CN107501313A - A kind of near infrared light hot dye and preparation and application based on azepine fluorine borine - Google Patents
A kind of near infrared light hot dye and preparation and application based on azepine fluorine borine Download PDFInfo
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- CN107501313A CN107501313A CN201710737140.0A CN201710737140A CN107501313A CN 107501313 A CN107501313 A CN 107501313A CN 201710737140 A CN201710737140 A CN 201710737140A CN 107501313 A CN107501313 A CN 107501313A
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- photo
- thermal
- near infrared
- infrared light
- dyestuff
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- 229910000085 borane Inorganic materials 0.000 title claims abstract description 15
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 title claims abstract description 15
- GQFIUXKQHAQQHA-UHFFFAOYSA-N [F].N1C=CC=CC=C1 Chemical compound [F].N1C=CC=CC=C1 GQFIUXKQHAQQHA-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000000975 dye Substances 0.000 claims abstract description 38
- 238000003384 imaging method Methods 0.000 claims abstract description 16
- 238000007626 photothermal therapy Methods 0.000 claims abstract description 5
- 238000007259 addition reaction Methods 0.000 claims abstract description 3
- 238000010719 annulation reaction Methods 0.000 claims abstract 2
- 238000010668 complexation reaction Methods 0.000 claims abstract 2
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 8
- 238000004440 column chromatography Methods 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005695 Ammonium acetate Substances 0.000 claims description 3
- 229940043376 ammonium acetate Drugs 0.000 claims description 3
- 235000019257 ammonium acetate Nutrition 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 238000001931 thermography Methods 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims 3
- 238000001914 filtration Methods 0.000 claims 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 1
- UOZDOLIXBYLRAC-UHFFFAOYSA-L [2-hydroxy-3-(trimethylazaniumyl)propyl]-trimethylazanium;diiodide Chemical compound [I-].[I-].C[N+](C)(C)CC(O)C[N+](C)(C)C UOZDOLIXBYLRAC-UHFFFAOYSA-L 0.000 claims 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 1
- 238000006467 substitution reaction Methods 0.000 claims 1
- 238000000967 suction filtration Methods 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 14
- 238000003786 synthesis reaction Methods 0.000 abstract description 14
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052731 fluorine Inorganic materials 0.000 abstract description 5
- 239000011737 fluorine Substances 0.000 abstract description 5
- XYOVOXDWRFGKEX-UHFFFAOYSA-N azepine Chemical compound N1C=CC=CC=C1 XYOVOXDWRFGKEX-UHFFFAOYSA-N 0.000 abstract description 4
- 230000003287 optical effect Effects 0.000 abstract description 4
- -1 aldehyde ketone Chemical class 0.000 abstract description 2
- 239000000090 biomarker Substances 0.000 abstract description 2
- 238000001514 detection method Methods 0.000 abstract description 2
- 238000002560 therapeutic procedure Methods 0.000 abstract description 2
- 150000002561 ketenes Chemical class 0.000 abstract 2
- OKZIUSOJQLYFSE-UHFFFAOYSA-N difluoroboron Chemical compound F[B]F OKZIUSOJQLYFSE-UHFFFAOYSA-N 0.000 abstract 1
- 238000003379 elimination reaction Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 18
- 239000007787 solid Substances 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 206010028980 Neoplasm Diseases 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 238000000295 emission spectrum Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000000074 matrix-assisted laser desorption--ionisation tandem time-of-flight detection Methods 0.000 description 4
- 230000005311 nuclear magnetism Effects 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 230000027756 respiratory electron transport chain Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-UHFFFAOYSA-N 0.000 description 2
- BWGRDBSNKQABCB-UHFFFAOYSA-N 4,4-difluoro-N-[3-[3-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)-8-azabicyclo[3.2.1]octan-8-yl]-1-thiophen-2-ylpropyl]cyclohexane-1-carboxamide Chemical compound CC(C)C1=NN=C(C)N1C1CC2CCC(C1)N2CCC(NC(=O)C1CCC(F)(F)CC1)C1=CC=CS1 BWGRDBSNKQABCB-UHFFFAOYSA-N 0.000 description 2
- FZRCKLPSHGTOAU-UHFFFAOYSA-N 6-amino-1,4-dimethylcyclohexa-2,4-diene-1-carbaldehyde Chemical compound CC1=CC(N)C(C)(C=O)C=C1 FZRCKLPSHGTOAU-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- LFZAGIJXANFPFN-UHFFFAOYSA-N N-[3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-thiophen-2-ylpropyl]acetamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CCC(C=1SC=CC=1)NC(C)=O)C LFZAGIJXANFPFN-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- IZKAAZRXQUFFQH-UHFFFAOYSA-N [N].C[N+]([O-])=O Chemical compound [N].C[N+]([O-])=O IZKAAZRXQUFFQH-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000006193 liquid solution Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 210000003739 neck Anatomy 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 229910001948 sodium oxide Inorganic materials 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000001225 therapeutic effect Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 description 1
- WDBQJSCPCGTAFG-QHCPKHFHSA-N 4,4-difluoro-N-[(1S)-3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-pyridin-3-ylpropyl]cyclohexane-1-carboxamide Chemical compound FC1(CCC(CC1)C(=O)N[C@@H](CCN1CCC(CC1)N1C(=NN=C1C)C(C)C)C=1C=NC=CC=1)F WDBQJSCPCGTAFG-QHCPKHFHSA-N 0.000 description 1
- KJNCZGIIEWUVKZ-UHFFFAOYSA-N B.[F] Chemical class B.[F] KJNCZGIIEWUVKZ-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 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
- 208000027418 Wounds and injury Diseases 0.000 description 1
- YPDSOAPSWYHANB-UHFFFAOYSA-N [N].[F] Chemical compound [N].[F] YPDSOAPSWYHANB-UHFFFAOYSA-N 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 238000002512 chemotherapy Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000000799 fluorescence microscopy Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 238000001215 fluorescent labelling Methods 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- 238000001959 radiotherapy Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
- A61K41/0052—Thermotherapy; Hyperthermia; Magnetic induction; Induction heating therapy
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/001—Preparation for luminescence or biological staining
- A61K49/0013—Luminescence
- A61K49/0017—Fluorescence in vivo
- A61K49/0019—Fluorescence in vivo characterised by the fluorescent group, e.g. oligomeric, polymeric or dendritic molecules
- A61K49/0021—Fluorescence in vivo characterised by the fluorescent group, e.g. oligomeric, polymeric or dendritic molecules the fluorescent group being a small organic molecule
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/22—Echographic preparations; Ultrasound imaging preparations ; Optoacoustic imaging preparations
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
-
- 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
- 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
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- 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
- C09K2211/1074—Heterocyclic compounds characterised by ligands containing more than three nitrogen atoms as heteroatoms
- C09K2211/1085—Heterocyclic compounds characterised by ligands containing more than three nitrogen atoms as heteroatoms with other heteroatoms
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- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Pharmacology & Pharmacy (AREA)
- Materials Engineering (AREA)
- Biomedical Technology (AREA)
- Physics & Mathematics (AREA)
- Acoustics & Sound (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Radiology & Medical Imaging (AREA)
- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention discloses a kind of near infrared light hot dye based on azepine fluorine borine and preparation and application.The photo-thermal dyestuff is made up of the electron-donating group containing lone pair electrons and basic azepine fluorine borine skeleton.Azepine fluorine borine photo-thermal dyestuff is prepared by following step:(1) synthesis of ketenes, both aldehyde ketone addition elimination reaction occur in the basic conditions obtain；(2) addition reaction of ketenes and nitromethane；(3) annulation；(4) complexation reaction, the product both obtained in (3) are coordinated to obtain target product with boron difluoride.Photo-thermal dyestuff can be used for the technical fields such as photothermal imaging, the optical dynamic therapy and photo-thermal therapy under photoacoustic imaging guiding, biomarker and detection.
Description
Technical field
The invention belongs to organic photoelectrical material technical field.Near-infrared is had based on azepine fluorine borine more particularly to a kind of
The photo-thermal dyestuff and its preparation method of absorption and its in the fields such as fluorescence imaging, photothermal imaging, photoacoustic imaging, photo-thermal therapy
Using.
Background technology
Tumour threatens the health of the mankind.Traditional oncotherapy means, such as operative treatment, chemotherapy, radiotherapy are deposited
In some problems, often along with side effect.As a kind of oncotherapy means of Noninvasive, photo-thermal therapy can be real-time
Carry out tumor locus accurately treat.Greatly improve the effect of oncotherapy.And the selection of optothermal material is controlled for photo-thermal
Therapeutic effect has decisive role.Therefore, preferable optothermal material how is selected to cause everybody extensive concern.
Some main illuminophores in recent years, for example, the dyestuff such as fluorine borine, Hua Jing, porphyrin is wide according to different demands
General design and synthesis.A kind of photostability that wherein fluorine boranes dyestuff has had as conventional dyestuff, the production of high quantum
Rate, big molar extinction coefficient and easily modify.This also causes it to be widely used in fluorescence labeling, optical imagery, optical tumor
The fields such as treatment.Compared with the fluorine borine with similar structure, azepine fluorine borine has longer absorbing wavelength, and it should in live body
The unique advantage in.But it still shows the radiation transistion that can not ignore, this partial radiation transition can weaken singlet and arrive
The transformation and nonradiative transition of triplet state and then weaken the conversion of photo-thermal.How to weaken radiation transistion raising nonradiative transition to come
Improving photothermal deformation is worth research.
Photo induced electron transfer refers to what molecule occurred after electromagnetic wave (visible light, ultraviolet light etc.) irradiation of specific wavelength
Electronics transfer phenomena between intramolecule or molecule.It is related to many chemical fields, such as：Solar cell, it is artificial synthesized,
Luminescence probe etc..In many photochemistry fields, molecular structure and energy level affect the effect and efficiency of photo induced electron transfer.Especially
It is that intramolecular photo induced electron transfer determines Quenching of fluorescence.
Azepine fluorine borine dyestuff is generally used for the fields such as biomarker, imaging, optical dynamic therapy, so far, few
People's report designs and synthesized the azepine fluorine borine dyestuff with good photo-thermal effect using effective theoretical direction.Based on photic
Electron-donating group is connected to near by the theoretical direction of electronics transfer and the excellent properties of azepine fluorine boranes dyestuff, the present invention
On the nitrogen fluorine borine dyestuff of infrared absorption, so as to make it have good photoacoustic imaging, photothermal imaging and the photo-thermal of tumor
Therapeutic effect.
The content of the invention
Technical problem：In view of above-mentioned technical problem in the prior art be present, it is an object of the invention to provide a kind of theoretical
The photo-thermal dyestuff of the new near infrared absorption of design and its preparation and application.
Technical scheme：The near infrared light hot dye of the present invention is function of the introducing containing electron donor on azepine BODIPY
Group, makes it not only have good photoacoustic imaging and photothermal imaging effect, and have good light thermal property so that its
Treatment under imaging guiding is significant, while has in the optothermal material of design, synthesis with good light thermal property
There is important directive significance.
The present invention provides a kind of near infrared light hot dye, has following general structure：
The synthetic route of photo-thermal dyestuff near infrared absorption is as follows：
Wherein, R1、R2At least one is selected from In one kind, R1、R2Can be with identical, can also be different, R3For the straight chain with 1 to 16 carbon atom, side chain or
Person's cyclic alkyl chain；
Wherein X is Br, I or H；
Specifically 1 and 2 reaction synthesis 3,3 are after occurring addition reaction, after then cyclization synthesis 5,5 and boron fluoride are coordinated,
Then the photo-thermal dyestuff C of halogenation synthesis near infrared absorption.
The application of the near infrared light hot dye is：Cell co-focusing imaging.
The application of the near infrared light hot dye is：Tumor mouse photoacoustic imaging.
The application of the near infrared light hot dye is：Tumor mouse photothermal imaging.
The application of the near infrared light hot dye is：Tumor mouse photo-thermal therapy.
The present invention has the advantages that：
Photo-thermal dyestuff near infrared light of the present invention excites, and so as to weaken injury of the excitation source to biological tissue, cuts
Influence of the weak background fluorescence to detection signal, and there are deeper tissue penetration depths；
Photo-thermal dyestuff of the present invention is instructed by photo induced electron transfer theory, realizes luminous quenching and light well
The conversion of heat and its red shift for absorbing emission spectrum；
The oncotherapy that photo-thermal dyestuff of the present invention can be used under photothermal imaging, photoacoustic imaging guiding, is good life
Object light heat cure material.
Photo-thermal dyestuff preparation method technique of the present invention is simple, abundant raw material, is easy to industrialized production；
Brief description of the drawings
C MALDI-TOF/TOF scheme in Fig. 1 embodiment of the present invention 1；
D MALDI-TOF/TOF scheme in Fig. 2 embodiment of the present invention 2；
C in Fig. 3 embodiment of the present invention 11H-NMR schemes；
D in Fig. 4 embodiment of the present invention 21H-NMR schemes；
C UV-visible spectrum in Fig. 5 embodiment of the present invention 1；
D UV-visible spectrum in Fig. 6 embodiment of the present invention 2；
C launching light spectrogram in Fig. 7 embodiment of the present invention 1；
D launching light spectrogram in Fig. 8 embodiment of the present invention 2；
The photo-thermal effect of the PBS solution of the various concentrations of C sample in Fig. 9 embodiment of the present invention 1；
The photo-thermal effect of the PBS solution of the various concentrations of D samples in Figure 10 embodiment of the present invention 2；
Embodiment
Technical scheme is more fully understood below by specific example, and further illustrates the skill of the present invention
Art scheme, specific synthesis and property are determined as follows.The following example is several examples in technical solution of the present invention, without
It is limitation of the present invention.
Embodiment 1：Azepine fluorine borine photo-thermal dyestuff C synthesis
The synthesis of compound 2
Take a clean two-mouth bottle, add magneton, 1.49g paradime thylaminobenzaldehyde (about 10mmol), 2.8g 1 (about
10mmol) and 40ml ethanol solution.Stirring is slowly added to 23ml sodium hydride solutions (hydrogen containing 2.0g after solid all dissolving
Sodium oxide molybdena).24h is stirred in the reaction at room temperature, there is yellow solid precipitation in course of reaction.After reaction terminates, 1M hydrochloric acid solution
Reaction solution is adjusted to neutrality, filters to obtain solid, deionized water is washed three times.It is dried in vacuo 2.1g light yellow solid.
1H NMR(400MHz,CDCl3):δ (ppm)=8.01 (d, J=8.0Hz, 2H), 7.78 (d, J=16.0Hz,
1H), 7.53 (d, J=8.0Hz, 2H), 7.35 (d, J=16.0Hz, 1H), 6.98 (d, J=8.0Hz, 2H), 6.69 (d, J=
8.0Hz,2H),4.21(t,2H),3.89(t,2H),3.77-3.65(m,6H),3.55(m, 2H),3.38(s,3H),3.04
(s,6H).
The synthesis of compound 3
Take a clean bottle with two necks, add magneton, 0.83g 2 (about 2mmol), 3.2ml are added under the protection of nitrogen
Nitromethane (about 60mmol), 6.2ml diethylamine (about 60mmol) and 25.0ml absolute methanol.After being heated to reflux 24h, use
1M hydrochloric acid solution adjusts reaction solution to neutrality, filters to obtain solid, cold methanol washs three times.0.6 gram is obtained after vacuum drying
Product.
1H NMR(400MHz,CDCl3):δ (ppm)=7.88 (d, J=8Hz 2H), 7.12 (d, J=8Hz 2H), 6.92
(d, J=8Hz, 2H), 6.66 (d, J=8Hz 2H), 4.80-4.75 (dd, J=8,12Hz, 1H), 4.64-4.58 (dd, J=
8,12 Hz, 1H), 4.18 (t, J=4Hz, 2H), 4.09 (m, 1H), 3.87 (t, J=4Hz, 2H), 3.75-3.63 (m, 6H),
3.55-3.53 (m, 2H), 3.40-3.27 (m J=12.0,6.6,3.3Hz, 1H), 3.40-3.27 (m, 5H), 2.91 (s,
6H).
The synthesis of compound 4
A clean 50ml single port bottles are taken, add magneton, 0.48g (1mmol) b1,10mL absolute ethyl alcohol, 2.7g (about
35mmol) ammonium acetate solid, about 12h is heated to reflux under magnetic agitation.It is concentrated under reduced pressure to the 1/4 of original volume, treats that solution cools down
To room temperature, brown solid is filtrated to get, absolute ethyl alcohol washing, 0.15g blue solid products are obtained after drying.
Compound C synthesis
A clean 50ml single port bottles are taken, add magneton, the dichloromethane dissolving that 0.15g (0.17mmol) c1,10mL is dried.
At 0~5 DEG C, the lower addition 0.11g of nitrogen protection newly steams triethylamine (1.1mmol), then is slowly added to Eorontrifluoride etherate dropwise
(0.22g, 1.6mmol), is added dropwise, and moves to and 6h is stirred at room temperature, and after reaction terminates, mixed solution is through washing, saturated sodium-chloride
Wash, anhydrous sodium sulfate drying, be concentrated under reduced pressure, column chromatography purifying, obtain 0.12g blue solid products.
1H NMR(400MHz,CDCl3):δ=8.07 (d, J=8.8Hz, 4H), 8.02 (d, J=8.4Hz, 4H), 6.99
(d, J=8.8Hz, 4H), 6.82 (s, 2H), 6.77 (d, J=8.8Hz, 4H), 4.20 (t, J=4.4Hz, 4H), 3.90-3.86
(t, J=4.8Hz, 4H), 3.77-3.75 (m, 4H), 3.71-3.66 (m, 8H), 3.56 (t, J=5.2Hz, 4H), 3.39 (s,
6H),3.08(s,12H).
[m/e]MALDI-TOF-MS calcd.For C50H60BF2N5O8:907.85,found 907.458
Embodiment 2：Azepine fluorine borine photo-thermal dyestuff D synthesis
The synthesis of compound 1
A clean two-mouth bottle is taken, adds magneton, 1.36g parahydroxyacet-ophenone (about 10mmol), 9.66g bromooctane
The anhydrous N,N-dimethylformamide solution of (about 50mmol), 6.91g potassium carbonate and 40ml.Under magnetic agitation, 80 DEG C of reactions
24h.After reaction terminates, water/dichloromethane extraction is multiple, merges organic phase.Through chromatographing post separation, light yellow liquid is obtained
2.46g (yield about 99%).
The synthesis of compound 2
Take a clean two-mouth bottle, add magneton, 1.24g 1 (about 5mmol), 0.75g paradime thylaminobenzaldehyde (about
5mmol) and 20ml ethanol solution.Stirring is slowly added to 5ml sodium hydride solutions (hydrogen containing 1.00g after solid all dissolving
Sodium oxide molybdena).24h is stirred in the reaction at room temperature, there is yellow solid precipitation in course of reaction.After reaction terminates, 1M hydrochloric acid solution
Reaction solution is adjusted to neutrality, filters to obtain solid, deionized water is washed three times.Be dried in vacuo 1.96g yellow solid (yield is about
96%).
1H NMR(400MHz,CDCl3):δ (ppm)=8.02 (d, J=8.8Hz, 2H), 7.79 (d, J=15.6Hz, 1H),
7.55 (d, J=8.8Hz, 2H), 7.36 (d, J=15.6Hz, 2H), 6.95 (d, J=8.8Hz, 2H), 6.69 (d, J=9.2Hz,
2H), 4.02 (t, J=6.8Hz, 2H), 3.03 (s, 6H), 1.84-1.77 (m, 2H), 1.50-1.29 (m, 10H), 0.91-0.89
(m, 3H).
The synthesis of compound 3
Take a clean bottle with two necks, add magneton, 1.90g 2 (about 5mmol), 1.3ml are added under the protection of nitrogen
Nitromethane (about 25mmol), 2.6ml diethylamine (about 25mmol) and 25.0ml absolute methanol.After being heated to reflux 24h, use
1M hydrochloric acid solution adjusts reaction solution to neutrality, filters to obtain solid, cold methanol washs three times.1.56 grams are obtained after vacuum drying
Product (yield about 82%).
1H NMR(400MHz,CDCl3):δ (ppm)=7.89 (d, J=8.8,2H), 7.13 (d, J=8.8,2H), 6.90
(d, J=8.8,2H), 6.67 (d, J=8.8,2H), 4.79 (dd, J=6.4Hz, 12.0Hz, 1H), 4.62 (dd, J=
7.6Hz, 12.4Hz, 1H), 4.14-4.07 (m, 1H), 4.01 (t, J=6.0Hz, 2H), 3.41-3.28 (m, 2H), 2.92 (s,
6H),1.83–1.76(m, 2H),1.49-1.29(m,10H),0.91-0.88(m,3H).
The synthesis of compound 4
A clean 100ml single port bottles are taken, add magneton, 1.56g (3.5mmol) 3,9.44g (about 123mmol) ammonium acetate
Solid, 20mL n-butanols, about 12h is heated to reflux under magnetic agitation.It is concentrated under reduced pressure to the 1/4 of original volume, treats that solution is cooled to
Room temperature, brown solid is filtrated to get, absolute ethyl alcohol washing, 0.64g blue solids product (yield about 46%) is obtained after drying.
The synthesis of compound 5
A clean 50ml single port bottles are taken, add the dichloromethane dissolving that magneton, 0.40g (0.5mmol) 4,10mL are dried.
At 0~5 DEG C, the lower addition 0.11g of nitrogen protection newly steams triethylamine (1.1mmol), then is slowly added to Eorontrifluoride etherate dropwise
(0.44g, 3.2mmol), is added dropwise, and moves to and 6h is stirred at room temperature, and after reaction terminates, mixed solution is through washing, saturated sodium-chloride
Wash, anhydrous sodium sulfate drying, be concentrated under reduced pressure, column chromatography purifying, obtain 0.30g blue solids product (yield about 90%).
1H NMR(400MHz,CDCl3):δ (ppm)=8.08 (t, J=8.0Hz, 8H), 7.48-7.41 (m, 4H), 6.83
(s, 2H) 7.04 (s, 2H), 6.77 (d, J=8.0Hz, 4H), 4.03 (t, J=6.0Hz, 4H), 1.81 (t, J=6.4Hz,
4H),1.49–1.27(m,20H),0.91-0.89(m,6H).
Compound D synthesis
A clean 50ml single port bottles are taken, add the dichloromethane dissolving that magneton, 0.30g (0.35mmol) 5,10mL are dried.
At 0 DEG C, after adding 0.125g NBS, 6h is stirred, after reaction terminates, mixed solution is washed through washing, saturated sodium-chloride, anhydrous sulphur
Sour sodium is dry, is concentrated under reduced pressure, and column chromatography purifying, obtains 0.17g blue solids product (yield about 50%).
1H NMR(400MHz,CDCl3):δ (ppm)=8.00 (d, J=8.8Hz, 4H), 7.71 (d, J=8.8 Hz, 4H),
6.94 (d, J=8.8Hz, 4H), 6.76 (d, J=9.2Hz, 4H), 3.98 (t, J=6.4Hz, 4H), 3.07 (s, 12H),
1.82–1.75(m,4H),1.49–1.42(m,4H),1.35-1.29(m,16H), 0.91-0.89(m,6H)
Embodiment 3：The test of C molecular weight
A small amount of sample C is taken, is mixed with matrix, then point sample, is measured with MALDI-TOF/TOF, such as Fig. 1, preliminary card
Understand the correctness of C molecules.
[m/e] (M, MALDI-TOF) theoretical value:907.85, experiment value:907.46
Embodiment 4：The test of D molecular weight
A small amount of sample D is taken, is mixed with matrix, then point sample, is measured with MALDI-TOF/TOF, such as Fig. 2, preliminary card
Understand the correctness of D molecules.
[m/e] (M, MALDI-TOF) theoretical value:997.72, experiment value:996.01
Embodiment 5:C nuclear-magnetism test
Take 0.5mg samples C to be dissolved in 0.5ml deuterochloroforms, tested through nuclear-magnetism, such as Fig. 3, further demonstrate C molecules
Correctness.
1H NMR(400MHz,CDCl3):δ (ppm)=8.08 (d, J=8Hz, 4H), 8.02 (d, J=8 Hz, 4H),
7.00 (d, J=8Hz, 4H), 6.82 (s, 2H), 6.79 (d, J=8Hz, 4H), 4.20 (t, J=4Hz, 4H), 3.89 (t, J=
4Hz, 4H), 3.76 (t, J=4Hz, 4H), 3.71-3.67 (m, 8H), 3.56 (t, J=8 Hz, 4H), 3.39 (m, 3H), 3.08
(m,36).
Embodiment 6:D nuclear-magnetism test
Take 0.5mg samples D to be dissolved in 0.5ml deuterochloroforms, tested through nuclear-magnetism, such as Fig. 4, further demonstrate D molecules
Correctness.
1H NMR(400MHz,CDCl3):δ (ppm)=8.00 (d, J=8.8Hz, 4H), 7.71 (d, J=8.8 Hz, 4H),
6.94 (d, J=8.8Hz, 4H), 6.76 (d, J=9.2Hz, 4H), 3.98 (t, J=6.4Hz, 4H), 3.07 (s, 12H),
1.82–1.75(m,4H),1.49–1.42(m,4H),1.35-1.29(m,16H), 0.91-0.89(m,6H)
Embodiment 7：C ultraviolet-visible spectrum test：
Configure the weak solution (10 of the C in embodiment 1-5M, toluene are solvent), pipette 2mL C solutions and carried out in cuvette
Ultraviolet-visible luminous spectrum is tested, as Fig. 5 shows：After electron-donating group is introduced, realize bigger near-infrared and inhale.
Embodiment 8：D ultraviolet-visible spectrum test：
Configure the weak solution (10 of the D in embodiment 1-5M, toluene are solvent), pipette 2mL solution Ds and carried out in cuvette
Ultraviolet-visible luminous spectrum is tested, as Fig. 6 shows：With the introducing of bromine atoms, compared with C, the absorption maximum blue shift of D samples.
Embodiment 9：C emission spectrum test：
Configure the weak solution (10 of the C in embodiment 1-5M, toluene are solvent), pipette 2mL C solutions and carried out in cuvette
Emission spectrum is tested.As Fig. 7 shows：Material C has good near infrared emission, emission maximum 785nm in toluene solution.
Embodiment 10：D emission spectrum test：
Configure the weak solution (10 of the D in embodiment 1-5M, toluene are solvent), pipette 2mL C solutions and carried out in cuvette
Emission spectrum is tested.As Fig. 8 shows：Material D has good near infrared emission, emission maximum about 820nm in toluene solution.
Embodiment 11:C photo-thermal effect
C in embodiment 1 is dissolved with DMSO, various concentrations gradient is diluted to pH=7.4 PBS cushioning liquid
Solution (0,5,10,15,25 μM), with 785nm laser illumination 7min (0.5W/cm2), recorded with light thermal imaging system different
Under time, various concentrations, the change of solution temperature.Shown by Fig. 9, as concentration increases, in embodiment 1, C solution temperature is most
Up to 23 DEG C of big change.
Embodiment 12:D photo-thermal effect
D in embodiment 2 is dissolved with DMSO, various concentrations gradient is diluted to pH=7.4 PBS cushioning liquid
Solution (0,5,10,15,25 μM), with 730nm laser illumination 7min (0.5W/cm2), recorded with light thermal imaging system different
Under time, various concentrations, the change of solution temperature.Up to 27 DEG C of the maximum change of D solution temperature in embodiment 2.
Claims (6)
1. a kind of near infrared light hot dye based on azepine fluorine borine, it is characterised in that there is following general structure：
Wherein, R1、R2It is selected fromIn one kind, R3
For the straight chain with 1 to 16 carbon atom, side chain or cyclic alkyl chain；
Wherein X is Br, I or H.
2. the preparation of photo-thermal dyestuff as claimed in claim 1, it is characterised in that concretely comprise the following steps：
Specifically：
(1) 1 (10.0mmol) and 2 (10.0mmol) are anti-in 10ml 10% sodium hydroxide (aq) and 20ml alcohol mixed solutions
After answering 12h, after adjusting reaction solution pH to 5~7 with watery hydrochloric acid, filtering, the washing of cold ethanol, product 3 is obtained；
(2) in the basic conditions, after with nitromethane (25.0mmol) addition reaction occurs for 3 (5.0mmol), adjusted with watery hydrochloric acid
Reaction solution pH to 5~7；Filtering, the washing of cold ethanol, obtain product 4；
After in ethanol solution with ammonium acetate annulation occurs for (3) 4 (2.0mmol), concentration, filtering, the washing of cold ethanol, obtain
Product 5；
(4) in dry methylene chloride solution, after with BFEE complexation reaction occurs for 5 (1.5mmol), concentration, water is added
After suction filtration, product 6 is obtained by column chromatography, target product C when halogen-free；In dichloromethane or chloroformic solution, propiodal or
Bromine source occurs substitution reaction with 6 (1.0mmol) and obtains target product C.
3. the application of near infrared light hot dye as claimed in claim 1, it is characterised in that it is glimmering that the photo-thermal dyestuff is used for biology
Photoimaging.
4. the application of near infrared light hot dye as claimed in claim 1, it is characterised in that the photo-thermal dyestuff is used for bio-light
Thermal imaging.
5. the application of near infrared light hot dye as claimed in claim 1, it is characterised in that the photo-thermal dyestuff is used for bio-light
Acoustic imaging.
6. the application of near infrared light hot dye as claimed in claim 1, it is characterised in that the photo-thermal dyestuff swells for live body
Knurl photo-thermal therapy.
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Application publication date: 20171222 |