CN102351957B - Oxidation method of natural polymeric amylose with high oxidisability - Google Patents
Oxidation method of natural polymeric amylose with high oxidisability Download PDFInfo
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- CN102351957B CN102351957B CN2011102376186A CN201110237618A CN102351957B CN 102351957 B CN102351957 B CN 102351957B CN 2011102376186 A CN2011102376186 A CN 2011102376186A CN 201110237618 A CN201110237618 A CN 201110237618A CN 102351957 B CN102351957 B CN 102351957B
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Abstract
The invention discloses an oxidation method of natural polymeric amylose with high oxidisability, comprising the following steps of: preparing hydrogel by using reductive polysacchride as a raw material under the action of an oxidizing agent while sodium periodate is used as the oxidizing agent and the catalyst contains at least one substance selected from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, formic acid, citric acid and a green solvent ion liquid with Lewis acidity; adjusting pH of the system within the acidic range, reacting for 4 hours at room temperature in shade, and carrying out post-treatment to obtain the high strength hydrogel of the natural high-molecular polysaccharide with different oxidisability. By the adoption of the method, the product has high oxidisability and is easier to crosslink with other reactants to form firmer chemical bonds, high strength hydrogel can be prepared, and the degradation rate of the gel can be controlled. In addition, the preparation method is suitable for the preparation of bone tissue function materials.
Description
Technical field
The present invention relates to the preparation field of oxidisability polysaccharide, especially prepare the method for the macromolecule polysaccharide of high oxidation degree.
Background technology
Organizational project is as the focus of current scientific research, to adopt the most frequently used in three kinds of strategies be hybrid systems normal, namely make up a three-dimensional stent material that biocompatibility is good, the histocyte absorption of vitro culture is increased on biomaterial, form the cytoskeleton works.This three-dimensional stent material should have certain hole, and the three-dimensional space of an existence can be provided for cell, is conducive to cell and obtains enough nutrition, carries out nutrition exchange, and can get rid of meta-bolites, make cell can be on the support of in advance design proliferation and differentiation.Therefore, the linking agent that impels material to form three-dimensional structure becomes key.Traditional chemical cross-linking agent is mainly glutaraldehyde, polyepoxides etc., but its toxic side effect that shows gradually along with material degradation has limited their application in tissue engineering bracket material.
Hydrogel has caused very large concern as a kind of tissue engineering material in biological chemistry and biomedical sector.It also will be in tissue filling, and the biomedical sectors such as microspheres capsule and medicine controlled releasing system make to have huge development potentiality.The intensity of hydrogel is a lot of people's outlines, and general requirement it become gellifying property good, and should have certain physical strength and stability.The method for preparing at present hydrogel is a lot, sodium alginate and chitosan crosslinked for example, and sodium alginate and gelatin are crosslinked, konjac glucomanna and chitosan crosslinked etc. method; But the hydrogel mechanical strength that obtains is not high, can't satisfy high intensity hydrogel to the requirement of mechanical strength.Material is one of key factor that determines the hydrogel performance.Take wherein common raw material sodium alginate as example, the hydrogel mechanical strength that common sodium alginate and other materials are cross-linked to form is very low.In order to obtain high intensity hydrogel, sodium alginate must be retrofited, synthetic oxidized sodium alginate can address the above problem to a certain extent.The preparation method of oxidized sodium alginate mainly contains sodium periodate oxidation, potassium permanganate oxidation method, sodium hypochlorite oxidization at present; Solvent used in the oxidising process mainly contains: water and ethanol.The oxidized sodium alginate oxidisability of aforesaid method preparation is lower, the gel degradation excessive velocities of formation, and the degraded mode is uncontrollable; And gel-strength is low, can't reach the requirement to the bone material mechanical strength during as bone material.
Summary of the invention
In view of the shortcoming of existing technology, the purpose of this invention is to provide a kind of preparation method of oxidized sodium alginate of high oxidation degree.
The objective of the invention is to realize by following means:
A kind of method for oxidation of natural macromolecule amylose of high oxidation degree, under the effect of oxygenant, produce hydrogel take the reductibility polysaccharide as raw material, comprise following processing condition: as oxygenant, described oxygenant and reductibility polysaccharide raw material equimolar ratio add with sodium periodate; Take at least a following material: hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, formic acid, citric acid, have the green solvent ionic liquid of Lewis Acidity as catalyzer; The pH of regulation system is at acid range, and the lucifuge reaction is 4 hours under the room temperature; Reaction finishes, and through absolute ethanol washing, suction filtration, vacuum-drying obtain the natural macromolecule amylose high intensity hydrogel of different oxidisabilities.
What compared with prior art, innovation of the present invention was product has a high oxidation degree.Its characteristics are that oxidisability is high, and the content of aldehyde radical is high, make crosslinked being more prone between oxidized sodium alginate and other reactants, the chemical bond that forms is more firm, can form high intensity hydrogel, and the degradation rate of gel can be controlled, is suitable for preparing the osseous tissue functional materials.Therefore, the present invention can solve the weak point of existing sodium alginate method for oxidation undoubtedly; Use mineral acid (hydrochloric acid, sulfuric acid, phosphoric acid etc.) in the oxidising process, organic acid (acetic acid, formic acid, citric acid etc.), and green solvent ionic liquid (1-butyl-3-methyl imidazolium tetrafluoroborate ([bmim] BF with Lewis Acidity
4), 1-butyl-3-Methylimidazole hexafluorophosphate ([bmim] PF
6) etc.) as catalyzer, ionic liquid ((bmim) BF wherein
4, (bmim) PF
6Deng) stable in properties, recoverable has reduced manufacturing cost; The used technique of the present invention is succinct, and equipment is simple, and is easy and simple to handle, can play the purpose of catalyzer by adding acid.Hyperoxia voltinism based on this product, the present invention has very widely application prospect, can be used for the various development researches about natural macromolecule amylose, is bio-medical material, macromolecular material, the development and application of intelligent sensitive material provide cheap well behaved material.
Description of drawings is as follows:
Fig. 1 is oxidized sodium alginate preparation technology schema of the present invention.
Fig. 2 is sodium alginate (1), and pH regulator is the infrared spectrogram of 2 oxidized sodium alginate (3) when the oxidized sodium alginate (2) of traditional method preparation and example 1 preparation.
The infrared spectrogram of the oxidized sodium alginate that Fig. 3 obtains for take hydrochloric acid as catalyzer the time.
Fig. 4 is the form before and after the gel formation of the prepared hydrogel that contains oxidized sodium alginate of example 1.
Fig. 5 is the scanning electron microscope (SEM) photograph of the prepared hydrogel tangent plane that contains oxidized sodium alginate of example 1.
Embodiment
Preparation technology's flow process of the present invention as shown in Figure 1, except special statement, the raw materials used chemical pure that is, the below describes the present invention in detail take sodium alginate as example:
Embodiment 1: take by weighing 1.0 gram sodium alginates, add the 50ml deionized water, stirring and dissolving becomes 2% sodium alginate soln; Take by weighing 1.0825 gram sodium periodates (in the ratio of n (sodium periodate): n (sodium alginate)=1: 1), join in the sodium alginate soln system, stir; With the pH of the hydrochloric acid soln regulation system of 1mol/L, (be respectively pH=2,3,4,5 and carry out parallel laboratory test), at room temperature lucifuge reaction 4 hours; Reaction finishes, with dehydrated alcohol repetitive scrubbing (5 times), and suction filtration; Add the appropriate amount of deionized water dissolving, solution is separated out with dehydrated alcohol; Use absolute ethanol washing (inferior), vacuum-drying can obtain the oxidized sodium alginate of different oxidisabilities again.
Embodiment 2: take by weighing 1.0 gram sodium alginates, add the 50ml deionized water, stirring and dissolving becomes 2% sodium alginate soln; Take by weighing 1.0825 gram sodium periodates (in the ratio of n (sodium periodate): n (sodium alginate)=1: 1), join in the sodium alginate ionic liquid system, stir: the pH that uses the sulphuric acid soln regulation system of 1mol/L, (be respectively pH=2,3,4,5 and carry out parallel laboratory test), at room temperature lucifuge reaction 4 hours; Reaction finishes, with dehydrated alcohol repetitive scrubbing (5 times), and suction filtration; Add the appropriate amount of deionized water dissolving, solution is separated out with dehydrated alcohol; Use absolute ethanol washing (inferior), vacuum-drying can obtain the oxidized sodium alginate of different oxidisabilities again.
Embodiment 3: take by weighing 1.0 gram sodium alginates, add the 50ml deionized water, stirring and dissolving becomes 2% sodium alginate soln; Take by weighing 1.0825 gram sodium periodates (in the ratio of n (sodium periodate): n (sodium alginate)=1: 1), join in the sodium alginate soln system, stir; With the pH of the acetum regulation system of 1mol/L, (be respectively pH=2,3,4,5 and carry out parallel laboratory test), at room temperature lucifuge reaction 4 hours; Reaction finishes, with dehydrated alcohol repetitive scrubbing (5 times), and suction filtration; Add the appropriate amount of deionized water dissolving, solution is separated out with dehydrated alcohol; Use absolute ethanol washing (inferior), vacuum-drying can obtain the oxidized sodium alginate of different oxidisabilities again.
Embodiment 5, take by weighing 1.0 gram sodium alginates, add 10ml ionic liquid ((bmim) BF
4), stir; Take by weighing 1.0825 gram sodium periodates (by the ratio of n (sodium periodate): n (sodium alginate)=1: 1), join in the sodium alginate ionic liquid system behind the adding 6ml deionized water dissolving, stir; With the pH of the hydrochloric acid soln regulation system of 1mol/L, (be respectively pH=2,3,4,5 and carry out parallel laboratory test), at room temperature lucifuge reaction 4 hours; Reaction finishes, with dehydrated alcohol repetitive scrubbing (5 times), and suction filtration; Add the appropriate amount of deionized water dissolving, solution is separated out with dehydrated alcohol; Use absolute ethanol washing (inferior), vacuum-drying obtains oxidized sodium alginate again.
Embodiment 6: take by weighing 1.0 gram sodium alginates, add 10ml ionic liquid ((bmim) BF
4), stir; Take by weighing 1.0825 gram sodium periodates (by the ratio of n (sodium periodate): n (sodium alginate)=1: 1), join in the sodium alginate ionic liquid system behind the adding 6ml deionized water dissolving, stir; With the pH of the sulphuric acid soln regulation system of 1mol/L, (be respectively pH=2,3,4,5 and carry out parallel laboratory test), at room temperature lucifuge reaction 4 hours; Reaction finishes, with dehydrated alcohol repetitive scrubbing (5 times), and suction filtration; Add the appropriate amount of deionized water dissolving, solution is separated out with dehydrated alcohol; Use absolute ethanol washing (inferior), vacuum-drying can obtain the oxidized sodium alginate of high oxidation degree again.
Embodiment 7: take by weighing 1.0 gram sodium alginates, add 10ml ionic liquid ((bmim) BF
4), stir; Take by weighing 1.0825 gram sodium periodates (by the ratio of n (sodium periodate): n (sodium alginate)=1: 1), join in the sodium alginate ionic liquid system behind the adding 6ml deionized water dissolving, stir; With the pH of the acetum regulation system of 1mol/L, (be respectively pH=2,3,4,5 and carry out parallel laboratory test), at room temperature lucifuge reaction 4 hours; Reaction finishes, with dehydrated alcohol repetitive scrubbing (5 times), and suction filtration; Add the appropriate amount of deionized water dissolving, solution is separated out with dehydrated alcohol; Use absolute ethanol washing (inferior), vacuum-drying can obtain the oxidized sodium alginate of high oxidation degree again.
Can be in the accompanying drawing 2 and find out, compared with prior art, adopt the oxidisability (expressing with aldehyde group content in scheming) of the inventive method products obtained therefrom (curve 3 among the figure) to have obvious raising.
The add-on of catalyst acid is also relevant with the product oxidisability, and as shown in Figure 3: (curve (1), (2), (3), (4) represent respectively to add catalyzer hydrochloric acid so that pH value of solution is respectively the infrared spectra curve of 2,3,4,5 o'clock systems.Along with the increase pH value of acidity reduces, the aldehyde radical peak is strengthened gradually as seen from the figure, oxidisability increases gradually), presented that the product oxidisability increases with PH acidity and the trend that increases.
Adopt general planning of the present invention, in reality is implemented, other multiple technical qualification conversion based on routine can be arranged, such as, described reductibility polysaccharide also can be sodium alginate, gelling gum, glucomannan etc.; Described and (bmim) BF
4Also can comprise phosphoric acid, acetic acid, formic acid, citric acid etc. with the common material that plays catalyst action.
Claims (1)
1. the method for oxidation of the natural macromolecule amylose of a high oxidation degree is produced hydrogel take sodium alginate as raw material under the effect of oxygenant, comprises following processing condition: as oxygenant, described oxygenant and sodium alginate equimolar ratio add with sodium periodate; Get in hydrochloric acid, sulfuric acid, the acetic acid a kind of together with 1-butyl-3-Methylimidazole tetrafluoro phosphate ion liquid together as catalyzer; Wherein 1-butyl-phosphatic add-on of 3-Methylimidazole tetrafluoro is pressed 10ml ionic liquid/1.0 gram sodium alginates addings, and the pH of regulation system is at acid range, and the lucifuge reaction is 4 hours under the room temperature; Reaction finishes, and through absolute ethanol washing, suction filtration, vacuum-drying obtain the natural macromolecule amylose high intensity hydrogel of high oxidation degree.
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| CN103342756B (en) * | 2013-07-15 | 2014-07-23 | 湖南尔康制药股份有限公司 | Production technology of medical sodium alginate |
| CN106421870A (en) * | 2016-11-16 | 2017-02-22 | 广东泰宝医疗科技股份有限公司 | Preparing method of compound alginate anti-adhesion material |
| CN109091707B (en) * | 2018-08-30 | 2021-03-26 | 西南交通大学 | Preparation method of composite 3D biological printing ink with biological activity |
| CN110833141A (en) * | 2019-11-23 | 2020-02-25 | 福建农林大学 | Boiling-resistant konjac glucomannan noodles and preparation method thereof |
| CN114621471A (en) * | 2022-04-02 | 2022-06-14 | 齐鲁工业大学 | Collagen gel and preparation method and application thereof |
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| CN100408112C (en) * | 2006-07-31 | 2008-08-06 | 中山大学附属第一医院 | Injectable hydrogel of sodium alginate crosslinked gelatin containing biphase calcium-phosphorus particles and preparation method and application thereof |
| CN101260160A (en) * | 2008-04-23 | 2008-09-10 | 海南大学 | Method for partially oxidizing sodium alginate |
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