CN105906675B - Novel concanavalin A fluorescent probe and application thereof - Google Patents
Novel concanavalin A fluorescent probe and application thereof Download PDFInfo
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- CN105906675B CN105906675B CN201610318644.4A CN201610318644A CN105906675B CN 105906675 B CN105906675 B CN 105906675B CN 201610318644 A CN201610318644 A CN 201610318644A CN 105906675 B CN105906675 B CN 105906675B
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- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 18
- 108010062580 Concanavalin A Proteins 0.000 title abstract description 76
- 239000000523 sample Substances 0.000 claims description 119
- 239000007853 buffer solution Substances 0.000 claims description 57
- 238000001514 detection method Methods 0.000 claims description 55
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 37
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000000412 dendrimer Substances 0.000 abstract description 23
- 229920000736 dendritic polymer Polymers 0.000 abstract description 23
- JLZUZNKTTIRERF-UHFFFAOYSA-N tetraphenylethylene Chemical group C1=CC=CC=C1C(C=1C=CC=CC=1)=C(C=1C=CC=CC=1)C1=CC=CC=C1 JLZUZNKTTIRERF-UHFFFAOYSA-N 0.000 abstract description 7
- 230000035945 sensitivity Effects 0.000 abstract description 6
- WQZGKKKJIJFFOK-PQMKYFCFSA-N alpha-D-mannose Chemical compound OC[C@H]1O[C@H](O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-PQMKYFCFSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 40
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 30
- 239000007787 solid Substances 0.000 description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 150000001875 compounds Chemical class 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 16
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000005259 measurement Methods 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 11
- 108010046016 Peanut Agglutinin Proteins 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 229920000962 poly(amidoamine) Polymers 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 238000013507 mapping Methods 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 7
- 230000004224 protection Effects 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 5
- 239000012043 crude product Substances 0.000 description 5
- 230000005284 excitation Effects 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 206010013786 Dry skin Diseases 0.000 description 4
- 125000003368 amide group Chemical group 0.000 description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 4
- 239000012964 benzotriazole Substances 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 238000002189 fluorescence spectrum Methods 0.000 description 4
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 235000010378 sodium ascorbate Nutrition 0.000 description 4
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 description 4
- 229960005055 sodium ascorbate Drugs 0.000 description 4
- 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 description 4
- 239000012265 solid product Substances 0.000 description 4
- 235000010520 Canavalia ensiformis Nutrition 0.000 description 3
- 235000010518 Canavalia gladiata Nutrition 0.000 description 3
- 240000001723 Entada phaseoloides Species 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000007306 functionalization reaction Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 150000003462 sulfoxides Chemical class 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 0 CC(OC*(C*C(C(C1OC(C)=O)OC(C)=O)OCCBr=C)C1O)=O Chemical compound CC(OC*(C*C(C(C1OC(C)=O)OC(C)=O)OCCBr=C)C1O)=O 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000006845 Michael addition reaction Methods 0.000 description 2
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 230000004520 agglutination Effects 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 238000005915 ammonolysis reaction Methods 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000012678 divergent method Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000007039 two-step reaction Methods 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 125000005999 2-bromoethyl group Chemical group 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 101710186708 Agglutinin Proteins 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- XUCNNZYGRJQSHZ-QVIHXGFCSA-N CCOC(COc(cc1)ccc1/C(/c1ccccc1)=C(\c1ccccc1)/c(cc1)ccc1Br)=O Chemical compound CCOC(COc(cc1)ccc1/C(/c1ccccc1)=C(\c1ccccc1)/c(cc1)ccc1Br)=O XUCNNZYGRJQSHZ-QVIHXGFCSA-N 0.000 description 1
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 description 1
- 238000007445 Chromatographic isolation Methods 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 101710146024 Horcolin Proteins 0.000 description 1
- 101710189395 Lectin Proteins 0.000 description 1
- 108090001090 Lectins Proteins 0.000 description 1
- 102000004856 Lectins Human genes 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 101710179758 Mannose-specific lectin Proteins 0.000 description 1
- 101710150763 Mannose-specific lectin 1 Proteins 0.000 description 1
- 101710150745 Mannose-specific lectin 2 Proteins 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 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
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000910 agglutinin Substances 0.000 description 1
- 230000006907 apoptotic process Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004900 autophagic degradation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- KDPAWGWELVVRCH-UHFFFAOYSA-M bromoacetate Chemical compound [O-]C(=O)CBr KDPAWGWELVVRCH-UHFFFAOYSA-M 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000011097 chromatography purification Methods 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 235000013601 eggs Nutrition 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- KDKYADYSIPSCCQ-UHFFFAOYSA-N ethyl acetylene Natural products CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N ethyl formate Chemical compound CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000002523 lectin Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 150000002703 mannose derivatives Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 210000004885 white matter Anatomy 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
- C07H15/26—Acyclic or carbocyclic radicals, substituted by hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/028—Polyamidoamines
-
- 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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- 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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
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- 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
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- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Biotechnology (AREA)
- Physics & Mathematics (AREA)
- Molecular Biology (AREA)
- Immunology (AREA)
- Genetics & Genomics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Materials Engineering (AREA)
- Optics & Photonics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention discloses a novel concanavalin A fluorescent probe, which relates to the field of fluorescent probes, the core of the fluorescent probe is a dendritic polymer, tetraphenylethylene and α -mannose are modified on the periphery of the dendritic polymer, and the concanavalin A fluorescent probe has strong identification, high sensitivity and selectivity.
Description
Technical field
The present invention relates to fluorescence probe fields.More particularly, to a kind of novel ConA A fluorescence probes and its
Using.
Background technology
In biosystem, the interaction between sugar-protein is of great significance, the agglutination on usual cell surface
Interaction between element and saccharide acceptor adjusts the identification process in organism.As the lectin of beans of first report, sword bean
Agglutinin A (Con A) being capable of inducing cell apoptosis and autophagy process.Therefore, develop quick, simple, sensitive Con A probes tool
It is significant.
Dendritic polymer, which is one kind, has accurate molecular structure, and peripheral segment is as the increase of algebraically is with index rank
The branched macromolecules of the nano-scale of growth.Modification is carried out in the core of dendritic polymer, skeleton and periphery to may be implemented to set
The functionalization of branch shape polymer, especially the characteristics of peripheral multiple reaction site make it be used widely in biosimulation field.
Research in recent years finds that aggregation-induced emission (AIE) property is presented in certain organic compounds, hardly shines in weak solution, and
Internal molecular motion is limited under state of aggregation or solid-state, and fluorescence quantum yield greatly improves.
Common Con A detection methods have the methods of Con A electrodes selectives, electrochemical luminescence, but there is it is of high cost,
The shortcomings of complicated for operation, not portable.In contrast, fluorescence chemical sensor has many advantages, such as convenient, fast, high sensitivity.
There are sugar-modified high-molecular compound, nano particle etc., wherein most to be based on fluorescent quenching in existing Con A fluorescence probes
Principle or absorption spectrum variation, usual sensitivity is relatively low, and toxicity is big, is not easily applicable to biosystem.
Insufficient existing for above method to solve, present invention design has synthesized fluorescence open type Con A probes, for the first time will be outer
The dendritic polymer for modifying multiple AIE chromophories is enclosed applied to Con A detections, has the characteristics that high sensitivity, selectivity are good.
Invention content
First of the present invention is designed to provide a kind of novel ConA A (Con A) fluorescence probe, for the first time will be outer
The dendritic polymer for modifying multiple AIE chromophories is enclosed applied to Con A detections, which is dendriform, right
Con A have very strong identity, high sensitivity and selectivity.
Second object of the present invention is to provide a kind of novel ConA A fluorescence probes in detection ConA
Application in A.
To reach above-mentioned first purpose, the present invention uses following technical proposals：
A kind of novel ConA A fluorescence probes, the fluorescence probe have the following structure any one of formula structure：
Or
,
Wherein,
Con A fluorescence probes in the present invention are prepared by the following method：
(1) according to the literature method (Macromolecules, 2009,42,9400；J.Mater.Chem.,2011,
21,4056) synthesis material compound tetraphenylethylene chromophore, synthetic route are as follows：
(2) method (Org.Biomol.Chem.2011,9,2219 according to the literature；ACS
Appl.Mater.Inter.2016,8,5813) ɑ-mannose micromolecular compound is synthesized, synthetic route is as follows：
(3) the divergent method synthesis of PAMAM (polyamide-amide) dendritic polymers skeleton according to the literature
(D.A.Tomalia,H.Baker,J.Dewald,M.E.Hall,G.Kallos,S.Martin,J.Roeck,J.Ryder,
P.Smith,Polym.J.1985,17,117.).It sets out by core of ethylenediamine, Michael additions is carried out with methyl acrylate
Reaction, is removed under reduced pressure unreacted methyl acrylate after the reaction was complete after amino, obtain the dendriform molecule that end is methyl esters, so
Ammonolysis is carried out with excessive ethylenediamine under nitrogen protection afterwards, vacuum distillation obtains 0 generation PAMAM after removing excessive reactant,
It repeats this two-step reaction and obtains 1~4 generation PAMAM dendritic polymer skeleton (Gn, n=1,2,3 or 4).
(4) according to the literature method (Polym.Chem., 2014,5,5978；J Polym.Sci.Pol.Chem.,
2011,49,4312 (mannose derivative synthetic methods)；Angew.Chem.Int.Ed., 2008,47,5022) ɑ-sweet dew is synthesized
The functionalization dendritic polymer of sugar and the modification of tetraphenylethylene chromophore, synthetic route are as follows：
To reach above-mentioned second purpose, the present invention uses following technical proposals：
The present invention protects application of the above-mentioned novel ConA A fluorescence probes in detecting ConA A.
Further, the present invention protects sword bean agglutination of the novel ConA A fluorescence probes in detecting water phase
The application of plain A.
ConA A in the novel ConA A fluorescence probes detection water phase includes following detecting step：
1) aqueous solution of fluorescent probe molecule is prepared；
2) the detection limit of various concentration fluorescent probe molecule is determined；
3) working curve of fluorescent probe molecule is drawn.
Preferably, it in step 1), prepares fluorescent probe molecule aqueous solution and includes the following steps：
A. the dimethyl sulphoxide solution of ConA A probe molecules is prepared；
B. the Tris-HCl buffer solutions of pH=7.6 are prepared；
C. the step a solution prepared is added in the buffer solution that step b is prepared, obtains being dispersed in buffer solution
The aqueous solution of probe molecule.
The detailed process of detection is as follows：
S1 configures the dimethyl sulphoxide solution that ConA A probe molecules periphery functional group concentration is 0.5mM；
S2 configuration concentrations are 10mM, the Tris-HCl buffer solutions of pH=7.6；
S3 takes in the buffer solution prepared in the 10mL S2 that the solution prepared in the S1 of 100 μ L is added to, and is dispersed in
The aqueous solution of probe molecule in buffer solution；
S4 takes the buffer solution dispersion of fluorescence probe obtained by 1-3mL series of steps S3, is separately added into 10-50 μ L not
The fluorescence intensity at 464nm is measured respectively after placing 1 minute with the Con A (0,20,40,60,80,100 μM) of concentration, by
This determines the detection limit of each fluorescent probe molecule；
S5 takes the buffer solution dispersion of fluorescence probe obtained by 1-3mL series of steps S3, and it is dense to be separately added into 10-50 μ L
Degree is 10-3The Tris-HCl buffer solutions of the Con A, PNA of M, after placing 1 minute, the fluorescence measured respectively at 464nm is strong
Thus degree verifies selectivity of the fluorescence probe to Con A；
S6 takes the buffer solution dispersion of fluorescence probe obtained by 1-3mL series of steps S3, is separately added into 10-50 μ L not
It is dense according to fluorescence intensity and Con A after placing 1 minute with the Con A (0,30,60,90,120,250,500,750 μM) of concentration
The relationship of degree makes working curve.
Testing principle schematic diagram such as Fig. 1 of novel ConA A fluorescence probes detection ConA A in the present invention
It is shown.
The present invention has ɑ-mannose of specific recognition successively by AIE chromophories tetraphenylethylene (TPE) and to Con A
Dendritic polymer periphery is modified, to prepare ConA A probes.Pass through the interaction of Con A and ɑ-mannose
The rotation of phenyl ring in restricted T PE inhibits excitation state Nonradiative decay to improve the fluorescence quantum yield of functionalization dendritic polymer,
To which Con A be identified.Result of study shows that the fluorescence probe of design synthesis is used successfully to the inspection of Con A by the present invention
It surveys, and has the characteristics that sensitivity is high and selectivity is good.
Unless otherwise specified, the raw material used in the present invention can be obtained or by this field routine hand by commercially available purchase
Section obtains.
Beneficial effects of the present invention are as follows：
1. solidifying for detection sword bean the present invention provides a kind of ConA A fluorescence probes of novel dendrimers
The fluorescence probe of collection element A provides a kind of new fluorescence probe structure.
2. the novel ConA A fluorescence probes of the present invention are to the high selectivity of ConA A, not by other eggs
The interference of white matter.
3. the probe molecule that the present invention uses has more chromophories, is not influenced, had by photobleaching in detection process
Applied to the potentially possible of organism.
4. the novel ConA A fluorescence probes of the present invention are used to detect the detection side of the ConA A in water phase
The detection limit of method is low.
Description of the drawings
Specific embodiments of the present invention will be described in further detail below in conjunction with the accompanying drawings.
Fig. 1 shows the testing principle signal of the novel ConA A fluorescence probes detection ConA A of the present invention
Figure.
Fig. 2 shows the fluorescence intensities of fluorescence probe detection Con A in the embodiment of the present invention 13 with Con A concentration (0-1.25
×10-6Mol/L) variation relation figure.
Fig. 3 show the fluorescence intensity of the detection Con of fluorescence probe in the embodiment of the present invention 13 A with Con A concentration (0-1.0 ×
10-5Mol/L) variation relation figure.
Fig. 4 shows fluorescence intensity ratio when fluorescence probe detection different testing sample in the embodiment of the present invention 13.
Fig. 5 shows the fluorescence intensity of fluorescence probe detection Con A in the embodiment of the present invention 14 with Con A concentration (0-1.25
×10-6Mol/L) variation relation figure.
Fig. 6 show the fluorescence intensity of the detection Con of fluorescence probe in the embodiment of the present invention 14 A with Con A concentration (0-1.0 ×
10-5Mol/L) variation relation figure.
Fig. 7 shows fluorescence intensity ratio when fluorescence probe detection different testing sample in the embodiment of the present invention 14.
Fig. 8 shows the fluorescence intensity of fluorescence probe detection Con A in the embodiment of the present invention 15 with Con A concentration (0-1.25
×10-6Mol/L) variation relation figure.
Fig. 9 show the fluorescence intensity of the detection Con of fluorescence probe in the embodiment of the present invention 15 A with Con A concentration (0-1.0 ×
10-5Mol/L) variation relation figure.
Figure 10 shows fluorescence intensity ratio when fluorescence probe detection different testing sample in the embodiment of the present invention 15.
Figure 11 shows the fluorescence intensity of fluorescence probe detection Con A in the embodiment of the present invention 16 with Con A concentration (0-1.25
×10-6Mol/L) variation relation figure.
Figure 12 shows the fluorescence intensity of fluorescence probe detection Con A in the embodiment of the present invention 16 with Con A concentration (0-1.0
×10-5Mol/L) variation relation figure.
Figure 13 shows fluorescence intensity ratio when fluorescence probe detection different testing sample in the embodiment of the present invention 16.
Specific implementation mode
In order to illustrate more clearly of the present invention, the present invention is done further with reference to preferred embodiments and drawings
It is bright.Similar component is indicated with identical reference numeral in attached drawing.It will be appreciated by those skilled in the art that institute is specific below
The content of description is illustrative and be not restrictive, and should not be limited the scope of the invention with this.
Embodiment 1
The synthesis of 1- (4- bromophenyls) -2- (4- hydroxy phenyls) -1,2- diphenylethlenes (1), molecular structural formula are：
Its reaction route is as follows：
2.61g (10mmol) 4- bromines benzophenone and 1.98g (10mmol) 4- hydroxyl hexichol are added in 250mL there-necked flasks
Ketone, the tetrahydrofuran of 2.6g (40mmol) zinc powders and 100mL dryings, is passed through nitrogen and system is placed in 0 DEG C of ice-water bath, will
2.2mL (20mmol) titanium tetrachloride is slowly injected into reaction system, is slowly heated up and is flowed back 5 hours.It after reaction, will be anti-
Liquid is answered to filter, filtrate collection uses ethyl acetate and 1M salt acid extractions reaction solution three times after being spin-dried for, and organic phase is washed three times with anhydrous
MgSO4It is dry, it is purified using column chromatography for separation after filtering and being spin-dried for filtrate.Eluant, eluent is dichloromethane/petroleum ether=2/1,
Obtain white solid 1.3g, yield 30%.1H NMR(400MHz,CDCl3),δ(ppm):7.19–7.24(m,2H),7.07–
7.15(m,6H),6.85–6.92(m,4H),6.55–6.62(m,2H)。MS(ESI-TOF):calc.426.0619,found
426.0623.
Embodiment 2
The synthesis of 1- (4- bromophenyls) -2- (4- ethoxycarbonylmethoxies phenyl) -1,2- diphenylethlenes (2), molecule
Structural formula is：
Its reaction route is as follows：
1.3g (3mmol) compound 1,1.9g (1.5mL, 13.8mmol) bromoacetic acid second are added in the two-mouth bottle of 50mL
Ester, the tetrahydrofuran of 2g (15mmol) Anhydrous potassium carbonates and 30mL dryings, leads to nitrogen deoxygenation, is heated to reflux 12 hours, is cooled to
Room temperature, is filtered to remove inorganic salts, and filtrate obtains crude product after being spin-dried for.Crude product is dissolved in ethyl acetate, is washed three times, anhydrous sulphur
Purifying is used column chromatography after sour magnesium drying.With petroleum ether it is first that eluant, eluent washes out bromoacetate, then with dichloromethane/stone
Oily ether (1/1,5/1, vol/vol) gradient elution, obtains faint yellow thick solid 1.5g, yield 94%.1H NMR
(400MHz,CDCl3)δ(ppm):7.19–7.24(m,2H),7.07–7.15(m,6H),6.85–6.92(m,4H),6.55–
6.62(m,2H),4.56(s,2H),4.25(m,2H),1.25(t,3H)。MS(EI-TOF):calc.512.0987,found[M+
Na]+:535.0891.
Embodiment 3
1- (4- ethoxycarbonylmethoxies phenyl) -2- (4- trimethyl silicane ethyl-acetylene bases phenyl) -1,2- diphenylethlenes (3)
Synthesis, molecular structural formula is：
Its reaction route is as follows：
1.0g (2mmol) compound 2,296mg (3mmol) trimethyl silicon substrate are added in the Schlenk reaction bulbs of 100mL
Acetylene, 103mg (0.1mmol) tetra-triphenylphosphine palladium, 57mg (0.3mmol) cuprous iodide, 79mg (0.3mmol) and 55mL dryings
Triethylamine and tetrahydrofuran mixed solvent (10/1), jelly extract oxygen after be heated to reflux 12 hours.It is cooled to room temperature, is filtered to remove
Inorganic salts, filtrate obtain crude product after being spin-dried for.Crude product is dissolved in ethyl acetate, washing three times, is used after anhydrous magnesium sulfate drying
Column chromatographic isolation and purification.It is eluted with dichloromethane/petroleum ether (2/1), obtains faint yellow thick solid 850mg, yield is
80%.1H NMR(400MHz,CDCl3)δ(ppm):7.18–7.23(d,2H),7.05–7.12(m,6H),6.90–7.02(m,
8H),6.55(d,2H),4.55(s,2H),4.25(m,2H),1.28(t,3H),0.22(s,9H)。MS(MALDI-TOF):
calc.530.2,found 530.4.
Embodiment 4
The synthesis of 1- (4- carboxy-- methoxyphenyls) -2- (4- ethynyl phenyls) -1,2- diphenylethlenes (4), molecule
Structural formula is：
Its reaction route is as follows：
2.1g (4mmol) compound 3 is added in 100mL round-bottomed flasks, 50mL THF/MeOH are added thereto successively
(1:1) mixed solvent and 10mL water, add 2.24g KOH, are heated to reflux 5h and are allowed to fully saponified, organic solvent is spin-dried for,
The dilution of 40mL water is added, adjusts pH value to 2 with concentrated hydrochloric acid, filters and wash precipitation solid, drained in vacuum drying oven, obtained white
Color solid 1.6g, yield 93%.1H NMR(400MHz,CDCl3)δ(ppm):7.23(d,2H),7.07–7.13(m,6H),
6.93–7.03(m,8H),6.69(d,2H),4.62(s,2H),3.04(s,1H)。MS(MALDI-TOF):calc.530.2,
found530.4.
Embodiment 5
2- bromoethyls -2,3, the synthesis (5) of 4,6- tetra-acetylated-ɑ-mannoses, molecular structural formula are：
Its reaction route is as follows：
3.9g (10mmol) 1,2,3,4,6- penta-acetyl-ɑ-mannose, 1.9g are added in 50mL round-bottomed flasks
7.1g (50mmol) boron trifluoride ether is added dropwise in (15mmol) ethylene bromohyrin, 20mL dry methylene chlorides under the conditions of 0 DEG C, by
Gradually reaction temperature is warmed to room temperature and is stirred 24 hours.It is dry with anhydrous sodium sulfate afterwards three times using saturated sodium bicarbonate solution washing
It is dry.With acetone/petroleum ether (1/2) for eluant, eluent, is isolated and purified with column chromatography, obtain white solid 4g, yield 88%.1H
NMR(400MHz,CDCl3)δ(ppm):5.25–5.38(m,3H),4.88(d,1H),4.24–4.31(m,1H),4.11–4.17
(m,2H),3.95–4.02(m,1H),3.85–3.92(m,1H),3.52(t,2H),2.16(s,3H),2.11(s,3H),2.06
(s,3H),2.00(s,3H)。MS(MALDI-TOF):calc.454.0,found 477.2.
Embodiment 6
2- Azidoethyls -2,3, the synthesis (6) of 4,6- tetra-acetylated-ɑ-mannoses, molecular structural formula are：
Its reaction route is as follows：
1.8g (4mmol) compound 5,1.3g (20mmol) sodium azide, 40mL dryings are added in 50mL round-bottomed flasks
Dimethylformamide reacts 16 hours under the conditions of 80 DEG C.With dichloromethane/petroleum ether (2/1) for eluant, eluent, column chromatography is used
It isolates and purifies, obtains white solid 1.4g, yield 84%.1H NMR(400MHz,CDCl3)δ(ppm):5.27–5.39(m,
3H),4.87(d,1H),4.27–4.32(m,1H),4.11–4.17(m,1H),4.02–4.08(m,1H),3.84–3.91(m,
1H),3.64–3.71(m,1H),3.42–3.52(m,2H),2.16(s,3H),2.11(s,3H),2.06(s,3H),2.00(s,
3H)。MS(MALDI-TOF):calc.417.1,found 417.2.
Embodiment 7
The synthesis (7) of 2- Azidoethyls-ɑ-mannose, molecular structural formula are：
Its reaction route is as follows：
1.3g (3mmol) compound 6 is added in 50mL round-bottomed flasks to be dissolved in 10mL absolute methanols, 1.6g is added
(30mmol) sodium methoxide reacts 5 hours at room temperature.It is 7 that cation exchange resin, which is added in reaction solution to reacting liquid pH value, mistake
It filters and is spin-dried for filtrate, obtain reaction product 600mg, yield 80%.1H NMR(400MHz,CDCl3)δ(ppm):4.93(d,
1H),3.98–4.01(m,1H),3.89–3.96(m,2H),3.83–3.87(m,1H),3.67–3.81(m,4H),3.47–3.59
(m,2H)。MS(ESI-TOF):calc.249.0961,found 249.0947.
Embodiment 8
For the synthesis of PAMAM dendritic polymers, molecular structural formula is respectively 1-4：
PAMAM dendritic polymers skeleton according to the literature divergent method synthesis (D.A.Tomalia, H.Baker,
J.Dewald,M.E.Hall,G.Kallos,S.Martin,J.Roeck,J.Ryder,P.Smith,Polym.J.1985,17,
117.).It sets out by core of ethylenediamine, carries out Michael addition reactions with methyl acrylate, depressurized after the reaction was complete after amino
Unreacted methyl acrylate is removed, the dendriform molecule that end is methyl esters is obtained, then under nitrogen protection with excessive second
Diamines carries out ammonolysis, and vacuum distillation obtains 0 generation PAMAM after removing excessive reactant, repeats this two-step reaction and obtained for 1~4 generation
PAMAM dendritic polymers skeleton (Gn, n=1,2,3 or 4).
Embodiment 9
The dendritic polymer ConA A fluorescence probes (G1-Man) in 1 generation are prepared, reaction route is as follows：
, wherein
431mg (1mmol) compound 4 and 5mL dimethyl sulfoxide (DMSO)s are added in 50mL two-mouth bottles, after solid dissolving successively
267mg (1.4mmol) 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides, 135mg (1mmol) 1- hydroxyls is added
Reaction 2 hours is stirred at room temperature under benzotriazole (HOBT) nitrogen protections, 10mL is slowly added dropwise dissolved with 129mg to reaction system
The dimethyl sulphoxide solution of (0.09mmol) G1, the ratio between tetraphenylethylene chromophore and the amount of substance of the peripheries G1 amido are 1.4:
1, continue to be stirred to react 96 hours, reaction solution is slowly poured into suitable quantity of water, filters and with appropriate water washing solid, crude product is existed
It is dried in 40 DEG C of vacuum drying ovens.With appropriate chloroform by dissolved solid, is precipitated in ether three times, filter and washed with appropriate ether
Solid.Obtained solid is placed in 50mL round-bottomed flasks, and 249mg (1mmol) compound 7 is added, with 10mL dimethyl sulfoxide (DMSO)s
After dissolving, it is passed through nitrogen 20 minutes, then sequentially adds the aqueous solution that 2mL contains 20.8mg (0.08mmol) Salzburg vitriol
Contain the aqueous solution of 33.2mg (0.16mmol) sodium ascorbate with 2mL.It is stirred 24 hours at 60 DEG C, stops reaction.It will be anti-
It answers liquid successively to dialyse repeatedly in methanol in water, obtains faint yellow solid product 255mg, yield 42%.1H NMR
(400MHz,(CD3)2SO,ppm):δ=8.47 (s, 8H), 7.64 (d, 16H), 7.18-6.89 (m, 112H), 6.72 (d, 16H),
4.75-4.67(m,8H),4.58(s,16H),4.61-4.43(m,24H),4.38-4.32(m,16H),4.03-3.94(m,
8H),3.86-3.78(m,8H),3.66-3.40(m,24H),3.17(m,40H),2.54(s,24H),2.25(s,12H),2.16
(s,24H).
Embodiment 10
The dendritic polymer probe (G2-Man) of the mannose-modified in 2 generations is prepared, reaction route is as follows：
, wherein
431mg (1mmol) compound 4 and 5mL dimethyl sulfoxide (DMSO)s are added in 50mL two-mouth bottles, after solid dissolving successively
267mg (1.4mmol) 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides, 135mg (1mmol) 1- hydroxyls is added
Reaction 2 hours is stirred at room temperature under benzotriazole (HOBT) nitrogen protections, 10mL is slowly added dropwise dissolved with 147mg to reaction system
The dimethyl sulphoxide solution of (0.045mmol) G2, tetraphenylethylene chromophore and the ratio between the amount of substance of the peripheries G2 amido are
1.4:1, continue to be stirred to react 96 hours, reaction solution is slowly poured into suitable quantity of water, filters and with appropriate water washing solid, it will be thick
Product are dried in 40 DEG C of vacuum drying ovens.With appropriate chloroform by dissolved solid, precipitates three times, filter and with appropriate ether in ether
Wash solid.Obtained solid is placed in 50mL round-bottomed flasks, and 249mg (1mmol) compound 7 is added, with 10mL dimethyl
After sulfoxide dissolving, it is passed through nitrogen 20 minutes, then sequentially adds the water that 2mL contains 20.8mg (0.08mmol) Salzburg vitriol
Solution and 2mL contain the aqueous solution of 33.2mg (0.16mmol) sodium ascorbate.It is stirred 24 hours at 60 DEG C, stops reaction.
Reaction solution is successively dialysed repeatedly in methanol in water, obtains faint yellow solid product 268mg, yield 43%.1H NMR
(400MHz,(CD3)2SO,ppm):δ=8.47 (s, 16H), 7.64 (d, 32H), 7.18-6.89 (m, 224H), 6.72 (d,
32H),4.75-4.67(m,16H),4.58(s,32H),4.61-4.43(m,48H),4.38-4.32(m,32H),4.03-3.94
(m,16H),3.86-3.78(m,16H),3.66-3.40(m,48H),3.17(m,88H),2.54(s,56H),2.25(s,
28H),2.16(s,56H).
Embodiment 11
The dendritic polymer probe (G3-Man) of the mannose-modified in 3 generations is prepared, reaction route is as follows：
, wherein
431mg (1mmol) compound 4 and 5mL dimethyl sulfoxide (DMSO)s are added in 50mL two-mouth bottles, after solid dissolving successively
267mg (1.4mmol) 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides, 135mg (1mmol) 1- hydroxyls is added
Reaction 2 hours is stirred at room temperature under benzotriazole (HOBT) nitrogen protections, 10mL is slowly added dropwise dissolved with 152mg to reaction system
The dimethyl sulphoxide solution of (0.022mmol) G3, tetraphenylethylene chromophore and the ratio between the amount of substance of the peripheries G3 amido are
1.4:1, continue to be stirred to react 96 hours, reaction solution is slowly poured into suitable quantity of water, filters and with appropriate water washing solid, it will be thick
Product are dried in 40 DEG C of vacuum drying ovens.With appropriate chloroform by dissolved solid, precipitates three times, filter and with appropriate ether in ether
Wash solid.Obtained solid is placed in 50mL round-bottomed flasks, and 249mg (1mmol) compound 7 is added, with 10mL dimethyl
After sulfoxide dissolving, it is passed through nitrogen 20 minutes, then sequentially adds the water that 2mL contains 20.8mg (0.08mmol) Salzburg vitriol
Solution and 2mL contain the aqueous solution of 33.2mg (0.16mmol) sodium ascorbate.It is stirred 24 hours at 60 DEG C, stops reaction.
Reaction solution is successively dialysed repeatedly in methanol in water, obtains faint yellow solid product 245mg, yield 40%.1H NMR
(400MHz,(CD3)2SO,ppm):δ=8.47 (s, 32H), 7.64 (d, 64H), 7.18-6.89 (m, 448H), 6.72 (d,
64H),4.75-4.67(m,32H),4.58(s,64H),4.61-4.43(m,96H),4.38-4.32(m,64H),4.03-3.94
(m,32H),3.86-3.78(m,32H),3.66-3.40(m,96H),3.17(m,184H),2.54(s,120H),2.25(s,
60H),2.19(s,120H).
Embodiment 12
It is as follows to prepare dendritic polymer probe (G4-Man) of the mannose-modified in 4 generations its reaction route：
, wherein
431mg (1mmol) compound 4 and 5mL dimethyl sulfoxide (DMSO)s are added in 50mL two-mouth bottles, after solid dissolving successively
267mg (1.4mmol) 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides, 135mg (1mmol) 1- hydroxyls is added
Reaction 2 hours is stirred at room temperature under benzotriazole (HOBT) nitrogen protections, 10mL is slowly added dropwise dissolved with 156mg to reaction system
The dimethyl sulphoxide solution of (0.011mmol) G4, tetraphenylethylene chromophore and the ratio between the amount of substance of the peripheries G4 amido are
1.4:1, continue to be stirred to react 96 hours, reaction solution is slowly poured into suitable quantity of water, filters and with appropriate water washing solid, it will be thick
Product are dried in 40 DEG C of vacuum drying ovens.With appropriate chloroform by dissolved solid, precipitates three times, filter and with appropriate ether in ether
Wash solid.Obtained solid is placed in 50mL round-bottomed flasks, and 249mg (1mmol) compound 7 is added, with 10mL dimethyl
After sulfoxide dissolving, it is passed through nitrogen 20 minutes, then sequentially adds the water that 2mL contains 20.8mg (0.08mmol) Salzburg vitriol
Solution and 2mL contain the aqueous solution of 33.2mg (0.16mmol) sodium ascorbate.It is stirred 24 hours at 60 DEG C, stops reaction.
Reaction solution is successively dialysed repeatedly in methanol in water, obtains faint yellow solid product 220mg, yield 35%.1H NMR
(400MHz,(CD3)2SO,ppm):δ=8.47 (s, 64H), 7.64 (d, 128H), 7.18-6.89 (m, 696H), 6.72 (d,
128H),4.75-4.67(m,64H),4.58(s,128H),4.61-4.43(m,192H),4.38-4.32(m,128H),4.03-
3.94(m,64H),3.86-3.78(m,64H),3.66-3.40(m,192H),3.17(m,376H),2.54(s,248H),2.25
(s,124H),2.19(s,248H).
Embodiment 13
Applications of the G1-Man in detecting Con A
One, the preparation of the buffer solution dispersion of G1-Man fluorescence probes
A concentration of 62.5 μM prepared in compound concentration is 10mM respectively Tris-HCl buffer solutions and embodiment 9
The dimethyl sulphoxide solution of G1-Man fluorescence probes takes 100 μ L fluorescent probe molecule dimethyl sulphoxide solutions with micro syringe,
It is injected into the Tris-HCl buffer solutions of 10mL, ultrasonic 30s, prepares the Tris-HCl buffer solutions of G1-Man fluorescence probes.
Two, the measurement of G1-Man fluorescence probes detection limit
The Tris-HCl buffer solution systems of the G1-Man fluorescence probes of 3mL are taken, various concentration (0-1.25 × 10 are added- 6Mol/L Con A buffer solutions) are excited with 350nm after placing 1 minute, fluorescence intensity are tested respectively with Fluorescence Spectrometer,
Using the fluorescence intensity at 464nm as ordinate, a concentration of abscissa mappings of Con A, as shown in Fig. 2, obtaining the oblique of fitting a straight line
Rate limits (limit of detection, LOD) calculation formula using detection：(wherein, S.D. is not add to LOD=3 × S.D./K
The standard deviation that probe molecule fluorescence spectrum changes when adding Con A, K is straight slope) detection that is calculated the probe is limited to
2.2×10-8M。
Three, the measurement of G1-Man fluorescence probes detection Con A working curves
The Tris-HCl buffer solution systems of the G1-Man fluorescence probes of 3mL are taken, various concentration (0-1.0 × 10 are added- 5Mol/L Con A buffer solutions) are excited with 350nm after placing 1 minute, fluorescence intensity are tested respectively with Fluorescence Spectrometer,
Using the fluorescence intensity at 464nm as ordinate, a concentration of abscissa mappings of Con A, fitting obtains fluorescence probe detection Con A's
Working curve, as shown in Figure 3；
Four, the measurement of G1-Man fluorescence probes selectivity
The Tris-HCl buffer solution systems for taking the G1-Man fluorescence probes of 3mL, the Con A for being separately added into 5 μm of ol/L are slow
Con A and the PNA buffer solutions for rushing solution, peanut agglutinin (PNA) buffer solution of 5 μm of ol/L, 5 μm of ol/L, are placed 1 minute
Afterwards under 350nm excitations, the fluorescence intensity of 464nm and the fluorescence intensity ratio not plus when detectable substance, as shown in Figure 4.
Embodiment 14
Applications of the G2-Man in detecting Con A
One, the preparation of the buffer solution dispersion of G2-Man fluorescence probes
A concentration of 31.3 μM prepared in compound concentration is 10mM respectively Tris-HCl buffer solutions and embodiment 10
The dimethyl sulphoxide solution of G2-Man fluorescence probes takes 100 μ L fluorescent probe molecule dimethyl sulphoxide solutions with micro syringe,
It is injected into the Tris-HCl buffer solutions of 10mL, ultrasonic 30s, prepares the Tris-HCl buffer solutions of G2-Man fluorescence probes.
Two, the measurement of G2-Man fluorescence probes detection limit
The Tris-HCl buffer solution systems of the G2-Man fluorescence probes of 3mL are taken, various concentration (0-1.25 × 10 are added- 6Mol/L Con A buffer solutions) are excited with 350nm after placing 1 minute, fluorescence intensity are tested respectively with Fluorescence Spectrometer,
Using the fluorescence intensity at 464nm as ordinate, a concentration of abscissa mappings of Con A, as shown in figure 5, obtaining the oblique of fitting a straight line
Rate limits (limit of detection, LOD) calculation formula using detection：(wherein, S.D. is not add to LOD=3 × S.D./K
The standard deviation that probe molecule fluorescence spectrum changes when adding Con A, K is straight slope) detection that is calculated the probe is limited to
1.4×10-8M。
Three, the measurement of G2-Man fluorescence probes detection Con A working curves
The Tris-HCl buffer solution systems of 3mL G2-Man fluorescence probes are taken, various concentration (0-1.0 × 10 are added- 5Mol/L Con A buffer solutions) are excited with 350nm after placing 1 minute, fluorescence intensity are tested respectively with Fluorescence Spectrometer,
Using the fluorescence intensity at 464nm as ordinate, a concentration of abscissa mappings of Con A, fitting obtains fluorescence probe detection Con A's
Working curve, as shown in Figure 6；
Four, the measurement of G2-Man fluorescence probes selectivity
The Tris-HCl buffer solution systems for taking the G2-Man fluorescence probes of 3mL, the Con A for being separately added into 5 μm of ol/L are slow
Con A and the PNA buffer solutions of solution, the PNA buffer solutions of 5 μm of ol/L, 5 μm of ol/L are rushed, 350nm is excited after placing 1 minute
Under light excitation, the fluorescence intensity of 464nm and the fluorescence intensity ratio not plus when detectable substance, as shown in Figure 7.
Embodiment 15
Applications of the G3-Man in detecting Con A
One, the preparation of the buffer solution dispersion of G3-Man fluorescence probes
A concentration of 15.6 μM prepared in compound concentration is 10mM respectively Tris-HCl buffer solutions and embodiment 11
The dimethyl sulphoxide solution of G3-Man fluorescence probes takes 100 μ L fluorescent probe molecule dimethyl sulphoxide solutions with micro syringe,
It is injected into the Tris-HCl buffer solutions of 10mL, ultrasonic 30s, prepares the Tris-HCl buffer solutions of G3-Man fluorescence probes.
Two, the measurement of G2-Man fluorescence probes detection limit
The Tris-HCl buffer solution systems of the G3-Man fluorescence probes of 3mL are taken, various concentration (0-1.25 × 10 are added- 6Mol/L Con A buffer solutions) are excited with 350nm after placing 1 minute, fluorescence intensity are tested respectively with Fluorescence Spectrometer,
Using the fluorescence intensity at 464nm as ordinate, a concentration of abscissa mappings of Con A, as shown in figure 8, obtaining the oblique of fitting a straight line
Rate limits (limit of detection, LOD) calculation formula using detection：(wherein, S.D. is not add to LOD=3 × S.D./K
The standard deviation that probe molecule fluorescence spectrum changes when adding Con A, K is straight slope) detection that is calculated the probe is limited to
1.5×10-8M。
Three, the measurement of G3-Man fluorescence probes detection Con A working curves
The Tris-HCl buffer solution systems of the G3-Man fluorescence probes of 3mL are taken, various concentration (0-1.0 × 10 are added- 5Mol/L Con A buffer solutions) are excited with 350nm after placing 1 minute, fluorescence intensity are tested respectively with Fluorescence Spectrometer,
Using the fluorescence intensity at 464nm as ordinate, a concentration of abscissa mappings of Con A, fitting obtains fluorescence probe detection Con A's
Working curve, as shown in Figure 9；
Four, the measurement of G3-Man fluorescence probes selectivity
The Tris-HCl buffer solution systems for taking the G3-Man fluorescence probes of 3mL, the Con A for being separately added into 5 μm of ol/L are slow
Con A and the PNA buffer solutions of solution, the PNA buffer solutions of 5 μm of ol/L, 5 μm of ol/L are rushed, 350nm is excited after placing 1 minute
Under light excitation, the fluorescence intensity of 464nm and the fluorescence intensity ratio not plus when detectable substance, as shown in Figure 10.
Embodiment 16
Applications of the G4-Man in detecting Con A
One, the preparation of the buffer solution dispersion of G4-Man fluorescence probes
A concentration of 7.8 μM prepared in compound concentration is 10mM respectively Tris-HCl buffer solutions and embodiment 11
The dimethyl sulphoxide solution of G4-Man fluorescence probes takes 100 μ L fluorescent probe molecule dimethyl sulphoxide solutions with micro syringe,
It is injected into the Tris-HCl buffer solutions of 10mL, ultrasonic 30s, prepares the Tris-HCl buffer solutions of G4-Man fluorescence probes.
Two, the measurement of G4-Man fluorescence probes detection limit
The Tris-HCl buffer solution systems of the G4-Man fluorescence probes of 3mL are taken, various concentration (0-1.25 × 10 are added- 6Mol/L Con A buffer solutions) are excited with 350nm after placing 1 minute, fluorescence intensity are tested respectively with Fluorescence Spectrometer,
Using the fluorescence intensity at 464nm as ordinate, a concentration of abscissa mappings of Con A as shown in figure 11, obtain the oblique of fitting a straight line
Rate limits (limit of detection, LOD) calculation formula using detection：(wherein, S.D. is not add to LOD=3 × S.D./K
The standard deviation that probe molecule fluorescence spectrum changes when adding Con A, K is straight slope) detection that is calculated the probe is limited to
1.4×10-8M。
Three, the measurement of G4-Man fluorescence probes detection Con A working curves
The Tris-HCl buffer solution systems of the G4-Man fluorescence probes of 3mL are taken, various concentration (0-1.0 × 10 are added- 5Mol/L Con A buffer solutions) are excited with 350nm after placing 1 minute, fluorescence intensity are tested respectively with Fluorescence Spectrometer,
Using the fluorescence intensity at 464nm as ordinate, a concentration of abscissa mappings of Con A, fitting obtains fluorescence probe detection Con A's
Working curve, as shown in figure 12.
Four, the measurement of G4-Man fluorescence probes selectivity
The Tris-HCl buffer solution systems for taking the G4-Man fluorescence probes of 3mL, the Con A for being separately added into 5 μm of ol/L are slow
Con A and the PNA buffer solutions of solution, the PNA buffer solutions of 5 μm of ol/L, 5 μm of ol/L are rushed, 350nm is excited after placing 1 minute
Under light excitation, the fluorescence intensity of 464nm and the fluorescence intensity ratio not plus when detectable substance, as shown in figure 13.
Comparative example 1
Embodiment 8 is repeated, difference lies in make core " ethylenediamine " into " propane diamine ", remaining condition is constant, prepares respectively
Obtain the dendritic polymer in 1~4 generation；
Dendritic polymer obtained above is substituted into 1~4 generation PAMAM again and is used for embodiment 9-12, remaining condition is constant,
Fluorescence probe a, b, c, d is prepared；
Embodiment 13-16 is repeated, difference lies in be changed to fluorescence probe a, b, c, d, remaining condition by fluorescence probe respectively
Constant, the detection limit that the probe is calculated is respectively 2.1 × 10-7M、1.6×10-7M、1.6×10-7M、1.7×10-7M。
Comparative example 2
Embodiment 8 is repeated, difference lies in make core " ethylenediamine " into " Putriscine ", remaining is constant, prepares respectively
Obtain the dendritic polymer in 1~4 generation；
Dendritic polymer obtained above is substituted into 1~4 generation PAMAM again and is used for embodiment 9-12, remaining condition is constant,
Fluorescence probe e, f, g, h is prepared；
Embodiment 13-16 is repeated, difference lies in be changed to fluorescence probe e, f, g, h, remaining condition by fluorescence probe respectively
Constant, the detection limit that the probe is calculated is respectively 1.8 × 10-7M、1.4×10-7M、1.4×10-7M、1.5×10-7M。
Comparative example 3
Embodiment 9-12 is repeated, difference lies in change compound 4 into " 1- (4- carboxy-- methoxyphenyls) -2- (4- acetylene
Base phenyl) -1,2- diphenyl diethylenes ", remaining condition is constant, and fluorescence probe i, j, k, l is prepared；
Embodiment 13-16 is repeated, difference lies in be changed to fluorescence probe e, f, g, h, remaining condition by fluorescence probe respectively
Constant, the detection limit that the probe is calculated is respectively 9.1 × 10-7M、8.8×10-7M、7.9×10-7M、7.9×10-7M。
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention may be used also on the basis of the above description for those of ordinary skill in the art
To make other variations or changes in different ways, all embodiments can not be exhaustive here, it is every to belong to this hair
Row of the obvious changes or variations that bright technical solution is extended out still in protection scope of the present invention.
Claims (5)
1. a kind of ConA A fluorescence probes, which is characterized in that the fluorescence probe has the following structure any one of formula
Structure：
Wherein,
2. application of the ConA A fluorescence probes as described in claim 1 in detecting ConA A.
3. application according to claim 2, which is characterized in that the ConA A fluorescence probes are in detecting water phase
ConA A application.
4. application according to claim 3, which is characterized in that in the ConA A fluorescence probes detection water phase
ConA A includes following detecting step：
1) aqueous solution of fluorescent probe molecule is prepared；
2) the detection limit of various concentration fluorescent probe molecule is determined；
3) working curve of fluorescent probe molecule is drawn.
5. application according to claim 4, which is characterized in that in step 1), preparing fluorescent probe molecule aqueous solution includes
Following steps：
A. the dimethyl sulphoxide solution of ConA A probe molecules is prepared；
B. the Tris-HCl buffer solutions of pH=7.6 are prepared；
C. the step a solution prepared is added in the buffer solution that step b is prepared, obtains being dispersed in the probe in buffer solution
The aqueous solution of molecule.
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| WO2010027108A1 (en) * | 2008-09-08 | 2010-03-11 | 国立大学法人東京工業大学 | Fluorescent sugar derivative compound and sensor using same |
| CN104017222A (en) * | 2013-03-01 | 2014-09-03 | 中国科学院理化技术研究所 | Dendritic polymer with periphery modified aggregation-induced emission enhanced chromophore and preparation method and application thereof |
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