CN109718394A - Nano combined biological support in the multiple dimensioned hole of a kind of driving shape memory of photo-thermal and preparation method thereof - Google Patents
Nano combined biological support in the multiple dimensioned hole of a kind of driving shape memory of photo-thermal and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to intellectual material, composite function nano material and biomedical material technologies, disclose nano combined biological support in the multiple dimensioned hole of a kind of driving shape memory of photo-thermal and preparation method thereof.The method of the present invention the following steps are included: (1) using low molecular weight band carboxyl end group polylactic acid to graphene oxide carry out hydrophobically modified, obtain the graphene oxide of hydrophobically modified；(2) the graphene oxide of hydrophobically modified, biodegradable shape memory polymeric, rheological agent be added it is organic by form in solvent oil phase；Water is added in oily phase, mixing and emulsifying obtains the sticky pickering emulsion of water-in-oil type；(3) using the sticky pickering emulsion of water-in-oil type as ink, three-dimensional porous lotion bracket is obtained using extruded type 3D printing, it is dry, obtain compound bio bracket；It is made of multiple dimensioned hole, porosity 65-95%；There is excellent in shape memory performance under heating or two kinds of near infrared light stimulations, has good application prospect in field of tissue engineering technology.
Description
Technical field
The invention belongs to intellectual material, composite function nano material and biomedical material technology, in particular to one
Kind nano combined biological support in the multiple dimensioned hole of the driving shape memory of photo-thermal and preparation method thereof.
Background technique
Shape-memory polymer (SMPs) is that one kind can deform under specific external condition and be fixed into temporary shapes,
It can restore the intelligent polymer material of its original-shape again after by stimulation appropriate.SMPs is big with deformation quantity, molding adds
The characteristics such as work easy, structure designability strong, shape responsiveness is adjustable, light inexpensive, good corrosion resistance, so that this kind of material
Material has good application prospect in fields such as biomedicine, space flight and aviation, intelligence weaving, automatic controls.In numerous SMPs materials
In material, biodegradable shape memory polymeric (BSMPs) is excellent due to its nontoxicity, biocompatibility, biodegradable etc.
Point makes it be concerned and pay attention in the application of the field of tissue engineering technology such as such as drug loading, regeneration and reparation.Especially with
BSMPs is the multiporous biological bracket of host material building, and minimally invasive implantation not only may be implemented in field of tissue engineering technology application,
" from being adapted to " irregular defective tissue shape, also can avoid second operation, not only simplifies surgical procedures, and alleviate patient's
Pain and medical expense.
The BSMPs material of existing research is mostly thermal shape memory type, i.e., realizes material in such a way that thermostimulation drives
The shape memory function of material.However BSMPs material is directly heated using Environmental Heat Source, ambient temperature can be caused
Hot-spot is increased and is easy, when handling using BSMPs material of the mode that directly heats to implantation organism, easily
Surrounding biologic body tissue is caused to damage, thus is realized using " remote control stimulation " mode, that is, contactless induction induction heating
The shape memory effect of BSMPs, the application requirement that BSMPs will be made more to be able to satisfy field of tissue engineering technology.Compared with thermostimulation, light is
A kind of particularly attractive stimulus not only has intensity and the easy tonality of wavelength, also has convenient and fast contactless long-range behaviour
Control property, especially near infrared light are by feat of the penetrability and innocuousness to tissue, so that near infrared light driving shape note
Recall intellectual material to have broad application prospects in field of tissue engineering technology.
Graphene oxide is a kind of two-dimentional carbon nanomaterial of monoatomic layer thickness, has efficient photothermal conversion and good
Infrared luminous energy near infrared light optical absorption intensity with higher, and can be converted to thermal energy and form " heating by good heat conductivity
Device ".Therefore graphene oxide and thermotropic BSMPs is compound, the graphene oxide under Infrared irradiation in composite material absorbs
Thermal energy is converted to after infrared light, and then triggers BSMPs sub-chain motion and conformation change, to assign BSMPs optical drive shape note
Recall characteristic.Therefore graphene oxide carbon nanomaterial and BSMPs is compound, the shape near infrared light induction driving can be constructed
The nanocomposite of memory, i.e. composite material have the function of contactless induced shape-memory, so as to meet a group weaver
Journey etc. cannot directly heat the special applications requirement in field.Li Lulu is with graphene oxide and thermotropic BSMPs polylactic acid-trimethyl
Carbonate copolymer (PLMC) is raw material, constructs graphene oxide/PLMC shape memory function using high-voltage electrostatic spinning method
Nano compound stephanoporate membrane material, constructed porous film material have good shape-memory properties, high mechanical strength, good biological can
The characteristics of degradability, (Li Lulu, the preparation of graphene oxide/PLMC shape memory function film and performance study, Kunming medical courses in general were big
It learns, 2017).But the studies above has only been investigated Environmental Heat Source and has been directly heated to stimulate the shape memory for driving porous film material
Can, but shape-memory properties are driven without inquiring into the near infrared light stimulation of porous film material；In addition the research uses high-pressure electrostatic
The porous film material pore structure of spin processes building is single, size is difficult to control, and causes the more difficult accuracy controlling of internal pore structure, and structure
Time-consuming is built to be difficult to produce in enormous quantities.It is worth noting that, being applied to the material of field of tissue engineering technology, internal pore structure is very heavy
: connectivity between high porosity and good hole is conducive to the conveying of cytotrophy ingredient and metabolite excretion；Different pore size size
Play different important function, the hole (microcellular structure) of a few to tens of microns is conducive to cell adhesion, Cellular Signaling Transduction Mediated, thin
Born of the same parents' proliferation, several hundred microns of hole (macroporous structure) are conducive to cell migration, extracellular matrix aggregation and organize the formation of.That is
Applied to field of tissue engineering technology, excellent bionical tissue repair function is realized, tissue engineering bracket material needs to have higher
Porosity and connection multiple dimensioned pore structure.In summary, be highly desirable exploitation shape memory graphene oxide/
Convenient, the controllable construction method of the nano combined biologic bracket material in the multiple dimensioned hole BSMPs studies the photo-thermal driving shape of timbering material
Shape memory performance.
In numerous multiporous biological bracket constructing technologies, 3D printing technique is able to satisfy the multiporous biological branch of organizational project application
The requirement of frame aperture structure diversification carries out connectivity etc. bracket shape, aperture size, porosity, hole according to actual demand
Effective control.Therefore it can use 3D printing technique to construct the multiple dimensioned hole biological support of the fine organizational project of internal structure
Material realizes the application requirement of bracket individual character manufacturing.It is noted, however, that preparing bracket, structure using 3D printing technique
The micro-structure built is finer, that is, the precision printed is higher, and print speed is slower, has so as to cause 3D printing technique building micro-
The porous support materials of pore structure are very time-consuming.Therefore, research and development can be using 3D printing technique to effective, convenient, controllably structure
Building is highly desirable with photo-thermal driving shape memory graphene oxide/nano combined biologic bracket material in the multiple dimensioned hole BSMPs,
And it is up to the present rarely reported.
Summary of the invention
In order to overcome the shortcomings and deficiencies of the prior art described above, the primary purpose of the present invention is that providing a kind of photo-thermal driving
The preparation method of the nano combined biological support in the multiple dimensioned hole of type shape memory.
Nano combined biological support preparation of the invention is the water-in-oil type pik stable based on 3D printing hydrophobically modified GO
Woods lotion (in oily phase contain thermal shape memory biodegradable polyesters) template constructs multiple dimensioned hole nano-composite scaffolds.GO
For hydrophilic inorganic nanoparticle, the present invention carries out surface hydrophobicity to GO using low molecular weight carboxyl end group polylactic acid (PLLA) and repairs
Decorations, for preparing stable water-in-oil type pickering emulsion.3D printing shape is maintained in order to realize smoothly to print and stablize,
Pickering emulsion needs suitable viscosity and rheological characteristic, and the present invention determines that acquisition can be used as 3D printing by each group distribution ratio
The lotion of ink constructs stable porous lotion bracket, the fixed lotion of drying processing by pneumatic extruded type 3D printing
Template obtains photo-thermal and drives the nano combined biological support in the multiple dimensioned hole of shape memory.
Another object of the present invention is to provide the multiple dimensioned Kong Na of the driving shape memory of photo-thermal that the above method is prepared
Rice compound bio bracket.
Still a further object of the present invention is to provide the multiple dimensioned hole of the driving shape memory of above-mentioned photo-thermal nano combined biological support
Application in application in field of tissue engineering technology, especially drug loading and tissue engineering bracket, can directly disperse drug
Or it is dissolved in lotion, then timbering material is obtained by 3D printing.
The purpose of the present invention is realized by following proposal:
A kind of preparation method of the nano combined biological support in the multiple dimensioned hole of driving shape memory of photo-thermal, including following step
It is rapid:
(1) hydrophobically modified is carried out to graphene oxide (GO) using low molecular weight band carboxyl end group polylactic acid, obtains hydrophobic change
The graphene oxide of property；
(2) the graphene oxide of hydrophobically modified, BSMPs, rheological agent be added it is organic by form in solvent oil phase；Water plus
Enter in oily phase, mixing and emulsifying, obtains the sticky pickering emulsion of water-in-oil type；
(3) using the sticky pickering emulsion of water-in-oil type as ink, three-dimensional porous lotion branch is obtained using extruded type 3D printing
Frame, it is dry, obtain the nano combined biological support in the multiple dimensioned hole of the driving shape memory of photo-thermal.
In the oil phase, quality volume fraction of the BSMPs in oily phase is preferably 4-16w/v%.
In the oil phase, quality volume fraction of the graphene oxide of hydrophobically modified in oily phase is preferably 3-12w/v%.
In the oil phase, quality volume fraction of the rheological agent in oily phase is preferably 0.5-4w/v%.
The volume ratio of the water and oily phase is 1:2-3:1.
Preparation method of the present invention, mass ratio of the low molecular weight used with carboxyl end group polylactic acid and graphene oxide is preferably 3:
1-1:2。
Preparation method of the present invention, the graphene oxide are preferably the graphite oxide using improvement Hummers method preparation
Alkene.
Preparation method of the present invention, molecular weight of the low molecular weight with carboxyl end group polylactic acid preferably 5 × 102-1×104g/
Mol, more preferably 1500g/mol.
Preparation method of the present invention, the BSMPs are the biodegradable rouge of the synthesis with thermal shape memory effect
Fat adoption ester, including it is polylactic acid-carbonate copolymer, poly lactic-co-glycolic acid-carbonate copolymer, poly-
At least one of lactic acid-caprol acton-carbonate copolymer etc..The molecular weight of the BSMPs is preferably 1 × 104-
1.5×105g/mol。
Preparation method of the present invention, the rheological agent are hydrophobicity rheological agent, preferably hydrophobic nano-silica, second
At least one of base cellulose etc..
In step (1), the progress hydrophobically modified is specially by low molecular weight band carboxyl end group polylactic acid, graphene oxide
(GO) it is scattered in solvent, is uniformly mixed respectively, remove solvent, be heat-treated and obtain under inert atmosphere.
Further, the heat treatment preferably calcines 5-36h at 180-210 DEG C, more preferably calcines at 200 DEG C
5-24h。
Further, described be uniformly mixed can be realized by mechanical stirring.
Further, the solvent can be the organic solvents, preferably low boiling point high volatile solvent such as methylene chloride.
Further, the inert atmosphere can be nitrogen etc..
Further, the dispersion carries out preferably in ice-water bath.
In step (2), the preparation process of the oil phase carries out preferably in ice-water bath and under ultrasonication.The ultrasound
Preferably in 200W ultrasound 20min.
In step (2), the organic solvent is low boiling point high volatile solvent, preferably methylene chloride.
In step (2), the mixing and emulsifying can be by vortex mixer in 800-3500r/min vortex oscillation 2-
25min is realized.
In step (3), the process conditions that three-dimensional porous lotion bracket is obtained using extruded type 3D printing are as follows: squeeze gas
Pressure is 0.01-0.2MPa；The internal diameter of syringe needle is 210-1430 μm；Print speed is 2-50mm/s.
In step (3), the drying can be by drying at room temperature 30-50h, or is freeze-dried 8-20h, at preferably -50 DEG C
It is freeze-dried 8-20h.
In preparation method of the present invention, hydrophobically modified is carried out to graphene oxide using low molecular weight band carboxyl end group polylactic acid,
It is added into oily phase again, has both realized the stable dispersion of graphene oxide, while playing particle emulsification in emulsion preparation process
The excellent stability of lotion is realized in the effect of agent.Meanwhile the graphene oxide doped of hydrophobically modified is into BSMPs backing substrate,
The mechanical property of bracket can also be improved, so that the compound support frame material of building is in the biomedical neck such as field of tissue engineering technology
There is good application prospect in domain.
The method of the present invention preparation condition is mild, and operation is simple, and reproducible, lower to equipment requirement, method is convenient
Easy, raw material sources are abundant, are suitable for industrialized production, are able to achieve supporting structure and shape personalization constructs.
The nano combined biological support in the multiple dimensioned hole of the driving shape memory of the photo-thermal that the method for the present invention is prepared, by more rulers
Spend Kong Zucheng (including aperture be about 200-1500 μm connection macropore and aperture be about 5-100 μm micropore), porosity 65-
95%；Excellent in shape memory performance can be shown under heating or two kinds of near infrared light stimulations, while being had good
The multi-functional characteristics such as biocompatibility, biological degradability and drug delivered payload capability, shape personalizable design, can be applied to tissue
In engineering field, especially drug load or non-bearing tissue engineering bracket in application, directly drug can be dispersed or dissolved
Timbering material is obtained in lotion, then through 3D printing, has good application prospect in field of tissue engineering technology.
The present invention compared with the existing technology, have the following advantages and the utility model has the advantages that
(1) preparation process condition of the photo-thermal driving nano combined biological support in the multiple dimensioned hole of shape memory provided by the invention
Mildly, condition is controllable, and method is convenient easy, and raw material sources are abundant.It is constructed can 3D printing pickering emulsion to have be suitable for glutinous
Consistency and rheological characteristic, it can be achieved that at normal temperature 3D printing form, to simplify corresponding 3D printing process and apparatus structure to drop
Low production cost, and free from admixture component in the biological support prepared, just can be used directly without post-processing, and this method is suitable for industry
Metaplasia produces.
(2) compound bio bracket provided by the invention is fast near infrared light stimuli responsive, can efficiently absorb near infrared light,
The thermotropic BSMPs shape memory of heat-driven is converted light energy into, so that compound bio bracket be made to remember with photo-thermal double drive shape
Recall effect.Compound bio bracket i.e. provided by the present invention can long-range by near infrared light, contactless driving arm shape note
Recall effect, overcomes tradition and directly heat the bio-tissue damage for stimulating thermotropic shape-memory stents completion recovery of shape to easily cause
The defect of wound, widened bracket in fields such as organizational projects should range.
(3) GO not only acts as the function of photothermal converting agent in compound bio bracket, acts also as particle reinforcements, can be certain
Mechanical strength, shape crystallized ability and the recovery capacity that BSMPs is improved in degree, are conducive to mentioning for bracket shape-memory properties
It is high.
(4) technology of preparing designed by the present invention can carry out bracket according to different design stent model pore structures and shape
Personalization building can construct personalized bracket printer model according to the structure and shape of missing or injury tissue, and matching is not
With the clinical demand of patient, to realize the personalized effective treatment use of field of tissue engineering technology.The shape memory of bracket simultaneously
Energy, mechanical property and degradability etc. can be adjusted easily by changing the amount of BSMPs type, composition ratio and modified GO,
The glass transition temperature (i.e. shape memory temperature) of especially prepared bracket can be adjusted near body temperature, and recovery of shape is promoted to drive
Move it is easy to accomplish so that bracket the fields such as organizational project have applications well.
(5) the nano combined biological support in the multiple dimensioned hole of the driving shape memory of photo-thermal constructed by the present invention is near infrared light
There are excellent shape-memory properties under two kinds of incentive conditions of irradiation and heating, and also there is the biological support multiple dimensioned hole to tie
Structure, higher porosity, the characteristics such as good biocompatibility, biological degradability and superior drug delivered payload capability, while may be used also
Realize bracket personalized customization.Prepared biological support can play bionical when the fields of biomedicine such as organizational project are applied
Function realizes that minimally invasive implantation, near infrared light remotely stimulate recovery of shape, avoids second operation, this can facilitate the implementation of operation,
Also it can mitigate the pain of patient.Therefore the compound bio bracket that constructs of the present invention the fields of biomedicine such as organizational project have compared with
Good application prospect.
Detailed description of the invention
Fig. 1 is pickering emulsion bottle handstand digital photograph prepared by embodiment 1.
Fig. 2 is the digital photograph of the nano combined biological support in the multiple dimensioned hole of the driving shape memory of 1 photo-thermal of embodiment.
Fig. 3 is the scanning in the multiple dimensioned hole of the driving shape memory of 1 photo-thermal of embodiment nano combined biological support lines section
Electromicroscopic photograph.
Fig. 4 is the differential scanning calorimetry of the nano combined biological support in the multiple dimensioned hole of the driving shape memory of 1 photo-thermal of embodiment
Curve.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Material involved in the following example can be obtained from commercial channel.Dosage of each component in terms of mass parts, parts by volume,
g、mL。
Embodiment 1
(1) it is dispersed 2 mass parts graphene oxides in 20 parts by volume methylene chloride using ultrasonic treatment in ice-water bath,
It is subsequently added into dichloromethane solution (containing 2 mass parts PLLA) mixing of 20 parts by volume low molecular weight carboxyl end group polylactic acid (PLLA).
Mixed liquor is placed in ice-water bath under nitrogen protection using after 500r/min mechanical stirring 15min, is volatilized and is removed in 30 DEG C of water-baths
Methylene chloride is removed, then is placed in the tube furnace of nitrogen atmosphere and calcines the graphene oxide for obtaining hydrophobically modified for 24 hours for 200 DEG C.
(2) ultrasound 20min configures 3 parts by volume methylene chloride suspensions (i.e. oil in ice-water bath under the effect of 200W ultrasonic machine
Phase), wherein polylactic acid-carbonate copolymer (lactic acid, trimethylene carbonate molar ratio be 70:30, molecular weight 5
×104G/mol), modified graphene oxide, dewatering nano silica quality volume fraction be 10w/v%, 5w/v%,
1.5w/v%；5 parts by volume water are added portionwise in oily phase, emulsify 5min through 3000r/min vortex oscillation after mixing, obtain oil packet
The sticky pickering emulsion of water type.
(3) pickering emulsion that step (2) obtain is transferred to the pneumatic extrusion equipped with micro needle head (internal diameter is 820 μm)
In formula 3D printer syringe, set print speed as 30mm/s and printing air pressure be 0.05MPa, then according to the length being pre-designed
The printing of cube (30mm × 30mm × 4mm) stent model motion profile constructs three-dimensional porous lotion bracket, then through in -18 DEG C of refrigerators
Freezing is placed on dry 10h in -50 DEG C of refrigerators for 8 hours, obtains the nano combined life in the multiple dimensioned hole of the driving shape memory of photo-thermal
Object bracket.
Pickering emulsion prepared by the present embodiment has higher stickiness, also without flowing when even emulsion bottle is stood upside down
Property (see Fig. 1), lotion smoothly smooth printing and can keep printing shape using extruded type 3D printer (see Fig. 2).Through cold
Be lyophilized it is dry after obtain nano combined biological support have high porosity (up to 93.7%), (aperture is about for multiple dimensioned pore structure
The microcellular structure for being about 8-60 μm for 1000-1200 μm of macroporous structure and aperture, is shown in Fig. 3)；The glass transition temperature of bracket is
39.9 DEG C (see Fig. 4), and good shape-memory properties can be shown under heating or near infrared light irradiation.
Embodiment 2
(1) it is dispersed 4 mass parts graphene oxides in 40 parts by volume methylene chloride using ultrasonic treatment in ice-water bath,
It is subsequently added into dichloromethane solution (containing 2 mass parts PLLA) mixing of 20 parts by volume low molecular weight carboxyl end group polylactic acid (PLLA).
Mixed liquor is placed in ice-water bath under nitrogen protection using after 500r/min mechanical stirring 15min, is volatilized and is removed in 30 DEG C of water-baths
Methylene chloride is removed, then is placed in the tube furnace of nitrogen atmosphere and calcines the graphene oxide for obtaining hydrophobically modified for 24 hours for 200 DEG C.
(2) ultrasound 20min configures 4 parts by volume methylene chloride suspensions (i.e. oil in ice-water bath under the effect of 200W ultrasonic machine
Phase), wherein (molecular weight is 5 × 10 to polylactic acid-carbonate copolymer4G/mol, wherein lactic acid, trimethylene carbonate
Molar ratio be 70:30), modified graphene oxide, dewatering nano silica quality volume fraction be 10w/v%, 6w/
V%, 1.5w/v%；7 parts by volume water are added portionwise in oily phase, emulsify 7min through 3500r/min vortex oscillation after mixing, are obtained
The sticky pickering emulsion of water-in-oil type.
(3) pickering emulsion that step (2) obtain is transferred to the pneumatic extrusion equipped with micro needle head (internal diameter is 420 μm)
In formula 3D printer syringe, set print speed as 35mm/s and printing air pressure be 0.03MPa, then according to the length being pre-designed
The printing of cube (60mm × 30mm × 3mm) stent model motion profile constructs three-dimensional porous lotion bracket, then through freezing 3 in liquid nitrogen
Minute is placed in -50 DEG C of refrigerators dry 10h, obtains the nano combined biology branch in the multiple dimensioned hole of the driving shape memory of photo-thermal
Frame.
Embodiment 3
(1) it is dispersed 2 mass parts graphene oxides in 20 parts by volume methylene chloride using ultrasonic treatment in ice-water bath,
It is subsequently added into dichloromethane solution (containing 2 mass parts PLLA) mixing of 20 parts by volume low molecular weight carboxyl end group polylactic acid (PLLA).
Mixed liquor is placed in ice-water bath under nitrogen protection using after 500r/min mechanical stirring 15min, is volatilized and is removed in 30 DEG C of water-baths
Methylene chloride is removed, then is placed in the tube furnace of nitrogen atmosphere and calcines the graphene oxide for obtaining hydrophobically modified for 24 hours for 200 DEG C.
(2) ultrasound 20min configures 5 parts by volume methylene chloride suspensions (i.e. oil in ice-water bath under the effect of 200W ultrasonic machine
Phase), wherein polylactic acid-carbonate copolymer (molecular weight 5.3 × 104G/mol, wherein lactic acid, trimethylene carbonate
Molar ratio be 80:20), modified graphene oxide, ethyl cellulose quality volume fraction be 10w/v%, 6w/v%,
3.5w/v%；10 parts by volume water are added portionwise in oily phase, emulsify 15min through 3000r/min vortex oscillation after mixing, obtain oil
The sticky pickering emulsion of water-in type.
(3) pickering emulsion that step (2) obtain is transferred to the pneumatic extrusion equipped with micro needle head (internal diameter is 520 μm)
In formula 3D printer syringe, set print speed as 20mm/s and printing air pressure be 0.02MPa, then according to the circle being pre-designed
The printing of cylinder (60mm × 60mm × 3mm) stent model motion profile constructs three-dimensional porous lotion bracket, then through in -18 DEG C of refrigerators
Freezing is placed on dry 10h in -50 DEG C of refrigerators for 8 hours, obtains the nano combined life in the multiple dimensioned hole of the driving shape memory of photo-thermal
Object bracket.
Embodiment 4
(1) it is dispersed 2 mass parts graphene oxides in 20 parts by volume methylene chloride using ultrasonic treatment in ice-water bath,
It is subsequently added into dichloromethane solution (containing 2 mass parts PLLA) mixing of 20 parts by volume low molecular weight carboxyl end group polylactic acid (PLLA).
Mixed liquor is placed in ice-water bath under nitrogen protection using after 500r/min mechanical stirring 15min, is volatilized and is removed in 30 DEG C of water-baths
Methylene chloride is removed, then is placed in the tube furnace of nitrogen atmosphere and calcines the graphene oxide for obtaining hydrophobically modified for 24 hours for 200 DEG C.
(2) ultrasound 20min configures 4 parts by volume methylene chloride suspensions (i.e. oil in ice-water bath under the effect of 200W ultrasonic machine
Phase), wherein poly lactic-co-glycolic acid-polytrimethylene carbonate copolymer (molecular weight 3 × 104G/mol, wherein lactic acid, hydroxyl
Acetic acid, trimethylene carbonate molar ratio be 80:10:10), modified graphene oxide, dewatering nano silica, ethyl it is fine
The quality volume fraction of dimension element is 10w/v%, 5w/v%, 1w/v%, 1.5w/v%；8 parts by volume water are added portionwise in oily phase,
16min is emulsified through 3000r/min vortex oscillation after mixing, obtains the sticky pickering emulsion of water-in-oil type.
(3) pickering emulsion that step (2) obtain is transferred to the pneumatic extrusion equipped with micro needle head (internal diameter is 610 μm)
In formula 3D printer syringe, set print speed as 50mm/s and printing air pressure be 0.02MPa, then according to the length being pre-designed
The printing of cube (Φ 60mm × 5mm) stent model motion profile constructs three-dimensional porous lotion bracket, then freezes in -18 DEG C of refrigerators of warp
It is placed within 8 hours in -50 DEG C of refrigerators dry 10h, obtains the nano combined biology branch in the multiple dimensioned hole of the driving shape memory of photo-thermal
Frame.
Embodiment 5
(1) it is dispersed 2 mass parts graphene oxides in 20 parts by volume methylene chloride using ultrasonic treatment in ice-water bath,
It is subsequently added into dichloromethane solution (containing 2 mass parts PLLA) mixing of 20 parts by volume low molecular weight carboxyl end group polylactic acid (PLLA).
Mixed liquor is placed in ice-water bath under nitrogen protection using after 500r/min mechanical stirring 15min, is volatilized and is removed in 30 DEG C of water-baths
Methylene chloride is removed, then is placed in the tube furnace of nitrogen atmosphere and calcines the graphene oxide for obtaining hydrophobically modified for 24 hours for 200 DEG C.
(2) ultrasound 20min configures 6 parts by volume methylene chloride suspensions (i.e. oil in ice-water bath under the effect of 200W ultrasonic machine
Phase), wherein polylactic acid-carbonate copolymer (molecular weight 5 × 104G/mol, wherein lactic acid, trimethylene carbonate
Molar ratio is 70:30), modified graphene oxide, dewatering nano silica quality volume fraction be 12w/v%, 6w/v%,
1.5w/v%；10 parts by volume water are added portionwise in oily phase, emulsify 25min through 3000r/min vortex oscillation after mixing, obtain oil
The sticky pickering emulsion of water-in type.
(3) pickering emulsion that step (2) obtain is transferred to the pneumatic extrusion equipped with micro needle head (internal diameter is 340 μm)
In formula 3D printer syringe, set print speed as 15mm/s and printing air pressure be 0.04MPa, then according to the circle being pre-designed
The printing of cylinder (Φ 50mm × 3mm) stent model motion profile constructs three-dimensional porous lotion bracket, then through drying at room temperature 40h, obtains
To the nano combined biological support in the multiple dimensioned hole of the driving shape memory of photo-thermal.
Embodiment 6
(1) it is dispersed 2 mass parts graphene oxides in 20 parts by volume methylene chloride using ultrasonic treatment in ice-water bath,
It is subsequently added into dichloromethane solution (containing 2 mass parts PLLA) mixing of 20 parts by volume low molecular weight carboxyl end group polylactic acid (PLLA).
Mixed liquor is placed in ice-water bath under nitrogen protection using after 500r/min mechanical stirring 15min, is volatilized and is removed in 30 DEG C of water-baths
Methylene chloride is removed, then is placed in the tube furnace of nitrogen atmosphere and calcines the graphene oxide for obtaining hydrophobically modified for 24 hours for 200 DEG C.
(2) ultrasound 20min configures 4 parts by volume methylene chloride suspensions (i.e. oil in ice-water bath under the effect of 200W ultrasonic machine
Phase), wherein polylactic acid-caprolactone-carbonate copolymer (molecular weight 8 × 104G/mol, wherein lactic acid, caprolactone, three
The molar ratio of carbonate is 80:10:10), modified graphene oxide, dewatering nano silica, brufen (anti-inflammatory agent
Object) quality volume fraction be 12w/v%, 5w/v%, 1.5w/v%, 0.5w/v%；Oily phase is added portionwise in 7 parts by volume water
In, 15min is emulsified through 3000r/min vortex oscillation after mixing, obtains the sticky pickering emulsion of water-in-oil type.
(3) pickering emulsion that step (2) obtain is transferred to the pneumatic extrusion equipped with micro needle head (internal diameter is 610 μm)
In formula 3D printer syringe, set print speed as 30mm/s and printing air pressure be 0.02MPa, then according to the circle being pre-designed
The printing of cylinder (Φ 30mm × 5mm) stent model motion profile constructs three-dimensional porous lotion bracket, then is passed through in -18 DEG C of refrigerators again
Freezing is placed on dry 10h in -50 DEG C of refrigerators for 8 hours, obtains the nano combined life in the multiple dimensioned hole of the driving shape memory of photo-thermal
Object bracket.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of the nano combined biological support in the multiple dimensioned hole of driving shape memory of photo-thermal, it is characterised in that including
Following steps:
(1) hydrophobically modified is carried out to graphene oxide using low molecular weight band carboxyl end group polylactic acid, obtains the oxidation of hydrophobically modified
Graphene；
(2) the graphene oxide of hydrophobically modified, BSMPs, rheological agent be added it is organic by form in solvent oil phase；Oil is added in water
Xiang Zhong, mixing and emulsifying obtain the sticky pickering emulsion of water-in-oil type；
(3) using the sticky pickering emulsion of water-in-oil type as ink, three-dimensional porous lotion bracket is obtained using extruded type 3D printing, is done
It is dry, obtain the nano combined biological support in the multiple dimensioned hole of the driving shape memory of photo-thermal.
2. the preparation side of the nano combined biological support in the multiple dimensioned hole of the driving shape memory of photo-thermal according to claim 1
Method, it is characterised in that: in the oil phase, quality volume fraction of the BSMPs in oily phase is 4-16w/v%；The oxygen of hydrophobically modified
Quality volume fraction of the graphite alkene in oily phase is 3-12w/v%；Quality volume fraction of the rheological agent in oily phase is 0.5-
4w/v%.
3. the preparation side of the nano combined biological support in the multiple dimensioned hole of the driving shape memory of photo-thermal according to claim 1
Method, it is characterised in that: the volume ratio of the water and oily phase is 1:2-3:1.
4. the preparation side of the nano combined biological support in the multiple dimensioned hole of the driving shape memory of photo-thermal according to claim 1
Method, it is characterised in that: mass ratio of the low molecular weight used with carboxyl end group polylactic acid and graphene oxide is 3:1-1:2.
5. the preparation side of the nano combined biological support in the multiple dimensioned hole of the driving shape memory of photo-thermal according to claim 1
Method, it is characterised in that: molecular weight of the low molecular weight with carboxyl end group polylactic acid is 5 × 102-1×104g/mol；The BSMPs
Molecular weight be 1 × 104-1.5×105g/mol。
6. the preparation side of the nano combined biological support in the multiple dimensioned hole of the driving shape memory of photo-thermal according to claim 1
Method, it is characterised in that: the BSMPs includes polylactic acid-carbonate copolymer, poly lactic-co-glycolic acid-trimethyl
At least one of carbonate copolymer, polylactic acid-caprolactone-carbonate copolymer；The rheological agent includes dredging
At least one of water-based nano silicon dioxide, ethyl cellulose.
7. the preparation side of the nano combined biological support in the multiple dimensioned hole of the driving shape memory of photo-thermal according to claim 1
Method, it is characterised in that: in step (1), the progress hydrophobically modified is specially by low molecular weight band carboxyl end group polylactic acid, oxidation stone
Black alkene is scattered in solvent respectively, is uniformly mixed, and is removed solvent, is heat-treated and obtains under inert atmosphere；It is described heat treatment for
5-36h is calcined at 180-210 DEG C.
8. the preparation side of the nano combined biological support in the multiple dimensioned hole of the driving shape memory of photo-thermal according to claim 1
Method, it is characterised in that: in step (3), the process conditions that three-dimensional porous lotion bracket is obtained using extruded type 3D printing are as follows:
Extruding air pressure is 0.01-0.2MPa；The internal diameter of syringe needle is 210-1430 μm；Print speed is 2-50mm/s.
9. a kind of nano combined biological support in the multiple dimensioned hole of driving shape memory of photo-thermal, it is characterised in that according to claim 1-
8 described in any item methods are prepared.
10. the nano combined biological support in the multiple dimensioned hole of the driving shape memory of photo-thermal as claimed in claim 9 is led in organizational project
Application in domain.
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