CN108129495A - A kind of organic semiconductor of near-infrared containing selenium and its preparation method and application - Google Patents
A kind of organic semiconductor of near-infrared containing selenium and its preparation method and application Download PDFInfo
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- CN108129495A CN108129495A CN201810043217.9A CN201810043217A CN108129495A CN 108129495 A CN108129495 A CN 108129495A CN 201810043217 A CN201810043217 A CN 201810043217A CN 108129495 A CN108129495 A CN 108129495A
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- containing selenium
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- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052711 selenium Inorganic materials 0.000 title claims abstract description 41
- 239000004065 semiconductor Substances 0.000 title claims abstract description 38
- 239000011669 selenium Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 206010028980 Neoplasm Diseases 0.000 claims abstract description 47
- 239000002086 nanomaterial Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 10
- OBISXEJSEGNNKL-UHFFFAOYSA-N dinitrogen-n-sulfide Chemical group [N-]=[N+]=S OBISXEJSEGNNKL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 27
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 19
- JEDHEMYZURJGRQ-UHFFFAOYSA-N 3-hexylthiophene Chemical compound CCCCCCC=1C=CSC=1 JEDHEMYZURJGRQ-UHFFFAOYSA-N 0.000 claims description 14
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims description 6
- 229930192474 thiophene Natural products 0.000 claims description 6
- PPHPRJQYDNAYPQ-UHFFFAOYSA-N N1N=CC=C1.[Se] Chemical compound N1N=CC=C1.[Se] PPHPRJQYDNAYPQ-UHFFFAOYSA-N 0.000 claims description 5
- KXCAEQNNTZANTK-UHFFFAOYSA-N stannane Chemical compound [SnH4] KXCAEQNNTZANTK-UHFFFAOYSA-N 0.000 claims description 5
- 229910000080 stannane Inorganic materials 0.000 claims description 5
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 claims 2
- 239000004020 conductor Substances 0.000 claims 2
- 239000002253 acid Substances 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 239000000779 smoke Substances 0.000 claims 1
- 210000004881 tumor cell Anatomy 0.000 abstract description 14
- 238000010521 absorption reaction Methods 0.000 abstract description 13
- 238000002560 therapeutic procedure Methods 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 230000012010 growth Effects 0.000 abstract description 4
- 238000001228 spectrum Methods 0.000 abstract description 4
- 238000001226 reprecipitation Methods 0.000 abstract description 3
- 230000008685 targeting Effects 0.000 abstract description 3
- 208000001894 Nasopharyngeal Neoplasms Diseases 0.000 abstract description 2
- 230000001225 therapeutic effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 21
- 239000000047 product Substances 0.000 description 18
- 210000004027 cell Anatomy 0.000 description 15
- 238000007626 photothermal therapy Methods 0.000 description 13
- 238000012360 testing method Methods 0.000 description 10
- 241000699666 Mus <mouse, genus> Species 0.000 description 9
- 210000001519 tissue Anatomy 0.000 description 9
- 239000008187 granular material Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 201000011510 cancer Diseases 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000005286 illumination Methods 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
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- 210000003462 vein Anatomy 0.000 description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
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- 238000005516 engineering process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- -1 product 2 (10.6g Chemical class 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 241000699660 Mus musculus Species 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- 238000011580 nude mouse model Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000004083 survival effect Effects 0.000 description 3
- 230000004614 tumor growth Effects 0.000 description 3
- PDQRQJVPEFGVRK-UHFFFAOYSA-N 2,1,3-benzothiadiazole Chemical class C1=CC=CC2=NSN=C21 PDQRQJVPEFGVRK-UHFFFAOYSA-N 0.000 description 2
- 206010008342 Cervix carcinoma Diseases 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 206010020843 Hyperthermia Diseases 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 208000006105 Uterine Cervical Neoplasms Diseases 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 201000010881 cervical cancer Diseases 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 231100000135 cytotoxicity Toxicity 0.000 description 2
- 230000003013 cytotoxicity Effects 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 2
- 230000036031 hyperthermia Effects 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000001727 in vivo Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000017074 necrotic cell death Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 238000001126 phototherapy Methods 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 238000001959 radiotherapy Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 150000004867 thiadiazoles Chemical class 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000820 toxicity test Toxicity 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000006144 Dulbecco’s modified Eagle's medium Substances 0.000 description 1
- 206010030113 Oedema Diseases 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- JWYFRSAIWSROES-UHFFFAOYSA-N [O-2].[O-2].[Ti+4].[SeH2] Chemical compound [O-2].[O-2].[Ti+4].[SeH2] JWYFRSAIWSROES-UHFFFAOYSA-N 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 229910052946 acanthite Inorganic materials 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 238000001636 atomic emission spectroscopy Methods 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 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
- 239000006227 byproduct Substances 0.000 description 1
- 239000012830 cancer therapeutic Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 238000002512 chemotherapy Methods 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- NXQGGXCHGDYOHB-UHFFFAOYSA-L cyclopenta-1,4-dien-1-yl(diphenyl)phosphane;dichloropalladium;iron(2+) Chemical compound [Fe+2].Cl[Pd]Cl.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 NXQGGXCHGDYOHB-UHFFFAOYSA-L 0.000 description 1
- 231100000263 cytotoxicity test Toxicity 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 238000000799 fluorescence microscopy Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 150000002433 hydrophilic molecules Chemical class 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- OVEHNNQXLPJPPL-UHFFFAOYSA-N lithium;n-propan-2-ylpropan-2-amine Chemical compound [Li].CC(C)NC(C)C OVEHNNQXLPJPPL-UHFFFAOYSA-N 0.000 description 1
- 231100001252 long-term toxicity Toxicity 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 210000003470 mitochondria Anatomy 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002829 nitrogen Chemical class 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 208000007578 phototoxic dermatitis Diseases 0.000 description 1
- 231100000018 phototoxicity Toxicity 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229940056910 silver sulfide Drugs 0.000 description 1
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000007920 subcutaneous administration Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D517/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having selenium, tellurium, or halogen atoms as ring hetero atoms
- C07D517/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having selenium, tellurium, or halogen atoms as ring hetero atoms in which the condensed system contains two hetero rings
- C07D517/04—Ortho-condensed systems
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Epidemiology (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- General Health & Medical Sciences (AREA)
- Biophysics (AREA)
- Optics & Photonics (AREA)
- Animal Behavior & Ethology (AREA)
- Pharmacology & Pharmacy (AREA)
- Medicinal Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
Application the present invention relates to a kind of organic semiconductor of near-infrared containing selenium and preparation method thereof and in terms of tumor thermal therapy.Organic semiconductor of the present invention introduces selenium atom in diazosulfide unit, and since selenium atom polarizability is strong, spectrum is moved to long wave length direction.The organic semiconductor obtains absorbing wavelength near infrared region by reprecipitation method（UV absorption is up to 906 nm, and fluorescent emission is up to 1040 nm）Organic nano material, this nanometer of reagent has higher photothermal conversion efficiency, excellent water dispersible, good tumor tissues targeting and preferable bio-compatibility, it may be used in tumour cell and live body treatment, effectively inhibit growth of tumour cell, and can effectively inhibit Nasopharyngeal neoplasms, so as to reach tumor thermal therapy effect.Therefore it will have huge application prospect in therapeutic field of tumor.
Description
Technical field
The invention belongs to materials and biomedicine field, and in particular to a kind of organic semi-conductor of near-infrared containing selenium preparation and
Its application in tumor thermal therapy.
Background technology
Cancer (malignant tumour) is one of primary killers of human life and health, main the having of Current cancer therapeutic scheme
It treats, perform the operation excision, radiotherapy etc., however these therapies have great side effect or defect, operation excision needs are accurate to be determined
The position of position tumour, and chemotherapy, radiotherapy can damage human normal cell simultaneously, and secondary injury is caused to patient health.Therefore, it opens
Sending out cancer treatment method significantly more efficient becomes current critical issue urgently to be resolved hurrily.
Photo-thermal therapy is minimally invasive oncotherapy technology a kind of in recent years, mainly by the way that light is shone directly into tumor locus
And the raising of its local temperature is made to substantially reduce whole body system toxicity, therefore photo-thermal therapy with killing tumor cell
(Photothermal therapy, PTT) is to be seen as a kind of one of very potential oncotherapy technology for substituting operation.For
Improve PTT efficiency and tumor-selective, it will usually which the photo-thermal therapy reagent with near-infrared absorption performance is imported into tumour portion
Position.And near infrared light is strong to the penetration capacity of tissue, ideal photothermal reagent is that have stronger absorption at 650-950nm.Closely
Nian Lai, a variety of nano materials with photo-thermal effect, such as metal nano material (gold, silver nano material), carbon nanomaterial (carbon
Nanotube, graphene), transition metal double sulfide (molybdenum disulfide, tungsten disulfide, silver sulfide), organic nano material etc..However
Most inorganic nano material poor biocompatibility, and have long term toxicity in vivo, limits it and clinically further applies.
Compared to inorganic nano material, the organic nano prepared by near-infrared (Near-infrared, NIR) organic semiconductor
Material has the characteristics that potential biological degradability, processing are simple.NIR organic semiconductors can absorb the near infrared light of specific wavelength
So as to reach excited singlet, the energy of part excited singlet can be released with the fluorescence of longer wavelength, therefore, near-infrared
Light can be effectively used for in-vivo tumour fluorescence imaging.And the near-infrared organic nano material of cancer target has high degree of specificity, it can
Distinguish tumor tissues and normal structure.Therefore near-infrared organic semiconductor has potential application value for oncotherapy.
Selenium (Se) belongs to the 6th major element, atomic radius 116pm；Se2-Ionic radius is 198pm, intermolecular phase
Interreaction force is weak, reduces intermolecular aggtegation, if being prepared into hydrophilic molecule, is conducive to recycle in blood.In addition
Due to the stronger polarizability of selenium atom, after selenium atom is introduced in organic semiconductor, the compound of more low-energy zone can be obtained,
Push ultraviolet spectra that red shift occurs.Energy band relatively low simultaneously causes molecule to have higher electron affinity energy in itself, can be effectively
Converting photons are reached into photo-thermal therapy purpose into thermal energy.Therefore selenium element will be introduced in organic semiconductor, spectrum can be effectively improved
Range and light thermal property.
Invention content
The technical problems to be solved by the invention are：A kind of organic semiconductor of near-infrared containing selenium and its nano material system are provided
Standby, this contains selenium near-infrared organic semiconductor nano material with bio-compatibility is good, water dispersible is good, good light stability, tumour
The advantages that targeting is good, in terms of can be applied to tumor diagnosis and therapy.
In order to solve the above technical problems, the technical solution adopted in the present invention is：
A kind of novel phototherapy reagent is provided --- the organic semiconductor of near-infrared containing selenium and its organic nano material SeBT NPs,
The organic semiconductor of near-infrared containing selenium main component is bis- (4- hexyl thiophene -2- the bases) -6- thio -2 of 4,7-, 1,3- benzo pair selenium two
Azoles, the compound have structure shown in below formula：
Wherein:
The organic semiconductor of near-infrared containing selenium can cooperate with photo-thermal, light power double mode treatment tumour.
It is as follows that it prepares reaction route：
Reaction condition is：
(1) trifluoromethane sulfonic acid and fuming nitric aicd stir at -5-0 DEG C, add in 4,7- dibromo diazosulfides, and heating is stirred
It mixes to obtain 4,7-, bis- bromo- 5,6- dinitros diazosulfides, i.e. product 4；
(2) under nitrogen protection, product 4 is dissolved in tetrahydrofuran, by tributyl (4- hexyl thiophene -2- bases) stannane,
[1,1'- bis- (diphenylphosphino) ferrocene] palladium chloride is added in above-mentioned solution, heating stirring purify to obtain 4,7- it is bis- (4- oneself
Base thiophene -2- bases) -5,6- dinitro diazosulfides, i.e. product 5；
(3) under nitrogen protection, product 5 is dissolved in acetic acid, adds in iron powder, heating stirring purifies to obtain the bis- (4- of 4,7-
Hexyl thiophene -2- bases) diazosulfide -5,6- diamines, i.e. product 6；
(4) under nitrogen protection, product 6 dissolves in ethanol, adds in selenium dioxide, and heating stirring purifies to obtain 4,7- bis-
(4- hexyl thiophene -2- bases) -6- thio -2, the double selenium diazole of 1,3- benzo, i.e. SeBT.
The method of the organic nano material SeBT NPs, reaction route are：
SeBT is dissolved in tetrahydrofuran, is rapidly injected in PBS, after ultrasonic reaction, stirring removes tetrahydrofuran, obtains
Above-mentioned organic nano material SeBT NPs.
Preferably, the molar ratio of step (1) trifluoromethane sulfonic acid and fuming nitric aicd is 1:(1.0-2.0).
Preferably, the molar ratio of step (1) 4, the 7- dibromos diazosulfide and fuming nitric aicd is 1:(2.0-10.0),
Preferred molar ratio is 1:(6.0-10.0).
Preferably, step (2) 4,7-, bis- bromo- 5, the 6- dinitros diazosulfides and tributyl (4- hexyl thiophenes -2-
Base) stannane molar ratio be 1:(1.0-2.0).
Preferably, step (2) 4,7-, bis- bromo- 5, the 6- dinitros diazosulfides and [1,1'- bis- (diphenylphosphinos)
Ferrocene] palladium chloride molar ratio be 1:(0.03-0.1).
Preferably, bis- (4- hexyl thiophene -2- bases) -5, the 6- dinitros diazosulfides of step (3) described 4,7- and iron powder
Molar ratio be 1:(6-15).
Preferably, bis- (4- hexyl thiophene -2- bases) diazosulfide -5, the 6- diamines of step (4) described 4,7- and titanium dioxide
The molar ratio of selenium is 1:(1-2).
Preferably, step (1) 30-60 DEG C of the heating temperature, heating stirring time are 24-48 hours.
Preferably, step (2) 50-100 DEG C of the heating temperature, heating stirring time are 12-24 hours.
Preferably, step (3) the heating stirring temperature is 50-100 DEG C, and the heating stirring time is 6-24 hours.
Preferably, step (4) 50-90 DEG C of the whipping temp, heating stirring time are 10-24 hours.
Preferably, step (5) described SeBT a concentration of 0.1-0.5 mg/mls, quick mixing speed in tetrahydrofuran
It is 500-1500 revs/min.
In addition, the organic semiconductor of near-infrared containing selenium dissolves in organic solvent, organic nano material water dispersible is good,
It can be applied to prepare oncotherapy reagent.
The beneficial effects of the invention are as follows：Compared with current material, the present invention provides a kind of photo-thermal reagent, i.e., containing selenium
Near-infrared organic semiconductor and its nano material, the organic semiconductor introduce selenium atom in diazosulfide unit, due to
Selenium atom polarizability is strong, and spectrum is moved to long wave length direction.The organic semiconductor obtains absorbing wavelength by reprecipitation method
In the organic nano material of near infrared region (UV absorption reaches 906nm, and fluorescent emission reaches 1040nm), this nanometer of reagent has higher
Photothermal conversion efficiency, excellent water dispersible, good tumor tissues targeting and preferable bio-compatibility, may be used on
In tumour cell and live body treatment, effectively inhibit growth of tumour cell, and can effectively inhibit Nasopharyngeal neoplasms, organism poison is secondary
Act on it is small, so as to reach tumor thermal therapy effect.
Description of the drawings
Fig. 1 is the particle diameter distribution test of SeBT NPs under the organic semiconductor of near-infrared containing selenium of the present invention its nm regime
With scanning electron microscope test figure；Test result shows that the particle diameter distribution of the nano particle is about 60nm.
Fig. 2 is near-infrared containing selenium organic semiconductor SeBT and its organic nanometer granule SeBT NPs described in invention
UV-vis absorption spectrum figure；SeBT has maximum absorption band at 825nm, and has wider absorption at 600-1000nm, and
Organic nanometer granule has absorption maximum at 906nm and has wider absorption at 600-1050nm, and spectral region reaches near-infrared
Region.
Fig. 3 is near-infrared containing selenium organic semiconductor SeBT and its organic nanometer granule SeBT NPs described in invention
Fluorescence emission spectrogram of compound；SeBT launch wavelengths are in 927nm, and for SeBT NPs launch wavelengths in 1030nm, spectral region reaches near red
Exterior domain.
Fig. 4 is the photothermal conversion curve graph of nano-particle SeBT NPs solution testings of the present invention；Its a concentration of 150 μ
The PBS solution of g/mL and pure PBS solution (808nm, 0.8W/cm under laser irradiation2), temperature time history plot.
Fig. 5 is toxicity test result schematic diagrams of the organic nano material SeBT NPs of the present invention for HeLa cells；
(808nm, 0.8W/cm under laser irradiation2), the cytotoxicity of SeBT NPs is stronger, can effectively kill tumour cell；And without sharp
Under light irradiation, SeBT NPs cytotoxicities are smaller.
Fig. 6 is organic nano material SeBT NPs of the present invention for photothermal imaging figure in mouse live body body；Tail vein
After injection, (808nm, 0.8W/cm under laser irradiation2), the nano particle can tumor region effectively convert light into for
Heat.
Fig. 7 is the result schematic diagram that organic nano material SeBT NPs of the present invention are used for live body treatment；Gross tumor volume
The curve changed with treatment time.SeBT NPs (808nm, 0.8W/cm under laser irradiation2), it can effectively inhibit tumour growth
And kill tumour.
Fig. 8 is the final result schematic diagram that organic nano material SeBT NPs of the present invention are used for live body treatment；In light
SeBT NPs can effectively inhibit tumour growth according in the case of.
Specific embodiment
Present invention design has synthesized a kind of organic semiconductor of near-infrared containing selenium, the material main component be 4,7- it is bis- (4- oneself
Base thiophene -2- bases) -6- thio -2, the double selenium diazole of 1,3- benzo, because diazosulfide is stronger electron acceptor, in structure
Middle introducing selenium atom, since selenium atom polarizability is strong, spectral red shift, while the molecule of more low-energy zone can be obtained.Low-energy zone
Luminous energy effectively can be converted to thermal energy by organic semiconductor, so as to reach photo-thermal therapy purpose.
Its synthetic route is as follows：
Said derivative SeBT obtains near-infrared organic nanometer granule by reprecipitation, which reaches
Near infrared region can obtain deeper tissue infiltration and better light thermal property.In addition the nano material also has preferable
Photothermal conversion ability, excellent water dispersible, tumor-targeting, bio-compatibility, applied to tumour cell and living body fluorescent into
In picture and photo-thermal therapy, tumour cell can be effectively killed.Therefore, which has potential in treatment of cancer
Application value.
The preparation of 1 SeBT of embodiment
In two-mouth bottle (1000mL), by o-phenylenediamine (10.00g, 92.46mmol) be dissolved in dichloromethane (400mL) and
Thionyl chloride (7.4mL, 101.70mmol) is slowly added dropwise in the in the mixed solvent of triethylamine (37.40g, 370.00mmol), heating
Reflux 20 hours removes dichloromethane, is filtered after adding in petroleum ether (600mL), concentrates, pale powder is obtained after purification
Benzo [c] [1,2,5] thiadiazoles, i.e. product 2 (10.6g, 84%).
In two-mouth bottle (1000mL), by product 2 (5.00g, 36.72mmol), add in hydrogen bromide (47%, 80mL) and stir extremely
Dissolving.The mixed solution of bromine (17.60g, 110.16mmol) and hydrogen bromide (47%, 50mL) is slowly added dropwise.Stirred at reflux 6
Hour, cooling filters, and concentration, purification obtains yellow powder 4,7- dibromos benzo [c] [1,2,5] thiadiazoles, i.e. product 3
(9.10g, 85%).
In two-mouth bottle (500mL), by fuming nitric aicd (2.50g, 71.40mmol) and trifluoromethane sulfonic acid (30.60g,
200.00mmol) it is mixed 30 minutes at 0 DEG C.Product 3 (5.00g, 17.00mmol) is added in, heating stirring 24 hours is cold
But it falls back middle suction filtration, obtains yellow powder 4, bis- bromo- 5,6- dinitros benzo [c] [1,2,5] thiadiazoles of 7-, i.e. product 4
(4.80g, 73%).
In two-mouth bottle (500mL), product 4 (4.00g, 10.40mmol) is dissolved in tetrahydrofuran (100mL), is substituted
Nitrogen three times, adds in thiophene pink salt, i.e., following products 8 (14.20g, 31.21mmol) and [1,1'- bis- (diphenylphosphinos) two cyclopentadienyl
Iron] palladium chloride (0.08g, 0.10mmol), heating stirring 12 hours, cool down, extract, concentration, purification obtain orange solids 4,
Bis- (4- hexyl thiophene -2- bases) -5,6- dinitros benzo [c] [1,2, the 5] thiadiazoles of 7-, i.e. product 5 (4.40g, 75%).1H
NMR(400MHz,CDCl3):δppm 7.32(s,2H),7.31(s,2H),2.66(t,J1=7.6, J2=8.0Hz, 4H),
1.68-1.60(m,4H),1.36-1.25(m,12H),0.90(t,J1=6.4, J2=7.2Hz, 6H)
In two-mouth bottle (500mL), product 5 (3.00g, 5.37mmol) is dissolved in acetic acid (40mL), substitutes nitrogen three
It is secondary, add in iron powder (1.80g, 32.22mmol).It flows back 6 hours, cools down under heating stirring, extract, concentrate, purification obtains yellow
Solid 4, bis- bis- amido benzo [c] [1,2, the 5] thiadiazoles of (4- hexyl thiophene -2- bases) -5,6- of 7-, i.e. product 6 (2.30g,
86%).1H NMR(400MHz,CDCl3):δ ppm 7.18 (s, 2H), 7.13 (s, 2H), 4.40 (s, 4H), 2.70 (dd, J1=
7.6,J2=4.7Hz, 4H), 1.72-1.58 (m, 4H), 1.42-1.25 (m, 12H), 0.90 (t, J1=6.4, J2=6.4Hz,
6H)。
In two-mouth bottle (100mL), product 6 (1.00g, 2.00mmol) is dissolved in ethyl alcohol (20mL), adds in titanium dioxide
Selenium (0.24g, 2.20mmol), substitutes nitrogen three times, and heating stirring flows back 12 hours, cools down, and filters, and purification obtains blackish green
Powder 4, bis- (4- hexyl thiophene -2- the bases) -6- thio -2 of 7-, the double selenium diazole of 1,3- benzo, i.e. product SeBT (0.80g, 69%)
。1H NMR(400MHz,CDCl3):δppm 8.83(s,2H),7.31(s,2H),2.77(t,J1=10.4, J2=10.0Hz,
4H),1.81-1.71(m,4H),1.44-1.27(m,12H),0.91(t,J1=9.2, J2=10.0Hz, 6H).
In two-mouth bottle (500mL), 3- hexyl thiophenes (10.00g, 59.42mmol) are dissolved in dry tetrahydrofuran
In (300mL), nitrogen is substituted three times.Be slowly added dropwise at -78 DEG C lithium diisopropylamine (32.68mL, 2.0M in THF,
65.40mmol) stir 2 hours after, be stirred at room temperature 12 hours, extract, concentration, obtain colourless liquid tributyl (4- hexyl thiophenes-
2- yls) stannane, i.e. product 8 (24.00g, 88%).
It is prepared by 2 SeBT NPs of embodiment
The above-mentioned SeBT (0.0020g) being prepared is dissolved into 1mL tetrahydrofurans, is rapidly injected in PBS (10mL),
Ultrasound 10 minutes, stirring at normal temperature 12 hours obtains organic nanometer granule SeBT NPs.Organic nano material SeBT as shown in Figure 1
Dynamic light scattering (DLS) test result of NPs and transmission electron microscope (TEM) figure, as known to Fig. 1, preparation with it is organic
The grain size of nano material is about 70nm, the nano particle of the size can effectively penetration cell film and smoothly enter cell.
3 SeBT of embodiment and SeBT NPs spectrum tests：
1cm wide quartz colorimetric utensils are chosen, add in 3mL SeBT toluene solutions (1 × 10-5M) test its ultra-violet absorption spectrum with
Fluorescence emission spectrum；The quartz colorimetric utensil of 1cm wide is chosen, adds in 3mL SeBT NPs PBS (50 μ g/mL) solution, tests its purple
Outer absorption spectrum and fluorescence emission spectrum.As shown in Fig. 2, SeBT has absorption peak at 825nm, and have at 600-1000nm compared with
Width absorbs, and organic nanometer granule SeBT NPs have absorption maximum at 906nm and have wider absorption at 600-1050nm, light
Spectral limit reaches near infrared region.As shown in figure 3, near-infrared organic semiconductor SeBT and its organic nanometer granule SeBT NPs are glimmering
Optical emission spectroscopy, SeBT launch wavelengths reach near infrared region in 927nm, SeBT NPs launch wavelengths in 1030nm, spectral region
Domain.
4 SeBT NPs photothermal conversion efficiencies of embodiment are tested：
The quartz colorimetric utensil of 1cm wide is chosen, PBS (150 μ g/mL) solution of 2mL SeBT NPs is added in, is swashed using 808nm
Light (0.8W/cm2) illumination, while the variation of record temperature in real time are carried out, when temperature reaches the stabilization sub stage, turn off laser, make
Solution is in temperature-fall period, real-time monitoring temperature.PBS is carried out to the process of same heating cooling.Calculate the light of the reagent
Thermal conversion efficiency.The curve of photo-thermal test as shown in Figure 4, at elevated temperatures, illumination 10 minutes, the PBS of SeBT NPs is molten
The temperature change value of liquid reaches 32 DEG C, and PBS solution heats up 1.6 DEG C under identical condition.
6 SeBT NPs tumour cells in vitro toxicity of embodiment is tested：
This experiment chooses HeLa (cervical cancer cell) cell line and carries out vitro cytotoxicity test, tests its dark poison and laser
Phototoxicity.Specific experiment step is as follows：The PBS solution of the SeBT NPs of 100 μ g/mL, different concentration gradients is made into DMEM
Solution (10,20,30,40 μ g/mL).HeLa cells are seeded on the culture plate in 96 hole of black matrix, are cultivated 24 hours at 37 DEG C
Make its adherent growth, cleaned with PBS solution, be separately added into the 80 μ L of drug (two groups, every group of 5 holes) of above-mentioned various concentration, train
After supporting 24 hours, one group of taking-up, near infrared laser (808nm, 0.8W/cm2) radiate 8 minutes, another group is still protected from light, after
Continuous culture 24 hours adds in MTT colorimetric methods and is measured.20 μ L of MTT (5mg/mL) is taken to be added in cell, in identical environment
After being incubated 4 hours, 200 μ L of DMSO are added in, the absorption that absorption peak is 490nm is measured using Bio-Tek microplates microplate reader
Value.SeBT NPs as shown in Figure 5 are for the toxicity test result of HeLa cells：Light group about under the drug concentration of 20 μ g/mL,
HeLa cell survival rates are 50%；And half-light group, under the drug concentration of 40 μ g/mL, HeLa cell survival rates are more than 90%.It is logical
It crosses control experiment to find, under four various concentration medical conditions, light group cell survival rate is below half-light group.
Photothermal imaging is tested in 7 SeBT NPs bodies of embodiment：
The nude mice using HeLa cells injection oxter is selected as tumor model.Concrete operations are as follows, when gross tumor volume is
200mm3, mouse is divided into two groups, first group of PBS solution (100 μ g/mL) that SeBT NPs are injected by tail vein, second group
Inject pure PBS solution.Laser (808nm, 0.8W/cm are used after 6 hours2) irradiation tumor region, while use near-infrared phase
Machine monitors the temperature change of tumor locus.Per illumination one minute, that is, record the temperature value at neutral position.As in Fig. 6 bodies photo-thermal into
As result shown in, tail vein injection SeBT NPs PBS solutions after, illumination 4 minutes, tumor locus temperature reaches 55 DEG C.And it notes
After penetrating PBS, illumination four minutes, tumor locus temperature only increases three degree.Experiment shows that SeBT NPs can effectively reach tumour
Position, and under laser irradiation, generate heat.
Photo-thermal therapy can be generally divided into hyperthermia and photo-thermal and melt two kinds, hyperthermia refer to tumor region be increased to 42~
Between 46 DEG C, and the ablation of irreversible photo-thermal can lead to tissue necrosis, and the 1s at a temperature of 54 DEG C is organized to be equivalent at 43 DEG C
240min.Photo-thermal therapy is typically to be heated by laser irradiation to tumor tissues, and general irradiation temperature is a few minutes and several ten points
Clock increases tumor tissues temperature.The heat that photo-thermal therapy generates often makes tumour cell that irreversible damage, main table occur
It is now mitochondria swelling, protein inactivation, birefringence are lost, oedema and tissue necrosis, cell membrane are loose and memebrane protein denaturation
Deng.When temperature reaches 55~95 DEG C, several minutes of inner tissue will substantially change.By above-mentioned experiment it is found that the present invention
The SeBT NPs can make tumor locus temperature reach 55 DEG C, so that irreversible damage quickly occurs for tumour cell, the light
The targeted tumour cell type of heat cure is not limited only to above-mentioned cervical cancer cell, effective to other tumour cells.
Phototherapy is tested in 8 SeBT NPs tumour cell bodies of embodiment：
It selects HeLa cells injecting subcutaneous nude mice as tumor model.Concrete operation step is：When gross tumor volume is
200mm3, 15 nude mices are divided into three groups.First group is injected PBS by tail vein, second and third group is injected respectively by tail vein
The PBS solution (100 μ g/mL) of SeBT NPs.After 6 hours, first group and third group mouse carry out near infrared light and shine 8 minutes
(808nm, 0.8W/cm2), and second group of no light, gross tumor volume is measured, weighs mouse weight.The above process repeats 20 days, sees
It examines and records three groups of mouse tumor volumes and (measured within every two days primary) with changes of weight.
Fig. 7 is mouse tumor volume size variation curve, and first group is injection PBS light groups, and the gross tumor volume of mouse exists
It is constantly increasing；Second group is the PBS solution half-light group for injecting SeBT NPs, and gross tumor volume is continuously increased, is compared compared with first group,
Growth is slower；Third group, to inject the PBS solution light group of SeBT NPs, it can be clearly seen that gross tumor volume reduces, until swollen
Knurl disappears.
Fig. 8 be mouse live body treatment Phenotypic Observation as a result, first group be inject PBS light group, mouse tumor volume
It is larger；Second group is the half-light group for injecting SeBT NPs PBS solutions, and tumour is larger to later stage volume；Third group is injection SeBT
The light group of the PBS solution of NPs, it can be seen that tumor disappearance.That is SeBT NPs can effectively inhibit tumour growth by photo-thermal therapy.
Basic principle, main feature and the advantages of the present invention of the present invention has been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (13)
1. a kind of organic semiconductor of near-infrared containing selenium, it is characterised in that this contains selenium near-infrared organic semiconductor and contains the bis- (4- of 4,7-
Hexyl thiophene -2- bases) -6- thio -2, the double selenium diazole of 1,3- benzo, the compound is with structure shown in below formula：
Wherein：
2. a kind of organic nano material SeBT NPs being prepared by the above-mentioned organic semiconductor of near-infrared containing selenium.
3. the organic semiconductor of near-infrared containing selenium according to claim 1, it is characterised in that the near-infrared containing selenium organic half
Conductor can cooperate with photo-thermal, light power double mode treatment tumour.
4. a kind of prepare the organic semi-conductor method of near-infrared containing selenium as described in claim 1, reaction route is as follows：
Reaction condition is：
(1) trifluoromethane sulfonic acid and fuming nitric aicd stir at -5-0 DEG C, add in 4,7- dibromo diazosulfides, and heating stirring obtains
To 4,7-, bis- bromo- 5,6- dinitros diazosulfides, i.e. product 4；
(2) under nitrogen protection, product 4 is dissolved in tetrahydrofuran, by tributyl (4- hexyl thiophene -2- bases) stannane, [1,
Bis- (diphenylphosphino) ferrocene of 1'-] palladium chloride added in above-mentioned solution, and heating stirring purifies to obtain bis- (the 4- hexyls of 4,7-
Thiophene -2- bases) -5,6- dinitro diazosulfides, i.e. product 5；
(3) under nitrogen protection, product 5 is dissolved in acetic acid, adds in iron powder, heating stirring purifies to obtain bis- (the 4- hexyls of 4,7-
Thiophene -2- bases) diazosulfide -5,6- diamines, i.e. product 6；
(4) under nitrogen protection, product 6 dissolves in ethanol, adds in selenium dioxide, heating stirring purify to obtain 4,7- it is bis- (4- oneself
Base thiophene -2- bases) -6- thio -2, the double selenium diazole of 1,3- benzo, i.e. SeBT.
5. a kind of method for preparing organic nano material SeBT NPs as claimed in claim 2, reaction route are：
SeBT is dissolved in tetrahydrofuran, is rapidly injected in PBS, after ultrasonic reaction, stirring removes tetrahydrofuran, obtains above-mentioned
Organic nano material SeBT NPs.
6. the organic semi-conductor of near-infrared containing selenium preparation method according to claim 4, which is characterized in that step (1) institute
The molar ratio for stating trifluoromethane sulfonic acid and fuming nitric aicd is 1:(1.0-2.0)；The 4,7- dibromos diazosulfide and smoke nitre
The molar ratio of acid is 1:(2.0-10.0).
7. the organic semi-conductor of near-infrared containing selenium preparation method according to claim 4, which is characterized in that step (2) institute
The molar ratio for stating bis- bromo- 5,6- dinitros diazosulfides of 4,7- and tributyl (4- hexyl thiophene -2- bases) stannane is 1:(1.0-
2.0)；The bis- bromo- 5,6- dinitros diazosulfides of 4,7- and [bis- (diphenylphosphino) ferrocene of 1,1'-] palladium chloride
Molar ratio is 1:(0.03-0.1).
8. the organic semi-conductor of near-infrared containing selenium preparation method according to claim 4, which is characterized in that step (3) institute
The molar ratio for stating bis- (4- hexyl thiophene -2- the bases) -5,6- dinitros diazosulfides of 4,7- and iron powder is 1:(6-15)；Step
(4) molar ratio of bis- (4- hexyl thiophene -2- bases) diazosulfide -5,6- diamines of the 4,7- and selenium dioxide is 1:(1-2).
9. the organic semi-conductor of near-infrared containing selenium preparation method according to claim 4, which is characterized in that step (1) institute
30-60 DEG C of heating temperature is stated, the heating stirring time is 24-48 hours；Step (2) 50-100 DEG C of the heating temperature, heating is stirred
It is 12-24 hours to mix the time；Step (3) the heating stirring temperature is 50-100 DEG C, and the heating stirring time is 6-24 hours；Step
Suddenly 50-90 DEG C of (4) described whipping temp, heating stirring time are 10-24 hours.
10. the organic semi-conductor of near-infrared containing selenium preparation method according to claim 4, which is characterized in that step (5) institute
SeBT a concentration of 0.1-0.5 mg/mls in tetrahydrofuran are stated, quick mixing speed is 500-1500 revs/min.
11. the organic semiconductor of near-infrared containing selenium according to claim 1, it is characterised in that the near-infrared containing selenium organic half
Conductor dissolves in organic solvent.
12. a kind of application of organic semiconductor of near-infrared containing selenium in terms of oncotherapy reagent is prepared described in claim 1.
13. applications of the organic nano material SeBT NPs described in claim 2 in terms of oncotherapy reagent is prepared.
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Application publication date: 20180608 |
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