CN104861172A - Preparation method of porphyrin core star copolymer with fluorescence effect, PH responsiveness and temperature responsiveness - Google Patents
Preparation method of porphyrin core star copolymer with fluorescence effect, PH responsiveness and temperature responsiveness Download PDFInfo
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Abstract
The invention relates to a preparation method of a porphyrin core star copolymer with fluorescence effect, PH responsiveness and temperature responsiveness. According to the method, 5,10,15,20-tetra-p-hydroxy phenyl porphyrin is converted into a four bromine group-containing porphyrin molecule, the bromine group-containing porphyrin molecule is used as a macromolecular initiator for atom transfer radical polymerization of N, N-dimethylamino ethyl methacrylate monomers and azidation, azide porphyrin core poly N, N-dimethylamino ethyl methacrylate and alkynyl polyethylene glycol are used as reaction module, and finally the porphyrin core star copolymer with fluorescence effect, PH responsiveness and temperature responsivenessis obtained by click chemistry. The porphyrin core star copolymer has biodegradability, biocompatibility, biological activity, fluorescence effect, PH responsiveness and temperature responsiveness, when the porphyrin core star copolymer is poured into water, stable nano micelle can be formed, and the porphyrin core star copolymer can be widely used in drug controlled release carrier, biological intelligent switch, biosensor and other fields. The preparation method is simple and practical, raw material production can be industrialized, and the porphyrin core star copolymer has the very good popularization and application value.
Description
Technical field
The invention belongs to macromolecular material and biomedical engineering field, being specifically related to a kind of take porphyrin as the preparation method with the star copolymer of fluorescent effect, pH responsiveness and temperature-responsive of core.
Background technology
Porphyrin is the another kind of most important bio-ligand outside isolating protein, nucleic acid base.Except the protoporphyrin extensively existed in life entity, people explore and have synthesized many synthetic porphyrins.Not only structure is simple for synthesis porphyrin, and can design, synthesize the compound of the wonderful workmanship excelling nature with ad hoc structure and performance as required, and there is the characteristic such as diversity and self-assembly of electronics resiliency and photoelectric magnetic property and steric configuration, therefore except being used as the model compound of research natural porphyrin, porphyrins is carried out to the design of functional molecular, give its much special character, be also widely used in the fields such as molecular recognition, DNA probe, catalysis.Because porphyrin has four functional groups and stable molecular structure, therefore can as the kernel of star polymer, in addition the special property that porphyrin has can give again polymkeric substance abundant functional, is no doubt that the star polymer of core has very large magnetism with porphyrin.In addition, porphyrins has specific recognition and inrichment to tumor tissues, and make it have potential medicinal application and be worth, the effective photosensitive medicament particularly as tumor diagnosis and therapy is subject to common concern.At present, in the treatment field of tumour, porphyrin is applied to light mainly as photosensitizers and moves therapy.
Environmental response type multipolymer enjoys people to pay close attention to because of the character of its uniqueness.When external environment generation subtle change, correspondingly can there is rapidly obvious physics or chemical transformation in environmental response type multipolymer.In this series of physical or chemical transformation, most study be the change of its properties of Aqueous Solution, namely in aqueous, when the outside atmospheres such as temperature, pH, illumination change, interaction on a molecular scale can change between polymer chain and chain or between polymer chain and solvent, and then experience is from being dissolved into insoluble change procedure.
Polyoxyethylene glycol (PEG) is the non-ionic water-soluble polymer having biocompatibility, obtain FDA certification, has lower toxicity to human body, is the polymkeric substance be widely used for most at present as polymer micelle hydrophilic segment.Mineo and Migliardo has prepared the water-soluble porphyrin star polymer taking PEO as outer arm.(Mineo P., Scamporrino E., Vitalini D. Macromolecular Rapid Communications,
2002, 23:681-687；Micali N., Villari V., Mineo P., et al. Journal of Physical Chemistry B,
2003,107:5095-5100.)
Poly-N, N-dimethylamino methyl ethyl propenoate, it is a kind of cationic polyelectrolyte polymkeric substance, alkene double bond in monomer whose molecular structure can be polymerized by reversible addion-fragmentation chain transfer, it is more meticulous that atom transfer radical polymerization (ATRP) isoreactivity polymerization means build molecular structure, the multi-arm that structure is more complicated, tree-shaped, comb-shaped polymer, owing to there is hydrophilic tertiary amine groups in molecular structure simultaneously, carbonyl and hydrophobic alkyl group, the amido being positioned at the cationic electrolyte characteristics of side again can to temperature, pH value is made corresponding, thus give multipolymer response function.
The kernel of the molecular structure utilizing porphyrin stable as star polymer and the rich functionality of special property imparting polymkeric substance thereof, in conjunction with living polymerisation process and " click chemistry " of this advanced person of atom transfer radical polymerization, there is the porphyrin of fluorescent effect for core, porphyrin four arm is introduced poly-N, the N-dimethylamino methyl ethyl propenoate simultaneously with pH responsiveness and temperature-responsive-
b-polyoxyethylene glycol block, can prepare porphyrin be core there is fluorescent effect and double responsiveness star block copolymer, this will have widespread use in fields such as biomedicine, nano-medicament carriers.
Summary of the invention
The object of the present invention is to provide a kind of take porphyrin as the preparation method with the star copolymer of fluorescent effect, pH responsiveness and temperature-responsive of core.
The object of the invention is to there is the polymkeric substance of pH and temperature dual response as block scion grafting in the porphyrin core with fluorescent effect, make obtained graft copolymer have good biocompatibility, biological degradability, biological activity, fluorescent effect, pH responsiveness and temperature-responsive simultaneously, and obtain the stable nanometer micelle with fluorescent effect, pH and temperature dual responsiveness by soluble in water for this graft copolymer.The present invention is with commercial 5,10,15,20-tetra-p-hydroxybenzene porphyrin, N, N dimethylamine amino ethyl methacrylate and polyoxyethylene glycol, adopt atom transfer radical polymerization and " click chemistry ", prepare poly-N, N-dimethylamino methyl ethyl propenoate that the different porphyrin of a series of monomer ratio is core-
b-polyoxyethylene glycol segment pH responsiveness, temperature-responsive segmented copolymer.
The preparation method of the porphyrin fluorescence effect that the present invention proposes, pH responsiveness, temperature-responsive stable nanometer micelle, is characterized in that concrete steps are as follows:
(1) by 5,10,15,20-tetra-p-hydroxybenzene porphyrin adds in reactor, and dispersion is dissolved in solvent orange 2 A, then adds 5 under ice-water bath, 10,15, the 2-bromo isobutyl acylbromide of 20-tetra-p-hydroxybenzene porphyrin contained end bromo mole number 1 ~ 10 times amount, time for adding is 10-40 minute, and system is reacted under argon gas or nitrogen protection, temperature of reaction is 10 ~ 40 DEG C, reacts 10 ~ 24 hours; Products therefrom, through washing, dewaters, suction filtration, concentrated, precipitation, suction filtration, and it is that 5,10,15,20-tetra-p-hydroxybenzene porphyrins of bromine are as ATRP reaction initiator that drying obtains end group;
(2) be 5 of bromine by the end group that step (1) obtains, 10,15,20-tetra-p-hydroxybenzene porphyrin is dissolved in solvent B, then monomer N is added, N dimethylamine amino ethyl methacrylate, monomer N, the add-on of N dimethylamine amino ethyl methacrylate is determined by designed molecular weight and performance thereof, add catalyzer C, system is reacted under argon gas or nitrogen protection, and temperature of reaction is 50-90 DEG C, reacts 1 ~ 5 hour; After filtration, precipitation, filters products therefrom, dry, and obtaining take porphyrin as the star-type polymer of core;
(3) step (2) being obtained is that the star-type polymer of core is dissolved in solvent B with porphyrin, and add the sodiumazide of porphyrin contained end bromo mole number 5-20 times amount, temperature of reaction is 40 ~ 80 DEG C, reacts 10 ~ 48 hours; Products therefrom is through precipitation, and suction filtration, dissolves, and washing is concentrated, precipitation, suction filtration, and after drying, obtaining take porphyrin as the azide star-type polymer of core;
(4) what step (3) obtained is that the azide star-type polymer of core is dissolved in solvent D with porphyrin; add the polyoxyethylene glycol of azido group mole number 1 ~ 5 times of alkynyl contained by porphyrin; the molecular weight amount of polyoxyethylene glycol is determined by designed molecular weight and performance thereof; add catalyzer C, system is reacted under argon gas or nitrogen protection, and temperature of reaction is 50 ~ 120 DEG C; react 24 ~ 72 hours; and through dialysis, lyophilize, namely obtains required product.
In the present invention, described solvent orange 2 A is one or more in methylene dichloride, dimethyl sulfoxide (DMSO) or trichloromethane.
In the present invention, described solvent B is one or more in DMF, N, N-diethylformamide, N,N-dimethylacetamide or dimethyl sulfoxide (DMSO).
In the present invention, catalyst system C is one or more in cuprous chloride/dipyridyl, cuprous bromide/dipyridyl, cuprous chloride/pentamethyl-diethylenetriamine, cuprous bromide/pentamethyl-diethylenetriamine, cuprous chloride/hexamethyl Triethylenetetramine (TETA) or cuprous bromide/hexamethyl Triethylenetetramine (TETA).
In the present invention, described solvent D is one or more in DMF, N, N-diethylformamide or N,N-dimethylacetamide.
Beneficial effect of the present invention is: raw material sources are extensive, 5,10,15,20-tetra-p-hydroxybenzene porphyrin has more ripe method to be prepared, N used, N dimethylamine amino ethyl methacrylate, polyoxyethylene glycol, solvent, initiator etc. all can suitability for industrialized production, and synthetic method is simple.The amphipathic of synthesis is that the star block copolymer of core has fluorescent effect, pH responsiveness, temperature-responsive, biocompatibility and biodegradability simultaneously with porphyrin.The minimum critical load factors of polymkeric substance and pH response performance can regulate by changing poly-N, N-dimethylamino methyl ethyl propenoate and polyoxyethylene glycol length in side chain.Multipolymer can be assembled into stable nanometer micelle easily in water.Gained stable nanometer micelle has fluorescent effect, pH responsiveness, temperature-responsive, biological degradability and biocompatibility simultaneously, has a wide range of applications in fields such as drug controlled release carrier, nano-reactor, biological intelligence switch, biosensors.
Accompanying drawing explanation
Fig. 1: porphyrin prepared by embodiment 1 is the pH responsiveness of core, the structural representation of temperature-responsive segmented copolymer.
Embodiment
Following examples further illustrate of the present invention, instead of limit the scope of the invention.
This porphyrin is that the pH responsiveness of core, the molecular structure magnetic nuclear resonance analyzer (NMR) of temperature-responsive segmented copolymer and Fourier transform infrared spectrometer (FTIR) measure.Lower critical solution temperature (LCST) ultraviolet-visible spectrophotometer of band thermal station measures, and LCST is defined as temperature corresponding when transmittance is down to 50% of initial value.
Embodiment 1
Take 5,10,15,20-tetra-p-hydroxybenzene porphyrin 679mg to add in reactor, and dispersion is dissolved in methylene dichloride, under ice-water bath, then add 2-bromo isobutyl acylbromide 4.6g, instills in 30 minutes, under 20 DEG C of argon shields, react 24 hours; Product, after suction filtration dewaters, is dissolved in DMF, adds monomer N, N dimethylamine amino ethyl methacrylate 24g, and cuprous bromide/pentamethyl-diethylenetriamine is catalyst system, reacts under argon shield, and temperature of reaction is 60 DEG C, reacts 2 hours; Filtration drying is dissolved in DMF, then adds sodiumazide 2.6g, reacts 24 hours at 60 DEG C; After suction filtration drying, be dissolved in DMF, add Polyethylene glycol-2000 5.57g; cuprous bromide/pentamethyl-diethylenetriamine is catalyst system, reacts under 80 DEG C of argon shields, reacts 36 hours; and through dialysis, lyophilize, namely obtains required product.
Embodiment 2
Take 5,10,15,20-tetra-p-hydroxybenzene porphyrin 679mg to add in reactor, and dispersion is dissolved in chloroform, under ice-water bath, then add 2-bromo isobutyl acylbromide 4.6g, instills in 40 minutes, under 40 DEG C of argon shields, react 12 hours; Product, after suction filtration dewaters, is dissolved in N,N-dimethylacetamide, adds monomer N, N dimethylamine amino ethyl methacrylate 36g, and cuprous chloride/pentamethyl-diethylenetriamine is catalyst system, reacts under argon shield, and temperature of reaction is 90 DEG C, reacts 1 hour; Filtration drying is dissolved in N,N-dimethylacetamide, then adds sodiumazide 2.6g, reacts 30 hours at 50 DEG C; After suction filtration drying, be dissolved in N,N-dimethylacetamide, add PEG-6000 1.57g; cuprous chloride/pentamethyl-diethylenetriamine is catalyst system, reacts under 120 DEG C of argon shields, reacts 24 hours; and through dialysis, lyophilize, namely obtains required product.
Embodiment 3
Take 5,10,15,20-tetra-p-hydroxybenzene porphyrin 679mg to add in reactor, and dispersion is dissolved in methylene dichloride, under ice-water bath, then add 2-bromo isobutyl acylbromide 4.6g, instills in 30 minutes, under 30 DEG C of argon shields, react 18 hours; Product, after suction filtration dewaters, is dissolved in N, in N-diethyl acetamide, adds monomer N, N dimethylamine amino ethyl methacrylate 24g, and cuprous bromide/dipyridyl is catalyst system, reacts under argon shield, and temperature of reaction is 50 DEG C, reacts 5 hours; Filtration drying is dissolved in N, in N-diethyl acetamide, then adds sodiumazide 2.6g, reacts 48 hours at 40 DEG C; After suction filtration drying, be dissolved in N, in N-diethyl acetamide, add polyoxyethylene glycol-3000 8.57g, cuprous bromide/dipyridyl is catalyst system, reacts under 50 DEG C of argon shields, reacts 72 hours, and through dialysis, lyophilize, namely obtains required product.
Embodiment 4
Take 5,10,15,20-tetra-p-hydroxybenzene porphyrin 679mg to add in reactor, and dispersion is dissolved in dimethyl sulfoxide (DMSO), under ice-water bath, then add 2-bromo isobutyl acylbromide 4.6g, instills in 30 minutes, under 40 DEG C of argon shields, react 12 hours; Product, after suction filtration dewaters, is dissolved in N, in N-diethylformamide, adds monomer N, N dimethylamine amino ethyl methacrylate 24g, and cuprous chloride/dipyridyl is catalyst system, reacts under argon shield, and temperature of reaction is 90 DEG C, reacts 1 hour; Filtration drying is dissolved in N, in N-diethylformamide, then adds sodiumazide 2.6g, reacts 10 hours at 80 DEG C; After suction filtration drying, be dissolved in N, in N-diethylformamide, add Polyethylene glycol-2000 5.57g, cuprous chloride/dipyridyl is catalyst system, reacts under 120 DEG C of argon shields, reacts 24 hours, and through dialysis, lyophilize, namely obtains required product.
Embodiment 5
Take 5,10,15,20-tetra-p-hydroxybenzene porphyrin 679mg to add in reactor, and dispersion is dissolved in methylene dichloride, under ice-water bath, then add 2-bromo isobutyl acylbromide 4.6g, instills in 30 minutes, under 20 DEG C of argon shields, react 24 hours; Product, after suction filtration dewaters, is dissolved in dimethyl sulfoxide (DMSO), adds monomer N, N dimethylamine amino ethyl methacrylate 36g, and cuprous chloride/hexamethyl Triethylenetetramine (TETA) is catalyst system, reacts under argon shield, and temperature of reaction is 80 DEG C, reacts 1.5 hours; Filtration drying is dissolved in dimethyl sulfoxide (DMSO), then adds sodiumazide 2.6g, reacts 18 hours at 70 DEG C; After suction filtration drying, be dissolved in DMF, add Polyethylene glycol-2000 5.57g; cuprous chloride/hexamethyl Triethylenetetramine (TETA) is catalyst system, reacts under 100 DEG C of argon shields, reacts 30 hours; and through dialysis, lyophilize, namely obtains required product.
Claims (5)
1. be a preparation method with the star copolymer of fluorescent effect, pH responsiveness and temperature-responsive for core with porphyrin, it is characterized in that concrete steps are as follows:
(1) by 5,10,15,20-tetra-p-hydroxybenzene porphyrin adds in reactor, and dispersion is dissolved in solvent orange 2 A, then adds 5 under ice-water bath, 10,15, the 2-bromo isobutyl acylbromide of 20-tetra-p-hydroxybenzene porphyrin contained end bromo mole number 1 ~ 10 times amount, time for adding is 10-40 minute, and system is reacted under argon gas or nitrogen protection, temperature of reaction is 10 ~ 40 DEG C, reacts 10 ~ 24 hours; Products therefrom, through washing, dewaters, suction filtration, concentrated, precipitation, suction filtration, and it is that 5,10,15,20-tetra-p-hydroxybenzene porphyrins of bromine are as ATRP reaction initiator that drying obtains end group;
(2) be 5 of bromine by the end group that step (1) obtains, 10,15,20-tetra-p-hydroxybenzene porphyrin is dissolved in solvent B, then monomer N is added, N dimethylamine amino ethyl methacrylate, monomer N, the add-on of N dimethylamine amino ethyl methacrylate is determined by designed molecular weight and performance thereof, add catalyzer C, system is reacted under argon gas or nitrogen protection, and temperature of reaction is 50-90 DEG C, reacts 1 ~ 5 hour; After filtration, precipitation, filters products therefrom, dry, and obtaining take porphyrin as the star-type polymer of core;
(3) step (2) being obtained is that the star-type polymer of core is dissolved in solvent B with porphyrin, and add the sodiumazide of porphyrin contained end bromo mole number 5-20 times amount, temperature of reaction is 40 ~ 80 DEG C, reacts 10 ~ 48 hours; Products therefrom is through precipitation, and suction filtration, dissolves, and washing is concentrated, precipitation, suction filtration, and after drying, obtaining take porphyrin as the azide star-type polymer of core;
(4) what step (3) obtained is that the azide star-type polymer of core is dissolved in solvent D with porphyrin; add the polyoxyethylene glycol of azido group mole number 1 ~ 5 times of alkynyl contained by porphyrin; the molecular weight amount of polyoxyethylene glycol is determined by designed molecular weight and performance thereof; add catalyzer C, system is reacted under argon gas or nitrogen protection, and temperature of reaction is 50 ~ 120 DEG C; react 24 ~ 72 hours; and through dialysis, lyophilize, namely obtains required product.
2. according to claim 1 take porphyrin as the preparation method with the star copolymer of fluorescent effect, pH responsiveness and temperature-responsive of core, it is characterized in that described solvent orange 2 A is one or more in methylene dichloride, dimethyl sulfoxide (DMSO) or trichloromethane.
3. according to claim 1 take porphyrin as the preparation method with the star copolymer of fluorescent effect, pH responsiveness and temperature-responsive of core, it is characterized in that described solvent B is N, dinethylformamide, N, one or more in N-diethylformamide, N,N-dimethylacetamide or dimethyl sulfoxide (DMSO).
4. according to claim 1 take porphyrin as the preparation method with the star copolymer of fluorescent effect, pH responsiveness and temperature-responsive of core, it is characterized in that catalyst system C is one or more in cuprous chloride/dipyridyl, cuprous bromide/dipyridyl, cuprous chloride/pentamethyl-diethylenetriamine, cuprous bromide/pentamethyl-diethylenetriamine, cuprous chloride/hexamethyl Triethylenetetramine (TETA) or cuprous bromide/hexamethyl Triethylenetetramine (TETA).
5. according to claim 1 take porphyrin as the preparation method with the star copolymer of fluorescent effect, pH responsiveness and temperature-responsive of core, it is characterized in that described solvent D is N, one or more in dinethylformamide, N, N-diethylformamide or N,N-dimethylacetamide.
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| CN111848966B (en) * | 2020-08-10 | 2022-02-01 | 上海市第十人民医院 | Porphyrin-based temperature-responsive self-healing hydrogel and preparation method, use method and application thereof |
| CN112028900A (en) * | 2020-09-10 | 2020-12-04 | 苏州大学 | Synthesis of star polymer and monomolecular micelle by light-operated in-situ bromine-iodine conversion RDRP method |
| CN112028900B (en) * | 2020-09-10 | 2021-08-31 | 苏州大学 | Synthesis of star polymer and monomolecular micelle by light-operated in-situ bromine-iodine conversion RDRP method |
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