CN101601986A - A kind of method for making of chitosan-silicon dioxide compound hollow microballoon and application - Google Patents

A kind of method for making of chitosan-silicon dioxide compound hollow microballoon and application Download PDF

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CN101601986A
CN101601986A CNA2009100321459A CN200910032145A CN101601986A CN 101601986 A CN101601986 A CN 101601986A CN A2009100321459 A CNA2009100321459 A CN A2009100321459A CN 200910032145 A CN200910032145 A CN 200910032145A CN 101601986 A CN101601986 A CN 101601986A
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chitosan
silicon dioxide
shitosan
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compound hollow
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CN101601986B (en
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胡勇
闫尔云
蒋锡群
丁寅
王雪
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Nanjing University
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Abstract

A kind of compound hollow microballoon of chitosan-silicon dioxide, ethyl orthosilicate is deposited on the surface of shitosan-polyacrylic acid microballoon through hydrolysis, polycondensation, finally obtain having macropore, the chitosan-silicon dioxide compound hollow microballoon of mesoporous two kinds of pore structures, average grain diameter is 50-200nm, wherein the molecular weight of shitosan is 10000-200000, and deacetylation is 70~95%.

Description

A kind of method for making of chitosan-silicon dioxide compound hollow microballoon and application
Technical field:
The present invention relates to the preparation of the compound nano material of organic-inorganic and medicine and discharge application, be specifically related to a kind of the have preparation method of macropore, mesoporous chitosan-silicon dioxide composite Nano tiny balloon and the carrier that discharges as medicine, the application of molecular sieve aspect.
Technical background:
Since the sixties in 20th century, controlled delivery of pharmaceutical agents discharges and the research of the target administration in human body is a research focus of chemistry, medical science and field of pharmacology always.Compare with traditional mode of administration, controlled delivery of pharmaceutical agents discharges and has lot of advantages, such as: the concentration that (1) medicine is discharged in the environment is more stable; (2) the highly effective medicine that utilizes of energy makes it that very high utilization rate be arranged; (3) can make the release of medicine as much as possible near lesions position, improve drug effect, avoid taking place the side effect of general; (4) can suitably reduce the medication number of times, safer to the patient.Therefore, in view of above-mentioned various advantages, the research that medicine control discharges has using value very widely to clinical medicine.
The key of medicine control release technic is processability excellent drug carrier.In numerous macromolecular materials, the natural polysaccharide material has obtained researcher's extensive concern with its better biocompatibility and cellular affinity.At present, the natural biological degradable macromolecule as pharmaceutical carrier mainly contains: shitosan, alginic acid, agar, fibrin and collagen etc.Wherein, shitosan has obtained using widely in pharmacy and field of biology with its avirulence, biocompatibility and degradability.(Biometerial,1993,(20),7-16;J?Control?Rel,1998,(52),109-18)。In the present invention, utilize shitosan tiny balloon as template just, the tiny balloon of preparation composite chitosan-silica with good biological performance.
Lot of domestic and international seminar is devoted to the preparation and the research of chitosan microball, and up to now, the method for preparing chitosan microball mainly contains cross-linking method, coacervation, emulsification-solvent evaporated method, spray drying process etc.Above several method preparation process relative complex, and to use harmful organic solvent unavoidably sometimes.In the present invention, our used template shitosan-polyacrylic tiny balloon, preparation process is simple, and carries out at aqueous phase fully, therefore very environmental protection (Advanced Materials, 2004, (16), 933-936.).Further preparing in the process of chitosan-silicon dioxide complex microsphere the removal of polyacrylic acid molecule quilt nature in processing procedure.
The ordered mesoporous silica dioxide microballoon has bigger specific area, aperture and volume adjustable size, and biologically inert and biocompatibility, so it is the inorganic material preferably as pharmaceutical carrier.But, unmodified silicon dioxide microsphere can not carry out controlled release to the medicine of parcel, if therefore the advantages of shitosan and silica can be got up, that will be a very significant job, because the specific area that mesoporous silicon oxide is big can make it have bigger medicine carrying amount, and have multiple functional group (amino, hydroxyl) on the shitosan segment, by the chemical action power between regulation and control functional group and the medicine, can reach the purpose that control discharges to medicine.The present invention has embodied this characteristic just.
Summary of the invention:
The object of the present invention is to provide a kind of biodegradable, chitosan-silicon dioxide composite nano-microsphere with biocompatibility.
Another object of the present invention is to provide a kind of preparation method with macropore, mesoporous chitosan-silicon dioxide composite Nano tiny balloon.The present invention adopts template, with shitosan-polyacrylic acid hollow microsphere is template, with the ethyl orthosilicate is the silica predecessor, under acetic acid or ammonia-catalyzed agent effect, ethyl orthosilicate is deposited on the surface of shitosan-polyacrylic acid microballoon through hydrolysis, polycondensation, finally obtains having macropore, the chitosan-silicon dioxide compound hollow microballoon of mesoporous two kinds of pore structures.
Technical scheme of the present invention is as follows: the compound hollow microballoon of chitosan-silicon dioxide, adopt ethyl orthosilicate to be deposited on the method on the surface of shitosan-polyacrylic acid microballoon through hydrolysis, polycondensation, finally obtain having macropore, the chitosan-silicon dioxide compound hollow microballoon of mesoporous two kinds of pore structures, average grain diameter is 50-200nm, wherein the molecular weight of shitosan is 10000-200000, and deacetylation is 70~95%.
The method of the compound hollow microballoon of preparation chitosan-silicon dioxide, shitosan-polyacrylic acid tiny balloon is dissolved in the alkaline distilled water, it is joined under stirring condition in the ethanolic solution of ethyl orthosilicate, promptly get the compound hollow microballoon of chitosan-silicon dioxide after the hydrolysis fully.After stirring at room 12-24 hour, under 50 ℃ of conditions, left standstill 12-24 hour filtration, the centrifugal compound hollow microballoon that promptly gets chitosan-silicon dioxide again.
Especially shitosan-polyacrylic acid emulsion is mixed with the ammoniacal liquor of isopyknic 1-2M, left standstill 48 hours, and ethyl orthosilicate is dissolved in the ethanol, shitosan-polyacrylic acid the emulsion of alkalescence slowly is added drop-wise in the ethanolic solution of ethyl orthosilicate, stirring at room 12-24 hour, be placed on afterwards under 50 ℃ of conditions and left standstill 12-24 hour, after filtration, the centrifugal chitosan-silicon dioxide compound hollow microballoon that promptly gets.
Other method is that shitosan-polyacrylic acid tiny balloon is dissolved in the acid distilled water, and it is joined under stirring condition in the ethanolic solution of ethyl orthosilicate, promptly gets the compound hollow microballoon of chitosan-silicon dioxide after the hydrolysis fully.Under the stirring at room condition, shitosan-polyacrylic acid tiny balloon the emulsion of acidity is joined in the ethanolic solution of ethyl orthosilicate, after the stirring at room 24 hours, under 50 ℃ of conditions, left standstill 24 hours filtration, the centrifugal compound hollow microballoon that promptly gets chitosan-silicon dioxide again.The purposes of described Nano microsphere as the carrier of medicine, albumen, can also be come isolated protein as molecular sieve.Load has the antineoplastic ADMh of broad spectrum activity.The chitosan-silicon dioxide microballoon has bigger cavity, therefore can improve its medicine carrying amount greatly, and by changing some condition of external environment, reaches the purpose to medicine controlled releasing.The corresponding pH value of acid and alkaline distilled water can be in the scope of pH4-pH10.
The chitosan-silicon dioxide composite nano-microsphere that the invention still further relates to the employing method for preparing separates the protein with different molecular weight and isoelectric point as molecular sieve.And, reach separation to protein by changing some condition of external environment.
As the carrier of medicine, it can add the medicine of wanting load in the solution of chitosan-silicon dioxide complex microsphere of the present invention, and is centrifugal after normal temperature stirs 24-48 hour, can obtain being enclosed with the chitosan-silicon dioxide compound hollow microballoon of medicine
As molecular sieve, it can add cromoci and bovine serum albumin in the solution of chitosan-silicon dioxide complex microsphere of the present invention, stirs more than 48 hours through normal temperature, goes out supernatant liquor by centrifugation.The complex microsphere that lower floor is wrapped up albumen is dissolved in the solution of certain pH value, and stirring at normal temperature is more than 48 hours, and is centrifugal, can be with two kinds of Separation of Proteins.
The invention provides a kind of average grain diameter is the chitosan-silicon dioxide composite Nano tiny balloon of 50-200nm, and it is hydrophilic, has stability preferably, biocompatibility in the pH scope widely.Experimentation carries out in aqueous phase system fully, does not use any organic solvent and surfactant.The microsphere surface rule has a lot of ducts on the outer shell silica wall, for the absorption and the release of medicine provides passage, and the mechanical strength height of silica shell, not yielding.Therefore, this microballoon meets the application need in biomedical and Biochemical Engineering field as a kind of carrier on performance.
Description of drawings:
Fig. 1 is the illustraton of model of chitosan-silicon dioxide compound hollow microballoon: 1 is shitosan, and 2 is silica.
Fig. 2 is the transmission electron microscope picture (amplifying 50,000 times) of chitosan-silicon dioxide compound hollow microballoon
The release profiles that Fig. 3 tests under cushioning liquid pH4 and pH7.4 checker condition for the chitosan-silicon dioxide compound hollow microballoon of load ADMh
Fig. 4 is the release profiles of SiO 2 hollow microsphere under pH4 and pH7.4 condition of load ADMh.
The specific embodiment
Embodiment 1:
At first prepare shitosan-polyacrylic tiny balloon.The shitosan of 0.25g and the acrylic acid of 0.12g are dissolved in the distilled water of 25mL, treat that it dissolves fully after, be warming up to 80 ℃, the potassium peroxydisulfate that adds 0.05g causes acroleic acid polymerization.When milky appears in system, system is cooled to room temperature, the glutaraldehyde that adds 0.1mL afterwards comes optionally cross-linked chitosan, promptly obtains the emulsion of shitosan-polyacrylic acid tiny balloon, but the REFERENCE TO RELATED people in first to file.
Get freshly prepd shitosan-polyacrylic acid emulsion 2.5mL and mix, left standstill 48 hours with the ammoniacal liquor of isopyknic 2M.The ethyl orthosilicate of 520 microlitres is dissolved in the 2mL ethanol.Shitosan-polyacrylic acid the emulsion of alkalescence slowly is added drop-wise in the ethanolic solution of ethyl orthosilicate.Stirring at room 24 hours is placed on afterwards under 50 ℃ of conditions and left standstill 24 hours, after filtration, the centrifugal chitosan-silicon dioxide compound hollow microballoon that promptly gets.
Chitosan-silicon dioxide compound hollow microballoon in the above-mentioned system, with the transmission electron microscope observing nano particle is regular spherical structure, and outer field silica and shitosan-polyacrylic acid template boundary are clearly, and average grain diameter is 120nm, can stable existence in pH value scope widely.
Embodiment 2:
Get freshly prepd shitosan-polyacrylic acid emulsion 2.5mL, emulsion is transferred to pH3, left standstill 48 hours with the acetic acid of 2M.520 microlitre ethyl orthosilicates are dissolved in the 2mL ethanol.Shitosan-polyacrylic acid the emulsion of acidity slowly is added drop-wise in the ethanolic solution of ethyl orthosilicate.Stirring at room 24 hours is placed on afterwards under 50 ℃ of conditions and left standstill 24 hours, after filtration, the centrifugal chitosan-silicon dioxide compound hollow microballoon that promptly gets.
Chitosan-silicon dioxide compound hollow microballoon in the above-mentioned system be regular spherical structure with the transmission electron microscope observing nano particle, and average grain diameter is 110nm, can stable existence in pH value scope widely.
Embodiment 3:
Get freshly prepd shitosan-polyacrylic acid emulsion 2.5mL and mix, left standstill 48 hours with the ammoniacal liquor of isopyknic 2M.520 microlitre ethyl orthosilicates are dissolved in the 2mL ethanol.Shitosan-polyacrylic acid the emulsion of alkalescence slowly is added drop-wise in the ethanolic solution of ethyl orthosilicate.Stirring at room 24 hours is placed on afterwards under 50 ℃ of conditions and left standstill 24 hours, after filtration, the centrifugal chitosan-silicon dioxide compound hollow microballoon that promptly gets.Be dispersed in the distilled water after this product repeatedly washed, freezing freezing, afterwards in freeze dryer with its freeze-drying.Getting the chitosan-silicon dioxide compound hollow microballoon powder 15mg of freeze-drying and the ADMh of certain mass is mixed in the distilled water, stirring at room 48 hours, centrifugal, the washing three times, remove the chitosan-silicon dioxide complex microsphere that supernatant liquid promptly gets the load ADMh.
In the above-mentioned complex microsphere, when the quality that adds ADMh was 1.5mg, the medicine carrying amount of particle was 8.9%, and medicine carrying efficient is 97.5%.The medicine release experiment shows: when release media solution was the cushioning liquid checker of pH4 and 7.4, the quality of the ADMh that is discharged presented pulsed; That is to say, be 4 o'clock in the pH of extraneous solution value, and a large amount of medicines are released, and is 7.4 o'clock in the pH of extraneous solution value, has only a spot of medicine to be released.
Embodiment 4.
Get freshly prepd shitosan-polyacrylic acid emulsion 2.5mL and mix, left standstill 48 hours with the ammoniacal liquor of isopyknic 2M.520 microlitre ethyl orthosilicates are dissolved in the 2mL ethanol.Shitosan-polyacrylic acid the emulsion of alkalescence slowly is added drop-wise in the ethanolic solution of ethyl orthosilicate.Stirring at room 24 hours is placed on afterwards under 50 ℃ of conditions and left standstill 24 hours, after filtration, the centrifugal chitosan-silicon dioxide compound hollow microballoon that promptly gets.Be dispersed in the distilled water after this product repeatedly washed, freezing freezing, afterwards in freeze dryer with its freeze-drying.With the powder of freeze-drying in Muffle furnace under 550 ℃ the condition calcining obtained the silica nanometer tiny balloon in 4 hours.Getting the SiO 2 hollow microsphere powder 15mg after the calcining and the ADMh of certain mass is mixed in the distilled water, stirring at room 48 hours, centrifugal, the washing three times, remove the chitosan-silicon dioxide compound hollow microballoon that supernatant liquid promptly gets the load ADMh.
In the above-mentioned complex microsphere, when the quality that adds ADMh was 1.5mg, the medicine carrying amount of particle was 4.2%, and medicine carrying efficient is 43.5%.The medicine release experiment shows: when the pH of extraneous solution value was 4, a large amount of medicines were released, and were 7.4 o'clock in the pH of extraneous solution value, had only a spot of medicine to be released.
Embodiment 5
Get freshly prepd shitosan-polyacrylic acid emulsion 2.5mL and mix, left standstill 48 hours with the ammoniacal liquor of isopyknic 2M.520 microlitre ethyl orthosilicates are dissolved in the 2mL ethanol.Shitosan-polyacrylic acid the emulsion of alkalescence slowly is added drop-wise in the ethanolic solution of ethyl orthosilicate.Stirring at room 24 hours is placed on afterwards under 50 ℃ of conditions and left standstill 24 hours, after filtration, the centrifugal chitosan-silicon dioxide compound hollow microballoon that promptly gets.Be dispersed in the distilled water after this product repeatedly washed, freezing freezing, afterwards in freeze dryer with its freeze-drying.Get the sample 15mg of freeze-drying, cromoci 5mg was dissolved in the PBS cushioning liquid of 2mLpH7.4 stirring at normal temperature 96 hours.Afterwards,, isolate upper solution and test, promptly obtain the quality of the cromoci that is wrapped this solution centrifugal.
Embodiment 6
Get freshly prepd shitosan-polyacrylic acid emulsion 2.5mL and mix, left standstill 48 hours with the ammoniacal liquor of isopyknic 2M.520 microlitre ethyl orthosilicates are dissolved in the 2mL ethanol.Shitosan-polyacrylic acid the emulsion of alkalescence slowly is added drop-wise in the ethanolic solution of ethyl orthosilicate.Stirring at room 24 hours is placed on afterwards under 50 ℃ of conditions and left standstill 24 hours, after filtration, the centrifugal chitosan-silicon dioxide compound hollow microballoon that promptly gets.Be dispersed in the distilled water after this product repeatedly washed, freezing freezing, afterwards in freeze dryer with its freeze-drying.Get the sample 15mg of freeze-drying, bovine serum albumin 5mg was dissolved in the PBS cushioning liquid of 2mL pH7.4 stirring at normal temperature 96 hours.Afterwards,, isolate upper solution and test, promptly obtain the quality of the bovine serum albumin that is wrapped this solution centrifugal.
Embodiment 7
Get freshly prepd shitosan-polyacrylic acid emulsion 2.5mL and mix, left standstill 48 hours with the ammoniacal liquor of isopyknic 2M.520 microlitre ethyl orthosilicates are dissolved in the 2mL ethanol.Shitosan-polyacrylic acid the emulsion of alkalescence slowly is added drop-wise in the ethanolic solution of ethyl orthosilicate.Stirring at room 24 hours is placed on afterwards under 50 ℃ of conditions and left standstill 24 hours, after filtration, the centrifugal chitosan-silicon dioxide compound hollow microballoon that promptly gets.Be dispersed in the distilled water after this product repeatedly washed, freezing freezing, afterwards in freeze dryer with its freeze-drying.Get the sample 15mg of freeze-drying, bovine serum albumin 5mg, cromoci 5mg was dissolved in the PBS cushioning liquid of 2mL pH7.4 stirring at normal temperature 96 hours.Afterwards, with this solution centrifugal, isolate upper solution.Lower sediment is dissolved in the cushioning liquid of pH10 stirring at normal temperature 48 hours.With this solution centrifugal, two kinds of protein can be separated.

Claims (6)

1. the compound hollow microballoon of a chitosan-silicon dioxide, it is characterized in that ethyl orthosilicate is deposited on the surface of shitosan-polyacrylic acid microballoon through hydrolysis, polycondensation, finally obtain having macropore, the chitosan-silicon dioxide compound hollow microballoon of mesoporous two kinds of pore structures, average grain diameter is 50-200nm, wherein the molecular weight of shitosan is 10000-200000, and deacetylation is 70~95%.
2. method for preparing the compound hollow microballoon of chitosan-silicon dioxide, it is characterized in that shitosan-polyacrylic acid tiny balloon is dissolved in alkaline distilled water or the ammoniacal liquor, left standstill 48 hours, and ethyl orthosilicate is dissolved in the ethanol, shitosan-polyacrylic acid the emulsion of alkalescence slowly is added drop-wise in the ethanolic solution of ethyl orthosilicate, stirring at room 12-24 hour, be placed on afterwards under 50 ℃ of conditions and left standstill 12-24 hour, after filtration, the centrifugal chitosan-silicon dioxide compound hollow microballoon that promptly gets.It is joined under stirring condition in the ethanolic solution of ethyl orthosilicate (volume ratio of ethyl orthosilicate/ethanol is about 1: 4), promptly get the compound hollow microballoon of chitosan-silicon dioxide after the hydrolysis fully.
3. method for preparing the described Nano microsphere of claim 1, it is characterized in that shitosan-polyacrylic acid tiny balloon is dissolved in the acid distilled water, it is joined under stirring condition in the ethanolic solution of ethyl orthosilicate, promptly get the compound hollow microballoon of chitosan-silicon dioxide after the hydrolysis fully.
4. method for preparing the described Nano microsphere of claim 2, it is characterized in that under the stirring at room condition, shitosan-polyacrylic acid tiny balloon the emulsion of alkalescence is joined in the ethanolic solution of ethyl orthosilicate, after the stirring at room 24 ± 8 hours, under 50 ± 10 ℃ of conditions, left standstill 24 ± 16 hours filtration, the centrifugal compound hollow microballoon that promptly gets chitosan-silicon dioxide again.
5. method for preparing the described Nano microsphere of claim 3, it is characterized in that under the stirring at room condition, shitosan-polyacrylic acid tiny balloon the emulsion of acidity is joined in the ethanolic solution of ethyl orthosilicate, after the stirring at room 24 ± 8 hours, under 50 ± 10 ℃ of conditions, left standstill 24 ± 16 hours filtration, the centrifugal compound hollow microballoon that promptly gets chitosan-silicon dioxide again.
6. the purposes of Nano microsphere according to claim 1 is characterized in that coming isolated protein as the carrier of medicine, albumen as molecular sieve.At first in the solution of chitosan-silicon dioxide complex microsphere, add cromoci and bovine serum albumin, stir more than 48 hours through normal temperature then, go out supernatant liquor by centrifugation again, the complex microsphere that then lower floor is wrapped up albumen is scattered in the solution of certain pH value, stirring at normal temperature is more than 48 hours, again through centrifugal, can be with two kinds of Separation of Proteins.
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CN113875507A (en) * 2021-10-09 2022-01-04 内蒙古自治区农牧业科学院 Grassland ecological restoration method
CN114887557B (en) * 2022-05-26 2023-07-11 江南大学 CO (carbon monoxide) 2 Preparation method and application of temperature double-response type chitosan composite microcapsule
CN114887557A (en) * 2022-05-26 2022-08-12 江南大学 CO (carbon monoxide) 2 Preparation method and application of-temperature dual-response type chitosan composite microcapsule
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