CN106008850A - Modified hydrogel material used for 3D printing and application of same to drug loading - Google Patents
Modified hydrogel material used for 3D printing and application of same to drug loading Download PDFInfo
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- CN106008850A CN106008850A CN201610404512.3A CN201610404512A CN106008850A CN 106008850 A CN106008850 A CN 106008850A CN 201610404512 A CN201610404512 A CN 201610404512A CN 106008850 A CN106008850 A CN 106008850A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/33—Heterocyclic compounds
- A61K31/335—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin
- A61K31/34—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin having five-membered rings with one oxygen as the only ring hetero atom, e.g. isosorbide
- A61K31/345—Nitrofurans
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/33—Heterocyclic compounds
- A61K31/395—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins
- A61K31/435—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins having six-membered rings with one nitrogen as the only ring hetero atom
- A61K31/47—Quinolines; Isoquinolines
- A61K31/4738—Quinolines; Isoquinolines ortho- or peri-condensed with heterocyclic ring systems
- A61K31/4745—Quinolines; Isoquinolines ortho- or peri-condensed with heterocyclic ring systems condensed with ring systems having nitrogen as a ring hetero atom, e.g. phenantrolines
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/33—Heterocyclic compounds
- A61K31/395—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins
- A61K31/495—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins having six-membered rings with two or more nitrogen atoms as the only ring heteroatoms, e.g. piperazine or tetrazines
- A61K31/505—Pyrimidines; Hydrogenated pyrimidines, e.g. trimethoprim
- A61K31/513—Pyrimidines; Hydrogenated pyrimidines, e.g. trimethoprim having oxo groups directly attached to the heterocyclic ring, e.g. cytosine
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/34—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyesters, polyamino acids, polysiloxanes, polyphosphazines, copolymers of polyalkylene glycol or poloxamers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/06—Ointments; Bases therefor; Other semi-solid forms, e.g. creams, sticks, gels
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
Abstract
The invention discloses a modified hydrogel material used for 3D printing and application of the same to drug loading, belonging to the technical field of 3D printing materials. The modified hydrogel material is prepared through the following steps: adding a hydrogel material, acryloyl chloride and triethylamine into a solvent, carrying out a reaction in an ice bath for 12 h and then carrying out a reaction at normal temperature for 12 h; and washing a reaction product with a saturated sodium bicarbonate solution and then carrying out rotary evaporation so as to obtain the modified hydrogel material. The modified hydrogel is of a long-chain structure and has an active chemical group at its tail end; and as a photopolymerization initiator is added into the aqueous solution of the modified hydrogel, a crosslinking reaction occurs under the illumination of light with a wavelength of 365 nm, so rapid shaping of the material is realized. The modified hydrogel material prepared by using 3D printing technology and used for drug loading can be subjected to injection and printing at normal temperature without extra high-temperature apparatuses, low-temperature apparatuses or the like; and the material is easy to shape, fast in gelating speed, excellent in mechanical properties and beneficial for loading and effective release of different medicine molecules.
Description
Technical field
The invention belongs to 3 D-printing field of material technology, particularly to a kind of modified water gel rubber material printed for 3D and the application on drug loading thereof.
Background technology
In tradition processing industry, forming objects be broadly divided into subtract material molding, by molded, increase material molding, growth shaping, and the most either in industrial use still in Technological research field, 3D printing technique is as the one of increasing material forming technique.3D printing technique is to be combined with quick automatic forming system by computer data model, under conditions of without further mold, the materials such as liquid, powder body, sheet material is successively processed superposition, is finally printed as required pattern.3D printing technique in the past few decades, has been successfully applied in clinical field, including neurosurgery, orthopaedics, the department of stomatology etc..At present, the main application that 3D prints is presented on medical assistance, such as 3D stigmatosis body Model, and 3D prints the medical instruments such as personalized surgical guide.
Along with development and the existing 3D printed material of living cells culture technique are the most constantly exposed shortcoming, as condition of molding is harsh, need heating, laser lamp, flexibility and mechanical property can not be compatible very well, and mechanical property is more single etc., prints biomaterial and be increasingly becoming study hotspot in recent years.Having foreign study team incorporation engineering principle and biology at present, the operation that hydrogel is applied on robot construction realize robot is detailed-oriented.Research council of Australia brilliance electronic material scientific center successfully passes 3D and prints tough and tensile fiber reinforcement hydrogel to simulate softness and the intensity of human body cartilage.Calcium chloride solution introducing calcium ion is immersed by 3D prints alginate structure in Univ Texas Tech and Texas A&M university, and the two forms crosslinking so that it is tensile strength is close to the natural cartilage of the mankind.But the material category being applied to 3D printing is the shortest.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art with not enough, the primary and foremost purpose of the present invention is to provide a kind of modified water gel rubber material printed for 3D.
Another object of the present invention is the application providing the above-mentioned modified water gel rubber material for 3D printing on carrying medicament.
The purpose of the present invention is realized by following proposal:
A kind of modified water gel rubber material printed for 3D, is mainly prepared by following methods:
Joining in solvent by hydrogel material, acryloyl chloride, triethylamine, react and react 12h under 12h, then room temperature under ice bath, then with saturated solution of sodium bicarbonate washing reaction product, then rotary evaporation i.e. obtains modified water gel rubber material.
Described hydrogel material is at least one in Pluronic series and Polyethylene Glycol series.
Preferably, described hydrogel material is PO-EO block copolymer, EO-PO block copolymer, PEG-2000, at least one in PEG-4000, PEG-6000.
Described solvent is at least one in dichloromethane, chloroform, methanol, toluene and acetone.
The consumption of hydrogel material used is the hydrogel material that every 100mL solvent uses 0.6~13g;The consumption of acryloyl chloride used is the acryloyl chloride that every 100mL solvent uses 3~6mL;The consumption of triethylamine used is the triethylamine that every 100mL solvent uses 3~6mL.
The application on drug loading of the above-mentioned modified water gel rubber material for 3D printing.
The application on drug loading of the described modified water gel rubber material for 3D printing is mainly realized by the following method:
Modified water gel rubber material is dissolved in water, then mixes with drug molecule, add Photoepolymerizationinitiater initiater, make printing solution;Solution will be printed and inject in three-dimensional printer, and under ultraviolet light irradiates, carry out 3D printing, obtain the hydrogel material of the carrying medicament that 3D prints.
In described printing solution, the mass fraction of each component is as follows:
Described drug molecule includes but not limited to treat tumor class medicine, the anti-inflammatory drugs for the treatment of skin wounds, hemostasis class medicine, antimicrobial DP finish and acceleration wound healing formulation.
Preferably, described treatment tumor class medicine is 5-FU or camptothecine.
Preferably, described acceleration wound healing formulation is nitrofural.
Described Photoepolymerizationinitiater initiater is 2,2-dimethoxy-2-Phenyl ethyl ketone.
Described ultraviolet light refers to that wavelength is 365nm, and energy is the ultraviolet light of 5~100W.
Described mixing refers to stir under room temperature 24h.
Drug molecule is replaced with other biological material, such as materials such as double sulfur classes, double selenium classes, the more diversified hydrogel that can be used for 3D printing can be prepared.
The mechanism of the present invention is:
Modified hydrogel is backbone, and at long-chain end with active chemical group, Photoepolymerizationinitiater initiater is added in the aqueous solution of modified water gel rubber material, initiator can produce free radical at the photoenvironment of 365nm, thus causes segment to react, and light irradiance is the strongest, speed and concentration that free radical produces are the strongest, make cross-linking reaction degree strengthen, accelerate the speed of material gel, it is achieved material rapid shaping.
On this basis, present invention application 3D printing technique, i.e. accumulation manufacturing technology, it it is a kind of machine of Rapid Prototyping technique, based on mathematical model file, by printer head, one layer of very thin mixing printing fluid spraying is printed upon on pallet, uses ultraviolet light treatment with irradiation simultaneously, pallet declines minimum distance afterwards, is carrying out next layer of printing fluid spraying, molding.
The present invention, relative to prior art, has such advantages as and beneficial effect:
The 3D stamping ink gel rubber material of the present invention is injected at normal temperatures and is printed, it is not necessary to the device such as additional high temperature, low temperature, it is easy to molding, and gelation speed is fast, excellent in mechanical performance, can be used for preparing the structure of various complexity, is conducive to loading different drug molecules and effectively discharging.
The 3D stamping ink gel rubber material of the present invention can be with other material mixing molding, there is good biocompatibility, improve chemicals load factor and make the variation of load contents thing, simultaneously improving the mechanical property etc. of printed material, being conducive to expanding printed material range.
Accompanying drawing explanation
Fig. 1 is the mixing printing fluid springform spirogram under different ultraviolet light irradiation times of embodiment 1~4 preparation.
Fig. 2 is the square model of the hydrogel material of the carrying medicament that embodiment 1~4 prints springform spirogram under different scanning frequency.
Fig. 3 is the medicament slow release comparison diagram of the hydrogel material of the carrying medicament of preparation in embodiment 8 and comparative example 1.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Used in the embodiment of the present invention, reagent all can obtain from market buying, and primary raw material information is as follows:
Pluronic F-127 (EO100-PO65-EO100): purchased from Sigma-Aldrich company
Acryloyl chloride: purchased from Schuchardt company
Triethylamine, dichloromethane, acetone, sodium bicarbonate: be purchased from China's Tianjin great Mao chemical reagent factory
2,2-dimethoxy-2-Phenyl ethyl ketones: purchased from Acros company
5-FU: purchased from Aladdin company
Camptothecine: purchased from Aladdin company
The preparation of the hydrogel material of the carrying medicament that embodiment 1:3D prints
(1) preparation of modified water gel rubber material: it is dichloromethane that 12.6g Pluronic F-127 is dissolved in 100mL volume ratio: in the mixed solution of acetone=1:1,3mL acryloyl chloride and 3mL triethylamine it is added dropwise under ice bath, ice bath reaction 12h, normal-temperature reaction 12h.Reaction terminate after, with saturated solution of sodium bicarbonate wash, rotary evaporation and 40 DEG C vacuum drying 24h modified F-127 (12g).
(2) preparation of the hydrogel material of the carrying medicament printed for 3D: 11g modification F-127 is dissolved in 100mL pure water, adds 1g camptothecine, adds 0.5g 2,2-dimethoxy-2-Phenyl ethyl ketone mix homogeneously again and obtain printing fluid after stirring at normal temperature 24h.
(3) 3D prints: utilizes the square of CAD design a size of 20*20*2mm (length, width and height) and is loaded in the middle of print software, mixing printing fluid is injected in 3D printer injection head, start instrument, injection head successively sprays out printing fluid, model is printed under ultraviolet lighting, simultaneously under different ultraviolet light irradiation times, it being carried out the detection of elastic modelling quantity, result is as it is shown in figure 1,10%F-127 in corresponding diagram 1.
The preparation of the hydrogel material of the carrying medicament that embodiment 2:3D prints
" the modified F-127 of 12g is dissolved in 100mL water " in embodiment 1 is revised as " the modified F-127 of 5.3g is dissolved in 100mL water ", and remaining is the most same as in Example 1.In the hydrogel material now printed, the mass fraction of modified F-127 is 5%.Under different ultraviolet light irradiation times, it being carried out the detection of elastic modelling quantity, result is as it is shown in figure 1,5%F-127 in corresponding diagram 1.
The preparation of the hydrogel material of the carrying medicament that embodiment 3:3D prints
" the modified F-127 of 12g is dissolved in 100mL water " in embodiment 1 is revised as " the modified F-127 of 18g is dissolved in 100mL water ", and remaining is the most same as in Example 1, and in the hydrogel material now printed, the mass fraction of modified F-127 is 15%.Under different ultraviolet light irradiation times, it being carried out the detection of elastic modelling quantity, result is as it is shown in figure 1,15%F-127 in corresponding diagram 1.
The preparation of the hydrogel material of the carrying medicament that embodiment 4:3D prints
" the modified F-127 of 12g is dissolved in 100mL water " in embodiment 1 is revised as " the modified F-127 of 25g is dissolved in 100mL water ", and remaining is the most same as in Example 1.In the hydrogel material now printed, the mass fraction of modified F-127 is 20%.Under different ultraviolet light irradiation times, it being carried out the detection of elastic modelling quantity, result is as it is shown in figure 1,20%F-127 in corresponding diagram 1.
From figure 1 it appears that mixing printing fluid has only to 4~10s the most plastic, illustrate that the gelation rate of the hydrogel material of the present invention is the fastest.
The preparation of the hydrogel material of the carrying medicament that embodiment 5:3D prints
" adding 1g camptothecine " in step (2) in embodiment 1 is replaced with " adding 2g 5-FU ", and what remaining operated is all same as embodiment 1.
The test of the elastic performance of the hydrogel material of the carrying medicament that embodiment 6:3D prints
Print 3D in embodiment 1~4 can test the elastic performance of square model of hydrogel material of carrying medicament, and result is as in figure 2 it is shown, from figure 2 it can be seen that elastic modelling quantity is all higher than 103Pa, excellent in mechanical performance, the model printed is the most broken.
The drug delivery amount detection of the hydrogel material of the carrying medicament that embodiment 7:3D prints
The square model of the hydrogel material of the carrying medicament that 3D in embodiment 1 and embodiment 5 prints is carried out drug delivery amount detection under ultraviolet spectrophotometer, understand modified F-127 and the drug loading of camptothecine is reached 100 μ g/mg, 5-FU drug loading is reached 250 μ g/mg.Illustrate that the hydrogel material of the present invention is conducive to loading different drug molecules.
The medicament slow release of the hydrogel material of the carrying medicament that embodiment 8:3D prints
The drafting of standard curve: camptothecine is each configured to 0.1 μ L/mL, 1 μ L/mL, 10 μ L/mL, 20 μ L/mL, 30 μ L/mL, 40 μ L/mL, 60 μ L/mL, 70 μ L/mL, 80 μ L/mL, 90 μ L/mL, 100 μ L/mL, 120 μ L/mL, 150 μ L/mL, sample is put ultraviolet spectrophotometer into, is drawn absorption value, the absorption value utilizing camptothecine concentration and its correspondence is mapped, and draws standard curve y=0.032x+0.1211 (wherein x is camptothecine concentration, and y is absorbance).
nullThe modified water gel 3D of the load camptothecine obtained in embodiment 1 step (2) is printed as the cube of 2cm*2cm*0.5cm,Print 5 samples,In the PBS solution of the pH=7.4 that sample is individually positioned in 10mL,At following time (15min,30min,1h,2h,3h,4h,6h,8h,18h,20h,24h,36h,48h) take sample ultraviolet spectrophotometer and survey the uv absorption intensity under 350nm,Take the meansigma methods of five samples,Substitute into standard curve,Draw the camptothecine concentration in the buffer solution under different time,And PBS solution volume is known,Therefore camptothecine concentration in slow release efficiency=PBS solution/put into the camptothecine total concentration after the sample in PBS solution is completely dissolved,By measure camptothecine absorbance under different time and sample be completely dissolved after the absorbance of solution,Can draw the hydrogel material of the carrying medicament that 3D in embodiment 8 prints under different time drug release efficiency figure,I.e. Fig. 3.
Comparative example 1: the medicament slow release of the hydrogel material of the carrying medicament of common print
nullThe printing fluid being loaded with camptothecine prepared in embodiment 1 step (2) is placed in the mould of plastics of the 2cm*2cm*0.5cm printed with FDM 3D in advance,Ultraviolet light irradiates,Take out after curing molding,In the PBS solution of the pH=7.4 that sample after molding is individually positioned in 10mL,At following time (15min,30min,1h,2h,3h,4h,6h,8h,18h,20h,24h,36h,48h) take sample ultraviolet spectrophotometer and survey the uv absorption intensity under 350nm,Average,Substitute into standard curve,Draw the camptothecine concentration in the buffer solution under different time,By measure camptothecine absorbance under different time and sample be completely dissolved after solution absorbance in comparative example 1 hydrogel material of the carrying medicament of common print under different time drug release efficiency figure.
Fig. 3 is the medicament slow release comparison diagram of the hydrogel material of the carrying medicament of preparation in embodiment 8 and comparative example 1, as can be seen from Figure 3, more than common die sample preparation of release amount of medicine that 3D prints, and the variance ratio common die sample preparation of 3D printed sample release amount of medicine is the least average, illustrate that the drug release efficiency of the hydrogel material of the carrying medicament of the 3D printing of the present invention is the highest more stable.
Above-described embodiment is the present invention preferably embodiment; but embodiments of the present invention are also not restricted to the described embodiments; the change made under other any spirit without departing from the present invention and principle, modify, substitute, combine, simplify; all should be the substitute mode of equivalence, within being included in protection scope of the present invention.
Claims (10)
1. the hydrogel material printed for 3D, it is characterised in that prepared by following methods:
Hydrogel material, acryloyl chloride, triethylamine are joined in solvent, reaction 12h under ice bath, more often
Reacting 12h under temperature, then with saturated solution of sodium bicarbonate washing reaction product, then rotary evaporation i.e. obtains modified
Hydrogel material.
The hydrogel material printed for 3D the most according to claim 1, it is characterised in that:
Described hydrogel material is at least one in Pluronic series and Polyethylene Glycol series;
Described solvent is at least one in dichloromethane, chloroform, methanol, toluene and acetone.
The hydrogel material printed for 3D the most according to claim 1, it is characterised in that:
Described hydrogel material is PO-EO block copolymer, EO-PO block copolymer, PEG-2000,
At least one in PEG-4000, PEG-6000.
The hydrogel material printed for 3D the most according to claim 1, it is characterised in that:
The consumption of hydrogel material used is the hydrogel material that every 100mL solvent uses 0.6~13g;
The consumption of acryloyl chloride used is the acryloyl chloride that every 100mL solvent uses 3~6mL;Three second used
The consumption of amine is the triethylamine that every 100mL solvent uses 3~6mL.
5. according to the modified water gel rubber material for 3D printing described in any one of Claims 1 to 4 at medicine
Application in thing load.
The modified water gel rubber material printed for 3D the most according to claim 5 is at drug loading
Application, it is characterised in that realized by following methods:
Modified water gel rubber material is dissolved in water, then mixes with drug molecule, add Photoepolymerizationinitiater initiater,
Make printing solution;Solution will be printed and inject in three-dimensional printer, under ultraviolet light irradiates, carry out 3D printing,
Obtain the hydrogel material of the carrying medicament that 3D prints.
The modified water gel rubber material printed for 3D the most according to claim 6 is at drug loading
Application, it is characterised in that:
In described printing solution, the mass fraction of each component is as follows:
The modified water gel rubber material printed for 3D the most according to claim 6 is at drug loading
Application, it is characterised in that:
Described drug molecule is treatment tumor class medicine, the anti-inflammatory drugs for the treatment of skin wounds, hemostasis class
Medicine, antimicrobial DP finish or acceleration wound healing formulation;
Described Photoepolymerizationinitiater initiater is 2,2-dimethoxy-2-Phenyl ethyl ketone.
The modified water gel rubber material printed for 3D the most according to claim 8 is at drug loading
Application, it is characterised in that:
Described treatment tumor class medicine is 5-FU or camptothecine;
Described acceleration wound healing formulation is nitrofural.
The modified water gel rubber material printed for 3D the most according to claim 6 is at drug loading
Application, it is characterised in that:
Described ultraviolet light refers to that wavelength is 365nm, and energy is the ultraviolet light of 5~100W;
Described mixing refers to stir under room temperature 24h.
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Cited By (14)
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WO2018090190A1 (en) * | 2016-11-15 | 2018-05-24 | 深圳先进技术研究院 | Clay-based hydrogel matrix for three-dimensional printing, preparation method therefor and use thereof |
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CN107033372A (en) * | 2017-05-15 | 2017-08-11 | 暨南大学 | Hydrogel with multiple response function and its production and use |
CN107033372B (en) * | 2017-05-15 | 2019-04-05 | 暨南大学 | Hydrogel and its preparation method and application with multiple response function |
CN107412853A (en) * | 2017-05-19 | 2017-12-01 | 暨南大学 | Shape memory gel and the application in controlled release preparation made of 3D printing |
CN107551320A (en) * | 2017-07-25 | 2018-01-09 | 华南理工大学 | A kind of 3D printing hydrogel porous support for possessing antibacterial functions and preparation method thereof |
ES2828509A1 (en) * | 2019-11-26 | 2021-05-26 | Fund Idonial | COMPOSITION FOR3D PRINTING OF SEMI-SOLID DRUGS (Machine-translation by Google Translate, not legally binding) |
WO2021105051A1 (en) | 2019-11-26 | 2021-06-03 | Fundacion Idonial | Composition for the 3d printing of semisolid drugs |
CN112843022A (en) * | 2021-03-31 | 2021-05-28 | 吉林大学 | Programmable intelligent controlled release capsule and application and preparation method thereof |
CN113230464A (en) * | 2021-04-01 | 2021-08-10 | 暨南大学 | Anti-restenosis 3D printing self-expanding degradable intravascular stent and preparation method thereof |
CN113230464B (en) * | 2021-04-01 | 2022-04-12 | 暨南大学 | Anti-restenosis 3D printing self-expanding degradable intravascular stent and preparation method thereof |
CN115154663A (en) * | 2022-07-05 | 2022-10-11 | 中国科学院化学研究所 | Hydrogel type tissue engineering scaffold with two-phase drug slow release function, photocuring 3D printing preparation method thereof and photosensitive resin |
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