CN106011834A - Preparation method of strontium chelated sodium alginate coating on titanium surface - Google Patents
Preparation method of strontium chelated sodium alginate coating on titanium surface Download PDFInfo
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- CN106011834A CN106011834A CN201610412738.8A CN201610412738A CN106011834A CN 106011834 A CN106011834 A CN 106011834A CN 201610412738 A CN201610412738 A CN 201610412738A CN 106011834 A CN106011834 A CN 106011834A
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- Prior art keywords
- strontium
- sodium alginate
- titanium
- solution
- dopamine
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- 239000010936 titanium Substances 0.000 title claims abstract description 236
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 170
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 169
- 229910052712 strontium Inorganic materials 0.000 title claims abstract description 83
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000000661 sodium alginate Substances 0.000 title claims abstract description 78
- 235000010413 sodium alginate Nutrition 0.000 title claims abstract description 78
- 229940005550 sodium alginate Drugs 0.000 title claims abstract description 78
- 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 title claims abstract description 77
- 239000011248 coating agent Substances 0.000 title claims abstract description 43
- 238000000576 coating method Methods 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 135
- 238000000034 method Methods 0.000 claims abstract description 83
- 229960003638 dopamine Drugs 0.000 claims abstract description 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910001631 strontium chloride Inorganic materials 0.000 claims abstract description 22
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 claims abstract description 22
- 235000010443 alginic acid Nutrition 0.000 claims abstract description 10
- 229920000615 alginic acid Polymers 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 101
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 61
- 239000008367 deionised water Substances 0.000 claims description 40
- 229910021641 deionized water Inorganic materials 0.000 claims description 40
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- 239000007983 Tris buffer Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 230000033228 biological regulation Effects 0.000 claims description 11
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 11
- 229960001126 alginic acid Drugs 0.000 claims description 8
- 239000000783 alginic acid Substances 0.000 claims description 8
- 150000004781 alginic acids Chemical class 0.000 claims description 8
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 4
- -1 hydrogen Sodium oxide Chemical class 0.000 claims description 4
- 238000005260 corrosion Methods 0.000 claims description 3
- 230000007797 corrosion Effects 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- HOGDNTQCSIKEEV-UHFFFAOYSA-N n'-hydroxybutanediamide Chemical compound NC(=O)CCC(=O)NO HOGDNTQCSIKEEV-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims 1
- WTDRDQBEARUVNC-UHFFFAOYSA-N L-Dopa Natural products OC(=O)C(N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-UHFFFAOYSA-N 0.000 claims 1
- 241001597008 Nomeidae Species 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- MHUWZNTUIIFHAS-CLFAGFIQSA-N dioleoyl phosphatidic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(COP(O)(O)=O)OC(=O)CCCCCCC\C=C/CCCCCCCC MHUWZNTUIIFHAS-CLFAGFIQSA-N 0.000 claims 1
- 229960001149 dopamine hydrochloride Drugs 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229960004502 levodopa Drugs 0.000 claims 1
- 229910001948 sodium oxide Inorganic materials 0.000 claims 1
- 229910001427 strontium ion Inorganic materials 0.000 abstract description 30
- 239000000463 material Substances 0.000 abstract description 20
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 8
- 210000000988 bone and bone Anatomy 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 230000001737 promoting effect Effects 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 abstract description 2
- 229940072056 alginate Drugs 0.000 abstract description 2
- 150000001408 amides Chemical class 0.000 abstract description 2
- 230000009920 chelation Effects 0.000 abstract 3
- MDFFNEOEWAXZRQ-UHFFFAOYSA-N aminyl Chemical compound [NH2] MDFFNEOEWAXZRQ-UHFFFAOYSA-N 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 abstract 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- FYFFGSSZFBZTAH-UHFFFAOYSA-N methylaminomethanetriol Chemical compound CNC(O)(O)O FYFFGSSZFBZTAH-UHFFFAOYSA-N 0.000 abstract 1
- 230000008569 process Effects 0.000 description 62
- PWYYWQHXAPXYMF-UHFFFAOYSA-N strontium(2+) Chemical compound [Sr+2] PWYYWQHXAPXYMF-UHFFFAOYSA-N 0.000 description 29
- 238000002474 experimental method Methods 0.000 description 20
- 101100496858 Mus musculus Colec12 gene Proteins 0.000 description 18
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 description 10
- 239000003513 alkali Substances 0.000 description 10
- 230000014759 maintenance of location Effects 0.000 description 10
- 238000007654 immersion Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000011010 flushing procedure Methods 0.000 description 8
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000002138 osteoinductive effect Effects 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000004071 biological effect Effects 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001582 osteoblastic effect Effects 0.000 description 2
- 210000002997 osteoclast Anatomy 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 208000010392 Bone Fractures Diseases 0.000 description 1
- 102000007350 Bone Morphogenetic Proteins Human genes 0.000 description 1
- 108010007726 Bone Morphogenetic Proteins Proteins 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 108090000723 Insulin-Like Growth Factor I Proteins 0.000 description 1
- 241000195474 Sargassum Species 0.000 description 1
- 102000013275 Somatomedins Human genes 0.000 description 1
- 229910003088 Ti−O−Ti Inorganic materials 0.000 description 1
- 206010060872 Transplant failure Diseases 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 229940112869 bone morphogenetic protein Drugs 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000005056 cell body Anatomy 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000011164 ossification Effects 0.000 description 1
- 230000002188 osteogenic effect Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
- C23C22/64—Treatment of refractory metals or alloys based thereon
-
- 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
- A61L27/54—Biologically active materials, e.g. therapeutic substances
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
- A61L2300/102—Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
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- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/412—Tissue-regenerating or healing or proliferative agents
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- A61L2430/00—Materials or treatment for tissue regeneration
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Abstract
The invention relates to a preparation method of a strontium chelated sodium alginate coating on a titanium surface. The preparation method comprises the steps that a trihydroxymethyl aminomethane water solution of dopamine is firstly utilized for treating the titanium surface, sodium alginate is grafted to the surface of the above material by means of an amide reaction of dopamine amidogen and sodium alginate carboxyl, then the obtained material is put into a strontium chloride solution, and chelation of strontium is achieved. A catechol functional group in the dopamine adheres to the titanium surface in a non-covalent manner, and then the coating is constructed on the surface of a substrate. The method is easy to operate, and bonding with a matrix is good. Sodium alginate biocompatibility is good, strontium alginate gel formed after a large quantity of carboxyl existing in molecules and strontium ions react has good chelation performance on the strontium, the strontium chelated sodium alginate coating on the titanium surface is prepared, and long-acting bone inductivity is given to transplant materials by means of slow release and degradation of the strontium. The adopted sodium alginate is good in biocompatibility and has good chelation performance with the strontium, slow release of the strontium is achieved, and quite high promotional value is achieved.
Description
Technical field
The invention belongs to biomedical material surface technical field of modification, relate generally to the preparation of titanium surface organic strontium coating, to carry
The biological property of high titanium material.
Background technology
Titanium or titanium alloy (Ti) light weight, intensity is high, good biocompatibility, and proportion is near with people's bone photo, moves as medical bone in recent years
Plant material and cause huge concern.The coating of organic strontium is prepared on titanium surface can not only utilize the biological property that titanium is good, Er Qiebiao
The strontium of finishing coat will promote skeletonization, but to prepare one problem demanding prompt solution of coating be that titanium surface is the most smooth on titanium surface, increases
Difficulty prepared by coating.At present conventional coating production is prepared by magnetron sputtering, electrochemical deposition, hydro-thermal, these
The use of method not only adds the cost that material surface processes, and makes simplification that surface processes and universality have a greatly reduced quality.
In this patent, we use dopamine (DOPA) success to be prepared for coating on titanium surface, solve coating preparation complexity and become
This high problem.The o-phenol functional group contained in dopamine molecule can be mutual with substrate material surface with non-covalent form
Effect, forms superpower adhesive force, and present in molecule amino can with the radical reaction such as carboxyl, sulfydryl, hydroxyl, thus
Can be at surface grafting somatomedin, bone morphogenetic protein etc., to improve the biological property of titanium material.
Parent's bone elements strontium (Sr) is of the same clan with calcium in periodic chart, and the same with calcium, strontium is also that skeleton becomes with the important composition of tooth
Point, research in recent years finds: strontium has the effect promoting Oesteoblast growth with suppression osteoclast activity, and strontium also has
There are the advantages such as low cost, activity are high, material character is stable, if strontium coating is prepared on the surface therefore at graft materials, it will for
Osteoblastic growth provides suitable external environment, it is possible to be effectively improved the osteoinductive of material.
But, study the strontium ion in organic strontium coating of preparation and be mostly that strontium ion is very presented in prominent releasing
Release is complete in the short time, and this can make the osteoinductive of graft materials relatively short for action time, causes graft materials and host
Combination between bone is poor, is finally easily caused graft failure, therefore in coating the slow release of strontium ion the success transplanted is played to
Close important effect.Substantial amounts of carboxyl and hydroxyl is there is it has been observed that have in sodium alginate (SA) molecule of good biocompatibility
Base, and there are some researches show: the existence of the functional group such as carboxyl, hydroxyl has the strongest sequestering for strontium ion, therefore this
The sequestering preparation coating that patent utilization sodium alginate is stronger to strontium, reaches the effect of slow release, and the sodium alginate used has
Degradability in good biocompatibility and organism, hydroxyl also is able to be effectively improved the parent of material surface present in molecule
Aqueous, the most osteoblastic Absorption Growth, improves the osteoinductive of graft materials.
Summary of the invention
The invention reside in and utilize strontium to have induced osteogenesis and the dual function of the broken bone of suppression, according to sodium alginate, strontium is had preferably
Sequestering, it is provided that the preparation method of a kind of organic strontium coating, to improve the osteogenic activity of titanium material.
Utilize the o-phenol functional group in dopamine to prepare titanium/dopamine sample, and be combined with sodium alginate.Sodium alginate is deposited
A large amount of carboxyls react with strontium ion after, strontium is had the most sequestering by the alginic acid strontium gel of formation, it is possible to realize strontium
Slow release, makes graft materials have osteoinductive for a long time.
Technical scheme is as follows:
A kind of preparation method of the sodium alginate coating of titanium chelated surface strontium, its step is as follows:
(1) in trishydroxymethylaminomethane aqueous solution, dopamine is added, after dopamine fully dissolves, by hydrochloric acid and hydroxide
Sodium regulation solution ph is 8～10, puts in solution by the titanium sheet of pretreatment, overnight soaks, the titanium of preparation/dopamine sample；
(2) configuration sodium alginate soln, stirring 10h～12h to the transparent gel of solution, add the carbon diformazan of equimolar amounts
Amine and N-hydroxy-succinamide activation 40min～60min, be immersed in sodium alginate soln by the titanium of preparation/dopamine sample
In, overnight, prepare titanium/dopamine/sodium alginate sample；
(3) filter the strontium chloride solution of configuration with filter, the titanium/dopamine/sodium alginate sample of preparation is immersed in strontium chloride
In solution, overnight, the sodium alginate coating of titanium chelated surface strontium is obtained.
Described titanium sheet pretreatment is first titanium sheet to be placed in HNO3In solution, corrosion treatmentCorrosion Science under room temperature, then it is put in NaOH molten
In liquid, isothermal holding, after corrosion treatmentCorrosion Science, with dehydrated alcohol and deionized water ultrasonic cleaning successively.
Described titanium is preferably the pure titanium of bio-medical.
The Tris-HCl pH value of solution that described configuration dopamine solution uses is preferably 8～10.
The mass fraction of described sodium alginate soln is preferably 0.5%.
The mass fraction of described strontium chloride solution is preferably 0.1%～0.5%.
Described trishydroxymethylaminomethane concentration of aqueous solution is preferably 10mM Tris.
Described filter pore size is preferably 0.22 μm.
Described dopamine solution processes, sodium alginate soln processes and strontium chloride solution processes, and this three-step reaction all keeps reaction
Time is overnight.
Specific experiment flow chart as shown in Figure 1, after titanium sheet processes with dopamine, is grafted dopamine molecule, when with sea on titanium surface
After sodium alginate processes, the amino in dopamine molecule and the reaction of the carboxyl generation amide in sodium alginate molecule, make sodium alginate molecule
It is grafted on dopamine, thus prepares sodium alginate coating, then with after strontium chloride solution process, sodium alginate reacts shape with strontium ion
Become alginic acid strontium gel coat, utilize the sequestering slow release realizing strontium that it is stronger to strontium.
It is scanned Electronic Speculum and transmissioning electric mirror test, to observe the pattern of coating to preparation process often walks the sample obtained.Such as figure
Shown in 2 (scanning electron microscope (SEM) photographs), the titanium plate surface after Fig. 2 a can be seen that acid-alkali treatment is Pinhole-shaped, relatively rough, is conducive to
The adhesion of dopamine, Fig. 2 b relative to Fig. 2 a this it appears that dopamine successfully sticks in titanium sheet, due to macromolecular solution
Mobility, grafted sodium alginate rear surface more smooth (Fig. 2 c), after strontium chloride processes, strontium is combined with sodium alginate formed extra large
Strontium alginate, is presented on surface, Fig. 2 d and Fig. 2 e with the shape of circular granular and can be seen that alginic acid strontium compares and be evenly distributed in
Titanium surface, shows prepared by the success of strontium coating.The test of Fig. 2 f contact angle illustrate equally titanium surface by successful modification, with original
Titanium sheet is compared, and after strontium process, the reduction of contact angle shows that the wettability on titanium surface is improved.The transmission of 1%Sr-Ti and 1%Sr-Ti
Electron microscopic picture is used for further observing the strontium granule that titanium surface is formed, as it is shown on figure 3, Fig. 3 b is permissible relative to Fig. 3 a
Will become apparent from when strontium concentration improves, alginic acid strontium granule showed increased, and be connected on sodium alginate surface, Sargassum is described
Strontium is had excellent sequestering by acid sodium.
Infrared test and XPS test are for illustrating the chemical composition of coating further.As shown in Figure 4,568cm in Fig. 4 a-1
Corresponding to the stretching vibration peak of Ti-O-Ti, after dopamine modification (Fig. 4 b), 3365cm-1, 2939cm-1, 1616cm-1With
1495cm-1It is corresponding in turn in-NH2Stretching vibration peak ,-CH2Stretching vibration peak ,-C=O stretching vibration peak and-CH2Bending vibration
Peak, the appearance explanation dopamine at these peaks is successfully grafted in titanium sheet, after sodium alginate modification (Fig. 4 c), 2243cm-1(-NH stretches
Contracting vibration peak) owing to the reaction of amino Yu carboxyl, show that sodium alginate is successfully grafted on dopamine.As it is shown in figure 5, former
In beginning titanium (Fig. 5 a), C 1s, Ti 2p and O 1s bond energy occur in 285eV, 460eV and 531eV, and the appearance of carbon is
The inevitably pollution of carbohydrate, after dopamine modification (Fig. 5 b), the N 1s in dopamine occurs in 399eV significantly,
Illustrating that dopamine is successfully grafted in titanium sheet, after sodium alginate is modified, Na KLL and Na 1s bond energy substantially occur in spectrogram,
After strontium chloride processes, the peak of strontium mainly appears on 135eV (Sr 3d), 270eV (Sr 3p3), 360eV (Sr 3s), carries
The concentration of high strontium chloride, the content of surface strontium the most correspondingly increases.
In order to the situation that strontium ion discharges is described, we have done strontium ion release experiment method.The titanium sheet processed through strontium chloride is placed in
In deionized water, keeping 37 DEG C of constant temperature, in 12h, 1d, 3d, 5d, 7d, 9d, 13d, 17d, 21d, 28d will
Titanium sheet is taken out, replacing deionized water, the concentration of strontium ion in ICP test solution, as shown in Figure 6, and sample 1%Sr-Ti and 5%Sr-Ti
Whole release process in two stages: the prominent slow release released with the later stage of early stage, start release first 5 days, be deposited on surface
First the alginic acid strontium of excess discharges, and the release rate of 1%Sr-Ti and 5%Sr-Ti respectively reaches 95.31% and 83.00%,
In 5～28 day time, what sample 1%Sr-Ti and 5%Sr-Ti presented is the slow release of strontium, and release efficiency nearly reaches a constant,
This is because strontium is had the most sequestering by the alginic acid strontium gel formed, illustrate that the strontium coating of preparation can be up to 28 days
The slow release of the existing strontium of time interior-excess.
The present invention is a kind of preparation method promoting cell skeletonization coating in the preparation of medical titanium alloy surface, implants bone and people to improve
Soma combines poor problem.The present invention be utilize strontium (Sr) promote Oesteoblast growth, suppression osteoclast activity effect and
Sodium alginate (SA) is to excellent sequestering of strontium, by combining closely of o-phenol functional group in dopamine and matrix material,
The sodium alginate coating of titanium surface preparation chelating strontium, realizes the slow release of strontium by sodium alginate to the chelating of strontium.First the present invention uses
Trishydroxymethylaminomethane (Tris) aqueous solution of dopamine (DOPA) processes titanium surface, utilizes dopamine amino and sodium alginate carboxyl
Amide reaction at the surface grafting sodium alginate of above-mentioned material, then the material obtained is placed in strontium chloride solution, it is achieved strontium
Chelating.It is an advantage of the current invention that: utilize the o-phenol functional group in dopamine to stick to titanium surface with non-covalent form
On, and then building coating at substrate surface, the method is simple to operate, is combined preferably with matrix.Sodium alginate good biocompatibility,
After present in molecule, a large amount of carboxyls react with strontium ion, strontium is had the most sequestering by the alginic acid strontium gel of formation, it is achieved
The preparation of the sodium alginate coating of titanium chelated surface strontium, the slow release degraded of strontium gives the osteoinductive that graft materials is long-acting.With other
Strontium coating is compared, and preparation method of the present invention is simple, and cost is relatively low, the sodium alginate good biocompatibility of employing, has relatively with strontium
Good is sequestering, it is achieved that the slow release of strontium, has good promotional value.
Accompanying drawing explanation
The sodium alginate coating preparation process schematic diagram of Fig. 1 titanium chelated surface strontium；
The scanning electron microscopic picture of Fig. 2 difference sample surface coating: (a) Ti, (b) DOPA-Ti, (c) SA-Ti, (d) 1%Sr-Ti, (e)
5%Sr-Ti (scale: 10 μm). the contact angle that (f) different sample surfaces is measured；
The transmission electron microscope picture of Fig. 3 sample 1%Sr-Ti and 5%Sr-Ti: (a) 1%Sr-Ti, (b) 5%Sr-Ti；
Fourier's infrared conversion spectrogram of Fig. 4 difference sample surface coating: (a) Ti, (b) DOPA-Ti, (c) SA-Ti, (d) 1%Sr-Ti, (e)
5%Sr-Ti；
The XPS spectrum figure of Fig. 5 difference sample surfaces: (a) Ti, (b) DOPA-Ti, (c) SA-Ti, (d) 1%Sr-Ti, (e) 5%Sr-Ti；
The time dependent function relation figure of strontium ion release efficiency of Fig. 6 sample 1%Sr-Ti and 5%Sr-Ti.
Detailed description of the invention
Below in conjunction with embodiment, present disclosure is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1: this example is the sodium alginate coating at titanium plate surface preparation chelating strontium, the Tris-HCl that configuration dopamine solution uses
The pH=8 of solution, the strontium concentration used during immersion is the SrCl of mass fraction 0.1%2Solution.Concrete experimental procedure is as follows:
1) titanium sheet is placed in the HNO that mass fraction is 40%3In, corrode 40min under room temperature, then titanium sheet is taken out, use deionized water
Flushing dries up, and puts in the NaOH solution of 5mol/L, isothermal holding 5h in 90 DEG C of water-baths, afterwards with dehydrated alcohol and going
Ionized water ultrasonic cleaning 10min successively, this step processes the titanium sheet obtained and is designated as Ti.
2) take 0.0606g Tris to be dissolved in the deionized water of 50ml, after fully dissolving, add 0.05g DOPA, and use 1mol/L
HCl and 1mol/L NaOH regulation pH value of solution is 8, the titanium sheet after above-mentioned acid-alkali treatment is immersed in this solution, lucifuge mistake
Night preserves, and this step processes the titanium sheet obtained and is designated as DOPA-Ti.
3) configuration quality mark is the sodium alginate soln of 0.5%, stirring 12h to the transparent gel of solution, adds equimolar amounts
EDC and NHS activates 40min, the titanium sheet that above-mentioned dopamine processed is placed in this solution, stands 24h, and this step processes
The titanium sheet obtained is designated as SA-Ti.
4) configuration quality mark is the SrCl of 0.1%wt2Aqueous solution, filters, by above-mentioned sea with the filter of 0.22 μm after fully dissolving
The titanium sheet that sodium alginate processes is placed in one, and takes out after 24h, and this step processes the titanium sheet obtained and is designated as 0.1%Sr-Ti.
Strontium ion release experiment method is that the titanium sheet processed through strontium chloride is placed in the deionized water of 5ml, keeps 37 DEG C of constant temperature, in
Titanium sheet is taken out by 12h, 1d, 3d, 5d, 7d, 9d, 13d, 17d, 21d, 28d, changes deionized water, and ICP surveys
The concentration of strontium ion in examination solution.
Embodiment 2: this example is the sodium alginate coating at titanium plate surface preparation chelating strontium, the Tris-HCl that configuration dopamine solution uses
The pH=8 of solution, the strontium concentration used during immersion is the SrCl of mass fraction 0.3%2Solution.Concrete experimental procedure is as follows:
5) titanium sheet is placed in the HNO that mass fraction is 40%3In, corrode 40min under room temperature, then titanium sheet is taken out, use deionized water
Flushing dries up, and puts in the NaOH solution of 5mol/L, isothermal holding 5h in 90 DEG C of water-baths, afterwards with dehydrated alcohol and going
Ionized water ultrasonic cleaning 10min successively, this step processes the titanium sheet obtained and is designated as Ti.
6) take 0.0606g Tris to be dissolved in the deionized water of 50ml, after fully dissolving, add 0.05g DOPA, and use 1mol/L
HCl and 1mol/L NaOH regulation pH value of solution is 8, the titanium sheet after above-mentioned acid-alkali treatment is immersed in this solution, lucifuge mistake
Night preserves, and this step processes the titanium sheet obtained and is designated as DOPA-Ti.
7) configuration quality mark is the sodium alginate soln of 0.5%, stirring 12h to the transparent gel of solution, adds equimolar amounts
EDC and NHS activates 40min, the titanium sheet that above-mentioned dopamine processed is placed in this solution, stands 24h, and this step processes
The titanium sheet obtained is designated as SA-Ti.
8) configuration quality mark is the SrCl of 0.3%wt2Aqueous solution, filters, by above-mentioned sea with the filter of 0.22 μm after fully dissolving
The titanium sheet that sodium alginate processes is placed in one, and takes out after 24h, and this step processes the titanium sheet obtained and is designated as 0.3%Sr-Ti.
Strontium ion release experiment method is that the titanium sheet processed through strontium chloride is placed in the deionized water of 5ml, keeps 37 DEG C of constant temperature, in
Titanium sheet is taken out by 12h, 1d, 3d, 5d, 7d, 9d, 13d, 17d, 21d, 28d, changes deionized water, and ICP surveys
The concentration of strontium ion in examination solution.
Embodiment 3: this example is the sodium alginate coating at titanium plate surface preparation chelating strontium, the Tris-HCl that configuration dopamine solution uses
The pH=8 of solution, the strontium concentration used during immersion is the SrCl of mass fraction 0.5%2Solution.Concrete experimental procedure is as follows:
1) titanium sheet is placed in the HNO that mass fraction is 40%3In, corrode 40min under room temperature, then titanium sheet is taken out, use deionized water
Flushing dries up, and puts in the NaOH solution of 5mol/L, isothermal holding 5h in 90 DEG C of water-baths, afterwards with dehydrated alcohol and going
Ionized water ultrasonic cleaning 10min successively, this step processes the titanium sheet obtained and is designated as Ti.
2) take 0.0606g Tris to be dissolved in the deionized water of 50ml, after fully dissolving, add 0.05g DOPA, and use 1mol/L HCl
It is 8 with 1mol/L NaOH regulation pH value of solution, the titanium sheet after above-mentioned acid-alkali treatment is immersed in this solution, keeps in Dark Place 24
H, this step processes the titanium sheet obtained and is designated as DOPA-Ti.
3) configuration quality mark is the sodium alginate soln of 0.5%, stirring 12h to the transparent gel of solution, adds equimolar amounts
EDC and NHS activates 40min, the titanium sheet that above-mentioned dopamine processed is placed in this solution, stands 24h, and this step processes
The titanium sheet obtained is designated as SA-Ti.
4) configuration quality mark is the SrCl of 0.5%wt2Aqueous solution, filters, by above-mentioned sea with the filter of 0.22 μm after fully dissolving
The titanium sheet that sodium alginate processes is placed in one, and takes out after 24h, and this step processes the titanium sheet obtained and is designated as 0.5%Sr-Ti.
Strontium ion release experiment method is that the titanium sheet processed through strontium chloride is placed in the deionized water of 5ml, keeps 37 DEG C of constant temperature, in
Titanium sheet is taken out by 12h, 1d, 3d, 5d, 7d, 9d, 13d, 17d, 21d, 28d, changes deionized water, and ICP surveys
The concentration of strontium ion in examination solution.
Embodiment 4: this example is in the sodium alginate coating of titanium plate surface preparation chelating strontium, processes what titanium sheet used with dopamine
The pH=9 of Tris-HCl solution, the strontium concentration used during immersion is the SrCl of mass fraction 0.1%2Solution, concrete experimental procedure
As follows:
1) titanium sheet is placed in the HNO that mass fraction is 40%3In, corrode 40min under room temperature, then titanium sheet is taken out, use deionized water
Flushing dries up, and puts in the NaOH solution of 5mol/L, isothermal holding 5h in 90 DEG C of water-baths, afterwards with dehydrated alcohol and going
Ionized water ultrasonic cleaning 10min successively, this step processes the titanium sheet obtained and is designated as Ti.
2) take 0.0606g Tris to be dissolved in the deionized water of 50ml, after fully dissolving, add 0.05g DOPA, and use 1mol/L HCl
It is 9 with 1mol/L NaOH regulation pH value of solution, the titanium sheet after above-mentioned acid-alkali treatment is immersed in this solution, keeps in Dark Place 24
H, this step processes the titanium sheet obtained and is designated as DOPA-Ti.
3) configuration quality mark is the sodium alginate soln of 0.5%, stirring 12h to the transparent gel of solution, adds equimolar amounts
EDC and NHS activates 40min, the titanium sheet that above-mentioned dopamine processed is placed in this solution, stands 24h, and this step processes
The titanium sheet obtained is designated as SA-Ti.
4) configuration quality mark is the SrCl of 0.1%wt2Aqueous solution, filters, by above-mentioned sea with the filter of 0.22 μm after fully dissolving
The titanium sheet that sodium alginate processes is placed in one, and takes out after 24h, and this step processes the titanium sheet obtained and is designated as 0.1%Sr-Ti.
Strontium ion release experiment method is that the titanium sheet processed through strontium chloride is placed in the deionized water of 5ml, keeps 37 DEG C of constant temperature, in
Titanium sheet is taken out by 12h, 1d, 3d, 5d, 7d, 9d, 13d, 17d, 21d, 28d, changes deionized water, and ICP surveys
The concentration of strontium ion in examination solution.
Embodiment 5: this example is the sodium alginate coating at titanium plate surface preparation chelating strontium, the Tris-HCl that configuration dopamine solution uses
The pH=9 of solution, the strontium concentration used during immersion is the SrCl of mass fraction 0.3%2Solution.Concrete experimental procedure is as follows:
9) titanium sheet is placed in the HNO that mass fraction is 40%3In, corrode 40min under room temperature, then titanium sheet is taken out, use deionized water
Flushing dries up, and puts in the NaOH solution of 5mol/L, isothermal holding 5h in 90 DEG C of water-baths, afterwards with dehydrated alcohol and going
Ionized water ultrasonic cleaning 10min successively, this step processes the titanium sheet obtained and is designated as Ti.
10) take 0.0606g Tris to be dissolved in the deionized water of 50ml, after fully dissolving, add 0.05g DOPA, and use 1mol/L
HCl and 1mol/L NaOH regulation pH value of solution is 8, the titanium sheet after above-mentioned acid-alkali treatment is immersed in this solution, lucifuge mistake
Night preserves, and this step processes the titanium sheet obtained and is designated as DOPA-Ti.
11) configuration quality mark is the sodium alginate soln of 0.5%, stirring 12h to the transparent gel of solution, adds equimolar amounts
EDC and NHS activates 40min, the titanium sheet that above-mentioned dopamine processed is placed in this solution, stands 24h, and this step processes
The titanium sheet obtained is designated as SA-Ti.
12) configuration quality mark is the SrCl of 0.3%wt2Aqueous solution, filters, by above-mentioned with the filter of 0.22 μm after fully dissolving
The titanium sheet that sodium alginate processes is placed in one, and takes out after 24h, and this step processes the titanium sheet obtained and is designated as 0.3%Sr-Ti.
Strontium ion release experiment method is that the titanium sheet processed through strontium chloride is placed in the deionized water of 5ml, keeps 37 DEG C of constant temperature, in
Titanium sheet is taken out by 12h, 1d, 3d, 5d, 7d, 9d, 13d, 17d, 21d, 28d, changes deionized water, and ICP surveys
The concentration of strontium ion in examination solution.
Embodiment 6: this example is in the sodium alginate coating of titanium plate surface preparation chelating strontium, processes what titanium sheet used with dopamine
The pH=9 of Tris-HCl solution, the strontium concentration used during immersion is the SrCl of mass fraction 0.5%2Solution, concrete experimental procedure
As follows:
1) titanium sheet is placed in the HNO that mass fraction is 40%3In, corrode 40min under room temperature, then titanium sheet is taken out, use deionized water
Flushing dries up, and puts in the NaOH solution of 5mol/L, isothermal holding 5h in 90 DEG C of water-baths, afterwards with dehydrated alcohol and going
Ionized water ultrasonic cleaning 10min successively, this step processes the titanium sheet obtained and is designated as Ti.
2) take 0.0606g Tris to be dissolved in the deionized water of 50ml, after fully dissolving, add 0.05g DOPA, and use 1mol/L HCl
It is 9 with 1mol/L NaOH regulation pH value of solution, the titanium sheet after above-mentioned acid-alkali treatment is immersed in this solution, keeps in Dark Place 24
H, this step processes the titanium sheet obtained and is designated as DOPA-Ti.
3) configuration quality mark is the sodium alginate soln of 0.5%, stirring 12h to the transparent gel of solution, adds equimolar amounts
EDC and NHS activates 40min, the titanium sheet that above-mentioned dopamine processed is placed in this solution, stands 24h, and this step processes
The titanium sheet obtained is designated as SA-Ti.
4) configuration quality mark is the SrCl of 0.5%wt2Aqueous solution, filters, by above-mentioned sea with the filter of 0.22 μm after fully dissolving
The titanium sheet that sodium alginate processes is placed in one, and takes out after 24h, and this step processes the titanium sheet obtained and is designated as 0.5%Sr-Ti.
Strontium ion release experiment method is that the titanium sheet processed through strontium chloride is placed in the deionized water of 5ml, keeps 37 DEG C of constant temperature, in
Titanium sheet is taken out by 12h, 1d, 3d, 5d, 7d, 9d, 13d, 17d, 21d, 28d, changes deionized water, and ICP surveys
The concentration of strontium ion in examination solution.
Embodiment 7: this example is in the sodium alginate coating of titanium plate surface preparation chelating strontium, processes what titanium sheet used with dopamine
The pH=10 of Tris-HCl solution, the strontium concentration used during immersion is the SrCl of mass fraction 0.1%2Solution, concrete experiment step
Rapid as follows:
1) titanium sheet is placed in the HNO that mass fraction is 40%3In, corrode 40min under room temperature, then titanium sheet is taken out, use deionized water
Flushing dries up, and puts in the NaOH solution of 5mol/L, isothermal holding 5h in 90 DEG C of water-baths, afterwards with dehydrated alcohol and going
Ionized water ultrasonic cleaning 10min successively, this step processes the titanium sheet obtained and is designated as Ti.
2) take 0.0606g Tris to be dissolved in the deionized water of 50ml, after fully dissolving, add 0.05g DOPA, and use 1mol/L HCl
It is 10 with 1mol/L NaOH regulation pH value of solution, the titanium sheet after above-mentioned acid-alkali treatment is immersed in this solution, keeps in Dark Place
24h, this step processes the titanium sheet obtained and is designated as DOPA-Ti.
3) configuration quality mark is the sodium alginate soln of 0.5%, stirring 12h to the transparent gel of solution, adds equimolar amounts
EDC and NHS activates 40min, the titanium sheet that above-mentioned dopamine processed is placed in this solution, stands 24h, and this step processes
The titanium sheet obtained is designated as SA-Ti.
4) configuration quality mark is the SrCl of 0.1%wt2Aqueous solution, filters, by above-mentioned sea with the filter of 0.22 μm after fully dissolving
The titanium sheet that sodium alginate processes is placed in one, and takes out after 24h, and this step processes the titanium sheet obtained and is designated as 0.1%Sr-Ti.
Strontium ion release experiment method is that the titanium sheet processed through strontium chloride is placed in the deionized water of 5ml, keeps 37 DEG C of constant temperature, in
Titanium sheet is taken out by 12h, 1d, 3d, 5d, 7d, 9d, 13d, 17d, 21d, 28d, changes deionized water, and ICP surveys
The concentration of strontium ion in examination solution.
Embodiment 8: this example is the sodium alginate coating at titanium plate surface preparation chelating strontium, the Tris-HCl that configuration dopamine solution uses
The pH=10 of solution, the strontium concentration used during immersion is the SrCl of mass fraction 0.3%2Solution.Concrete experimental procedure is as follows:
13) titanium sheet is placed in the HNO that mass fraction is 40%3In, corrode 40min under room temperature, then titanium sheet is taken out, use deionization
Water rinses and dries up, and puts in the NaOH solution of 5mol/L, isothermal holding 5h in 90 DEG C of water-baths, afterwards with dehydrated alcohol and
Deionized water ultrasonic cleaning 10min successively, this step processes the titanium sheet obtained and is designated as Ti.
14) take 0.0606g Tris to be dissolved in the deionized water of 50ml, after fully dissolving, add 0.05g DOPA, and use 1mol/L
HCl and 1mol/L NaOH regulation pH value of solution is 8, the titanium sheet after above-mentioned acid-alkali treatment is immersed in this solution, lucifuge mistake
Night preserves, and this step processes the titanium sheet obtained and is designated as DOPA-Ti.
15) configuration quality mark is the sodium alginate soln of 0.5%, stirring 12h to the transparent gel of solution, adds equimolar amounts
EDC and NHS activates 40min, the titanium sheet that above-mentioned dopamine processed is placed in this solution, stands 24h, and this step processes
The titanium sheet obtained is designated as SA-Ti.
16) configuration quality mark is the SrCl of 0.3%wt2Aqueous solution, filters, by above-mentioned with the filter of 0.22 μm after fully dissolving
The titanium sheet that sodium alginate processes is placed in one, and takes out after 24h, and this step processes the titanium sheet obtained and is designated as 0.3%Sr-Ti.
Strontium ion release experiment method is that the titanium sheet processed through strontium chloride is placed in the deionized water of 5ml, keeps 37 DEG C of constant temperature, in
Titanium sheet is taken out by 12h, 1d, 3d, 5d, 7d, 9d, 13d, 17d, 21d, 28d, changes deionized water, and ICP surveys
The concentration of strontium ion in examination solution.
Embodiment 9: this example is in the sodium alginate coating of titanium plate surface preparation chelating strontium, processes what titanium sheet used with dopamine
The pH=10 of Tris-HCl solution, the strontium concentration used during immersion is the SrCl of mass fraction 0.5%2Solution, concrete experiment step
Rapid as follows:
1) titanium sheet is placed in the HNO that mass fraction is 40%3In, corrode 40min under room temperature, then titanium sheet is taken out, use deionized water
Flushing dries up, and puts in the NaOH solution of 5mol/L, isothermal holding 5h in 90 DEG C of water-baths, afterwards with dehydrated alcohol and going
Ionized water ultrasonic cleaning 10min successively, this step processes the titanium sheet obtained and is designated as Ti.
2) take 0.0606g Tris to be dissolved in the deionized water of 50ml, after fully dissolving, add 0.05g DOPA, and use 1mol/L HCl
It is 10 with 1mol/L NaOH regulation pH value of solution, the titanium sheet after above-mentioned acid-alkali treatment is immersed in this solution, keeps in Dark Place
24h, this step processes the titanium sheet obtained and is designated as DOPA-Ti.
3) configuration quality mark is the sodium alginate soln of 0.5%, stirring 12h to the transparent gel of solution, adds equimolar amounts
EDC and NHS activates 40min, the titanium sheet that above-mentioned dopamine processed is placed in this solution, stands 24h, and this step processes
The titanium sheet obtained is designated as SA-Ti.
4) configuration quality mark is the SrCl of 0.5%wt2Aqueous solution, filters, by above-mentioned sea with the filter of 0.22 μm after fully dissolving
The titanium sheet that sodium alginate processes is placed in one, and takes out after 24h, and this step processes the titanium sheet obtained and is designated as 0.5%Sr-Ti.
Strontium ion release experiment method is that the titanium sheet processed through strontium chloride is placed in the deionized water of 5ml, keeps 37 DEG C of constant temperature, in
Titanium sheet is taken out by 12h, 1d, 3d, 5d, 7d, 9d, 13d, 17d, 21d, 28d, changes deionized water, and ICP surveys
The concentration of strontium ion in examination solution.
Claims (9)
1. a preparation method for the sodium alginate coating of titanium chelated surface strontium, is characterized in that step is as follows:
(1) in trishydroxymethylaminomethane aqueous solution, dopamine is added, after dopamine fully dissolves, with hydrochloric acid and hydrogen
Sodium oxide regulation solution ph is 8～10, puts in solution by the titanium sheet of pretreatment, overnight soaks, the titanium/DOPA of preparation
Amine sample；
(2) configuration sodium alginate soln, stirring 10h～12h to the transparent gel of solution, add the carbon of equimolar amounts
Dimethylamine and N-hydroxy-succinamide activation 40min～60min, be immersed in alginic acid by the titanium of preparation/dopamine sample
In sodium solution, overnight, the titanium/dopamine/sodium alginate sample of preparation；
(3) filter the strontium chloride solution of configuration with filter, the titanium/dopamine/sodium alginate sample of preparation is immersed in chlorine
Change in strontium solution, overnight, obtain the sodium alginate coating of titanium chelated surface strontium.
2. the method for claim 1, is characterized in that described titanium sheet pretreatment is first titanium sheet to be placed in HNO3Solution
In, corrosion treatmentCorrosion Science under room temperature, then it is put in NaOH solution, isothermal holding, then depends on dehydrated alcohol and deionized water
Secondary ultrasonic cleaning.
3. the method for claim 1, is characterized in that described dopamine includes dopamine, dopamine hydrochloride and contains
The dopamine derivant of o-phenol functional group.
4. the method for claim 1, is characterized in that described titanium is for biological medical pure titanium or titanium alloy.
5. the method for claim 1, is characterized in that the molecular weight of described sodium alginate is 10,000～2.5 ten thousand dalton.
6. the method for claim 1, it is characterized in that the mass fraction of described sodium alginate soln be 0.1%～
0.5%.
7. the method for claim 1, is characterized in that the mass fraction of described strontium chloride solution is 0.1%～0.5%.
8. the method for claim 1, is characterized in that described trishydroxymethylaminomethane concentration of aqueous solution is 5～10
mM Tris。
9. the method for claim 1, is characterized in that described filter pore size is 0.22 μm.
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| CN107335093A (en) * | 2017-08-18 | 2017-11-10 | 四川大学 | Porous support with surface orientation functionalized modification coating and preparation method thereof |
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