CN105148324B - Bone biomimetic material that a kind of nano-cellulose whisker by mineralising is built and preparation method thereof - Google Patents
Bone biomimetic material that a kind of nano-cellulose whisker by mineralising is built and preparation method thereof Download PDFInfo
- Publication number
- CN105148324B CN105148324B CN201510545412.8A CN201510545412A CN105148324B CN 105148324 B CN105148324 B CN 105148324B CN 201510545412 A CN201510545412 A CN 201510545412A CN 105148324 B CN105148324 B CN 105148324B
- Authority
- CN
- China
- Prior art keywords
- nano
- cellulose whisker
- hydroxyapatite
- bone
- solution
- 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.)
- Expired - Fee Related
Links
Landscapes
- Materials For Medical Uses (AREA)
Abstract
Bone biomimetic material built the present invention relates to a kind of nano-cellulose whisker by mineralising and preparation method thereof.It is to act on the substantial amounts of carboxyl of nano-cellulose whisker surface grafting by sodium hydroxide and sodium chloroacetate, and Ca (OH) is added dropwise simultaneously according to calcium phosphorus mol ratio 1. 67 under strong stirring2Suspension and H3PO 4Solution is into nano-cellulose suspension solution, it is 7.0 11.0 to control solution ph, obtain nano-cellulose whisker/hydroxyapatite compound particle, inserted after the silk fibroin protein solution of nano-complex particle addition various concentrations is fully reconciled uniformly in homemade mould, obtained nano bone biomimetic material is successively freeze-dried according to the order of mass concentration from high to low.The bone biomimetic material that nano-cellulose whisker produced by the present invention by mineralising is built being capable of bionical nature bone on composition and structure, with good mechanical property, rational porosity and good biocompatibility and bioactivity, reparation that can be as bone tissue or alternative materials, have broad application prospects.
Description
Technical field
Bone biomimetic material built the present invention relates to a kind of nano-cellulose whisker by mineralising and preparation method thereof, application
In Bone Defect Repari or bone alternate material, and in particular to biology medical material technical field.
Background technology
In field of orthopaedics, Cranial defect is very common as caused by wound, infection, osteopathy, bone tumour resection etc..Autologous bone or
Allograph bone is all there is increase postoperative complication, material source is limited, spreads disease or the problems such as immunological rejection, and it is clinical
Using receiving certain limitation.With the development of biomaterials art, artificial bone alternate material is increasingly being applied to
It is clinical.Bone alternate material grows mainly as framework in human body bone, osteocyte and collagenous fibres are inserted thereon, eventually becomes work
A part for body bone.Therefore, it is always the target that people make great efforts to find a kind of preferably bone transplantation substitute material.
Mainly there are metal, ceramics and several major classes of polymer currently used for bone tissue reparation.But metal material lack with
The bioactivity that tissue combines, ceramic-like materials are primarily present that matter is crisp, is easy to be broken and occur fatigue rupture etc. in vivo
Deficiency, polymer can have modulus similar in people's bone, but not possess the activity that biological key is formed with bone tissue.Therefore, find
It is still a difficult point clinically that more satisfactory material, which is used for bone tissue reparation,.Nature bone is that a kind of had by about 30%
The organic/inorganic Biocomposite material that machine matrix and 70% hydroxyapatite are formed, organic substrate mainly include non-collagen egg
In vain, mucopolysaccharide etc..Hydroxide radical phosphorite nanocrystalline body is embedded in collagen fiber matrix in an orderly manner, close between organic and inorganic constituent element
The unique assemblies of synergy and molecular level, impart the multilevel hierarchy of nature bone and excellent mechanical property.Therefore,
Prepare biocompatibility and mechanical compatibility are good, have bioactivity Bone Defect Repari or bone alternate material, it is necessary to be set from molecular level
Meter carries out Bionic Design, imitates the 26S Proteasome Structure and Function of nature bone.Nano whisker is a kind of nanometer extracted from natural fiber
The cellulose of level, it not only has the feature of nano particle, also with some unique intensity and optical property, has wide
Application prospect.Be modified by carboxylated make Cellulose nanocrystal must surface grafting it is a large amount of-COOH group, purposefully strengthen nanometer
The feature of whisker, while the advantages of intrinsic is not broken again, its application is extended,.
The content of the invention
A kind of preparation side of the bone biomimetic material built it is an object of the invention to provide nano-cellulose whisker by mineralising
Method.It is modified by the carboxylated of nano-cellulose whisker and electrostatic self-assembled biomimetic mineralization obtains nano-cellulose whisker/hydroxyl
Apatite nano-complex particle, makes that the fibroin of it and various concentrations is blended to obtain density and porosity is in using Freeze Drying Technique
The porous bone biomimetic material of gradient distribution.This bone biomimetic material not only simulates nature bone on composition, and in structure
It is bionical to nature bone, there is good biocompatibility, biological degradability and osteoinductive energy, and excellent mechanical property.
Realizing the technical scheme of the object of the invention is, the bionical material of bone that a kind of nano-cellulose whisker by mineralising is built
Material, it is made up of inorganic carboxylated nano-cellulose whisker and hydroxyapatite with organic fibroin, described inorganic constituents
The mass ratio of carboxy methylation nano whisker and hydroxyapatite is 1:Its quality of 0-1, described inorganic constituents and organic principle
Than for 1:0.5-2.
The bone biomimetic material is made up of carboxylated nano-cellulose whisker, hydroxyapatite and Bombyx mori Silk Fibroin, carboxylated
The mass ratio of nano-cellulose whisker, hydroxyapatite and Bombyx mori Silk Fibroin is 1:1-10:0.5-5, its density gradient is from outside to inside
Respectively 75.3%-82.3%, 57.4%-67.2%, 11.6%-30.6%.
The draw ratio of described nano whisker is about 20:1-2, described fibroin albumen are Bombyx mori Silk Fibroin and tussah silk peptide,
The inherent viscosity of its protein molecular is more than or equal to 0.50, and needle-like distribution is presented in described hydroxyapatite, and its particle length exists
50-300nm, particle width is in 10-50nm.
The method for preparing the bone biomimetic material that this nano-cellulose whisker by mineralising is built, using following steps：
（1）By in the ethanol solution of nano-cellulose whisker ultrasonic disperse to 0.1-2mol/L sodium hydroxides, bath raio 1:
500, alkalize 10-120 min at 20-80 DEG C.0.125-2.5 mol/L sodium chloroacetate solution is added, at 30-75 DEG C
Lower ultrasonic agitation 15-100min, and adjust solution ph to dialyse three to neutrality and in distilled water with 0.1-0.5mol/L hydrochloric acid
My god, obtain the nano-cellulose crystalline substance suspension solution of carboxylated modification；
（2）The ratio between amount according to calcium phosphorus substance is 1.67, by 0.01-0.1mol/L Ca (OH)2With the H of dilution3PO4It is molten
Liquid buret instills step simultaneously（1）1-6h is stirred in obtained solution and in ultrasound, ammoniacal liquor control reaction is added dropwise
PH value is 8.0~10.0, and controlling reaction temperature is 20-80 DEG C, obtains nano-cellulose whisker/hydroxyapatite ratio as 1：1-
10 compound particle suspension；
（3）By step（2）Nano-cellulose whisker/hydroxyapatite nano-complex particle suspension of gained is stored at room temperature
Supernatant liquor is removed after 48 hours, centrifuges out sediment, after distilling water washing three times, is freeze-dried and nano-cellulose is made
Whisker/hydroxyapatite compound particle；
（4）By step（3）In resulting nano-cellulose whisker/hydroxyapatite compound particle ultrasonic disperse to concentration point
Not Wei 5%-15%, 35%-45%, 55%-65% silk fibroin solution, obtain nano-cellulose whisker/hydroxyapatites of various concentrations/
The mass ratio of fibroin blend solution, wherein nano-cellulose whisker/hydroxyapatite nano-complex particle and fibroin is 65:35；
（5）By step（4）In the blending of obtained mass concentration highest nano-cellulose whisker/hydroxyapatite/fibroin
Solution is poured into homemade mould, after the quenching of liquid nitrogen condition, is pressed in -50--80 DEG C of freeze-dryings, then by other blend solutions
Successively be freeze-dried according to the order of mass concentration from high to low, be made density and porosity distribution gradient containing graphene,
The nano bone biomimetic material of hydroxyapatite and fibroin.
Compared with existing bone alternate material and preparation method thereof, the present invention has advantages below：
（1）The compound grain that the nano-cellulose whisker and hydroxyapatite self assembly being modified in the present invention by carboxylated form
In son, due to electrostatic interaction, bar-shaped hydroxyapatite is distributed in nano-cellulose whisker surface, by bar-shaped nano-cellulose
Whisker links together, and carboxylated nano-cellulose whisker and hydroxyapatite layer are alternately arranged to form steel-concrete structures.
Thus, the resistance to compression mechanical strength and toughness of hydroxyapatite can be improved；
（2）The porous bone biomimetic material prepared in the present invention has the pore structure that gradient is distributed, so as to macroscopically right
Nature bone carries out bionical.Compound support frame material prepared by the present invention can readily obtain required shapes and sizes；Can be with shape
Into the hole of certain structure and content, the requirement to bone biomimetic material type during bone collection disclosure satisfy that；
（3）The bone biomimetic material prepared in the present invention has non-toxic, nonirritant, good biocompatibility, cell affine
The mechanical property that property is good, biodegradability is good and excellent.
The bone biomimetic material that nano-cellulose whisker by mineralising prepared by the present invention is built, is mainly based upon carboxy methylation
Modified nano-cellulose whisker, it is compound that nano-cellulose whisker/hydroxyapatite is obtained by electrostatic self-assembled biomimetic mineralization
Particle, and zygomite usually prepares the porous bone biomimetic material of density and porosity gradient distribution.
Brief description of the drawings
The pattern of nano-cellulose whisker after Fig. 1 carboxy methylations；
Fig. 2 Cellulose nanocrystals must be 1 with hydroxyapatite ratio:The pattern of 1 compound particle；
Fig. 3 Cellulose nanocrystals must be 1 with hydroxyapatite ratio:The pattern of 2 compound particle；
Fig. 4 Cellulose nanocrystals must be 1 with hydroxyapatite ratio:The pattern of 4 compound particle.
Embodiment
By example, the present invention is described in more detail below in conjunction with the accompanying drawings.
The bone biomimetic material that a kind of nano-cellulose whisker by mineralising is built, it is by inorganic carboxylated nano-cellulose
Whisker and hydroxyapatite and organic fibroin composition, described inorganic constituents carboxy methylation nano whisker and hydroxyapatite
Mass ratio is 1:Its mass ratio of 0-1, described inorganic constituents and organic principle is 1:0.5-2, the bone biomimetic material is by carboxylic
Base nano-cellulose whisker, hydroxyapatite and Bombyx mori Silk Fibroin composition, carboxylated nano-cellulose whisker, hydroxyapatite and
The mass ratio of Bombyx mori Silk Fibroin is 1:1-10:0.5-5, its density gradient are respectively 75.3%-82.3%, 57.4%- from outside to inside
67.2%, 11.6%-30.6%.The draw ratio of described nano whisker is about 20:1-2, described fibroin albumen be Bombyx mori Silk Fibroin and
Tussah silk peptide, the inherent viscosity of its protein molecular are more than or equal to 0.50, and needle-like distribution, its grain is presented in described hydroxyapatite
Sub- length is in 50-300nm, and particle width is in 10-50nm.
Embodiment 1
A kind of preparation method for the bone biomimetic material that nano-cellulose whisker by mineralising is built, is carried out according to the following steps：
（1）Ethanol by nano-cellulose whisker ultrasonic disperse to 0.5mol/L sodium hydroxides（85%）In solution, bath raio
For 1:500, alkalize 60 min at 30 DEG C, adds 0.725mol/L sodium chloroacetate solution, is stirred by ultrasonic at 60 DEG C
50min, and adjust solution ph to be dialysed three days to neutrality and in distilled water with 0.1mol/L hydrochloric acid, obtain carboxylated modification
Nano-cellulose whisker suspension solution；
（2）The ratio between amount according to calcium phosphorus substance is 1.67, by 0.05mol/L Ca (OH)2With the H of dilution3PO4Solution is used
Buret instills step simultaneously（1）4h is stirred in obtained solution and in ultrasound, ammoniacal liquor is added dropwise and controls the pH value in reaction to be
8.0~9.0, controlling reaction temperature is 60 DEG C, obtains nano-cellulose whisker/hydroxyapatite ratio as 1：1 compound particle
Suspension；
（3）By step（2）Nano-cellulose whisker/hydroxyapatite nano-complex particle suspension of gained is stored at room temperature
Supernatant liquor is removed after 48 hours, centrifuges out sediment, after distilling water washing three times, is freeze-dried and nano-cellulose is made
Whisker/hydroxyapatite compound particle；
（4）By step（3）In resulting nano-cellulose whisker/hydroxyapatite compound particle ultrasonic disperse to concentration point
Not Wei 5%, 35,55% silk fibroin solution, obtain nano-cellulose whisker/hydroxyapatite/fibroin blend solution of various concentrations,
Wherein the mass ratio of nano-cellulose whisker/hydroxyapatite nano-complex particle and fibroin is 65:35；
（5）By step（4）In the blending of obtained mass concentration highest nano-cellulose whisker/hydroxyapatite/fibroin
Solution is poured into homemade mould, after the quenching of liquid nitrogen condition, in -54 DEG C of freeze-dryings, then by other blend solutions according to matter
The order of amount concentration from high to low is successively freeze-dried, and the porous bone biomimetic material of density and porosity distribution gradient is made,
The bone biomimetic material is made up of carboxylated nano-cellulose whisker, hydroxyapatite and Bombyx mori Silk Fibroin, and its mass ratio is 1:2:2,
Its density gradient is respectively 78.4%, 57.4%, 11.6% from outside to inside, and its porosity gradient is respectively 17.2% from outside to inside,
37.4%, 80.2%.
Table 1 shows the mechanics of the porous nano bone biomimetic material containing nano-cellulose whisker/hydroxyapatite/fibroin
Performance and porosity, nano whisker, nano-cellulose whisker/hydroxyapatite composite particle structures after its carboxy methylation
SEM photograph such as Fig. 1 and Fig. 2（Multiplication factor is 50,000 times in Fig. 1, and multiplication factor is 20,000 times in Fig. 2）It is shown, it can be seen by Fig. 1
Go out, the average aspect ratio of carboxy methylation nano whisker prepared by the present invention is about 10:1, it is only least a portion of as seen from Figure 2
Nano whisker is covered by hydroxyapatite.
Embodiment 2
A kind of preparation method for the bone biomimetic material that nano-cellulose whisker by mineralising is built, is carried out according to the following steps：
（1）Ethanol by nano-cellulose whisker ultrasonic disperse to 1mol/L sodium hydroxides（85%）In solution, bath raio is
1:500, alkalize 20min at 50 DEG C, adds 1.25 mol/L sodium chloroacetate solution, is stirred by ultrasonic at 50 DEG C
100min, and adjust solution ph to be dialysed three days to neutrality and in distilled water with 0.3mol/L hydrochloric acid, obtain carboxylated modification
Nano-cellulose whisker suspension solution；
（2）The ratio between amount according to calcium phosphorus substance is 1.67, by 0.1mol/L Ca (OH)2With the chitosan of the dilution of dilution
And H3PO4Solution buret instills step simultaneously（1）2h is stirred in obtained solution and in ultrasound, ammoniacal liquor control is added dropwise
PH value in reaction processed is 8.0~10.0, and controlling reaction temperature is 75 DEG C, and obtaining nano-cellulose whisker/hydroxyapatite ratio is
1：2 compound particle suspension；
（3）By step（2）Nano-cellulose whisker/hydroxyapatite nano-complex particle suspension of gained is stored at room temperature
Supernatant liquor is removed after 48 hours, centrifuges out sediment, after distilling water washing three times, is freeze-dried and nano-cellulose is made
Whisker/hydroxyapatite compound particle；
（4）By step（3）In resulting nano-cellulose whisker/hydroxyapatite compound particle ultrasonic disperse to concentration point
Not Wei 10%, 40%, 60% silk fibroin solution, it is molten to obtain nano-cellulose whisker/hydroxyapatites of various concentrations/fibroin blending
The mass ratio of liquid, wherein nano-cellulose whisker/hydroxyapatite nano-complex particle and fibroin is 65:35；
（5）By step（4）In the blending of obtained mass concentration highest nano-cellulose whisker/hydroxyapatite/fibroin
Solution is poured into homemade mould, after the quenching of liquid nitrogen condition, in -60 DEG C of freeze-dryings, then by other blend solutions according to matter
The order of amount concentration from high to low is successively freeze-dried, and the porous bone biomimetic material of density and porosity distribution gradient is made,
The bone biomimetic material is made up of carboxylated nano-cellulose whisker, hydroxyapatite and Bombyx mori Silk Fibroin, and its mass ratio is 1:4:3,
Its density gradient is respectively 79%, 61%, 120% from outside to inside, and its porosity gradient is respectively 18.1%, 26.4% from outside to inside,
77.2%, the mechanical property and porosity of the bone biomimetic material of preparation are as shown in table 1, its nano-cellulose whisker/hydroxyapatite
The SEM photograph of the structure of compound particle such as Fig. 3（Multiplication factor is 20,000 times in figure）It is shown, as seen from Figure 3, carboxy methylation
Nano whisker almost covered by hydroxyapatite.
Embodiment 3
A kind of preparation method for the bone biomimetic material that nano-cellulose whisker by mineralising is built, is carried out according to the following steps：
（1）Ethanol by nano-cellulose whisker ultrasonic disperse to 0.08mol/L sodium hydroxides（85%）In solution, bath raio
For 1:500, alkalize 30 min at 40 DEG C, adds 0.1 mol/L sodium chloroacetate solution, is stirred by ultrasonic at 55 DEG C
60min, and adjust solution ph to be dialysed three days to neutrality and in distilled water with 0.2mol/L hydrochloric acid, obtain carboxylated modification
Nano-cellulose whisker suspension solution；
（2）The ratio between amount according to calcium phosphorus substance is 1.67, by 0.03mol/L Ca (OH)2With the H of dilution3PO4Solution is used
Buret instills step simultaneously（1）3h is stirred in obtained solution and in ultrasound, ammoniacal liquor is added dropwise and controls the pH value in reaction to be
8.0~10.0, controlling reaction temperature is 80 DEG C, obtains nano-cellulose whisker/hydroxyapatite ratio as 1：4 compound particle
Suspension；
（3）By step（2）After the graphene/hydroxyapatite nano compound particle suspension of gained is stored at room temperature 48 hours
Supernatant liquor is removed, centrifuges out sediment, after distilling water washing three times, is freeze-dried and nano-cellulose whisker/hydroxyl is made
Base apatite compound particle；
（4）By step（3）In resulting nano-cellulose whisker/hydroxyapatite compound particle ultrasonic disperse to concentration point
Not Wei 15%, 45%, 65% silk fibroin solution, it is molten to obtain nano-cellulose whisker/hydroxyapatites of various concentrations/fibroin blending
The mass ratio of liquid, wherein nano-cellulose whisker/hydroxyapatite nano-complex particle and fibroin is 65:35；
（5）By step（4）In the blending of obtained mass concentration highest nano-cellulose whisker/hydroxyapatite/fibroin
Solution is poured into homemade mould, after the quenching of liquid nitrogen condition, in -75 DEG C of freeze-dryings, then by other blend solutions according to matter
The order of amount concentration from high to low is successively freeze-dried, and the porous bone biomimetic material of density and porosity distribution gradient is made,
The bone biomimetic material is made up of carboxylated nano-cellulose whisker, hydroxyapatite and Bombyx mori Silk Fibroin, and its mass ratio is 1:8:6,
Its density gradient is respectively 81.6%, 63.2%, 24.9% from outside to inside, and its porosity gradient is respectively 19.4% from outside to inside,
37.5%, 75.3%, the mechanical property and porosity of the bone biomimetic material of preparation are as shown in table 1, its nano-cellulose whisker/hydroxyl
The SEM photograph of the structure of apatite compound particle such as Fig. 4（Multiplication factor is 20,000 times in figure）It is shown, as seen from Figure 4,
Nano-cellulose whisker is not observed in the visual field, the yardstick of hydroxyapatite its length 50-300 nanometers, width is in 10-50
Nanometer.
The performance for the bone biomimetic material that table 1 is built by the nano-cellulose whisker of mineralising
Therefore, the present invention obtains, by the bone biomimetic material of the nano-cellulose whisker structure of mineralising, in structure having big
The micropore that the nanometer that interconnects arrives micro-meter scale, and the porosity with graded are measured, in abundant bionical nature bone
The distributed architecture of compact bone and cancellous bone.Fibroin albumen with good biocompatibility is have selected on composition and function is excellent
The carboxy methylation nano-cellulose whisker of change, enhance the compression strength and toughness of hydroxyapatite.The method according to the invention
The bone biomimetic material of preparation has good mechanical property, good formability and rational porosity, can be used as embedded type
Degradable bone renovating material.
Claims (5)
- A kind of 1. bone biomimetic material that nano-cellulose whisker by mineralising is built, it is characterised in that：The bone biomimetic material by Carboxylated nano-cellulose whisker, hydroxyapatite and Bombyx mori Silk Fibroin composition, carboxylated nano-cellulose whisker, hydroxyapatite Mass ratio with Bombyx mori Silk Fibroin is 1:1-10:0.5-5, the bone biomimetic material that the nano-cellulose whisker by mineralising is built Preparation method, carry out according to the following steps：（1）By in the ethanol solution of nano-cellulose whisker ultrasonic disperse to 0.1-2mol/L sodium hydroxides, bath raio 1:500, Alkalize 10-120 min at 20-80 DEG C, adds 0.125-2.5 mol/L sodium chloroacetate solution, surpasses at 30-75 DEG C Sound stirs 15-100min, and adjusts solution ph to be dialysed three days to neutrality and in distilled water with 0.1-0.5mol/L hydrochloric acid, obtains The nano-cellulose whisker suspension solution being modified to carboxylated；（2）The ratio between amount according to calcium phosphorus substance is 1.67, by 0.01-0.1mol/L Ca (OH)2With diluting H3PO4Solution drips Fixed tube instills step simultaneously（1）1-6h is stirred in obtained solution and in ultrasound, ammoniacal liquor is added dropwise and controls the pH value in reaction to be 8.0~10.0, controlling reaction temperature is 20-80 DEG C, obtains nano-cellulose whisker/hydroxyapatite ratio as 1：1-10's answers Close particle suspension；（3）By step（2）The nano-cellulose whisker of gained/hydroxyapatite nano-complex particle suspension is stored at room temperature 48 is small When after remove supernatant liquor, centrifuge out sediment, distillation water washing three times after, be freeze-dried that nano-cellulose is made is brilliant Palpus/hydroxyapatite compound particle；（4）By step（3）In resulting nano-cellulose whisker/hydroxyapatite compound particle ultrasonic disperse be respectively to concentration 5%-15%, 35%-45%, 55%-65% Bombyx mori Silk Fibroin solution, obtain nano-cellulose whisker/hydroxyapatites of various concentrations/ The mass ratio of fibroin blend solution, wherein nano-cellulose whisker/hydroxyapatite nano-complex particle and fibroin is 65:35；（5）By step（4）In obtained mass concentration highest nano-cellulose whisker/hydroxyapatite/fibroin blend solution Pour into homemade mould, after the quenching of liquid nitrogen condition, in -50--80 DEG C of freeze-dryings, then by other blend solutions according to matter The order of amount concentration from high to low is successively freeze-dried, and the porous bone biomimetic material of density and porosity distribution gradient is made.
- 2. the bone biomimetic material that the nano-cellulose whisker according to claim 1 by mineralising is built, it is characterised in that：Institute The interconnected nanometer micropore containing gradient distribution in bone biomimetic material is stated, the porosity gradient of nanometer micropore divides from outside to inside Wei not 17.7%-24.7%, 32.8%-42.6%, 69.4-88.4%.
- 3. the bone biomimetic material that the nano-cellulose whisker according to claim 1 by mineralising is built, it is characterised in that：Institute The draw ratio for stating carboxylated nano-cellulose whisker is 20:1-10:1, the inherent viscosity of the Bombyx mori silk fibroin molecule is more than Or equal to 0.50, needle-like distribution is presented in described hydroxyapatite, and its particle length is in 50-300nm, and particle width is in 10- 50nm。
- 4. the bone biomimetic material that the nano-cellulose whisker according to claim 1 by mineralising is built, it is characterised in that：Institute State hydroxyapatite and nano-cellulose whisker is self-assembly of compound particle.
- 5. the bone biomimetic material that the nano-cellulose whisker according to claim 1 by mineralising is built, it is characterised in that：Institute The volumetric concentration for stating ethanol solution is 85%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510545412.8A CN105148324B (en) | 2015-08-31 | 2015-08-31 | Bone biomimetic material that a kind of nano-cellulose whisker by mineralising is built and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510545412.8A CN105148324B (en) | 2015-08-31 | 2015-08-31 | Bone biomimetic material that a kind of nano-cellulose whisker by mineralising is built and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105148324A CN105148324A (en) | 2015-12-16 |
| CN105148324B true CN105148324B (en) | 2018-02-16 |
Family
ID=54789574
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510545412.8A Expired - Fee Related CN105148324B (en) | 2015-08-31 | 2015-08-31 | Bone biomimetic material that a kind of nano-cellulose whisker by mineralising is built and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105148324B (en) |
Families Citing this family (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 |
| KR102455255B1 (en) * | 2017-02-28 | 2022-10-18 | 신토고교 가부시키가이샤 | Method for producing a composite material molded article containing acicular hydroxyapatite and a composite material molded article |
| 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 |
| CN109810255B (en) * | 2019-01-23 | 2019-12-03 | 三峡大学 | A kind of method of modifying of plant fiber |
| CN112870447B (en) * | 2021-01-08 | 2022-03-11 | 东华大学 | Bone regeneration multi-bionic scaffold material and preparation method thereof |
| CN114870099B (en) * | 2022-03-30 | 2022-11-22 | 浙江大学 | All-natural polysaccharide-based degradable composite bone screw material with oriented-concentric circle structure and preparation method thereof |
| CN114949375B (en) * | 2022-05-05 | 2023-06-30 | 同济大学 | Biomimetic mineralized nano cellulose film and preparation method and application thereof |
| CN114891342B (en) * | 2022-05-31 | 2023-07-25 | 重庆大学 | Application of shape memory polyurethane composite material in preparation of bone tissue engineering biological material |
| CN115737911B (en) * | 2022-12-16 | 2024-06-21 | 华南理工大学 | High-strength and high-toughness bone repair composite material and preparation method thereof |
Citations (3)
| 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 |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FI20116163L (en) * | 2011-11-23 | 2013-05-24 | Upm Kymmene Corp | Method and system for making cellulosic material |
-
2015
- 2015-08-31 CN CN201510545412.8A patent/CN105148324B/en not_active Expired - Fee Related
Patent Citations (3)
| 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 |
| 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 |
|---|
| 棒状纳米纤维素仿生矿化及光谱分析;曲萍等;《光谱学与光谱分析》;20120515;第32卷(第5期);第1418页左栏末段至右栏第1段 * |
| 纤维素纳米晶须/柞蚕丝素纳米纤维是制备与表征;何建新等;《东华大学学报（自然科学版）》;20140615;第40卷(第3期);第259页左栏第1-6段、第261页右栏第1段 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105148324A (en) | 2015-12-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105148324B (en) | Bone biomimetic material that a kind of nano-cellulose whisker by mineralising is built and preparation method thereof | |
| Yuan et al. | A novel bovine serum albumin and sodium alginate hydrogel scaffold doped with hydroxyapatite nanowires for cartilage defects repair | |
| Rajzer et al. | Layered gelatin/PLLA scaffolds fabricated by electrospinning and 3D printing-for nasal cartilages and subchondral bone reconstruction | |
| Esmaeili et al. | An artificial blood vessel fabricated by 3D printing for pharmaceutical application | |
| WO2018072679A1 (en) | Biomimetic biomineralized artificial bone repair material and preparation method therefor and use thereof | |
| Fan et al. | Silk materials for medical, electronic and optical applications | |
| US11696974B2 (en) | Method for preparing a functionally gradient material for guided periodontal hard and soft tissue regeneration | |
| CN105169475A (en) | Preparation method of biomimetic bone material containing graphene, hydroxyapatite and fibroin | |
| CN1301137C (en) | Silk fibrin and hydroxyapatite compound material and preparation process thereof | |
| Jiang et al. | Preparation of cellulose nanocrystal/oxidized dextran/gelatin (CNC/OD/GEL) hydrogels and fabrication of a CNC/OD/GEL scaffold by 3D printing | |
| Jiang et al. | Preparation of cellulose nanofiber-reinforced gelatin hydrogel and optimization for 3d printing applications. | |
| Liu et al. | 3D-printed porous PEEK scaffold combined with CSMA/POSS bioactive surface: A strategy for enhancing osseointegration of PEEK implants | |
| CN109260522A (en) | A kind of biodegradable hard tissue repair compound rest and preparation method thereof of 3D printing technique preparation | |
| CN105521525B (en) | A kind of bone tissue engineer porous compound support frame and preparation method thereof | |
| Zhang et al. | 3D-printed pre-tapped-hole scaffolds facilitate one-step surgery of predictable alveolar bone augmentation and simultaneous dental implantation | |
| HUE031178T2 (en) | Biomimetic collagen-hydroxyapatite composite material | |
| CN104984393B (en) | A kind of bone tissue engineering stent material and preparation method thereof | |
| CN107320787A (en) | A kind of periodontal reparation porous fibre membrane material and preparation method thereof | |
| CN107213529A (en) | A kind of preparation method for being used to improve the degradable medical polymer three-dimensional material of Gegenbaur's cell adhesion and bone formation performance | |
| CN106860916B (en) | GO/nHA/collagen composite bone repair material and preparation method thereof | |
| CN110639063A (en) | Mineralized collagen bionic bone repair material modified by hyaluronic acid oligosaccharide | |
| Liao et al. | Preparation, characterization and properties of nano-hydroxyapatite/polypropylene carbonate biocomposite | |
| CN114504407A (en) | 3D printing skull repairing titanium mesh containing growth factors and preparation method thereof | |
| ITMI20092073A1 (en) | COMPOSITE BIO-MIMETIC MATERIALS, RELATED PREPARATION PROCESS AND THEIR USE FOR THE IMPLEMENTATION OF MONO-, BI- OR MULTI-LAYER STRUCTURES FOR THE REGENERATION OF BONE, CARTILAGE OR OSTEOCARTILAGE | |
| Yan et al. | An interference screw made using a silk fibroin-based bulk material with high content of hydroxyapatite for anterior cruciate ligament reconstruction in a rabbit model |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Shao Weili Inventor after: Liu Fan Inventor after: Mei Shuo Inventor after: He Jianxin Inventor after: Wang Lidan Inventor after: Ding Bin Inventor after: Cui Shizhong Inventor before: He Jianxin Inventor before: Han Qiming Inventor before: Tan Weilin Inventor before: Zhou Yuman Inventor before: Wang Lidan Inventor before: Lian Yanping Inventor before: Ding Bin Inventor before: Cui Shizhong |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180216 Termination date: 20210831 |