CN109293949A - A kind of double-network hydrogel material and preparation method thereof of the filler of calcium phosphate granules containing antimicrobial nano - Google Patents
A kind of double-network hydrogel material and preparation method thereof of the filler of calcium phosphate granules containing antimicrobial nano Download PDFInfo
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
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- 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
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- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/04—Polyamides derived from alpha-amino carboxylic acids
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/04—Alginic acid; Derivatives thereof
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Abstract
The invention discloses a kind of double-network hydrogel materials and preparation method thereof of filler of calcium phosphate granules containing antimicrobial nano.The modification of general-polyglutamic acid mixes copper nano-calcium phosphate and aqueous suspensions is made, then initiator ammonium persulfate and crosslinking agent N are added, N '-methylene-bisacrylamide, pH value is adjusted to 5.0~6.5, sodium alginate is added to stir evenly, then tetramethylethylenediamine is added, is stirred to react, the double-network hydrogel material of the filler of calcium phosphate granules containing antimicrobial nano is cleaned, is dried to obtain.Copper calcium phosphate warp-polyglutamic acid modification is mixed, the substitution rate of copper ion in calcium phosphate is not only improved, and strengthen bonding action, effectively slows down the spilling of copper ion, slow down the cytotoxicity at release initial stage again on the basis of with antibacterial action.Antibacterial calcium phosphate granules are that nanometer is spherical, and granular size is mainly between 10nm-70nm.
Description
Technical field:
The invention belongs to technical field of biological materials, more particularly, to a kind of the double of filler of calcium phosphate granules containing antimicrobial nano
Network aqueous gel material.
Background technique:
Copper is closely bound up with bone health, osteoporosis generation is easily led to when human body lacks copper, so that bone is easily fractured.Its
Main cause is that copper can influence collagen maturation, and copper shortage will be such that the synthesis quantity of collagenous fibres in bone declines, lead to epiphysis
Growth is suppressed, and new born bone tissue is loose, long bone fragility and termination bone uptake.Supplementation with copper can in the culture medium of osteoblast
To increase the crosslinking of collagenous fibres, be conducive to the synthesis of collagen.Ostosis is by including that angiogenesis and cell induce
Equal many factors synergy as a result, copper ion promotes angiogenesis.More importantly copper has good antibacterial activity, with
Silver is compared with zinc, and the antibacterial activity of copper is strong, cheap, and environmental safety is higher.It is being related to tissue grafts or biomedicine
In the operation of implantation material, infection is implantation material failure and the main reason for postoperative complication.Therefore, copper nano particles are mixed
Bracket can promote Bone Defect Repari and revascularization, and can reduce the risk of infection to the maximum extent.Adulterate inorganic antibacterial gold
The hydroxyapatite for belonging to ion not only has good biocompatibility, but also strong antibacterial, highly-safe, it is expected to for facing
Bed, is with a wide range of applications.It is at present the Antibacterial agent preparation method of carrier based on ion-exchange using hydroxyapatite,
The disadvantages of the method are as follows the combination of copper ion and carrier is weaker, causing copper ion quickly to dissociate, product is permanent to be resisted without being able to maintain
Bacterium property, it is furthermore toxic using the too high meeting of initial stage free copper ion concentration out, and bone metabolism is interfered, inhibit the synthesis of collagen,
The collagen that will lead to backbone and epiphysis is reduced.
Summary of the invention:
The object of the present invention is to provide a kind of double-network hydrogel material of filler of calcium phosphate granules containing antimicrobial nano and its
Preparation method, it, which not only can be improved, mixes copper ion substitution rate in copper calcium phosphate, and can reinforce bonding action, effectively slow down copper from
The spilling of son；The nanometer that the Copper-cladding Aluminum Bar calcium phosphate of this method preparation is 10-70nm is spherical, favorable dispersibility.Additionally, due to-poly- paddy
Propylhomoserin forms copolymer with copper calcium phosphate is mixed, so that calcium phosphate shows that describing property of biology is good rich in amide groups and carboxylic group,
And hydrogel material can be formed under the conditions of low temperature ultrasonic.
The present invention is by being rich in amide groups and carboxyl in nano-calcium phosphate particle, under the conditions of low temperature ultrasonic and initiator mistake
Under ammonium sulfate (APS) and crosslinking agent N, N '-methylene-bisacrylamide (BIS) enhancing, tetramethylethylenediamine (APS catalyst) is made
Under, the hydrogel with certain rheological properties can be formed；Additionally by adjusting pH value to slightly acidic condition, it is poly- to mix copper calcium phosphate/-
Calcium ion slowly dissolves out in glutamic acid, and sodium alginate soln is added with this condition, and being good for calcium ion formation ionomer can shape
At uniform Sodium Alginate Hydrogel Films.It mixes copper calcium phosphate/- polyglutamic acid and sodium alginate two parts polymer network passes through amidated peptide
Carboxyl on amido and sodium alginate segment on chain forms covalent crosslink, and mutually winds, and forms dual network structure.
The double-network hydrogel material of the filler of calcium phosphate granules containing antimicrobial nano of the invention, including antibacterial calcium phosphate nano
Particle and hydrogel material, antibacterial calcium phosphate nanoparticles are dispersed in hydrogel material, and the antibacterial calcium phosphate is received
Rice grain is that nanometer is spherical, and granular size is between 10nm~70nm.
The double-network hydrogel material of the filler of calcium phosphate granules containing antimicrobial nano preferably-polyglutamic acid modification mix
Copper nano-calcium phosphate.
The double-network hydrogel material of the filler of calcium phosphate granules containing antimicrobial nano of the invention is to give by the following method
Preparation:
The modification of general-polyglutamic acid mixes copper nano-calcium phosphate and aqueous suspensions is made, then adds initiator ammonium persulfate and crosslinking agent
N, N '-methylene-bisacrylamide adjust pH value to 5.0~6.5, sodium alginate are then added and stirs evenly, is eventually adding and urges
Agent tetramethylethylenediamine, is stirred to react, and cleans, is dried to obtain the double-network hydrogel of the filler of calcium phosphate granules containing antimicrobial nano
Material.
It is preferred that, the specific steps are as follows:
A, solubility calcium salting liquid and soluble copper salting liquid are uniformly mixed, obtain calcium copper solution；
B ,-polyglutamic acid is added in phosphate solution, adjusts pH value to 10.0 or more, is then added to calcium copper solution
In, 30 DEG C~80 DEG C, pH value maintain between 9.0~10.0, be stirred to react 3-12 hours, it is still aging after reaction, receive
Take precipitated nanocrystals particle, be washed with water, be then dried to obtain-polyglutamic acid modification mix copper nano-calcium phosphate；
C, general-polyglutamic acid it is modified mix copper nano-calcium phosphate be added in deionized water water and in 0~30 DEG C of ultrasound until
Aqueous suspensions are formed, then add initiator ammonium persulfate and crosslinking agent N, N '-methylene-bisacrylamide in aqueous suspensions, 10 DEG C ±
It is stirred to react under the conditions of 5 DEG C, and adjusting pH value is 5.0~6.5, then adds sodium alginate soln, is stirred to react, is further continued for adding
Add tetramethylethylenediamine, be stirred to react, after reaction, mixed liquor is put into mold, exhaust is stood, then washed, dry
The double-network hydrogel material of the filler of calcium phosphate granules containing antimicrobial nano is obtained afterwards.
It is preferred that the soluble calcium salt is calcium chloride or four water-calcium nitrate.
It is preferred that the phosphate solution is dipotassium hydrogen phosphate, disodium hydrogen phosphate, diammonium hydrogen phosphate, potassium dihydrogen phosphate, phosphorus
The aqueous solution of acid dihydride sodium or ammonium dihydrogen phosphate, concentration 0.1mol/L.
It is preferred that the soluble copper salt is nitrate trihydrate copper.
The step a's is uniformly mixed solubility calcium salting liquid and soluble copper salting liquid, is by calcium ion
The amount of substance: the ratio that copper ion the mass ratio of the material is 20~1:1 mixes.
The step b's is added to-polyglutamic acid in phosphate solution ,-polyglutamic acid final concentration of 0.5~
4.0mg/mL。
The step b's is added to phosphate solution in calcium copper solution, is total according to calcium copper ion in calcium copper solution
The amount of substance: the amount of the substance of phosphate anion is 1.5~2:1 in phosphate solution.
The step b's is stirred to react, and stirring rate is 600~1000rpm.
The step c general-polyglutamic acid is modified mixes copper nano-calcium phosphate and be added to the water, additive amount is 0.5~
50mg/ml water, i.e. be added in every milliliter of water 0.5~50mg-polyglutamic acid modification mixes copper nano-calcium phosphate, ultrasonic time 5
~45min.
The concentration of sodium alginate soln is 0.5~50mg/ml in the step c.
In the step c ,-polyglutamic acid is modified mix copper nano-calcium phosphate and sodium alginate dosage quality than range be 10~
1:1；Copper nano-calcium phosphate addition 1~50mg of ammonium sulfate, N, N '-methylene-bisacrylamide are mixed by every gram-polyglutamic acid is modified
0.25~15mg, 1~20mg of tetramethylethylenediamine amount be added.
Using method of the invention, the modified preparation method for mixing copper calcium phosphate of biodegradable material-polyglutamic acid is utilized
It not only can be improved and mix copper ion substitution rate in copper calcium phosphate, and bonding action can be reinforced, effectively slow down the spilling of copper ion,
It is stood in the PBS buffer solution of PH7.2, as time goes by, copper ion slow release, cumulative release amount is 0.52ppm- after 15 days
Then 0.95ppm maintains dynamic equilibrium release rule.；The nanosphere that the Copper-cladding Aluminum Bar calcium phosphate of this method preparation is 10-70nm
Shape, favorable dispersibility.It additionally, due to-polyglutamic acid and mixes copper calcium phosphate and forms copolymer, so that calcium phosphate shows rich in amide
Base and carboxylic group, describing property of biology is good, and hydrogel material can be formed under the conditions of low temperature ultrasonic.
Specific embodiment:
The following examples are further illustrations of the invention, rather than limitation of the invention.
In addition to being defined, technical term used in following embodiment has universal with those skilled in the art of the invention
The identical meanings of understanding.Test reagent used in following embodiment is unless otherwise specified conventional biochemical reagent；It is described
Experimental method is unless otherwise specified conventional method.
Embodiment 1
(1) 0.1mol/L nitric acid calcium salt soln and 0.1mol/L nitric acid copper salt solution are uniformly mixed by 20:1 volume ratio,
Obtain calcium copper solution；
(2) 200mg- polyglutamic acid is added in 50ml 0.1mol/L phosphate (dipotassium hydrogen phosphate) solution, is then adjusted
PH value is to 10.0, according to the amount of calcium copper ion total material in calcium copper solution: the amount of the substance of phosphate anion in phosphate solution
Phosphate solution containing-polyglutamic acid is slowly dropped in calcium copper solution by the ratio of=3:2, constant temperature under the conditions of 80 DEG C,
1000rpm high speed magnetic stirring, and pH value maintains between 9.0-10.0, reacts 3 hours；
(3) still aging overnight after reaction, centrifugation obtains nano particle, and is successively washed repeatedly with distilled water, institute
It obtains product and is freeze-dried as-polyglutamic acid and is modified and mix copper nano-calcium phosphate；
(4) weigh 20mg-the modified copper nano-calcium phosphate of mixing of polyglutamic acid is added in 20 milliliters of ultra-pure water solutions and 0 DEG C
Ultrasound 5 minutes forms the aqueous suspensions that nano particle is evenly distributed.
(5) 30 μ g initiator ammonium persulfates (APS) and 5 μ g crosslinking agent N, N '-methylene are added in the aqueous suspensions in (4)
Bisacrylamide (BIS) stirs under the conditions of 5 DEG C 30 minutes, then adjusts pH value to 6.0；
(6) 10mg/ml sodium alginate 20ml solution is taken to be slowly added in the solution of step (5) and quickly stir 20 minutes；
(7) it takes the tetramethylethylenediamine (APS catalyst) of 30 μ g to be added in the mixed solution of (6) step, continues quickly stirring
10 minutes；
(8) mixed liquor of (7) is put into grinding tool, and slight oscillatory purging vacuum ten minutes, is then allowed to stand, used
0.15MNaCl solution is rinsed, up to the double-network hydrogel material of the filler of calcium phosphate granules containing antimicrobial nano after freeze-drying.
This method is made-and the modified antimicrobial nano calcium phosphate nano ball size of polyglutamic acid is 10-20nm, made dual network water
For the gel swelling degree of balance up to 12.45 times, hydrogel elastic modulus is 0.28MPa, tensile strength 2.74MPa.PH7.2's
It is stood in PBS buffer solution, as time goes by, copper ion slow release, cumulative release amount is 0.95ppm after 15 days, is then tieed up
It holds in 0.95 ± 0.14ppm dynamic equilibrium release rule.
Embodiment 2
(1) 0.1mol/L nitric acid calcium salt soln and 0.1mol/L nitric acid copper salt solution are uniformly mixed by 1:1 volume ratio；
(2) 10mg- polyglutamic acid solution is added in 20ml 0.1mol/L phosphate (disodium hydrogen phosphate) solution, so
Adjust pH value to 10.3 afterwards, according to the amount of calcium copper ion total material in calcium copper solution: the substance of phosphate anion in phosphate solution
Amount=5:3 ratio, the phosphate solution containing-polyglutamic acid is slowly dropped in calcium copper solution, it is permanent under the conditions of 30 DEG C
Temperature, 600rpm high speed magnetic stirring, and pH value maintains between 9.0-10.0, reacts 10 hours；
(3) still aging overnight after reaction, centrifugation obtains nano particle, and is successively washed repeatedly with distilled water, institute
It obtains product and is freeze-dried as-polyglutamic acid and is modified and mix copper nano-calcium phosphate；
(4) weigh 10mg-the modified copper nano-calcium phosphate of mixing of polyglutamic acid is added in 20 milliliters of ultra-pure water solutions and 30
DEG C ultrasound 15 minutes, form the aqueous suspensions that nano particle is evenly distributed.
(5) 10 μ g initiator ammonium persulfates (APS) and 10 μ g crosslinking agent N, N '-methylene are added in the aqueous suspensions of (4)
Bisacrylamide (BIS) stirs under the conditions of 10 DEG C 30 minutes, then adjusts pH value to 5.0；
(6) 0.5mg/ml sodium alginate 20ml solution is taken to be slowly added in the solution of step (5) and quickly stir 5 minutes；
(7) it takes the tetramethylethylenediamine (APS catalyst) of 10 μ g to be added in the mixed solution of (6) step, continues quickly stirring 5
Minute；
(8) mixed liquor of (7) is put into grinding tool, and slight oscillatory purging vacuum ten minutes, is then allowed to stand, used
0.15MNaCl solution is rinsed, up to the double-network hydrogel material of the filler of calcium phosphate granules containing antimicrobial nano after freeze-drying.
This method is made-and the modified antimicrobial nano calcium phosphate nano ball size of polyglutamic acid is 50-70nm, made dual network water
For the gel swelling degree of balance up to 10 times, hydrogel elastic modulus is 0.21MPa, tensile strength 2.53MPa.In the PBS of PH7.2
It is stood in buffer, as time goes by, copper ion slow release, cumulative release amount is 0.52ppm after 15 days, is maintained at
0.52 ± 0.09ppm dynamic equilibrium release rule.
Embodiment 3
(1) 0.05mol/L nitric acid calcium salt soln and 0.05mol/L nitric acid copper salt solution are mixed by 16:5 volume ratio equal
It is even；
(2) 100mg- polyglutamic acid solution is added in 100ml 0.05mol/L phosphate (potassium dihydrogen phosphate) solution,
Then adjust pH value to 10.5, according to the amount of calcium copper ion total material in calcium copper solution: the object of phosphate anion in phosphate solution
Phosphate solution containing-polyglutamic acid is slowly dropped in calcium copper solution, under the conditions of 30 DEG C by amount=2:1 ratio of matter
Constant temperature, 1000rpm high speed magnetic stirring, and pH value maintains between 9.0-10.0, reacts 12 hours；
(3) still aging overnight after reaction, centrifugation obtains nano particle, and is successively washed repeatedly with distilled water, institute
It obtains product and is freeze-dried as-polyglutamic acid and is modified and mix copper nano-calcium phosphate；
(4) weigh 1.0g-the modified copper nano-calcium phosphate of mixing of polyglutamic acid is added in 20 milliliters of ultra-pure water solutions and 0 DEG C
Ultrasound 45 minutes forms the aqueous suspensions that nano particle is evenly distributed.
(5) 50mg initiator ammonium persulfate (APS) and 15mg crosslinking agent N, N '-methylene are added in the aqueous suspensions of (4)
Bisacrylamide (BIS) stirs under the conditions of 15 DEG C 30 minutes, then adjusts pH value to 6.5；
(6) 50mg/ml sodium alginate 20ml is taken to be slowly added in the solution of step (5) and quickly stir 30 minutes；
(7) it takes the tetramethylethylenediamine (APS catalyst) of 20mg to be added in the mixed solution of (6) step, continues quickly stirring
15 minutes；
(8) mixed liquor of (7) is put into grinding tool, and slight oscillatory purging vacuum ten minutes, is then allowed to stand, used
0.15MNaCl solution is rinsed, up to the double-network hydrogel material of the filler of calcium phosphate granules containing antimicrobial nano after freeze-drying.
This method is made-the modified antimicrobial nano calcium phosphate of polyglutamic acid be two kinds of sizes nanosphere (10-20nm and 50-
60nm), made double-network hydrogel swelling equilibrium degree can be 13.39 times big, and hydrogel elastic modulus is 0.32MPa, tensile strength
For 3.1MPa.It is stood in the PBS buffer solution of PH7.2, as time goes by, copper ion slow release, cumulative release after 15 days
Amount is 0.88ppm, is maintained at 0.88 ± 0.11ppm dynamic equilibrium release rule.
For presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the spirit and principles in the present invention it
Interior, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of double-network hydrogel material of the filler of calcium phosphate granules containing antimicrobial nano, which is characterized in that including antibacterial phosphoric acid
Calcium nano and hydrogel material, antibacterial calcium phosphate nanoparticles are dispersed in hydrogel material, the antibacterial phosphorus
Sour calcium nano is that nanometer is spherical, and granular size is between 10nm~70nm.
2. double-network hydrogel material according to claim 1, which is characterized in that the antibacterial calcium phosphate nanoparticles
Be-polyglutamic acid modification mix copper antimicrobial nano calcium phosphate.
3. a kind of preparation side of the double-network hydrogel material of the filler of calcium phosphate granules containing antimicrobial nano as claimed in claim 2
Method, which is characterized in that characterized by comprising the following steps:
The modification of general-polyglutamic acid mixes copper nano-calcium phosphate and aqueous suspensions is made, then adds initiator ammonium persulfate and crosslinking agent N, N '-
Methylene-bisacrylamide adjusts pH value to 5.0~6.5, sodium alginate soln is then added and stirs evenly, is eventually adding catalysis
Agent tetramethylethylenediamine, is stirred to react, and cleans, is dried to obtain the double-network hydrogel material of the filler of calcium phosphate granules containing antimicrobial nano
Material.
4. preparation method according to claim 3, which is characterized in that specific step is as follows:
A, solubility calcium salting liquid and soluble copper salting liquid are uniformly mixed, obtain calcium copper solution；
B ,-polyglutamic acid is added in phosphate solution, adjusts pH value to 10.0 or more, is then added in calcium copper solution, 30
DEG C~80 DEG C, pH value maintain between 9.0~10.0, be stirred to react 3-12 hours, it is still aging after reaction, collect precipitating
Nano particle is washed with water, be then dried to obtain-polyglutamic acid modification mix copper nano-calcium phosphate；
C, the modified copper nano-calcium phosphate of mixing of general-polyglutamic acid is add to deionized water and in 0~30 DEG C of ultrasound until forming water
Suspension, then initiator ammonium persulfate and crosslinking agent N, N '-methylene-bisacrylamide are added, it is stirred under the conditions of 10 DEG C ± 5 DEG C anti-
It answers, and adjusting pH value is 5.0~6.5, then adds sodium alginate soln, is stirred to react, and is further continued for addition tetramethylethylenediamine,
It is stirred to react, after reaction, mixed liquor is put into mold, exhaust is stood, then is obtained after washed, drying containing antimicrobial nano
The double-network hydrogel material of calcium phosphate granules filler.
5. the preparation method according to claim 4, which is characterized in that the soluble calcium salt is calcium chloride or four water nitre
Sour calcium；The phosphate solution is dipotassium hydrogen phosphate, disodium hydrogen phosphate, diammonium hydrogen phosphate, potassium dihydrogen phosphate, sodium dihydrogen phosphate
Or the aqueous solution of ammonium dihydrogen phosphate；The soluble copper salt is nitrate trihydrate copper.
6. the preparation method according to claim 4, which is characterized in that the step a by solubility calcium salting liquid and
Soluble copper salting liquid is uniformly mixed, and is the amount in the substance of calcium ion: copper ion the mass ratio of the material is the ratio of 20~1:1
Mixing.
7. the preparation method according to claim 4, which is characterized in that the step b's is added to phosphorus for-polyglutamic acid
In acid salt solution, final concentration of 0.5~4.0mg/mL of-polyglutamic acid.
8. the preparation method according to claim 4, which is characterized in that the step b's is added to calcium for phosphate solution
It is the amount according to calcium copper ion total material in calcium copper solution in copper solution: the substance of phosphate anion in phosphate solution
Amount is 1.5~2:1.
9. the preparation method according to claim 4, which is characterized in that the step c general-polyglutamic acid modification mix copper
Nano-calcium phosphate is add to deionized water, and additive amount is 0.5~50mg/ml water, i.e. 0.5~50mg is added in every milliliter of water
- polyglutamic acid is modified mixes copper nano-calcium phosphate, ultrasonic time is 5~45min；Sodium alginate soln in the step c
Concentration is 0.5~50mg/ml.
10. the preparation method according to claim 4, which is characterized in that in the step c, the modification of-polyglutamic acid is mixed copper and received
Rice calcium phosphate is 10~1:1 than range with sodium alginate dosage quality；Copper nano-calcium phosphate is mixed by the modification of every gram-polyglutamic acid to add
Add 1~50mg of ammonium sulfate, N, 0.25~15mg of N '-methylene-bisacrylamide, 1~20mg of tetramethylethylenediamine amount added
Add.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110773008A (en) * | 2019-11-29 | 2020-02-11 | 天津工业大学 | Preparation method of copper phosphate-containing alginate hydrogel antibacterial filtering membrane |
| CN110773006A (en) * | 2019-12-02 | 2020-02-11 | 天津工业大学 | Preparation method of hydrogel antibacterial filtering membrane containing copper oxide/cuprous oxide/carbon nano tube |
| CN112480434A (en) * | 2020-11-30 | 2021-03-12 | 西安交通大学 | Copper ion antibacterial hydrogel and preparation method and application thereof |
| CN112515981A (en) * | 2020-11-24 | 2021-03-19 | 湖南御家化妆品制造有限公司 | Light absorption core-shell structure particle and preparation method and application thereof |
| CN115141447A (en) * | 2021-03-30 | 2022-10-04 | 合肥杰事杰新材料股份有限公司 | Antibacterial poly (hydroxyethyl methacrylate) material and preparation method and application thereof |
| CN116023679A (en) * | 2022-12-01 | 2023-04-28 | 中山大学附属口腔医院 | Thermosensitive slow-release calcium-phosphorus antibacterial nano hydrogel and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070122362A1 (en) * | 2005-11-26 | 2007-05-31 | Giniger Martin S | Hydrogel sheets and shapes for oral care |
| CN103709737A (en) * | 2013-12-05 | 2014-04-09 | 吴江中瑞机电科技有限公司 | High-molecular composite powder material for SLS and preparation method therefor |
| CN103751846A (en) * | 2013-12-24 | 2014-04-30 | 广东省微生物研究所 | Novel strontium-doped gamma-polyglutamic acid/tricalcium phosphate composite material and preparation method thereof |
| CN106928908A (en) * | 2017-02-19 | 2017-07-07 | 广州市芯检康生物科技有限公司 | A kind of new aeroge multifunctional material and preparation method thereof |
-
2018
- 2018-09-13 CN CN201811068536.1A patent/CN109293949A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070122362A1 (en) * | 2005-11-26 | 2007-05-31 | Giniger Martin S | Hydrogel sheets and shapes for oral care |
| CN103709737A (en) * | 2013-12-05 | 2014-04-09 | 吴江中瑞机电科技有限公司 | High-molecular composite powder material for SLS and preparation method therefor |
| CN103751846A (en) * | 2013-12-24 | 2014-04-30 | 广东省微生物研究所 | Novel strontium-doped gamma-polyglutamic acid/tricalcium phosphate composite material and preparation method thereof |
| CN106928908A (en) * | 2017-02-19 | 2017-07-07 | 广州市芯检康生物科技有限公司 | A kind of new aeroge multifunctional material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| VOJISLAV STANIC ET AL.: "Synthesis, characterization and antimicrobial activity of copper and zinc-doped hydroxyapatite nanopowders", 《APPLIED SURFACE SCIENCE》 * |
| 鲁路等: "海藻酸-纳米羟基磷灰石构建可降解原位成型水凝胶", 《中国科学: 技术科学》 * |
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| CN110773006B (en) * | 2019-12-02 | 2021-10-01 | 中科瑞阳膜技术（北京）有限公司 | Preparation method of hydrogel antibacterial filtering membrane containing copper oxide/cuprous oxide/carbon nano tube |
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