CN106188152A - A kind of near-infrared metal complex and preparation thereof and application - Google Patents
A kind of near-infrared metal complex and preparation thereof and application Download PDFInfo
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- CN106188152A CN106188152A CN201610559832.6A CN201610559832A CN106188152A CN 106188152 A CN106188152 A CN 106188152A CN 201610559832 A CN201610559832 A CN 201610559832A CN 106188152 A CN106188152 A CN 106188152A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 47
- 150000004696 coordination complex Chemical class 0.000 title claims abstract description 40
- 239000000975 dye Substances 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 18
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims abstract description 13
- 150000003233 pyrroles Chemical class 0.000 claims abstract description 13
- 239000003446 ligand Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000003384 imaging method Methods 0.000 claims abstract description 10
- 239000000090 biomarker Substances 0.000 claims abstract description 6
- 238000010668 complexation reaction Methods 0.000 claims abstract description 5
- 238000001514 detection method Methods 0.000 claims abstract description 5
- 238000007626 photothermal therapy Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 30
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 21
- 239000000654 additive Substances 0.000 claims description 12
- 230000000996 additive effect Effects 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 11
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 10
- 229910052723 transition metal Inorganic materials 0.000 claims description 10
- 150000003624 transition metals Chemical group 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical class CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 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
- 235000019257 ammonium acetate Nutrition 0.000 claims description 3
- 229940043376 ammonium acetate Drugs 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 3
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 150000003935 benzaldehydes Chemical class 0.000 claims description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzenecarboxaldehyde Natural products O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 238000006053 organic reaction Methods 0.000 claims description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 230000007704 transition Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- 238000010521 absorption reaction Methods 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 8
- XYOVOXDWRFGKEX-UHFFFAOYSA-N azepine Chemical compound N1C=CC=CC=C1 XYOVOXDWRFGKEX-UHFFFAOYSA-N 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-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 16
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000003208 petroleum Substances 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 238000001819 mass spectrum Methods 0.000 description 7
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 6
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000007850 fluorescent dye Substances 0.000 description 4
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000001052 transient effect Effects 0.000 description 4
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 4
- 229920001817 Agar Polymers 0.000 description 3
- 208000035126 Facies Diseases 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000008272 agar Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- JVZRCNQLWOELDU-UHFFFAOYSA-N gamma-Phenylpyridine Natural products C1=CC=CC=C1C1=CC=NC=C1 JVZRCNQLWOELDU-UHFFFAOYSA-N 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910020427 K2PtCl4 Inorganic materials 0.000 description 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 2
- 238000006069 Suzuki reaction reaction Methods 0.000 description 2
- -1 azepine dipyrrole Chemical compound 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000002560 therapeutic procedure Methods 0.000 description 2
- 238000003809 water extraction Methods 0.000 description 2
- WYECURVXVYPVAT-UHFFFAOYSA-N 1-(4-bromophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Br)C=C1 WYECURVXVYPVAT-UHFFFAOYSA-N 0.000 description 1
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 description 1
- DGPBVJWCIDNDPN-UHFFFAOYSA-N 2-(dimethylamino)benzaldehyde Chemical compound CN(C)C1=CC=CC=C1C=O DGPBVJWCIDNDPN-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 239000002027 dichloromethane extract Substances 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- BFMYDTVEBKDAKJ-UHFFFAOYSA-L disodium;(2',7'-dibromo-3',6'-dioxido-3-oxospiro[2-benzofuran-1,9'-xanthene]-4'-yl)mercury;hydrate Chemical compound O.[Na+].[Na+].O1C(=O)C2=CC=CC=C2C21C1=CC(Br)=C([O-])C([Hg])=C1OC1=C2C=C(Br)C([O-])=C1 BFMYDTVEBKDAKJ-UHFFFAOYSA-L 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000000074 matrix-assisted laser desorption--ionisation tandem time-of-flight detection Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 238000002428 photodynamic therapy Methods 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0086—Platinum compounds
-
- 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
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- 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
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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
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- 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
- G01N21/6486—Measuring fluorescence of biological material, e.g. DNA, RNA, cells
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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
- C09K2211/18—Metal complexes
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
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- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
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- Pharmacology & Pharmacy (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Physics & Mathematics (AREA)
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Abstract
The invention belongs to organic photoelectrical material technical field, relate to a kind of near-infrared metal complex and its preparation method and application.Described metal complex is prepared by following step: step S1: two pyrroles methine dyes C, the i.e. preparation of N^N assistant ligand；Step S2: the preparation of metal dichloro bridge；Step S3: the preparation of near-infrared metal complex: two pyrroles's methine dyess and metal dichloro bridge obtain near-infrared metal complex by complexation reaction.Described preparation method technique is simple, abundant raw material, it is simple to industrialized production.Described metal complex can be used for the technical fields such as photoacoustic imaging, photo-thermal therapy, biomarker and detection.Metal is incorporated into azepine two pyrroles's methine compounds by the present invention, thus obtains a kind of having near infrared absorption performance, good photo-thermal and the metal complex of chemical stability.Described metal complex has the general structure being shown below.
Description
Technical field
The invention belongs to organic photoelectrical material technical field, be specifically related to a kind of near-infrared metal complex, described cooperation
The preparation method of thing and the application in the fields such as photoacoustic imaging, photo-thermal therapy, biomarker and detection thereof.
Background technology
Near infrared fluorescent dye is a class Functional dye, owing to it has well absorption in near-infrared region, the most closely
Infrared technique suffers from widely should in solaode, oncotherapy, radio frequency identification system, anti-counterfeit printing etc.
With.
Azepine two pyrroles's methine dyes is the novel near infrared fluorescent dye of class received significant attention in recent years, such dye
Material has absorption and launches the features such as wavelength is longer, good light stability, half-peak width, quantum yield high, molar extinction coefficient is big,
Owing to azepine dipyrrole methenyl fluorochrome has so many advantage, be widely used in photodynamic therapy, fluorescent probe,
The fields such as the transmission of near infrared fluorescent dye, signal, bio-imaging.In the more than ten years in past, scientific research personnel is repaiied by structure
Azepine two pyrroles's methine is modified, thus is improved its optical physics and photochemical properties by decorations, the mode such as conversion of group, thus
Make it have and be more widely applied (Li, K.；Liu,B.Poly.Chem.2010,1,252).
Phosphorescence transient metal complex can utilize singlet exciton and triplet excitons simultaneously, causes the weight of people
Depending on.It is found that there is the photoelectric property that phosphorescence transient metal complex is much excellent, such as high triplet state photo-quantum efficiency, good
Good photochemical stability, the transmitting wavelength easily regulated, longer emission lifetime and big Stokes shift, organic aobvious
Show, the field such as optical dynamic therapy, chemical sensor and cell imaging has a wide range of applications.The performance master of transient metal complex
Metal center to be depended on and ligand structure, so the structure of regulation part is the most direct of the phosphor material of acquisition excellent properties
Mode (Zhao, Q.；Li,F.Y.；Huang,C.H.Chemical Society Reviews2010,39,3007).
Azepine two pyrroles's methine dyes is substantially all and is introduced into boron atom, generation BODIP (Ehrenschwender,
T.；Wagenknechet, H.A.J.Org.Chem., 2011,76 (7): 2301-2304), so far, seldom have scientific research people
Member, is incorporated into transition metal in two pyrroles's methine dyess.Based on two pyrroles's methine dyess and phosphorescence transient metal complex
Excellent properties, the present invention introduces metal complex in azepine two pyrroles's methine dyes, and it will be caused to absorb red shift, singlet oxygen
Yield is high, optical stability is more preferable, has bigger advantage at the aspect such as optical dynamic therapy and photoacoustic imaging.
Summary of the invention
In view of prior art exists above-mentioned technical problem, it is an object of the invention to provide a kind of novel near-infrared gold
Metal complex and preparation thereof and application, this material combines azepine two pyrroles's methine dyes and the feature of phosphorescence transition metal, tool
There are near infrared absorption performance, good photo-thermal and chemical stability, can be used for photoacoustic imaging, photo-thermal therapy, biomarker and inspection
In the fields such as survey.The technical solution used in the present invention is as described below:
The present invention provides a kind of near-infrared metal complex, and described metal complex has a following general structure:
Wherein R1、R2It is each independently selected from H-, Br-, OCH3-、N(CH3)2、C2H5O-、OH-、CF3-、COCH3-、In one, wherein, R3For having 1
Straight chain, side chain or cyclic alkyl chain to 32 carbon atoms；
M is transition metal；
Wherein, n is 1 or 2, C^N part be following in one:
In following content, the R related to1、R2, C^N part, except special instruction in addition to be all suitable for above-mentioned scope.
In further technical scheme, described transition metal is the one in Pt, Pd, Ir.
The present invention also provides for the preparation method of above-mentioned near-infrared metal complex, concretely comprising the following steps of described method:
Step S1: two pyrroles methine dyes C, i.e. the preparation of N^N assistant ligand, the molecular formula of two pyrroles methine dyes C is:
Step S2: the preparation of metal dichloro bridge, the molecular formula of described metal dichloro bridge is:
Step S3: the preparation of near-infrared metal complex: two pyrroles's methine dyess and metal dichloro bridge pass through complexation reaction
Obtain near-infrared metal complex.
In above-mentioned preparation method, the process of step S1 is:
(1): the preparation of unsaturated arone A:
In organic solvent, para-position is by R1Substituted benzaldehyde and para-position are by R2Substituted 1-Phenylethanone., sends out in the basic conditions
Raw reaction obtains unsaturated arone A, and the molecular formula of unsaturated arone A is:
(2): the preparation of unsaturated nitro additive compound B:
Being dissolved in organic solvent by unsaturation arone A, in the basic conditions, unsaturated arone A and nitromethane occur to step
Ke Er additive reaction obtains unsaturated nitro additive compound B, and the molecular formula of unsaturated nitro additive compound B is:
(3): two pyrroles methine dyes C, the i.e. preparation of N^N assistant ligand:
Unsaturation nitro additive compound B and ammonium acetate being dissolved in organic solvent, reaction obtains two pyrroles's methine dyess
C, i.e. N^N assistant ligand.
In above-mentioned steps S1, substituent R1、R2Can also be carried out more by the organic reaction such as substitution reaction, coupling reaction
Change.
In above-mentioned preparation method, the step of step S2 is: the chloride of C^N part and transition metal M is in organic solvent
Reaction, obtains metal dichloro bridge.
In above-mentioned steps S2, described transition metal is the one in Pt, Pd, Ir.
The step of step 3 is: under a nitrogen atmosphere, and two pyrroles methine dyes C, metal dichloro bridge are dissolved in ethylene glycol
In, in alkalescence condition, occur complexation reaction to obtain near-infrared metal complex.
In above-mentioned steps S3, described catalyst is sodium carbonate, and described organic solvent is ethylene glycol.
Following chemical reaction is, an example of the preparation process of near-infrared metal complex of the present invention (can not generation
All technical schemes of table preparation method of the present invention):
The present invention also provides for the application of above-mentioned near-infrared metal complex, and described coordination compound can be used for photoacoustic imaging, photo-thermal
The technical fields such as treatment, biomarker and detection.
The present invention passes through a series of organic synthesiss, is incorporated into by transition metal in azepine two pyrroles's methine compounds, from
And obtain a class and there is near infrared absorption performance, good light thermal property and the metal complex of chemical stability.Contrast is described
The change of spectrum spectrogram before and after coordination of near-infrared metal complex understands, and the introduction of metal complex provides electronics to center
Ability strengthen so that the spectrum of material there occurs red shift, i.e. has near infrared absorption performance.
There is advantages that 1, described metal complex can realize it and absorb and launch red shift, chemistry
Stability is more preferable；2, described preparation method technique is simple, abundant raw material, it is simple to industrialized production；3, described metal complex can
For technical fields such as photoacoustic imaging, photo-thermal therapy, biomarker and detections.
Accompanying drawing explanation
Fig. 1. the ultraviolet-visible spectrum variation diagram of C1, D1 of embodiment 1 in the present invention；
Fig. 2. the ultraviolet-visible spectrum variation diagram of C2, D2 of embodiment 2 in the present invention；
Fig. 3. the C1 mass spectrum of embodiment 3 in the present invention
Fig. 4. the D1 mass spectrum of embodiment 4 in the present invention；
Fig. 5. the C2 mass spectrum of embodiment 5 in the present invention；
Fig. 6. the D2 mass spectrum of embodiment 6 in the present invention.
Fig. 7. the D1 photoacoustce signal intensity-concentration map of embodiment 7 in the present invention
Detailed description of the invention
In order to be more fully understood that technical scheme, further illustrate the present invention's below by concrete example
Technical scheme, specifically includes synthesis, property testing.It is to be understood that these embodiments are technical solution of the present invention
In several examples rather than limitation of the present invention.
Embodiment 1,
Current embodiment require that the metal complex preparing near infrared absorption is, in above-mentioned formula, to work as R1For N, N diformazan ammonia
Base, R2For bromine, M be Pt, n be 1, C^N isTime coordination compound D1, its molecular formula is:
Step S1: two pyrroles methine dyes C1, i.e. the preparation of N^N assistant ligand: concretely comprise the following steps:
(1): the preparation of unsaturated arone A1, wherein the molecular formula of unsaturated arone A1 is:
Weighing parabromoacetophenone (1000mg), dimethylaminobenzaldehyde (745mg), KOH (84mg) joins in single port bottle,
In system, add ethanol/water solution (85:15v/v 100mL), be stirred at room temperature, response time about 12h.Process: sucking filtration, second
Alcohol recrystallization.1H NMR(400MHz,CDCl3): δ=7.88 (d, J=8.4Hz, 2H), 7.81 (d, J=15.6Hz, 1H), 7.63
(d, J=8.4Hz, 2H), 7.55 (d, J=8.8Hz, 2H), 7.26 (d, J=15.6Hz, 1H), 6.70 (d, J=8.8Hz, 2H),
3.05(s,6H)ppm.
(2): the preparation of unsaturated nitro additive compound B1, the molecular formula of wherein unsaturated nitro additive compound B1
For:
Weigh Compound A1 (1320mg) in reaction bulb, adds the methanol that 50mL is dried and makes it dissolve, then in system
Add nitromethane (1070mg) and diethylamine (1460mg), be heated to reflux 24h.After having reacted, reaction system is cooled down quiet
Putting to room temperature, be acidified to faintly acid with the hydrochloric acid of 1mol/L, with dichloromethane/distilled water extraction mixed liquor, organic facies is with anhydrous
MgSO4Being dried, filter and filter off solid, filtrate obtains crude product after major part solvent being evaporated off with Rotary Evaporators rotation, then with two
Chloromethanes, petroleum ether recrystallization, sucking filtration, rinses with petroleum ether, obtains white solid (0.92g, 64.7%).1H NMR(400MHz,
CDCl3): δ=7.78 (d, J=8.8Hz, 2H), 7.60 (d, J=8.4Hz, 2H), 7.12 (d, J=8.8Hz, 2H), 6.67 (d,
J=8.8Hz, 2H), 4.78 (m, 1H), 4.65 (m, 1H), 4.11 (m, 1H), 3.38 (m, 2H), 2.92 (s, 6H) ppm.
(3): two pyrroles methine dyes C1, i.e. the preparation of N^N assistant ligand, the molecular formula of two pyrroles methine dyes C1 is:
Weigh Compound B1 (1080mg) and ammonium acetate (7040mg) in reaction bulb, add the ethanol that 60mL steamed and make it
Dissolve, be heated to reflux 48h, after raw material reacts completely, system be cooled to room temperature, sucking filtration, obtain blackish green with cold alcohol flushing
Color solid, normal hexane recrystallization, productivity: 60%.1H NMR(400MHz,CDCl3): δ=8.03 (d, J=8.8Hz, 4H),
7.78 (d, J=8.8Hz, 4H), 7.65 (d, J=8.8Hz, 4H), 7.01 (s, 2H), 6.79 (m, 5H), 3.05 (s, 12H) ppm.
Its MALDI-TOF spectrogram, theoretical (experiment) value: 693.47 (692.907).
Step S2: the preparation of metal dichloro bridge, the molecular formula of described metal dichloro bridge is:
Weigh phenylpyridine (245mg) and K2PtCl4(311mg) join in two-mouth bottle, inject (9ml) ethylene glycol
With deionized water (3ml), evacuation-inflated with nitrogen-evacuation on biexhaust pipe, circulate three times, finally protect reactant with nitrogen
System, and reaction system is increased to 110 DEG C, in about 24 hours response time, after terminating, add a large amount of water, have the most yellowish green
Color separates out admittedly, is product.
Step S3: the preparation of near-infrared metal complex D1:
Weighing C1 (104mg), sodium carbonate (40mg), platinum dichloro bridge (58mg) joins in two-mouth bottle, takes out on biexhaust pipe
Vacuum-inflated with nitrogen-evacuation, circulates three times, finally protects reaction system with nitrogen.Ethylene glycol (5ml) is added to reaction
In Ping, stirring, and the temperature of reaction system is raised to 110 DEG C, about 24 hours response time.Process: with water and dichloromethane
Extraction, vacuum is spin-dried for, dichloromethane: petroleum ether=2:1 is eluant, crosses pillar.Productivity: 30%.1H NMR(400MHz,
CDCl3): δ=8.34 (d, J=8.4Hz, 4H), 8.04 (m, 4H), 7.53 (m, 1H), 7.47 (d, J=8.4Hz, 2H), 7.41
(m, 3H), 7.22 (m, 3H), 6.79 (m, 6H), 6.61 (m, 1H), 6.41 (m, 1H), 3.05 (s, 12H) its MALDI-TOF of ppm.
Its mass spectrum, theoretical (experiment) value: 1041.74 (1042.982).
Embodiment 2:
The metal complex with near infrared absorption that current embodiment require that preparation is to work as R1For N, N dimethylamino, R2ForTime, M be Pt, n be 1, C^N isTime coordination compound D2, its molecular formula is:
Step S1: two pyrroles methine dyes C2, i.e. the preparation of N^N assistant ligand: concretely comprise the following steps:
First, two pyrroles methine dyes C1 are prepared according to step S1 (1), the process of (2) (3) in embodiment 1；Then
(4) prepare C2 as steps described below, and the molecular formula of two pyrroles methine dyes C2 is；
Step (4) is by Suzuki reaction preparation C2:
A) preparation of 9-propyl group carbazole-3-borate:
Weigh carbazole (1.67g, 10mmol) and tetrabutyl ammonium bromide (0.322g) in reaction bulb, with oil pump evacuation-
After inflated with nitrogen-evacuation cycle three times, nitrogen protection reaction system, in system add dimethyl sulfoxide DMSO (40mL) and
8.0g 50%KOH, system is added dropwise over N-Propyl Bromide (6.15g, 50mmol), stirred overnight at room temperature when stirring.Treat former
After material reaction completely, extract with a large amount of water and dichloromethane, be dried with anhydrous MgSO4 again after the washing of organic facies saturated common salt,
Filter, gained filtrate is removed major part solvent with Rotary Evaporators, then using petroleum ether as eluent, cross pillar.Obtain 9-
Propyl group carbazole, productivity 90%.1H NMR(400MHz,CDCl3): δ=8.21 (dd, J=78.8,7.6Hz, 1H), 7.71 7.38
(m, 2H), 7.24 (dt, J=8.0,5.4,1.9Hz, 2H), 4.29 (t, J=7.2Hz, 1H), 2.09 1.81 (m, 1H), 1.16
0.89(m,2H).
Weigh 9-propyl group carbazole (4.18g, 20.0mmol) in reaction bulb, follow with oil pump evacuation-inflated with nitrogen-evacuation
Ring three times, nitrogen protection system, in system, add CHCl3(100mL), reaction unit lucifuge.Reaction system is down to 0 DEG C,
Slowly dropping N-bromo-succinimide (3.56g, 20.0mmol).Reaction temperature is returned to room temperature and is stirred overnight.Treat former
After material reaction completely, being removed by CHCl3 with Rotary Evaporators, crude product with water and dichloromethane extraction, with petroleum ether and acetic acid
Ethyl ester=9:1 crosses pillar.Obtain 9-propyl group-3-bromine carbazole.1H NMR(400MHz,CDCl3): δ=8.22 (t, J=9.9Hz,
1H), 8.05 (d, J=7.8Hz, 1H), 7.59 7.46 (m, 2H), 7.41 (d, J=8.2Hz, 1H), 7.25-7.22 (m, 3H),
4.33–4.15(m,3H),1.98–1.81(m,3H),0.99–0.88(m,4H).
Weigh 9-propyl group-3-bromine carbazole (3.3g, 10mmol), frequently that borate (3g, 12mmol), potassium acetate (6g) and two
Palladous chloride. 200mg in reaction bulb, evacuation, drum nitrogen, add Isosorbide-5-Nitrae-dioxane (100ml), 85 DEG C of return stirrings overnight,
Water and dichloromethane extract three times, and inorganic salt is dried, ethyl acetate: petroleum ether=1:4 crosses pillar, obtains yellow solid, is 9-
Propyl group-3-borate, productivity 80%.1H NMR(400MHz,CDCl3): δ=8.60 (s, 1H), 8.14 (d, J=7.7Hz, 1H),
7.92 (d, J=8.2Hz, 1H), 7.53 7.36 (m, 3H), 7.23 (d, J=6.9Hz, 1H), 4.29 (t, J=7.1Hz, 2H),
2.05–1.80(m,2H),1.40(s,12H),1.05–0.90(m,3H).
B) by Suzuki reaction preparation C2:
Weigh substance C 1 (277mg), 9-propyl group-3-borate (220mg) and four (triphenyl phosphorus) palladium catalyst
(20.8mg) in reaction bulb, evacuation-inflated with nitrogen-evacuation cycle three times, nitrogen protection reaction system, inject and rouse nitrogen in advance
The wet chemical (1mL) of the halfhour toluene of deoxygenation (2mL), ethanol (1mL) and 2M, is heated to 85 DEG C of backflows by system
Overnight.After raw material reacts completely, system being cooled to room temperature, with dichloromethane/distilled water extraction, organic facies is with anhydrous
MgSO4 is dried, and filters and filters off solid, and filtrate obtains crude product, the most again after major part solvent being evaporated off with Rotary Evaporators rotation
Purify as eluent column chromatography using the mixed solvent (2:1v/v) of petroleum ether and dichloromethane, after purification, obtain green solid
(152mg, 50%), is C2.1H NMR (400MHz, DMSO) δ :=8.67 (d, J=1.4Hz, 2H), 8.30 (d, J=
7.8Hz, 2H), 8.17 (d, J=8.6Hz, 4H), 8.08 (dd, J=11.3,8.8Hz, 8H), 7.93 (dd, J=8.7,1.6Hz,
2H), 7.72 (d, J=8.6Hz, 2H), 7.64 (d, J=8.4Hz, 2H), 7.48 (dd, J=13.3,5.1Hz, 4H), 7.22 (t,
J=7.6Hz, 2H), 6.81 (d, J=9.1Hz, 4H), 4.40 (t, J=7.0Hz, 4H), 3.01 (s, 12H), 1.82 (dd, J=
14.2,7.1Hz, 4H), 0.89 (t, J=8Hz, 6H) ppm. its mass spectrum of its MALDI-TOF, theoretical (experiment) value: 950.22
(949.107)。
Step S2: the preparation of metal dichloro bridge, the molecular formula of described metal dichloro bridge is:
Weigh phenylpyridine (245mg) and K2PtCl4(311mg) join in two-mouth bottle, inject (9ml) ethylene glycol
With deionized water (3ml), evacuation-inflated with nitrogen-evacuation on biexhaust pipe, circulate three times, finally protect reactant with nitrogen
System, and reaction system is increased to 110 DEG C, in about 24 hours response time, after terminating, add a large amount of water, have the most yellowish green
Color separates out admittedly, is product.
Step S3: the preparation of near-infrared metal complex D2:
Weighing C2 (124mg), sodium carbonate (42mg), platinum dichloro bridge (58mg) joins in two-mouth bottle, takes out on biexhaust pipe
Vacuum-inflated with nitrogen-evacuation, circulates three times, finally protects reaction system with nitrogen.Ethylene glycol (5ml) is added to reaction
In Ping, stirring, and the temperature of reaction system is raised to 110 DEG C, about 24 hours response time.Process: with water and dichloromethane
Extraction, vacuum is spin-dried for, dichloromethane: petroleum ether=2:1 is eluant, crosses pillar.1H NMR(400MHz,CDCl3) δ :=8.64
(d, J=7.6Hz, 4H), 8.34 (s, 2H), 8.16 (dd, J=19.9,7.4Hz, 6H), 7.75 (dd, J=19.1,8.6Hz,
6H), 7.61 7.30 (m, 10H), 7.25 7.16 (m, 5H), 6.99 (d, J=8.7Hz, 1H), 6.90 6.69 (m, 4H), 6.63
(t, J=6.9Hz, 1H), 6.41 (d, J=6.3Hz, 1H), 4.30 (d, J=6.4Hz, 4H), 3.06 (s, 12H), 2.05 1.86
(m, 4H), its MALDI-TOF spectrogram of 0.99 (dd, J=11.2,7.2Hz, 6H) ppm., theoretical (experiment) value: 1248.43
(1247.236)。
The ultraviolet-visible spectrum test of embodiment 3:C1 and D1:
The weak solution (dichloromethane is solvent) of the two kinds of compounds of C1 and D1 in configuration embodiment 1, pipettes 2mL coordination compound
Solution, in fluorescence cuvette, then carries out ultraviolet-visible luminous spectrum, and such as Fig. 1, test data show: coordinate along with introducing Pt
After thing, it is achieved that red shift.
The ultraviolet-visible spectrum test of embodiment 4:C2 and D2:
The weak solution (dichloromethane is solvent) of the two kinds of compounds of C2 and D2 in configuration embodiment 2, pipettes 2mL coordination compound
Solution, in fluorescence cuvette, then carries out ultraviolet-visible luminous.Such as Fig. 2, test data show: along with introducing Pt coordination compound
After, it is achieved that red shift.
Embodiment 5:
In centrifuge tube, dissolving a small amount of sample with dichloromethane, then point sample on point template, uses Bruker
Substance assistant laser desorpted ionization times-the time of-flight mass spectrometer of autoflex (MALDI-TOF/TOF) is measured, and records
D1, C2, D2 mass spectrum such as Fig. 3,4,5, it was demonstrated that the correct synthesis of material.Wherein part D2 is due to mass spectrometric high-energy, beats
Fall a phenylpyridine, less than original molecular weight by 153.
Embodiment 6:
Make it be dispersed therein by the D1 of variable concentrations is injected separately in agar block, then agar block is put into light
Acoustic imaging instrument observes the agar block of variable concentrations on photoacoustce signal intensity and the impact of the degree of depth, such as Fig. 6.Test data show:
The intensity of photoacoustic signal increases along with the increase of the concentration of D1, and when concentration is in certain value, signal intensity will vary less.
Claims (10)
1. a near-infrared metal complex, it is characterised in that described metal complex has a following general structure:
Wherein, R1、R2It is each independently selected from H-, Br-, OCH3-、N(CH3)2、C2H5O-、OH-、CF3-、COCH3-、、In one, wherein R3For have 1 to
The straight chain of 32 carbon atoms, side chain or cyclic alkyl chain, R1、R2Can be identical, it is also possible to different；
M is transition metal；N is 1 or 2, in the following molecule one of C^N part:
2. near-infrared metal complex as claimed in claim 1, it is characterised in that described transition metal is in Pt, Pd, Ir
A kind of.
3. the preparation method of a near-infrared metal complex as claimed in claim 1 or 2, it is characterised in that described method
Concretely comprise the following steps:
Step S1: two pyrroles methine dyes C, i.e. the preparation of N^N assistant ligand, the molecular formula of two pyrroles methine dyes C is:
Step S2: the preparation of metal dichloro bridge, the molecular formula of described metal dichloro bridge is:
Step S3: the preparation of near-infrared metal complex: two pyrroles's methine dyess are obtained by complexation reaction with metal dichloro bridge
Near-infrared metal complex.
4. preparation method as claimed in claim 3, it is characterised in that the process of above-mentioned steps S1 is:
(1): the preparation of unsaturated arone A:
In organic solvent, para-position is by R1Substituted benzaldehyde and para-position are by R2Substituted 1-Phenylethanone., occurs anti-in the basic conditions
Should obtain unsaturated arone A, the molecular formula of unsaturated arone A is:
(2): the preparation of unsaturated nitro additive compound B:
Being dissolved in organic solvent by unsaturation arone A, in the basic conditions, there is Michael with nitromethane in unsaturated arone A
Additive reaction obtains unsaturated nitro additive compound B, and the molecular formula of unsaturated nitro additive compound B is:
(3): two pyrroles methine dyes C, the i.e. preparation of N^N assistant ligand:
Unsaturation nitro additive compound B and ammonium acetate being dissolved in organic solvent, reaction obtains two pyrroles methine dyes C, i.e. N
^N assistant ligand.
5. preparation method as claimed in claim 4, it is characterised in that in above-mentioned steps S1, its substituent R1、R2Can pass through
The organic reaction such as substitution reaction, coupling reaction is replaced.
6. preparation method as claimed in claim 3, it is characterised in that the step of above-mentioned steps S2 is: C^N part and transition gold
The chloride belonging to M reacts in organic solvent, obtains metal dichloro bridge.
7. preparation method as claimed in claim 5, it is characterised in that in above-mentioned steps S2, described transition metal be Pt,
One in Pd, Ir.
8. preparation method as claimed in claim 3, it is characterised in that the step of above-mentioned steps 3 is: under a nitrogen atmosphere, will
Two pyrroles methine dyes C, metal dichloro bridge are dissolved in organic solvent, under alkalescence, occur complexation reaction to obtain near-infrared metal
Coordination compound.
9. preparation method as claimed in claim 7, it is characterised in that in above-mentioned steps S3, described catalyst is sodium carbonate,
Described organic solvent is ethylene glycol.
10. the application of a metal complex as claimed in claim 1 or 2, it is characterised in that described metal complex can be used
In photoacoustic imaging, photo-thermal therapy succinum biomarker and detection field.
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| CN111253296A (en) * | 2020-02-19 | 2020-06-09 | 天津大学 | Transition metal complex aza-dipyrromethene amphiphilic near-infrared dye and preparation method thereof |
| CN118373859A (en) * | 2024-06-19 | 2024-07-23 | 化学与精细化工广东省实验室 | Surface antibody modified organic platinum complex nanoparticle and preparation and tumor light therapy application thereof |
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| CN108795088A (en) * | 2018-04-17 | 2018-11-13 | 南京邮电大学 | It is a kind of that there is the nir dye for enhancing light power and photo-thermal effect and its preparation and application |
| CN108503673A (en) * | 2018-04-28 | 2018-09-07 | 南京邮电大学 | A kind of near-infrared aza pyrrolidines dyestuff and its preparation method and application |
| CN108503673B (en) * | 2018-04-28 | 2020-12-29 | 南京邮电大学 | Near-infrared azapyrrolidine dye and preparation method and application thereof |
| CN111253296A (en) * | 2020-02-19 | 2020-06-09 | 天津大学 | Transition metal complex aza-dipyrromethene amphiphilic near-infrared dye and preparation method thereof |
| CN111253296B (en) * | 2020-02-19 | 2023-01-10 | 天津大学 | Transition metal complex aza-dipyrromethene amphiphilic near-infrared dye and preparation method thereof |
| CN118373859A (en) * | 2024-06-19 | 2024-07-23 | 化学与精细化工广东省实验室 | Surface antibody modified organic platinum complex nanoparticle and preparation and tumor light therapy application thereof |
| CN118373859B (en) * | 2024-06-19 | 2024-09-03 | 化学与精细化工广东省实验室 | Surface antibody modified organic platinum complex nanoparticle and preparation and tumor light therapy application thereof |
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