CN114907549B - Hyperbranched conjugated polymer, preparation method thereof and application of hyperbranched conjugated polymer as photosensitizer - Google Patents
Hyperbranched conjugated polymer, preparation method thereof and application of hyperbranched conjugated polymer as photosensitizer Download PDFInfo
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- CN114907549B CN114907549B CN202210393778.8A CN202210393778A CN114907549B CN 114907549 B CN114907549 B CN 114907549B CN 202210393778 A CN202210393778 A CN 202210393778A CN 114907549 B CN114907549 B CN 114907549B
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- 229920000547 conjugated polymer Polymers 0.000 title claims abstract description 57
- 239000003504 photosensitizing agent Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 238000002428 photodynamic therapy Methods 0.000 claims abstract description 8
- JUFYHUWBLXKCJM-UHFFFAOYSA-N 2,6-dibromoanthracene-9,10-dione Chemical compound BrC1=CC=C2C(=O)C3=CC(Br)=CC=C3C(=O)C2=C1 JUFYHUWBLXKCJM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000007983 Tris buffer Substances 0.000 claims abstract description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 7
- 150000001412 amines Chemical class 0.000 claims abstract description 6
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 6
- 230000001699 photocatalysis Effects 0.000 claims abstract description 6
- 239000010865 sewage Substances 0.000 claims abstract description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 14
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 12
- 229910052763 palladium Inorganic materials 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000003446 ligand Substances 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 6
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000975 dye Substances 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 4
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 3
- 150000004056 anthraquinones Chemical class 0.000 claims description 3
- 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 claims description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 claims description 3
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 claims description 3
- KPZYAGQLBFUTMA-UHFFFAOYSA-K tripotassium;phosphate;trihydrate Chemical compound O.O.O.[K+].[K+].[K+].[O-]P([O-])([O-])=O KPZYAGQLBFUTMA-UHFFFAOYSA-K 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 2
- 229920005603 alternating copolymer Polymers 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 9
- 239000001301 oxygen Substances 0.000 abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 abstract description 9
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 8
- -1 superoxide anion free radical Chemical class 0.000 abstract description 7
- 238000005286 illumination Methods 0.000 abstract description 6
- 229920000587 hyperbranched polymer Polymers 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 15
- 238000005481 NMR spectroscopy Methods 0.000 description 10
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 5
- 230000005284 excitation Effects 0.000 description 5
- 206010028980 Neoplasm Diseases 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000006069 Suzuki reaction reaction Methods 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical compound CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000002165 photosensitisation Effects 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 2
- UKSZBOKPHAQOMP-SVLSSHOZSA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 UKSZBOKPHAQOMP-SVLSSHOZSA-N 0.000 description 1
- ORPNDFMZTDVBGA-UHFFFAOYSA-N (2-methoxyphenyl)phosphane Chemical compound COC1=CC=CC=C1P ORPNDFMZTDVBGA-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- WTAPZWXVSZMMDG-UHFFFAOYSA-N 1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].C=1C=CC=CC=1C=CC(=O)C=CC1=CC=CC=C1 WTAPZWXVSZMMDG-UHFFFAOYSA-N 0.000 description 1
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002512 chemotherapy Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- ZOCHARZZJNPSEU-UHFFFAOYSA-N diboron Chemical compound B#B ZOCHARZZJNPSEU-UHFFFAOYSA-N 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000003642 reactive oxygen metabolite Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- VRLDDYIKZCBFEZ-UHFFFAOYSA-N trimethoxy(phenyl)phosphanium Chemical compound CO[P+](OC)(OC)C1=CC=CC=C1 VRLDDYIKZCBFEZ-UHFFFAOYSA-N 0.000 description 1
- 210000004881 tumor cell Anatomy 0.000 description 1
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- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
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- C08G83/005—Hyperbranched macromolecules
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Abstract
The invention belongs to the technical field of photosensitizers, and discloses a hyperbranched conjugated polymer, a preparation method thereof and application thereof as a photosensitizer, wherein tris (4- (4, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) phenyl) amine and 2, 6-dibromoanthraquinone are used as raw materials, and the target hyperbranched polymer is synthesized through Suzuki polymerization. The hyperbranched conjugated polymer provided by the invention has excellent photosensitive performance, can efficiently generate various active oxygen with strong oxidability including singlet oxygen, superoxide anion free radical, hydroxyl free radical and the like under illumination, and can be used as a photosensitizer material in the fields of photodynamic therapy, photocatalytic oxidation reaction, sewage treatment, organic dye and the like.
Description
Technical Field
The invention belongs to the technical field of photosensitizers, and particularly relates to a hyperbranched conjugated polymer, a preparation method thereof and application of the hyperbranched conjugated polymer as a photosensitizer.
Background
Photosensitizers are substances capable of absorbing light with specific wavelength and further inducing a series of photochemical reactions, and are widely applied to the fields of photodynamic therapy, photocatalytic oxidation reaction, sewage treatment, organic dyes and the like. Taking photodynamic therapy of tumors as an example: when a tumor site is irradiated with light of a specific wavelength, a photosensitizer accumulated in tumor tissue is excited to an excited state, and then energy is transferred to surrounding oxygen to generate active oxygen with strong oxidizing ability to oxidize nearby biomacromolecules, generate cytotoxicity and thus kill tumor cells. Compared with the traditional cancer treatment means (operation treatment, radiation treatment and chemotherapy), photodynamic therapy has the advantages of high spatial selectivity, small side effect, no invasiveness and the like, and has attracted great attention in recent years. Active oxygen (including superoxide anion radical, hydroxyl radical, singlet oxygen, etc., wherein a photosensitizer capable of generating superoxide anion radical, hydroxyl radical, etc. under illumination is referred to as a type I photosensitizer, and a photosensitizer capable of generating singlet oxygen under illumination is referred to as a type II photosensitizer) production efficiency under illumination is an important indicator for characterizing the quality of the photosensitizer. How to increase the active oxygen production efficiency is a major research focus in the field.
Hyperbranched polymers are highly branched polymers with three-dimensional ellipsoidal structures, and generally have the advantages of low viscosity, difficult inter-chain entanglement, good solubility, a large number of terminal functional groups, easy further modification and the like. In recent years, functionalized hyperbranched polymers and their use have become a hotspot in the field of polymer research. Currently, hyperbranched polymers have been widely used in conductive polymers, light emitting diodes, drug delivery, chemical sensors, and the like.
Disclosure of Invention
The invention aims to widen a design method of a photosensitizer material, provides a hyperbranched conjugated polymer, a preparation method thereof and application of the hyperbranched conjugated polymer as a photosensitizer, innovatively uses the hyperbranched conjugated polymer for designing the photosensitizer, and can simultaneously and efficiently generate superoxide anion free radicals, hydroxyl free radicals and singlet oxygen under illumination.
In order to solve the technical problems, the invention is realized by the following technical scheme:
according to one aspect of the present invention, there is provided a hyperbranched conjugated polymer having the structure shown below:
wherein n is the number of repeated units, and the value is a positive integer.
Further, the hyperbranched conjugated polymer takes triphenylamine as an electron donor, anthraquinone as an electron acceptor, and the hyperbranched conjugated polymer passes through A 3 +B 2 And polymerizing in a mode.
According to another aspect of the present invention, there is provided a method for preparing the above hyperbranched conjugated polymer, comprising the steps of: and mixing tris (4- (4, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) phenyl) amine and 2, 6-dibromoanthraquinone according to the mass ratio of 1:1-3 in an inert gas atmosphere, adding a palladium catalyst, a ligand and alkali, adding a solvent, reacting for 6-96 hours at 40-100 ℃, and purifying to obtain the hyperbranched conjugated polymer.
Further, the palladium catalyst may be, but is not limited to, bis dibenzylidene acetone palladium, tetraphenylphosphine palladium, 1' -bis diphenylphosphine ferrocene palladium dichloride, palladium acetate.
Further, the ligand may be, but is not limited to, triphenylphosphine, tri-t-butylphosphine, tri-o-methyltriphenylphosphine, tricyclohexylphosphine.
Further, the base may be any one of, but not limited to, tetrabutylammonium hydroxide aqueous solution, potassium carbonate aqueous solution, and potassium phosphate trihydrate.
Further, the solvent may be, but is not limited to, tetrahydrofuran or toluene.
According to another aspect of the present invention there is provided the use of a hyperbranched conjugated polymer as described above as a photosensitizer.
Further, the hyperbranched conjugated polymer can be applied to photodynamic therapy, photocatalytic oxidation reaction, sewage treatment or organic dye as a photosensitizer.
The present invention starts from commercial tris (4- (4, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) phenyl) amine and 2, 6-dibromoanthraquinone to prepare the final target polymer by suzuki polymerization. The hyperbranched conjugated polymer has excellent photosensitive performance, can efficiently generate various active oxygen with strong oxidability including singlet oxygen, superoxide anion free radical, hydroxyl free radical and the like under illumination, and can be used as a photosensitizer material in the fields of photodynamic therapy, photocatalytic oxidation reaction, sewage treatment, organic dye and the like.
The beneficial effects of the invention are as follows:
the invention provides a design idea of a novel conjugated polymer photosensitizer, namely, an internal cavity brought by hyperbranched polymer hyperbranched is utilized to promote the contact between the novel conjugated polymer photosensitizer and surrounding oxygen, so that the photosensitizing effect of the novel conjugated polymer photosensitizer is improved.
The method for synthesizing the hyperbranched conjugated polymer is simple and convenient, and the hyperbranched conjugated polymer can be prepared by one-step suzuki polymerization reaction through a commercial reagent.
The hyperbranched conjugated polymer provided by the invention has extremely high photosensitivity and good stability, and has a very wide application prospect as a photosensitizer.
Drawings
FIG. 1 is a block diagram of a hyperbranched conjugated polymer provided by the invention;
FIG. 2 is a synthetic route diagram of hyperbranched conjugated polymers provided by the invention;
FIG. 3 shows the hydrogen nuclear magnetic resonance spectrum and the carbon nuclear magnetic resonance spectrum of HPPS1 obtained in example 1;
FIG. 4 is a graph showing the UV-visible absorption spectrum and fluorescence spectrum of HPPS1 obtained in example 1 in water;
FIG. 5 is a graph of the photosensitizing effect test of HPPS1 in water obtained in example 1, with the results of the test under equivalent conditions for the commercial photosensitizer Semiphene as a comparison;
FIG. 6 is a block diagram of the main chain type conjugated polymer Control 1 in comparative example 1 of the present invention and a synthetic route diagram thereof;
FIG. 7 is a hydrogen nuclear magnetic resonance spectrum and a carbon nuclear magnetic resonance spectrum of a main chain type conjugated polymer Control 1 in comparative example 1 of the present invention;
FIG. 8 is a schematic diagram of the side chain type conjugated polymer Control 2 in comparative example 2 and a synthetic route diagram thereof;
FIG. 9 shows the hydrogen nuclear magnetic resonance spectrum and the carbon nuclear magnetic resonance spectrum of the side chain type conjugated polymer Control 2 in comparative example 2 of the present invention.
Detailed Description
The invention provides a hyperbranched conjugated polymer, which has a structure shown in figure 1.
The hyperbranched conjugated polymer of the invention takes triphenylamine as an electron donor,anthraquinone is electron acceptor, through "A 3 +B 2 "mode polymerization, its synthetic route is shown in figure 2; the method specifically comprises the following steps: and mixing tris (4- (4, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) phenyl) amine and 2, 6-dibromoanthraquinone according to the mass ratio of 1:1-3 in an inert gas atmosphere, adding a palladium catalyst, a ligand and alkali, adding a solvent, reacting for 6-96 hours at 40-100 ℃, and purifying to obtain the hyperbranched conjugated polymer.
Wherein, the palladium catalyst can be selected from bis (dibenzylidene) palladium acetonate, tetraphenylphosphine palladium, 1' -bis (diphenylphosphine) ferrocene palladium dichloride, palladium acetate and the like, so long as the Suzuki reaction can be catalyzed normally.
Wherein, the ligand can be selected from triphenylphosphine, tri-tert-butylphosphine, tri-o-methyltriphenylphosphine, tricyclohexylphosphine and the like, so long as the ligand can be matched with a palladium catalyst to catalyze Suzuki reaction.
Wherein, the alkali can be selected from tetrabutylammonium hydroxide aqueous solution, potassium carbonate aqueous solution, potassium phosphate trihydrate and the like, so long as the suzuki reaction can be normally promoted.
Among them, the solvent is generally selected from tetrahydrofuran or toluene.
The hyperbranched conjugated polymer can be used as a photosensitizer material to be applied in the fields of photodynamic therapy, photocatalytic oxidation reaction, sewage treatment, organic dye and the like.
For a better understanding of the present invention, the following detailed description of the present invention will be made with reference to specific examples and corresponding comparative examples, but the specific examples described herein are merely illustrative of the present invention and are not intended to limit the present invention.
The starting materials used in the examples and comparative examples of the present invention are commercially available or may be synthesized by methods known in the art.
Example 1:
tris (4- (4, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) phenyl) amine (207.7 mg,0.33 mmol) and 2, 6-dibromoanthraquinone (183 mg,0.50 mmol) were mixed under an inert gas atmosphere, followed byAdding trimethoxy phenylphosphine (15 mg) as ligand, bis (dibenzylidene) palladium acetonate (7.5 mg) as catalyst, adding ultra-dry toluene (8 mL) and 20% tetrabutylammonium hydroxide aqueous solution (2 mL), reacting at 80deg.C for 40 hr, cooling to room temperature after reaction, reprecipitating in methanol for 3 times, and drying to obtain red solid which is HPPS1 (87 mg,47% yield). M w ＝13000,M w /M n ＝1.36. 1 H NMR(400MHz,CDCl 3 ,298K)δ(TMS,ppm):8.56-8.49(ArH),8.47-8.42(ArH),8.39-8.31(ArH),8.21-8.15(ArH),8.04-7.92(ArH),7.70-7.59(ArH),7.40-7.25(ArH),7.21-7.08(ArH). 13 C NMR(100MHz,CDCl 3 ,298K)δ(ppm):148.72,147.27,137.38,137.00,131.56,130.34,130.24,130.14,129.45,129.13,129.07,128.27,128.02,125.05,123.69,123.60,122.91,122.78.
FIG. 3 shows the hydrogen nuclear magnetic resonance spectrum and the carbon nuclear magnetic resonance spectrum of HPPS1 obtained in example 1. As can be seen from fig. 3, the HPPS1 prepared in example 1 has the structure of the hyperbranched conjugated polymer provided by the present invention.
FIG. 4 is a graph showing the UV-visible absorption spectrum and fluorescence spectrum of HPPS1 obtained in example 1 in water. As can be seen from fig. 4, the HPPS1 prepared in example 1 has a very broad absorption spectrum, can be excited by various common light sources, and has deep red/near infrared fluorescence emission.
FIG. 5 is a graph of the reactive oxygen species production of the hyperbranched conjugated polymer obtained in example 1 tested by the indicator method, and the result shows that under excitation of the 530nm laser, the production efficiency of the superoxide anion radical of HPPS1 in the example of the invention is 3.5 times that of the commercial photosensitizer Semiphene, the production efficiency of the hydroxyl radical of HPPS1 is 21 times that of Semiphene, and the production efficiency of the singlet oxygen of HPPS1 is slightly higher than that of sea foam. In addition, after 1 year of storage under normal conditions, the active oxygen production efficiency of HPPS1 did not change at all, indicating that it has good stability.
The foregoing is merely exemplary of the application and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the application and are intended to be comprehended within the scope of the application.
Comparative example 1:
comparative example 1 is a backbone conjugated polymer similar in structure to the hyperbranched conjugated polymer provided by the invention, and the specific structure and synthetic route are shown in fig. 6. The specific synthesis conditions are as follows: n, N-bis (4- (4, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) phenyl) aniline (249 mg,0.50 mmol)) and 2, 6-dibromoanthraquinone (183mg, 0.50 mmol) were mixed under an inert gas atmosphere, then tris (o-methoxyphenylphosphine) (15 mg) was added as a ligand, bis (dibenzylideneacetone) palladium (7.5 mg) was added as a catalyst, ultra-dry toluene (8 mL) and 20% aqueous tetrabutylammonium hydroxide solution (2 mL) were added, the reaction was refluxed for 40 hours, cooled to room temperature after the completion of the reaction, reprecipitated 3 times in methanol, and a red solid obtained after drying was Control 1 (77 mg,34% yield). M w ＝9300,M w /M n ＝1.24. 1 H NMR(400MHz,CDCl 3 ,298K)δ(TMS,ppm):8.47-8.35(ArH),8.31-8.23(ArH),8.12-8.08(ArH),7.95-7.87(ArH),7.86-7.82(ArH),7.62-7.50(ArH),7.31-7.15(ArH),7.12-6.95(ArH). 13 C NMR(100MHz,CDCl 3 ,298K)δ(TMS,ppm):181.99,181.50,180.61,166.62,147.70,146.18,145.21,135.98,132.99,130.40,129.07,128.31,127.89,127.05,124.03,123.84,122.57,121.60.
As can be seen from the hydrogen nuclear magnetic resonance spectrum and the carbon nuclear magnetic resonance spectrum in FIG. 7, control 1 prepared in comparative example 1 has a desired structure. The results of the indicator method show that under the excitation of 530nm laser, the generation efficiency of the superoxide anion radical of HPPS1 in the embodiment 1 of the invention is 2.1 times that of the main chain conjugated polymer Control 1 in the comparative example 1, and the generation efficiency of singlet oxygen of HPPS1 is 1.8 times that of Control 1. In particular, control 1 does not generate hydroxyl radicals under excitation of 530nm laser, which is far inferior to hyperbranched conjugated polymer HPPS1.
Comparative example 2:
comparative example 2 is a side chain conjugated polymer similar in structure to the hyperbranched conjugated polymer provided by the invention, and the specific structure and synthetic route are shown in fig. 8. The specific synthesis steps are as follows:
monomer M1 can be prepared by reference (H.Zhan, Y.Wang, K.Li, Y.Chen, X.Yi, K.Bai, G.Xie and Y.Cheng, front.Chem.,2020,8,332).
Synthesis of monomer M2: to a 100mL Schlenk reaction tube under argon, monomer M1 (319 mg,1.0 mmol), bis-glutaryl diboron (630 mg,2.5 mmol), potassium acetate (490 mg,5.0 mmol), 1' -bis-diphenylphosphino ferrocene palladium dichloride (15 mg,0.02 mmol), 1, 4-dioxane (10 mL) were charged. After stirring at 80℃for 12 hours under argon atmosphere, the reaction solution was cooled to room temperature, water was added thereto, and then extracted three times with methylene chloride. After evaporation of the solvent, the crude product was separated by column chromatography using petroleum ether/ethyl acetate (v/v=2/1) as eluent to give monomer M2 (590 mg) as a red solid in 84% yield. 1 H NMR(400MHz,CDCl 3 ,298K)δ(TMS,ppm):8.51(s,1H,ArH),8.36-8.32(m,3H,ArH),8.01-7.98(d,1H,ArH),7.81-7.79(m,2H,ArH),7.73-7.71(m,4H,ArH),7.64-7.61(m,2H,ArH),7.21-7.19(d,2H,ArH),7.13-7.11(m,4H,ArH),1.34(m,24H,-CH 3 ). 13 C NMR(100MHz,CDCl 3 ,298K)δ(TMS,ppm):149.72,148.04,146.22,136.14,134.26,134.10,133.72,133.58,133.38,131.82,128.20,127.37,125.01,124.80,123.57,83.82,24.79.HRMS(ESI),calcd for(C 44 H 43 B 2 NO 6 ):m/z[M+H] + :703.3355；found:m/z 704.3364.
Synthesis of side chain conjugated polymer Control 2: mixing monomer M1 (305 mg,0.50 mmol) and monomer M2 (352 mg,0.50 mmol) under inert gas atmosphere, adding tri-o-methoxyphenylphosphine (15 mg) as ligand, bis-dibenzylideneacetone palladium (7.5 mg) as catalyst, adding ultra-dry toluene (8 mL) and 20% tetrabutylammonium hydroxide aqueous solution (2 mL), reflux reacting for 40 hours, cooling to room temperature after the reaction, reprecipitating 3 times in methanol, and obtaining red solid after drying which is Control 2 (75 mg,17% yield). M w ＝4800,M w /M n ＝1.15. 1 H NMR(400MHz,CDCl 3 ,298K)δ(TMS,ppm):8.55-8.50(ArH),8.38-8.31(ArH),8.04-7.98(ArH),7.85-7.77(ArH),7.69-7.62(ArH),7.59-7.48(ArH),7.36-7.28(ArH),7.25-7.08(ArH). 13 C NMR(100MHz,CDCl 3 ,298K)δ(ppm):183.50,182.84,148.61,147.17,146.18,145.71,134.34,134.05,133.56,131.32,129.39,127.80,127.62,127.46,125.23,124.76,123.00.
It can be seen from the nuclear magnetic resonance hydrogen spectrum and the nuclear magnetic resonance carbon spectrum in fig. 9 that Control 2 prepared in comparative example 2 has a desired structure. The results of the indicator method show that under the excitation of 530nm laser, the generation efficiency of the superoxide anion free radical of HPPS1 in the embodiment 1 of the invention is 9.7 times that of the main chain conjugated polymer Control 2 in the comparative example 2, and the generation efficiency of singlet oxygen of HPPS1 is 2.5 times that of Control 2. In particular, control 2 does not generate hydroxyl radicals under excitation of 530nm laser, much less than hyperbranched conjugated polymer HPPS1.
As can be seen from comparison of the photosensitive properties of example 1 and comparative examples 1 and 2, the hyperbranched conjugated polymers of the present invention have significantly improved active oxygen generating ability as compared with other common types of conjugated polymers. In addition, the photosensitive property of the HPPS1 obtained in the embodiment 1 of the invention is obviously better than that of a commercial photosensitive agent, namely the sea mepofungin, and the invention has good application prospect.
Although the preferred embodiments of the present invention have been described above with reference to the accompanying drawings, the present invention is not limited to the above-described embodiments, which are merely illustrative, not restrictive, and many changes may be made by those having ordinary skill in the art without departing from the spirit of the present invention and the scope of the appended claims, which are to be construed as falling within the scope of the present invention.
Claims (8)
1. A hyperbranched conjugated polymer characterized by having the structure:
wherein n is the number of repeated units, and the value is a positive integer;
the hyperbranched conjugated polymer takes triphenylamine as electron donorThe anthraquinone is an electron acceptor and is prepared by the method of A 3 +B 2 "alternating copolymer polymerized in a manner.
2. The method of preparing the hyperbranched conjugated polymer of claim 1, comprising the steps of: and mixing tris (4- (4, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) phenyl) amine and 2, 6-dibromoanthraquinone according to the mass ratio of 1:1-3 in an inert gas atmosphere, adding a palladium catalyst, a ligand and alkali, adding a solvent, reacting for 6-96 hours at 40-100 ℃, and purifying to obtain the hyperbranched conjugated polymer.
3. The method for preparing the hyperbranched conjugated polymer according to claim 2, wherein the palladium catalyst is any one of bis-dibenzylidene acetone palladium, tetra-triphenylphosphine palladium, 1' -bis-diphenylphosphine ferrocene palladium dichloride and palladium acetate.
4. The method for preparing hyperbranched conjugated polymer according to claim 2, wherein the ligand is any one of triphenylphosphine, tri-tert-butylphosphine, tri-o-methyltriphenylphosphine, and tricyclohexylphosphine.
5. The method for preparing hyperbranched conjugated polymer according to claim 2, wherein the base is any one of tetrabutylammonium hydroxide aqueous solution, potassium carbonate aqueous solution, and potassium phosphate trihydrate.
6. The method for preparing a hyperbranched conjugated polymer according to claim 2, wherein the solvent is tetrahydrofuran or toluene.
7. A photosensitizer, characterized in that it comprises a hyperbranched conjugated polymer according to any one of claims 1 to 2.
8. A photosensitizer according to claim 7, characterized in that it is used for photodynamic therapy, photocatalytic oxidation, sewage treatment or organic dyes.
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| Ultrasound-assisted synthesis of fluorescent oligomers of triphenylamine modified polyquinones: A comparison of experimental and computational spectral studies;Ufana Riaz et al;《Journal of Molecular Structure》;第1217卷;第128374页 * |
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