CN102397581A - Method for generating chitosan/calcium phosphate hybrid material by electrochemical biomimetic mineralization - Google Patents
Method for generating chitosan/calcium phosphate hybrid material by electrochemical biomimetic mineralization Download PDFInfo
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- CN102397581A CN102397581A CN2011103706408A CN201110370640A CN102397581A CN 102397581 A CN102397581 A CN 102397581A CN 2011103706408 A CN2011103706408 A CN 2011103706408A CN 201110370640 A CN201110370640 A CN 201110370640A CN 102397581 A CN102397581 A CN 102397581A
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- chitosan
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- hybrid material
- gel
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- 229920001661 Chitosan Polymers 0.000 title claims abstract description 87
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000000463 material Substances 0.000 title claims abstract description 27
- 230000003592 biomimetic effect Effects 0.000 title claims abstract description 15
- 230000033558 biomineral tissue development Effects 0.000 title claims abstract description 14
- 239000001506 calcium phosphate Substances 0.000 title claims abstract description 6
- 229910000389 calcium phosphate Inorganic materials 0.000 title abstract description 3
- 235000011010 calcium phosphates Nutrition 0.000 title abstract 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 239000010452 phosphate Substances 0.000 claims abstract description 11
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 10
- -1 phosphate radical ion Chemical class 0.000 claims abstract description 9
- 230000007935 neutral effect Effects 0.000 claims abstract description 7
- 238000004108 freeze drying Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 16
- 238000009396 hybridization Methods 0.000 claims description 10
- 239000011575 calcium Substances 0.000 claims description 8
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 8
- 230000001376 precipitating effect Effects 0.000 claims description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 238000005868 electrolysis reaction Methods 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 229910000391 tricalcium phosphate Inorganic materials 0.000 claims description 4
- 229940078499 tricalcium phosphate Drugs 0.000 claims description 4
- 230000000536 complexating effect Effects 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000011010 flushing procedure Methods 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- OVYTZAASVAZITK-UHFFFAOYSA-M sodium;ethanol;hydroxide Chemical compound [OH-].[Na+].CCO OVYTZAASVAZITK-UHFFFAOYSA-M 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 abstract 2
- 230000001276 controlling effect Effects 0.000 abstract 1
- 238000002848 electrochemical method Methods 0.000 abstract 1
- 239000012528 membrane Substances 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 210000000988 bone and bone Anatomy 0.000 description 8
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 4
- 230000006196 deacetylation Effects 0.000 description 4
- 238000003381 deacetylation reaction Methods 0.000 description 4
- 238000007710 freezing Methods 0.000 description 4
- 230000008014 freezing Effects 0.000 description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000012890 simulated body fluid Substances 0.000 description 2
- 210000001519 tissue Anatomy 0.000 description 2
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 241000251539 Vertebrata <Metazoa> Species 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000002138 osteoinductive effect Effects 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
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- Cosmetics (AREA)
- Micro-Organisms Or Cultivation Processes Thereof (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention discloses a method for generating a chitosan/calcium phosphate salt hybrid material by biomimetic mineralization through an electrochemical method. Preparing a chitosan solution with a certain concentration, pouring the chitosan solution into a mould, and immersing the chitosan solution into a precipitation solution for precipitation for a period of time to prepare chitosan gel. Putting the chitosan gel which is washed to be neutral by deionized water into an electrolytic device, adding the prepared phosphate radical ion solution at one side of an anode, adding the prepared calcium ion solution at one side of a cathode, and switching on a power supply to mineralize to obtain the chitosan/calcium phosphate salt gel hybrid material. The chitosan/calcium phosphate hybrid scaffold or membrane can be further prepared by freeze drying. The method has simple operation and short time, and can control the composition and the structure of the generated inorganic matter by regulating and controlling the preparation conditions and improve the content of the inorganic matter in the organic/inorganic hybrid material.
Description
Technical field
The present invention relates to the method that the electrochemical process biomimetic mineralization generates chitosan/synthos hybrid material.
Background technology
(Chitosan CS), is the natural polysaccharide that nature the most extensively exists to chitosan, and also being that nature is unique has a cationic electrolyte hybrid of alkalescence.It has good biocompatibility, biodegradability, good biochemical properties such as antibiotic property and easy film property.In addition, chitosan molecule has hydroxyl and amino, can carry out chemical modification to chitosan.Amino all right complexing calcium ions provides the nucleation site for generating hydroxyapatite and tricalcium phosphate.In recent years, be that feedstock production becomes chitosan gel rubber with the chitosan, chitosan film and chitosan stent are widely used in drug delivery system, tissue engineering bracket etc. in biomedical materials field.
Hydroxyapatite and bata-tricalcium phosphate are vertebrates sclerous tissues such as bone, and the main composition of tooth etc. has fabulous biological activity, osteoinductive and bone conductibility.Form by the collagen of 70% hydroxyapatite and 30% like human body natural's bone.Thereby adopt the organic/inorganic hybridization material of bionical method type of preparing bone structure to have great importance in bone reparation field.
The organic/inorganic hybridization material that adopts at present biomimetic method preparation type of having bone structure is to adopt organic material is put into the method for carrying out mineralising in the middle of the simulated body fluid to realize mostly.Although this method for preparing is fairly simple, also have following shortcoming: (1) is time-consuming, generate fully hydroxyapatite often will be in simulated body fluid mineralising 2～3 months; (2) inorganic content that generates is low, and inorganic content contained in the organic/inorganic hybridization material of preparation generally is not higher than 20%, and the inorganic content gap is too big in forming with bone; (3) be difficult to control in the organic/inorganic hybridization material of generation inorganic matter and form structure.
Summary of the invention
It is simple to the purpose of this invention is to provide a kind of technology, helps improving the method that the electrochemical process biomimetic mineralization of inorganic content in the middle of the organic/inorganic hybridization material generates chitosan/synthos hybrid material.
For achieving the above object, the technical scheme that the present invention adopts is: the electrochemical process biomimetic mineralization generates the method for chitosan/synthos hybrid material, it is characterized in that comprising the following steps:
1) prepares ionic calcium soln and the phosphate anion solution that calcium ion and phosphorus acid ion concentration are 10～100 mmol/L respectively; Regulate pH with the Tris-HCl buffer, making ionic calcium soln pH is 7～9, and the phosphate anion pH value of solution is 9～12;
2) be that the chitosan solution of 3～10 % is poured in the middle of the mould with mass fraction, this mould be immersed in the precipitating liquid, generate chitosan gel rubber, with deionized water with the chitosan gel rubber flushing to neutral;
3) chitosan gel rubber is put into electrolysis unit, add the phosphate anion solution that step 1) is prepared, add the ionic calcium soln that step 1) is prepared in negative electrode one side in anode one side; Energized, the chitosan gel rubber complexing calcium ions obtains chitosan/synthos gel hybridization material.
Further characteristic of the present invention is that chitosan/synthos gel hybridization material is carried out lyophilization, obtains chitosan/synthos hydridization support or chitosan/synthos hybridized film.
Among the present invention, said calcium ion derives from CaCl
2Or Ca (NO
3)
2Phosphate anion derives from K
2HPO
4, KH
2PO
4, Na
2HPO
4, NaH
2PO
4Or NH
4H
2PO
4
Among the present invention, said power supply is that voltage is dc source or the alternating current power supply of 1～200 v, is generally 5～240 min conduction time.
Among the present invention, described precipitating liquid is that mass fraction is the sodium hydrate aqueous solution of 2～10 %, or mass fraction is the sodium hydroxide ethanol water of 2～10 %, and wherein the ethanol volumetric concentration is 5～100 %.
Among the present invention, described electrochemical process biomimetic mineralization generates the method for chitosan/synthos hybrid material, it is characterized in that: the synthos that generated are hydroxyapatite (HA) or bata-tricalcium phosphate (β-TCP).
The method of electrochemical process biomimetic mineralization generation chitosan/synthos hybrid material of the present invention is simple to operate; Adopt electrochemical process can promote the migration of calcium ion and phosphate anion; Shorten the mineralising time greatly, through the pH value of regulation and control cathode and anode both sides, voltage, conduction time and ion concentration; Can control the The Nomenclature Composition and Structure of Complexes of the inorganic matter of type of having bone structure, improve the central inorganic content of organic/inorganic hybridization material.
The specific embodiment
Further specify the present invention below in conjunction with instantiation.
Embodiment 1:
(1) with chitosan solution 100 ml of 2% acetum preparation 4%, the deacetylation 65% of the chitosan that adopts, weight average molecular weight 4.5 * 10
5, standing and defoaming;
(2) above-mentioned chitosan solution is poured in the middle of 24 well culture plates, the chitosan solution height is 4 mm, and 2 h in the 5% NaOH precipitating liquid that puts it into mass fraction and be make the chitosan gel rubber that gel thicknesses is 4 mm, with deionized water rinsing to neutral;
(3) chitosan gel rubber is put into electrolysis unit, negative electrode one side adds the CaCl of 20 an amount of mmol/L
2Solution (pH=7.0), anode one side adds the Na of 20 mmol/L of equivalent
2HPO
4Solution (pH=10.0);
(4) adopt dc source, voltage is 20 v, and at this moment, the calcium ion anode moves; Phosphate anion moves to negative electrode, behind 1 h that switches on, takes out chitosan/synthos gel, uses deionized water rinsing; Remove calcium ion unnecessary in the chitosan, phosphate anion, sodium ion etc.;
(5) above-mentioned chitosan/synthos gel is drained behind freezing 4 h in freeze dryer, made chitosan/synthos hydridization support.
Embodiment 2:
(1) with chitosan solution 100 ml of 2% acetum preparation 4%, the deacetylation 80% of the chitosan that adopts, weight average molecular weight 4.5 * 10
5, standing and defoaming;
(2) above-mentioned chitosan solution is poured in the middle of 24 well culture plates, the chitosan solution height is 5 mm, and 1 h in the 5% NaOH precipitating liquid that puts it into mass fraction and be makes the chitosan gel rubber that gel thicknesses is about 5 mm, with deionized water rinsing to neutral;
(3) chitosan gel rubber is put into electrolysis unit, negative electrode one side adds the CaCl of 20 an amount of mmol/L
2Solution (pH=7.0), anode one side adds the Na of 20 mmol/L of equivalent
2HPO
4Solution (pH=10.0);
(4) adopt dc source, voltage is 20 v, behind 1 h that switches on, takes out chitosan/synthos gel, with deionized water rinsing several times, removes calcium ion unnecessary in the chitosan, phosphate anion, sodium ion etc.;
(5) above-mentioned chitosan/synthos gel is drained behind freezing 4 h in freeze dryer, made chitosan/synthos hydridization support.
Embodiment 3:
(1) with chitosan solution 100 ml of 2% acetum preparation 4%, the deacetylation 95% of the chitosan that adopts, weight average molecular weight 4.5 * 10
5, standing and defoaming;
(2) above-mentioned chitosan solution is poured in the middle of 24 well culture plates, the chitosan solution height is 4 mm, and 2h in the 6% NaOH precipitating liquid that puts it into mass fraction and be makes the chitosan gel rubber that gel thicknesses is 4 mm, with deionized water rinsing to neutral;
(3) chitosan gel rubber is put into electrolysis unit, negative electrode one side adds the CaCl of 20 an amount of mmol/L
2Solution (pH=7.0), anode one side adds the Na of 20 mmol/L of equivalent
2HPO
4Solution (pH=10.0);
(4) adopt dc source, voltage is 20 v, behind 2 h that switch on, takes out chitosan/synthos gel, with deionized water rinsing several times, removes calcium ion unnecessary in the chitosan, phosphate radical, sodium ion etc.;
(5) above-mentioned chitosan/synthos gel is drained behind freezing 4 h in freeze dryer, made chitosan/synthos hydridization support.
Embodiment 4:
(1) with chitosan solution 100 ml of 2% acetum preparation 4%, the deacetylation 80% of the chitosan that adopts, weight average molecular weight 4.5 * 10
5, standing and defoaming;
(2) above-mentioned chitosan solution is poured in the middle of 24 well culture plates, the chitosan solution height is 1 mm, and 2 h in the 5% NaOH precipitating liquid that puts it into mass fraction and be make the chitosan gel rubber that gel thicknesses is about 1 mm, with deionized water rinsing to neutral
(3) chitosan gel rubber is put into electrolysis unit, negative electrode one side adds the CaCl of 10 an amount of mmol/L
2Solution (pH=7.0), anode one side adds the Na of 10 mmol/L of equivalent
2HPO
4Solution (pH=10.0);
(4) adopt dc source, voltage is 30 v, behind 1 h that switches on, takes out chitosan/synthos gel, with deionized water rinsing several times, removes calcium ion unnecessary in the chitosan, phosphate radical, sodium ion etc.;
(5) above-mentioned chitosan/synthos gel is drained behind freezing 4 h in freeze dryer, made chitosan/synthos hybridized film.
Above-mentioned instance only is explanation technical conceive of the present invention and characteristics, and its purpose is to let the personage that is familiar with this technology can understand content of the present invention and is applied, and can not limit protection scope of the present invention with this.All equivalences that spirit is done according to the present invention change or modify, and all should be encompassed within protection scope of the present invention.
Claims (6)
1. the electrochemical process biomimetic mineralization generates the method for chitosan/synthos hybrid material, it is characterized in that comprising the following steps:
1) prepares ionic calcium soln and the phosphate anion solution that calcium ion and phosphorus acid ion concentration are 10～100 mmol/L respectively; Regulate pH with the Tris-HCl buffer, making ionic calcium soln pH is 7～9, and the phosphate anion pH value of solution is 9～12;
2) be that the chitosan solution of 3～10 % is poured in the middle of the mould with mass fraction, this mould be immersed in the precipitating liquid, generate chitosan gel rubber, with deionized water with the chitosan gel rubber flushing to neutral;
3) chitosan gel rubber is put into electrolysis unit, add the phosphate anion solution that step 1) is prepared, add the ionic calcium soln that step 1) is prepared in negative electrode one side in anode one side; Energized, the chitosan gel rubber complexing calcium ions obtains chitosan/synthos gel hybridization material.
2. electrochemical process biomimetic mineralization according to claim 1 generates the method for chitosan/synthos hybrid material; It is characterized in that: chitosan/synthos gel hybridization material is carried out lyophilization, obtain chitosan/synthos hydridization support or chitosan/synthos hybridized film.
3. electrochemical process biomimetic mineralization according to claim 1 generates the method for chitosan/synthos hybrid material, and it is characterized in that: said calcium ion derives from CaCl
2Or Ca (NO
3)
2Phosphate anion derives from K
2HPO
4, KH
2PO
4, Na
2HPO
4, NaH
2PO
4Or NH
4H
2PO
4
4. electrochemical process biomimetic mineralization according to claim 1 generates the method for chitosan/synthos hybrid material, and it is characterized in that: said power supply is that voltage is dc source or the alternating current power supply of 1～200 v, and be 5～240 min conduction time.
5. electrochemical process biomimetic mineralization according to claim 1 generates the method for chitosan/synthos hybrid material; It is characterized in that: described precipitating liquid is that mass fraction is the sodium hydrate aqueous solution of 2～10 %; Or mass fraction is the sodium hydroxide ethanol water of 2～10 %, and wherein the ethanol volumetric concentration is 5～100 %.
6. electrochemical process biomimetic mineralization according to claim 1 generates the method for chitosan/synthos hybrid material, it is characterized in that: the synthos that generated are hydroxyapatite (HA) or bata-tricalcium phosphate (β-TCP).
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103706408A CN102397581A (en) | 2011-11-21 | 2011-11-21 | Method for generating chitosan/calcium phosphate hybrid material by electrochemical biomimetic mineralization |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103706408A CN102397581A (en) | 2011-11-21 | 2011-11-21 | Method for generating chitosan/calcium phosphate hybrid material by electrochemical biomimetic mineralization |
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| Publication Number | Publication Date |
|---|---|
| CN102397581A true CN102397581A (en) | 2012-04-04 |
Family
ID=45880473
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103463683A (en) * | 2013-09-09 | 2013-12-25 | 浙江大学 | Preparation method of chitosan/calcium phosphate bone tissue healing porous scaffold |
| CN106539693A (en) * | 2016-10-13 | 2017-03-29 | 浙江大学 | The method of the biomimetic mineralization pad pasting and its external evoked remineralization of macromolecule filming material load ACP |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1389503A (en) * | 2002-07-15 | 2003-01-08 | 浙江大学 | In-situ compounding process of synthesizing nano composite chitosan/hydroxyapatite material |
-
2011
- 2011-11-21 CN CN2011103706408A patent/CN102397581A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1389503A (en) * | 2002-07-15 | 2003-01-08 | 浙江大学 | In-situ compounding process of synthesizing nano composite chitosan/hydroxyapatite material |
Non-Patent Citations (2)
| Title |
|---|
| GAO LIU ET AL.: "Three-Dimensional Biomimetic Mineralization of Dense Hydrogel Templates", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| MARISA M. BEPPU ET AL.: "Influence of Calcification Solution on in vitro Chitosan Mineralization", 《MATERIALS RESEARCH》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103463683A (en) * | 2013-09-09 | 2013-12-25 | 浙江大学 | Preparation method of chitosan/calcium phosphate bone tissue healing porous scaffold |
| CN103463683B (en) * | 2013-09-09 | 2015-01-14 | 浙江大学 | Preparation method of chitosan/calcium phosphate bone tissue healing porous scaffold |
| CN106539693A (en) * | 2016-10-13 | 2017-03-29 | 浙江大学 | The method of the biomimetic mineralization pad pasting and its external evoked remineralization of macromolecule filming material load ACP |
| CN106539693B (en) * | 2016-10-13 | 2019-10-29 | 浙江大学 | The method that macromolecule filming material loads the biomimetic mineralization pad pasting and its external evoked remineralization of ACP |
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Application publication date: 20120404 |