CN105148324A - Bone bionic materials built by mineralized nano cellulose whiskers and production method of bone bionic materials - Google Patents
Bone bionic materials built by mineralized nano cellulose whiskers and production method of bone bionic materials Download PDFInfo
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Abstract
The invention relates to bone bionic materials built by mineralized nano cellulose whiskers and a production method of the bone bionic materials. The production method includes: grafting a large amount of carboxyl to the surfaces of the nano cellulose whiskers through the effects of sodium hydroxide and sodium chloroacetate, simultaneously dripping Ca(OH)2 suspension and H3PO4 solution into nano cellulose suspension solution according to calcium phosphate mole ratio of 1.67 under intense stirring, controlling solution pH to be 7.0-11.0 to obtain nano cellulose whisker/hydroxyapatite composite particles, adding the composite particles into silk fibroin solutions of different concentration, placing into self-made molds after sufficient and even mixing, and performing freeze drying layer by layer according the sequence from high concentration to low concentration to obtain the nano bone bionic materials. The bone bionic materials can simulate natural bones in components and structures, have good mechanical property, reasonable porosity and good biocompatibility and bioactivity, can be used as bone tissue repairing or substituting materials, and are promising in application prospect.
Description
Technical field
The present invention relates to a kind of bone biomimetic material built by the nano-cellulose whisker of mineralising and preparation method thereof, be applied to Bone Defect Repari or bone alternate material, be specifically related to biology medical material technical field.
Background technology
At field of orthopaedics, the Cranial defect caused by wound, infection, osteopathia, bone tumour resection etc. is very common.Autologous bone or allograph bone all also exist increase postoperative complication, material source limited, spread disease or the problem such as immunological rejection, its clinical practice receives certain restriction.Along with the development of biomaterials art, artificial bone alternate material is applied to clinical more and more.Bone alternate material is mainly as inserting framework in human bone, and osteocyte and collagen fiber grow thereon, finally becomes a part for live body bone.Therefore, find a kind of desirable bone transplantation substitute material is the target that people make great efforts always.
Several large class of metal, pottery and polymer is mainly contained at present for bone tissue restoration.But metal material lacks the biological activity be combined with tissue, ceramic-like materials mainly exist matter crisp, be easy to fracture and the deficiency such as fatigue rupture occur in vivo, polymer can have the near modulus of people's bone photo, but does not possess the activity forming biological key with osseous tissue.Therefore, find more satisfactory material and remain a difficult point clinically for bone tissue restoration.Nature bone is a kind of organic/inorganic Biocomposite material be made up of the organic substrate of about 30% and the hydroxyapatite of 70%, and organic substrate mainly comprises noncollagen protein, mucopolysaccharide etc.Hydroxide radical phosphorite nanocrystalline body is embedded in collagen fiber matrix in an orderly manner, the close cooperation effect between organic and inorganic constituent element and the unique assemblies of molecular level, imparts the multilevel hierarchy of nature bone and excellent mechanical property.Therefore, biocompatibility be prepared and mechanical compatibility is good, have bioactive Bone Defect Repari or bone alternate material, need to carry out Bionic Design from molecular level design, imitate the 26S Proteasome Structure and Function of nature bone.Nano whisker is the nano level cellulose of one extracted from natural fiber, and it not only has the feature of nano-particle, also has intensity and the optical property of some uniquenesses, has broad application prospects.By carboxylated modification make Cellulose nanocrystal must surface grafting a large amount of-COOH group, have object to strengthen the functional of nano whisker, simultaneously broken intrinsic advantage again, extend its range of application.
Summary of the invention
The object of this invention is to provide a kind of preparation method of the bone biomimetic material built by the nano-cellulose whisker of mineralising.Obtain nano-cellulose whisker/hydroxyapatite nano-complex particle by the carboxylated modification of nano-cellulose whisker and electrostatic self-assembled biomimetic mineralization, utilize Freeze Drying Technique to make the blended porous bone biomimetic material obtaining density and porosity distribution gradient of fibroin of it and variable concentrations.This bone biomimetic material not only simulates nature bone on composition, and structurally bionical to nature bone, has good biocompatibility, biological degradability and self-bone grafting performance, and the mechanical property of excellence.
The technical scheme realizing the object of the invention is, a kind of bone biomimetic material built by the nano-cellulose whisker of mineralising, it is made up of inorganic carboxylated nano-cellulose whisker and hydroxyapatite and organic fibroin, described inorganic constituents carboxy methylation nano whisker and the mass ratio of hydroxyapatite are 1:0-1, and its mass ratio of described inorganic constituents and organic principle is 1:0.5-2.
Described bone biomimetic material is made up of carboxylated nano-cellulose whisker, hydroxyapatite and Bombyx mori Silk Fibroin, the mass ratio of carboxylated nano-cellulose whisker, hydroxyapatite and Bombyx mori Silk Fibroin is 1:1-10:0.5-5, its density gradient is respectively 75.3%-82.3% from outside to inside, 57.4%-67.2%, 11.6%-30.6%.
The draw ratio of described nano whisker is about 20:1-2, described fibroin albumen is Bombyx mori Silk Fibroin and tussah silk peptide, and the intrinsic viscosity of its protein molecular is more than or equal to 0.50, and described hydroxyapatite presents needle-like distribution, its particle length is at 50-300nm, and particle width is at 10-50nm.
Prepare the method for this bone biomimetic material built by the nano-cellulose whisker of mineralising, adopt following steps:
(1) by nano-cellulose whisker ultrasonic disperse in the alcoholic solution of 0.1-2mol/L sodium hydroxide, bath raio is 1:500, and alkalize 10-120min at 20-80 DEG C.Add the sodium chloroacetate solution of 0.125-2.5mol/L again, ultrasonic agitation 15-100min at 30-75 DEG C, and adjust solution ph to neutrality with the hydrochloric acid of 0.1-0.5mol/L and dialyse three days in distilled water, obtain the brilliant suspension solution of nano-cellulose of carboxylated modification;
(2) be 1.67 according to the ratio of the amount of calcium phosphorus substance, by the Ca (OH) of 0.01-0.1mol/L
2with the H of dilution
3pO
4solution burette to instill in the obtained solution of step (1) and at ultrasonic middle stirring 1-6h simultaneously, dropwise adding ammonia control pH value in reaction is 8.0 ~ 10.0, control reaction temperature is 20-80 DEG C, obtains the compound particle suspension that nano-cellulose whisker/hydroxyapatite ratio is 1:1-10;
(3) supernatant is removed after the nano-cellulose whisker of step (2) gained/hydroxyapatite nano-complex particle suspension room temperature being left standstill 48 hours, centrifugalize goes out precipitate, after distilled water wash three times, lyophilization obtains nano-cellulose whisker/hydroxyapatite compound particle;
(4) the nano-cellulose whisker that obtains/hydroxyapatite compound particle ultrasonic disperse in step (3) is respectively 5%-15% to concentration, 35%-45%, the silk fibroin solution of 55%-65%, obtain the nano-cellulose whisker/hydroxyapatite/fibroin blend solution of variable concentrations, wherein the mass ratio of nano-cellulose whisker/hydroxyapatite nano-complex particle and fibroin is 65:35;
(5) nano-cellulose whisker/hydroxyapatite/fibroin blend solution the highest for mass concentration obtained in step (4) is poured in homemade mould, after the quenching of liquid nitrogen condition, in-50--80 DEG C of lyophilization, again by other blend solution according to mass concentration order successively lyophilization from high to low, the nano bone biomimetic material containing Graphene, hydroxyapatite and fibroin of obtained density and porosity distribution gradient.
Compared with existing bone alternate material and preparation method thereof, the present invention has the following advantages:
(1) in the present invention by the nano-cellulose whisker of carboxylated modification and the compound particle of hydroxyapatite self assembly, due to electrostatic interaction, bar-shaped hydroxyapatite is distributed in nano-cellulose whisker surface, linked together by bar-shaped nano-cellulose whisker, carboxylated nano-cellulose whisker and hydroxyapatite layer are alternately arranged formation steel-concrete structures.Thus, resistance to compression mechanical strength and the toughness of hydroxyapatite can be improved;
(2) the porous bone biomimetic material prepared in the present invention has the pore structure of Gradient distribution, thus is macroscopically carrying out bionical to nature bone.Compound support frame material prepared by the present invention can be easy to obtain needed for shape and size; The hole of a fixed structure and content can be formed, the requirement to bone biomimetic material type in bone collection process can be met;
(3) the bone biomimetic material prepared in the present invention has avirulence, nonirritant, good biocompatibility, cellular affinity is good, biodegradability is good and excellent mechanical property.
The bone biomimetic material built by the nano-cellulose whisker of mineralising prepared by the present invention, mainly based on the nano-cellulose whisker of carboxymethyl-modification, obtain nano-cellulose whisker/hydroxyapatite compound particle by electrostatic self-assembled biomimetic mineralization, and zygomite usually prepares the porous bone biomimetic material of density and porosity gradient distribution.
Accompanying drawing explanation
The pattern of nano-cellulose whisker after Fig. 1 carboxy methylation;
Fig. 2 Cellulose nanocrystal must be the pattern of the compound particle of 1:1 with hydroxyapatite ratio;
Fig. 3 Cellulose nanocrystal must be the pattern of the compound particle of 1:2 with hydroxyapatite ratio;
Fig. 4 Cellulose nanocrystal must be the pattern of the compound particle of 1:4 with hydroxyapatite ratio.
Detailed description of the invention
Below in conjunction with accompanying drawing, by example, the present invention is described in more detail.
A kind of bone biomimetic material built by the nano-cellulose whisker of mineralising, it is made up of inorganic carboxylated nano-cellulose whisker and hydroxyapatite and organic fibroin, described inorganic constituents carboxy methylation nano whisker and the mass ratio of hydroxyapatite are 1:0-1, its mass ratio of described inorganic constituents and organic principle is 1:0.5-2, described bone biomimetic material is by carboxylated nano-cellulose whisker, hydroxyapatite and Bombyx mori Silk Fibroin composition, carboxylated nano-cellulose whisker, the mass ratio of hydroxyapatite and Bombyx mori Silk Fibroin is 1:1-10:0.5-5, its density gradient is respectively 75.3%-82.3% from outside to inside, 57.4%-67.2%, 11.6%-30.6%.The draw ratio of described nano whisker is about 20:1-2, described fibroin albumen is Bombyx mori Silk Fibroin and tussah silk peptide, and the intrinsic viscosity of its protein molecular is more than or equal to 0.50, and described hydroxyapatite presents needle-like distribution, its particle length is at 50-300nm, and particle width is at 10-50nm.
embodiment 1
A preparation method for the bone biomimetic material built by the nano-cellulose whisker of mineralising, carry out according to the following steps:
(1) by nano-cellulose whisker ultrasonic disperse in ethanol (85%) solution of 0.5mol/L sodium hydroxide; bath raio is 1:500; alkalize 60min at 30 DEG C; add the sodium chloroacetate solution of 0.725mol/L again; ultrasonic agitation 50min at 60 DEG C; and adjust solution ph to neutral and dialyse three days in distilled water with the hydrochloric acid of 0.1mol/L, obtains the nano-cellulose whisker suspension solution of carboxylated modification;
(2) be 1.67 according to the ratio of the amount of calcium phosphorus substance, by the Ca (OH) of 0.05mol/L
2with the H of dilution
3pO
4solution burette to instill in the obtained solution of step (1) and at ultrasonic middle stirring 4h simultaneously, dropwise adding ammonia control pH value in reaction is 8.0 ~ 9.0, controlling reaction temperature is 60 DEG C, obtains the compound particle suspension that nano-cellulose whisker/hydroxyapatite ratio is 1:1;
(3) supernatant is removed after the nano-cellulose whisker of step (2) gained/hydroxyapatite nano-complex particle suspension room temperature being left standstill 48 hours, centrifugalize goes out precipitate, after distilled water wash three times, lyophilization obtains nano-cellulose whisker/hydroxyapatite compound particle;
(4) the nano-cellulose whisker that obtains/hydroxyapatite compound particle ultrasonic disperse in step (3) is respectively 5% to concentration, 35, the silk fibroin solution of 55%, obtain the nano-cellulose whisker/hydroxyapatite/fibroin blend solution of variable concentrations, wherein the mass ratio of nano-cellulose whisker/hydroxyapatite nano-complex particle and fibroin is 65:35;
(5) nano-cellulose whisker/hydroxyapatite/fibroin blend solution the highest for mass concentration obtained in step (4) is poured in homemade mould, after the quenching of liquid nitrogen condition, in-54 DEG C of lyophilizations, again by other blend solution according to mass concentration order successively lyophilization from high to low, the porous bone biomimetic material of obtained density and porosity distribution gradient, this bone biomimetic material is by carboxylated nano-cellulose whisker, hydroxyapatite and Bombyx mori Silk Fibroin composition, its mass ratio is 1:2:2, its density gradient is respectively 78.4% from outside to inside, 57.4%, 11.6%, its porosity gradient is respectively 17.2% from outside to inside, 37.4%, 80.2%.
Table 1 shows mechanical property and the porosity of the porous nano bone biomimetic material containing nano-cellulose whisker/hydroxyapatite/fibroin, (in Fig. 1, amplification is 50,000 times to SEM photo such as Fig. 1 and Fig. 2 of nano whisker after its carboxy methylation, nano-cellulose whisker/hydroxyapatite composite particle structures, in Fig. 2, amplification is 20,000 times) shown in, as seen from Figure 1, the average aspect ratio of carboxy methylation nano whisker prepared by the present invention is about 10:1, only has the nano whisker of small part to be covered by hydroxyapatite as seen from Figure 2.
embodiment 2
A preparation method for the bone biomimetic material built by the nano-cellulose whisker of mineralising, carry out according to the following steps:
(1) by nano-cellulose whisker ultrasonic disperse in ethanol (85%) solution of 1mol/L sodium hydroxide; bath raio is 1:500; alkalize 20min at 50 DEG C; add the sodium chloroacetate solution of 1.25mol/L again; ultrasonic agitation 100min at 50 DEG C; and adjust solution ph to neutral and dialyse three days in distilled water with the hydrochloric acid of 0.3mol/L, obtains the nano-cellulose whisker suspension solution of carboxylated modification;
(2) be 1.67 according to the ratio of the amount of calcium phosphorus substance, by the Ca (OH) of 0.1mol/L
2with chitosan and the H of the dilution of dilution
3pO
4solution burette to instill in the obtained solution of step (1) and at ultrasonic middle stirring 2h simultaneously, dropwise adding ammonia control pH value in reaction is 8.0 ~ 10.0, controlling reaction temperature is 75 DEG C, obtains the compound particle suspension that nano-cellulose whisker/hydroxyapatite ratio is 1:2;
(3) supernatant is removed after the nano-cellulose whisker of step (2) gained/hydroxyapatite nano-complex particle suspension room temperature being left standstill 48 hours, centrifugalize goes out precipitate, after distilled water wash three times, lyophilization obtains nano-cellulose whisker/hydroxyapatite compound particle;
(4) the nano-cellulose whisker that obtains/hydroxyapatite compound particle ultrasonic disperse in step (3) is respectively 10% to concentration, 40%, the silk fibroin solution of 60%, obtain the nano-cellulose whisker/hydroxyapatite/fibroin blend solution of variable concentrations, wherein the mass ratio of nano-cellulose whisker/hydroxyapatite nano-complex particle and fibroin is 65:35;
(5) nano-cellulose whisker/hydroxyapatite/fibroin blend solution the highest for mass concentration obtained in step (4) is poured in homemade mould, after the quenching of liquid nitrogen condition, in-60 DEG C of lyophilizations, again by other blend solution according to mass concentration order successively lyophilization from high to low, the porous bone biomimetic material of obtained density and porosity distribution gradient, this bone biomimetic material is by carboxylated nano-cellulose whisker, hydroxyapatite and Bombyx mori Silk Fibroin composition, its mass ratio is 1:4:3, its density gradient is respectively 79% from outside to inside, 61%, 120%, its porosity gradient is respectively 18.1% from outside to inside, 26.4%, 77.2%, mechanical property and the porosity of the bone biomimetic material of preparation are as shown in table 1, the SEM photo of the structure of its nano-cellulose whisker/hydroxyapatite compound particle is as shown in Fig. 3 (in figure, amplification is 20,000 times), as seen from Figure 3, carboxymethylated nano whisker is almost covered by hydroxyapatite.
embodiment 3
A preparation method for the bone biomimetic material built by the nano-cellulose whisker of mineralising, carry out according to the following steps:
(1) by nano-cellulose whisker ultrasonic disperse in ethanol (85%) solution of 0.08mol/L sodium hydroxide; bath raio is 1:500; alkalize 30min at 40 DEG C; add the sodium chloroacetate solution of 0.1mol/L again; ultrasonic agitation 60min at 55 DEG C; and adjust solution ph to neutral and dialyse three days in distilled water with the hydrochloric acid of 0.2mol/L, obtains the nano-cellulose whisker suspension solution of carboxylated modification;
(2) be 1.67 according to the ratio of the amount of calcium phosphorus substance, by the Ca (OH) of 0.03mol/L
2with the H of dilution
3pO
4solution burette to instill in the obtained solution of step (1) and at ultrasonic middle stirring 3h simultaneously, dropwise adding ammonia control pH value in reaction is 8.0 ~ 10.0, controlling reaction temperature is 80 DEG C, obtains the compound particle suspension that nano-cellulose whisker/hydroxyapatite ratio is 1:4;
(3) supernatant is removed after the graphene/hydroxyapatite nano compound particle suspension room temperature of step (2) gained being left standstill 48 hours, centrifugalize goes out precipitate, after distilled water wash three times, lyophilization obtains nano-cellulose whisker/hydroxyapatite compound particle;
(4) the nano-cellulose whisker that obtains/hydroxyapatite compound particle ultrasonic disperse in step (3) is respectively 15% to concentration, 45%, the silk fibroin solution of 65%, obtain the nano-cellulose whisker/hydroxyapatite/fibroin blend solution of variable concentrations, wherein the mass ratio of nano-cellulose whisker/hydroxyapatite nano-complex particle and fibroin is 65:35;
(5) nano-cellulose whisker/hydroxyapatite/fibroin blend solution the highest for mass concentration obtained in step (4) is poured in homemade mould, after the quenching of liquid nitrogen condition, in-75 DEG C of lyophilizations, again by other blend solution according to mass concentration order successively lyophilization from high to low, the porous bone biomimetic material of obtained density and porosity distribution gradient, this bone biomimetic material is by carboxylated nano-cellulose whisker, hydroxyapatite and Bombyx mori Silk Fibroin composition, its mass ratio is 1:8:6, its density gradient is respectively 81.6% from outside to inside, 63.2%, 24.9%, its porosity gradient is respectively 19.4% from outside to inside, 37.5%, 75.3%, mechanical property and the porosity of the bone biomimetic material of preparation are as shown in table 1, the SEM photo of the structure of its nano-cellulose whisker/hydroxyapatite compound particle is as shown in Fig. 4 (in figure, amplification is 20,000 times), as seen from Figure 4, nano-cellulose whisker has not been observed in the visual field, its length 50-300 nanometer of the yardstick of hydroxyapatite, width is in 10-50 nanometer.
The performance of the bone biomimetic material that table 1 is built by the nano-cellulose whisker of mineralising
Therefore, the present invention obtains the bone biomimetic material built by the nano-cellulose whisker of mineralising, structurally there is the nanometer that interconnects the in a large number micropore to micro-meter scale, and there is the porosity of graded, the distributed architecture of Compact bone and spongy bone in fully bionical nature bone.Composition have selected the carboxy methylation nano-cellulose whisker of fibroin albumen and the function optimization with good biocompatibility, enhance comprcssive strength and the toughness of hydroxyapatite.Prepared according to the methods of the invention bone biomimetic material has good mechanical property, good formability and rational porosity, can as the degradable bone renovating material of embedded type.
Claims (7)
1. the bone biomimetic material built by the nano-cellulose whisker of mineralising, it is characterized in that: it is made up of inorganic carboxylated nano-cellulose whisker and hydroxyapatite and organic fibroin, described inorganic constituents carboxy methylation nano whisker and the mass ratio of hydroxyapatite are 1:0-1, and its mass ratio of described inorganic constituents and organic principle is 1:0.5-2.
2. the bone biomimetic material built by the nano-cellulose whisker of mineralising according to claim 1, it is characterized in that: described bone biomimetic material is made up of carboxylated nano-cellulose whisker, hydroxyapatite and Bombyx mori Silk Fibroin, the mass ratio of carboxylated nano-cellulose whisker, hydroxyapatite and Bombyx mori Silk Fibroin is 1:1-10:0.5-5, its density gradient is respectively 75.3%-82.3% from outside to inside, 57.4%-67.2%, 11.6%-30.6%.
3. the bone biomimetic material built by the nano-cellulose whisker of mineralising according to claim 1, it is characterized in that: the nanometer micropore be interconnected containing Gradient distribution in described bone biomimetic material, the porosity gradient of nanometer micropore is respectively 17.7%-24.7% from outside to inside, 32.8%-42.6%, 69.4-88.4%.
4. the bone biomimetic material built by the nano-cellulose whisker of mineralising according to claim 1, it is characterized in that: the draw ratio of described carboxylated nano-cellulose whisker is about 20:1-10:1, described fibroin albumen is Bombyx mori Silk Fibroin or tussah silk peptide, the intrinsic viscosity of its protein molecular is more than or equal to 0.50, described hydroxyapatite presents needle-like distribution, its particle length is at 50-300nm, and particle width is at 10-50nm.
5. the bone biomimetic material built by the nano-cellulose whisker of mineralising according to claim 1, is characterized in that: described hydroxyapatite and the self assembly of nano-cellulose whisker form compound particle.
6. the preparation method of the bone biomimetic material built by the nano-cellulose whisker of mineralising as described in claim 1 or 2 or 3 or 4 or 5, is characterized in that carrying out according to the following steps:
(1) by nano-cellulose whisker ultrasonic disperse in the alcoholic solution of 0.1-2mol/L sodium hydroxide; bath raio is 1:500; alkalize 10-120min at 20-80 DEG C; add the sodium chloroacetate solution of 0.125-2.5mol/L again; ultrasonic agitation 15-100min at 30-75 DEG C; and adjust solution ph to neutral and dialyse three days in distilled water with the hydrochloric acid of 0.1-0.5mol/L, obtains the brilliant suspension solution of nano-cellulose of carboxylated modification;
(2) be 1.67 according to the ratio of the amount of calcium phosphorus substance, by the Ca (OH) of 0.01-0.1mol/L
2with dilution H
3pO
4solution burette to instill in the obtained solution of step (1) and at ultrasonic middle stirring 1-6h simultaneously, dropwise adding ammonia control pH value in reaction is 8.0 ~ 10.0, control reaction temperature is 20-80 DEG C, obtains the compound particle suspension that nano-cellulose whisker/hydroxyapatite ratio is 1:1-10;
(3) supernatant is removed after the nano-cellulose whisker of step (2) gained/hydroxyapatite nano-complex particle suspension room temperature being left standstill 48 hours, centrifugalize goes out precipitate, after distilled water wash three times, lyophilization obtains nano-cellulose whisker/hydroxyapatite compound particle;
(4) the nano-cellulose whisker that obtains/hydroxyapatite compound particle ultrasonic disperse in step (3) is respectively 5%-15% to concentration, 35%-45%, the organic silk cellulose solution of 55%-65%, obtain the nano-cellulose whisker/hydroxyapatite/fibroin blend solution of variable concentrations, wherein the mass ratio of nano-cellulose whisker/hydroxyapatite nano-complex particle and fibroin is 65:35;
(5) nano-cellulose whisker/hydroxyapatite/fibroin blend solution the highest for mass concentration obtained in step (4) is poured in homemade mould, after the quenching of liquid nitrogen condition, in-50--80 DEG C of lyophilization, again by other blend solution according to mass concentration order successively lyophilization from high to low, the porous bone biomimetic material of obtained density and porosity distribution gradient.
7. the preparation method of the bone biomimetic material built by the nano-cellulose whisker of mineralising according to claim 6, is characterized in that: the volumetric concentration of described alcoholic solution is 85%.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105731830A (en) * | 2016-02-01 | 2016-07-06 | 济南大学 | Preparation method of hydroxyapatite-modified glass fiber |
| CN105839294A (en) * | 2016-05-23 | 2016-08-10 | 浙江理工大学 | Method for preparing nanocrystalline cellulose-fibroin film by electrostatic spinning method |
| CN109364307A (en) * | 2018-10-15 | 2019-02-22 | 福建工程学院 | A kind of gradient porous bone holder material and preparation method thereof |
| CN109810255A (en) * | 2019-01-23 | 2019-05-28 | 三峡大学 | A kind of method of modifying of plant fiber or nano-cellulose |
| CN110114309A (en) * | 2017-02-28 | 2019-08-09 | 新东工业株式会社 | The manufacturing method and composite material molded body of composite material molded body containing needle-like hydroxyapatite |
| CN112870447A (en) * | 2021-01-08 | 2021-06-01 | 东华大学 | Bone regeneration multi-bionic scaffold material and preparation method thereof |
| CN114790329A (en) * | 2022-05-31 | 2022-07-26 | 重庆大学 | High-mechanical-property linear shape memory polyurethane/cellulose nanocrystalline composite material and preparation method and application thereof |
| CN114870099A (en) * | 2022-03-30 | 2022-08-09 | 浙江大学 | All-natural polysaccharide-based degradable composite bone screw material with oriented-concentric circle structure and preparation method thereof |
| CN114949375A (en) * | 2022-05-05 | 2022-08-30 | 同济大学 | Bionic mineralized nano cellulose film and preparation method and application thereof |
| CN115737911A (en) * | 2022-12-16 | 2023-03-07 | 华南理工大学 | High-toughness bone repair composite material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1386763A (en) * | 2002-05-27 | 2002-12-25 | 中国科学院广州化学研究所 | Surface modified nano cellulose crystal and its preparing process |
| WO2013076376A1 (en) * | 2011-11-23 | 2013-05-30 | Upm-Kymmene Corporation | A method and a system for manufacturing cellulose material |
| CN103285428A (en) * | 2013-04-26 | 2013-09-11 | 中国国旅贸易有限责任公司 | Artificial bone material and preparation method thereof |
| CN104399121A (en) * | 2014-11-10 | 2015-03-11 | 苏州维泰生物技术有限公司 | Material for preparing artificial bones and preparation method thereof |
-
2015
- 2015-08-31 CN CN201510545412.8A patent/CN105148324B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1386763A (en) * | 2002-05-27 | 2002-12-25 | 中国科学院广州化学研究所 | Surface modified nano cellulose crystal and its preparing process |
| WO2013076376A1 (en) * | 2011-11-23 | 2013-05-30 | Upm-Kymmene Corporation | A method and a system for manufacturing cellulose material |
| CN103285428A (en) * | 2013-04-26 | 2013-09-11 | 中国国旅贸易有限责任公司 | Artificial bone material and preparation method thereof |
| CN104399121A (en) * | 2014-11-10 | 2015-03-11 | 苏州维泰生物技术有限公司 | Material for preparing artificial bones and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 何建新等: "纤维素纳米晶须/柞蚕丝素纳米纤维是制备与表征", 《东华大学学报（自然科学版）》 * |
| 曲萍等: "棒状纳米纤维素仿生矿化及光谱分析", 《光谱学与光谱分析》 * |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105731830A (en) * | 2016-02-01 | 2016-07-06 | 济南大学 | Preparation method of hydroxyapatite-modified glass fiber |
| CN105839294A (en) * | 2016-05-23 | 2016-08-10 | 浙江理工大学 | Method for preparing nanocrystalline cellulose-fibroin film by electrostatic spinning method |
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