CN104845382A - Silk protein/cellulose derivative blending hydrogel and preparation method thereof - Google Patents
Silk protein/cellulose derivative blending hydrogel and preparation method thereof Download PDFInfo
- Publication number
- CN104845382A CN104845382A CN201510231242.6A CN201510231242A CN104845382A CN 104845382 A CN104845382 A CN 104845382A CN 201510231242 A CN201510231242 A CN 201510231242A CN 104845382 A CN104845382 A CN 104845382A
- Authority
- CN
- China
- Prior art keywords
- hydrogel
- aqueous solution
- preparation
- bombyx
- silk protein
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Materials For Medical Uses (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention belongs to the technical field of natural polymer materials and biomedical materials, and particularly relates to a silk protein/cellulose derivative blending hydrogel and a preparation method thereof. A silk protein water solution and a blending water solution of hydroxypropyl methyl cellulose or methylcellulose or hydroxypropyl cellulose are heated to prepare the high strength hydrogel with the solid content of 4-20%. The preparation process is simple, green and mild, energy-saving and efficient and low in cost, and the physical properties of the final hydrogel can be controlled by simply changing the solid content; the prepared high strength hydrogel based on natural polymers can be applied to the field of biomedicine.
Description
Technical field
The invention belongs to natural macromolecular material and biology medical material technical field, be specifically related to a kind of high-strength natural Bio-macromolecular hydrogel and preparation method thereof.
Background technology
Macromolecule hydrogel be a kind of water content up to 90% three-dimensional network, but wherein polymer is in swelling undissolved state in water.In general, hydrogel is divided into two kinds: chemically crosslinked aquagel and physical cross-linking hydrogel.The advantage of general chemistry cross-linked hydrogel is the mechanical property that can control final hydrogel by changing chemical structure, and shortcoming is that biocompatibility is poor and needs to introduce chemical cross-linking agent.The advantage of physical cross-linking hydrogel be its often by natural polymer or as PVA and so on through FDA certification synthesis polymer the three-dimensional network that formed, have relative to reasonable biocompatibility chemical gel, shortcoming is the mechanical property being difficult to control final hydrogel by changing chemical structure, and the mechanical property of final hydrogel is difficult to be able to artificial control in other words.In addition, the mechanical property of physical cross-linking hydrogel is compared to far short of what is expected chemical water gel.But no matter traditional chemical water gel and physical hydrogel are from Compression and Expansion modulus or ductility, be all in a relatively low level, also poor far compared with the demand of practical application.Therefore, the mechanical property how promoting hydrogel always in recent years is the focus of research, preparing double-network hydrogel, Nanometer composite hydrogel and topological gel is the three kinds of common methods promoting hydrogel mechanical property now, but the preparation method of above three kinds of hydrogels is limited to the macromolecular suitability of natural biological.
Silk is a kind of ancient natural protein material.Due to its inherent excellent mechanical property and biocompatibility and originate widely, silk and the material based on fibroin have application prospect very widely in bio-medical field.Utilizing regenerated silk protein solution to prepare hydrogel has been in the news many times, but its mechanical property all cannot reach the mechanical property of synthetic chemical water gel or the requirement to the higher tissue of mechanical property requirements, such as ligament or cartilage etc.Water-soluble cellulose derivative such as Vltra tears, methylcellulose gum and hydroxypropylcellulose etc. are natural polysaccharide-cellulosic derivative, hydrophobic grouping on its side chain makes it have Thermo-sensitive, as the Vltra tears aqueous solution or methylated cellulose aqueous solution can become gel by clear solution through heating, after falling back room temperature, be returned to solution state again; Heating hydroxypropyl cellulose aqueous solution then causes precipitation to occur, but still becomes solution after cooling.Meanwhile, the same with fibroin, these three kinds of derivatived celluloses have good biocompatibility.
The present invention is by heating the blended aqueous solution of Bombyx-mori Silk Proteins and derivatived cellulose, obtain that a class modulus is high, toughness is strong and there is the hydrogel of fine biocompatibility, this type of hydrogel can regulate and control final mechanical property by controlling solid content, overcomes a large shortcoming of conventional physical gel.In addition, its preparation method is compared to the more easy gentleness of preparation of chemical gel, and environmental protection, it also avoid the use of chemical cross-linking agent simultaneously, and biocompatibility obtains good maintenance.This simple and quick preparation method is also for its industrialization scale operation from now on provides feasibility.
Summary of the invention
The object of the present invention is to provide and a kind of there is hydrogel of good biocompatibility and excellent mechanical property and preparation method thereof simultaneously.
Hydrogel provided by the invention, for the Blend hydrogel of a kind of Bombyx-mori Silk Proteins and derivatived cellulose, with mass concentration be respectively 4 ~ 20% the Bombyx-mori Silk Proteins aqueous solution and the derivatived cellulose aqueous solution be mixed by certain volume ratio, the massfraction that Bombyx-mori Silk Proteins accounts for overall decorating film in final Blend hydrogel is 30% ~ 90%; Described derivatived cellulose is Vltra tears or methylcellulose gum or hydroxypropylcellulose.
The preparation method of the Blend hydrogel of Bombyx-mori Silk Proteins/derivatived cellulose provided by the invention, concrete steps are:
(1) the preparation regeneration Bombyx-mori Silk Proteins aqueous solution, makes its ultimate density be 4% ~ 20%;
(2), under stirring, Vltra tears or methylcellulose gum or hydroxypropyl cellulose aqueous solution powder dissolution in deionized water, its ultimate density is made to be 4% ~ 20%;
(3) step (1) is mixed with two kinds of solution of step (2) gained, heating in water bath.
In step (3), the Bombyx-mori Silk Proteins aqueous solution: the volume ratio of the derivatived cellulose aqueous solution is 3:7 ~ 9:1.
In step (3), water bath heating temperature is 65 DEG C to 90 DEG C.
In step (3), the heating in water bath time is 2 little of 24 hours.
Hydrogel preparation method of the present invention is simply efficient, and environmental protection, does not relate to any chemical cross-linking agent or Biological cross-linker in preparation process, and while obtaining not second to chemical gel mechanical property, the character of natural polymer is retained in preparation process.
The biocompatibility of subject hydrogel and biodegradability are far above synthesis macromolecule hydrogel.
Advantage of the present invention:
(1) preparation method of hydrogel of the present invention is compared to the preparation method of chemical gel, and more simple efficient, preparation condition is gentle, and environmental protection, is conducive to realizing large-scale commercial production;
(2) raw material sources of hydrogel of the present invention are more extensive compared to the raw material sources of chemical gel, and cost is cheaper;
(3) hydrogel of the present invention is while having excellent mechanical performance, and biocompatibility is also fine.
Accompanying drawing explanation
Fig. 1 is the inventive method flow process diagram.
Fig. 2 is that high intensity hydrogel mechanical property of the present invention is shown, arrow indication is hydrogel prepared by the present invention, and its volume is about 1 cm
3, be highly about 10 mm, diameter is about 9 mm, and hydrogel solid content is 10%.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
Prepare regenerated fibroin and the Vltra tears aqueous solution that concentration is 6%, 8% and 10% respectively, the fibroin aqueous solution of same concentrations is mixed with volume ratio 9:1 with the Vltra tears aqueous solution, ensure that final mixing solutions concentration (being following solid content value) is 6%, 8% or 10%, 65
oc heating in water bath 2h forms hydrogel.The tensile modulus that Mechanics Performance Testing obtains solid content 6% hydrogel is 0.37 MPa, and elongation at break is 120 %, and modulus of compression is 0.47 MPa; Solid content 8% hydrogel tensile modulus is 0.75 MPa, and elongation at break is 116 %, and modulus of compression is 0.75 MPa; Solid content 10% hydrogel tensile modulus is 1.23 MPa, and elongation at break is 108%, and modulus of compression is 1.45 MPa.
Embodiment 2
Preparation concentration is 10% regenerated silk protein aqueous solution and concentration is the 10% Vltra tears aqueous solution, is mixed by the fibroin aqueous solution, ensure that final mixing solutions concentration is 10% with the Vltra tears aqueous solution with volume ratio 9:1.65
oc heating in water bath 2h finally obtains cylindrical sample, and it is 1.40 MPa that Mechanics Performance Testing obtains its tensile modulus, and elongation at break is 105%, and modulus of compression is 1.34 MPa.
Embodiment 3
Preparation concentration is 10% regenerated silk protein aqueous solution and concentration is the 10% Vltra tears aqueous solution, is mixed by the fibroin aqueous solution, ensure that final mixing solutions concentration is 10% with the Vltra tears aqueous solution with volume ratio 9:1.90
oc heating in water bath 2h finally obtains cylindrical sample, and it is 1.28 MPa that Mechanics Performance Testing obtains its tensile modulus, and elongation at break is 117%, and modulus of compression is 1.34 MPa.
Embodiment 4
Preparation concentration is 10% regenerated silk protein aqueous solution and concentration is the 10% Vltra tears aqueous solution, is mixed by the fibroin aqueous solution, ensure that final mixing solutions concentration is 10% with the Vltra tears aqueous solution with volume ratio 5:5 or 7:3.65
oc heating in water bath 2h obtains hydrogel, and modulus of compression is respectively 0.34 MPa(5:5) and 0.92 MPa(7:3); And be not enough to strong to implementing stretching experiment with hydrogel prepared by this proportioning, and gel is very uneven.
Embodiment 5
Preparation concentration is 10% regenerated silk protein aqueous solution and concentration is 10% methylated cellulose aqueous solution, is mixed by the fibroin aqueous solution, ensure that final mixing solutions concentration is 10% with methylated cellulose aqueous solution with volume ratio 9:1.65
oc heating in water bath 2h finally obtains cylindrical sample, and it is 0.58 MPa that Mechanics Performance Testing obtains its modulus of compression.
Embodiment 6
Preparation concentration is 10% regenerated silk protein aqueous solution and concentration is 10% hydroxypropyl cellulose aqueous solution, is mixed by the fibroin aqueous solution, ensure that final mixing solutions concentration is 10% with hydroxypropyl cellulose aqueous solution with volume ratio 9:1.65
oc heating in water bath 2h finally obtains cylindrical sample, and it is 0.27 MPa that Mechanics Performance Testing obtains its modulus of compression.
Embodiment 7
Preparation concentration is 10% regenerated silk protein aqueous solution and concentration is the 10% Vltra tears aqueous solution, is mixed by the fibroin aqueous solution, ensure that final mixing solutions concentration is 10% with the Vltra tears aqueous solution with volume ratio 9:1.65
oc heating in water bath 2 hours, obtains high intensity hydrogel, and with its biocompatibility of L929 cell tests after sterilizing, after three days, cell survival rate reaches 93.9 ± 6.29%, proves that it does not have cytotoxicity, therefore possesses the Potential feasibility serving as bio-medical material.
Claims (3)
1. the Blend hydrogel of fibroin/derivatived cellulose, it is characterized in that with mass concentration be respectively 4 ~ 20% the Bombyx-mori Silk Proteins aqueous solution and the derivatived cellulose aqueous solution be mixed by certain volume ratio, the massfraction that Bombyx-mori Silk Proteins accounts for overall decorating film in final Blend hydrogel is 30% ~ 90%; Described derivatived cellulose is Vltra tears or methylcellulose gum or hydroxypropylcellulose.
2. a preparation method for the Blend hydrogel of fibroin/derivatived cellulose as claimed in claim 1, is characterized in that concrete steps are:
(1) the preparation regeneration Bombyx-mori Silk Proteins aqueous solution, makes its ultimate density be 4% ~ 20%;
(2), under stirring, Vltra tears or methylcellulose gum or hydroxypropyl cellulose aqueous solution powder dissolution in deionized water, its ultimate density is made to be 4% ~ 20%;
(3) step (1) is mixed with two kinds of solution of step (2) gained, heating in water bath.
3. preparation method according to claim 2, is characterized in that: in step (3), the Bombyx-mori Silk Proteins aqueous solution: the volume ratio of the derivatived cellulose aqueous solution is 3:7 ~ 9:1; Water bath heating temperature is 65 DEG C to 90 DEG C; The heating in water bath time is 2 little of 24 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510231242.6A CN104845382A (en) | 2015-05-08 | 2015-05-08 | Silk protein/cellulose derivative blending hydrogel and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510231242.6A CN104845382A (en) | 2015-05-08 | 2015-05-08 | Silk protein/cellulose derivative blending hydrogel and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104845382A true CN104845382A (en) | 2015-08-19 |
Family
ID=53845390
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510231242.6A Pending CN104845382A (en) | 2015-05-08 | 2015-05-08 | Silk protein/cellulose derivative blending hydrogel and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104845382A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105199115A (en) * | 2015-10-27 | 2015-12-30 | 中国林业科学研究院林产化学工业研究所 | Preparation and application of porous injectable hydrogel adopting three-dimensional network structure |
| CN106750393A (en) * | 2016-11-15 | 2017-05-31 | 河南工业大学 | A kind of enzyme process and the compound method for preparing dual network gel of heat treatment |
| CN108794771A (en) * | 2018-06-25 | 2018-11-13 | 华中科技大学 | Dual network cross-linked cellulose/fibroin albumen high intensity hydrogel and its preparation and application |
| CN108904873A (en) * | 2018-06-25 | 2018-11-30 | 东莞市联洲知识产权运营管理有限公司 | A kind of preparation method for the luffa medical gel dressing that netted loofah fiber element/silk fibroin powder is modified |
| CN109706531A (en) * | 2019-01-16 | 2019-05-03 | 南通纺织丝绸产业技术研究院 | Regenerated silk fibroin/hydroxypropyl methyl cellulose nanofiber preparation method |
| CN110144123A (en) * | 2019-04-08 | 2019-08-20 | 复旦大学 | A kind of fibroin/cellulose derivative composite material and preparation method |
| CN110623250A (en) * | 2019-09-20 | 2019-12-31 | 西北农林科技大学 | Preparation method of cellulose nanocrystal-whey protein isolate composite thermal gel |
| CN112225937A (en) * | 2020-10-14 | 2021-01-15 | 中山大学 | Temperature-sensitive macroporous biological hydrogel and preparation method and application thereof |
| CN115737915A (en) * | 2022-12-01 | 2023-03-07 | 刘玉增 | Injectable bone filling material and preparation method thereof |
| CN116118177A (en) * | 2021-11-12 | 2023-05-16 | 复旦大学 | 3D printing hydrogel stent based on high molecular weight regenerated silk fibroin and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101804218A (en) * | 2010-04-13 | 2010-08-18 | 王艳 | Human-body absorbable trauma dressing containing Yunnan white drug powder or Yunnan white drug powder extractive |
| CN102068719A (en) * | 2011-01-18 | 2011-05-25 | 复旦大学 | Adhesion prevention material formed by physical crosslinking hydrogel composition and preparation method and application thereof |
| CN103441300A (en) * | 2013-08-23 | 2013-12-11 | 浙江地坤键新能源科技有限公司 | Gel polymer electrolyte containing natural high molecular material as well as preparation method and application thereof |
| CN103893820A (en) * | 2013-11-06 | 2014-07-02 | 浙江经贸职业技术学院 | Silk fibroin composite biomaterial scaffold and preparation method thereof |
| CN104069120A (en) * | 2014-06-10 | 2014-10-01 | 复旦大学 | Double-drug loaded thixotropic hydrogel for tumor local treatment and preparation method thereof |
| CN104327282A (en) * | 2014-10-16 | 2015-02-04 | 苏州经贸职业技术学院 | Multicomponent polymerization silk fibroin hydrogel and preparation method thereof |
-
2015
- 2015-05-08 CN CN201510231242.6A patent/CN104845382A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101804218A (en) * | 2010-04-13 | 2010-08-18 | 王艳 | Human-body absorbable trauma dressing containing Yunnan white drug powder or Yunnan white drug powder extractive |
| CN102068719A (en) * | 2011-01-18 | 2011-05-25 | 复旦大学 | Adhesion prevention material formed by physical crosslinking hydrogel composition and preparation method and application thereof |
| CN103441300A (en) * | 2013-08-23 | 2013-12-11 | 浙江地坤键新能源科技有限公司 | Gel polymer electrolyte containing natural high molecular material as well as preparation method and application thereof |
| CN103893820A (en) * | 2013-11-06 | 2014-07-02 | 浙江经贸职业技术学院 | Silk fibroin composite biomaterial scaffold and preparation method thereof |
| CN104069120A (en) * | 2014-06-10 | 2014-10-01 | 复旦大学 | Double-drug loaded thixotropic hydrogel for tumor local treatment and preparation method thereof |
| CN104327282A (en) * | 2014-10-16 | 2015-02-04 | 苏州经贸职业技术学院 | Multicomponent polymerization silk fibroin hydrogel and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| SHENGJIE LING, ET AL.: "Directed Growth of Silk Nanofibrils on Graphene and Their Hybrid Nanocomposites", 《ACS MACRO LETTERS》 * |
| YINGXIN LIU, ET AL.: "Thixotropic silk nanofibril-based hydrogel with extracellular matrix-like structure", 《BIOMATER. SCI.》 * |
| ZUGUANG GONG ET AL.: "Injectable thixotropic hydrogel comprising regenerated silk fibroin and hydroxypropylcellulose", 《SOFT MATTER》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105199115A (en) * | 2015-10-27 | 2015-12-30 | 中国林业科学研究院林产化学工业研究所 | Preparation and application of porous injectable hydrogel adopting three-dimensional network structure |
| CN105199115B (en) * | 2015-10-27 | 2021-01-12 | 中国林业科学研究院林产化学工业研究所 | Preparation and application of injectable hydrogel with porous three-dimensional network structure |
| CN106750393A (en) * | 2016-11-15 | 2017-05-31 | 河南工业大学 | A kind of enzyme process and the compound method for preparing dual network gel of heat treatment |
| CN108794771A (en) * | 2018-06-25 | 2018-11-13 | 华中科技大学 | Dual network cross-linked cellulose/fibroin albumen high intensity hydrogel and its preparation and application |
| CN108904873A (en) * | 2018-06-25 | 2018-11-30 | 东莞市联洲知识产权运营管理有限公司 | A kind of preparation method for the luffa medical gel dressing that netted loofah fiber element/silk fibroin powder is modified |
| CN109706531A (en) * | 2019-01-16 | 2019-05-03 | 南通纺织丝绸产业技术研究院 | Regenerated silk fibroin/hydroxypropyl methyl cellulose nanofiber preparation method |
| CN110144123A (en) * | 2019-04-08 | 2019-08-20 | 复旦大学 | A kind of fibroin/cellulose derivative composite material and preparation method |
| CN110623250A (en) * | 2019-09-20 | 2019-12-31 | 西北农林科技大学 | Preparation method of cellulose nanocrystal-whey protein isolate composite thermal gel |
| CN112225937A (en) * | 2020-10-14 | 2021-01-15 | 中山大学 | Temperature-sensitive macroporous biological hydrogel and preparation method and application thereof |
| CN116118177A (en) * | 2021-11-12 | 2023-05-16 | 复旦大学 | 3D printing hydrogel stent based on high molecular weight regenerated silk fibroin and preparation method thereof |
| CN116118177B (en) * | 2021-11-12 | 2024-09-24 | 复旦大学 | 3D printing hydrogel stent based on high molecular weight regenerated silk fibroin and preparation method thereof |
| CN115737915A (en) * | 2022-12-01 | 2023-03-07 | 刘玉增 | Injectable bone filling material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104845382A (en) | Silk protein/cellulose derivative blending hydrogel and preparation method thereof | |
| Li et al. | Controllable fabrication of hydroxybutyl chitosan/oxidized chondroitin sulfate hydrogels by 3D bioprinting technique for cartilage tissue engineering | |
| Chen et al. | 3D printing of multifunctional hydrogels | |
| Kumar et al. | 3D printable carboxylated cellulose nanocrystal-reinforced hydrogel inks for tissue engineering | |
| CN107602884B (en) | Silk fibroin/chitosan composite intelligent hydrogel and preparation method thereof | |
| Li et al. | Submerged and non-submerged 3D bioprinting approaches for the fabrication of complex structures with the hydrogel pair GelMA and alginate/methylcellulose | |
| CN107236135A (en) | Gelatin hydrogel and preparation method and application thereof | |
| Nkhwa et al. | Poly (vinyl alcohol): physical approaches to designing biomaterials for biomedical applications | |
| CN108047465A (en) | A kind of methacrylate gelatin/chitosan interpenetration network hydrogel, preparation method and application | |
| CN105153438A (en) | Preparation method of high-strength high-swelling nanocellulose and polyving akohol composite hydrogel | |
| Ghorbani et al. | Construction of collagen/nanocrystalline cellulose based-hydrogel scaffolds: synthesis, characterization, and mechanical properties evaluation | |
| JP2013544944A (en) | Method for producing crosslinked gel | |
| Zhao et al. | Digestion degree is a key factor to regulate the printability of pure tendon decellularized extracellular matrix bio-ink in extrusion-based 3D cell printing | |
| Li et al. | A novel injectable pH/temperature sensitive CS-HLC/β-GP hydrogel: the gelation mechanism and its properties | |
| El Fray et al. | Morphology assessment of chemically modified cryostructured poly (vinyl alcohol) hydrogel | |
| Han et al. | Effects of nanocellulose on alginate/gelatin bio-inks for extrusion-based 3D printing | |
| CN104059234A (en) | PH responsive self-repairing PVA-metal complexing hydrogel | |
| CN103225126A (en) | Fibroin/sodium alginate composite nanofiber scaffold preparation method | |
| Sekar et al. | Carboxymethyl cellulose-agarose-gelatin: A thermoresponsive triad bioink composition to fabricate volumetric soft tissue constructs | |
| Jia et al. | Construction of highly stretchable silica/polyacrylamide nanocomposite hydrogels through hydrogen bond strategy | |
| CN106267366B (en) | A method of high-strength and high ductility polyion hydrogel scaffold is prepared using 3D printing | |
| Roshanghias et al. | Functional and gel properties of whey protein nanofibrils as influenced by partial substitution with cellulose nanocrystal and alginate | |
| CN108409988A (en) | A kind of preparation method of spongy macroporous polyvinyl alcohol hydrogel | |
| CN107973881A (en) | A kind of preparation of high stretch hydroxyethyl cellulose/polyacrylamide hydrogel | |
| Kodavaty et al. | Mechanical and Swelling Properties of Poly (vinyl alcohol) and Hyaluronic Acid Gels used in Biomaterial Systems--a Comparative Study. |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20150819 |