CN109825835A - Surface has silane/magnesium of Sodium Hyaluronate composite coating and the preparation method of magnesium alloy - Google Patents
Surface has silane/magnesium of Sodium Hyaluronate composite coating and the preparation method of magnesium alloy Download PDFInfo
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- CN109825835A CN109825835A CN201910287100.XA CN201910287100A CN109825835A CN 109825835 A CN109825835 A CN 109825835A CN 201910287100 A CN201910287100 A CN 201910287100A CN 109825835 A CN109825835 A CN 109825835A
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Abstract
A kind of surface of the present invention has silane/magnesium of Sodium Hyaluronate composite coating and the preparation method of magnesium alloy.This method is that hydro-thermal process, magnesium hydroxide film of the acquisition with activity hydroxy as the substrate with protective effect and improve the pretreatment layer with silane binding force in alkaline solution by magnesium and magnesium alloy；Silane molecule is assembled on magnesium and magnesium alloy by molecular link again；The EDC/NHS for finally obtaining covalent bond grafting in silanization sample surfaces with infusion process cross-linking modified Sodium Hyaluronate coating, obtains composite coating after drying.The method of the invention can be effectively controlled the corrosion rate of magnesium and magnesium alloy, reduce corrosion rate, no objectionable impurities introduces, with good biocompatibility and degradability, the magnesium ion of slow release also plays a positive role to treatment of eye disorders, guarantees success rate of operation, and product cost is low, patient's expense is reduced, is expected to become new ophthalmology interventional therapy method, brings new approaches for treatment of eye disorders.
Description
Technical field
The invention belongs to technical field of biological materials, in particular to a kind of surface has the compound painting of silane/Sodium Hyaluronate
The magnesium of layer and the preparation method of magnesium alloy.
Background technique
Magnesium and magnesium alloy have light-weight, high-biocompatibility, nothing as a kind of emerging biological medical degradable magnesium alloy
The advantages that malicious, compared with conventional medical metal (cobalt-base alloys, stainless steel, titanium-base alloy) material, maximum feature is exactly in people
Body class can be degradable, on the one hand can be to avoid second operation to patient's bring pain and financial burden；On the other hand exist
The intracorporal catabolite of biology does not generate toxic side effect, avoids implantation material long-term existence when internal bring hidden danger, degradation
The magnesium ion of slow release can play very important effect in eye, such as: (1) maintain physiological function and the angle of retina
Film normal configuration and function, (2) adjust intracellular ion concentration, and (3) are used as calcium ion channel blocker, and having improves eye blood
The function of stream, protection optic nerve, this is to ophthalmology disease (cataract, disease of cornea, neuroretinopathy etc.)
Treatment has positive effect, therefore magnesium and magnesium alloy are with a wide range of applications on ophthalmology interventional therapy, receive life
The extensive concern of object medical field.
However, can discharge a large amount of hydrogen after implanting because its activity is higher due to magnesium and magnesium alloy and make to be implanted into
Position pH changes, this is that unfavorable, excessively high corrosion rate becomes the maximum of its application and hinders to implant site tissue,
The corrosion rate for how controlling magnesium and magnesium alloy becomes one of the emphasis studied at present.
Currently, being used to regulate and control there are mainly three types of the technologies of magnesium and corrosion resistance of magnesium alloy: purity, the design for improving magnesium are novel
Magnesium alloy and material surface modifying technology.Material surface modifying technology can also change while controlling magnesium alloy degradation speed
Therefore how material surface property improves its biocompatibility and bioactivity etc., be promoted material property important means and
Research hotspot.
Silanized surface modification be it is a kind of can effectively anti-corrosion and surface coating layer treatment method at low cost.It is silane coupled
Hydrolysis occurs in water and generates silanol groups (Si-OH) for agent, and provides after hydro-thermal process with magnesium metal material surface
Hydroxyl occur dehydration condensation generate covalent bond (Si-O-metal)；Remaining silanol groups (Si-OH) passes through to be formed simultaneously
Siloxanes key (Si-O-Si) carries out self-crosslinking, forms the substrate for the protective layer that organic chemistry combines, it can also make coating function simultaneously
Energyization, for example, it is compound with other organic polymers.
Sodium Hyaluronate is the important component for constituting skin, vitreum, knuckle synovia and cartilaginous tissue, is had viscous well
Elasticity, hydrophily adjust osmotic pressure and inhibit inflammatory reaction, and fibroblast proliferation and anti-scar is inhibited to have obviously
Effect, be widely used in the treatment of ophthalmology disease (cataract, dry eyes, keratitis etc.), be a kind of biofacies
The extraordinary organic polymer of capacitive is implanted into material.But that there are stability is poor due to Sodium Hyaluronate, to hyaluronidase and
Free radical is sensitive, retention time is short in vivo, lacks in aqueous systems the disadvantages of mechanical strength, it is therefore necessary to change to it
It learns and is modified, to improve its mechanical strength and anti-degradation property.
Summary of the invention
The object of the present invention is to provide a kind of surfaces to have silane/magnesium of Sodium Hyaluronate composite coating and the system of magnesium alloy
Preparation Method, this method obtain the magnesium hydroxide film of even compact by hydro-thermal process, as with protective effect substrate and
Improve the pretreatment layer with silane binding force.Then greatly improve the corrosion resistance of coating, process operation letter using silane treatment
Single, no objectionable impurities introduces, at low cost, finally by covalent bond effect on it is compound by EDC NHS modified hyalomitome
Sour sodium coating, so that obtaining has biocompatibility and corrosion resistant silane/Sodium Hyaluronate coating.
Realize the technical scheme is that
Surface has silane/magnesium of Sodium Hyaluronate composite coating and the preparation method of magnesium alloy, there is following steps:
1) magnesium and magnesium alloy materials are cleaned, are cleaned by ultrasonic again after polishing；It is subsequently placed into the NaOH solution of pH=10~12 and carries out water
Heat treatment, the temperature of hydro-thermal process are 100~140 DEG C, and soaking time is 2~6h；
2) the resulting magnesium of step 1) and magnesium alloy materials are cleaned by ultrasonic in dehydrated alcohol, are dried up；It is subsequently placed into and is hydrolyzed
30~60s is impregnated in silane ethanol solution, is dried with nitrogen, is obtained the magnesium and magnesium alloy materials with silane transition zone；
3) Sodium Hyaluronate of magnesium and magnesium alloy materials after being put into crosslinking described in step 2 with silane transition zone is molten
2~6h is reacted in liquid；
4) magnesium obtained by step 3) and magnesium alloy materials are placed in -10~-20 DEG C of freezing chambers and are freezed, then move into -20~-80 DEG C it is cold
It is freeze-dried in lyophilizer, obtains surface with silane/Sodium Hyaluronate composite coating magnesium and magnesium alloy.
It is cleaned by ultrasonic described in step 1), is carried out in dehydrated alcohol, the time of ultrasonic cleaning is 10~20min.
The configuration method of the silane ethanol solution: silane parts by volume in the silane ethanol solution of 100 parts by volume is 3~
7 parts, deionized water parts by volume is 8 parts, and surplus is dehydrated alcohol；
Hydrolysis time is 24~72h.
Silane described in step 2 is that alkyl one type of silane or aminopropyl one type of silane or epoxy group one type of silane etc. are dissolved in organic solvent
Avirulent silane coupling agent.
The solidification temperature of silane transition zone described in step 2 is 100~120 DEG C, and curing time is 0.5h~1.5h.
The preparation method of cross-linking hyaluronic acid sodium described in step 3) is to be dissolved in Sodium Hyaluronate in deionized water for 24 hours
Afterwards, EDC/NHS crosslinking agent is added, reacts 4h~6h at room temperature, the pH value 4-5 of solution is adjusted and kept with 0.01mol/L HCl.
The mass concentration of the Sodium Hyaluronate is 5~20g/L, and the mass concentration of crosslinking agent is 5g/L.
The molar ratio of crosslinking agent EDC:NHS is 4:1.
Cooling time described in step 4) is 12~48h, and sublimation drying is 6~36h.
The present invention has the following advantages:
1. magnesium and magnesium alloy have the advantages that the cost of material is low, processing cost is low etc. compared with conventional medical metal material, and
Present invention process is simple, production is at low cost.
2. the present invention is effectively controlled the corrosion rate of magnesium and magnesium alloy in vivo.The electro-chemical test of applicant
The result shows that the corrosion electric current density of the material handled through the method for the present invention is not than using the material of the method for the present invention processing to reduce
Two orders of magnitude.
3. the present invention is suitable for magnesium of various shapes and magnesium alloy materials, can all be obtained with corrosion-resistant through the method for the present invention
The multi-functional coatings of property, good biocompatibility, the coating is very thin, will not influence the size of material.
4. the present invention obtains the equal and cause with activity hydroxy by the hydro-thermal process in NaOH solution, in Mg alloy surface
Close magnesium hydroxide film as the substrate with protective effect and improves the pretreatment layer with silane binding force, not only improves
The corrosion resistance of matrix, additionally provides hydroxyl, combines closely so that forming covalent bond with the silanol groups after silane hydrolyzate
Together, and if be directly directly coated with silane in magnesium and Mg alloy surface, cannot combine well.
5. in method of the present invention, silanization treatment is that silane molecule is assembled into magnesium and magnesium alloy by molecular link
On, the corrosion resistance of matrix on the one hand can be greatly improved, on the other hand can pass through covalent bond effect compound process on it
EDC/NHS modified Sodium Hyaluronate coating, with good biocompatibility and corrosion resistance.With traditional silicon alkanisation
Unlike processing, the magnesium and magnesium alloy of the method for the invention processing carry out nitrogen after impregnating in ethyl alcohol solution of silane and blow
It is dry, the generation of silane film crackle in curing and drying can be effectively prevented, improve the corrosion resistance and finished product rate of coating.
6. in method of the present invention, the cross-linking modified mechanical strength that Sodium Hyaluronate can be improved of Sodium Hyaluronate
With anti-degradation property, degradation time of the Sodium Hyaluronate in ocular environment, and crosslinking agent EDC/ of the invention are greatly extended
NHS ratio is if not 4:1, then cross-linking reaction cannot carry out completely, while pH value is answered when the cross-linking modified reaction of Sodium Hyaluronate
When controlling 4~5, if pH value is too low, the integrality and dissolubility of Sodium Hyaluronate chain can be destroyed；If pH value is excessively high,
It can then make Sodium Hyaluronate and reacting for EDC/NHS incomplete.
EDC/NHS of the present invention cross-linking modified hyaluronic acid sodium gel film has stable structure, mechanical strength high, saturating
Feature bright, cell compatibility is good.
The method of the invention can be effectively controlled the corrosion rate of magnesium and magnesium alloy, reduce corrosion rate, no objectionable impurities
It introduces, there is good biocompatibility and degradability, the magnesium ion of slow release also plays treatment of eye disorders actively
Effect guarantees success rate of operation, and product cost is low, reduces patient's expense, is expected to become new ophthalmology interventional therapy method,
New approaches are brought for treatment of eye disorders.
The magnesium alloy of the method for the invention can be Mg, Mg-Ca, Mg-Zn, Mg-Mn, Mg-Li, Mg-Li-Ca, Mg-
Zn-Ca, Mg-Mn-Ca etc..
The corrosion resistance of magnesium and magnesium alloy can be improved in the method for the present invention, regulates and controls the degradation rate of magnesium；And hyaluronic acid
Sodium coating can promote wound healing, inhibit inflammatory reaction, anti-scar, adjust osmotic pressure, to ophthalmology disease (glaucoma, it is white in
Barrier, dry eyes, keratonosus etc.) there is a good therapeutic effect, the magnesium ion of slow release also has the treatment of ophthalmology disease when degradation
There is positive effect.The method of the present invention compensate for ophthalmology implantation high molecular material (such as: amnion, chitosan) due to the filling time not
Foot causes the problem of scar secondary generation, while compared with traditional inertia ophthalmology is implanted into material, degradable used in the present invention
Surface-functionalized modification magnesium and its alloy, not only eliminate second operation bring pain or long-term rejection；And
Therapeutic effect of the Sodium Hyaluronate to ophthalmology disease is had both, magnesium and magnesium alloy aqueous humor drainage and magnesium ion can also be played to eye
The double action of positive function；In addition, preparation method simple process of the present invention is convenient, at low cost, coating is free of to be had with to human body
Evil substance, has good biocompatibility, has very big application value in ophthalmology implant surgery.
Volume of the present invention is liter or milliliter.
Reagent of the present invention is commercial product, wherein pure magnesium uses the product of mass fraction 99.99%；Hydroxide
It is pure that sodium, dehydrated alcohol are all made of analysis；1,2- bis- (triethoxysilane) ethane (BTSE), 1- (3- dimethylamino-propyl) -3-
Ethyl-carbodiimide hydrochloride (EDC) is all made of the product that purity is 99%；N- hydroxysuccinimide (NHS) use purity for
98% product；Sodium Hyaluronate use purity for 97% product.
Detailed description of the invention
Fig. 1 is magnesium and Mg alloy surface multi-functional coatings preparation process；
Fig. 2 is polarization curve of the magnesium material in simulated body fluid (SBF)；
Fig. 3 is the infrared spectroscopy (FTIR) of composite coating；
Fig. 4 be magnesium material before modification after cytotoxicity experiment result figure.
Specific embodiment
The reagent of the present embodiment:
Pure magnesium (mass fraction 99.99%, Henan aerospace metal material Co., Ltd)；
Sodium hydroxide (NaOH analyzes pure, Chongqing Chuan Dong Chemical Co., Ltd.)；
Dehydrated alcohol (CH3CH2OH analyzes pure, Chongqing Chuan Dong Chemical Co., Ltd.)；
1,2- bis- (triethoxysilane) ethane (BTSE, purity 99%, Sa grace chemical technology Shanghai Co., Ltd)；
Sodium Hyaluronate (Shanghai Ai Lan Chemical Industry Science Co., Ltd, purity 97%)；
(EDC, purity 99%, it is limited that Chinese mugwort lookes at Shanghai chemical science and technology to 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride
Company)；
N- hydroxysuccinimide (NHS, purity 98%, Chongqing Ze Heng Bioisystech Co., Ltd).
Embodiment 1
Pure magnesium metal material is taken to prepare multi-functional coatings according to the method for the present invention:
A. mechanical decontamination and cleaning:
Sand paper cleans pure magnesium after being polishing to 1200#, at room temperature, is cleaned by ultrasonic 20 minutes in dehydrated alcohol；
B. hydro-thermal process:
Cleaned above-mentioned pure magnesium metal material is placed on 120 DEG C, pH=12, in the reaction kettle for the NaOH solution that degree of filling is 50%
4h；It is air-cooled to room temperature；
C. it cleans:
Pure magnesium metal material after hydro-thermal process is cleaned by ultrasonic 10 minutes in dehydrated alcohol, drying；
D. silanization treatment:
The pure magnesium metal material that step C is cleaned is placed in the configuration method of the silane ethanol solution: the silane second of 100 parts by volume
Silane parts by volume in alcoholic solution is 7 parts, and deionized water parts by volume is 8 parts, and surplus is dehydrated alcohol.Hydrolyze the silane second of 48h
Alcohol solution for soaking 30s is dried with nitrogen after taking-up, then is handled through 120 DEG C of time 1h curing and dryings, cools to room temperature with the furnace to obtain the final product
To the pure magnesium metal material with silane coating；
E. cross-linking hyaluronic acid sodium solution is configured:
After the Sodium Hyaluronate that mass concentration is 10g/L is dissolved in deionized water for 24 hours, then the friendship of mass concentration 50g/L
Connection agent, which is added to, reacts 4h to get the sodium hyaluronate solution to after being crosslinked in above-mentioned solution；EDC:NHS in the crosslinking agent
Molar ratio is=4:1.
F. the resulting pure magnesium metal material of step D is immersed in 37 DEG C of cross-linking hyaluronic acid sodium solution and reacts 4h, so
After be put into and freezed for 24 hours in -20 DEG C of freezing chambers after, place into -80 DEG C of freeze driers and be freeze-dried 36h and have to get to surface
There is the pure magnesium metal material of silane/Sodium Hyaluronate composite coating.
Fig. 2 is the polarization curve that the embodiment of the present invention 1 obtains.It is multiple from figure it is recognised that relatively with unmodified pure magnesium
After closing coating modified pure magnesium, corrosion electric current density reduces two orders of magnitude, shows corrosion-resistant great raising.(note: Mg-
OH is the magnesium hydroxide obtained after hydro-thermal process, and Mg-B is the silane coating prepared on magnesium hydroxide surface, and Mg-B-CHA is
The Sodium Hyaluronate prepared on silane film)
Fig. 3 is the infrared spectrogram that the embodiment of the present invention 1 obtains.It can be appreciated that being 3691cm in absorption frequency from figure-1
Place is the-OH, the 1012cm in Mg-B in magnesium hydroxide-1Place is Si-O-Si key, the 1613cm in Mg-B-CHA-1Place is
C=O key shows the successful preparation of composite coating.
The cytotoxicity experiment result figure that Fig. 4 embodiment of the present invention 1 obtains.From in figure it is recognised that culture five days after,
The toxic grade of unmodified pure magnesium is 1 grade, and the toxic grade of the modified experiment of composite coating is 0 grade, shows pure magnesium through compound painting
Layer is modified to show good cell compatibility.
Embodiment 2
Except the ZM61-Ca0.5 that the pure magnesium in step A is changed into Mg-Ca system alloy, remaining step is same as Example 1, can obtain
There are silane/Sodium Hyaluronate composite coating magnesium alloy materials to surface.
Embodiment 3
Except 120 DEG C in step B are changed into 100 DEG C, 4h changes 6h into, remaining step is same as Example 1.
Embodiment 4
Except the silane volume fraction in step D is become 3% from 7%, remaining step is same as Example 1.
Embodiment 5
Except the mass concentration of the Sodium Hyaluronate in step E is become 20g/L from 10g/L, remaining step is same as Example 1.
Embodiment described above can not be interpreted as pair merely to clearly demonstrate several embodiments of the invention
The limitation of the invention patent range.To those skilled in the art, on the basis of the present invention, one can also be made
A little to improve and change, these are all within the scope of protection of the present invention.Therefore, the scope of protection of the patent of the present invention should be with appended right
Subject to it is required that.
Claims (9)
1. a kind of surface has silane/magnesium of Sodium Hyaluronate composite coating and the preparation method of magnesium alloy, which is characterized in that have
Following steps:
1) magnesium and magnesium alloy materials are cleaned, are cleaned by ultrasonic again after polishing；It is subsequently placed into the NaOH solution of pH=10~12 and carries out water
Heat treatment, the temperature of hydro-thermal process are 100~140 DEG C, and soaking time is 2~6h；
2) the resulting magnesium of step 1) and magnesium alloy materials are cleaned by ultrasonic in dehydrated alcohol, are dried up；It is subsequently placed into and is hydrolyzed
30~60s is impregnated in silane ethanol solution, is dried with nitrogen, is obtained the magnesium and magnesium alloy materials with silane transition zone；
3) Sodium Hyaluronate of magnesium and magnesium alloy materials after being put into crosslinking described in step 2 with silane transition zone is molten
2~6h is reacted in liquid；
4) magnesium obtained by step 3) and magnesium alloy materials are placed in -20 DEG C of freezing chambers and are freezed, then moved into -20~-80 DEG C of freezings and do
It is freeze-dried in dry machine, obtains surface with silane/Sodium Hyaluronate composite coating magnesium and magnesium alloy.
2. according to the method described in claim 1, it is characterized by: described in step 1) be cleaned by ultrasonic, carried out in dehydrated alcohol,
Its time being cleaned by ultrasonic is 10~20min.
3. according to the method described in claim 1, it is characterized by: the configuration method of silane ethanol solution described in step 2: 100
Silane parts by volume in the silane ethanol solution of parts by volume is 3~7 parts, and deionized water parts by volume is 8 parts, and surplus is anhydrous second
Alcohol；
Hydrolysis time is 24~72h.
4. according to the method described in claim 1, it is characterized by: silane described in step 2 is alkyl one type of silane or aminopropyl class
Silane or epoxy group one type of silane are dissolved in organic solvent.
5. according to the method described in claim 1, it is characterized by: the solidification temperature of silane transition zone described in step 2 is
100~120 DEG C, curing time is 0.5h~1.5h.
6. according to the method described in claim 1, it is characterized by: the preparation method of cross-linking hyaluronic acid sodium described in step 3)
It is after being dissolved in Sodium Hyaluronate in deionized water for 24 hours, EDC/NHS crosslinking agent to be added, reacts 4h at room temperature, use
0.01mol/L HCl is adjusted and is kept the pH value 4-5 of solution.
7. according to the method described in claim 6, it is characterized by: the mass concentration of the Sodium Hyaluronate be 5~20g/L,
The mass concentration of crosslinking agent is 5g/L.
8. according to the method described in claim 6, it is characterized by: the molar ratio ratio of crosslinking agent EDC:NHS is 4:1.
9. according to the method described in claim 1, freezing is dry it is characterized by: cooling time described in step 4) is 12~48h
The dry time is 6~36h.
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| CN115581817A (en) * | 2022-09-16 | 2023-01-10 | 南京神奇科技开发有限公司 | Biomedical coating material with antibacterial and lubricating functions and preparation method thereof |
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