CN101864138B - Preparation method of chitosan temperature sensitivity stable nanometer micelle - Google Patents
Preparation method of chitosan temperature sensitivity stable nanometer micelle Download PDFInfo
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- CN101864138B CN101864138B CN2010102070814A CN201010207081A CN101864138B CN 101864138 B CN101864138 B CN 101864138B CN 2010102070814 A CN2010102070814 A CN 2010102070814A CN 201010207081 A CN201010207081 A CN 201010207081A CN 101864138 B CN101864138 B CN 101864138B
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Abstract
The invention relates to a preparation method of a chitosan temperature sensitivity stable nanometer micelle. The preparation method comprises the following steps of: carrying out esterification on hydroxyl or amino in the backbone of chitosan and bromine containing compounds under the protection of inert gases such as nitrogen or argon to convert hydroxyl or amino into a bromine group; carrying out atom transfer radical polymerization on N-isopropylacrylamide monomer by taking the bromine group as a macromolecule initiator to form a temperature sensitivity polymer and finally obtain a temperature sensitivity graft copolymer which takes the chitosan as the backbone; and dissolving the temperature sensitivity graft copolymer into water to form the stable temperature sensitivity nanometer micelle. The chitosan temperature sensitivity stable nanometer micelle has biodegradability, biocompatibility, bioactivity and temperature sensitivity, and has wide application in the fields of medicament control release carriers, biological intelligent switches, biosensors and the like. The preparation method is simple and practicable and has very good application and dissemination value, and the raw materials can be industrially produced.
Description
Technical field
The invention belongs to macromolecular material and biomedical engineering field, be specifically related to a kind of preparation method of chitosan temperature sensitivity stable nanometer micelle.
Background technology
Amphipathic nature polyalcohol is assembled, can prepare nano-micelle and be used for medicine controlled release carrier etc., yet for general amphiphilic polymer, by assembling resulting nano-micelle owing to the connection that does not have covalent linkage, be difficult in complex environment, keep form stable, break easily.Therefore keeping the stability of nano-micelle under various environment, is must consider one of key issue when preparation and using polymer micella.
Chitosan is one of the abundantest natural biological macromolecular material of nature reserves, has excellent biocompatibility, biological degradability and biological activity.Dong Changming (Feng, H.; Dong, C.M.Biomacromolecules, 2006,7,3069)) etc. prepared chitosan-polylactide amphipathic graft copolymer by ring-opening polymerization, and in water, be assembled into stable micella.Not only can prepare nano-micelle by graft modification based on chitosan to chitosan, and can expand the function of chitosan, have favorable biological degradability and solvability (Liu, L. as multipolymers such as chitosan-polylactide or chitosan-polycaprolactones; Chen, L.X.; Fang, Y.E.Macromol.Rapid Commun.2006,27,1988).
Poly-(N-N-isopropylacrylamide) is because of the amide group and the hydrophobic sec.-propyl of while possess hydrophilic property on its side chain, thereby present excellent temperature sensitive characteristic, response is made in the slight change of envrionment temperature to external world, and produces the macromolecular material of respective physical structure and chemical property variation even sudden change.Under the normal temperature, poly-(N-N-isopropylacrylamide) can be dissolved in the water and form uniform solution, and when temperature was increased to a certain temperature between 30-35 ℃, solution was separated.Up to the present, poly-(N-N-isopropylacrylamide) becomes research maximum temperature sensitive polymer (Xu, F.J.; Li, J.; Yuan, S.J.; Zhang, Z.X.; Kang, E.T.; Neoh, K.G.Biomacromolecules, 2008,9,331; You Y.Z.; Hong C.Y.; Wang W.P.; Lu W.Q.; Pan C.Y.Macromolecules, 2004,37,9761.).
To gather (N-N-isopropylacrylamide) by the atom transferred free radical method and be connected on the chitosan main chain, obtain the amphipathic temperature sensitive function graft copolymer of chitosan as side chain.Can obtain nano-micelle at an easy rate with this multipolymer is soluble in water.The chitosan main chain is as the nuclear of nano-micelle, and gathers (N-N-isopropylacrylamide) shell as nano-micelle.Because poly-(N-N-isopropylacrylamide) is to be connected to as on the chitosan main chain of examining by covalent linkage, thereby resulting micella is highly stable, can not break.
Utilize biocompatibility, biological degradability and the biological activity of chitosan, polymerization process in conjunction with this advanced person of atom transfer radical polymerization, on the chitosan side group, introduce poly-(N-N-isopropylacrylamide) segment with temperature sensitivity, synthetic chitosan is the temperature sensitivity graft copolymer of main chain, and preparation stabilized nano micella, this will have widespread use in fields such as biomedicines.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of preparation method of chitosan temperature sensitivity stable nanometer micelle, this method is by being incorporated into temperature sensitive polymer on the chitosan as side chain, make the graft copolymer that is obtained have excellent biocompatibility, biological degradability, temperature sensitivity simultaneously, and with this graft copolymer stable nanometer micelle that obtains having temperature sensitivity soluble in water.The present invention adopts atom transfer radical polymerization method with commercial chitosan and N-N-isopropylacrylamide monomer, prepares the chitosan temperature sensitivity grafting polyarylene block copolymer of poly-(N-N-isopropylacrylamide) side chain of a series of different chain length.
For solving the problems of the technologies described above, the present invention by the following technical solutions:
A kind of preparation method of chitosan temperature sensitivity stable nanometer micelle may further comprise the steps:
Chitosan is added reactor, and dispersing and dissolving is in solvent orange 2 A, the acid binding agent B of terminal hydroxy group or 1～20 times of amount of amino mole number on the adding chitosan main chain, the bromine-containing compound C of hydroxyl and 1～20 times of amount of amino mole number on dropping chitosan main chain under 0～15 ℃ of condition, the dropping time is 20～70 minutes, after dripping end, adjusting temperature of reaction is 10～40 ℃, and the reaction times is 18～72 hours.The gained reaction product is removed post precipitation through suction filtration, and filtrate is precipitated through deionized water, suction filtration again, and after gained precipitated vacuum-drying, obtain the end capped chitosan macromole evocating agent of bromo.Resulting bromo end-blocking chitosan macromole evocating agent is dissolved in solvent D, and the amount according to 10～500 times of the contained end bromo of bromo end-blocking chitosan macromole evocating agent mole numbers adds monomer N-N-isopropylacrylamide in this solution, and the amount according to 1～5 times of the contained end bromo of bromo end-blocking chitosan macromole evocating agent mole number adds catalyzer E simultaneously.Under catalyzer E effect, system is reacted under argon gas or nitrogen protection, temperature of reaction is 20～100 ℃, the reaction times is 2～48 hours.Then, after catalyzer E was removed in the deionized water dialysis, lyophilize obtained chitosan and is the temperature sensitivity graft copolymer of main chain, and this multipolymer is soluble in water, promptly obtains chitosan temperature sensitivity stable nanometer micelle of the present invention with the previous reaction product.
Among the present invention, described solvent orange 2 A is N, dinethylformamide, N, one or more in N-diethylformamide, N,N-dimethylacetamide or the dimethyl sulfoxide (DMSO).
Among the present invention, described acid binding agent B is one or more in diethylamine, triethylamine, pyridine or the sodium acetate.
Among the present invention, described bromine-containing compound C is one or both in 2 bromo propionyl bromide or the 2-bromine isobutyl acylbromide.
Among the present invention, described solvent D is methyl-phenoxide, N, dinethylformamide, N, a kind of in N-diethylformamide or the N,N-dimethylacetamide or several.
Among the present invention, described catalyzer E is one or both in cuprous chloride/hexamethyl Triethylenetetramine (TETA) or the cuprous bromide/hexamethyl Triethylenetetramine (TETA).
The invention has the advantages that: raw material sources are extensive, but equal suitability for industrialized production such as used chitosan, N-N-isopropylacrylamide monomer, solvent, catalyzer, and synthetic method is simple, all can obtain by market channel.Synthetic is that the amphipathic graft copolymer of main chain possesses temperature sensitivity, biocompatibility and degradability simultaneously with the chitosan.Multipolymer can easily be assembled into stable nanometer micelle in water.The micella particle diameter can be realized by the length of regulating poly-(N-N-isopropylacrylamide).The gained stable nanometer micelle has biological degradability, biocompatibility, temperature sensitivity simultaneously, thereby has application widely in fields such as medicine sustained release carrier, biological intelligence switch, biosensors.
Description of drawings
Fig. 1 is the structural representation of the temperature sensitivity graft copolymer of main chain for the chitosan of embodiment 1 preparation.
Fig. 2 is the atomic force microscope photo of the chitosan temperature sensitivity stable nanometer micelle of embodiment 2 preparations.
Embodiment
The present invention will be further described below in conjunction with embodiment and accompanying drawing, rather than limit the scope of the invention.
Following examples gained chitosan is that the molecular structure of the temperature sensitivity graft copolymer of main chain is measured with Fourier transform infrared spectrometer (FTIR) and magnetic nuclear resonance analyzer (NMR).Lower critical solution temperature (LCST) is measured with the ultraviolet-visible spectrophotometer with hot platform, and LCST is defined as 50% o'clock pairing temperature that transmittance is reduced to initial value.Assembling gained nano-micelle is measured with transmission electron microscope (TEM) and atomic force microscope (AFM).The nano-micelle particle diameter is measured with dynamic laser light scattering apparatus (DLS).
Embodiment 1
Take by weighing chitosan 5 grams, use N, behind the dinethylformamide dispersing and dissolving, add triethylamine 15 grams, drip 2-bromine isobutyl acylbromide 30 grams, dripped off in 20 minutes, drip and finish the back 10 ℃ of reactions 72 hours at 0 ℃.Reaction product is removed post precipitation through suction filtration, and filtrate is precipitated through deionized water, and again through suction filtration, the gained precipitation is carried out vacuum-drying, obtains the end capped chitosan macromole evocating agent of bromo.Take by weighing aforementioned bromo end-blocking chitosan macromole evocating agent 0.1 gram and be dissolved in N; dinethylformamide; in this solution, add 2 gram N-N-isopropylacrylamide and catalyzer cuprous bromide (20 milligrams)/hexamethyl Triethylenetetramine (TETA)s (40 milligrams); reaction system is through vacuumizing-inflated with nitrogen process 3 times, reaction 48 hours in 20 ℃ of oil baths under nitrogen protection.Reaction product after catalyzer is removed in deionized water dialysis, lyophilize, promptly getting chitosan is the temperature sensitivity graft copolymer of main chain, promptly obtains chitosan temperature sensitivity stable nanometer micelle of the present invention with this multipolymer is soluble in water.
Above-mentioned chitosan be main chain the temperature sensitivity graft copolymer the exemplary configuration formula as shown in Figure 1, be with Fourier transform infrared spectrometer (FTIR) and magnetic nuclear resonance analyzer (NMR) mensuration.
The atomic force microscope photo of above-mentioned chitosan temperature sensitivity stable nanometer micelle is to measure with transmission electron microscope (TEM) and atomic force microscope (AFM) as shown in Figure 2.Described nano-micelle particle diameter is measured with dynamic laser light scattering apparatus (DLS).。
Embodiment 2
Take by weighing chitosan 5 grams, use N, behind the dinethylformamide dispersing and dissolving, add diethylamine 20 grams, drip 2 bromo propionyl bromide 40 grams, dripped off in 30 minutes, drip and finish the back 15 ℃ of reactions 60 hours at 5 ℃.Reaction product is removed post precipitation through suction filtration, and filtrate is precipitated through deionized water, and again through suction filtration, gained precipitates through vacuum-drying, obtains the end capped chitosan macromole evocating agent of bromo.Take by weighing aforementioned bromo end-blocking chitosan macromole evocating agent 0.1 gram and be dissolved in N; the N-N,N-DIMETHYLACETAMIDE; in this solution, add N-N-isopropylacrylamide 3 gram and catalyzer cuprous bromide (25 milligrams)/hexamethyl Triethylenetetramine (TETA)s (40 milligrams); reaction system is through vacuumizing-inflated with nitrogen process 3 times, and reaction 36 hours in 40 ℃ of oil baths under nitrogen protection.After catalyzer is removed in reaction product deionized water dialysis, lyophilize, obtaining chitosan is the temperature sensitivity graft copolymer of main chain, promptly gets chitosan temperature sensitivity stable nanometer micelle of the present invention with this multipolymer is soluble in water.
Embodiment 3
Take by weighing chitosan 5 grams, behind the N,N-dimethylacetamide dispersing and dissolving, add pyridine 18 grams, drip 2-bromine isobutyl acylbromide 36 grams, dripped off in 40 minutes, drip and finish the back 20 ℃ of reactions 48 hours at 8 ℃.Reaction product is removed post precipitation through suction filtration, and filtrate is precipitated through deionized water, and behind suction filtration, gained precipitates through vacuum-drying again, obtains the end capped chitosan macromole evocating agent of bromo.Take by weighing aforementioned bromo end-blocking chitosan macromole evocating agent 0.1 gram and be dissolved in N; the N-diethylformamide; in this solution, add N-N-isopropylacrylamide 4 grams; add catalyzer cuprous chloride (28 milligrams)/hexamethyl Triethylenetetramine (TETA) (46 milligrams) again; through vacuumizing-inflated with nitrogen process 3 times, and reaction 10 hours in 50 ℃ of oil baths under nitrogen protection.Reaction product after catalyzer is removed in deionized water dialysis, lyophilize, obtaining chitosan is the temperature sensitivity graft copolymer of main chain, promptly gets chitosan temperature sensitivity stable nanometer micelle of the present invention with this multipolymer is soluble in water.
Embodiment 4
Take by weighing chitosan 5 grams, behind the dimethyl sulfoxide (DMSO) dispersing and dissolving, add diethylamine 26 grams, drip 2 bromo propionyl bromide 45 grams, dripped off in 50 minutes, drip and finish the back 30 ℃ of reactions 36 hours at 10 ℃.Reaction product is removed post precipitation through suction filtration, and gained filtrate is precipitated through deionized water, and behind suction filtration, gained precipitates through vacuum-drying again, obtains the end capped chitosan macromole evocating agent of bromo.Take by weighing aforementioned bromo end-blocking chitosan macromole evocating agent 0.1 gram and be dissolved in methyl-phenoxide; in this solution, add N-N-isopropylacrylamide 4.6 grams; add catalyzer cuprous chloride (30 milligrams)/hexamethyl Triethylenetetramine (TETA) (50 milligrams) again; reaction system is through vacuumizing-inflated with nitrogen process 3 times, and reaction 6 hours in 60 ℃ of oil baths under nitrogen protection.After catalyzer is removed in reaction product deionized water dialysis, lyophilize, obtaining chitosan is the temperature sensitivity graft copolymer of main chain, promptly gets chitosan temperature sensitivity stable nanometer micelle of the present invention with this multipolymer is soluble in water.
Embodiment 5
Take by weighing chitosan 5 grams, use N, behind the N-diethylformamide dispersing and dissolving, add sodium acetate 32 grams, drip 2-bromine isobutyl acylbromide 48 grams, dripped off in 60 minutes, drip and finish the back 35 ℃ of reactions 24 hours at 12 ℃.Reaction product is removed post precipitation through suction filtration, and gained filtrate is precipitated through deionized water, and behind suction filtration, gained precipitates through vacuum-drying again, obtains the end capped chitosan macromole evocating agent of bromo.Take by weighing aforementioned bromo end-blocking chitosan macromole evocating agent 0.1 gram and be dissolved in N; dinethylformamide; in this solution, add N-N-isopropylacrylamide 5 grams; add catalyzer cuprous chloride (32 milligrams)/hexamethyl Triethylenetetramine (TETA) (52 milligrams) again; reaction system is through vacuumizing-inflated with nitrogen process 3 times, and reaction 3 hours in 80 ℃ of oil baths under nitrogen protection.Products therefrom after catalyzer is removed in deionized water dialysis, lyophilize, obtaining chitosan is the temperature sensitivity graft copolymer of main chain, promptly gets chitosan temperature sensitivity stable nanometer micelle of the present invention with this multipolymer is soluble in water.
Embodiment 6
Take by weighing chitosan 5 grams, use N, behind the dinethylformamide dispersing and dissolving, adding triethylamine 30 grams drip 2-bromine isobutyl acylbromides 50 at 15 ℃ and restrain, and drip off in 70 minutes, drip the end back and react 18 hours down at 40 ℃.Reaction product is removed post precipitation through suction filtration, and gained filtrate is through precipitating through deionized water, and behind suction filtration, gained precipitates through vacuum-drying again, obtains the end capped chitosan macromole evocating agent of bromo.Take by weighing aforementioned bromo end-blocking chitosan macromole evocating agent 0.5 gram and be dissolved in methyl-phenoxide; in this solution, add N-N-isopropylacrylamide 5.3 grams; add catalyzer cuprous bromide (35 milligrams)/hexamethyl Triethylenetetramine (TETA) (60 milligrams) again; reaction system is through vacuumizing-inflated with nitrogen process 3 times, and reaction 2 hours in 100 ℃ of oil baths under nitrogen protection.Reaction product after catalyzer is removed in deionized water dialysis, lyophilize, obtaining chitosan is the temperature sensitivity graft copolymer of main chain, promptly gets chitosan temperature sensitivity stable nanometer micelle of the present invention with this multipolymer is soluble in water.
Above-mentioned description to embodiment is can understand and apply the invention for the ease of those skilled in the art.The person skilled in the art obviously can easily make various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and not breaking away from the improvement that category of the present invention makes and revise all should be within protection scope of the present invention.
Claims (3)
1. the preparation method of a chitosan temperature sensitivity stable nanometer micelle may further comprise the steps:
Chitosan is added reactor, and dispersing and dissolving is in solvent orange 2 A, the acid binding agent B of terminal hydroxy group or 1～20 times of amount of amino mole number on the adding chitosan main chain, the bromine-containing compound C of hydroxyl and 1～20 times of amount of amino mole number on dropping chitosan main chain under 0～15 ℃ of condition, the dropping time is 20～70 minutes, after dripping end, adjusting temperature of reaction is 10～40 ℃, and the reaction times is 18～72 hours;
The gained reaction product is removed post precipitation through suction filtration, and filtrate is precipitated through deionized water, suction filtration again, and after gained precipitated vacuum-drying, obtain the end capped chitosan macromole evocating agent of bromo;
The end capped chitosan macromole evocating agent of gained bromo is dissolved in solvent D, and the amount according to 10～500 times of the contained end bromo of bromo end-blocking chitosan macromole evocating agent mole numbers adds monomer N-N-isopropylacrylamide in this solution, and the amount according to 1～5 times of the contained end bromo of bromo end-blocking chitosan macromole evocating agent mole number adds catalyzer E simultaneously;
Under catalyzer E effect, system is reacted under argon gas or nitrogen protection, temperature of reaction is 20～100 ℃, the reaction times is 2～48 hours;
After catalyzer E was removed in the deionized water dialysis, lyophilize obtained chitosan and is the temperature sensitivity graft copolymer of main chain, and this multipolymer is soluble in water, promptly obtains chitosan temperature sensitivity stable nanometer micelle of the present invention with the previous reaction product;
Described acid binding agent B is one or more in diethylamine, triethylamine, pyridine or the sodium acetate;
Described bromine-containing compound C is one or both in 2 bromo propionyl bromide or the 2-bromine isobutyl acylbromide;
Described catalyzer E is one or both in cuprous chloride/hexamethyl Triethylenetetramine (TETA) or the cuprous bromide/hexamethyl Triethylenetetramine (TETA).
2. preparation method according to claim 1 is characterized in that: described solvent orange 2 A is N, dinethylformamide, N, one or more in N-diethylformamide, N,N-dimethylacetamide or the dimethyl sulfoxide (DMSO).
3. preparation method according to claim 1 is characterized in that: described solvent D is methyl-phenoxide, N, dinethylformamide, N, a kind of in N-diethylformamide or the N,N-dimethylacetamide or several.
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| CN104119631B (en) * | 2014-07-07 | 2016-06-22 | 中国日用化学工业研究院 | Preparation has the method for the temperature sensitive modified manometer silicon dioxide complex of different critical response temperature |
| CN104387537B (en) * | 2014-10-22 | 2017-04-12 | 同济大学 | Preparation method of thermo-sensitive chitosan polymer connected with sugar molecules |
| CA2918904A1 (en) * | 2015-03-20 | 2016-09-20 | Queen's University At Kingston | Switchable polysaccharides, methods and uses thereof |
| CN107312137A (en) * | 2017-06-28 | 2017-11-03 | 安庆师范大学 | A kind of nano-cellulose base dendritic macromole temperature sensing material and preparation method thereof |
| CN110527026B (en) * | 2019-09-06 | 2020-08-14 | 安徽农业大学 | Amphiphilic nucleobase functionalized cellulose polymer, micelle and preparation method thereof |
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