CN103242474A - Phosphorylcholine structure modified-perylene imide derivative and preparation method thereof - Google Patents
Phosphorylcholine structure modified-perylene imide derivative and preparation method thereof Download PDFInfo
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- CN103242474A CN103242474A CN2013101683932A CN201310168393A CN103242474A CN 103242474 A CN103242474 A CN 103242474A CN 2013101683932 A CN2013101683932 A CN 2013101683932A CN 201310168393 A CN201310168393 A CN 201310168393A CN 103242474 A CN103242474 A CN 103242474A
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- Prior art keywords
- phosphorylcholine
- perylene diimide
- preparation
- diimide derivative
- perylene
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- 238000002360 preparation method Methods 0.000 title claims abstract description 47
- NJNWCIAPVGRBHO-UHFFFAOYSA-N 2-hydroxyethyl-dimethyl-[(oxo-$l^{5}-phosphanylidyne)methyl]azanium Chemical group OCC[N+](C)(C)C#P=O NJNWCIAPVGRBHO-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 claims abstract description 6
- KJOLVZJFMDVPGB-UHFFFAOYSA-N perylenediimide Chemical class C=12C3=CC=C(C(NC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)NC(=O)C4=CC=C3C1=C42 KJOLVZJFMDVPGB-UHFFFAOYSA-N 0.000 claims description 133
- 229950004354 phosphorylcholine Drugs 0.000 claims description 51
- PYJNAPOPMIJKJZ-UHFFFAOYSA-N phosphorylcholine chloride Chemical compound [Cl-].C[N+](C)(C)CCOP(O)(O)=O PYJNAPOPMIJKJZ-UHFFFAOYSA-N 0.000 claims description 50
- 150000001262 acyl bromides Chemical class 0.000 claims description 43
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 238000012986 modification Methods 0.000 claims description 32
- 230000004048 modification Effects 0.000 claims description 32
- -1 acryloxy propyl group Chemical group 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000007810 chemical reaction solvent Substances 0.000 claims description 8
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 8
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 7
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- OXJGJKIURHREKH-UHFFFAOYSA-O CC(=C)C(=O)OCCP(=O)=C(O)C[N+](C)(C)C Chemical compound CC(=C)C(=O)OCCP(=O)=C(O)C[N+](C)(C)C OXJGJKIURHREKH-UHFFFAOYSA-O 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- KTJUKBKEZPKRNP-UHFFFAOYSA-O C(C(=C)C)(=O)OCCCP(=O)=C(O)C[N+](C)(C)C Chemical compound C(C(=C)C)(=O)OCCCP(=O)=C(O)C[N+](C)(C)C KTJUKBKEZPKRNP-UHFFFAOYSA-O 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 4
- DZIXGCNEOPKAQX-UHFFFAOYSA-N 2-[butyl(2-methylprop-2-enoyloxy)phosphoryl]oxyethyl-trimethylazanium Chemical compound C(C(=C)C)(=O)OP(=O)(CCCC)OCC[N+](C)(C)C DZIXGCNEOPKAQX-UHFFFAOYSA-N 0.000 claims description 3
- AIMHLEQGNVUOEP-UHFFFAOYSA-N 2-[butyl(prop-2-enoyloxy)phosphoryl]oxyethyl-trimethylazanium Chemical compound C(C=C)(=O)OP(=O)(CCCC)OCC[N+](C)(C)C AIMHLEQGNVUOEP-UHFFFAOYSA-N 0.000 claims description 3
- JFEFKRHTZIGOKQ-UHFFFAOYSA-N 2-[ethyl(prop-2-enoyloxy)phosphoryl]oxyethyl-trimethylazanium Chemical compound C(C=C)(=O)OP(=O)(CC)OCC[N+](C)(C)C JFEFKRHTZIGOKQ-UHFFFAOYSA-N 0.000 claims description 3
- VHJFWJXYEWHCGD-UHFFFAOYSA-N 4-nonyl-2-(4-nonylpyridin-2-yl)pyridine Chemical compound CCCCCCCCCC1=CC=NC(C=2N=CC=C(CCCCCCCCC)C=2)=C1 VHJFWJXYEWHCGD-UHFFFAOYSA-N 0.000 claims description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 3
- 229940045803 cuprous chloride Drugs 0.000 claims description 3
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical group [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 3
- TXNLQUKVUJITMX-UHFFFAOYSA-N 4-tert-butyl-2-(4-tert-butylpyridin-2-yl)pyridine Chemical group CC(C)(C)C1=CC=NC(C=2N=CC=C(C=2)C(C)(C)C)=C1 TXNLQUKVUJITMX-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 150000007530 organic bases Chemical group 0.000 claims description 2
- 230000010355 oscillation Effects 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 12
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 abstract description 9
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 abstract description 8
- 238000006862 quantum yield reaction Methods 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 description 27
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 12
- 239000000047 product Substances 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 238000013019 agitation Methods 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 238000011010 flushing procedure Methods 0.000 description 6
- 238000001027 hydrothermal synthesis Methods 0.000 description 6
- 239000005457 ice water Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000010526 radical polymerization reaction Methods 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- NRTLTGGGUQIRRT-UHFFFAOYSA-N triethylazanium;bromide Chemical compound [Br-].CC[NH+](CC)CC NRTLTGGGUQIRRT-UHFFFAOYSA-N 0.000 description 6
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 6
- 238000001132 ultrasonic dispersion Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 2
- 229960001701 chloroform Drugs 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N n-propyl alcohol Natural products CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 2
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 2
- OWPUOLBODXJOKH-UHFFFAOYSA-N 2,3-dihydroxypropyl prop-2-enoate Chemical compound OCC(O)COC(=O)C=C OWPUOLBODXJOKH-UHFFFAOYSA-N 0.000 description 1
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 239000000090 biomarker Substances 0.000 description 1
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- 125000005843 halogen group Chemical group 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
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- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- CAEZDMPOKQDNEA-UHFFFAOYSA-N perylen-1-ol Chemical group C1=CC(C=2C(O)=CC=C3C=2C2=CC=C3)=C3C2=CC=CC3=C1 CAEZDMPOKQDNEA-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a phosphorylcholine structure modified-perylene imide derivative. The structural formula is as shown in the specification. The invention also provides a preparation method of the phosphorylcholine structure modified-perylene imide derivative. The phosphorylcholine structure modified-perylene imide derivative provided by the invention is grafted with a hydrophilic phosphorylcholine structure by a chemical method, and is good in water solubility, high in fluorescence quantum yield, and good in biocompatibility. According to the preparation method, two oligomers containing the phosphorylcholine structures are connected to perylene bisimide to form a segment of grafted oligomer chain by an atom transfer radical polymerization grafting method. The preparation method is simple and reliable in preparation technology, and easy to achieve.
Description
Technical field
The invention belongs to the field of chemical synthesis, particularly a kind of Phosphorylcholine structural modification De perylene diimide derivative also relates to the preparation method of Phosphorylcholine structural modification De perylene diimide derivative.
Background technology
Perylene is that derivative has superior photochemistry, chemistry and calorifics stability, light from the visible light to the ultraviolet region there is very strong absorption, be the special molectronics material of a class performance, have at aspects such as liquid crystal display material, laserable material, solar cell and photo luminescent devices very widely and use.Perylene has high fluorescence quantum yield, high-light-fastness and chemical stability, can avoid the background fluorescence of organism in the absorption of visible region, and modify easily, and these character are laid a good foundation as biomarker for it.
Making perylene is that derivative has the water miscible high-fluorescence quantum yield that is difficult to simultaneously keep, and all is unusual popular topic all the time.， Shi perylene is that the modifying method that derivative has a good aqueous solubility is to introduce solubilization radical at imido nitrogen-atoms or Bay-position in the existing research document.(Gao B, et al.Water-soluble and fluorescent dendritic perylenebisimides for live-cell imaging.Chemical Communications.2011 such as Gao; 47 (13): 3894-3896) with dendritic polyoxyethylene glycol (PEG) Jie Zhi Dao the nitrogen-atoms of perylene diimide, the polyethyleneglycol modified De perylene diimide derivative (PEPBI) that obtains has good water-solubility, lower cytotoxicity and higher fluorescent yield, can be applicable to the fluorescent mark of cell.(Xu LQ, et al.Functionalization of reduced graphene oxide nanosheets via stacking interactions with the fluorescent and water-soluble perylenebisimide-containing polymers.Polymer.2011 such as Xu; 52 (11): 2376-2383) vinylformic acid glyceryl ester is utilized ATRP method graft polymerization Dao perylene diimide, obtain De perylene diimide derivative (PBIPGA) and have good water-solubility and higher fluorescent yield, product is used for the grapheme modified water-soluble Graphene that obtains.Chinese patent application number is that 200910229526.6 patent document discloses a kind of synthetic method that contains the water-soluble perylene diimide derivatives of N-pyridine oxide group, this analog derivative replaces reagent react by perylene diimide derivative and the corresponding hydroxyl of halo, form by hydrogen peroxide oxidation then, preparation method's condition is controlled easily, reaction is relatively gentleer, raw material economics, the water-soluble perylene diimide derivatives toxicity that contains the N-pyridine oxide group of preparation is little and fluorescence quantum yield is high.Chinese patent application number is that 200910204975.5 patent document discloses a kind of Weather-resistance perylene imide dye and preparation method thereof, the Nai that water soluble group is modified is Yu the Bay-position modified water-soluble group of perylene diimide reaction Qie Zai perylene ring, obtain having excellent weather resistance De perylene diimide derivative, can be used as the tinting material in the material.
Perylene is that derivative has the water miscible high-fluorescence quantum yield that is difficult to simultaneously keep, and this is that the puzzlement investigator expands the difficult problem that it is used in living things system always.
Summary of the invention
Goal of the invention: first purpose of the present invention provides a kind of perylene diimide derivative with Phosphorylcholine structural modification of good aqueous solubility and high-fluorescence quantum yield, more specifically provides the perylene diimide derivative of the basic Phosphorylcholine structural modification of a kind of (methyl) acryloxy alkane (oxygen).
Second purpose of the present invention provides the preparation method of said derivative.
Technical scheme: Phosphorylcholine structural modification De perylene diimide derivative provided by the invention, its structural formula is as follows:
Wherein, R
1Be H, CH
3
R
2Be C
nH
2n+1, n=2,3 or 4;
R
3Be C
mH
2m+1, m=2,3 or 4;
x≥1。
The present invention also provides the preparation method of above-mentioned Phosphorylcholine structural modification De perylene diimide derivative, may further comprise the steps:
(1) N, the preparation: You perylene tetracarboxylic acid dianhydride of N '-Qiang Wan Ji perylene diimide (PBI-OH) and alkyl alcoholamine reaction obtain N, N '-Qiang Wan Ji perylene diimide;
(2) 2-bromo-2-methyl-prop acylbromide is modified the preparation of De perylene diimide derivative (PBI-Br): N, and N '-Qiang Wan Ji perylene diimide and the reaction of 2-bromo-2-methyl-prop acylbromide get 2-bromo-2-methyl-prop acylbromide and modify De perylene diimide derivative;
(3) preparation of Phosphorylcholine structural modification De perylene diimide derivative: the method for utilizing atom transfer radical polymerization (ATRP) grafting, in inert atmospheres such as nitrogen, argon gas, the perylene diimide derivative that 2-bromo-2-methyl-prop acylbromide is modified is induced at initiator system with the polymerizable compound that contains the Phosphorylcholine structure and is issued living Raolical polymerizable, namely.
Wherein, in the step (1), a kind of in described amino hydramine preferred alcohol amine, n-propyl alcohol amine and the propyl carbinol amine.
Wherein, (mol ratio of 1) Zhong ， perylene tetracarboxylic acid dianhydride and alkyl alcoholamine is 1:2-1:100 to step, is preferably 1:60-1:80; Temperature of reaction is 100-190 ℃, preferred 140-180 ℃; Reaction times is 3h-30h, and the preferred time is 12-24h.
Wherein, in the step (2), N, N '-Qiang Wan Ji perylene diimide (PBI-OH) is 1:3-1:10 with the mol ratio of 2-bromo-2-methyl-prop acylbromide, is preferably 1:3-1:6; Temperature of reaction is 0-40 ℃, is preferably 4-25 ℃; Reaction times is 1h-24h, is preferably 4-12h.
Wherein, in the step (2), reaction solvent is halogenated alkane, is preferably one or more the composition in trichloromethane, methylene dichloride, monochloro methane, ethylene dichloride, trichloroethane, the monochlorethane; Reaction solvent and N, N '-Qiang Wan Ji perylene diimide (PBI-OH) amount ratio is 100-250mL:1mmol, is preferably 150-200mL:1mmol.
Wherein, in the step (2), also comprise acid binding agent in the reaction system, described acid binding agent is organic bases, be preferably one or more the composition in Tributylamine, tripropyl amine, triethylamine, Trimethylamine 99, the pyridine, the mol ratio of described acid binding agent and 2-bromo-2-methyl-prop acylbromide is 1:1.
Wherein, in the step (3), the perylene diimide derivative that the present invention proposes confession adopts the polymerizable compound contain the Phosphorylcholine structure to modify, and the described polymerizable compound structural formula that contains the Phosphorylcholine structure is as follows:
R
1=H,CH
3
R
2=C
nH
2n+1,n=2,3,4
Wherein, the polymerizable compound that contains the Phosphorylcholine structure is one or more the composition in acryloxy ethyl Phosphorylcholine, acryloxy propyl group Phosphorylcholine, acryloxy butyl Phosphorylcholine, methacryloxyethyl Phosphorylcholine, methacryloxypropyl Phosphorylcholine or the methacryloxy butyl Phosphorylcholine.
Wherein, in the step (3), containing the polymerizable compound of Phosphorylcholine structure and the mol ratio of the perylene diimide derivative (PBI-Br) that 2-bromo-2-methyl-prop acylbromide is modified is 20-60:1, is preferably 20-40:1; Temperature of reaction is 30-100 ℃, preferred 50-80 ℃; Reaction times is 8-24h, preferred 10-16h; Reaction system adopts ultra-sonic oscillation.
Wherein, in the step (3), described initiator system is the combination of transition metal salt and part, and described transition metal salt is a kind of in ferrous sulfate, iron protochloride, cuprous chloride and the cuprous bromide, and described part is bipyridine (bpy), 4,4 '-di-tert-butyl-2,2 '-dipyridyl (dTbpy), 4,4 '-two n-heptyls-2,2 '-dipyridyl (dHbpy), 4,4 '-two (5-nonyls)-2,2 '-a kind of in the dipyridyl (dNbpy), pentamethyl-diethylenetriamine (PMDETA); The mole number of described transition metal salt and part is identical; The mole number of described transition metal salt is that 2-bromo-2-methyl-prop acylbromide is modified more than 2 times of De perylene diimide derivative mole number, preferred 2 times.
Wherein, in the step (3), reaction solvent is one or more the composition in benzene, dimethylbenzene, pimelinketone, methyl-phenoxide and the tetrahydrofuran (THF); The amount ratio that reaction solvent and 2-bromo-2-methyl-prop acylbromide are modified De perylene diimide derivative (PBI-Br) is 10-100mL:0.05mmol, is preferably 10-20mL:0.05mmol.
Beneficial effect: Phosphorylcholine structural modification De perylene diimide derivative provided by the invention has adopted the chemical process grafting hydrophilic Phosphorylcholine structure, good water solubility, fluorescence quantum yield height, good biocompatibility.
Owing to the Phosphorylcholine structure is the interior intrinsic compounds of organism such as the part in the phosphatide, adopt Phosphorylcholine structural modification De perylene diimide derivative to have excellent biological compatibility, have very high fluorescence quantum yield owing to product simultaneously, so Gai perylene diimide derivative has in the bio-medical field as fluorescently-labeled potential use.
The preparation method of Phosphorylcholine structural modification De perylene diimide derivative provided by the invention, method by the atom transfer radical polymerization grafting forms the oligomer chain of one section grafting with two oligopolymer Lian Jie that contain the Phosphorylcholine structure Dao perylene diimide, preparation technology is easy, reliable, be easy to realize.
Description of drawings
Fig. 1 be Phosphorylcholine structural modification De perylene diimide derivative nuclear-magnetism hydrogen (
1H-NMR) spectrogram;
Fig. 2 is the ultraviolet-visible spectrogram of the perylene diimide derivative of Phosphorylcholine structural modification;
Fig. 3 is the fluorescence radiation spectrogram of Phosphorylcholine structural modification De perylene diimide derivative.
Embodiment
According to following embodiment, the present invention may be better understood.Yet, those skilled in the art will readily understand that the described concrete material proportion of embodiment, processing condition and result thereof only are used for explanation the present invention, and should also can not limit the present invention described in detail in claims.
Phosphorylcholine structural modification De perylene diimide derivative, its structural formula is:
Its preparation method may further comprise the steps:
(1) preparation of Qiang Yi Ji perylene diimide: take by weighing the hydrothermal reaction kettle that 0.8g perylene tetracarboxylic acid dianhydride places inner liner polytetrafluoroethylene, add the 9.76g thanomin, reactor is placed 180 ℃ of reaction 24h.The reaction back adds 25mL distilled water, stirs the back centrifugation, and solution last time that inclines repeats this process 3 times, obtains Qiang Yi Ji perylene diimide after 60 ℃ of vacuum-dryings.
(2) 2-bromo-2-methyl-prop acylbromide is modified the preparation of De perylene diimide derivative (PBI-Br): take by weighing 550mg Qiang Yi Ji perylene diimide in the 250mL three-necked bottle, add the methylene dichloride of 150mL drying and the triethylamine of 0.43mL, ultra-sonic dispersion.Three-necked bottle is placed ice-water bath, dropwise add the 2-bromo-2-methyl-prop acylbromide of 0.69g, continue to stir 1h.Then, three-necked bottle is placed room temperature continue to stir 24h.To react after product and filter, remove unreacted Qiang Yi Ji perylene diimide and triethylamine hydrobromide.With the filtrate evaporate to dryness that obtains, obtain 2-bromo-2-methyl-prop acylbromide and modify De perylene diimide derivative (PBI-Br).
(3) radical polymerization grafting Phosphorylcholine structure: take by weighing 43mg2-bromo-2-methyl-prop acylbromide and modify De perylene diimide derivative (PBI-Br), 3mmol methylacryoyloxyethyl Phosphorylcholine, 14.4mg cuprous bromide, the 8mL tetrahydrofuran (THF) in the 25mL flask, magnetic agitation.In flask, lead to 20min nitrogen.Add 17.3mg pentamethyl-diethylenetriamine (PMDETA) rapidly, with the flask sealing, in 60 ℃ of oil baths, stir 8h.The dispersion liquid that obtains is passed through 0.22 μ m filter membrane, with tetrahydrofuran (THF) flushing 3 times.In 60 ℃ of oven dry, obtain grafting Phosphorylcholine Jie Gou De perylene diimide derivative.
Final product PBI-PCn in this example has been carried out characterizing mensuration.
In the proton nmr spectra of accompanying drawing 1,8.0-8.5ppm between two Feng Wei perylene rings on the peak of 8 hydrogen, scheme last 0.86,1.05,1.11ppm locate the peak and be to be connected on the Phosphorylcholine structure on two key methyl and the 2-bromo-2-methyl-prop acylbromide signal of hydrogen on two methyl, 1.82ppm locate the peak and be to connect in the final product signal of hydrogen on the methylene radical of two carbon atoms, 3.2ppm locate signal and be on the quaternary amine signal of hydrogen on three methyl, 3.66ppm that locates is bimodal for connecting the signal of hydrogen on the methylene radical between nitrogen-atoms and the carbon atom in the final product, 4.18ppm the multiplet of locating is the signal of hydrogen on the methylene radical that connects in the final product between Sauerstoffatom and the carbon atom, 4.7ppm what locate is the water peak
1The H-NMR collection of illustrative plates understands that from structure Shanghai Stock Exchange the Phosphorylcholine structure successfully is grafted on the perylene diimide, by to the unimodal integration ratio in two peaks, 8.0-8.5ppm place and 3.2ppm place, calculate to such an extent that the Phosphorylcholine structural unit number that gets on of grafting is 32, so x ≈ 16 herein.
The visible spectrum Zhong ， perylene of accompanying drawing 2 is that three characteristic peaks of derivative at 475nm, 501nm and 543nm place have all appeared in the spectrogram, and solution is even, has proved that from another point of view the Phosphorylcholine structure successfully is grafted on the perylene diimide.
In the Ultraluminescence spectrum of accompanying drawing 3, use the exciting light of 373nm wavelength that different concns solution is excited, be under the 5mg/mL concentration in concentration, fluorescence is mainly the ruddiness of 600nm, and the solution of fluorescence intensity ratio 2.5mg/mL is low, this is because self quenching can take place the fluorescence of high concentration De perylene diimide derivative solution, when concentration gradually during step-down, send the fluorescence of 550nm and 600nm wavelength simultaneously, and fluorescence intensity is stronger, when the perylene diimide derivative that has proved the Phosphorylcholine structural modification has good aqueous solubility, has high-intensity fluorescence.
Phosphorylcholine structural modification De perylene diimide derivative, its structural formula is:
Its preparation method may further comprise the steps:
(1) preparation of hydroxyl Zheng Bing Ji perylene diimide: get the hydrothermal reaction kettle that 2mmol perylene tetracarboxylic acid dianhydride places inner liner polytetrafluoroethylene, add 4mmol n-propyl alcohol amine, reactor is placed 190 ℃ of reaction 3h.The reaction back adds 25mL distilled water, stirs the back centrifugation, and solution last time that inclines repeats this process 3 times, obtains hydroxyl Zheng Bing Ji perylene diimide after 60 ℃ of vacuum-dryings.
(2) 2-bromo-2-methyl-prop acylbromide is modified the preparation of De perylene diimide derivative (PBI-Br): get 1mmol hydroxyl Zheng Bing Ji perylene diimide in the 250mL three-necked bottle, add the trichloromethane of 100mL drying and the Tributylamine of 3mmol, ultra-sonic dispersion.Three-necked bottle is placed ice-water bath, dropwise add the 2-bromo-2-methyl-prop acylbromide of 3mmol, continue to stir 1h.Then, three-necked bottle is placed 0 ℃ continue to stir 24h.To react after product and filter, remove unreacted Qiang Yi Ji perylene diimide and triethylamine hydrobromide.With the filtrate evaporate to dryness that obtains, obtain 2-bromo-2-methyl-prop acylbromide and modify De perylene diimide derivative (PBI-Br).
(3) radical polymerization grafting Phosphorylcholine structure: get 0.05mmol2-bromo-2-methyl-prop acylbromide and modify De perylene diimide derivative (PBI-Br), 1mmol methylacryoyloxyethyl Phosphorylcholine, 0.1mmol ferrous sulfate, 10mL benzene in the 25mL flask, magnetic agitation.In flask, lead to 20min nitrogen.Add 0.1mmol bipyridine (bpy) rapidly, with the flask sealing, in 70 ℃ of oil baths, stir 13h.The dispersion liquid that obtains is passed through 0.22 μ m filter membrane, with tetrahydrofuran (THF) flushing 3 times.In 60 ℃ of oven dry, obtain grafting Phosphorylcholine Jie Gou De perylene diimide derivative.
Phosphorylcholine structural modification De perylene diimide derivative, its structural formula is:
Its preparation method may further comprise the steps:
(1) preparation of hydroxyl Yi Bing Ji perylene diimide: take by weighing the hydrothermal reaction kettle that 2mmol perylene tetracarboxylic acid dianhydride places inner liner polytetrafluoroethylene, add the 200mmol Yi Bingchunan, reactor is placed 100 ℃ of reaction 30h.The reaction back adds 25mL distilled water, stirs the back centrifugation, and solution last time that inclines repeats this process 3 times, obtains hydroxyl Yi Bing Ji perylene diimide after 60 ℃ of vacuum-dryings.
(2) 2-bromo-2-methyl-prop acylbromide is modified the preparation of De perylene diimide derivative (PBI-Br): get 1mmol hydroxyl Yi Bing Ji perylene diimide in the 250mL three-necked bottle, add the ethylene dichloride of 250mL drying and the tripropyl amine of 6mmol, ultra-sonic dispersion.Three-necked bottle is placed ice-water bath, dropwise add the 2-bromo-2-methyl-prop acylbromide of 6mmol, continue to stir 1h.Then, three-necked bottle is placed 40 ℃ continue to stir 1h.To react after product and filter, remove unreacted Qiang Yi Ji perylene diimide and triethylamine hydrobromide.With the filtrate evaporate to dryness that obtains, obtain 2-bromo-2-methyl-prop acylbromide and modify De perylene diimide derivative (PBI-Br).
(3) radical polymerization grafting Phosphorylcholine structure: get 0.05mmol2-bromo-2-methyl-prop acylbromide and modify De perylene diimide derivative (PBI-Br), 3mmol acryloxy propyl group Phosphorylcholine, 0.1mmol iron protochloride, 100mL dimethylbenzene in the 150mL flask, magnetic agitation.In flask, lead to 20min nitrogen.Add 0.1mmol4 rapidly, 4 '-di-tert-butyl-2,2 '-dipyridyl (dTbpy), with the flask sealing, in 80 ℃ of oil baths, stir 10h.The dispersion liquid that obtains is passed through 0.22 μ m filter membrane, with tetrahydrofuran (THF) flushing 3 times.In 60 ℃ of oven dry, obtain grafting Phosphorylcholine Jie Gou De perylene diimide derivative.
Phosphorylcholine structural modification De perylene diimide derivative, its structural formula is:
Its preparation method may further comprise the steps:
(1) preparation of hydroxyl Zheng Ding Ji perylene diimide: take by weighing the hydrothermal reaction kettle that 2mmol perylene tetracarboxylic acid dianhydride places inner liner polytetrafluoroethylene, add 120mmol propyl carbinol amine, reactor is placed 140 ℃ of reaction 12h.The reaction back adds 25mL distilled water, stirs the back centrifugation, and solution last time that inclines repeats this process 3 times, obtains hydroxyl Zheng Ding Ji perylene diimide after 60 ℃ of vacuum-dryings.
(2) 2-bromo-2-methyl-prop acylbromide is modified the preparation of De perylene diimide derivative (PBI-Br): get 1mmol hydroxyl Zheng Ding Ji perylene diimide in the 250mL three-necked bottle, add the trichloroethane of 150mL drying and the Trimethylamine 99 of 10mmol, ultra-sonic dispersion.Three-necked bottle is placed ice-water bath, dropwise add the 2-bromo-2-methyl-prop acylbromide of 10mmol, continue to stir 1h.Then, three-necked bottle is placed 4 ℃ continue to stir 12h.To react after product and filter, remove unreacted Qiang Yi Ji perylene diimide and triethylamine hydrobromide.With the filtrate evaporate to dryness that obtains, obtain 2-bromo-2-methyl-prop acylbromide and modify De perylene diimide derivative (PBI-Br).
(3) radical polymerization grafting Phosphorylcholine structure: get 0.05mmol2-bromo-2-methyl-prop acylbromide and modify De perylene diimide derivative (PBI-Br), 2mmol methacryloxypropyl Phosphorylcholine, 0.1mmol cuprous chloride, the 20mL pimelinketone in the 25mL flask, magnetic agitation.In flask, lead to 20min nitrogen.Add 0.1mmol4 rapidly, 4 '-two n-heptyls-2,2 '-dipyridyl (dHbpy), with the flask sealing, in 50 ℃ of oil baths, stir 16h.The dispersion liquid that obtains is passed through 0.22 μ m filter membrane, with tetrahydrofuran (THF) flushing 3 times.In 60 ℃ of oven dry, obtain grafting Phosphorylcholine Jie Gou De perylene diimide derivative.
Embodiment 5
Phosphorylcholine structural modification De perylene diimide derivative, its structural formula is:
Its preparation method may further comprise the steps:
(1) preparation of the different fourth base of hydroxyl perylene diimide: take by weighing the hydrothermal reaction kettle that 2mmol perylene tetracarboxylic acid dianhydride places inner liner polytetrafluoroethylene, add 40mmol isobutyl hydramine, reactor is placed 170 ℃ of reaction 18h.The reaction back adds 25mL distilled water, stirs the back centrifugation, and solution last time that inclines repeats this process 3 times, obtains hydroxyl Yi Ding Ji perylene diimide after 60 ℃ of vacuum-dryings.
(2) 2-bromo-2-methyl-prop acylbromide is modified the preparation of De perylene diimide derivative (PBI-Br): get 1mmol hydroxyl Yi Ding Ji perylene diimide in the 250mL three-necked bottle, add the monochloro methane of 200mL drying and the pyridine of 5mmol, ultra-sonic dispersion.Three-necked bottle is placed ice-water bath, dropwise add the 2-bromo-2-methyl-prop acylbromide of 5mmol, continue to stir 1h.Then, three-necked bottle is placed 25 ℃ continue to stir 4h.To react after product and filter, remove unreacted Qiang Yi Ji perylene diimide and triethylamine hydrobromide.With the filtrate evaporate to dryness that obtains, obtain 2-bromo-2-methyl-prop acylbromide and modify De perylene diimide derivative (PBI-Br).
(3) radical polymerization grafting Phosphorylcholine structure: get 0.05mmol2-bromo-2-methyl-prop acylbromide and modify De perylene diimide derivative (PBI-Br), 1.5mmol acryloxy propyl group Phosphorylcholine, 0.1mg cuprous bromide, the 50mL methyl-phenoxide in the 100mL flask, magnetic agitation.In flask, lead to 20min nitrogen.Add 0.1mmol4 rapidly, 4 '-two (5-nonyls)-2,2 '-dipyridyl (dNbpy), with the flask sealing, in 100 ℃ of oil baths, stir 8h.The dispersion liquid that obtains is passed through 0.22 μ m filter membrane, with tetrahydrofuran (THF) flushing 3 times.In 60 ℃ of oven dry, obtain grafting Phosphorylcholine Jie Gou De perylene diimide derivative.
Embodiment 6
Phosphorylcholine structural modification De perylene diimide derivative, its structural formula is:
Its preparation method may further comprise the steps:
(1) preparation of hydroxymethyl Bing Ji perylene diimide: take by weighing the hydrothermal reaction kettle that 2mmol perylene tetracarboxylic acid dianhydride places inner liner polytetrafluoroethylene, add the 160mmol3-amino butanol, reactor is placed 180 ℃ of reaction 24h.The reaction back adds 25mL distilled water, stirs the back centrifugation, and solution last time that inclines repeats this process 3 times, obtains Qiang base Jia Ji perylene diimide after 60 ℃ of vacuum-dryings.
(2) 2-bromo-2-methyl-prop acylbromide is modified the preparation of De perylene diimide derivative (PBI-Br): get 1mmol Qiang base Jia Ji perylene diimide in the 250mL three-necked bottle, add the monochlorethane of 175mL drying and the triethylamine of 8mmol, ultra-sonic dispersion.Three-necked bottle is placed ice-water bath, dropwise add the 2-bromo-2-methyl-prop acylbromide of 8mmol, continue to stir 1h.Then, three-necked bottle is placed 20 ℃ continue to stir 8h.To react after product and filter, remove unreacted Qiang Yi Ji perylene diimide and triethylamine hydrobromide.With the filtrate evaporate to dryness that obtains, obtain 2-bromo-2-methyl-prop acylbromide and modify De perylene diimide derivative (PBI-Br).
(3) radical polymerization grafting Phosphorylcholine structure: get 0.05mmol2-bromo-2-methyl-prop acylbromide and modify De perylene diimide derivative (PBI-Br), 2.5mmol methacryloxypropyl Phosphorylcholine, 0.1mmol cuprous bromide, the 15mL tetrahydrofuran (THF) in the 25mL flask, magnetic agitation.In flask, lead to 20min nitrogen.Add 0.1mmol pentamethyl-diethylenetriamine (PMDETA) rapidly, with the flask sealing, in 30 ℃ of oil baths, stir 24h.The dispersion liquid that obtains is passed through 0.22 μ m filter membrane, with tetrahydrofuran (THF) flushing 3 times.In 60 ℃ of oven dry, obtain grafting Phosphorylcholine Jie Gou De perylene diimide derivative.
Embodiment 7
Identical with embodiment 1, just the consumption with the 2-bromo-2-methyl-prop acylbromide in second step is increased to 1.3g, obtains grafting Phosphorylcholine Jie Gou De perylene diimide derivative.
Embodiment 8
Identical with embodiment 1, the triethylamine in just going on foot second changes the Trimethylamine 99 of equimolar amount into, obtains grafting Phosphorylcholine Jie Gou De perylene diimide derivative.
Embodiment 9
The iron protochloride identical with embodiment 1, that the cuprous bromide in just going on foot the 3rd and pentamethyl-diethylenetriamine initiator system change equimolar amount at 60 ℃ of following ultrasonic reaction 12h, obtains grafting Phosphorylcholine Jie Gou De perylene diimide derivative.Embodiment 10
Identical with embodiment 1, but change the methacryloxyethyl Phosphorylcholine in the 3rd step into 1g acryloxy ethyl Phosphorylcholine 60 ℃ of following stirring reactions 8 hours, obtained grafting Phosphorylcholine Jie Gou De perylene diimide derivative.
Embodiment 11
Identical with embodiment 1, but change the methacryloxyethyl Phosphorylcholine in the 3rd step into 2g acryloxy butyl Phosphorylcholine 60 ℃ of nitrogen atmosphere stirring reactions 12 hours, obtained grafting Phosphorylcholine Jie Gou De perylene diimide derivative.
Embodiment 13
Identical with embodiment 1, but change the methacryloxyethyl Phosphorylcholine in the 3rd step into 2g methacryloxy butyl Phosphorylcholine 30 ℃ of nitrogen atmosphere stirring reactions 8 hours, obtained grafting Phosphorylcholine Jie Gou De perylene diimide derivative.
Claims (10)
1. Phosphorylcholine structural modification De perylene diimide derivative, its structural formula is as follows:
Wherein, R
1Be H, CH
3
R
2Be C
mH
2m+1, m=2,3 or 4;
R
3Be C
nH
2n+1, n=2,3 or 4;
x≥1。
2. the preparation method of the described Phosphorylcholine structural modification of claim 1 De perylene diimide derivative is characterized in that:
May further comprise the steps:
(1) N, the preparation: You perylene tetracarboxylic acid dianhydride of N '-Qiang Wan Ji perylene diimide and alkyl alcoholamine reaction obtain N, N '-Qiang Wan Ji perylene diimide;
(2) 2-bromo-2-methyl-prop acylbromide is modified the preparation of De perylene diimide derivative: N, and N '-Qiang Wan Ji perylene diimide and the reaction of 2-bromo-2-methyl-prop acylbromide get 2-bromo-2-methyl-prop acylbromide and modify De perylene diimide derivative;
(3) preparation of Phosphorylcholine structural modification De perylene diimide derivative: the method for utilizing the atom transfer radical polymerization grafting, in inert atmospheres such as nitrogen, argon gas, the perylene diimide derivative that 2-bromo-2-methyl-prop acylbromide is modified is induced at initiator system with the polymerizable compound that contains the Phosphorylcholine structure and is issued living Raolical polymerizable, namely.
3. the preparation method of Phosphorylcholine structural modification De perylene diimide derivative according to claim 2, it is characterized in that: (mol ratio of 1) Zhong ， perylene tetracarboxylic acid dianhydride and alkyl alcoholamine is 1:2-1:100 to step; Temperature of reaction is 100-190 ℃; Reaction times is 3h-30h.
4. the preparation method of Phosphorylcholine structural modification De perylene diimide derivative according to claim 2, it is characterized in that: in the step (2), N, the mol ratio of N '-Qiang Wan Ji perylene diimide and 2-bromo-2-methyl-prop acylbromide is 1:3-1:10, temperature of reaction is 0-40 ℃; Reaction times is 1h-24h.
5. the preparation method of Phosphorylcholine structural modification De perylene diimide derivative according to claim 2, it is characterized in that: in the step (2), reaction solvent is halogenated alkane; Reaction solvent and N, N '-Qiang Wan Ji perylene diimide amount ratio is 100-250mL:1mmol.
6. the preparation method of Phosphorylcholine structural modification De perylene diimide derivative according to claim 2, it is characterized in that: in the step (2), also comprise acid binding agent in the reaction system, described acid binding agent is organic bases, and the mol ratio of described acid binding agent and 2-bromo-2-methyl-prop acylbromide is 1:1.
7. the preparation method of Phosphorylcholine structural modification De perylene diimide derivative according to claim 2, it is characterized in that: in the step (3), the polymerizable compound that contains the Phosphorylcholine structure is one or more the composition in acryloxy ethyl Phosphorylcholine, acryloxy propyl group Phosphorylcholine, acryloxy butyl Phosphorylcholine, methacryloxyethyl Phosphorylcholine, methacryloxypropyl Phosphorylcholine or the methacryloxy butyl Phosphorylcholine.
8. the preparation method of Phosphorylcholine structural modification De perylene diimide derivative according to claim 2, it is characterized in that: in the step (3), containing the polymerizable compound of Phosphorylcholine structure and the mol ratio of the perylene diimide derivative that 2-bromo-2-methyl-prop acylbromide is modified is 20-60:1; Temperature of reaction is 30-100 ℃; Reaction times is 8-24h; Reaction system adopts ultra-sonic oscillation.
9. the preparation method of Phosphorylcholine structural modification De perylene diimide derivative according to claim 2, it is characterized in that: in the step (3), described initiator system is the combination of transition metal salt and part, described transition metal salt is ferrous sulfate, iron protochloride, a kind of in cuprous chloride and the cuprous bromide, described part is bipyridine (bpy), 4,4 '-di-tert-butyl-2,2 '-dipyridyl (dTbpy), 4,4 '-two n-heptyls-2,2 '-dipyridyl (dHbpy), 4,4 '-two (5-nonyls)-2,2 '-dipyridyl (dNbpy), a kind of in the pentamethyl-diethylenetriamine.
10. the preparation method of Phosphorylcholine structural modification De perylene diimide derivative according to claim 2 is characterized in that: in the step (3), reaction solvent is one or more the composition in benzene, dimethylbenzene, pimelinketone, methyl-phenoxide and the tetrahydrofuran (THF); The amount ratio that reaction solvent and 2-bromo-2-methyl-prop acylbromide are modified De perylene diimide derivative is 10-100mL:0.05mmol.
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| US4668623A (en) * | 1980-04-09 | 1987-05-26 | Ksv-Chemicals Oy | Method of fluorometrically measuring the activity of fat-degrading enzymes |
| CN101704816A (en) * | 2009-10-29 | 2010-05-12 | 山东师范大学 | Water-soluble perylene diimide derivatives containing N-pyridine oxide groups and synthetic method thereof |
| CN102674336A (en) * | 2012-06-01 | 2012-09-19 | 南京大学 | Phosphorylcholine structure-modified graphene oxide and preparation method thereof |
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| US4668623A (en) * | 1980-04-09 | 1987-05-26 | Ksv-Chemicals Oy | Method of fluorometrically measuring the activity of fat-degrading enzymes |
| CN101704816A (en) * | 2009-10-29 | 2010-05-12 | 山东师范大学 | Water-soluble perylene diimide derivatives containing N-pyridine oxide groups and synthetic method thereof |
| CN102674336A (en) * | 2012-06-01 | 2012-09-19 | 南京大学 | Phosphorylcholine structure-modified graphene oxide and preparation method thereof |
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| CN115466392A (en) * | 2022-09-13 | 2022-12-13 | 中国科学技术大学 | Perylene bisimide cage type polysilsesquioxane polymer material, preparation method thereof and fluorescence regulation and control method |
| CN115466392B (en) * | 2022-09-13 | 2023-07-14 | 中国科学技术大学 | Perylene bisimide cage polysilsesquioxane polymer material and preparation and fluorescence regulation method thereof |
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