CN115382009B - PH-sensitive naringin-mesoporous silica-chitosan magnesium alloy coating and preparation method thereof - Google Patents
PH-sensitive naringin-mesoporous silica-chitosan magnesium alloy coating and preparation method thereof Download PDFInfo
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- CN115382009B CN115382009B CN202211001655.1A CN202211001655A CN115382009B CN 115382009 B CN115382009 B CN 115382009B CN 202211001655 A CN202211001655 A CN 202211001655A CN 115382009 B CN115382009 B CN 115382009B
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- 229920001661 Chitosan Polymers 0.000 title claims abstract description 73
- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 63
- 239000011248 coating agent Substances 0.000 title claims abstract description 31
- 238000000576 coating method Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 100
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 claims abstract description 51
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 50
- 239000002105 nanoparticle Substances 0.000 claims abstract description 48
- 239000001606 7-[(2S,3R,4S,5S,6R)-4,5-dihydroxy-6-(hydroxymethyl)-3-[(2S,3R,4R,5R,6S)-3,4,5-trihydroxy-6-methyloxan-2-yl]oxyoxan-2-yl]oxy-5-hydroxy-2-(4-hydroxyphenyl)chroman-4-one Substances 0.000 claims abstract description 26
- DFPMSGMNTNDNHN-ZPHOTFPESA-N naringin Chemical compound O[C@@H]1[C@H](O)[C@@H](O)[C@H](C)O[C@H]1O[C@H]1[C@H](OC=2C=C3O[C@@H](CC(=O)C3=C(O)C=2)C=2C=CC(O)=CC=2)O[C@H](CO)[C@@H](O)[C@@H]1O DFPMSGMNTNDNHN-ZPHOTFPESA-N 0.000 claims abstract description 26
- 229940052490 naringin Drugs 0.000 claims abstract description 26
- 229930019673 naringin Natural products 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 71
- 239000000243 solution Substances 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 15
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000004570 mortar (masonry) Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000007790 solid phase Substances 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 230000006698 induction Effects 0.000 abstract description 3
- 239000007943 implant Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 239000005445 natural material Substances 0.000 abstract description 2
- 238000010883 osseointegration Methods 0.000 abstract description 2
- 230000011164 ossification Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 30
- 229960000583 acetic acid Drugs 0.000 description 14
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 210000000988 bone and bone Anatomy 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 235000010413 sodium alginate Nutrition 0.000 description 3
- 239000000661 sodium alginate Substances 0.000 description 3
- 229940005550 sodium alginate Drugs 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- NOQGZXFMHARMLW-UHFFFAOYSA-N Daminozide Chemical compound CN(C)NC(=O)CCC(O)=O NOQGZXFMHARMLW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000002468 ceramisation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 229960001680 ibuprofen Drugs 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000012890 simulated body fluid Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/047—Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
-
- 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/28—Materials for coating prostheses
-
- 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/28—Materials for coating prostheses
- A61L27/30—Inorganic materials
- A61L27/306—Other specific inorganic materials not covered by A61L27/303 - A61L27/32
-
- 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/28—Materials for coating prostheses
- A61L27/34—Macromolecular materials
-
- 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
-
- 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
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/12—Nanosized materials, e.g. nanofibres, nanoparticles, nanowires, nanotubes; Nanostructured surfaces
-
- 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
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
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- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Transplantation (AREA)
- Dermatology (AREA)
- Medicinal Chemistry (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Silicon Compounds (AREA)
Abstract
The invention provides a pH sensitive naringin-mesoporous silica-chitosan magnesium alloy coating and a preparation method thereof, wherein naringin-mesoporous silica-chitosan comprises mesoporous silica nanoparticles, naringin coated in the mesoporous silica nanoparticles and chitosan modified on the surfaces of the mesoporous silica nanoparticles; the coating is obtained by covering naringin-mesoporous silica-chitosan on magnesium alloy by a micro-arc oxidation method. The naringin natural substance can increase bone formation and biological induction, and obviously promote osseointegration of the implant material, thereby providing theoretical basis for clinical application.
Description
Technical Field
The invention belongs to the biomedical orthopaedics field, in particular to a pH sensitive naringin-mesoporous silica-chitosan magnesium alloy coating and a preparation method thereof.
Background
Micro-arc oxidation, also known as plasma enhanced electrochemical surface ceramization, is a new technology for generating self metal oxide by in-situ reaction of aluminum, magnesium, titanium and alloy surfaces thereof in electrolyte by means of an external electric field. The specific principle is as follows: the magnesium alloy product is used as anode, stainless steel tank is used as cathode, the magnesium alloy product is placed in electrolyte in the pulsed electric field environment, plasma discharge is generated on the surface of the sample due to the action of terminal voltage, and the generated high temperature and high pressure condition makes magnesium atoms in micro-areas combine with oxygen in the solution to generate a magnesium oxide ceramic layer metallurgically combined with the matrix. Magnesium and magnesium alloy have wide market prospect in bone repair because of the characteristics of good bone inducibility, degradability, biocompatibility and the like.
At present, a magnesium alloy micro-arc oxidation process in the orthopaedics field has some researches, but the researches have the defect of insufficient bone induction capability.
Disclosure of Invention
In view of the above, the invention aims to overcome the defects in the prior art, and provides a preparation method and application of a pH-sensitive naringin-mesoporous silica-chitosan magnesium alloy coating.
In order to achieve the above purpose, the technical scheme of the invention is realized as follows:
as a first aspect of the present invention, there is provided a pH-sensitive naringin-mesoporous silica-chitosan magnesium alloy coating, the naringin-mesoporous silica-chitosan comprising mesoporous silica nanoparticles, naringin entrapped in the mesoporous silica nanoparticles, and chitosan modified on the surfaces of the mesoporous silica nanoparticles; the coating is obtained by covering naringin-mesoporous silica-chitosan on magnesium alloy by a micro-arc oxidation method.
Preferably, the preparation method of the mesoporous silica nanoparticle comprises the following steps:
s11: dissolving cetyl trimethyl ammonium bromide and polyvinylpyrrolidone in deionized water, adding concentrated ammonia water, continuously stirring at room temperature for 25-40min, adding tetraethoxysilane, continuously stirring until the reaction is finished, and filtering, washing and drying the obtained solution to obtain a white solid.
S12: grinding the white solid for 10-30min by using a mortar, placing the crushed powder into a muffle furnace for calcination, wherein the calcination temperature is set at 450-600 ℃ in the process of heating for 30-40 min. Calcining for 8-10h to obtain the mesoporous silica nano particles.
Preferably, the mass ratio of the cetyl trimethyl ammonium bromide to the polyvinylpyrrolidone is 1:2-1:4.
Preferably, the concentration of the concentrated ammonia solution is 22% -25%, and the addition amount of the concentrated ammonia solution is 150-250mL of the concentrated ammonia solution is added for every 0.7g of cetyltrimethylammonium bromide.
Preferably, the ethyl orthosilicate is added in an amount of 2-3mL of ethyl orthosilicate per 0.7g of cetyltrimethylammonium bromide.
Preferably, the mass ratio of naringin to mesoporous silica nano particles is 5:1-8:1
Preferably, the mesoporous silica nanoparticle activated at 100-200 ℃ and naringin are subjected to solid phase mixing, stirring is carried out for 10-30min at 20-30 ℃ in a dark environment, methanol is added after uniform mixing, ultrasonic treatment is carried out for 10-20min, stirring is carried out for 3-5h at 20-30 ℃, centrifugation is carried out, all washing liquid is collected after centrifugation, filtration is carried out, and the product after filtration is dried in vacuum, thus obtaining the naringin-coated mesoporous silica nanoparticle.
Preferably, the mass ratio of naringin to mesoporous silica nanoparticles is 5:1-8:1.
Preferably, the addition amount of naringin in the mixed solution is 40-80mg naringin added into every 1mL of methanol;
preferably, the concentration of the mesoporous silica nanoparticles in the mixed solution is 10-20mg/mL.
Preferably, the preparation method of naringin-mesoporous silica-chitosan comprises the following steps: preparing chitosan and dissolving the chitosan in acetic acid to form chitosan/acetic acid solution, regulating the pH of the chitosan/acetic acid solution to 6.0, adding the chitosan/acetic acid solution into mesoporous silica nanoparticles coated with naringin, magnetically stirring the mixture at room temperature for 34 to 40 hours, centrifuging the product after the reaction is finished, washing the product with deionized water, and drying the product to obtain naringin-mesoporous silica-chitosan.
Preferably, the concentration of chitosan in the chitosan/acetic acid solution is 0.4-0.6% w/V, and the concentration of acetic acid is 8-10% V/V.
Preferably, the mesoporous silica nanoparticles are added in an amount of 0.15-0.25g of mesoporous silica nanoparticles per 40mL of chitosan/acetic acid solution.
As a second aspect of the present invention, there is provided a method for preparing a pH-sensitive naringin-mesoporous silica-chitosan magnesium alloy composite coating, the method comprising the steps of:
s1: preparation of mesoporous silica nanoparticles
S11: dissolving cetyl trimethyl ammonium bromide and polyvinylpyrrolidone in deionized water, adding concentrated ammonia water, continuously stirring at room temperature for 25-40min, adding tetraethoxysilane, continuously stirring until the reaction is finished, and filtering, washing and drying the obtained solution to obtain a white solid.
S12: grinding the white solid for 10-30min by using a mortar, placing the crushed powder into a muffle furnace for calcination, wherein the calcination temperature is set at 450-600 ℃ in the process of heating for 30-40 min. Calcining for 8-10h to obtain the mesoporous silica nano particles.
S2: preparation of naringin-entrapped mesoporous silica nanoparticle
Mixing the activated mesoporous silica nanoparticles with naringin at 100-200deg.C in solid phase, stirring at 20-30deg.C in dark environment for 10-30min, adding methanol, performing ultrasonic treatment for 10-20min, stirring at 20-30deg.C for 3-5 hr, centrifuging, collecting all washing liquid, filtering, and vacuum drying to obtain naringin-coated mesoporous silica nanoparticles;
s3: preparation of naringin-mesoporous silica-chitosan
Preparing chitosan/acetic acid solution, regulating pH of the chitosan/acetic acid solution to 6.0, adding naringin-entrapped mesoporous silica nanoparticle into the chitosan/acetic acid solution, magnetically stirring at room temperature for 34-40h, centrifuging the product after the reaction, washing with deionized water, and drying to obtain naringin-mesoporous silica-chitosan
S4: preparation of magnesium alloy coating covered with naringin-mesoporous silica-chitosan
And covering naringin-mesoporous silica-chitosan on magnesium alloy subjected to micro-arc oxidation by adopting a dipping and pulling method according to positive current of 0.6, negative current of 0.1, frequency of 500Hz, positive duty ratio of 40, negative duty ratio of 20 and time of 12min, so as to obtain the naringin-mesoporous silica-chitosan magnesium alloy composite coating.
Compared with the prior art, the invention has the following advantages:
the naringin natural substance can increase bone formation and biological induction, and obviously promote osseointegration of the implant material, thereby providing theoretical basis for clinical application.
Drawings
FIG. 1 is an electron microscope scan of NG@SA-MAO prepared in example 4, MAO prepared in comparative example 1, SA-MAO prepared in comparative example 2;
FIG. 2 shows XRD patterns of NG@SA-MAO prepared in example 4, MAO prepared in comparative example 1, and SA-MAO prepared in comparative example 2;
FIG. 3 is an infrared spectrum of NG@SA-MAO prepared in example 4, MAO prepared in comparative example 1, SA-MAO prepared in comparative example 2;
FIG. 4 is a graph of impedance-capacitance arcs of NG@SA-MAO prepared in example 4 and MAO prepared in comparative example 1 and SA-MAO prepared in comparative example 2;
FIG. 5 is a graph of the electrochemical AC impedance modulus of NG@SA-MAO prepared in example 4 and MAO prepared in comparative example 1 and SA-MAO prepared in comparative example 2;
FIG. 6 is a graph of the electrochemical AC impedance phase angle of NG@SA-MAO prepared in example 4 and of MAO prepared in comparative example 1 and SA-MAO prepared in comparative example 2;
FIG. 7 is a graph showing the corrosion resistance of NG@SA-MAO prepared in example 4, MAO prepared in comparative example 1, and SA-MAO prepared in comparative example 2.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meaning as commonly understood by one of ordinary skill in the art to which the inventive concepts pertain. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The invention will be described in detail with reference to examples.
Main raw materials and reagents:
ethyl orthosilicate (TEOS, analytically pure, the ford morning chemical reagent factory, the Tianjin city); concentrated ammonia (NH) 4 OH, analytically pure, dehn chemical company, of the Tianjin city); mesitylene (TMS, analytically pure, alar Ding Shiji limited); absolute ethanol (analytically pure, division of chemical reagents for wind boats, tianjin); 95% methanol (analytically pure, tianjin, fengsha chemical technologies Co., ltd.); cetyl trimethylammonium bromide (CTAB, analytically pure, division of fine chemical industry, north of the body of the division, of the body of the division, of the Tianjin); polyvinylpyrrolidone (PVP, analytically pure, shanghai city source leaf biology company); deionized water (medium and high purity water plant in zheng state); polyether F127 (analytically pure, sigma); chitosan (CS, biochemical reagent, molecular weight 11-15 ten thousand, amerco); ibuprofen, n-hexane (analytically pure, deuten chemical company, tianjin); glacial acetic acid (CH) 3 COOH, analytically pure, dense euler reagent development center, tianjin, city);
example 1 preparation and characterization of mesoporous silica nanoparticles
Weighing 0.7g of cetyl trimethyl ammonium bromide and 2.1g of polyvinylpyrrolidone, dissolving in 200mL of deionized water, rapidly adding 7mL of concentrated ammonia water in the stirring process, continuously stirring at room temperature for 25-40min, rapidly adding 2.4mL of ethyl orthosilicate, continuously stirring for 5h until the reaction is finished, and carrying out suction filtration, washing and drying on the obtained solution to obtain a white solid;
grinding the white solid for 10-30min by using a mortar, placing the crushed powder into a muffle furnace for calcination, wherein the calcination temperature is set at 450-600 ℃ in the process of heating for 30-40 min. Calcining for 8-10h to obtain the mesoporous silica nano particles.
EXAMPLE 2 naringin loading in mesoporous silica nanoparticles
400mg of mesoporous silica nano particles activated at 100-200 ℃ and 2.4g of naringin are weighed and subjected to solid phase mixing, stirring is carried out for 10-30min at 20-30 ℃ in a dark environment, 30mL of methanol is added after uniform mixing, ultrasonic treatment is carried out for 10-20min, stirring is carried out for 3-5h at 20-30 ℃ and then centrifugation is carried out, all washing liquid is collected after centrifugation and then filtered, and the filtered product is dried in vacuum to obtain the naringin-coated mesoporous silica nano particles
Example 3 preparation of Chitosan-mesoporous silica drug-loaded nanoparticle
A chitosan/acetic acid solution (acetic acid 10% V/V) was prepared at 0.6% w/V, and the pH was adjusted to 6.0 with a 1M NaOH solution. 40ml of chitosan/acetic acid solution with pH of 6.0 was added with 0.2g of mesoporous silica/naringin. Magnetically stirring for 36h at room temperature. After the reaction is finished, centrifugally separating the product, washing the product with deionized water twice, and vacuum drying the product at room temperature to obtain the chitosan/mesoporous silica drug-loaded nanoparticle.
Example 4 preparation of magnesium alloy coating covering naringin-mesoporous silica-chitosan
The magnesium alloy composite coating (NG@SA-MAO) of naringin-mesoporous silica-chitosan is obtained by covering magnesium alloy subjected to micro-arc oxidation with naringin-mesoporous silica-chitosan by a dipping and pulling method under the conditions of positive current of 0.6, negative current of 0.1, frequency of 500Hz, positive duty ratio of 40 and negative duty ratio of 20 for 12 min.
Comparative example 1
The magnesium alloy surface was subjected to micro-arc oxidation operation using the same micro-arc oxidation method and parameters as in example 4 to obtain a Magnesium Alloy (MAO) with micro-arc oxidized surface.
Comparative example 2
And covering sodium alginate on the surface of the magnesium alloy with micro-arc oxidation to obtain a magnesium alloy coating (SA-MAO) with the surface covered with sodium alginate.
FIG. 1 shows electron microscope scans of NG@SA-MAO prepared in example 4 and of MAO prepared in comparative example 1 and of SA-MAO prepared in comparative example 2 (in FIG. 1, a, b and c are MAO, SA-MAO and NG@SA-MAO, respectively). From FIG. 1, it can be seen that the porosity of NG@SA-MAO becomes low, indicating that NG is successfully supported on the magnesium alloy surface after NG micro-arc oxidation.
FIG. 2 shows XRD patterns of NG@SA-MAO prepared in example 4, MAO prepared in comparative example 1 and SA-MAO prepared in comparative example 2. As can be seen from fig. 2, the content of each element changes after the XRD detection of the crystalline phase element, wherein the change in Mg content is particularly remarkable.
FIG. 3 is an infrared spectrum of NG@SA-MAO prepared in example 4, MAO prepared in comparative example 1, and SA-MAO prepared in comparative example 2. As can be seen from fig. 3, the characteristic peaks of each substance are detected by infrared spectrum, which illustrates SA; mesoporous silica; NG is successfully micro-arc oxidized on Mg alloy.
FIG. 4 shows the impedance-capacitance arc diagrams of NG@SA-MAO prepared in example 4 and of MAO prepared in comparative example 1 and SA-MAO prepared in comparative example 2 (NG@SA-MAO, SA-MAO, MAO in FIG. 4, b, c, respectively). From fig. 4, it can be seen that the Z value is significantly improved after ng@sa-MAO by the impedance-capacitance arc test.
FIG. 5 is a graph showing the electrochemical AC impedance modulus of NG@SA-MAO prepared in example 4, MAO prepared in comparative example 1, and SA-MAO prepared in comparative example 2. From fig. 5 it can be seen that after passing the impedance modulus test, ng@sa-MAO, the Z value is significantly increased.
FIG. 6 is a graph of the electrochemical AC impedance phase angle of NG@SA-MAO prepared in example 4 and of the MAO prepared in comparative example 1 and of the SA-MAO prepared in comparative example 2. From fig. 6 it can be seen that after passing the impedance phase angle test, ng@sa-MAO, the impedance phase angle is significantly increased.
The NG@SA-MAO prepared in example 4, the MAO prepared in comparative example 1, and the SA-MAO prepared in comparative example 2 were tested for corrosion resistance in simulated body fluid solutions, and the self-corrosion currents are shown in FIG. 7. As can be seen from fig. 7, the self-corrosion current density of the magnesium alloy coating covered with naringin-mesoporous silica-chitosan is reduced by one order of magnitude, and the corrosion speed is slower, compared with the magnesium alloy coated with micro-arc oxidation and the magnesium alloy coated with sodium alginate. The magnesium alloy coating covering naringin-mesoporous silica-chitosan has excellent corrosion resistance, so that the polarization process can be effectively inhibited in the application process, and the corrosion rate is reduced.
The above embodiments are merely preferred embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (12)
1. A pH sensitive naringin-mesoporous silica-chitosan magnesium alloy coating is characterized in that: the naringin-mesoporous silica-chitosan comprises mesoporous silica nanoparticles, naringin coated in the mesoporous silica nanoparticles and chitosan modified on the surfaces of the mesoporous silica nanoparticles; the coating is obtained by covering naringin-mesoporous silica-chitosan on magnesium alloy by adopting a micro-arc oxidation method;
the preparation method of the naringin-entrapped mesoporous silica nanoparticle comprises the following steps: mixing the activated mesoporous silica nanoparticles at 100-200 ℃ with naringin in a solid phase, stirring for 10-30min at 20-30 ℃ in a dark environment, adding methanol after uniform mixing, performing ultrasonic treatment for 10-20min, stirring for 3-5h at 20-30 ℃ and centrifuging, collecting all washing liquid after centrifuging, filtering, and vacuum drying the filtered product to obtain the naringin-coated mesoporous silica nanoparticles.
2. The pH sensitive naringin-mesoporous silica-chitosan magnesium alloy coating of claim 1, wherein: the preparation method of the mesoporous silica nanoparticle comprises the following steps:
s11: dissolving cetyl trimethyl ammonium bromide and polyvinylpyrrolidone in deionized water, adding concentrated ammonia water, continuously stirring at room temperature for 25-40min, adding ethyl orthosilicate, continuously stirring until the reaction is finished, and filtering, washing and drying the obtained solution to obtain a white solid;
s12: grinding the white solid for 10-30min by using a mortar, placing the crushed powder into a muffle furnace for calcination, wherein the calcination temperature is set at 450-600 ℃ for 8-10h in the process of heating for 30-40min, and obtaining the mesoporous silica nano particles.
3. The pH sensitive naringin-mesoporous silica-chitosan magnesium alloy coating of claim 2, wherein: the mass ratio of the cetyl trimethyl ammonium bromide to the polyvinylpyrrolidone in the step S11 is 1:2-1:4.
4. The pH sensitive naringin-mesoporous silica-chitosan magnesium alloy coating of claim 2, wherein: the concentration of the concentrated ammonia water solution is 22-25%, and the addition amount of the concentrated ammonia water solution is 150-250mL of the concentrated ammonia water solution is added for every 0.7g of cetyltrimethylammonium bromide.
5. The pH sensitive naringin-mesoporous silica-chitosan magnesium alloy coating of claim 2, wherein: the addition amount of the ethyl orthosilicate is 2-3mL of ethyl orthosilicate added per 0.7g of cetyltrimethylammonium bromide.
6. The pH sensitive naringin-mesoporous silica-chitosan magnesium alloy coating of claim 1, wherein: the mass ratio of naringin to mesoporous silica nano particles is 5:1-8:1.
7. The pH sensitive naringin-mesoporous silica-chitosan magnesium alloy coating of claim 1, wherein: the addition amount of naringin in the mixed solution is 40-80mg naringin per 1mL methanol.
8. The pH sensitive naringin-mesoporous silica-chitosan magnesium alloy coating of claim 1, wherein: the concentration of the mesoporous silica nano particles in the mixed solution is 10-20mg/mL.
9. The pH sensitive naringin-mesoporous silica-chitosan magnesium alloy coating of claim 1, wherein: the preparation method of naringin-mesoporous silica-chitosan comprises the following steps: preparing chitosan and dissolving the chitosan in acetic acid to form chitosan/acetic acid solution, regulating the pH of the chitosan/acetic acid solution to 6.0, adding the chitosan/acetic acid solution into mesoporous silica nanoparticles coated with naringin, magnetically stirring the mixture at room temperature for 34 to 40 hours, centrifuging the product after the reaction is finished, washing the product with deionized water, and drying the product to obtain naringin-mesoporous silica-chitosan.
10. The pH sensitive naringin-mesoporous silica-chitosan magnesium alloy coating of claim 9, wherein: the concentration of chitosan in the chitosan/acetic acid solution is 0.4-0.6% W/V, and the concentration of acetic acid is 8-10% V/V.
11. The pH sensitive naringin-mesoporous silica-chitosan magnesium alloy coating of claim 9, wherein: the adding amount of the mesoporous silica nanoparticles is that 0.15-0.25g of mesoporous silica nanoparticles are added into each 40mL of chitosan/acetic acid solution.
12. A preparation method of a pH-sensitive naringin-mesoporous silica-chitosan magnesium alloy composite coating is characterized by comprising the following steps: the preparation method comprises the following steps:
s1: preparing mesoporous silica nanoparticles;
s11: dissolving cetyl trimethyl ammonium bromide and polyvinylpyrrolidone in deionized water, adding concentrated ammonia water, continuously stirring at room temperature for 25-40min, adding ethyl orthosilicate, continuously stirring until the reaction is finished, and filtering, washing and drying the obtained solution to obtain a white solid;
s12: grinding the white solid for 10-30min by using a mortar, placing the crushed powder into a muffle furnace for calcination, wherein the calcination temperature is set at 450-600 ℃ for 8-10h in the process of heating for 30-40min, and obtaining the mesoporous silica nano particles;
s2: preparation of naringin-entrapped mesoporous silica nanoparticle
Mixing the activated mesoporous silica nanoparticles with naringin at 100-200deg.C in solid phase, stirring at 20-30deg.C in dark environment for 10-30min, adding methanol, performing ultrasonic treatment for 10-20min, stirring at 20-30deg.C for 3-5 hr, centrifuging, collecting all washing liquid, filtering, and vacuum drying to obtain naringin-coated mesoporous silica nanoparticles;
s3: preparation of naringin-mesoporous silica-chitosan
Preparing chitosan/acetic acid solution, regulating the pH of the chitosan/acetic acid solution to 6.0, adding naringin-entrapped mesoporous silica nanoparticles into the chitosan/acetic acid solution, magnetically stirring at room temperature for 34-40h, centrifuging the product after the reaction is finished, washing with deionized water, and drying to obtain naringin-mesoporous silica-chitosan;
s4: preparation of magnesium alloy coating covered with naringin-mesoporous silica-chitosan
And covering naringin-mesoporous silica-chitosan on magnesium alloy subjected to micro-arc oxidation by adopting a dipping and pulling method according to positive current of 0.6, negative current of 0.1, frequency of 500Hz, positive duty ratio of 40, negative duty ratio of 20 and time of 12min, so as to obtain the naringin-mesoporous silica-chitosan magnesium alloy composite coating.
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| CN114652841A (en) * | 2022-03-11 | 2022-06-24 | 常州大学 | Double-drug-loading system with pH, redox and near-infrared triple responses, and preparation method and application thereof |
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| CN111407923A (en) * | 2020-04-09 | 2020-07-14 | 佳木斯大学 | Drug release controlled magnesium or magnesium alloy bionic bone and preparation method thereof |
| CN114652841A (en) * | 2022-03-11 | 2022-06-24 | 常州大学 | Double-drug-loading system with pH, redox and near-infrared triple responses, and preparation method and application thereof |
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| Nano‐silica/chitosan composite coatings on biodegradablemagnesium alloys for enhanced corrosion resistance insimulated body fluid;Yucong Ma等;Materials and Corrosion;第73卷(第3期);第436-450页 * |
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