CN1833725A - Chitosan pellet/microsac and prepn. thereof - Google Patents
Chitosan pellet/microsac and prepn. thereof Download PDFInfo
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- CN1833725A CN1833725A CN 200510055380 CN200510055380A CN1833725A CN 1833725 A CN1833725 A CN 1833725A CN 200510055380 CN200510055380 CN 200510055380 CN 200510055380 A CN200510055380 A CN 200510055380A CN 1833725 A CN1833725 A CN 1833725A
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Abstract
A chitosan microsphere or microcapsule is prepared through proportionally mixing oil phase with surfactant, stirring, proportionally adding chitosan solution (water phase), stirring, proportionally adding ammonium sulfate solution, stirring, centrifugal separation of deposit, washing and drying.
Description
Technical field
The invention belongs to pharmaceutical engineering and bioengineering field, relate to specifically that a kind of particle diameter is controlled, apparent condition is controlled, controlled, the mutual adhesion of swelling character, biodegradable chitosan microsphere/microcapsule, and preparation method thereof.
Background technology
Chitosan [β-(1-4)-2-amino-2-deoxidation-D-glucosan] be the deacetylation product of the abundant chitin of nature reserves; because it has excellent biological compatibility, biological degradability, bioadhesive, is subjected to field of medicaments and biological engineering material area research person's extensive attention.Chitosan microball/microcapsule has very big surface-to-volume ratio, uses as pharmaceutical carrier can to obtain slow release and the controlled release effect obtains ideal drug release character; Chitosan microball/the microcapsule of certain particle diameter has targeting, medicine can be concentrated in focus, improves therapeutic effect and reduces the toxic and side effects of medicine.In addition, chitosan microball/microcapsule fixation support of also can be used as enzyme, cell uses as artificial organ or industrial obtaining.Therefore, preparing satisfactory chitosan microball/microcapsule can make this natural resources of chitosan obtain high value added utilization.
At present, the preparation method of chitosan microball/microcapsule mainly contains emulsifying decentralized crosslinking method, solvent evaporation method, coacervation and spray drying method.Emulsifying decentralized crosslinking method can obtain circular and chitosan microball/microcapsule that have certain mechanical strength, but this method must be introduced cross-linking agent such as glutaraldehyde, formaldehyde, epoxychloropropane, and these cross-linking agent all are deleterious.Solvent evaporation method will add harmful organic solvent in the process of preparation chitosan microball/microcapsule, organic solvent residue brings safety problem will inevitably for the use of the chitosan microball/microcapsule of this method preparation.Coacervation is to be used for forming microsphere/microcapsule mutually by the material that makes chitosan and sodium tripolyphosphate, sodium alginate etc. and chitosan oppositely charged, but the product mechanical strength that this method obtains is not high, and is spherical bad, must add cross-linking agent in addition.The mechanical strength of the chitosan microball/microcapsule of spray drying method for preparation is not high yet, brings a lot of problems to application.Therefore the preparation method that searches out the high chitosan microball/microcapsule that does not use toxic material of a kind of mechanical strength of gentleness is highly significant.
Summary of the invention
When the objective of the invention is to overcome prior art for preparing chitosan microball/microcapsule, use emulsifying decentralized crosslinking method or solvent evaporation method to introduce the defective that chitosan microball/the microcapsule mechanical strength is not high of deleterious cross-linking agent or organic solvent, use coacervation or spray drying method for preparation, thereby provide a kind of and do not introduce harmful substances such as chemical cross-linking agent, organic solvent and particle diameter is controlled, apparent condition is controlled, controlled, the mutual adhesion of swelling character, biodegradable chitosan microsphere/microcapsule, and preparation method thereof.
The objective of the invention is to realize by the following technical solutions:
The invention provides a kind of chitosan microball/microcapsule, it obtains for using emulsifying dispersion-ammonium sulfate precipitation method, and concrete steps are as follows:
1) oil phase and the surfactant that accounts for its 0.1～4v% were stirred 5～30 minutes together, rotating speed is 500～2000 rev/mins;
Described oil phase is the mixture of liquid paraffin, Oleum Gossypii semen, Oleum Arachidis hypogaeae semen, Semen Maydis oil, soybean oil, olive oil, Oleum Helianthi or itself and petroleum ether;
Described surfactant is the mixture of Span 20, Span 40, Span 60, Span 65, Span 80, Span 83, Span 85, Tween20, Tween40, Tween60, Tween61, Tween80, Tween81, Tween85 or its arbitrary proportion;
2) chitosan solution (water) of 0.5～5% (w/v) is added in the dispersion that step 1) makes, the volume ratio of chitosan solution and oil phase is 1: 2～20, continues stirring 30～60 minutes, and rotating speed is 500～2000 rev/mins;
The used solvent of described chitosan solution is formic acid, acetic acid, propanoic acid, hydrochloric acid, citric acid, tartaric acid or glutamic acid;
3) to step 2) to add concentration in the dispersion that makes be the ammonium sulfate of 1～65% (w/v), the volume ratio of ammonium sulfate and chitosan solution is 1: 1～20, continues stirring 0.5～5 hour;
4) step with centrifugal separation 3) dispersion that makes, supernatant liquid is poured out, told the chitosan microball/microcapsule of lower floor's ammonium sulfate precipitation, use pure water, petroleum ether, dehydrated alcohol thorough washing successively, the room temperature vacuum drying promptly gets chitosan microball/microcapsule of the present invention.
The invention provides a kind of preparation method of above-mentioned chitosan microball/microcapsule, specifically comprise the steps:
1) oil phase and the surfactant that accounts for its 0.1～4v% were stirred 5～30 minutes together, rotating speed is 500～2000 rev/mins;
Described oil phase is the mixture of liquid paraffin, Oleum Gossypii semen, Oleum Arachidis hypogaeae semen, Semen Maydis oil, soybean oil, olive oil, Oleum Helianthi or itself and petroleum ether;
Described surfactant is the mixture of Span 20, Span 40, Span 60, Span 65, Span 80, Span 83, Span 85, Tween20, Tween40, Tween60, Tween61, Tween80, Tween81, Tween85 or its arbitrary proportion;
2) chitosan solution (water) of 0.5～5% (w/v) is added in the dispersion that step 1) makes, the volume ratio of chitosan solution and oil phase is 1: 2～20, continues stirring 30～60 minutes, and rotating speed is 500～2000 rev/mins;
The used solvent of described chitosan solution is formic acid, acetic acid, propanoic acid, hydrochloric acid, citric acid, tartaric acid or glutamic acid;
3) to step 2) to add concentration in the dispersion that makes be the ammonium sulfate of 1～65% (w/v), the volume ratio of ammonium sulfate and chitosan solution is 1: 1～20, continues stirring 0.5～5 hour;
4) step with centrifugal separation 3) dispersion that makes, supernatant liquid is poured out, told the chitosan microball/microcapsule of lower floor's ammonium sulfate precipitation, use pure water, petroleum ether, dehydrated alcohol thorough washing successively, the room temperature vacuum drying promptly gets chitosan microball/microcapsule of the present invention.
The present invention uses the chitosan microball/microcapsule of emulsifying dispersion-ammonium sulfate precipitation method preparation to have good new property: its configuration of surface is controlled, can be prepared into porous or slick form as required; Its particle diameter is controlled, but in the scope of 10～2000 μ m free adjustment; This chitosan microball/microcapsule has controlled swelling character, and different swelling character is arranged in the solution of different pH; In addition, the mutual adhesion of this chitosan microball/microcapsule has good dispersibility, and is biodegradable, and its mechanical strength also is improved.
Compared with prior art, the advantage of the preparation method of chitosan microball/microcapsule provided by the invention is: the preparation process gentleness, do not use virose chemical cross-linking agent and organic solvent, solved the problem of using virose chemical cross-linking agent and organic solvent in the process that present emulsion-crosslinking method, solvent evaporation method prepare chitosan microball/microcapsule; Also solved high, the not loosely organized problem of mechanical strength of the chitosan microball/microcapsule of coacervation and spray drying method for preparation.And in preparation process, do not introduce the factor that any virose chemical cross-linking agent and organic solvent etc. easily cause the biotech drug inactivation, be expected on the preparation of drug carriers of biotech drug, chemicals and fixation support, to obtain important application as enzyme, zooblast, plant cell.For example, when preparation is used for the chitosan microball of embedding polypeptide, protein, vaccine, genomic medicine/microcapsule medicament carrier, can reduce the loss of activity of such medicine in preparation process, become the effective carrier of such medicine; This preparation method also can be used for preparing the chitosan microball/microcapsule fixation support of embedding enzyme, plant cell, zooblast, can reduce its loss of activity in preparation process; This preparation method also can be used for embedding hydrophilic and hydrophobic chemicals.
Description of drawings
Fig. 1 is the sem photograph of 100 times of amplifications of the chitosan microball of embodiment 1 preparation;
Fig. 2 is that 1500 times sem photograph is amplified on the surface of the chitosan microball of embodiment 1 preparation;
Fig. 3 is the sem photograph of 100 times of amplifications of the chitosan microball of embodiment 2 preparation;
Fig. 4 is that 1000 times sem photograph is amplified on the surface of the chitosan microball of embodiment 2 preparations;
Fig. 5 is the sem photograph of 100 times of amplifications of the chitosan microball of embodiment 3 preparation;
Fig. 6 is the sem photograph of 60 times of amplifications of the chitosan microcapsules of embodiment 4 preparation;
Fig. 7 is the sem photograph of 1500 times of amplifications of the chitosan microcapsules surface holes form of embodiment 5 preparation;
Fig. 8 is the sem photograph of 4000 times of amplifications of the chitosan microcapsules surface holes form of embodiment 6 preparation.
Fig. 9 is the particle size distribution figure of the chitosan microball of embodiment 1 preparation, and the particle size distribution coefficient is 20.34%.
The specific embodiment
Chitosan is dissolved in the solution that is mixed with 2% (w/v) in the 0.2mol/L acetic acid solution, getting the 50mL liquid paraffin joins in the reactor, add 0.5mLSpan80 and 1mLTween80, stirred 10 minutes, rotating speed is 1500 rev/mins, add the 10mL chitosan solution of above-mentioned preparation after, continue dispersed with stirring after 30 minutes with same rotating speed, adding concentration is the ammonium sulfate 40mL of 50% (w/v), continues to stir after 1 hour to stop.Supernatant liquid is poured out in centrifugalize, tells the chitosan microball of lower floor's ammonium sulfate precipitation, and with pure water, petroleum ether, dehydrated alcohol thorough washing precipitation, the room temperature vacuum drying promptly gets chitosan microball of the present invention successively.
Its configuration of surface shown in the sem photograph of Fig. 1 and Fig. 2, as seen, this chitosan microball smooth surface, mean diameter is 168.2 microns, and good dispersibility is arranged.Survey its particle size distribution with laser particle analyzer COULTER LS230, as shown in Figure 9, the particle size distribution coefficient of this chitosan microball is 20.34%.
Embodiment 2
Chitosan is dissolved in the solution that is mixed with 5% (w/v) in the 0.25mol/L acetic acid solution, gets 50mL Oleum Arachidis hypogaeae semen and join in the reactor, add 0.5mLSpan60 and 1mLTween60, stirred 5 minutes, rotating speed is 2000 rev/mins; After adding the chitosan solution of the above-mentioned preparation of 10mL, continue stirring after 60 minutes with same rotating speed, adding concentration is the ammonium sulfate 100mL of 30% (w/v), continues to stir after 2 hours to stop.Supernatant liquid is poured out in centrifugalize, tells the chitosan microball of lower floor's ammonium sulfate precipitation, and with pure water, petroleum ether, dehydrated alcohol thorough washing precipitation, the room temperature vacuum drying promptly gets chitosan microball of the present invention successively.
Its configuration of surface shown in the sem photograph of Fig. 3 and Fig. 4, as seen, this chitosan microball porous surface, particle diameter is 154.1 microns, and good dispersibility is arranged.Survey its particle size distribution with laser particle analyzer COULTER LS230, the particle size distribution coefficient of this chitosan microball is 22.69%.
Chitosan is dissolved in the solution that is mixed with 4% (w/v) in the 0.25mol/L acetic acid solution, gets the 50mL Semen Maydis oil and join in the reactor, add 1mLTween65, stirred 20 minutes, rotating speed is 500 rev/mins; After adding the chitosan solution of the above-mentioned preparation of 2.5mL, continue stirring after 40 minutes with same rotating speed, adding concentration is the ammonium sulfate 50mL of 65% (w/v), continues to stir after 3 hours to stop.Supernatant liquid is poured out in centrifugalize, tells the chitosan microball of lower floor's ammonium sulfate precipitation, and with pure water, petroleum ether, dehydrated alcohol thorough washing precipitation, the room temperature vacuum drying promptly gets chitosan microball of the present invention successively.
The profile of this microsphere as shown in Figure 5, as seen its internal structure densification is blocky ball.
Chitosan is dissolved in the solution that is mixed with 0.5% (w/v) in the 0.2mol/L formic acid solution, gets the 50mL olive oil and join in the reactor, add 1mLSpan20 and 1mLTween61, stirred 20 minutes, rotating speed is 600 rev/mins; After adding the chitosan solution of the above-mentioned preparation of 25mL, continue stirring after 30 minutes with same rotating speed, adding concentration is the ammonium sulfate 150mL of 2% (w/v), continues to stir after 0.5 hour to stop.Supernatant liquid is poured out in centrifugalize, tells the chitosan microcapsules of lower floor's ammonium sulfate precipitation, and with pure water, petroleum ether, dehydrated alcohol thorough washing precipitation, the room temperature vacuum drying promptly gets chitosan microcapsules of the present invention successively.
The profile of this microcapsule as shown in Figure 6, as seen there are a lot of spaces its inside, is balloon-like structure.
Embodiment 5
Chitosan is dissolved in the solution that is mixed with 3% (w/v) in the 0.3mol/L citric acid solution, gets the 50mL soybean oil and join in the reactor, add 1mLSpan20 and 1mLTween61, stirred 20 minutes, rotating speed is 1000 rev/mins; After adding the chitosan solution of the above-mentioned preparation of 15mL, continue to stir with same rotating speed, after 30 minutes, adding concentration is the ammonium sulfate 300mL of 10% (w/v), continues to stir after 2 hours to stop.Supernatant liquid is poured out in centrifugalize, tells the chitosan microcapsules of lower floor's ammonium sulfate precipitation, and with pure water, petroleum ether, dehydrated alcohol thorough washing precipitation, the room temperature vacuum drying promptly gets chitosan microcapsules of the present invention successively.
Its configuration of surface shown in the sem photograph of Fig. 7, as seen, this chitosan microcapsules porous surface, average pore size is 1.24 microns.
Embodiment 6
Chitosan is dissolved in the solution that is mixed with 3% (w/v) in the 0.3mol/L tartaric acid solution, gets the 25mL soybean oil and the 25mL petroleum ether joins in the reactor, add 1mLSpan20 and 1mLTween61, stirred 20 minutes, rotating speed is 1000 rev/mins; After adding the chitosan solution of the above-mentioned preparation of 5mL, continue to stir with same rotating speed, after 30 minutes, adding concentration is the ammonium sulfate saturated solution 50mL of 10% (w/v), continues to stir after 5 hours to stop.Supernatant liquid is poured out in centrifugalize, tells the chitosan microcapsules of lower floor's ammonium sulfate precipitation, with pure water, petroleum ether, dehydrated alcohol thorough washing precipitation, promptly gets chitosan microcapsules of the present invention behind the room temperature vacuum drying successively.
Its configuration of surface shown in the sem photograph of Fig. 8, as seen, this chitosan microcapsules porous surface, mean diameter is 1.05 microns.
Claims (8)
1, a kind of chitosan microball/microcapsule, it obtains for using emulsifying dispersion-ammonium sulfate precipitation method, and concrete steps are as follows:
1) oil phase and the surfactant that accounts for its 0.1～4v% are stirred together, obtain a dispersion;
2) chitosan solution of 0.5～5% (w/v) is added in the dispersion that step 1) makes, the volume ratio of chitosan solution and oil phase is 1: 2～20, continues stirring;
3) to step 2) to add concentration in the dispersion that makes be the ammonium sulfate of 1～65% (w/v), the volume ratio of ammonium sulfate and chitosan solution is 1: 1～20, continues stirring;
4) step with centrifugal separation 3) dispersion that makes, supernatant liquid is poured out, tell the lower sediment thing, washing, drying obtains chitosan microball/microcapsule of the present invention.
2, chitosan microball/microcapsule as claimed in claim 1 is characterized in that: described oil phase is the mixture of liquid paraffin, Oleum Gossypii semen, Oleum Arachidis hypogaeae semen, Semen Maydis oil, soybean oil, olive oil, Oleum Helianthi or itself and petroleum ether.
3, chitosan microball/microcapsule as claimed in claim 1 is characterized in that: described surfactant is the mixture of Span20, Span 40, Span 60, Span 65, Span 80, Span 83, Span 85, Tween20, Tween40, Tween60, Tween61, Tween80, Tween81, Tween85 or its arbitrary proportion.
4, chitosan microball/microcapsule as claimed in claim 1 is characterized in that: the used solvent of described chitosan solution is formic acid, acetic acid, propanoic acid, hydrochloric acid, citric acid, tartaric acid or glutamic acid.
5, the preparation method of the described chitosan microball/microcapsule of a kind of claim 1 comprises following step:
1) oil phase and the surfactant that accounts for its 0.1～4v% are stirred together, obtain a dispersion;
2) chitosan solution of 0.5～5% (w/v) is added in the dispersion that step 1) makes, the volume ratio of chitosan solution and oil phase is 1: 2～20, continues stirring;
3) to step 2) to add concentration in the dispersion that makes be the ammonium sulfate of 1～65% (w/v), the volume ratio of ammonium sulfate and chitosan solution is 1: 1～20, continues stirring;
4) step with centrifugal separation 3) dispersion that makes, supernatant liquid is poured out, tell the lower sediment thing, washing, drying obtains chitosan microball/microcapsule of the present invention.
6, the preparation method of chitosan microball/microcapsule as claimed in claim 5 is characterized in that: described oil phase is the mixture of liquid paraffin, Oleum Gossypii semen, Oleum Arachidis hypogaeae semen, Semen Maydis oil, soybean oil, olive oil, Oleum Helianthi or itself and petroleum ether.
7, the preparation method of chitosan microball/microcapsule as claimed in claim 5 is characterized in that: described surfactant is the mixture of Span 20, Span 40, Span 60, Span 65, Span 80, Span 83, Span 85, Tween20, Tween40, Tween60, Tween61, Tween80, Tween81, Tween85 or its arbitrary proportion.
8, the preparation method of chitosan microball/microcapsule as claimed in claim 5 is characterized in that: the used solvent of described chitosan solution is formic acid, acetic acid, propanoic acid, hydrochloric acid, citric acid, tartaric acid or glutamic acid.
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| CNB200510055380XA CN100522246C (en) | 2005-03-18 | 2005-03-18 | Chitosan pellet/microsac and preparation thereof |
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| CNB200510055380XA CN100522246C (en) | 2005-03-18 | 2005-03-18 | Chitosan pellet/microsac and preparation thereof |
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| CN1833725A true CN1833725A (en) | 2006-09-20 |
| CN100522246C CN100522246C (en) | 2009-08-05 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101889985A (en) * | 2010-07-08 | 2010-11-24 | 东华大学 | Medicament-carrying nano microspheres and preparation method thereof |
| CN104622845A (en) * | 2015-01-02 | 2015-05-20 | 吉林大学 | Preparation method of chitosan microcapsules containing magnetic nano particles inside |
| WO2020195132A1 (en) * | 2019-03-28 | 2020-10-01 | 富士フイルム株式会社 | Perfume microcapsules, perfume microcapsule composition, softener, and detergent |
| CN113980154A (en) * | 2021-11-19 | 2022-01-28 | 南开大学 | High-strength chitosan ligand exchange resin and preparation method thereof |
| CN117883405A (en) * | 2023-12-25 | 2024-04-16 | 湖南省博世康中医药有限公司 | Preparation method of rhizoma polygonati instant drink powder based on nano microencapsulation technology |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5141110B2 (en) | 1974-05-04 | 1976-11-08 | ||
| CN1165037A (en) * | 1997-06-04 | 1997-11-19 | 天津大学 | PH value response medicine controlled release carrier |
| CN1290524A (en) * | 1999-09-30 | 2001-04-11 | 浙江大学 | Ion crosslinking process of preparing medicinal slow-releasing chitosan microball |
| CN1185048C (en) * | 2003-06-03 | 2005-01-19 | 清华大学 | Method for covering high polymer gel microsphere by using emulsion method |
-
2005
- 2005-03-18 CN CNB200510055380XA patent/CN100522246C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101889985A (en) * | 2010-07-08 | 2010-11-24 | 东华大学 | Medicament-carrying nano microspheres and preparation method thereof |
| CN101889985B (en) * | 2010-07-08 | 2011-11-23 | 东华大学 | Medicament-carrying nano microspheres and preparation method thereof |
| CN104622845A (en) * | 2015-01-02 | 2015-05-20 | 吉林大学 | Preparation method of chitosan microcapsules containing magnetic nano particles inside |
| WO2020195132A1 (en) * | 2019-03-28 | 2020-10-01 | 富士フイルム株式会社 | Perfume microcapsules, perfume microcapsule composition, softener, and detergent |
| CN113980154A (en) * | 2021-11-19 | 2022-01-28 | 南开大学 | High-strength chitosan ligand exchange resin and preparation method thereof |
| CN113980154B (en) * | 2021-11-19 | 2022-12-02 | 南开大学 | High-strength chitosan ligand exchange resin and preparation method thereof |
| CN117883405A (en) * | 2023-12-25 | 2024-04-16 | 湖南省博世康中医药有限公司 | Preparation method of rhizoma polygonati instant drink powder based on nano microencapsulation technology |
| CN117883405B (en) * | 2023-12-25 | 2024-07-09 | 湖南省博世康中医药有限公司 | Preparation method of rhizoma polygonati instant drink powder based on nano microencapsulation technology |
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