CN103044693A - Preparation method for bacterial cellulose/polyvinyl alcohol composite hydrogel - Google Patents
Preparation method for bacterial cellulose/polyvinyl alcohol composite hydrogel Download PDFInfo
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- CN103044693A CN103044693A CN2012105879143A CN201210587914A CN103044693A CN 103044693 A CN103044693 A CN 103044693A CN 2012105879143 A CN2012105879143 A CN 2012105879143A CN 201210587914 A CN201210587914 A CN 201210587914A CN 103044693 A CN103044693 A CN 103044693A
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Abstract
The invention discloses a preparation method for bacterial cellulose/polyvinyl alcohol composite hydrogel, and relates to the field of biomaterial composite preparation. The preparation method comprises the following steps: through fermental cultivation of bacterial strains, acquiring bacterial cellulose, purifying and dewatering the bacterial cellulose and acquiring bacterial cellulose hydrogel with 30% to 50% water; enabling polyvinyl alcohol to go into the bacterial cellulose hydrogel by adopting the impregnation method, freezing and unfreezing the reaction product for a plurality of times; then, dewatering the reaction product for 6-24 hours in vacuum; at last, acquiring bacterial cellulose/polyvinyl alcohol composite hydrogel through high energy rays (HER) irradiation. The preparation method has simple technology, is low in cost and pollution-free; and moreover, the prepared composite hydrogel has excellent mechanical property, chemical stability and biocompatibility, and enjoys enormous application prospect in the field of biomedicine, such as wound dressing, drug release, cartilage tissue repairing and the like.
Description
Technical field
The present invention relates to the compound preparation field of a kind of biomaterial, particularly a kind of preparation of bacteria cellulose/polyvinyl alcohol composite aquogel.
Background technology
Macromolecule hydrogel, be a kind of can be in water swelling, absorption and keep large quantity of moisture and don't be dissolved in the hydrophilic net high-polymer swelling body of water, smooth surface, good biocompatibility has obtained studying widely and using in biological and engineering in medicine field.Macromolecule hydrogel has the advantage similar to the tissue performance, such as higher water content, snappiness and hypotoxicity.And the surface tension of hydrogel is lower, substantially can be from body fluid adsorbed proteins, thereby its impact on human body significantly reduces.In addition, small molecules is free to diffuse into and diffuse out hydrogel, so that hydrogel becomes the ideal carrier of medicament slow release.Macromolecule hydrogel also can be widely used in wound dressings and organ and repair field (as: aspects such as cornea, muscle, skin, cartilage).
The water-soluble swollen body of polyvinyl alcohol (PVA) the hydrogel network-like structure that to be hydrophilic polyethene alcohol macromole form after crosslinked.The PVA hydrogel has stable chemical property, good physical and mechanical properties, is easy to moulding, the biocompatibility good with tissue, especially the PVA hydrogel physical properties similar to the tissue performance, to the excellent perviousness such as water molecules, suitable extendability, good snappiness etc., these characteristics make the PVA hydrogel can be used as the biomedical sectors such as wound dressings, drug release carrier, artificial tissue, organizational project.Studies confirm that particularly the PVA hydrogel has and the similar bio-mechanical property of human articular cartilage and good biocompatibility, the cartilage surface of energy reconstruct smooth behind the implant into body, alleviate wearing and tearing, part substitutes joint cartilage, delaying or stop the arthritic generation of traumatic bone, is a kind of desirable joint cartilage equivalent material.But the mechanical strength of comparing the PVA hydrogel with human articular cartilage a little less than, for improving the mechanical property of PVA hydrogel, the present invention is compound with the bacteria cellulose aquagel with excellent mechanical property with the PVA hydrogel.
Bacteria cellulose (BC) is with β-1 by glucose, the macromolecular compound that the 4-glycosidic linkage is formed by connecting, as a kind of good biomaterial, the bacteria cellulose aquagel that BC forms under moisture state has its unique physics, chemical property: it has natural three-dimensional manometer network structure; Good mechanical property; High-hydrophilic, good ventilative, suction, water permeability.Simultaneously, bacteria cellulose also has in the good body, biocompatibility in vitro and good biodegradability, and this is so that bacteria cellulose is widely used in bio-medical material, such as dressing for skin, artificial skin, artificial blood vessel, tissue engineering bracket material etc.Studies show that the mechanical property of bacteria cellulose aquagel excellence (tensile modulus and Young's modulus) can reach the level similar to normal cartilage; The chondrocyte shows high-caliber growth at bacteria cellulose simultaneously, and can keep cartilage differentiation, support chondrocyte's migration propagation.
This patent adopts pickling process, freeze-thaw method and irradiation crosslinking, prepares a kind of bacteria cellulose/polyvinyl alcohol composite aquogel.This hydrogel has the inierpeneirating network structure of PVA hydrogel network shape structure and the formation of BC hydrogel network structure, the physical properties similar to human body cartilaginous tissue performance, good mechanical property, chemical stability and biocompatibility.Technique of the present invention is simple, cost is low, pollution-free, the bacteria cellulose/polyvinyl alcohol composite aquogel of preparation has huge application prospect in wound dressings, drug release and tissue repair in the cartilaginous tissue reparations such as especially joint cartilage reparation, meniscal repairs.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of bacteria cellulose/polyvinyl alcohol composite aquogel.Relate to the compound preparation field of a kind of biomaterial.Technique of the present invention is simple, cost is low, pollution-free, and the composite aquogel of preparation has good mechanical property, chemical stability and biocompatibility, has huge application prospect in bio-medical fields such as wound dressings, drug release and cartilaginous tissue reparations.
The preparation method of a kind of bacteria cellulose/polyvinyl alcohol composite aquogel that this patent relates to.Comprise: cultivating the purified processing of bacteria cellulose obtain and processed by strain fermentation, to obtain water content be 30～50% bacteria cellulose aquagel.Adopt pickling process, make polyvinyl alcohol enter bacteria cellulose aquagel inside, the reaction product freeze-thaw several that obtains, then processed 6～24h under vacuum obtains the bacteria cellulose/polyvinyl alcohol composite aquogel finally by the high-energy ray irradiation processing.
As preferred technical scheme:
Wherein, the preparation method of aforesaid a kind of bacteria cellulose/polyvinyl alcohol composite aquogel is characterized in that: the bacterial strain of described fermentation culture bacteria cellulose is one or more in acetobacter xylinum, rhizobium, Sarcina, Rhodopseudomonas, achromobacter, Alcaligenes, aerobacter or the Azotobacter.
The preparation method of aforesaid a kind of bacteria cellulose/polyvinyl alcohol composite aquogel, it is characterized in that: described purification treating method is, under 70～100 ℃ temperature, be that 4～8% NaOH aqueous wash medium is washed 4～6h at the quality percentage composition, repeatedly wash to neutrality with distilled water again.To remove the tropina and the residual media that sticks on the cellulose membrane on the bacteria cellulose.Described dehydration treatment method is, it is 30～50% bacteria cellulose aquagel that bacteria cellulose obtains water content through high speed centrifugation, vacuum hydro-extraction or press dewatering.The treatment process of this partial dehydration, purpose are to remove unnecessary water molecules on the basis of not destroying the bacteria cellulose aquagel three-dimensional net structure.Enter the content of the polyvinyl alcohol water solution of bacteria cellulose aquagel inside when simultaneously, improving dip treating.
The preparation method of aforesaid a kind of bacteria cellulose/polyvinyl alcohol composite aquogel is characterized in that: described polyvinyl alcohol molecule amount is 2～200,000, and alcoholysis degree is 87～99%.Polyvinyl alcohol is to generate polyvinyl acetate by the vinyl acetate polyisocyanate polyaddition, then, and polyvinyl acetate alcoholysis and prepare polyvinyl alcohol.The alcoholysis degree of polyvinyl alcohol and molecular weight are very large on the physical properties impact of polyvinyl alcohol.Alcoholysis degree is that 87～89% polyvinyl alcohol is water-soluble better, can dissolve fast in water; And 90%～99% polyvinyl alcohol need to could dissolve in hot water.
The preparation method of aforesaid a kind of bacteria cellulose/polyvinyl alcohol composite aquogel, it is characterized in that: described pickling process is under 60～100 ℃, bacteria cellulose aquagel is immersed in to contain the polyvinyl alcohol massfraction be 4～12h in 10～25% the polyvinyl alcohol water solution.
The preparation method of aforesaid a kind of bacteria cellulose/polyvinyl alcohol composite aquogel is characterized in that: described freeze-thaw method is under-40～-10 ℃, freezing 6～24h, and 1～4h then at room temperature thaws.The number of occurrence is 1～4 time.。Repeatedly behind the freeze-thaw, some physicalies of PVA hydrogel and mechanical property etc. are improved a lot.The freezing kinestate of the molecular chain of PVA in the aqueous solution that makes " is freezed " to get off, and can occur between molecular chain to interact and chain entanglement, even can form ordered structure.After thawing, these compact orderly microcells no longer separate, and become " entanglement point ".Have again new orderly microcell to form when again freezing, these microcells are called " physical crosslinking point ".Can promote molecular motion with the freeze-thaw method, rearrange to have the PVA hydrogel of hypocrystalline structure by the folding acquisition of molecular chain.
The preparation method of aforesaid a kind of bacteria cellulose/polyvinyl alcohol composite aquogel is characterized in that: described vacuum hydro-extraction treatment process is that reaction product is 0.02～0.09MPa in vacuum tightness, and temperature is 30～40 ℃ of lower 6～24h of placement.Vacuum hydro-extraction can remove the part moisture content in the PVA hydrogel, make the molecular chain in the PVA hydrogel tightr, promote molecular chain to form three-dimensional network by hydrogen bond and crystallite district, improve the crystalline texture of PVA hydrogel interior molecules chain, thereby further improve the mechanical property of PVA hydrogel.
The preparation method of aforesaid a kind of bacteria cellulose/polyvinyl alcohol composite aquogel is characterized in that: described high-energy ray irradiation is treated to gamma-radiation, electron beam, X-ray or ultraviolet ray, and irradiation dose is 15～60kGy.Under high-energy ray irradiation processing effect, the polyvinyl alcohol molecule interchain is crosslinked together by the free radical that produces.The PVA aqueous solution is more than finite concentration during by radiation, degree of crosslinking increases with the increase of radiation dose, the cross-linking density of hydrogel increases, the size of micropore will reduce in the network structure, thereby make the reductions such as swelling ratio, water content of hydrogel, so can realize regulation and control to cross-linking density by the control radiation dose.The energetic ray that radiation crosslinking adopts can act on the PVA equably, and the cross-linking set of PVA is evenly distributed, and degree of crosslinking is easy to control, can further improve the cross-linking density of PVA hydrogel, so that product reaches the mechanical property requirements of human body cartilaginous tissue; Cross-linking radiation need not to add initiator or linking agent simultaneously, and product purity is high and have preferably optical clarity, and also can realize synchronously the sterilization to the bacteria cellulose/polyvinyl alcohol composite aquogel in the course of processing.
Compared with prior art, the invention has the beneficial effects as follows:
This patent adopts pickling process, freeze-thaw method and irradiation crosslinking, prepares a kind of bacteria cellulose/polyvinyl alcohol composite aquogel.This hydrogel has the inierpeneirating network structure of PVA hydrogel network shape structure and the formation of BC hydrogel network structure, the physical properties similar to human body cartilaginous tissue performance, good mechanical property, chemical stability and biocompatibility.Technique of the present invention is simple, cost is low, pollution-free, need not to add initiator or linking agent in the preparation of gels process, in cross-linking radiation, finished the sterilization of goods.The bacteria cellulose/polyvinyl alcohol composite aquogel of preparation has huge application prospect in wound dressings, drug release and tissue repair in the cartilaginous tissue reparations such as especially joint cartilage reparation, meniscal repairs.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1:
To be immersed in by the bacteria cellulose that the acetobacter xylinum fermentation culture obtains the quality percentage composition and be in 4% the NaOH aqueous solution, under 100 ℃ temperature, heat 6h, repeatedly wash to neutrality with distilled water again.Adopting the high speed centrifugation partial dehydration to obtain water content is 50% bacteria cellulose aquagel.
Under 60 ℃, be 200,000 with molecular weight, alcoholysis degree is that 87% polyvinyl alcohol is dissolved in the distilled water, is mixed with that to contain the polyvinyl alcohol massfraction be 10% polyvinyl alcohol water solution.Bacteria cellulose aquagel is immersed in the polyvinyl alcohol water solution, under 60 ℃, 4h.
Mixture after the dip treating under-10 ℃, freezing 24h, the 1h that at room temperature thaws, the number of occurrence is 4 times.Then be 0.02MPa in vacuum tightness, temperature is 30 ℃ of lower 24h of placement.Adopt the gamma-radiation radiation treatment, irradiation dose is 60kGy, obtains the bacteria cellulose/polyvinyl alcohol composite aquogel.
Embodiment 2:
To be immersed in by the bacteria cellulose that the rhizobium fermentation culture obtains the quality percentage composition and be in 5% the NaOH aqueous solution, under 90 ℃ temperature, heat 5h, repeatedly wash to neutrality with distilled water again.Adopting the high speed centrifugation partial dehydration to obtain water content is 40% bacteria cellulose aquagel.
Under 60 ℃, be 150,000 with molecular weight, alcoholysis degree is that 89% polyvinyl alcohol is dissolved in the distilled water, is mixed with that to contain the polyvinyl alcohol massfraction be 25% polyvinyl alcohol water solution.Bacteria cellulose aquagel is immersed in the polyvinyl alcohol water solution, under 70 ℃, 6h.
Mixture after the dip treating under-20 ℃, freezing 20h, the 2h that at room temperature thaws, the number of occurrence is 4 times.Then be 0.04MPa in vacuum tightness, temperature is 40 ℃ of lower 6h of placement.Adopt the gamma-radiation radiation treatment, irradiation dose is 50kGy, obtains the bacteria cellulose/polyvinyl alcohol composite aquogel.
Embodiment 3:
To be immersed in by the bacteria cellulose that the Sarcina fermentation culture obtains the quality percentage composition and be in 6% the NaOH aqueous solution, under 80 ℃ temperature, heat 4h, repeatedly wash to neutrality with distilled water again.Adopting vacuum hydro-extraction to process to obtain water content is 30% bacteria cellulose aquagel.
Under 70 ℃, be 120,000 with molecular weight, alcoholysis degree is that 90% polyvinyl alcohol is dissolved in the distilled water, is mixed with that to contain the polyvinyl alcohol massfraction be 15% polyvinyl alcohol water solution.Bacteria cellulose aquagel is immersed in the polyvinyl alcohol water solution, under 80 ℃, 8h.
Mixture after the dip treating under-20 ℃, freezing 16h, the 3h that at room temperature thaws, the number of occurrence is 3 times.Then be 0.06MPa in vacuum tightness, temperature is 30 ℃ of lower 16h of placement.The employing electron beam irradiation is processed, and irradiation dose is 40kGy, obtains the bacteria cellulose/polyvinyl alcohol composite aquogel.
Embodiment 4:
To be immersed in by the bacteria cellulose that the Rhodopseudomonas fermentation culture obtains the quality percentage composition and be in 7% the NaOH aqueous solution, under 70 ℃ temperature, heat 6h, repeatedly wash to neutrality with distilled water again.Adopting vacuum hydro-extraction to process to obtain water content is 50% bacteria cellulose aquagel.
Under 80 ℃, be 100,000 with molecular weight, alcoholysis degree is that 92% polyvinyl alcohol is dissolved in the distilled water, is mixed with that to contain the polyvinyl alcohol massfraction be 10% polyvinyl alcohol water solution.Bacteria cellulose aquagel is immersed in the polyvinyl alcohol water solution, under 90 ℃, 10h.
Mixture after the dip treating under-30 ℃, freezing 12h, the 3h that at room temperature thaws, the number of occurrence is 3 times.Then be 0.09MPa in vacuum tightness, temperature is 40 ℃ of lower 12h of placement.The employing electron beam irradiation is processed, and irradiation dose is 30kGy, obtains the bacteria cellulose/polyvinyl alcohol composite aquogel.
Embodiment 5:
To be immersed in by the bacteria cellulose that the achromobacter fermentation culture obtains the quality percentage composition and be in 8% the NaOH aqueous solution, under 70 ℃ temperature, heat 5h, repeatedly wash to neutrality with distilled water again.Adopting press dewatering to obtain water content is 40% bacteria cellulose aquagel.
Under 100 ℃, be 20,000 with molecular weight, alcoholysis degree is that 99% polyvinyl alcohol is dissolved in the distilled water, is mixed with that to contain the polyvinyl alcohol massfraction be 25% polyvinyl alcohol water solution.Bacteria cellulose aquagel is immersed in the polyvinyl alcohol water solution, under 100 ℃, 12h.
Mixture after the dip treating under-30 ℃, freezing 6h, the 4h that at room temperature thaws, the number of occurrence is 2 times.Then be 0.02MPa in vacuum tightness, temperature is 30 ℃ of lower 12h of placement.Adopt the X-ray radiation treatment, irradiation dose is 20kGy, obtains the bacteria cellulose/polyvinyl alcohol composite aquogel.
Embodiment 6
To be immersed in by the bacteria cellulose that the aerobacter fermentation culture obtains the quality percentage composition and be in 6% the NaOH aqueous solution, under 90 ℃ temperature, heat 4h, repeatedly wash to neutrality with distilled water again.Adopting press dewatering to obtain water content is 30% bacteria cellulose aquagel.
Under 100 ℃, be 80,000 with molecular weight, alcoholysis degree is that 96% polyvinyl alcohol is dissolved in the distilled water, is mixed with that to contain the polyvinyl alcohol massfraction be 20% polyvinyl alcohol water solution.Bacteria cellulose aquagel is immersed in the polyvinyl alcohol water solution, under 100 ℃, 6h.
Mixture after the dip treating under-40 ℃, freezing 24h, 4h at room temperature thaws.Then be 0.09MPa in vacuum tightness, temperature is 40 ℃ of lower 24h of placement.The employing ultraviolet irradiation is processed, and irradiation dose is 15kGy, obtains the bacteria cellulose/polyvinyl alcohol composite aquogel.
Claims (8)
1. the preparation method of a bacteria cellulose/polyvinyl alcohol composite aquogel, comprise: cultivating the purified processing of bacteria cellulose obtain and processed by strain fermentation, to obtain water content be 30～50% bacteria cellulose aquagel, adopt pickling process, make polyvinyl alcohol enter bacteria cellulose aquagel inside, the reaction product freeze-thaw that obtains for several times, then processed 6～24h under vacuum obtains the bacteria cellulose/polyvinyl alcohol composite aquogel finally by the high-energy ray irradiation processing.
2. such as claim 1, a kind of preparation method of bacteria cellulose/polyvinyl alcohol composite aquogel is characterized in that: the bacterial strain of described fermentation culture bacteria cellulose is one or more in acetobacter xylinum, rhizobium, Sarcina, Rhodopseudomonas, achromobacter, Alcaligenes, aerobacter or the Azotobacter.
3. such as claim 1, a kind of preparation method of bacteria cellulose/polyvinyl alcohol composite aquogel, it is characterized in that: described purification treating method is, under 70～100 ℃ temperature, be that 4～8% NaOH aqueous wash medium is washed 4～6h at the quality percentage composition, repeatedly wash to neutrality with distilled water again; Described dehydration treatment method is, it is 30～50% bacteria cellulose aquagel that bacteria cellulose obtains water content through high speed centrifugation, vacuum hydro-extraction or press dewatering.
4. such as claim 1, a kind of preparation method of bacteria cellulose/polyvinyl alcohol composite aquogel is characterized in that: described polyvinyl alcohol molecule amount is 2～200,000, and alcoholysis degree is 87～99%.
5. such as claim 1, a kind of preparation method of bacteria cellulose/polyvinyl alcohol composite aquogel, it is characterized in that: described pickling process is under 60～100 ℃, bacteria cellulose aquagel is immersed in to contain the polyvinyl alcohol massfraction be 4～12h in 10～25% the polyvinyl alcohol water solution.
6. such as claim 1, a kind of preparation method of bacteria cellulose/polyvinyl alcohol composite aquogel is characterized in that: described freeze-thaw method is under-40～-10 ℃, freezing 6～24h, and the 1～4h that then at room temperature thaws, the number of occurrence is 1～4 time.
7. such as claim 1, a kind of preparation method of bacteria cellulose/polyvinyl alcohol composite aquogel is characterized in that: described vacuum hydro-extraction treatment process is that reaction product is 0.02～0.09MPa in vacuum tightness, and temperature is 30～40 ℃ of lower 6～24h of placement.
8. such as claim 1, a kind of preparation method of bacteria cellulose/polyvinyl alcohol composite aquogel is characterized in that: described high-energy ray irradiation is treated to gamma-radiation, electron beam, X-ray or ultraviolet ray, and irradiation dose is 15～60kGy.
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| CN104195030A (en) * | 2014-08-14 | 2014-12-10 | 国家纳米科学中心 | Micro-fluidic chip and method for evaluating wound dressing by using micro-fluidic chip |
| CN104208759A (en) * | 2014-08-29 | 2014-12-17 | 东华大学 | Porous elastic polyvinyl alcohol/bacterial nano-cellulose composite hydrogel tube, as well as preparation method and application of composite hydrogel tube |
| CN105237925A (en) * | 2015-11-05 | 2016-01-13 | 南京理工大学 | Nanometer bacterial cellulose\polyvinyl alcohol\polyethylene glycol porous composite hydrogel |
| CN105664241A (en) * | 2016-01-18 | 2016-06-15 | 西北工业大学 | Production method for mechanical property controllable polyvinyl alcohol cartilage stents |
| CN106279791A (en) * | 2016-08-05 | 2017-01-04 | 湖北科技学院 | A kind of latent fingerprint extracts/manifests gel compound membrane and radiation preparation method thereof |
| CN110256725A (en) * | 2019-06-28 | 2019-09-20 | 陕西科技大学 | A kind of HEC/PVA interpenetrating networks aeroge and preparation method thereof |
| CN111135340A (en) * | 2018-11-06 | 2020-05-12 | 海南光宇生物科技有限公司 | Biological cellulose composite gel material and application thereof as wound dressing |
| CN111234266A (en) * | 2020-03-11 | 2020-06-05 | 河南省科学院同位素研究所有限责任公司 | Preparation method of chitosan/polyvinyl alcohol hydrogel dressing |
| CN113333032A (en) * | 2021-06-24 | 2021-09-03 | 南京林业大学 | Preparation method and application of nano-cellulose-based metal nanoparticle loaded material |
| CN114015076A (en) * | 2021-11-30 | 2022-02-08 | 福州大学 | Photothermal conversion PVA/rGO/wood aerogel composite hydrogel and preparation method and application thereof |
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| CN104195030A (en) * | 2014-08-14 | 2014-12-10 | 国家纳米科学中心 | Micro-fluidic chip and method for evaluating wound dressing by using micro-fluidic chip |
| CN104208759A (en) * | 2014-08-29 | 2014-12-17 | 东华大学 | Porous elastic polyvinyl alcohol/bacterial nano-cellulose composite hydrogel tube, as well as preparation method and application of composite hydrogel tube |
| CN105237925A (en) * | 2015-11-05 | 2016-01-13 | 南京理工大学 | Nanometer bacterial cellulose\polyvinyl alcohol\polyethylene glycol porous composite hydrogel |
| CN105664241A (en) * | 2016-01-18 | 2016-06-15 | 西北工业大学 | Production method for mechanical property controllable polyvinyl alcohol cartilage stents |
| CN106279791A (en) * | 2016-08-05 | 2017-01-04 | 湖北科技学院 | A kind of latent fingerprint extracts/manifests gel compound membrane and radiation preparation method thereof |
| CN111135340A (en) * | 2018-11-06 | 2020-05-12 | 海南光宇生物科技有限公司 | Biological cellulose composite gel material and application thereof as wound dressing |
| CN111135340B (en) * | 2018-11-06 | 2022-06-21 | 海南光宇生物科技有限公司 | Biological cellulose composite gel material and application thereof as wound dressing |
| CN110256725A (en) * | 2019-06-28 | 2019-09-20 | 陕西科技大学 | A kind of HEC/PVA interpenetrating networks aeroge and preparation method thereof |
| CN110256725B (en) * | 2019-06-28 | 2021-12-24 | 陕西科技大学 | HEC/PVA interpenetrating network aerogel and preparation method thereof |
| CN111234266A (en) * | 2020-03-11 | 2020-06-05 | 河南省科学院同位素研究所有限责任公司 | Preparation method of chitosan/polyvinyl alcohol hydrogel dressing |
| CN113333032A (en) * | 2021-06-24 | 2021-09-03 | 南京林业大学 | Preparation method and application of nano-cellulose-based metal nanoparticle loaded material |
| CN114015076A (en) * | 2021-11-30 | 2022-02-08 | 福州大学 | Photothermal conversion PVA/rGO/wood aerogel composite hydrogel and preparation method and application thereof |
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Application publication date: 20130417 |