CN108452375A - A kind of graphene oxide conductive hydrogel of 3D printing and its preparation method and application - Google Patents
A kind of graphene oxide conductive hydrogel of 3D printing and its preparation method and application Download PDFInfo
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/22—Polypeptides or derivatives thereof, e.g. degradation products
- A61L27/222—Gelatin
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/08—Carbon ; Graphite
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/18—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/52—Hydrogels or hydrocolloids
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/56—Porous materials, e.g. foams or sponges
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y80/00—Products made by additive manufacturing
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/20—Materials or treatment for tissue regeneration for reconstruction of the heart, e.g. heart valves
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/30—Materials or treatment for tissue regeneration for muscle reconstruction
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/32—Materials or treatment for tissue regeneration for nerve reconstruction
Abstract
The present invention discloses a kind of preparation method of the graphene oxide conductive hydrogel of 3D printing, includes the following steps：(1) marking ink is prepared：The gelatin-compounded object of polycaprolactone, acrylic modified gelatin, graphene oxide and photoinitiator are added in deionized water, are uniformly mixed, marking ink is made, is preserved for use；(2) design and loading 3D models：With 3DS Max Software Design Models, the model is imported into 3D printer control software, slicing treatment simultaneously designs internal print structure；(3) prepared by 3D printing：Marking ink made from step (1) is transferred in the extruded tube of 3D printer, prints and graphene oxide conductive hydrogel first product is made, immediately after with UV radiation curing to get the graphene oxide conductive hydrogel.The present invention realizes the preparation of internal fine structure and the controllable conductive hydrogel of external structure, and the porosity height of this conductive hydrogel, toughness, elasticity are good, have preferable biocompatibility and electric conductivity.
Description
Technical field
The present invention relates to a kind of hydrogel more particularly to a kind of graphene oxide conductivity waters prepared based on 3D printing technique
Gel and its preparation method and application.
Background technology
Organizational engineering is one and is related to the multi-field new branch of science such as life science, engineering science and materialogy.Group weaver
The basic principle of journey is：Seed cell is attached on the biomaterial with good biocompatibility, growth factor is passed through
Stimulation and induction promote proliferation and the differentiation of seed cell, and at the same time, biomaterial is gradually degraded and absorbed, and ultimately forms
Respective organization with certain function form and organ realize tissue repair, reconstruction, regenerated target.Electro photoluminescence is adjustable thin
The multi-functional (such as stick, be proliferated, migrate and break up) of born of the same parents, and conducting polymer can be passed intelligently due to its unique electric conductivity
Delivery cell electrochemical signals, are widely used in field of tissue engineering technology.Hydrogel is a major class material of tissue engineering bracket, tool
Structure, good biocompatibility and the superior drug conveying carrier for having similar cell epimatrix, in soft tissue structure and device
It has a good application prospect in terms of official's regeneration.Extraneous physics and chemical factor for example temperature, pH value, light, electricity, magnetic, sound, power and
Under the stimulation of chemical substance etc., self property such as phase, volume, shape, optics, mechanics, electric field, the table of certain polyalcohol hydrogels
Area, reaction rate and recognition performance etc. will change therewith, while externally acting, this to have to extraneous environmental change
The hydrogel of stimulating responsive becomes intelligent aqueous gel.Intelligent aqueous gel is to integrate perception, driving and information processing, is formed
A kind of functional material similar to organism, with intelligent attributes.In recent years, conductive hydrogel is as intelligent aqueous gel family
A member is widely paid close attention to by people.Currently, being concentrated mainly in mechanical performance and loading performance to the research of hydrogel, to water
The research of gel internal fine structure extremely lacks, and the difference of internal structure can cause hydrogel in mechanical strength, drug control
Release and cell culture etc. there are significant differences.The existing method for preparing conductive hydrogel can often encounter hydrogel shaping speed
Slowly, poor mechanical property and the problems such as not good enough electric conductivity.
For this purpose, the present invention provides a kind of conductive hydrogel that can be prepared with 3D printing technique, conductivity water is on the one hand realized
Prepared by structure (including external structure and internal structure) controllableization of gel, can be according to the physiological property of human body specific organization organ
Matching preparation is carried out, the electric conductivity of hydrogel is on the other hand improved, is with a wide range of applications in biomedicine.
Invention content
It is an object of the invention to solve above-mentioned shortcoming and defect of the existing technology, a kind of oxidation of 3D printing is provided
Graphene conductive hydrogel and its preparation method and application.
To solve its technical problem, the technical solution adopted in the present invention is：A kind of graphene oxide of 3D printing is conductive
The preparation method of hydrogel, includes the following steps：
(1) marking ink is prepared：By the gelatin-compounded object of polycaprolactone-, acrylic modified gelatin, graphene oxide and
Photoinitiator is added in deionized water, is uniformly mixed, and marking ink is made, and preserves for use；
(2) design and loading 3D models：With 3DS Max Software Design Models, the model is imported into 3D printer control
Software, slicing treatment simultaneously design internal print structure；
(3) prepared by 3D printing：Marking ink made from step (1) is transferred in the extruded tube of 3D printer, printing system
Graphene oxide conductive hydrogel first product is obtained, immediately after with UV radiation curing to get the graphene oxide conductivity water
Gel.
Preferably, the 3D printer is extrusion type biology 3D printer.
The present invention prepares conductive hydrogel using the gelatin-compounded object of polycaprolactone-and acrylic modified gelatin as base-material,
The shaping speed of conductive hydrogel is effectively improved, and the base-material of the present invention is suitable for 3D printing technique, realizes conductivity water
Prepared by the structure-controllableization of gel, conductive hydrogel obtained has good biocompatibility.The gelatin-compounded object of polycaprolactone-
It is the combination product of polycaprolactone and gelatin, with degradation rate and biocompatibility that tissue engineering bracket needs, solves list
Existing degradation and biocompatibility issues when with polycaprolactone or gelatin is applied alone；Acrylic modified gelatin is to use methyl
Acrylic acid gelatin is modified after product, effectively improve the physicochemical property of gelatin, can be in normal body temperature condition
It is lower to keep gel form for a long time.Under the collective effect of ultraviolet light and photoinitiator, acrylic modified gelatin can with it is poly-
The gelatin-compounded object of caprolactone-crosslinks, generating structure stabilization, the conductive water-setting with good mechanical properties and high porosity
Glue.
The preferred embodiment of preparation method as graphene oxide conductive hydrogel of the present invention, the marking ink
The mass-volume concentration of raw material components is：Gelatin-compounded 0.05~the 0.1g/mL of object of polycaprolactone-, acrylic modified gelatin
0.2~1mg/mL of 0.03~0.05g/mL, 0.05~0.3mg/mL of graphene oxide and photoinitiator.The present inventor passes through creation
Property labour obtain with good printing effect and solidification effect formula, wherein when the height of printer model be more than 5mm when,
Under the premise of inventive formulation, the gelatin-compounded object of polycaprolactone-of higher concentration is chosen；When the internal structure of printer model is more smart
When close, under the premise of inventive formulation, the acrylic modified gelatin of higher concentration is chosen.The graphene oxide it is dense
When degree is 0.05~0.3mg/mL, the electric conductivity of hydrogel is preferable, and toxicity is smaller, will not do harm to huamn body.It is described
Photoinitiator can adjust the modulus change of hydrogel, when a concentration of 0.2~1mg/mL of the photoinitiator, the solidification of hydrogel
Effect is preferable, and will not do harm to huamn body.When hydrogel is used for soft tissue, under the premise of inventive formulation, choose
The photoinitiator of low concentration.
The preferred embodiment of preparation method as graphene oxide conductive hydrogel of the present invention, in the step (3)
The print temperature of 3D printing is 26 DEG C, and print speed is 10~15mm/s, and printing pressure is 0.4~0.8kPa, print platform
Temperature is 30 DEG C, a diameter of 0.25~0.4mm of printing head.The present inventor obtains that 3D printing is suitble to prepare by creative work
The print conditions of the graphene oxide conductive hydrogel enable graphene oxide conductive hydrogel obtained effectively to cure
Molding, and there is fine internal structure and good biocompatibility.
The preferred embodiment of preparation method as graphene oxide conductive hydrogel of the present invention, in the step (3)
Cure the magnetic resonance development hydrogel first product using the irradiation of 380nm ultraviolet radiator, irradiation time is 3~6min.
The preferred embodiment of preparation method as graphene oxide conductive hydrogel of the present invention, the step (1) will
Marking ink obtained is placed in 34 DEG C of water-baths and preserves for use.
The preferred embodiment of preparation method as graphene oxide conductive hydrogel of the present invention, the graphene oxide
For stannic oxide/graphene nano piece.The stannic oxide/graphene nano piece is a kind of excellent conductive material, possesses abundant functional group,
With excellent drug carrying ability, moreover it is possible to which the mechanical performance for effectively promoting conductive hydrogel enhances the flexibility of conductive hydrogel.
Existing preparation side can be used in the gelatin-compounded object of polycaprolactone-of the present invention and acrylic modified gelatin
Method is prepared, and can also be obtained by modes such as purchases, and the present invention is not construed as limiting it, implements the protection all in the present invention
Within the scope of.
Preferably, the preparation method of the gelatin-compounded object of the polycaprolactone-is：Dimethyl sulfoxide (DMSO) is added in the gelatin of purifying
(DMSO) in, 65 DEG C are heated to, is made into the gelatin solution that mass fraction is 18%；By polycaprolactone and isophorone diisocyanate
Ester is uniformly mixed and is dissolved in dimethyl sulfoxide (DMSO), obtains solution A；Two bays of 10~20 drops are added dropwise into institute's gelatine solution
After sour dibutyl tin catalyst, the solution A is slowly added dropwise, 65 DEG C of 6~7h of high-speed stirred after reaction shift product
It is deposited in n-hexane into chloroform, then by product, is dried in vacuo, obtains the gelatin-compounded object of the polycaprolactone-.Preferably,
The molecular weight of the polycaprolactone is 1000~9000；Preferably, the mass ratio of the polycaprolactone and gelatin is 1:1, it is described
The volume ratio of gelatin solution and the solution A is 1:1, the mass ratio of the polycaprolactone and isophorone diisocyanate is
30:1。
Preferably, the preparation method of the acrylic modified gelatin is：By 2g purifying Gelatin in pH=7~
In 8 PBS solution, it is made into the gelatin solution that mass fraction is 10%；0.7~1.0mL is slowly added dropwise into institute's gelatine solution
Methacrylic acid, 50 DEG C, high-speed stirred 4h of maintaining reaction temperature, after reaction, to reaction system be added 3 times of volumes institute
PBS solution is stated, room temperature is dialysed 5 days, and freeze-drying obtains the acrylic modified gelatin.Preferably, the PBS solution
PH=7.3.
The present invention also provides a kind of graphene oxide conductive hydrogels of 3D printing, by graphite oxide of the present invention
The preparation method of alkene conductive hydrogel is made.
Graphene oxide conductive hydrogel of the present invention has the characteristic of hydrogel and good electric conductivity, can be used as
Tissue engineering bracket is applied to organizational project and repairs field, the especially application in the tissue repairs such as cardiac muscle and nerve.
Compared with prior art, beneficial effects of the present invention are：The preparation method of the present invention combines 3D printing technique, energy
According to the personalized printer model of the physiological property of human tissue organ and physicochemical property structure, realize internal fine structure and
The preparation of the controllable conductive hydrogel of external structure, to realize the effectively treatment of the personalization in terms of organizational project reparation,
Clinical demand with different patients.The graphene oxide conductive hydrogel made from preparation method of the present invention draws in ultraviolet light and light
The rapid solidifying and setting of energy under the action of hair agent, porosity is high, and toughness and elasticity are good, has preferable biocompatibility and conduction
Property, nutrition and metabolism channel can be provided for the growth of cell, can be cell growth in the specific organizations such as nerve, muscle and cardiac muscle
Special microenvironment needed for providing.
Description of the drawings
Fig. 1 is the principle of crosslinking figure of graphene oxide conductive hydrogel of the present invention；
Fig. 2 is the shape assumption diagram of the graphene oxide conductive hydrogel of the embodiment of the present invention 1；
Fig. 3 is the shape assumption diagram of the graphene oxide conductive hydrogel of the embodiment of the present invention 2；
Fig. 4 is the elasticity modulus test result figure of graphene oxide conductive hydrogel of the present invention；
Fig. 5 is the storage modulus test result figure of the graphene oxide conductive hydrogel of the embodiment of the present invention 1~3；
Fig. 6 is the loss modulus test result figure of the graphene oxide conductive hydrogel of the embodiment of the present invention 1~3；
Fig. 7 is scanning electron microscope (SEM) figure of the graphene oxide conductive hydrogel of the embodiment of the present invention 1；
Fig. 8 is scanning electron microscope (SEM) figure of the graphene oxide conductive hydrogel of the embodiment of the present invention 2；
Fig. 9 is scanning electron microscope (SEM) figure of the graphene oxide conductive hydrogel of the embodiment of the present invention 3；
Figure 10 is the cytotoxicity experiment result figure of graphene oxide conductive hydrogel of the present invention.
Specific implementation mode
The photoinitiator of the embodiment of the present invention is 2,2- dimethoxy -2- phenyl acetophenones.
The present invention provides a kind of preparation method of the gelatin-compounded object of polycaprolactone-, includes the following steps：
(1) it is added in the gelatin and dimethyl sulfoxide (DMSO) of purifying in flask, is heated to 65 DEG C, it is 18% to be made into mass fraction
Gelatin solution；
(2) polycaprolactone is uniformly mixed with isophorone diisocyanate and is dissolved in dimethyl sulfoxide (DMSO), obtained molten
The mass ratio of liquid A, polycaprolactone and gelatin is 1:1, the volume ratio of gelatin solution and solution A is 1:1, polycaprolactone and different Fo Er
The mass ratio of ketone diisocyanate is 30:1, the molecular weight of the polycaprolactone is 1000~9000；
(3) it after the dibutyltin dilaurate catalyst of 15 drops being added dropwise in gelatine solution upwards, is slowly added dropwise above-mentioned molten
Liquid A, product is transferred in chloroform by 65 DEG C of high-speed stirred 6.5h after reaction, then product is deposited in n-hexane, very
Sky is dry, obtains the gelatin-compounded object of the polycaprolactone-.
The present invention provides a kind of preparation method of acrylic modified gelatin, includes the following steps：
(1) using the PBS solution of pH=7.3 as solvent, the gelatin of 2g purifying is added, prepares the gelatin that mass fraction is 10%
Solution；
(2) methacrylic acid for measuring 1.0mL, is slowly added in the gelatin solution of step (1), maintaining reaction temperature 50
DEG C, the PBS solution of the pH=7.3 of 3 times of volumes is added after reaction in high-speed stirred 4h, and room temperature is dialysed 5 days, freeze-drying,
Obtain the acrylic modified gelatin.
Embodiment 1
A kind of preparation method of the graphene oxide conductive hydrogel of 3D printing, includes the following steps：
(1) marking ink is prepared：Using deionized water as solvent, the gelatin-compounded object of polycaprolactone-is added, methacrylic acid changes
Property gelatin, stannic oxide/graphene nano piece and photoinitiator, under magnetic stirring uniformly mixing, be made marking ink, be placed on 34 DEG C
It is preserved in water-bath for use；The mass-volume concentration of the raw material components of marking ink is：The gelatin-compounded object 0.05g/ of polycaprolactone-
ML, acrylic modified gelatin 0.03g/mL, stannic oxide/graphene nano piece 0.05mg/mL and photoinitiator 0.2mg/mL；
(2) design and loading 3D models：For clinical common injury model, modelling is carried out with 3DS Max softwares,
Then model is imported into 3D printer control software, slicing treatment simultaneously designs internal print structure；
(3) prepared by 3D printing：Marking ink made from step (1) is transferred in printer extruded tube, printer uses
Extrusion type biology 3D printer, set print temperature as 26 DEG C, print speed 10mm/s, printing pressure be 0.4kPa and printing
The temperature of platform is 30 DEG C, a diameter of 0.25mm of printing head, prints and graphene oxide conductive hydrogel first product is made, then stand
Original shape is fixed with 380nm ultraviolet radiator irradiation 3min, obtains graphene oxide conductive hydrogel.
Electric conductivity measuring is carried out to the graphene oxide conductive hydrogel of the present embodiment with Malvern granularity potentiometer, is measured
Three times, mean value is taken.Measurement result：The conductivity of the graphene oxide conductive hydrogel of the present embodiment is 2.09 ± 0.41 × 10-4S
cm-1。
Embodiment 2
A kind of preparation method of the graphene oxide conductive hydrogel of 3D printing, includes the following steps：
(1) marking ink is prepared：Using deionized water as solvent, the gelatin-compounded object of polycaprolactone-is added, methacrylic acid changes
Property gelatin, stannic oxide/graphene nano piece and photoinitiator, under magnetic stirring uniformly mixing, be made marking ink, be placed on 34 DEG C
It is preserved in water-bath for use；The mass-volume concentration of the raw material components of marking ink is：The gelatin-compounded object 0.08g/ of polycaprolactone-
ML, acrylic modified gelatin 0.04g/mL, stannic oxide/graphene nano piece 0.1mg/mL and photoinitiator 0.4mg/mL；
(2) design and loading 3D models：For clinical common injury model, modelling is carried out with 3DS Max softwares,
Then model is imported into 3D printer control software, slicing treatment simultaneously designs internal print structure；
(3) prepared by 3D printing：Marking ink made from step (1) is transferred in printer extruded tube, printer uses
Extrusion type biology 3D printer, set print temperature as 26 DEG C, print speed 12mm/s, printing pressure be 0.6kPa and printing
The temperature of platform is 30 DEG C, a diameter of 0.3mm of printing head, prints and graphene oxide conductive hydrogel first product is made, then stand
Original shape is fixed with 380nm ultraviolet radiator irradiation 5min, obtains graphene oxide conductive hydrogel.
Electric conductivity measuring is carried out to the graphene oxide conductive hydrogel of the present embodiment with Malvern granularity potentiometer, is measured
Three times, mean value is taken.Measurement result：The conductivity of the graphene oxide conductive hydrogel of the present embodiment is 4.55 ± 0.19 × 10-4S
cm-1。
Embodiment 3
A kind of preparation method of the graphene oxide conductive hydrogel of 3D printing, includes the following steps：
(1) marking ink is prepared：Using deionized water as solvent, the gelatin-compounded object of polycaprolactone-is added, methacrylic acid changes
Property gelatin, stannic oxide/graphene nano piece and photoinitiator, under magnetic stirring uniformly mixing, be made marking ink, be placed on 34 DEG C
It is preserved in water-bath for use；The mass-volume concentration of the raw material components of marking ink is：The gelatin-compounded object 0.1g/ of polycaprolactone-
ML, acrylic modified gelatin 0.05g/mL, stannic oxide/graphene nano piece 0.3mg/mL and photoinitiator 1mg/mL；
(2) design and loading 3D models：For clinical common injury model, modelling is carried out with 3DS Max softwares,
Then model is imported into 3D printer control software, slicing treatment simultaneously designs internal print structure；
(3) prepared by 3D printing：Marking ink made from step (1) is transferred in printer extruded tube, printer uses
Extrusion type biology 3D printer, set print temperature as 26 DEG C, print speed 15mm/s, printing pressure be 0.8kPa and printing
The temperature of platform is 30 DEG C, a diameter of 0.4mm of printing head, prints and graphene oxide conductive hydrogel first product is made, then stand
Original shape is fixed with 380nm ultraviolet radiator irradiation 6min, obtains graphene oxide conductive hydrogel.
Electric conductivity measuring is carried out to the graphene oxide conductive hydrogel of the present embodiment with Malvern granularity potentiometer, is measured
Three times, mean value is taken.Measurement result：The conductivity of the graphene oxide conductive hydrogel of the present embodiment is 1.09 ± 0.21 × 10-3S
cm-1。
Fig. 4 is graphene oxide conductive hydrogel made from preparation method of the present invention, under the photoinitiator of different content
Elasticity modulus test result figure.As can be seen from Figure 4, in graphene oxide conductive hydrogel of the invention, photoinitiator contains
Amount is higher, and mechanical performance is better, and its flexibility reduces, rigidity rises.
Measuring mechanical property is carried out to graphene oxide conductive hydrogel made from Examples 1 to 3, test result refers to
Shown in Fig. 5 and Fig. 6.Wherein, Fig. 5 is the storage modulus test result to hydrogel, and the G' in figure indicates storage modulus；From Fig. 5
It can be seen that, the graphene oxide conductive hydrogel of Examples 1 to 3 all has larger storage modulus, the especially oxygen of embodiment 3
Graphite alkene conductive hydrogel；Illustrate that hydrogel prepared by the embodiment of the present invention all has preferable storage elastic deformation energy
Ability, deformed resilience performance are preferable.Fig. 6 is the loss modulus test result to hydrogel, and the G " in figure indicates loss
Modulus.It can be seen that from Fig. 5 and Fig. 6, hydrogel prepared by the embodiment of the present invention has good mechanical performance, is suitable for group weaver
The fields Cheng Xiufu.
SEM scannings are carried out to graphene oxide conductive hydrogel made from Examples 1 to 3, Fig. 7 is the oxidation of embodiment 1
The scanning electron microscope (SEM) photograph of graphene conductive hydrogel, Fig. 8 are the scanning electron microscope (SEM) photograph of the graphene oxide conductive hydrogel of embodiment 2,
Fig. 9 is the scanning electron microscope (SEM) photograph of the graphene oxide conductive hydrogel of embodiment 3.
Can be seen that from the result of electron-microscope scanning, the embodiment of the present invention 1~3 prepare graphene oxide conductive hydrogel it is interior
Portion all has a large amount of pore space structures, and porosity is high, and the connectivity between hole is high, is conducive to the adherency and growth of cell, also sharp
In the transmission of nutriment and the metabolism of waste.
Cytotoxicity experiment is carried out to graphene oxide conductive hydrogel made from Examples 1 to 3 and (uses CCK-8ELISA
Kit carries out oxicity analysis)：The experimental result of embodiment 1 and embodiment 2 is as shown in Figure 10, the experimental result of embodiment 3 with
Embodiment 2 approaches.It can be seen that from experimental result, graphene oxide conductive hydrogel made from Examples 1 to 3 is to cell without bright
Aobvious toxicity inhibition effect, can preferably maintain the growth of cell.
Graphene oxide conductive hydrogel made from Examples 1 to 3 is tested by ISO101993 biocompatibilities, to skin
Skin is friendly.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than is protected to the present invention
The limitation of range is protected, although being explained in detail to the present invention with reference to preferred embodiment, those skilled in the art should
Understand, technical scheme of the present invention can be modified or replaced equivalently, without departing from the essence of technical solution of the present invention
And range.
Claims (10)
1. a kind of preparation method of the graphene oxide conductive hydrogel of 3D printing, which is characterized in that include the following steps：
(1) marking ink is prepared：The gelatin-compounded object of polycaprolactone-, acrylic modified gelatin, graphene oxide and light are drawn
It sends out agent to be added in deionized water, be uniformly mixed, marking ink is made, preserve for use；
(2) design and loading 3D models：With 3DS Max Software Design Models, the model is imported into 3D printer control software,
Slicing treatment simultaneously designs internal print structure；
(3) prepared by 3D printing：Marking ink made from step (1) is transferred in the extruded tube of 3D printer, prints and oxygen is made
Graphite alkene conductive hydrogel first product, immediately after with UV radiation curing to get the graphene oxide conductive hydrogel.
2. the preparation method of graphene oxide conductive hydrogel as described in claim 1, which is characterized in that the marking ink
The mass-volume concentrations of raw material components be：It is the gelatin-compounded 0.05~0.1g/mL of object of polycaprolactone-, acrylic modified bright
0.2~1mg/mL of 0.03~0.05g/mL of glue, 0.05~0.3mg/mL of graphene oxide and photoinitiator.
3. the preparation method of graphene oxide conductive hydrogel as described in claim 1, which is characterized in that the step (3)
The print temperature of middle 3D printing is 26 DEG C, and print speed is 10~15mm/s, and printing pressure is 0.4~0.8kPa, print platform
Temperature be 30 DEG C, a diameter of 0.25~0.4mm of printing head.
4. the preparation method of graphene oxide conductive hydrogel as described in claim 1, which is characterized in that the step (3)
Middle to cure the graphene oxide conductive hydrogel first product using the irradiation of 380nm ultraviolet radiator, irradiation time is 3~6min.
5. the preparation method of graphene oxide conductive hydrogel as described in claim 1, which is characterized in that the step (1)
Marking ink obtained is placed in 34 DEG C of water-baths and is preserved for use.
6. the preparation method of graphene oxide conductive hydrogel as claimed in claim 2, which is characterized in that the graphite oxide
Alkene is stannic oxide/graphene nano piece.
7. such as the preparation method of claim 1~6 any one of them graphene oxide conductive hydrogel, which is characterized in that institute
The preparation method for stating the gelatin-compounded object of polycaprolactone-is：The gelatin of purifying is added in dimethyl sulfoxide (DMSO), 65 DEG C is heated to, matches
The gelatin solution for being 18% at mass fraction；Polycaprolactone is uniformly mixed with isophorone diisocyanate and is dissolved in diformazan
In base sulfoxide, solution A is obtained；After the dibutyltin dilaurate catalyst of 10~20 drops is added dropwise into institute's gelatine solution, delay
Slowly the solution A is added dropwise, product is transferred in chloroform by 65 DEG C of 6~7h of high-speed stirred after reaction, then product is precipitated
Into n-hexane, vacuum drying obtains the gelatin-compounded object of the polycaprolactone-；Preferably, the molecular weight of the polycaprolactone is
1000~9000；Preferably, the mass ratio of the polycaprolactone and gelatin is 1:1, the body of institute's gelatine solution and the solution A
Product is than being 1:1, the mass ratio of the polycaprolactone and isophorone diisocyanate is 30:1.
8. such as the preparation method of claim 1~6 any one of them graphene oxide conductive hydrogel, which is characterized in that institute
The preparation method for stating acrylic modified gelatin is：By the Gelatin of 2g purifying in the PBS solution of pH=7~8, it is made into
The gelatin solution that mass fraction is 10%；The methacrylic acid of 0.7~1.0mL is slowly added dropwise into institute's gelatine solution, maintains
The PBS solution of 3 times of volumes is added to reaction system after reaction for 50 DEG C, high-speed stirred 4h of reaction temperature, and room temperature is saturating
Analysis 5 days, freeze-drying, obtains the acrylic modified gelatin.
9. a kind of graphene oxide conductive hydrogel of 3D printing, which is characterized in that by claim 1~8 any one of them
Preparation method is made.
10. application of the graphene oxide conductive hydrogel of 3D printing as claimed in claim 9 in organizational project reparation.
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