) * | 2011-10-27 | 2017-12-29 | 麻省理工学院 | 能够形成药物包封微球的在n末端上官能化的氨基酸衍生物 |
| WO2017049402A1 (en) * | 2015-09-22 | 2017-03-30 | Khashayar Ghandi | Multi-functional anti-microbial polymers and compositions containing same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108467475A (zh) | 2018-08-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Bai et al. | AIEgens for microbial detection and antimicrobial therapy | |
| Kang et al. | Evaluation of structure–function relationships of aggregation-induced emission luminogens for simultaneous dual applications of specific discrimination and efficient photodynamic killing of Gram-positive bacteria | |
| CN108467475B (zh) | 一种环状聚合物及其制备方法和应用 | |
| Lee et al. | Ultrafast discrimination of Gram-positive bacteria and highly efficient photodynamic antibacterial therapy using near-infrared photosensitizer with aggregation-induced emission characteristics | |
| Frimannsson et al. | Light induced antimicrobial properties of a brominated boron difluoride (BF2) chelated tetraarylazadipyrromethene photosensitizer | |
| Zhu et al. | Conjugated Polymer with Aggregation-Directed Intramolecular Förster Resonance Energy Transfer Enabling Efficient Discrimination and Killing of Microbial Pathogens | |
| CN108329460B (zh) | 一种光动力杀菌聚合物及其制备方法和应用 | |
| Shi et al. | Aggregation-induced emission-based ionic liquids for bacterial killing, imaging, cell labeling, and bacterial detection in blood cells | |
| Zhai et al. | Efficient antibacterial performance and effect of structure on property based on cationic conjugated polymers | |
| CN111187299B (zh) | 一种基于噻吩并[3,4-b]噻吩的有机光敏剂及制备方法和应用 | |
| CN110950779B (zh) | 集细菌荧光成像与光动力杀菌于一体的光敏剂及其制备方法和应用 | |
| Wu et al. | Daylight-stimulated antibacterial activity for sustainable bacterial detection and inhibition | |
| Spagnul et al. | Synthesis and bactericidal properties of porphyrins immobilized in a polyacrylamide support: influence of metal complexation on photoactivity | |
| CN102020675B (zh) | 一种季鏻盐及其制备方法与应用 | |
| Li et al. | Molecular structural evolution of near-infrared cationic aggregation-induced emission luminogens: preclinical antimicrobial pathogens activities and tissues regeneration | |
| Shao et al. | Nano adamantane-conjugated BODIPY for lipase affinity and light driven antibacterial | |
| JP2014522881A (ja) | 治療的使用のための新しいフタロシアニン誘導体 | |
| Wang et al. | Bioactive AIEgens tailored for specific and sensitive theranostics of Gram-positive bacterial infection | |
| CN113200913B (zh) | 一种光激活i型光敏剂及其制备方法和应用 | |
| CN111943868B (zh) | 一种含二乙胺的吖嗪联肼类化合物及其制备方法与应用 | |
| CN115433367B (zh) | 一种卟啉类cof材料及制备方法和应用 | |
| CN116354954A (zh) | 一种靶向溶酶体的aie探针及其制备方法与应用 | |
| CN111187226B (zh) | 一种特异性杀伤革兰氏阴性菌的化合物及制备方法和应用 | |
| CN112480377A (zh) | 一种以精氨酸为侧链的共轭聚合物的制备方法及其应用 | |
| Mohammed et al. | Antibacterial activity of quaternary ammonium salt from diethylaminoethyl methacrylate |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200214 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |