CN107177355A - The conjugate oligomeric thing of superelevation fluorescence quantum yield and the preparation method of silica fluorescent composite nanoparticle - Google Patents
The conjugate oligomeric thing of superelevation fluorescence quantum yield and the preparation method of silica fluorescent composite nanoparticle Download PDFInfo
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- CN107177355A CN107177355A CN201710342142.XA CN201710342142A CN107177355A CN 107177355 A CN107177355 A CN 107177355A CN 201710342142 A CN201710342142 A CN 201710342142A CN 107177355 A CN107177355 A CN 107177355A
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- quantum yield
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000002131 composite material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000006862 quantum yield reaction Methods 0.000 title claims abstract description 21
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910000077 silane Inorganic materials 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 10
- 239000000839 emulsion Substances 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 5
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 150000004678 hydrides Chemical class 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- -1 chloro, methoxyl group Chemical group 0.000 claims description 15
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- 239000002585 base Substances 0.000 claims description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 8
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 229940125904 compound 1 Drugs 0.000 claims description 5
- 229940126214 compound 3 Drugs 0.000 claims description 5
- 238000007872 degassing Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- 125000001246 bromo group Chemical group Br* 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 229940125782 compound 2 Drugs 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- LQQKFGSPUYTIRB-UHFFFAOYSA-N 9,9-dihexylfluorene Chemical class C1=CC=C2C(CCCCCC)(CCCCCC)C3=CC=CC=C3C2=C1 LQQKFGSPUYTIRB-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 2
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 229920001214 Polysorbate 60 Polymers 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- BTKXSYWWRGMQHR-UHFFFAOYSA-N [amino(diethoxy)silyl]oxyethane Chemical compound CCO[Si](N)(OCC)OCC BTKXSYWWRGMQHR-UHFFFAOYSA-N 0.000 claims description 2
- 239000003377 acid catalyst Substances 0.000 claims description 2
- 238000007259 addition reaction Methods 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 229940125898 compound 5 Drugs 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 2
- 150000002220 fluorenes Chemical class 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 150000002390 heteroarenes Chemical class 0.000 claims description 2
- 125000001072 heteroaryl group Chemical group 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 claims description 2
- 229960003493 octyltriethoxysilane Drugs 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims description 2
- 229920000136 polysorbate Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- WQQPDTLGLVLNOH-UHFFFAOYSA-M sodium;4-hydroxy-4-oxo-3-sulfobutanoate Chemical class [Na+].OC(=O)CC(C([O-])=O)S(O)(=O)=O WQQPDTLGLVLNOH-UHFFFAOYSA-M 0.000 claims description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims 2
- RZYKUPXRYIOEME-UHFFFAOYSA-N CCCCCCCCCCCC[S] Chemical compound CCCCCCCCCCCC[S] RZYKUPXRYIOEME-UHFFFAOYSA-N 0.000 claims 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims 1
- 241000790917 Dioxys <bee> Species 0.000 claims 1
- GORXRFCHPRVABO-UHFFFAOYSA-N O(C)[SiH](OC)OC.C=C Chemical compound O(C)[SiH](OC)OC.C=C GORXRFCHPRVABO-UHFFFAOYSA-N 0.000 claims 1
- 210000000481 breast Anatomy 0.000 claims 1
- SXGBREZGMJVYRL-UHFFFAOYSA-N butan-1-amine;hydrobromide Chemical compound [Br-].CCCC[NH3+] SXGBREZGMJVYRL-UHFFFAOYSA-N 0.000 claims 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 claims 1
- 229910000029 sodium carbonate Inorganic materials 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 238000003384 imaging method Methods 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- 239000002904 solvent Substances 0.000 description 10
- 229910052786 argon Inorganic materials 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000002027 dichloromethane extract Substances 0.000 description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- ABRVLXLNVJHDRQ-UHFFFAOYSA-N [2-pyridin-3-yl-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound FC(C1=CC(=CC(=N1)C=1C=NC=CC=1)CN)(F)F ABRVLXLNVJHDRQ-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
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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
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1876—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-C linkages
-
- 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
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
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Abstract
The invention belongs to fluorescent composite nanoparticle field, it is related to the preparation method of a kind of conjugate oligomeric thing of superelevation fluorescence quantum yield and silica fluorescent composite nanoparticle.The fluorescent composite nanoparticle is prepared from using the method for reversed-phase emulsion, it is first that the progress of conjugate oligomeric thing is hydride modified, and it is mixed with silane reagent, it is added to inverse emulsion system, using acid or alkali as catalyst, centrifuge washing obtains fluorescent composite nanoparticle after the completion of reaction.Fluorescent composite nanoparticle prepared by the present invention overcomes the existing low shortcoming of fluorescent nano particles quantum yield, with superelevation fluorescence quantum yield, excellent stability and biocompatibility, there is good application prospect in fields such as cell imaging, print development, fluorescent tracing, sensing detection, biological medicines.
Description
Technical field
The invention belongs to fluorescent composite nanoparticle field, and in particular to a kind of conjugate oligomeric of superelevation fluorescence quantum yield
The preparation method of thing and silica fluorescent composite nanoparticle.
Background technology
Conventional fluorescent chromophore is generally the rigid plane molecule with pi-conjugated system, there is higher fluorescence in weak solution
Quantum yield, but fluorescent weakening does not light even in the collected state, i.e. aggregation result in fluorescent quenching.Cause this phenomenon
Main cause be that intermolecular interaction result in non-radiative energy conversion or form the species for being unfavorable for fluorescent emission.
Organic fluorescence molecule is prepared after turning into nano-particle can occur aggregation and be quenched mostly, thus cause its fluorescence quantum yield to reduce and
Reduce its use value.
To solve the above problems, proposing the organic/inorganic composite Nano of conjugate oligomeric thing covalence graft to silica
Particle.Nano particles of silicon dioxide is frequently used for life science, and size conveniently regulating and controlling, surface can be internal with function dough
Available for encapsulating other materials, and show low-down cytotoxicity.In fluorescent composite nanoparticle system, silica
As the matrix dispersion that physical chemistry is stable, the distance between increase conjugate oligomeric thing reduces aggregation and is quenched, and protects fluorescence
Group is not disturbed by extraneous factor, so that system has the fluorescence quantum yield of excellent stability and superelevation.Cause
This, disperses fluorescence molecule using the silica of high stable hypotoxicity, and the raising to fluorescence quantum yield is significant.
The content of the invention
In order to solve the above problems, the present invention provides a kind of the conjugate oligomeric thing and silica of superelevation fluorescence quantum yield
The preparation method of fluorescent composite nanoparticle, the preparation method first conjugate oligomeric thing is carried out it is hydride modified, and by itself and silicon
Alkane reagent is mixed, and is added to inverse emulsion system, and using acid or alkali as catalyst, centrifuge washing obtains fluorescence after the completion of reaction
Composite nanoparticle；
Further, the preparation method specifically includes following steps：
1. conjugate oligomeric thing fluorene kind derivative shown in synthesis type 1：
2. the conjugate oligomeric thing of step 1. is dissolved in organic solvent；
3. by step, 2. solution is well mixed according to a certain percentage with silane reagent；
4. nano-particle is prepared using the method for reversed-phase emulsion, organic solvent, surface is sequentially added into round-bottomed flask and is lived
Property agent, deionized water, be stirring evenly and then adding into the mixed solution of step 3., add catalyst, react certain time；
5. organic solvent is added into step reaction solution 4. and is stirred certain time, centrifuge washing obtains high fluorescent quantum
The fluorescent composite nanoparticle of yield；
Further, in the formula 1, the scope of n values is 1-12；R1、R2、R3It can be the same or different, can be chlorine
Base, methoxyl group, ethyoxyl, methoxy ethoxy, trimethylsiloxy group or ester group；In formula 1 (a), Ar1It is hexa-atomic aromatic ring, six
Hetero-aromatic ring, five yuan of heteroaromatics, fluorenes class, biphenyl, polycyclic aromatic hydrocarbon, alkene and one kind or several in the structural derivative of member
Kind；In formula 1 (b), Ar2And Ar3The group and Ar of representative1It is identical, Ar2And Ar3Both can be the same or different；
Further, step 1. described compound for shown in formula 2：
Wherein, Ar1For 9,9- dihexyl fluorenes, n is 1, R1、R2、R3It is methoxyl group；
Further, the preparation method of step 1. described (a), (b) two class conjugate oligomeric thing fluorene kind derivative, it passes through
Following reaction is carried out
Wherein, n, Ar1、Ar2、R1、R2、R3It is identical with defined in formula 1, in second step coupling reaction is carried out, compound 1
In bromo can be exchanged with the boric acid ester group in compound 2, the boric acid ester group in the bromo in compound 4 and compound 5
It can exchange；
Further, compound 1 and 4 is under potassium hydroxide aqueous solution, TBAB existence condition 70~100
Heating is obtained for 5~30 minutes at DEG C；Compound 3 and 6 is the reaction dissolvent choosing in the presence of the catalysis of palladium catalyst and alkali
From the one or more and degassing potassium carbonate or carbonic acid in the organic solvents such as degassed toluene, dimethylformamide, dimethyl sulfoxide (DMSO)
Sodium water solution, 75~100 DEG C of heating are obtained；Conjugate oligomeric thing (a), (b) are that compound 3, compound 6 exist with silane reagent respectively
Platinum or gold make catalyst and obtained by Si―H addition reaction；
Further, step 2. in：Described organic solvent can for n-hexane, hexamethylene, toluene, dimethylbenzene, n-hexyl alcohol,
N-butanol, normal propyl alcohol, isopropanol, ethanol, methanol, tetrahydrofuran, dioxane, ether, dimethylformamide, dimethyl are sub-
One or more in sulfone, dichloromethane, chloroform, water；Described certain proportion is 1:1~1:10000；
Further, step 3. described in silane reagent be tetraethoxysilane, tetramethoxy-silicane, ethene trimethoxy
Base silane, propyl trimethoxy silicane, octyltri-ethoxysilane, sodium metasilicate, amino triethoxysilane or sulfydryl trimethoxy
Base silane；
Further, step 4. in：Described organic solvent can be hexamethylene, n-hexane, heptane, octane, nonane, the last of the ten Heavenly stems
Alkane, isooctane, carbon tetrachloride, benzene, hexamethylene, atoleine, toluene, dimethylbenzene, n-hexyl alcohol, n-butanol, normal propyl alcohol, isopropyl
One or more in alcohol, ethanol, methanol, tetrahydrofuran, ether, dichloromethane, chloroform；Described surfactant is
Two (2- ethylhexyls) sodium sulfosuccinates, lauryl sodium sulfate, dodecyl sodium sulfate, cetyl trimethyl bromination
Ammonium, Value 3608, methyl tricapryl ammonium chloride, PVP, polyvinyl alcohol, polyoxyethylene,
Polyoxyethylene sorbitan fatty acid ester (tween) or sorbitan fatty acid ester (sapn)；Described catalyst for acid or
Base catalyst, wherein acid catalyst include acetate and hydrochloride, and base catalyst includes ammoniacal liquor and sodium hydroxide；Described certain time
For 1~48 hour；
Further, step 5. in：Described organic solvent is acetone, butanone, chloroform, dichloromethane, tetrahydrochysene furan
Mutter or ether etc.；Described certain time is 1~20 minute；Described superelevation fluorescence quantum yield is more than 80%；
Beneficial effects of the present invention are as follows：
1) by making it to introduce Nano particles of silicon dioxide by covalent bond to the progress of conjugate oligomeric thing is hydride modified,
The ratio of silane reagent and silane-modified conjugate oligomeric thing is adjusted, the fluorescence that obtained fluorescence quantum yield reaches as high as 98% is answered
Nano-particle is closed, the fluorescence quantum yield of conjugate oligomeric thing is effectively raised；
2) preparation method is simple to operate, and Nano particles of silicon dioxide improves the stability of photoluminescence of fluorophor, and raw
Thing compatibility is preferable；
3) fluorescent composite nanoparticle is in cell imaging, print development, fluorescent tracing, sensing detection, biological medicine etc.
Field has wide practical use.
Brief description of the drawings
Fig. 1 is the conjugate oligomeric thing and silica fluorescent composite nanoparticle of superelevation fluorescence quantum yield in the present invention
Transmission electron microscope picture.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is explained in further detail.It should be appreciated that specific embodiment described herein is used only for explaining the present invention, and
It is not used in the restriction present invention.On the contrary, the present invention cover it is any be defined by the claims the present invention spirit and scope on do
Replacement, modification, equivalent method and scheme.Further, in order that the public has a better understanding to the present invention, below to this
It is detailed to describe some specific detail sections in the detailed description of invention.It is thin without these for a person skilled in the art
The description of section part can also understand the present invention completely.
The invention will be further described with specific embodiment below in conjunction with the accompanying drawings, but not as a limitation of the invention.
Below most preferred embodiment is enumerated for the present invention：
Embodiment 1
1. the fluorescence conjugated oligomer OPF-Si-1 that synthesizing silane is modified, it is as follows：
Compound 1-1 synthesis：2- bromines fluorenes (5.07g, 20.67mmol), TBAB (1.31g, 4.1mmol) and
50% potassium hydroxide (41.3mL) is added in allyl bromide, bromoallylene (25g, 206.65mmol), and 75 DEG C are heated 15 minutes, and cooling adds water
Extracted three times with dichloromethane, after organic layer anhydrous sodium sulfate drying, remove solvent, obtained solid is purified with column chromatography
Obtain compound 1-1.
Compound 1-3 synthesis：Compound 1 (2.33g, 7.16mmol), compound 2 are added in 50mL round-bottomed flasks
(2.14g, 2.87mmol), tetrakis triphenylphosphine palladium (656 mg, 0.52mmol), tetra-n-butyl ammonium bromide (160mg,
0.52mmol), argon gas is protected 10 minutes, degassed toluene 48mL and 2mol/L degassing solution of potassium carbonate 12mL is added, by taking out
Vacuum/applying argon gas repeatedly for three times after, be raised to 85 DEG C react 48 hours, cooling, add water with dichloromethane extract three times, organic layer
After anhydrous sodium sulfate drying, solvent is removed, obtained solid column chromatography purification obtains compound 1-3.
Conjugate oligomeric thing OPF-Si-1 synthesis：Compound 3 (1.89g) is dissolved in chloroform, adds the ethanol of trimethylamine
Solution (30wt%, 5mL), is stirred 48 hours at room temperature, vacuum drying removing solvent, obtained product (0.70g,
0.745mmol) be added in the anhydrous chloroforms of 50mL, cross vacuumize/applying argon gas repeatedly for three times after, add trimethoxy
Base silane (0.77mL, 6.05mmol) and catalyst platinum (0) -1,3- divinyls -1,1,3,3- tetramethyl disiloxanes, 60 DEG C
Lower reaction 12 hours, is removed in vacuum solvent and excessive trimethoxy silane, obtains OPF-Si-1.
2. OPF-Si-1 is dissolved in chloroform, concentration is 5mg/mL；
3. by 64 μ L steps, 2. solution is well mixed with 100 μ L tetraethoxysilanes, silane-modified conjugate oligomeric thing with
The mol ratio of tetraethoxysilane is 1:2000；
4. fluorescent composite nanoparticle is prepared using the method for reversed-phase emulsion, hexamethylene is sequentially added into round-bottomed flask
7.6mL, n-hexyl alcohol 1.8mL, Value 3608 1.8 mL, deionized water 0.48mL, at room temperature strong stirring 10
Minute, the mixed solution of step 3. is added dropwise after stirring, then the ammonia that 100 μ L mass fractions are 25~28% is added dropwise
Water reacts 24 hours at room temperature as catalyst.
5. 6mL acetone is added into step reaction solution 4. and is stirred 10 minutes, centrifuge washing obtains fluorescence quantum yield
Fluorescent composite nanoparticle higher than 90%.
Embodiment 2
1. the fluorescence conjugated oligomer OPF-Si-2 that synthesizing silane is modified, it is as follows：
Compound 2-1 synthesis：2- bromines fluorenes (5.07g, 20.67mmol), TBAB (1.31g, 4.1mmol) and
50% potassium hydroxide (41.3mL) is added in allyl bromide, bromoallylene (25g, 206.65mmol), and 75 DEG C are heated 15 minutes, and cooling adds water
Extracted three times with dichloromethane, after organic layer anhydrous sodium sulfate drying, remove solvent, obtained solid is purified with column chromatography
Obtain compound 2-1.
Compound 2-3 synthesis：Compound 2-1 (2.33 g, 7.16mmol), compound are added in 50mL round-bottomed flasks
2-2 (1.11g, 2.87mmol), tetrakis triphenylphosphine palladium (656mg, 0.52mmol), tetra-n-butyl ammonium bromide (160mg,
0.52mmol), argon gas is protected 10 minutes, degassed toluene 48mL and 2mol/L degassing solution of potassium carbonate 12mL is added, by taking out
Vacuum/applying argon gas repeatedly for three times after, be raised to 85 DEG C react 48 hours, cooling, add water with dichloromethane extract three times, it is organic
After layer anhydrous sodium sulfate drying, solvent is removed, obtained solid column chromatography purification obtains compound 2-3.
Conjugate oligomeric thing OPF-Si-2 synthesis：It is anhydrous that compound 2-3 (0.47g, 0.745mmol) is added to 50mL
In chloroform, cross vacuumize/applying argon gas repeatedly for three times after, add trimethoxy silane and (0.77mL, 6.05mmol) and urge
Agent platinum (0) -1,3- divinyls -1,1,3,3- tetramethyl disiloxanes react 12 hours at 60 DEG C, solvent and mistake are removed in vacuum
The trimethoxy silane of amount, obtains OPF-Si-2.
2. OPF-Si-2 is dissolved in chloroform, concentration is 5mg/mL；
3. by 32 μ L steps, 2. solution is well mixed with 100 μ L tetraethoxysilanes, silane-modified conjugate oligomeric thing with
The mol ratio of tetraethoxysilane is 1:3000；
4. fluorescent composite nanoparticle is prepared using the method for reversed-phase emulsion, hexamethylene is sequentially added into round-bottomed flask
7.6mL, n-hexyl alcohol 1.8mL, Value 3608 1.8 mL, deionized water 0.48mL, at room temperature strong stirring 10
Minute, the mixed solution of step 3. is added dropwise after stirring, then the ammonia that 100 μ L mass fractions are 25~28% is added dropwise
Water reacts 24 hours at room temperature as catalyst.
5. 6mL acetone is added into step reaction solution 4. and is stirred 10 minutes, centrifuge washing obtains fluorescence quantum yield
Fluorescent composite nanoparticle higher than 80%.
Embodiment 3
1. the fluorescence conjugated oligomer OPF-Si-3 that synthesizing silane is modified, it is as follows：
Compound 3-1 synthesis：2- bromines fluorenes (5.07g, 20.67mmol), TBAB (1.31g, 4.1mmol) and
50% potassium hydroxide (41.3mL) is added in allyl bromide, bromoallylene (25g, 206.65mmol), and 75 DEG C are heated 15 minutes, and cooling adds water
Extracted three times with dichloromethane, after organic layer anhydrous sodium sulfate drying, remove solvent, obtained solid is purified with column chromatography
Obtain compound 3-1.
Compound 3-3 synthesis：Compound 3-1 (2.33 g, 7.16mmol), compound are added in 50mL round-bottomed flasks
3-2 (2.14g, 2.87mmol), tetrakis triphenylphosphine palladium (656mg, 0.52mmol), tetra-n-butyl ammonium bromide (160mg,
0.52mmol), argon gas is protected 10 minutes, degassed toluene 48mL and 2mol/L degassing solution of potassium carbonate 12mL is added, by taking out
Vacuum/applying argon gas repeatedly for three times after, be raised to 85 DEG C react 48 hours, cooling, add water with dichloromethane extract three times, it is organic
After layer anhydrous sodium sulfate drying, solvent is removed, obtained solid column chromatography purification obtains compound 3-3.
Conjugate oligomeric thing OPF-Si-3 synthesis：It is anhydrous that compound 3-3 (0.61g, 0.745mmol) is added to 50mL
In chloroform, cross vacuumize/applying argon gas repeatedly for three times after, add trimethoxy silane and (0.77mL, 6.05mmol) and urge
Agent platinum (0) -1,3- divinyls -1,1,3,3- tetramethyl disiloxanes react 12 hours at 60 DEG C, solvent and mistake are removed in vacuum
The trimethoxy silane of amount, obtains OPF-Si-3.
2. OPF-Si-3 is dissolved in chloroform, concentration is 5mg/mL；
3. by 29 μ L steps, 2. solution is well mixed with 100 μ L tetraethoxysilanes, silane-modified conjugate oligomeric thing with
The mol ratio of tetraethoxysilane is 1:4000；
4. fluorescent composite nanoparticle is prepared using the method for reversed-phase emulsion, hexamethylene is sequentially added into round-bottomed flask
7.6mL, n-hexyl alcohol 1.8mL, Value 3608 1.8 mL, deionized water 0.48mL, at room temperature strong stirring 10
Minute, the mixed solution of step 3. is added dropwise after stirring, then the ammonia that 100 μ L mass fractions are 25~28% is added dropwise
Water reacts 24 hours at room temperature as catalyst.
5. 6mL acetone is added into step reaction solution 4. and is stirred 10 minutes, centrifuge washing obtains fluorescence quantum yield
Fluorescent composite nanoparticle higher than 90%.
One kind of embodiment described above, simply more preferably embodiment of the invention, those skilled in the art
The usual variations and alternatives that member is carried out in the range of technical solution of the present invention all should be comprising within the scope of the present invention.
Claims (10)
1. the preparation method of the conjugate oligomeric thing of superelevation fluorescence quantum yield and silica fluorescent composite nanoparticle, its feature
It is, the preparation method is first hydride modified by the progress of conjugate oligomeric thing, and it is mixed with silane reagent, is added to anti-phase breast
Liquid system, using acid or alkali as catalyst, centrifuge washing obtains fluorescent composite nanoparticle after the completion of reaction.
2. preparation method according to claim 1, it is characterised in that the preparation method specifically includes following steps：
1. conjugate oligomeric thing fluorene kind derivative shown in synthesis type 1：
2. the conjugate oligomeric thing of step 1. is dissolved in organic solvent；
3. by step, 2. solution is well mixed according to a certain percentage with silane reagent；
4. nano-particle is prepared using the method for reversed-phase emulsion, sequentially added into round-bottomed flask organic solvent, surfactant,
Deionized water, is stirring evenly and then adding into the mixed solution of step 3., adds catalyst, reacts certain time；
5. organic solvent is added into step reaction solution 4. and is stirred certain time, centrifuge washing obtains high-fluorescence quantum yield
Fluorescent composite nanoparticle.
3. preparation method according to claim 2, it is characterised in that in the formula 1, the scope of n values is 1-12；R1、R2、
R3It can be the same or different, can be chloro, methoxyl group, ethyoxyl, methoxy ethoxy, trimethylsiloxy group or ester
Base；In formula 1 (a), Ar1It is hexa-atomic aromatic ring, hexa-atomic hetero-aromatic ring, five yuan of heteroaromatics, fluorenes class, biphenyl, polycyclic aromatic hydrocarbon, alkene
And the one or more in the structural derivative；In formula 1 (b), Ar2And Ar3The group and Ar of representative1It is identical, Ar2And Ar3Two
Person can be the same or different.
4. preparation method according to claim 2, it is characterised in that step 1. described compound for shown in formula 2：
Wherein, Ar1For 9,9- dihexyl fluorenes, n is 1, R1、R2、R3It is methoxyl group.
5. preparation method according to claim 3, it is characterised in that step 1. described (a), (b) two class conjugate oligomeric
The preparation method of thing fluorene kind derivative, it is carried out by following reaction：
Wherein, n, Ar1、Ar2、R1、R2、R3It is identical with defined in formula 1, in second step coupling reaction is carried out, in compound 1
Bromo can be exchanged with the boric acid ester group in compound 2, and the bromo in compound 4 can also with the boric acid ester group in compound 5
Exchange.
6. preparation method according to claim 5, it is characterised in that compound 1 and 4 is in potassium hydroxide aqueous solution, four
Under butylammonium bromide existence condition, heating is obtained for 5~30 minutes at 70~100 DEG C；Compound 3 and 6 be palladium catalyst with
And in the presence of the catalysis of alkali, reaction dissolvent is in the organic solvents such as degassed toluene, dimethylformamide, dimethyl sulfoxide (DMSO)
One or more of and degassing potassium carbonate or aqueous sodium carbonate, 75~100 DEG C of heating are obtained；Conjugate oligomeric thing (a), (b) are point
Other compound 3, compound 6 are made catalyst in platinum or gold with silane reagent and obtained by Si―H addition reaction.
7. preparation method according to claim 2, it is characterised in that step 2. in：Described organic solvent can for just oneself
Alkane, hexamethylene, toluene, dimethylbenzene, n-hexyl alcohol, n-butanol, normal propyl alcohol, isopropanol, ethanol, methanol, tetrahydrofuran, dioxy six
One or more in ring, ether, dimethylformamide, dimethyl sulfoxide (DMSO), dichloromethane, chloroform, water；Described is certain
Ratio is 1:1~1:10000.
8. preparation method according to claim 2, it is characterised in that step 3. described in silane reagent be tetraethoxy
Silane, tetramethoxy-silicane, ethene trimethoxy silane, propyl trimethoxy silicane, octyltri-ethoxysilane, sodium metasilicate,
Amino triethoxysilane or sulfydryl trimethoxy silane.
9. preparation method according to claim 2, it is characterised in that step 4. in：Described organic solvent can be hexamethylene
Alkane, n-hexane, heptane, octane, nonane, decane, isooctane, carbon tetrachloride, benzene, hexamethylene, atoleine, toluene, dimethylbenzene,
One kind in n-hexyl alcohol, n-butanol, normal propyl alcohol, isopropanol, ethanol, methanol, tetrahydrofuran, ether, dichloromethane, chloroform
Or it is several；Described surfactant is two (2- ethylhexyls) sodium sulfosuccinates, lauryl sodium sulfate, dodecyl sulphur
Sour sodium, cetyl trimethylammonium bromide, Value 3608, methyl tricapryl ammonium chloride, polyvinylpyrrolidine
Alkanone, polyvinyl alcohol, polyoxyethylene, polyoxyethylene sorbitan fatty acid ester (tween) or sorbitan fatty acid ester
(sapn)；Described catalyst is acid or base catalyst, and wherein acid catalyst includes acetate and hydrochloride, and base catalyst includes ammoniacal liquor
And sodium hydroxide；Described certain time is 1~48 hour.
10. preparation method according to claim 2, it is characterised in that step 5. in：Described organic solvent be acetone,
Butanone, chloroform, dichloromethane, tetrahydrofuran or ether etc.；Described certain time is 1~20 minute；Described superelevation
Fluorescence quantum yield is more than 80%.
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