CN109927285A - A kind of biomaterial and non-intruding near-infrared laser assist 3D printing method - Google Patents
A kind of biomaterial and non-intruding near-infrared laser assist 3D printing method Download PDFInfo
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- CN109927285A CN109927285A CN201711378409.7A CN201711378409A CN109927285A CN 109927285 A CN109927285 A CN 109927285A CN 201711378409 A CN201711378409 A CN 201711378409A CN 109927285 A CN109927285 A CN 109927285A
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Abstract
The invention belongs to 3D biometric print technical fields, and in particular to assist digital light processing in body 3D printing method to the near-infrared laser of a kind of biomaterial and non-intruding.Technical problem to be solved by the invention is to provide a kind of biomaterials that the photoinitiator compound by photosensitive polymer monomer and based on upper conversion nano material forms, it is additionally provided simultaneously using the biomaterial as printed material, the 3D printing technique printed in vivo is realized using near infrared light.
Description
Technical field
The invention belongs to 3D biometric print technical fields, and in particular to arrive a kind of biomaterial and non-intruding near-infrared laser
Assist digital light processing in body 3D printing method.
Background technique
Since nineteen fifties, hundreds and thousands of ten thousand patient with incurable disease has been saved in organ transplant,
But at present to the demand of portable organ considerably beyond organ donation amount.Therefore there is an urgent need to a kind of technologies to meet day
The patient for urgently receiving organ transplant that benefit increases, in addition organ transplant also have immune response and organ rejection intrinsic lack
It falls into.3D biometric print technology (being originated from increasing material manufacturing) achieves marked improvement in past 10 years.As a kind of organizational project
In strategy, in regenerative medicine, it can be used and have wide practical use conscientiously.3D biometric print technology is repaired in manufacture institutional framework
The tissue and organ of multiple or replacement damage or lesion.The tissue or organ of most 3D printings need to give birth in vitro before operation transplantation
It is cultivated in object reactor mature.Three kinds of methods of 3D biometric print manufacture histoorgan have bionical, automatic self assembly and micro-assembly robot
Construct module.Common 3D biological printing system has laser writing technology, ink-jet extrusion and cell electrostatic spinning.Wherein, laser
Direct writing technology is commonly referred to as free form manufacture or rapid shaping, can be suitable for manufacture 3D bracket by controlling preparation parameter.
The technology mainly utilizes light ultraviolet light manufacture micron and nanoscale 3D biological structure, but the use of usually ultraviolet laser is to thin
Born of the same parents have negative effect.
The penetration capacity of the ultraviolet light used due to common laser writing technology is weak, and has stronger kill to histocyte
Hurt ability, therefore the 3D printing technique of ultraviolet light auxiliary cannot achieve and print in body.However the near-infrared of long wavelength (NIR) light has
Deeper tissue penetration and normal cell is damaged it is less, and because upper conversion nano grain can absorb the near-infrared of long wavelength
Light and the UV, visible light and NIR for being converted into having higher energy are widely used in color monitor, bio-imaging and more
The fields such as electronic equipment.The exciting light can be used for having the photoinitiator of specific absorption to generate free radicals in turn in this wave-length coverage
Cause oligomer or polymer monomer carries out chain polymerization and reacts to form highly cross-linked network structure polymer such as hydrogel.Benefit
With the advantage of the preferable tissue penetration of near infrared light, the present invention is novel using the compound based on up-conversion nano material
Photoinitiator, to provide a new means and technology in body 3D printing.
Summary of the invention
The technical problem to be solved by the present invention is to provide at a kind of novel biomaterial and near-infrared laser auxiliary digital light
Reason is in body 3D printing technique, it is intended to realize that internal 3D biometric print tissue or organ provide new strategy and new technology.This technology
It is on the one hand not needing the mode of cumbersome surgical operation implantation with the advantage of traditional 3D printing portable tissue or organ,
It only needs biomaterial and cell infusion manufacture tissue or organ in vivo can be realized to intracorporal appointed part, on the other hand
Without external biological reactor, manufactured tissue or organ can using human body as a kind of natural bioreactor culture at
It is ripe and play its function.
First technical problem to be solved by this invention is to provide a kind of biomaterial.The biomaterial can inject biology
In vivo, assist digital light processing in body 3D printing using near-infrared laser, to realize internal printing technique.
Biomaterial of the invention, by photosensitive polymer monomer and based on the upper photoinitiator compound for converting nano material
Composition.
Specifically, above-mentioned biomaterial, is drawn by photosensitive polymer monomer solution and the light based on upper conversion nano material
Hair agent compound water solution mixes.
Preferably, above-mentioned biomaterial, photosensitive polymer monomer concentration is 5~50% in the solution mixed.
Photoinitiator complex concentration based on upper conversion nano material in the solution mixed is 0.1~10%.Described
Photosensitive polymer monomer concentration is to contain 5~50mg photosensitive polymer monomer in 5~50% every 100 μ L mixed solutions of expression.Institute
The photoinitiator complex concentration stated is compound containing 1~10mg photoinitiator in 0.1~10% every 100 μ L mixed solution of expression
Object.
Specifically, above-mentioned biomaterial, the photosensitive polymer monomer is selected from hyaluronic acid, the methyl of methacrylation
The polyethylene glycol of acrylated gelatin, methacrylation, methacrylation chitosan, methacrylation albumin,
At least one of methyl-prop alkylene alginic acid or methyl-prop alkylene glucan.
Specifically, above-mentioned biomaterial, the photoinitiator compound based on upper conversion nano material is upper by what is adulterated
Conversion nano material and photoinitiator composition, it is described to be doped to mixed with Tm3+And Yb3+。
Preferably, above-mentioned biomaterial, the up-conversion nano material of the doping is also doped with Er3+、Pr3+、Sm3+、Tb3+、
Gd3+、Ho3+、Nd3+、Dy3+At least one of.
Preferably, above-mentioned biomaterial, Er in the up-conversion nano material of the doping3+、Pr3+、Sm3+、Tb3+、Gd3+、
Ho3+、Nd3+、Dy3+At least one of molar content be 0.01~5%.Total amount is cation mole total amount.When upper conversion material
When material is oxide or fluoride, for example, Gd2O3、Lu2O3、CaF2、LaF3、ZnF2、Y2O3Or YF3When, the cation mole
Total amount is the moles total number of the cation of the cation and doping in compound；When up-conversion is GdYF4、NaYF4、
LiYF4、KYF4、BaF2、BaYF5Or Ba2YF7When, the cation mole total amount is the sun of the Y-ion and doping in compound
The moles total number of ion.
Preferably, above-mentioned biomaterial, Yb in the up-conversion nano material of the doping3+Molar content be 5~40%,
Tm3+Molar content be 0.01~3%.Total amount is cation mole total amount.When upper converting material is oxide or fluoride,
For example, Gd2O3、Lu2O3、CaF2、LaF3、ZnF2、Y2O3Or YF3When, the cation mole total amount be compound in sun from
The moles total number of son and the cation of doping；When up-conversion is GdYF4、NaYF4、LiYF4、KYF4、BaF2、BaYF5Or
Ba2YF7When, the cation mole total amount is the moles total number of the cation of the Y-ion and doping in compound.
Further, above-mentioned biomaterial, Yb in the up-conversion nano material of the doping3+Molar content be 20~
40%, Tm3+Molar content be 0.1~1.5%.
Further, in above-mentioned biomaterial, there are also a protective layer outside the upper conversion nano material of the doping.Institute
Stating protective layer is NaYF4Or NaGdF4.The protective layer can reduce ligand, the solvent or impure of conversion nano-material surface
It shines and is quenched caused by substance, improve the luminous intensity of nano material.
Further, the cation mole total amount in above-mentioned biomaterial, in the upper conversion nano material of the doping
It is 10 ︰, 1~1 ︰ 10 with the cation mole ratio in protective layer.1~1 ︰ 2 of preferably 2 ︰.Such as NaYF4Adulterate Yb3+, Tm3+When, it protects
Sheath is NaYF4When, then Y in core3+、Yb3+、Tm3+The cationic Y of moles total number and protective layer3+Molar ratio be 10 ︰, 1~1 ︰
10.1~1 ︰ 2 of preferably 2 ︰.Such as NaYF4Adulterate Yb3+, Tm3+When, protective layer NaGdF4When, then Y in core3+、Yb3+、Tm3+It rubs
The cationic Gd of your total amount and protective layer3+Molar ratio be 10 ︰, 1~1 ︰ 10.1~1 ︰ 2 of preferably 2 ︰.
Preferably, in above-mentioned biomaterial, the mass ratio of the up-conversion nano material of doping and photoinitiator be 10 ︰ 1~
1 ︰ 10.
Further, in above-mentioned biomaterial, the mass ratio of the up-conversion nano material of doping and photoinitiator be 2 ︰ 1~
1 ︰ 2.
Specifically, the up-conversion nano material is Gd in above-mentioned biomaterial2O3、GdYF4、Lu2O3、CaF2、LaF3、
ZnF2、Y2O3、YF3、NaYF4、LiYF4、KYF4、BaF2、BaYF5Or Ba2YF7At least one of.
Specifically, the photoinitiator is benzoin and derivative, benzil class compound, alkane in above-mentioned biomaterial
At least one of base benzene ketone compounds, acyl group phosphorous oxides, benzophenone compound or thioxanthones compound.
Preferably, in above-mentioned biomaterial, the benzoin and derivative are styrax, benzoin dimethylether, styrax
At least one of ether, benzoin isopropyl ether or benzoin isobutyl ether.
Preferably, in above-mentioned biomaterial, the benzil class compound is diphenylethan or α, alpha, alpha-dimethyl oxygroup-α-
Phenyl acetophenone.
Preferably, in above-mentioned biomaterial, the alkylbenzene ketone compounds are α, α-diethoxy acetophenone, α-hydroxyl second
At least one of base benzophenone or α-amine ethyl benzophenone.
Preferably, in above-mentioned biomaterial, the acyl group phosphorous oxides is 2,4,6- trimethyl benzoyl diphenyl base oxygen
Change phosphine or phenyl -2,4,6- trimethylbenzoyl phosphonous acid lithium salts.
Preferably, in above-mentioned biomaterial, the benzophenone compound is benzophenone, 2,4- dihydroxy hexichol first
At least one of ketone, Michler's keton or 2- hydroxyl -4'- (2- hydroxy ethoxy) -2- methyl phenyl ketone.
Preferably, in above-mentioned biomaterial, the thioxanthones compound is thio propoxyl group thioxanthone or isopropyl
Base thioxanthone.
The present invention also provides a kind of biomaterial containing cell, be by above-mentioned biomaterial add cell and
At.The amount of the cell is to have cell 1 × 10 in every 1mL biomaterial5~1 × 108It is a.The cell is according to organism
Position, to add same or matched cell tissue.
The present invention also provides the near-infrared laser for non-intruding assist based on DLP principle in body 3D printing method,
Include the following steps:
A, the mathematical model of sample to be printed is established on computers；
B, biomaterial or biomaterial injection containing cell are placed in printer to the appointed part of organism
Platform on；
C, near-infrared laser is by the digital micromirror elements DMD that is made of numerous small lens array in certain exposure
Between project to appointed part described in step B in range and printed.
Preferably, in above-mentioned Method of printing step C, the maximum emission wavelength of the near-infrared laser is 980nm, when exposure
Between range be 1~60s.
In the present invention, up-conversion nano material is doped, the up-conversion nano material adulterated, by the upper of doping
Conversion nano material dispersion forms uniform nanomaterial solution in a solvent；Photoinitiator dissolves in a solvent, and doping is added dropwise
Up-conversion nano material solution stirs sufficiently reaction, is centrifuged, washs to obtain solid, the light as based on upper conversion nano material draws
Send out agent compound.The temperature is 0~200 DEG C.Preferably room temperature.The solvent is hexamethylene, n-hexane, pentane, dichloro
At least one of methane, chloroform, acetonitrile, N,N-dimethylformamide, dimethyl sulfoxide or water.Or the upper conversion of doping is received
Rice material and photoinitiator are simply uniformly mixed, namely obtain the photoinitiator compound based on upper conversion nano material.
In the present invention, the up-conversion nano material preparation method of doping, comprising the following steps: rare earth element chloride (Y,
Yb, Tm), it is mixed according to certain molar concentration with oleic acid and 1- octadecylene, is thermally formed uniform oleic acid mixture solution, with
Ammonium fluoride is added afterwards and presoma is made in the methanol solution of sodium hydroxide, then passes through oersted watt under conditions of high-temperature heating
Er De cures up to NaYF4: Tm, Yb up-conversion nano material, post treatment acid eliminate oleic acid.
Further, using formation core-shell structure nanometer particle NaYF under above-mentioned similar method4:Tm,Yb@NaYF4, i.e.,
NaYF4: the nanoparticle periphery of Tm, Yb are by NaYF4Protective layer package, then acidification removes oleic acid and is prepared with positive electricity and water
Dissolubility has NaYF4The NaYF of nucleocapsid4: Tm, Yb up-conversion nano material.
The beneficial effects of the present invention are: the Yb adulterated in up-conversion of the present invention3+Can absorb has relatively deep tissue to wear
Saturating ability and the light of less 980nm is damaged to normal cell and excites Tm3+The ultraviolet light of 345nm and 361nm wavelength is released,
Upper conversion nano grain can absorb and then be attracted to nanoparticle surface or be distributed in surrounding photoinitiator and absorb to be formed
Free radical has potential application value in body 3D printing research field so as to be used for laser writing technology 3D biometric print.It beats
It successively include the upper conversion nano grain emitting ultraviolet light near infrared light excitation photoinitiator compound during print, by described multiple
It closes the initiator in object and absorbs ultraviolet light and form free radical, and then cause photosensitive polymer monomer polymerization and curing molding.
Detailed description of the invention
Fig. 1 is that a kind of near-infrared laser of non-intruding of the invention assists digital light processing to illustrate in body 3D printing technique
Figure.The mathematical model for establishing sample to be printed on computers first, the digital micro-mirror member being made of numerous small lens array
Part DMD is projected in the Mice Body for being loaded with biomaterial and cell, the photoinitiator of the up-conversion nano material in biomaterial
Compound is initiated to form free radical, and then causes polymer monomer and polymerize to form hydrogel, and mixed cell is embedded in poly-
In the network for closing object hydrogel.
Fig. 2 be using the technology of the present invention in nude mouse printing shaping
Specific embodiment
Biomaterial of the invention, by photosensitive polymer monomer and based on the upper photoinitiator compound for converting nano material
Composition.
Specifically, above-mentioned biomaterial, is drawn by photosensitive polymer monomer solution and the light based on upper conversion nano material
Hair agent compound water solution mixes.
Further, photosensitive polymer monomer concentration is 5~50% in the solution mixed.It is described to mix
Solution in based on it is upper conversion nano material photoinitiator complex concentration be 0.1~10%.The photosensitive polymer list
Bulk concentration is to contain 5~50mg photosensitive polymer monomer in 5~50% every 100 μ L mixed solutions of expression.The photoinitiator
Complex concentration is to contain 1~10mg photoinitiator compound in 0.1~10% every 100 μ L mixed solution of expression.
Specifically, the photosensitive polymer monomer be selected from the hyaluronic acid of methacrylation, methacrylation it is bright
Glue, the polyethylene glycol of methacrylation, methacrylation chitosan, methacrylation albumin, methyl-prop alkylene sea
At least one of alginic acid or methyl-prop alkylene glucan.
Specifically, the photoinitiator compound based on up-conversion is drawn by the up-conversion nano material and light adulterated
Agent composition is sent out, it is described to be doped to mixed with Tm3+And Yb3+；Wherein Tm3+As stimulator, Yb3+As sensitizer.
Further, the upper conversion nano material of the doping also adulterates Er3+、Pr3+、Sm3+、Tb3+、Gd3+、Ho3+、Nd3+、
Dy3+At least one of, it is doped in up-conversion nano material as exciting agent.
Further, when photoinitiator addition is excessive, then the up-conversion nano material adulterated is then relatively fewer, then excites
Light out is weaker, and photoinitiator is insufficient to allow sufficiently to decompose release free radical, thus keep polymer monomer photopolymerization reaction slower,
Influence curing molding.It is 10 ︰, 1~1 ︰ 10 it is advantageous to the mass ratio of the up-conversion nano material of doping and photoinitiator.It is more excellent
Select 2 ︰, 1~1 ︰ 2.
In the photoinitiator compound based on up-conversion, band after the up-conversion nano material surface modification
Charge, then with the photoinitiator of oppositely charged compound can be formed on the surface of the particle by electrostatic interaction absorption；As light draws
Agent neutral is sent out, is dispersed in around the up-conversion nano material of doping.
In the present invention, up-conversion nano material is doped using conventional method, the upper conversion nano material adulterated
Material；Photoinitiator is prepared using conventional method.Such as:
In the present invention, the up-conversion nano material preparation method of doping, comprising the following steps: rare earth element chloride (Y,
Yb, Tm), it is mixed according to certain molar concentration with oleic acid and 1- octadecylene, is thermally formed uniform oleic acid mixture solution, with
Ammonium fluoride is added afterwards and presoma is made in the methanol solution of sodium hydroxide, then passes through oersted watt under conditions of high-temperature heating
Er De cures up to NaYF4: Tm, Yb up-conversion nano material, post treatment acid eliminate oleic acid.
Further, using formation core-shell structure nanometer particle NaYF under above-mentioned similar method4:Tm,Yb@NaYF4, i.e.,
NaYF4: the nanoparticle periphery of Tm, Yb are by NaYF4Protective layer package, then acidification removes oleic acid and is prepared with positive electricity and water
Dissolubility has NaYF4The NaYF of nucleocapsid4: Tm, Yb up-conversion nano material.
In the present invention, photoinitiator phenyl -2,4,6- trimethylbenzoyl phosphonous acid lithium salts is the preparation method is as follows: dimethyl
Phenylphosphine hydrochlorate and the mixing of 2,4,6- tri-methyl chloride occur meter Xie Er-A Erbuzuofu and react to obtain phenyl -2,4,6-
Phenyl -2,4 with negative electricity, 6- front three is prepared in trimethylbenzoyl methylphosphinate, the butanone solution that lithium bromide is added
Base benzoyl phosphonous acid lithium salts.
Embodiment 1
1.NaYF4: the synthesis of Tm, Yb up-conversion nano material, that is, the synthesis of the up-conversion nano material adulterated
Yttrium chloride (108.3mg, 0.556mmol) is added in the round-bottomed flask of 100mL, ytterbium chloride (67.0mg,
0.24mmol) and thulium chloride (1.1mg, 0.004mmol) and 6mL oleic acid and 14mL octadecylene is added, is slowly risen under vacuum condition
Temperature is to 140 DEG C and maintains 30min until forming transparent solution, and 50 DEG C are then cooled under nitrogen protection, is slowly added to be fluorinated
The methanol solution 10mL of ammonium (118.4mg, 3.2mmol) and sodium hydroxide (80mg, 2mmol) simultaneously stirs 30min at 50 DEG C, rises
Methanol is removed under reduced pressure to 70 DEG C, be then rapidly heated to 300 DEG C and maintains 1.5h, is cooled to room temperature and 10mL ethanol precipitation is added,
6500rpm is centrifuged 5min and collects precipitating, abandons supernatant, and 2mL hexamethylene redisperse is added, adds 18mL ethanol precipitation, 6000rpm
It is centrifuged 3min and collects precipitating, so three times, final product is dispersed in 4mL hexamethylene repeated washing.
2.NaYF4:Tm,Yb@NaYF4The synthesis of core-shell structure up-conversion nano material, the i.e. upper conversion of the doping with nucleocapsid
The synthesis of nano material
Yttrium chloride (78mg, 0.4mmol) is added in the round-bottomed flask of 50mL, and 3mL oleic acid and 7mL octadecylene is added, very
It is to slowly warm up to 140 DEG C under empty condition and maintains 30min until forming transparent solution, is then cooled to 50 under nitrogen protection
DEG C, the NaYF of 2mL brand-new is added4: Tm, Yb, be slowly added to ammonium fluoride (59.2mg, 1.6mmol) and sodium hydroxide (40mg,
Methanol solution 5mL 1mmol) simultaneously stirs 30min at 50 DEG C, rises to 70 DEG C and methanol and hexamethylene is removed under reduced pressure, then quickly
It is warming up to 300 DEG C and maintains 1.5h, be cooled to room temperature and 10mL ethanol precipitation is added, 6500rpm is centrifuged 5min collection and precipitates, in abandoning
Clearly, 2mL hexamethylene redisperse is added, adds 18mL ethanol precipitation, 6000rpm is centrifuged 3min and collects precipitating, so repeats to wash
It washs three times, final product is dispersed in 4mL hexamethylene.
3. the NaYF that post-processing is wrapped up except oleic acid to get no oleic acid4:Tm,Yb@NaYF4
The UCNPs of oleic acid package is mixed with 0.1N hydrochloric acid solution, 45 DEG C of ultrasound 1h, the oil on the surface UCNPs in reaction process
Sour ligand is protonated generation oleic acid, then high speed centrifugation, abandons supernatant, and ethanol washing, high speed centrifugation, so repeatedly three is added
Secondary, the nanoparticle finally without oleic acid package disperses in deionized water.
4. the synthesis of phenyl -2,4,6- trimethylbenzoyl phosphonous acid lithium salts
At room temperature under the protective condition of nitrogen, 2,4,6- tri-methyl chlorides are added in the round-bottomed flask of 250mL
(3.2g, 18mmol) is added dropwise 3,5-dimethylphenyl phosphonate (3.0g, 18mol), stirs 18h at room temperature.Reaction solution is heated
To 50 DEG C, the butanone solution of 100mL lithium bromide (6.1g, 72mmol) is added, available white precipitate after 10min is cooled to
4h is stood after room temperature, filters, is washed 3 times with butanone, removes the complete lithium bromide of unreacted.White solid is collected, is drained.
5. the preparation of the photoinitiator compound based on up-conversion nano material
The NaYF of a certain amount of no oleic acid package4:Tm,Yb@NaYF4It is dispersed in water, phenyl -2,4 under stirring condition, 6-
The aqueous solution of trimethylbenzoyl phosphonous acid lithium salts, is stirred overnight at room temperature, and solid is collected by centrifugation, and to obtain up-conversion light-initiated
Agent compound.
6. printing in body
A, the mathematical model such as rectangle of sample to be printed is established on computers；
B, 8 weeks or so nude mice abdominal cavity injection 60 μ L, 10% chloraldurate aqueous solutions are anaesthetized, and then contain 20 μ L
25% polyethyleneglycol diacrylate PEGDA (being purchased from sigma), 2.5% photoinitiator based on up-conversion nano material are compound
Object and 5 × 105The mixed solution of a cell is injected into that mouse is subcutaneous, is subsequently placed on the platform of printer；
C, 980nm near-infrared laser projects to step by the digital micromirror elements DMD being made of numerous small lens array
Appointed part 15s described in rapid B；
D, it is dissected and observed and takes pictures.
Claims (10)
1. biomaterial, it is characterised in that: by photosensitive polymer monomer and the photoinitiator based on upper conversion nano material is compound
Object composition.
2. biomaterial according to claim 1, it is characterised in that: by photosensitive polymer monomer solution and be based on upper turn
The photoinitiator compound water solution for changing nano material mixes；Preferably, photosensitive polymerization in the solution mixed
Object monomer concentration is 5~50%；Photoinitiator compound based on upper conversion nano material in the solution mixed is dense
Degree is 0.1~10%.
3. biomaterial according to claim 1 or 2, it is characterised in that: the photosensitive polymer monomer is selected from methyl-prop
The acylated hyaluronic acid of alkene, the gelatin of methacrylation, the polyethylene glycol of methacrylation, methacrylation shell are poly-
At least one of sugar, methacrylation albumin, methyl-prop alkylene alginic acid or methyl-prop alkylene glucan；It is described based on upper
The photoinitiator compound of conversion nano material is made of the up-conversion nano material and photoinitiator adulterated, described to be doped to
There is Tm3+And Yb3+。
4. biomaterial according to claim 3, it is characterised in that: the up-conversion nano material of the doping also doped with
Er3+、Pr3+、Sm3+、Tb3+、Gd3+、Ho3+、Nd3+、Dy3+At least one of；Preferably, the upper conversion nano material of the doping
Er in material3+、Pr3+、Sm3+、Tb3+、Gd3+、Ho3+、Nd3+、Dy3+At least one of molar content be 0.01~5%.
5. biomaterial according to claim 3 or 4, it is characterised in that: Yb in the up-conversion nano material of the doping3+
Molar content be 5~40%, Tm3+Molar content be 0.01~3%；Preferably, the up-conversion nano material of the doping
Middle Yb3+Molar content be 20~40%, Tm3+Molar content be 0.1~1.5%.
6. according to the described in any item biomaterials of claim 3~5, it is characterised in that: the upper conversion nano material of the doping
Material is external there are also a protective layer, and the protective layer is NaYF4Or NaGdF4；Preferably, the upper conversion nano material of the doping
In cation mole total amount and protective layer in cation mole ratio be 10 ︰, 1~1 ︰ 10；1~1 ︰ 2 of further preferably 2 ︰.
7. according to the described in any item biomaterials of claim 3~6, it is characterised in that: by mass, the upper conversion of doping is received
The mass ratio of rice material and photoinitiator is 10 ︰, 1~1 ︰ 10；Preferably, the up-conversion nano material and photoinitiator of doping
Mass ratio is 2 ︰, 1~1 ︰ 2.
8. according to the described in any item biomaterials of claim 3~7, it is characterised in that: the up-conversion nano material is
Gd2O3、GdYF4、Lu2O3、CaF2、LaF3、ZnF2、Y2O3、YF3、NaYF4、LiYF4、KYF4、BaF2、BaYF5Or Ba2YF7In at least
It is a kind of；The photoinitiator is benzoin and derivative, benzil class compound, alkylbenzene ketone compounds, acyl group phosphorus oxidation
At least one of object, benzophenone compound or thioxanthones compound.
9. biomaterial containing cell, it is characterised in that: by being added in biomaterial according to any one of claims 1 to 8
Cell forms；The amount of the cell is to have cell 1 × 10 in every 1mL biomaterial5~1 × 108It is a.
10. near-infrared laser auxiliary based on DLP principle in body 3D printing method, characterized by the following steps:
A, the mathematical model of sample to be printed is established on computers；
B, biomaterial according to any one of claims 1 to 8 or biomaterial containing cell as claimed in claim 9 are infused
It is mapped to the appointed part of organism, is finally placed on the platform of printer；
C, near-infrared laser is printed by projecting to appointed part by digital micromirror elements DMD；
Preferably, the maximum emission wavelength of the near-infrared laser is 980nm, and exposure time range is 1~60s.
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| CN111590877A (en) * | 2020-05-19 | 2020-08-28 | 江南大学 | Ink direct-writing three-dimensional printing method based on near-infrared photopolymerization |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109232776A (en) * | 2017-07-10 | 2019-01-18 | 四川大学 | Photoinitiator compound based on up-conversion and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109232776A (en) * | 2017-07-10 | 2019-01-18 | 四川大学 | Photoinitiator compound based on up-conversion and its preparation method and application |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111590877A (en) * | 2020-05-19 | 2020-08-28 | 江南大学 | Ink direct-writing three-dimensional printing method based on near-infrared photopolymerization |
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