CN107233632A - Degradable recoverable 4D printings organic human body support of line style and preparation method thereof - Google Patents
Degradable recoverable 4D printings organic human body support of line style and preparation method thereof Download PDFInfo
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- CN107233632A CN107233632A CN201710476845.1A CN201710476845A CN107233632A CN 107233632 A CN107233632 A CN 107233632A CN 201710476845 A CN201710476845 A CN 201710476845A CN 107233632 A CN107233632 A CN 107233632A
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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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L31/148—Materials at least partially resorbable by the body
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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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/04—Macromolecular materials
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- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/04—Macromolecular materials
- A61L31/06—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
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- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—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
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- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L31/16—Biologically active materials, e.g. therapeutic substances
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- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/20—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
- A61L2300/252—Polypeptides, proteins, e.g. glycoproteins, lipoproteins, cytokines
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- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/20—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
- A61L2300/252—Polypeptides, proteins, e.g. glycoproteins, lipoproteins, cytokines
- A61L2300/254—Enzymes, proenzymes
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- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
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- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
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Abstract
The present invention relates to degradable recoverable 4D printings organic human body support of line style of one kind and preparation method thereof, human body support includes skeleton portion, functional protein film and chitosan film；The Surface mulch in skeleton portion functional protein film, and the Surface mulch of functional protein film chitosan film；Skeleton portion is prepared from using PLA and carboxymethyl chitosan.The human body support that the present invention is provided, the PLA and chitosan of use all have good human compatibility, will not occur rejection；The functional protein of use can play a part of melting thrombus, with good biocompatibility and bioresorbable；The 4D of use can remember deformation printed material, after implantation narrow positions, early stage can provide effective support, ensure vascular patency, after later stage support absorbs, its catabolite can be absorbed by the body, using or excrete, noresidue foreign matter in target vessel, at utmost recover the systolic and diastolic function of blood vessel, and allow some leeway to secondary intervention.
Description
Technical field
The present invention relates to human body support's technical field, and in particular to a kind of degradable recoverable 4D printings organic human body of line style
Support and preparation method thereof.
Background technology
According to《China Health counts summary》Data display, at present China Patients with Cardiovascular/Cerebrovascular Diseases already exceed 2.7
Hundred million people, cardiovascular and cerebrovascular disease causes death toll close to the 40% of national total toll, " the head already as compatriots' health
Number killer ".The Etiological of angiocardiopathy is that superabundant fats class material and calcium are allowed to thickening in vascular wall deposition, causes blood vessel
Narrow or block and cause blood circulation difficult, and then produce angina pectoris, miocardial infarction until dead.To anti-cardiovascular disease
Main Means are the intervenient cures that special support insertion diseased region is diagnosed and treated using percutaneous puncture approach.Its
Principle is the blood vessel that stenter to implant has narrowed, and can produce a lasting radial pressure to its inwall, force and be attached to
Deposit on vascular wall concentrates and supports it and make unobstructed blood vessel.
Some existing intravascular stents are metal materials, and non-degradable, Chinese patent 201410266420.4 is disclosed
A kind of intravascular stent, is made up of nondegradable metal material.Be implanted into the patient of this metallic blood vessel bracket can not do nuclear-magnetism be total to
Shake.Intravascular stent can just complete the mission of its support blood vessels general some months, and blood vessel recovers normal thereafter, and no longer needs blood
Pipe holder.At this moment secondary narrow risk can be faced by implanting the patient for the intravascular stent that can not be degraded, once it is secondary narrow
The pain of bypass surgery must just be received.
Hirudin is to extract a kind of small protein (polypeptide) in leech and its salivary gland.Hirudin has very strong
Blood coagulation resisting function, its act on performance be by with fibrin ferment by 1:1 ratio combines closely to form compound, fibrin ferment is gone out
It is living.It is different from heparin, and its anticoagulation does not need the presence of AT III in blood plasma, AT III and needs anti-freezing to control available for lacking
The patient for the treatment of.It is weak to Platelet, thrombocytopenic purpura can be caused unlike heparin, available for the reduction of its platelet
The patient of anticoagulant therapy is needed again.But serum half-life is too short in use for hirudin, direct injection or it is oral all
It is difficult to the lasting anti-bolt effect of performance.Lumbrokinase has special affinity with thrombus (fibrin), can track thrombolysis, effectively molten
Xie Weishuan, improves microcirculation, strengthens the heart, cerebrovascular Doppler flow mapping, and opening repairs vascular injury endothelial cell, increases blood vessel bullet
Property, improve blood vessel oxygen supply function, reduce blood viscosity, reduce platelet aggregation rate, suppress thrombus and formed again.Lumbrokinase is current
Clinical practice mainly in the form of oral medicine, side effect includes causing digestive tract reaction, and absorbed by alimentary canal
Efficiency is also than relatively low.
Except intravascular stent, same problem is also faced with the human body support such as intestinal stent, biliary tract prosthesis field.
The content of the invention
For defect of the prior art, present invention aims at providing, a kind of degradable recoverable 4D printings line style is organic
Human body support and preparation method thereof, to improve the compatibility of human body support and human body, reduces the stimulation to vascular wall, it is to avoid occur
Rejection；Also, chitosan, PLA and the protein that the present invention is used all are the things that can be decomposed or degrade in vivo
Matter, eliminates the secondary narrow pain being followed by by bypass surgery.
To achieve the above object, the technical scheme that provides of the present invention is：
In a first aspect, the invention provides a kind of human body support, it is poly- that human body support includes skeleton portion, functional protein film and shell
Sugared film；The Surface mulch in skeleton portion functional protein film, and the Surface mulch of functional protein film chitosan film；Skeleton portion is to use
PLLA, dextrorotation PLA and carboxymethyl chitosan are prepared from.
In the further embodiment of the present invention, the shape of the body profile structure of human body support is helical tubular,
Human body support includes spire and mounting ring；Wherein, mounting ring is located at the two ends of spire, and mounting ring is provided with a fixation
Hole.
In the further embodiment of the present invention, spire includes multiple spiral elements being sequentially connected, each spiral
Unit includes circumference unit and multiple support units；Wherein, the shape of support unit is the arch axially in parallel with human body support
Protuberance, the shape of circumference unit is spiral shape, and support unit is evenly distributed on circumference unit, the interval of each support unit
Angle is equal, adjacent two support units it is in opposite direction.
In the further embodiment of the present invention, chamfering is provided between mounting ring and spire；Support unit and circumference
Chamfering is provided between unit.
In the further embodiment of the present invention, in each spiral element：The number of support unit is even number, is preferably
4；The interval angles of each support unit are 90 degree.
In the further embodiment of the present invention, mounting ring is formed after a support unit and circumference unit closure.
The present invention further embodiment in, human body support be used for blood vessel, pancreatic duct, bile duct, enteron aisle, ureter,
The support of oesophagus or nasal cavity.
In the further embodiment of the present invention, the shape of the axial line of support unit includes sinusoidal waveform, arc, U
Shape and it is parabola shaped in one or more.
Second aspect, the invention provides the preparation method of human body support, comprises the following steps：S1：By PLLA
It is well mixed with dextrorotation PLA, obtain mixed-powder；S2：By mixed-powder heating and melting, mould extrusion molding is then utilized
4D printing raw material thread；S3：4D printing raw material threads are printed as by default human body support's shape using 4D printing techniques, people is obtained
Body support frame blank；S4：Human body support's blank is immersed in functional protein biofilm liquid, carry out frozen dried is then taken out, obtains
To human body support's semi-finished product；S5：Human body support's semi-finished product are immersed in chitosan biofilm liquid, the lyophilized place of progress is then taken out
Reason, obtains human body support's finished product.
In the further embodiment of the present invention, in S1, PLLA, dextrorotation PLA and carboxymethyl chitosan
Mass ratio is 1:(0.8~1.1)：(0.4~0.5)；In S2, the temperature of the heating is 130~155 DEG C, and the 4D printings are former
Expect a diameter of 1~3mm of silk；In S4, the time of immersion is 2~5 seconds, and lyophilized temperature is -40 DEG C；In S5, the time of immersion
For 2~5 seconds, lyophilized temperature was -40 DEG C.
In the further embodiment of the present invention, in S4, the raw material components of functional protein biofilm liquid include：Hirudin
20 parts by weight, the parts by weight of Lumbrokinase 20, the parts by weight of thickener 2 and the parts by weight of hexafluoroisopropanol 160；Wherein, thickener includes poly-
The mass ratio of vinyl pyrrolidone and polyvinyl alcohol, PVP and polyvinyl alcohol is 1:1；Functional protein is hung
The preparation method of film liquid comprises the following steps：S101：Hexafluoroisopropanol, hirudin and Lumbrokinase are mixed, then stirred to complete
Fully dissolved, obtains functional protein solution；S102：Thickener is added in functional protein solution, is stirred, function is obtained
Protein biofilm liquid.It should be noted that PVP is preferably PVP-K30, the number-average molecular weight of polyvinyl alcohol
Preferably 15000~16000.
In the further embodiment of the present invention, in S5, the raw material components of chitosan biofilm liquid include：Chitosan solution
And thickener；In chitosan solution：The mass percent of solute chitosan is 8%~20%, and solvent is hexafluoroisopropanol and three
The volume ratio of fluoroacetic acid, hexafluoroisopropanol and trifluoroacetic acid is 9:1；Thickener includes PVP and polyethylene
The mass ratio of alcohol, PVP and polyvinyl alcohol is 1:1；The preparation method of chitosan biofilm liquid includes following step
Suddenly：S201：Hexafluoroisopropanol and trifluoroacetic acid are mixed, chitosan solvent is obtained；S202：Shell is added in chitosan solvent to gather
Sugar, then stirs to being completely dissolved, obtains chitosan solution；S203：Thickener is added in chitosan solution, is stirred,
Obtain chitosan biofilm liquid.
The technical scheme that the present invention is provided, with following beneficial effect：(1) human body support that the present invention is provided, uses
PLA and chitosan all have good human compatibility, will not occur rejection；Chitosan, PLA, protein
All it is the material that can be decomposed or degrade in vivo, eliminates the secondary narrow pain being followed by by bypass surgery；(2) present invention is adopted
Functional protein can play a part of melting thrombus, with human body friendly；(3) the 4D printing materials that the present invention is used
Material will not produce stimulation to vascular wall.
The additional aspect and advantage of the present invention will be set forth in part in the description, and will partly become from the following description
Obtain substantially, or recognized by the practice of the present invention.
Brief description of the drawings
Fig. 1 is human body support's schematic diagram in the embodiment of the present invention one；
Fig. 2 is the cross-sectional structure schematic diagram of human body support of the present invention；
Fig. 3 is the schematic diagram of the single spiral element of human body support of the present invention.
Reference：
1- mounting rings；2- fixing holes；3- circumference units；4- support units；5- skeletons portion；6- functional protein films；7- shells gather
Sugared film；8- spires.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation is described.The following examples are only intended to illustrate the technical solution of the present invention more clearly, therefore is intended only as example, without
It can be limited the scope of the invention with this.
Experimental method in following embodiments, is conventional method unless otherwise specified.Examination used in following embodiments
Material is tested, is to be commercially available from routine biochemistry reagent shop unless otherwise specified.Quantitative test in following examples,
Three repetition experiments are respectively provided with, data are the average value or mean+SD of three repetition experiments.The embodiment of the present invention is adopted
The dextrorotation PLA that PLA provides for Shanghai Li Ang Chemical Co., Ltd.s and the left-handed poly- breast that No. CAS is 33135-50-1
Acid, the medical grade chitosan that chitosan provides for the Qingdao special sea hydrobiont pharmacy of rich benefit.
The present invention provides a kind of human body support, and human body support includes skeleton portion, functional protein film and chitosan film；Skeleton portion
Surface mulch functional protein film, the Surface mulch of functional protein film chitosan film；Skeleton portion is to use PLLA
It is prepared from dextrorotation PLA.
Preferably, the shape of the body profile structure of human body support is helical tubular, human body support include spire and
Mounting ring；Wherein, mounting ring is located at the two ends of spire, and mounting ring is provided with a fixing hole.
Preferably, spire includes multiple spiral elements being sequentially connected, and each spiral element includes circumference unit and many
Individual support unit；Wherein, the shape of support unit is swelled with the axially in parallel arch of human body support, and the shape of circumference unit is
Spiral shape, support unit is evenly distributed on circumference unit, and the interval angles of each support unit are equal, two adjacent branch
Support the in opposite direction of unit.
Preferably, chamfering is provided between mounting ring and spire；Chamfering is provided between support unit and circumference unit.
Preferably, mounting ring is formed after a support unit and circumference unit closure.
Preferably, human body support is used for the support of blood vessel, pancreatic duct, bile duct, enteron aisle, ureter, oesophagus or nasal cavity.
Preferably, in each spiral element：The number of support unit is even number, preferably 4；Between each support unit
Every angle be 90 degree.
Preferably, the shape of the axial line of support unit include sinusoidal waveform, arc, U-shaped and it is parabola shaped in one kind
Or it is a variety of.
In addition, present invention also offers the preparation method of above-mentioned human body support, comprising the following steps：
S1：By PLLA, dextrorotation PLA and carboxymethyl chitosan with 1:(0.8~1.1)：The matter of (0.4~0.5)
Amount obtains mixed-powder than well mixed；
S2：By 130~155 DEG C of heating and meltings of mixed-powder, a diameter of 1~3mm of mould extrusion molding is then utilized
4D prints raw material thread；
S3：4D printing raw material threads are printed as by default human body support's shape using 4D printing techniques, human body support is obtained
Blank；
S4：Human body support's blank is immersed in functional protein biofilm liquid, the time of immersion is 2~5 seconds, is then taken out
Frozen dried is carried out at -40 DEG C, human body support's semi-finished product are obtained；Wherein, the raw material components of functional protein biofilm liquid include：Water
20 parts by weight of leech element, the parts by weight of Lumbrokinase 20, the parts by weight of thickener 2 and the parts by weight of hexafluoroisopropanol 160；Wherein, thickener bag
Include PVP and polyvinyl alcohol, the mass ratio of PVP and polyvinyl alcohol is 1:1；Functional protein
The preparation method of matter biofilm liquid comprises the following steps：S101：Hexafluoroisopropanol, hirudin and Lumbrokinase are mixed, then stirred
To being completely dissolved, functional protein solution is obtained；S102：Thickener is added in functional protein solution, is stirred, is obtained
Functional protein biofilm liquid；
S5：Human body support's semi-finished product are immersed in chitosan biofilm liquid, the time of immersion is 2~5 seconds, is then taken out
Frozen dried is carried out at -40 DEG C, human body support's finished product is obtained；Wherein, the raw material components of chitosan biofilm liquid include：Chitosan is molten
Liquid and thickener；In chitosan solution：The mass percent of solute chitosan be 8%~20%, solvent be hexafluoroisopropanol and
The volume ratio of trifluoroacetic acid, hexafluoroisopropanol and trifluoroacetic acid is 9:1；Thickener includes PVP and polyethylene
The mass ratio of alcohol, PVP and polyvinyl alcohol is 1:1；The preparation method of chitosan biofilm liquid includes following step
Suddenly：S201：Hexafluoroisopropanol and trifluoroacetic acid are mixed, chitosan solvent is obtained；S202：Shell is added in chitosan solvent to gather
Sugar, then stirs to being completely dissolved, obtains chitosan solution；S203：Thickener is added in chitosan solution, is stirred,
Obtain chitosan biofilm liquid.
Human body support provided with reference to specific embodiment the present invention and preparation method thereof is described further.
Embodiment one
The present embodiment provides a kind of human body support, and as shown in Figure 1, Figure 2 with shown in Fig. 3 structures, human body support includes skeleton portion, work(
Can protein film and chitosan film；The Surface mulch in skeleton portion functional protein film, and the Surface mulch of functional protein film chitosan
Film；Skeleton portion is prepared from using PLLA, dextrorotation PLA and carboxymethyl chitosan.
Specifically, the shape of the body profile structure of human body support is helical tubular, and human body support includes the He of spire 8
Mounting ring 1；Wherein, mounting ring 1 is located at the two ends of spire 8, and mounting ring 1 is provided with a fixing hole 2；Mounting ring 1 and spiral
Chamfering is provided between portion 8.
Specifically, spire 8 includes multiple spiral elements being sequentially connected, and each spiral element includes circumference unit 3 and 4
Individual support unit 4, is provided with chamfering between support unit 4 and circumference unit 3；Wherein, the shape of support unit 4 is and human body support
Axially in parallel arch protuberance, the shape of circumference unit 3 is spiral shape, and support unit 4 is evenly distributed on circumference unit 3,
Two adjacent support units 4 it is in opposite direction, the interval angles of each support unit 4 are 90 degree, the axial line of support unit 4
Be shaped as arc.
Embodiment two
The present embodiment provides the preparation method of the human body support shown in embodiment one a kind of, comprises the following steps：
S1：By PLLA, dextrorotation PLA and carboxymethyl chitosan with 1:0.8:0.4 mass ratio is well mixed,
Obtain mixed-powder；
S2：By 130 DEG C of heating and meltings of mixed-powder, then the 4D printings using a diameter of 1mm of mould extrusion molding are former
Expect silk；
S3：4D printing raw material threads are printed as by default human body support's shape using 4D printing techniques, human body support is obtained
Blank；
S4：Human body support's blank is immersed in functional protein biofilm liquid, time of immersion is 2 seconds, then take out-
40 DEG C of progress frozen drieds, obtain human body support's semi-finished product；Wherein, the preparation method of functional protein biofilm liquid includes following step
Suddenly：S101：Hexafluoroisopropanol 160g is taken, hirudin 20g, Lumbrokinase 20g is added, stirs to being completely dissolved, obtains functional protein
Matter solution；S102：Thickener (PVP 1g, polyvinyl alcohol 1g), stirring are added in functional protein solution
Uniformly, functional protein biofilm liquid is obtained；
S5：Human body support's semi-finished product are immersed in chitosan biofilm liquid, the time of immersion is 2 seconds, is then taken out -40
DEG C carry out frozen dried, obtain human body support's finished product；Wherein, the preparation method of chitosan biofilm liquid comprises the following steps：S201：
90ml hexafluoroisopropanols are taken, 10ml trifluoroacetic acids is added, obtains chitosan solvent 100ml；S202：Added in chitosan solvent
Chitosan, is then stirred to being completely dissolved, and is configured to the chitosan solution that mass fraction is 8%；S203：In chitosan solution
Thickener (PVP 1g, polyvinyl alcohol 1g) is added, stirs, obtains chitosan biofilm liquid.
Embodiment three
The present embodiment provides a kind of preparation method of human body support, comprises the following steps：
S1：By PLLA, dextrorotation PLA and carboxymethyl chitosan with 1:1.1:0.5 mass ratio is well mixed,
Obtain mixed-powder；
S2：By 155 DEG C of heating and meltings of mixed-powder, then the 4D printings using a diameter of 3mm of mould extrusion molding are former
Expect silk；
S3：4D printing raw material threads are printed as by default human body support's shape using 4D printing techniques, human body support is obtained
Blank；
S4：Human body support's blank is immersed in functional protein biofilm liquid, time of immersion is 5 seconds, then take out-
40 DEG C of progress frozen drieds, obtain human body support's semi-finished product；Wherein, the preparation method of functional protein biofilm liquid includes following step
Suddenly：S101：Hexafluoroisopropanol 160g is taken, hirudin 20g, Lumbrokinase 20g is added, stirs to being completely dissolved, obtains functional protein
Matter solution；S102：Thickener (PVP 1g, polyvinyl alcohol 1g), stirring are added in functional protein solution
Uniformly, functional protein biofilm liquid is obtained；
S5：Human body support's semi-finished product are immersed in chitosan biofilm liquid, the time of immersion is 5 seconds, is then taken out -40
DEG C carry out frozen dried, obtain human body support's finished product；Wherein, the preparation method of chitosan biofilm liquid comprises the following steps：S201：
90ml hexafluoroisopropanols are taken, 10ml trifluoroacetic acids is added, obtains chitosan solvent 100ml；S202：Added in chitosan solvent
Chitosan, is then stirred to being completely dissolved, and is configured to the chitosan solution that mass fraction is 20%；S203：In chitosan solution
Middle addition thickener (PVP 1g, polyvinyl alcohol 1g), stirs, obtains chitosan biofilm liquid.
Example IV
The present embodiment provides a kind of preparation method of human body support, comprises the following steps：
S1：By PLLA, dextrorotation PLA and carboxymethyl chitosan with 1:1:0.45 mass ratio is well mixed, and is obtained
To mixed-powder；
S2：By 139 DEG C of heating and meltings of mixed-powder, then the 4D printings using a diameter of 2mm of mould extrusion molding are former
Expect silk；
S3：4D printing raw material threads are printed as by default human body support's shape using 4D printing techniques, human body support is obtained
Blank；
S4：Human body support's blank is immersed in functional protein biofilm liquid, time of immersion is 4 seconds, then take out-
40 DEG C of progress frozen drieds, obtain human body support's semi-finished product；Wherein, the preparation method of functional protein biofilm liquid includes following step
Suddenly：S101：Hexafluoroisopropanol 160g is taken, hirudin 20g, Lumbrokinase 20g is added, stirs to being completely dissolved, obtains functional protein
Matter solution；S102：Thickener (PVP 1g, polyvinyl alcohol 1g), stirring are added in functional protein solution
Uniformly, functional protein biofilm liquid is obtained；
S5：Human body support's semi-finished product are immersed in chitosan biofilm liquid, the time of immersion is 4 seconds, is then taken out -40
DEG C carry out frozen dried, obtain human body support's finished product；Wherein, the preparation method of chitosan biofilm liquid comprises the following steps：S201：
90ml hexafluoroisopropanols are taken, 10ml trifluoroacetic acids is added, obtains chitosan solvent 100ml；S202：Added in chitosan solvent
Chitosan, is then stirred to being completely dissolved, and is configured to the chitosan solution that mass fraction is 14%；S203：In chitosan solution
Middle addition thickener (PVP 1g, polyvinyl alcohol 1g), stirs, obtains chitosan biofilm liquid.
The human body support that the embodiment of the present invention two to example IV is prepared, by function assessment experiment come system evaluation
Its effect.
1st, radial support power
The radial direction branch for the degradable human body support that the embodiment of the present invention two is prepared to example IV is detected by mechanical test
Support force.Determine obtained result as shown in table 1 below.
The radial support power of table 1
| Group | Embodiment two | Embodiment three | Example IV |
| Radial support power (N) | 17.84 | 18.02 | 18.91 |
2nd, dissolution time window
Degradable human body support prepared by degradable human body support prepared by the embodiment of the present invention two to example IV exists
Simulate and (environmental condition is soaked in blood：37 DEG C, 3%CO2, humidity 99%), determine degradable human body support's radial support power drop
As little as 12N time and maximum dissolution time.Determine obtained result as shown in table 2 below.
The dissolution time window of table 2
| Group | Embodiment two | Embodiment three | Example IV |
| Support force be reduced to 12N time (my god) | 210 | 213 | 215 |
| Maximum dissolution time (my god) | 374 | 378 | 382 |
The technical scheme that the present invention is provided, with following beneficial effect：(1) human body support that the present invention is provided, uses
PLA and chitosan all have good human compatibility, will not occur rejection；Chitosan, PLA, protein
All it is the material that can be decomposed or degrade in vivo, eliminates the pain for receiving bypass surgery again；(2) work(that the present invention is used
Energy property protein can play a part of melting thrombus, with human body friendly；(3) change for the 4D printed materials that the present invention is used
Shape is slower than the rebound velocity of wire, will not produce stimulation to vascular wall.
It should be noted that unless otherwise indicated, technical term or scientific terminology used in this application should be this hair
The ordinary meaning that bright one of ordinary skill in the art are understood.Unless specifically stated otherwise, otherwise illustrate in these embodiments
Part and relative step, numerical expression and the numerical value of step are not limit the scope of the invention.It is illustrated and described herein
In all examples, unless otherwise prescribed, any occurrence should be construed as merely exemplary, not as limitation, because
This, other examples of exemplary embodiment can have different values.
Finally it should be noted that：Various embodiments above is merely illustrative of the technical solution of the present invention, rather than its limitations；To the greatest extent
The present invention is described in detail with reference to foregoing embodiments for pipe, it will be understood by those within the art that：Its according to
The technical scheme described in foregoing embodiments can so be modified, or which part or all technical characteristic are entered
Row equivalent substitution；And these modifications or replacement, the essence of appropriate technical solution is departed from various embodiments of the present invention technology
The scope of scheme, it all should cover among protection scope of the present invention.
Claims (10)
1. a kind of human body support, it is characterised in that：
The human body support includes skeleton portion, functional protein film and chitosan film；The Surface mulch in the skeleton portion the work(
Energy protein film, the Surface mulch of the functional protein film the chitosan film；The skeleton portion is to use PLLA, the right side
Rotation PLA and carboxymethyl chitosan are prepared from.
2. human body support according to claim 1, it is characterised in that：
The shape of the body profile structure of the human body support is helical tubular, and the human body support includes spire and installation
Ring；Wherein, the mounting ring is located at the two ends of the spire, and the mounting ring is provided with a fixing hole.
3. human body support according to claim 2, it is characterised in that：
The spire includes multiple spiral elements being sequentially connected, and each spiral element includes circumference unit and multiple support lists
Member；Wherein, the shape of the support unit is swelled with the axially in parallel arch of human body support, and the shape of the circumference unit is
Spiral shape, the support unit is evenly distributed on circumference unit, and the interval angles of each support unit are equal, and adjacent two
Individual support unit it is in opposite direction；Chamfering is provided between the mounting ring and the spire；The support unit and the circle
Chamfering is provided between Zhou Danyuan.
4. human body support according to claim 3, it is characterised in that：
The mounting ring is by a support unit with being formed after circumference unit closure.
5. human body support according to claim 3, it is characterised in that：
The human body support is used for the support of blood vessel, pancreatic duct, bile duct, enteron aisle, ureter, oesophagus or nasal cavity.
6. the human body support according to claim any one of 3-5, it is characterised in that：
The shape of the axial line of the support unit include sinusoidal waveform, arc, U-shaped and it is parabola shaped in one or more.
7. the preparation method of the human body support described in claim any one of 1-6, it is characterised in that comprise the following steps：
S1：PLLA, dextrorotation PLA and carboxymethyl chitosan are well mixed, mixed-powder is obtained；
S2：By the mixed-powder heating and melting, the 4D printing raw material threads of mould extrusion molding are then utilized；
S3：4D printing raw material threads are printed as by default human body support's shape using 4D printing techniques, human body support is obtained
Blank；
S4：Human body support's blank is immersed in functional protein biofilm liquid, carry out frozen dried is then taken out, obtains people
Body support frame semi-finished product；
S5：Human body support's semi-finished product are immersed in chitosan biofilm liquid, carry out frozen dried is then taken out, obtain described
Human body support's finished product.
8. the preparation method of human body support according to claim 7, it is characterised in that：
In the S1, the mass ratio of the PLLA, dextrorotation PLA and carboxymethyl chitosan is 1:(0.8~1.1):
(0.4~0.5)；
In the S2, the temperature of the heating is 130~155 DEG C, and the 4D prints a diameter of 1~3mm of raw material thread；
In the S4, the time of the immersion is 2~5 seconds, and the lyophilized temperature is -40 DEG C；
In the S5, the time of the immersion is 2~5 seconds, and the lyophilized temperature is -40 DEG C.
9. the preparation method of human body support according to claim 7, it is characterised in that：
In the S4, the raw material components of the functional protein biofilm liquid include：The parts by weight of hirudin 20, the weight of Lumbrokinase 20
Part, the parts by weight of thickener 2 and the parts by weight of hexafluoroisopropanol 160；Wherein, the thickener includes PVP and poly-
The mass ratio of vinyl alcohol, the PVP and the polyvinyl alcohol is 1:1；
The preparation method of the functional protein biofilm liquid comprises the following steps：
S101：Hexafluoroisopropanol, hirudin and Lumbrokinase are mixed, then stirs to being completely dissolved, obtains functional protein molten
Liquid；
S102：Thickener is added in the functional protein solution, is stirred, the functional protein biofilm liquid is obtained.
10. the preparation method of human body support according to claim 7, it is characterised in that：
In the S5, the raw material components of the chitosan biofilm liquid include：Chitosan solution and thickener；The chitosan solution
In：The mass percent of solute chitosan is 8%~20%, and solvent is hexafluoroisopropanol and trifluoroacetic acid, the hexafluoro isopropyl
The volume ratio of alcohol and the trifluoroacetic acid is 9:1；The thickener includes PVP and polyvinyl alcohol, described poly-
The mass ratio of vinyl pyrrolidone and the polyvinyl alcohol is 1:1；
The preparation method of the chitosan biofilm liquid comprises the following steps：
S201：Hexafluoroisopropanol and trifluoroacetic acid are mixed, chitosan solvent is obtained；
S202：Chitosan is added in the chitosan solvent, then stirs to being completely dissolved, obtains chitosan solution；
S203：Thickener is added in the chitosan solution, is stirred, the chitosan biofilm liquid is obtained.
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| CN201710476845.1A CN107233632B (en) | 2017-06-21 | 2017-06-21 | Degradable and recoverable 4D printing linear organic human body stent and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2589682A (en) * | 2019-09-16 | 2021-06-09 | Univ Qingdao | Preparation method of 4D chitosan-based thermosensitive hydrogel |
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| CN107233632B (en) | 2020-05-15 |
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