CN102766220A - Hydrophobic modified beta-1, 3-D-glucan and preparation method and applications thereof - Google Patents
Hydrophobic modified beta-1, 3-D-glucan and preparation method and applications thereof Download PDFInfo
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- CN102766220A CN102766220A CN2012102551866A CN201210255186A CN102766220A CN 102766220 A CN102766220 A CN 102766220A CN 2012102551866 A CN2012102551866 A CN 2012102551866A CN 201210255186 A CN201210255186 A CN 201210255186A CN 102766220 A CN102766220 A CN 102766220A
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Abstract
The invention relates to a hydrophobic modified beta-1, 3-D-glucan and a preparation method and applications thereof. The hydrophobic modified beta-1, 3-D-glucan is prepared through the steps of carrying out degradation on beta-1, 3-D-glucan by using a formic acid; then dissolving the beta-1, 3-D-glucan in pyridine; adding acetic oxide into the obtained mixture to react; carrying out dialysis on the obtained product by using a dialysis bag; and drying the obtained object. The hydrophobic modified beta-1, 3-D-glucan can be used for preparing biomedical materials such as nano micro-capsules, nano fiber fabrics or porous square brackets and the like.
Description
Technical field
The present invention relates to field of biomedical materials, particularly a kind of hydrophobically modified
β-1, the 3-D-VISOSE.
Background technology
β-1, the 3-D-VISOSE is a fungi, and the constituent of yeast cell or alginic cell wall belongs to a kind of compound that possesses multiple physiologically active.
β-1, the 3-D-VISOSE can activated macrophage, neutrophils etc., stimulates the immunity system of body, regulates human body immune function, makes body more effectively resist the disease that is caused by mikrobe.Through specific step extraction and do not contain endotoxic
β-1, the 3-D VISOSE has assert it is a kind of safe biologically active substance at U.S. FDA, can be added on normal food, exercises and regulates functions of immune system; Research shows the oral yeast of mouse
β-1, the 3-D-VISOSE can increase the antibiotic phagolysis of strong peritoneal cell.
Simultaneously
β-1, the 3-D-VISOSE occupies consequence, still as the natural macromolecular material of a kind of wide material sources and good biocompatibility in the research of biomaterial
β-1, the 3-D-VISOSE contains poly-hydroxy, and wetting ability is strong, is unfavorable for processing, has limited its application at biomedical engineering field.
Existing
β-1, the 3-D-dextran modification mainly concentrates on the following aspects: (1)
β-1,3-D-VISOSE sulfonated, amination, phosphorylation or methylolation are used for antitumor, anti-HIV and improve immunocompetence; (2), or Septochol is replaced carboxymethylation through the hydrophobicity sulfonylurea being connected to 6 carbon hydroxyls
b-1, the part carboxyl carries out hydrophobization in the 3-D-VISOSE; (3) through oleyl amine and Sensor Chip CM 5 reaction, obtain the hydrophobization product.
By in May, 2012, obtain following information from State Intellectual Property Office's patent retrieval DB:
| Search key | The patent of invention number | The utility model number | Remarks |
| VISOSE | 1228 | 5 | - |
| β-1, the 3-D-VISOSE | 3 | 0 | - |
| VISOSE+modification | 12 | 0 | - |
| VISOSE+hydrophobic | 3 | 0 | - |
| Hydrophobic fiber | 10 | 0 | - |
| Immune microsphere | 9 | 0 | - |
From present domestic patent,, relate to although more about the application document of VISOSE
β-1, the work of 3-D-VISOSE comprises modification, hydrophobization, fibrosis and less as the work of pharmaceutical carrier.Modified glucan comprises as the work of carrier: long circulating liposomes that 201010231936.7 lyophobic and modified glucan are modified and preparation method thereof; 201110051515.0 modified glucan transgene carrier and preparation method thereof and the VISOSE of application 2 00780035666.9 by functionalized with hydrophobic amino acids; These work all do not relate to the acetyl hydrophobic modification.
In addition, from Chinese scientific and technical literature database lookup and the present invention
β-1, the identical document of 3-D-VISOSE hydrophobically modified method does not have to find and the identical report of this technology yet.
From external technical paper and patent aspect,
β-1, the 3-D-VISOSE is applied to medicine or foodstuff additive mainly as function ingredients, the exploitation of functional feed or crosslinked as the tissue regeneration support.As 90104813.5 through certain method with non-hot gelling
β-1, the 3-D-VISOSE changes into can hot agglomerative
β-1, the 3-D-VISOSE, said method comprises with the non-hot gelling of alkali dissolution
β-1, the 3-D-VISOSE is regulated this pH that dissolves and is made it be no more than 10, can hot agglomerative thereby be settled out
β-1, the 3-D-VISOSE.(preparation can hot agglomerative
βThe method of-1-3-D-VISOSE); 93109362.7 invention relates to the VISOSE with immunostimulating, with and preparation method thereof with the medicinal compsns that contains this type of VISOSE.VISOSE with immunostimulatory activity; 98110182.8 the invention relate to
β-1,3-D-VISOSE and verivate thereof are the application of the tissue restoration accelerator of effective constituent.Be handle specifically
β-1; 3-D-VISOSE and verivate thereof are used for the reparation and the treatment of tissue injury property diseases such as ulcer, erosion, burn, scald, frostbite, wound, operative incision and corneal injury as effective constituent; Have to strengthen and organize anti-infection ability; Promote (acceleration) wound healing, improve repairing quality, reduce the effect of recurrence; Also can be used as effective constituent and be used for skin protection cosmetics, metabolism that can strengthen skin and protection function make that skin is tender, plentiful, gloss and fitness, have important medicine and healthcare applications value; 200810066102.8 disclosure of the Invention relate to nanometer polysaccharide as the preparation antitumor drug application; This medicine is transformed into the low relative molecular mass polysaccharide anti-tumor agent below the 1000nm by high molecular weight polysaccharide (1,000～hundreds thousand of do not wait), and this particulate has the target property that is superior to initial molecule; The polysaccharide main chemical compositions be by
β-1,3-D,
β-1,4-D,
β-1, VISOSEs such as 6-D are formed, and relate generally to field of immunology, more specifically relate to multiple biological activity and functions such as cancer immunotherapy.Nanometer polysaccharide is as the application of preparation antitumor drug; 201080005258.0 invention relates to a kind of through using radiation integration technology manufacturing to be used for bioengineered tissue
β-VISOSE base support, and relate to its method of manufacture.Right according to the present invention
βThe method of manufacture of-VISOSE base support, organizational project is merged in radiation, will
β-VISOSE water-soluble solution pours into, and then to its radiation-induced crosslinking reaction, to form the support of gel shape or solid shape, also creates a kind of bionical environment that growth and the differentiation of stem cell are had the coinduction effect like a cork thereby promote cell to adsorb.Therefore; Can beta-glucan base support according to the present invention be used for tissue regeneration, cell cultures and Cosmetics Surgery as weighting material; Be used for the drainage of biological tissue as weighting material, be used for rebuilding and proofreading and correct Cosmetics Surgery, and be used for Transplanted cells and medicine is sent as support.The bioengineered tissue that is used for through radiation integration technology manufacturing
β-VISOSE base support and method of manufacture thereof.
Comprehensively both at home and abroad about
β-1, the research of 3-D-VISOSE and technical patent document.Their major side overweight
β-1, the functional development of 3-D-VISOSE and application; Less for itself as the research that biomacromolecule is used for biomaterial.Therefore, existing technology does not all have or can not change through grafting
β-1, under the prerequisite of 3-D-VISOSE chemical structure, improve
β-1, the hydrophobicity of 3-D-VISOSE material is used for pharmaceutical carrier or tissue regeneration support also separately as biomedical material.
Summary of the invention
For solving the problems referred to above that prior art exists, primary and foremost purpose of the present invention is to provide a kind of hydrophobically modified
β-1, that the preparation method of 3-D-VISOSE, this method do not adopt is poisonous, pungency and human body is produced dysgenic solvent, need not carry out complicated chemical reaction, can accomplish scale production.
Another object of the present invention is to provide by said hydrophobically modified
β-1, the hydrophobically modified that the preparation method of 3-D-VISOSE prepares
β-1, the 3-D-VISOSE.
A further object of the invention is to provide said hydrophobically modified
β-1, the 3-D-VISOSE is as the application of biomedical material.
Above-mentioned purpose of the present invention is achieved through following technical scheme:
A kind of hydrophobically modified
β-1, the preparation method of 3-D-VISOSE comprises the steps:
(1) exists
β-1, add formic acid in the 3-D-VISOSE, temperature is controlled at 50-90
oC, magnetic agitation backflow 1-4h;
(2) reaction finishes postcooling to room temperature, and stirring reaction liquid adds absolute ethyl alcohol, separates out
Post precipitation continues to stir 0.5-2h;
(3) the centrifugal clear liquid of removing precipitates 5 times to neutral with washing with alcohol, uses 8-14kDa again
With keeping the liquid freeze-drying in the dialysis tubing, obtain the white powder solid and be degraded after the molecular weight dialysis tubing was dialysed in zero(ppm) water 3 days
β-1, the 3-D-VISOSE;
(4) degraded that makes in step (3)
β-1, add in the 3-D-VISOSE powder pyridine with
Diacetyl oxide, controlled temperature is at 50-90
oC, magnetic agitation backflow 1-10h;
(5) reaction solution in the step (4) is under agitation added zero(ppm) water, separate out post precipitation
Continue to stir 0.5-2h;
(6) the centrifugal clear liquid of removing adds zero(ppm) water in deposition, stirs down and regulates pH to slight alkalinity with saturated sodium bicarbonate;
(7) centrifugal washing is 3-10 time, and after in zero(ppm) water, dialysing 3 days with 8-14kDa molecular weight dialysis tubing reservation liquid freeze-drying in the dialysis tubing being obtained hydrophobic white powder solid is hydrophobically modified
β-1, the 3-D-VISOSE;
Described in the step (1)
β-1, the 3-D-VISOSE is 1g:10-100ml with the mass/volume ratio of formic acid, is preferably 1g:50ml, and said temperature of reaction is preferably 70
oC or 90
oC, return time are preferably 2h or 4h; The absolute ethyl alcohol volume ratio of described reaction solution of step (2) and adding is 1:2-5, is preferably 1:2; Degraded described in the step (4)
β-1, the 3-D-VISOSE is 1g:10-100ml with the mass/volume ratio of the pyridine of adding, is preferably 1g:50ml, described degraded
β-1, the 3-D-VISOSE is 1g:4-20ml with the mass/volume ratio of the diacetyl oxide of adding, is preferably 1:7.5 ml, and described temperature of reaction is preferably 80
oC, return time are preferably 3h or 5h; The zero(ppm) water volume ratio of reaction solution described in the step (5) and adding is 1:1-4, is preferably 1:4.
Prepare a kind of hydrophobically modified by above-mentioned preparation method
β-1,3-D-VISOSE, this hydrophobically modified
β-1, the hydrophobic property of 3-D-VISOSE is adjustable, mainly is through controlling reaction time, and the degree of esterification that the sugared ring of adjustment is gone up hydroxyl realizes.
Described hydrophobically modified
β-1, the 3-D-VISOSE can be used as the application of biological medicine material.
Described application as the biological medicine material specifically is meant as the application in preparation nano-microcapsule, nano-fiber cloth, the porous square set.Its preparation method is following: with hydrophobically modified
β-1, the 3-D-VISOSE is dissolved in the acetone, and configuration quality concentration is 1-20%; Can directly be dispersed in to contain and obtain medicament-carried nano micro-capsule (or together be dissolved in acetone with medicine) in the liquid medicine; Or electric spinning obtains cloth, or with after the salt particle blend drying, the salt stripping obtained the porous square set.
Compared with prior art, the present invention has following beneficial effect:
(1) hydrophobically modified of the present invention
β-1, the preparation method is simple for the 3-D-VISOSE, need not carry out complicated chemical reaction, can accomplish scale production; Do not adopt poisonous, pungency in the modifying process and human body is produced dysgenic solvent or other chemical reagent;
(2) hydrophobically modified that obtains of this method
β-1,3-D-VISOSE hydrophobic property is adjustable, and does not change
β-1, the basic chemical chain structure of 3-D-VISOSE, its biomedical characteristic is maintained;
(3) hydrophobically modified of this method acquisition
β-1, the 3-D-VISOSE can obtain the goods of different shape without chemically crosslinked, like nano-microcapsule, nano-fiber cloth, porous square set.
Embodiment
Come further to explain the present invention below in conjunction with specific embodiment, but embodiment does not do any type of qualification to the present invention.
Embodiment 1
(1) takes by weighing 2g
β-1,3-D-VISOSE powder (200kDa) is poured in the 250ml there-necked flask, adds 100ml formic acid, 90
oC magnetic agitation backflow 4h;
(2) reaction finishes postcooling to room temperature, and reaction solution is poured in the 500ml beaker, under agitation adds the 200ml absolute ethyl alcohol, separates out post precipitation and continues to stir 0.5h;
(3) the centrifugal clear liquid of removing precipitates 5 times to neutral with washing with alcohol;
(4) keep liquid in the freeze-drying dialysis tubing after in zero(ppm) water, dialysing 3 days with 8-14kDa molecular weight dialysis tubing and obtain white powder
Solid is promptly degraded
β-1,3-D-VISOSE, productive rate 30%;
(5) take by weighing the 2g degraded
β-1,3-D-VISOSE powder is poured in the 250ml there-necked flask,
Add the 100ml pyridine, the 15ml diacetyl oxide.80
oC magnetic agitation backflow 3h;
(6) reaction finishes postcooling to room temperature, pours the reaction solution in the step (5) into 500ml
In the beaker, under agitation add 400ml zero(ppm) water, separate out post precipitation and continue to stir 0.5h;
(7) the centrifugal clear liquid of removing adds 200ml zero(ppm) water in the deposition, stir down and regulate PH to slight alkalinity with saturated sodium bicarbonate;
(8) washing is 10 times.Concentrate 0.5h and remove remaining pyridine.Keep liquid in the freeze-drying dialysis tubing after freeze-drying was dialysed 3 days with 8-14kDa molecular weight dialysis tubing then in zero(ppm) water.Obtaining hydrophobic white powder solid is hydrophobically modified
β-1, the 3-D-VISOSE;
(9) get the hydrophobically modified for preparing in the 1g step (8)
β-1, the 3-D-VISOSE is dissolved in 20ml acetone, it is splashed in the 500ml water that contains vulcabond (FITC) disperse, and detects through the ZETA potentiometer and obtains the nano-microcapsule that contains the FITC fluorescent substance that mean diameter is 120 nanometers.
Embodiment 2
(1) takes by weighing 2g
β-1,3-D-VISOSE powder is poured in the 250ml there-necked flask, adds
Go into 100ml formic acid, 70
oC magnetic agitation backflow 2h;
(2) reaction finishes postcooling to room temperature, reaction solution is poured in the 500ml beaker,
Stir adding 200ml absolute ethyl alcohol down, separate out post precipitation and continue to stir 0.5h;
(3) the centrifugal clear liquid of removing precipitates 5 times to neutral with washing with alcohol;
(4) keeping liquid after in zero(ppm) water, dialysing 3 days with 8-14kDa molecular weight dialysis tubing in the freeze-drying dialysis tubing obtains the white powder solid and is degraded
β-1,3-D-VISOSE, productive rate 30%;
(5) take by weighing 2g degraded β-1,3-D-VISOSE powder is poured in the 250ml there-necked flask, adds the 100ml pyridine, the 15ml diacetyl oxide.80
oC magnetic agitation backflow 5h;
(6) reaction finishes postcooling to room temperature, and the reaction solution in the step (5) is poured in the 500ml beaker, under agitation adds 400ml zero(ppm) water, separates out post precipitation and continues to stir 0.5h;
(7) the centrifugal clear liquid of removing adds 200ml zero(ppm) water in the deposition, stir down and regulate pH to slight alkalinity with saturated sodium bicarbonate;
(8) washing is 10 times.Concentrate 0.5h and remove remaining pyridine.Keep liquid in the freeze-drying dialysis tubing after freeze-drying was dialysed 3 days with 8-14kDa molecular weight dialysis tubing then in zero(ppm) water.Obtaining hydrophobic white powder solid is hydrophobically modified
β-1, the 3-D-VISOSE;
(9) get the 1g hydrophobically modified
β-1, the 3-D-VISOSE is dissolved in 20ml acetone or the N,N-DIMETHYLACETAMIDE, and electric spinning 6h obtains nano-fiber cloth.
Embodiment 3
(1) gets hydrophobic that instance 2 steps (8) obtain
β-1,3-D-VISOSE 1g is dissolved in 20ml acetone, and is even with the blend of 6gNaCl particle, pours square dies rapidly into;
(2) soaked 3 days in zero(ppm) water dry back, separates out the NaCl particle.Drying obtains the porous square set.
Claims (5)
1. hydrophobically modified
β-1, the preparation method of 3-D-VISOSE is characterized in that comprising the steps:
(1) exists
β-1, add formic acid in the 3-D-VISOSE, temperature is controlled at 50-90
oC, magnetic agitation backflow 1-4h;
(2) reaction finishes postcooling to room temperature, and stirring reaction liquid adds absolute ethyl alcohol, separates out post precipitation and continues to stir 0.5-2h;
(3) the centrifugal clear liquid of removing precipitates 5 times to neutral with washing with alcohol, with keeping the liquid freeze-drying in the dialysis tubing, obtains degrading after dialysing 3 days with 8-14kDa molecular weight dialysis tubing
β-1, the 3-D-VISOSE;
(4) degraded that makes in step (3)
β-1, add pyridine and diacetyl oxide in the 3-D-VISOSE powder, controlled temperature is at 50-90
oC, magnetic agitation backflow 1-10h;
(5) reaction solution in the step (4) is under agitation added zero(ppm) water, separate out post precipitation and continue to stir 0.5-2h;
(6) the centrifugal clear liquid of removing adds zero(ppm) water in deposition, stirs down and regulates pH to slight alkalinity with saturated sodium bicarbonate;
(7) centrifugal washing is 3-10 time, obtains hydrophobically modified with keeping the liquid freeze-drying in the dialysis tubing with the dialysis of 8-14kDa molecular weight dialysis tubing after 3 days again
β-1, the 3-D-VISOSE;
Described in the step (1)
β-1, the 3-D-VISOSE is 1g:10-100ml with the mass/volume ratio of formic acid, and the absolute ethyl alcohol volume ratio of described reaction solution of step (2) and adding is 1:2-5, the degraded described in the step (4)
β-1, the 3-D-VISOSE is 1g:10-100ml, the degraded described in the step (4) with the mass/volume ratio of the pyridine of adding
β-1, the 3-D-VISOSE is 1g:4-20ml with the mass/volume ratio of the diacetyl oxide of adding, and the zero(ppm) water volume ratio of reaction solution described in the step (5) and adding is 1:1-4.
2. a kind of hydrophobically modified according to claim 1
β-1, the preparation method of 3-D-VISOSE is characterized in that, described in the step (1)
β-1, the 3-D-VISOSE is 1g:50ml with the mass/volume ratio of formic acid, and temperature of reaction is 70
oC or 90
oC, return time are 2h or 4h, and the absolute ethyl alcohol volume ratio of described reaction solution of step (2) and adding is 1:2, the degraded described in the step (4)
β-1, the 3-D-VISOSE is 1g:50ml, degraded with the mass/volume ratio of the pyridine of adding
β-1, the 3-D-VISOSE is 1g:7.5ml with the mass/volume ratio of the diacetyl oxide of adding, and temperature of reaction is 80
oC, return time are 3h or 5h, and the zero(ppm) water volume ratio of reaction solution described in the step (5) and adding is 1:4.
3. the hydrophobically modified for preparing of claim 1 or 2 said preparing methods
β-1, the 3-D-VISOSE.
4. the described a kind of hydrophobically modified of claim 3
β-1, the 3-D-VISOSE is as the application of biomedical material.
5. application according to claim 4 is characterized in that described hydrophobically modified
β-1, the 3-D-VISOSE is as the application of preparation nano-microcapsule, nano-fiber cloth or porous square set.
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| CN2012102551866A CN102766220A (en) | 2012-07-23 | 2012-07-23 | Hydrophobic modified beta-1, 3-D-glucan and preparation method and applications thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015109164A1 (en) * | 2014-01-17 | 2015-07-23 | E. I. Du Pont De Nemours And Company | Production of gelled networks of poly alpha-1,3-glucan formate and films therefrom |
| CN106986951A (en) * | 2016-01-21 | 2017-07-28 | 蚌埠医学院 | A kind of hydrophobic polysaccharide and its preparation method and application |
| US10059778B2 (en) | 2014-01-06 | 2018-08-28 | E I Du Pont De Nemours And Company | Production of poly alpha-1,3-glucan films |
| CN108623712A (en) * | 2018-05-21 | 2018-10-09 | 广州暨南生物医药研究开发基地有限公司 | A kind of hydrophobically modified laminarin and the preparation method and application thereof |
| US10106626B2 (en) | 2014-01-17 | 2018-10-23 | Ei Du Pont De Nemours And Company | Production of poly alpha-1,3-glucan formate films |
| CN110156911A (en) * | 2019-05-20 | 2019-08-23 | 蚌埠医学院 | Hydrophobic polysaccharide and its preparation method and application |
Citations (1)
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| KR20090058420A (en) * | 2007-12-04 | 2009-06-09 | 전남대학교산학협력단 | Preparation method of dextran acetate nanoparticles for drug delivery and of drug delivery media using dextran acetate nanoparticles |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20090058420A (en) * | 2007-12-04 | 2009-06-09 | 전남대학교산학협력단 | Preparation method of dextran acetate nanoparticles for drug delivery and of drug delivery media using dextran acetate nanoparticles |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10059778B2 (en) | 2014-01-06 | 2018-08-28 | E I Du Pont De Nemours And Company | Production of poly alpha-1,3-glucan films |
| WO2015109164A1 (en) * | 2014-01-17 | 2015-07-23 | E. I. Du Pont De Nemours And Company | Production of gelled networks of poly alpha-1,3-glucan formate and films therefrom |
| US10106626B2 (en) | 2014-01-17 | 2018-10-23 | Ei Du Pont De Nemours And Company | Production of poly alpha-1,3-glucan formate films |
| CN106986951A (en) * | 2016-01-21 | 2017-07-28 | 蚌埠医学院 | A kind of hydrophobic polysaccharide and its preparation method and application |
| CN108623712A (en) * | 2018-05-21 | 2018-10-09 | 广州暨南生物医药研究开发基地有限公司 | A kind of hydrophobically modified laminarin and the preparation method and application thereof |
| CN110156911A (en) * | 2019-05-20 | 2019-08-23 | 蚌埠医学院 | Hydrophobic polysaccharide and its preparation method and application |
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Application publication date: 20121107 |