CN104861172B - A kind of preparation method of the star copolymer with fluorescent effect, pH responses and temperature-responsive with porphyrin as core - Google Patents
A kind of preparation method of the star copolymer with fluorescent effect, pH responses and temperature-responsive with porphyrin as core Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of the star copolymer with fluorescent effect, pH responses and temperature-responsive with porphyrin as core.By 5,10,15,20 4 p-hydroxybenzene Porphyrin mutations are the Porphyrin Molecule containing four bromine groups, it is macromole evocating agent by N with the Porphyrin Molecule containing four bromine groups, the atom transfer radical polymerization of N dimethylamino methyl acrylic acid ethyl ester monomers, and carry out Azide, and with Azide to porphyrin to check poly- N, N dimethylamino methyls ethyl acrylate is with alkynyl polyethylene glycol as reaction module, eventually through click chemistry, the star block copolymer with fluorescent effect, pH responses and temperature-responsive is obtained.The present invention has biological degradability, biocompatibility, biological activity, fluorescent effect, pH responses, temperature-responsive, in input water, strong opponent forms stable nano-micelle, has a wide range of applications in fields such as drug controlled release carrier, biological intelligence switch, biosensors.The inventive method is simple, raw material can industrialized production, with good application value.
Description
Technical field
The invention belongs to macromolecular material and biomedical engineering field, and in particular to it is a kind of with porphyrin as core with glimmering
The preparation method of the star copolymer of photo effect, pH responses and temperature-responsive.
Background technology
Porphyrin is isolating protein, the another kind of most important bio-ligand outside nucleic acid base.Except wide in life entity
Outside the protoporphyrin of general presence, people explore and have synthesized many synthetic porphyrins.Synthesis porphyrin is not only simple in structure, Er Qieke
To design, synthesize the compound of the wonderful workmanship excelling nature with ad hoc structure and performance as needed, and also there is electronics resiliency
With the characteristic such as the multiformity and self assembly of photoelectric magnetic property and spatial configuration, therefore except the modelling as research natural porphyrin
Outside compound, the design of functional molecular is carried out to porphyrinses, give its many special property, be also widely used for molecule
The fields such as identification, DNA probe, catalysis.As porphyrin has four functional groups and stable molecular structure, therefore can be used as star
The kernel of shape polymer, the special nature that porphyrin has in addition can give polymer abundant feature again, no doubt with porphin
Quinoline has very big captivation for the star polymer of core.Additionally, porphyrinses have specific recognition to tumor tissues
And enrichment so as to it is worth with potential medicinal application, especially as the effective photosensitive medicament of tumor diagnosis and therapy
By common concern.At present, in the therapy field of tumor, porphyrin is applied to the dynamic therapy of light mainly as photosensitizer.
Environmental response type copolymer enjoys people to pay close attention to because of its unique property.When external environment occurs minor variations
When, environmental response type copolymer correspondingly can occur rapidly obvious physically or chemically change.In this series of physical or
In chemical change, most study be its properties of Aqueous Solution change, i.e., in aqueous, when external rings such as temperature, pH, illumination
When border changes, the interaction between polymer chain and chain or between polymer chain and solvent on a molecular scale can occur
Change, and then experience from being dissolved into insoluble change procedure.
Polyethylene Glycol（PEG）It is with biocompatibility, has obtained the non-ionic water-soluble polymer of FDA certifications, to people
Body has relatively low toxicity, is most to be widely used for the polymer as polymer micelle hydrophilic segment at present.Mineo and
Migliardo is prepared for the water-soluble porphyrin star polymer with 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- dimethylaminoethyl methacrylate, is a kind of cationic polyelectrolyte polymer, monomer molecule knot
Alkene double bond in structure can be by reversible addion-fragmentation chain transfer polymerization, atom transfer radical polymerization（ATRP）Deng
Molecular structure is more fine to build for living polymerization means, the increasingly complex multi-arm of structure, tree-shaped, comb-shaped polymer, due to dividing
There is in minor structure hydrophilic tertiary amine groups, carbonyl and hydrophobic alkyl group simultaneously, the cationic positioned at side is electrolysed
The amido of matter characteristic can be made to temperature, pH value again accordingly, so as to give copolymer response function.
The rich of polymer is given by the use of the stable molecular structure of porphyrin as the kernel of star polymer and its special nature
Rich feature, with reference to this advanced living polymerisation process of atom transfer radical polymerization and " click chemistry ", with fluorescence
The porphyrin of effect is core, and the poly- N with pH responses and temperature-responsive, N- dimethylaminos are introduced on four arm of porphyrin
Ethyl methacrylate-b- Polyethylene Glycol block, can prepare porphyrin for the star-like with fluorescent effect and double responsiveness of core
Block copolymer, tool is widely used by this in fields such as biomedicine, nano-medicament carriers.
The content of the invention
It is an object of the invention to provide it is a kind of with porphyrin as core with fluorescent effect, pH responses and temperature-responsive
Star copolymer preparation method.
The purpose of the present invention is the polymer that will be responded with pH and temperature dual as block scion grafting to fluorescence effect
In the porphyrin core answered, obtained graft copolymer is made while having good biocompatibility, biological degradability, biology living
Property, fluorescent effect, pH responses and temperature-responsive, and obtain this graft copolymer soluble in water with fluorescent effect, pH
With the stable nanometer micelle of temperature dual response.The tetra- p-hydroxybenzene porphyrins of 5,10,15,20- of present invention commercialization, N,
N dimethylamine amino ethyl methacrylate and Polyethylene Glycol, using atom transfer radical polymerization and " click chemistry ", prepare one
Poly- N of the different porphyrin of series monomers ratio for core, N- dimethylaminoethyl methacrylates-b- Polyethylene Glycol segment pH is responded
Property, temperature-responsive block copolymer.
Porphyrin fluorescence effect proposed by the present invention, pH responses, the preparation method of temperature-responsive stable nanometer micelle, its
It is characterised by comprising the following steps that：
(1) by 5,10,15,20- tetra- p-hydroxybenzene porphyrins are added in reactor, and dispersion is dissolved in solvent orange 2 A, Ran Hou
The 2- bromo isobutyls of contained 1～10 times of amount of end bromo molal quantity of tetra- p-hydroxybenzene porphyrins of 5,10,15,20- are added under ice-water bath
Acylbromide, time for adding be 10-40 minutes, system argon or nitrogen protection under react, reaction temperature be 10～40 DEG C, reaction 10
～24 hours；Products therefrom is scrubbed, eliminating water, sucking filtration, concentration, precipitation, sucking filtration, be dried to obtain end group be bromine 5,10,15,
Tetra- p-hydroxybenzene porphyrins of 20- are used as ATRP reaction initiators；
(2) end group for obtaining step (1) is dissolved in solvent B, so for 5,10,15,20- tetra- p-hydroxybenzene porphyrins of bromine
Monomer N is added afterwards, and N dimethylamine amino ethyl methacrylate, monomer N, the addition of N dimethylamine amino ethyl methacrylate are pressed
Designed molecular weight and its performance determine that add catalyst C, system to react under argon or nitrogen protection, reaction temperature is
50-90 DEG C, react 1～5 hour；Products therefrom Jing is filtered, precipitation, is filtered, and is dried, is obtained the star polymerization with porphyrin as core
Thing；
(3) star-type polymer that step (2) is obtained with porphyrin as core is dissolved in solvent B, adds the contained end bromine of porphyrin
The Hydrazoic acid,sodium salt that 5-20 times of base molal quantity is measured, reaction temperature are 40～80 DEG C, are reacted 10～48 hours；Products therefrom Jing is precipitated,
Sucking filtration, dissolving, washing, concentration, precipitation, sucking filtration, after being dried, obtain the Azide star-type polymer with porphyrin as core；
(4) the Azide star-type polymer with porphyrin as core that step (3) is obtained is dissolved in solvent D, adds porphyrin
The Polyethylene Glycol of contained 1～5 times of alkynyl of azido group molal quantity, the molecular weight amount of Polyethylene Glycol press designed molecular weight and
Its performance determines that add catalyst C, system to react under argon or nitrogen protection, reaction temperature is 50～120 DEG C, reaction 24
～72 hours, and Jing dialysis, lyophilization obtain required product.
In the present invention, the solvent orange 2 A is one or more in dichloromethane, dimethyl sulfoxide or chloroform.
In the present invention, the solvent B be DMF, N, N- diethylformamide, N, N- dimethylacetamides
One or more in amine or dimethyl sulfoxide.
In the present invention, catalyst system C is Cu-lyt ./bipyridyl, cuprous bromide/bipyridyl, Cu-lyt ./pentamethyl
Diethylenetriamine, cuprous bromide/pentamethyl-diethylenetriamine, Cu-lyt ./hexamethyl trien or cuprous bromide/six
One or more in methyl trien.
In the present invention, the solvent D is DMF, N, N- diethylformamide or N, N- dimethylacetamide
One or more in amine.
The beneficial effects of the present invention is：Extensively, 5,10,15,20- tetra- p-hydroxybenzene porphyrins have more ripe to raw material sources
Method be prepared, N used, N dimethylamine amino ethyl methacrylate, Polyethylene Glycol, solvent, initiator etc. can works
Industry metaplasia is produced, and synthetic method is simple.The amphipathic star block copolymer with porphyrin as core of synthesis has fluorescence simultaneously
Effect, pH responses, temperature-responsive, biocompatibility and biodegradability.The minimum critical load factors of polymer
Can be by changing poly- N in side chain with pH response performances, N- dimethylaminoethyl methacrylates are carried out with Polyethylene Glycol length
Adjust.Copolymer can easily be assembled into stable nanometer micelle in water.Gained stable nanometer micelle has fluorescence simultaneously
Effect, pH responses, temperature-responsive, biological degradability and biocompatibility, react in drug controlled release carrier, nanometer
The fields such as device, biological intelligence switch, biosensor have a wide range of applications.
Description of the drawings
Fig. 1：PH responses, the structural representation of temperature-responsive block copolymer of the porphyrin prepared by embodiment 1 for core.
Specific embodiment
Following examples are that the present invention is further illustrated, rather than limit the scope of the present invention.
PH response, the molecular structure magnetic nuclear resonance analyzer of temperature-responsive block copolymer of the porphyrin for core
（NMR）And Fourier transform infrared spectrometer（FTIR）Determine.Lower critical solution temperature（LCST）With the ultraviolet-visible with thermal station
Spectrophotometric determination, LCST are defined as light transmittance and are down to temperature corresponding during the 50% of initial value.
Embodiment 1
Weigh 5,10,15,20- tetra- p-hydroxybenzene porphyrin 679mg to add in reactor, and dispersion is dissolved in dichloromethane
In, then 2- bromo isobutyl acylbromide 4.6g are added under ice-water bath, instill in 30 minutes, under 20 DEG C of argon protections, reaction 24 is little
When；Product is dissolved in DMF Jing after sucking filtration eliminating water, adds monomer N, N dimethylamine amino ethyl methacrylate
24g, cuprous bromide/pentamethyl-diethylenetriamine are catalyst system and catalyzing, are reacted under argon protection, and reaction temperature is 60 DEG C, reaction 2
Hour；Filtration drying is dissolved in DMF, is subsequently adding Hydrazoic acid,sodium salt 2.6g, is reacted 24 hours at 60 DEG C；Take out
Be filtered dry it is dry after, be dissolved in DMF, add Polyethylene glycol-2000 5.57g, cuprous bromide/pentamethyl diethyl
Alkene triamine is catalyst system and catalyzing, reacts, react 36 hours under 80 DEG C of argon protections, and Jing dialysis, lyophilization, that is, needed for obtaining
Product.
Embodiment 2
Weigh 5,10,15,20- tetra- p-hydroxybenzene porphyrin 679mg to add in reactor, and dispersion is dissolved in chloroform, so
2- bromo isobutyl acylbromide 4.6g are added under ice-water bath afterwards, is instilled in 40 minutes, under 40 DEG C of argon protections, reacted 12 hours；Produce
Thing is dissolved in N,N-dimethylacetamide Jing after sucking filtration eliminating water, adds monomer N, N dimethylamine amino ethyl methacrylate 36g,
Cu-lyt ./pentamethyl-diethylenetriamine is catalyst system and catalyzing, is reacted under argon protection, and reaction temperature is 90 DEG C, and reaction 1 is little
When；Filtration drying is dissolved in N,N-dimethylacetamide, is subsequently adding Hydrazoic acid,sodium salt 2.6g, is reacted 30 hours at 50 DEG C；Sucking filtration
After drying, it is dissolved in N,N-dimethylacetamide, adds PEG-6000 1.57g, Cu-lyt ./pentamethyl divinyl
Triamine is catalyst system and catalyzing, reacts, react 24 hours under 120 DEG C of argon protections, and Jing dialysis, lyophilization, that is, needed for obtaining
Product.
Embodiment 3
Weigh 5,10,15,20- tetra- p-hydroxybenzene porphyrin 679mg to add in reactor, and dispersion is dissolved in dichloromethane
In, then 2- bromo isobutyl acylbromide 4.6g are added under ice-water bath, instill in 30 minutes, under 30 DEG C of argon protections, reaction 18 is little
When；Product is dissolved in N Jing after sucking filtration eliminating water, in N- diethyl acetamides, adds monomer N, N dimethylamine amino ethyl methacrylate
24g, cuprous bromide/bipyridyl are catalyst system and catalyzing, are reacted under argon protection, and reaction temperature is 50 DEG C, is reacted 5 hours；Filter
Drying is dissolved in N, in N- diethyl acetamides, is subsequently adding Hydrazoic acid,sodium salt 2.6g, reacts 48 hours at 40 DEG C；After sucking filtration is dried,
N is dissolved in, in N- diethyl acetamides, -3000 8.57g of Polyethylene Glycol is added, cuprous bromide/bipyridyl is catalyst system and catalyzing,
React under 50 DEG C of argon protections, react 72 hours, and Jing dialyses, lyophilization obtains required product.
Embodiment 4
Weigh 5,10,15,20- tetra- p-hydroxybenzene porphyrin 679mg to add in reactor, and dispersion is dissolved in dimethyl sulfoxide
In, then 2- bromo isobutyl acylbromide 4.6g are added under ice-water bath, instill in 30 minutes, under 40 DEG C of argon protections, reaction 12 is little
When；Product is dissolved in N Jing after sucking filtration eliminating water, in N- diethylformamide, adds monomer N, N dimethylamine amino ethyl methacrylate
24g, Cu-lyt ./bipyridyl are catalyst system and catalyzing, are reacted under argon protection, and reaction temperature is 90 DEG C, is reacted 1 hour；Filter
Drying is dissolved in N, in N- diethylformamide, is subsequently adding Hydrazoic acid,sodium salt 2.6g, reacts 10 hours at 80 DEG C；After sucking filtration is dried,
N is dissolved in, in N- diethylformamide, Polyethylene glycol-2000 5.57g is added, Cu-lyt ./bipyridyl is catalyst system and catalyzing,
React under 120 DEG C of argon protections, react 24 hours, and Jing dialyses, lyophilization obtains required product.
Embodiment 5
Weigh 5,10,15,20- tetra- p-hydroxybenzene porphyrin 679mg to add in reactor, and dispersion is dissolved in dichloromethane
In, then 2- bromo isobutyl acylbromide 4.6g are added under ice-water bath, instill in 30 minutes, under 20 DEG C of argon protections, reaction 24 is little
When；Product is dissolved in dimethyl sulfoxide Jing after sucking filtration eliminating water, adds monomer N, N dimethylamine amino ethyl methacrylate 36g, chlorine
Cuprous/hexamethyl the trien of change is catalyst system and catalyzing, is reacted under argon protection, and reaction temperature is 80 DEG C, and reaction 1.5 is little
When；Filtration drying is dissolved in dimethyl sulfoxide, is subsequently adding Hydrazoic acid,sodium salt 2.6g, is reacted 18 hours at 70 DEG C；Sucking filtration is dried
Afterwards, it is dissolved in DMF, adds Polyethylene glycol-2000 5.57g, Cu-lyt ./hexamethyl triethylene four
Amine is catalyst system and catalyzing, reacts, react 30 hours under 100 DEG C of argon protections, and Jing dialysis, and lyophilization obtains required product
Thing.
Claims (4)
1. a kind of preparation side of the star copolymer with fluorescent effect, pH responses and temperature-responsive with porphyrin as core
Method, it is characterised in that comprise the following steps that：
(1) by 5,10,15,20- tetra- p-hydroxybenzene porphyrins are added in reactor, and dispersion is dissolved in solvent orange 2 A, then in frozen water
The lower 2- bromo isobutyl acylbromides for adding contained 1～10 times of amount of end bromo molal quantity of 5,10,15,20- tetra- p-hydroxybenzene porphyrins of bath,
Time for adding be 10-40 minutes, system argon or nitrogen protection under react, reaction temperature be 10～40 DEG C, reaction 10～24
Hour；Products therefrom is scrubbed, eliminating water, sucking filtration, concentration, precipitation, sucking filtration, is dried to obtain end group for 5, the 10,15,20- tetra- of bromine
P-hydroxybenzene porphyrin is used as ATRP reaction initiators；
(2) end group for obtaining step (1) is dissolved in solvent B for 5,10,15,20- tetra- p-hydroxybenzene porphyrins of bromine, Ran Houjia
Enter monomer N, N dimethylamine amino ethyl methacrylate, monomer N, the addition of N dimethylamine amino ethyl methacrylate press set
The molecular weight of meter and its performance determine that add catalyst C, system to react under argon or nitrogen protection, reaction temperature is 50-90
DEG C, react 1～5 hour；Products therefrom Jing is filtered, precipitation, is filtered, and is dried, is obtained the star-type polymer with porphyrin as core；
(3) star-type polymer that step (2) is obtained with porphyrin as core is dissolved in solvent B, adds the contained end bromo of porphyrin to rub
The Hydrazoic acid,sodium salt that your 5-20 times of number is measured, reaction temperature are 40～80 DEG C, are reacted 10～48 hours；Products therefrom Jing is precipitated, sucking filtration,
Dissolving, washing, concentration, precipitation, sucking filtration, after being dried, obtain the Azide star-type polymer with porphyrin as core；
(4) the Azide star-type polymer with porphyrin as core that step (3) is obtained is dissolved in solvent D, is added contained by porphyrin
The Polyethylene Glycol of 1～5 times of alkynyl of azido group molal quantity, the molecular weight of Polyethylene Glycol press designed molecular weight and its performance
It is determined that, add catalyst C, system to react under argon or nitrogen protection, reaction temperature is 50～120 DEG C, and reaction 24～72 is little
When, and Jing dialysis, lyophilization obtain required product；
Wherein：Catalyst system C is Cu-lyt ./bipyridyl, cuprous bromide/bipyridyl, Cu-lyt ./pentamethyl divinyl three
Amine, cuprous bromide/pentamethyl-diethylenetriamine, Cu-lyt ./hexamethyl trien or cuprous bromide/hexamethyl Sanya
One or more in tetramine.
2. it is according to claim 1 with porphyrin as core with the star-like of fluorescent effect, pH responses and temperature-responsive
The preparation method of copolymer, is characterized in that the solvent orange 2 A for the one kind or several in dichloromethane, dimethyl sulfoxide or chloroform
Kind.
3. it is according to claim 1 with porphyrin as core with the star-like of fluorescent effect, pH responses and temperature-responsive
The preparation method of copolymer, is characterized in that the solvent B for DMF, N, N- diethylformamide, N, N- bis-
One or more in methylacetamide or dimethyl sulfoxide.
4. it is according to claim 1 with porphyrin as core with the star-like of fluorescent effect, pH responses and temperature-responsive
The preparation method of copolymer, is characterized in that the solvent D is DMF, N, N- diethylformamide or N, N- bis-
One or more in methylacetamide.
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| CN105647517B (en) * | 2016-01-29 | 2018-09-14 | 济宁学院 | A kind of porphyrin fluorescence nano-probe and its preparation method and application |
| CN105732919A (en) * | 2016-03-25 | 2016-07-06 | 同济大学 | Preparation method of porphyrin-containing temperature/multi-metal-ion-responsive block copolymer gel |
| CN105778897B (en) * | 2016-04-11 | 2017-12-26 | 湖南大学 | PH sensitive fluorescence dyes and its preparation method and application |
| CN106344929B (en) * | 2016-11-11 | 2019-09-27 | 苏州大学 | Covalent organic polymer of a kind of reduction responsiveness and its preparation method and application |
| CN106582860B (en) * | 2016-12-24 | 2019-05-07 | 华北科技学院 | Load has noble metal nano particles/metalloporphyrin composite micelle and preparation method |
| US10467211B2 (en) | 2017-11-15 | 2019-11-05 | International Business Machines Corporation | Representing and analyzing cloud computing data as pseudo systems |
| US10584191B2 (en) | 2017-11-28 | 2020-03-10 | International Business Machines Corporation | Antimicrobial star polymers with light-activated enhanced antimicrobial activity |
| US10561146B2 (en) * | 2017-11-28 | 2020-02-18 | International Business Machines Corporation | Star polymers with enhanced antimicrobial activity in response to light |
| CN108827480B (en) * | 2018-04-11 | 2020-03-27 | 山东师范大学 | Anti-oxidation interference temperature sensor based on phosphorescence emission |
| CN109232899B (en) * | 2018-09-14 | 2021-09-14 | 陕西师范大学 | PH and photoresponse polymer carrier material, preparation thereof and application of immobilized pectinase |
| US10778709B2 (en) | 2018-10-31 | 2020-09-15 | International Business Machines Corporation | Cloud-native extensibility provided to security analytics |
| CN109646398B (en) * | 2019-01-03 | 2021-04-16 | 西南交通大学 | Nano micelle and preparation method and application thereof |
| 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 |
| 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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