CN104984394A - Preparation method for medical metal implant surface chitosan quaternary ammonium salt/collagen composite coating - Google Patents
Preparation method for medical metal implant surface chitosan quaternary ammonium salt/collagen composite coating Download PDFInfo
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Abstract
The invention discloses a preparation method for a medical metal implant surface chitosan quaternary ammonium salt/collagen composite coating. The method includes the steps that an electrolyte containing calcium, phosphorus, collagen and chitosan quaternary ammonium salt is prepared; a platinum sheet serves as a counter electrode; a metal substrate washed through acid serves as a work electrode; and electrochemical deposition is performed in a multi-potential-step manner. The positive and negative condition and the amplitude of each step work electrode potential and deposition time of each segment are adjusted, so that deposition does not need to be performed multiple times, the purpose of controllable space distribution of the chitosan quaternary ammonium salt in a mineralized collagen coating on the surface of the substrate can be quickly and easily achieved, and in other words, the inner layer and the outer layer of the collagen coating are rich in chitosan quaternary ammonium salt. The feature that the chitosan quaternary ammonium salt is provided with positive charges and biological growth factors are carried in different space positions of the collagen coating, so that the biological growth factor release behavior can be controlled and adjusted. Meanwhile, the capacity of the coating for carrying biological growth factors is improved and the method has the wide application prospect in hard-bone tissue regeneration field.
Description
Technical field
The present invention relates to the preparation method of medical metal implant surfaces coating, especially the preparation method of the mineralized collagen coating of medical metal implant surfaces.
Background technology
In Bone Defect Repari process, in body, own cells produces different somatomedin at different times and carries out smoothly to regulate and control Integrated implant process, and the release behavior of somatomedin usually determines Bone Defect Repari whether success.Therefore, for novel metal implant material, it not only should have good biocompatibility, more should have the bearing capacity of better somatomedin or medicine and have controlled ability to release behaviors such as the somatomedin that it carries.The organic substance that normally at metal implant surface-coated one deck there is slow-release function embed simultaneously somatomedin agent meeting biocompatibility, grow the requirement that therefore bearing capacity and release behavior control.But coating one deck has the Organic substance coating of slow-release function to control growth factor release behavior, usually need multistep, complicated preparation means, limit its application in implant surfaces is modified.
At present, the method preparing by metallic matrix organic coating mainly contains electrochemical deposition method, spin-coating method and bionical sedimentation.Wherein, electrochemical deposition method has reaction condition gentleness, coating chemical composition and advantage, being widely used in prepared by coating such as thickness is controlled.Chinese patent CN101545886B adopts potential step method to make the gold chloride in conducting polymer be reduced to nano Au particle, and then fixed biologically sensitive materials form composite sensitive film.But based on potential step method, adopt the research of the distribution of alternation potential deposition method regulation and control chitosan quaternary ammonium salt in collagenic coating to have no report.Chitosan quaternary ammonium salt within the scope of wider pH with positive charge, it is rapid to the response of electric field, by adopting alternation potential deposition method, the depositing behavior of chitosan quaternary ammonium salt can be regulated and controled, realize the spatial distribution of chitosan quaternary ammonium salt in collagenic coating controlled, and then effectively control the release behavior of somatomedin, for raising Bone Defect Repari speed and quality significant.
Collagen protein is one of constituent main in natural bone, and the signal transmission effect that functional group exposed in its molecule has, thus has good biocompatibility.But the bearing capacity of collagen coating to biotic factor etc. is limited.There is much research to be devoted to improve bearing capacity, as Chinese patent CN103074659A utilizes constant potential electrodeposition process to introduce chitosan in mineralized collagen coating, improve coating medicine, somatomedin equivalent-load ability.Chinese patent CN102028969A utilizes constant potential electrodeposition process to be built with fine and close chitosan layer, porous mineralising chitosan layer and mineralized collagen/chitosan crosslinked body layer from bottom to top successively at implant surfaces, improves biology performance and the drug carrying ability of coating.But according to mineralized collagen sedimentation mechanism, pH gradient can be produced near substrate in electrochemical deposition process, chitosan the certain depth depositing to coating along with pH raise after lose proton, the response of chitosan to electric field losing proton sharply declines, nexine or the skin of mineralized collagen coating can not be enriched in by controllable adjustment chitosan, limit the control of coating to somatomedin equivalent-load locus, the Coulomb force simultaneously lost between the chitosan of proton and somatomedin sharply declines, and makes whole coating improve limited to the bearing capacity of somatomedin etc.
Summary of the invention
The object of the present invention is to provide the preparation method that a kind of technique is simple, have the controlled medical metal implant surfaces chitosan quaternary ammonium salt/collagen composite coating of high biological response and efficient growth factor bearing capacity and growth factor release behavior.
The preparation method of medical metal implant surfaces chitosan quaternary ammonium salt/collagen composite coating of the present invention, comprises the following steps:
1) be dissolved in distilled water by chitosan quaternary ammonium salt, compound concentration is the chitosan quaternary ammonium saline solution of 0.5g/L, be placed in 4 DEG C stand-by; Be dissolved in by type i collagen in 0.005mol/L acetic acid, compound concentration is the collagen acetum of 0.5g/L, be placed in 4 DEG C stand-by;
2) prepare electrolyte: calcium containing compound is soluble in water, be mixed with the calcic aqueous solution that concentration is 10mmol/L ~ 100mmol/L; Phosphorus-containing compound is soluble in water, be mixed with the phosphorous aqueous solution that concentration is 10mmol/L ~ 100mmol/L; Calcic aqueous solution and phosphorous aqueous solution are uniformly mixed, obtain solution A, by step 1) obtained type i collagen acetum and chitosan quaternary ammonium saline solution mix with solution A, make the quaternary ammonium root concentration of calcium in mixed liquor, phosphorus, collagen, chitosan quaternary ammonium salt be respectively 4 ~ 8mmol/L, 8 ~ 16 mmol/L, 0.3g/L, 0.32 ~ 0.016mmol/L, adjustment electrolyte ph is 4.3 ~ 4.6;
3) electrolyte is placed in the temperature chamber that temperature is 37 DEG C, using platinized platinum as to electrode, the metal basal board crossed using sour cleaning treatment is as working electrode, and the spacing of two electrodes is 1 ~ 2cm, adopts many potential steps pattern to carry out electrochemical deposition, the positive voltage applied on metallic substrates is 2.0 ~ 2.8V, negative voltage is-1.5 ~-2.5V, and step hop count is 3 ~ 7 sections, and every section of sedimentation time is 1-20min, take out metal basal board, with stand-by after washed with de-ionized water;
4) prepare the biotic factor solution of 0.1 ~ 2 μ g/mL, the pH regulating biotic factor solution is 3 ~ 10, by 3) metal basal board prepared is immersed in biotic factor solution, takes out after 1-3 days, dry at 37 DEG C.
In the present invention, described chitosan quaternary ammonium salt is quaternary ammonium root substitution value is 20% ~ 99%, molecular mass be 1000 ~ 100000 2-hydroxypropyltrimethyl ammonium chloride chitosan or quaternary ammonium root substitution value be 20% ~ 99%, molecular mass is the N of 1000 ~ 100000, N, N-N-trimethyl chitosan TMC quaternary ammonium salt.
In the present invention, described type i collagen is the liquid type i collagen of times Pedicellus et Pericarpium Trapae.
In the present invention, to be pH be described biotic factor 3 ~ 10 with BMP-2, BMP-6 or BSA of negative charge.
In the present invention, described calcium containing compound can be Ca (NO
3)
26H
2o or CaCl
2.
In the present invention, described phosphorus-containing compound can be NH
4h
2pO
4or NaH
2pO
4.
In the present invention, described metal basal board can be titanium plate, tantalum plate or magnesium plate.
The present invention adopts many potential steps pattern to carry out electrochemical deposition, realize the chitosan quaternary ammonium salt/collagen composite coating of the Seedling height factor carrying of medical metal implant surfaces, high cellular response, by adjusting positive and negative, size and every section of sedimentation time of every section of step working electrode potential, without the need to Multiple depositions, can quickly and easily realize chitosan quaternary ammonium salt to be distributed to collagenic coating different spaces, i.e. collagenic coating nexine enrichment chitosan quaternary ammonium salt and the outer enrichment chitosan quaternary ammonium salt of collagenic coating.Utilize chitosan quaternary ammonium salt with the character of positive charge, Biological somatomedin is carried to collagenic coating different spatial, achieve Biological somatomedin release behavior controllable adjustment, increase the ability of coating carrying Biological somatomedin simultaneously, be with a wide range of applications in hard bone tissue field of repairing.
Accompanying drawing explanation
Fig. 1 is titanium implants surface composite coating nexine enrichment 2-hydroxypropyltrimethyl ammonium chloride chitosan pattern.
Fig. 2 is titanium implants surface composite coating outer enrichment 2-hydroxypropyltrimethyl ammonium chloride chitosan pattern.
Fig. 3 is the nexine/skin carrying BMP-2 ability comparison diagram of titanium implants surface composite coating.
Detailed description of the invention
Below in conjunction with instantiation, the present invention is described:
Embodiment 1
1) be 98% by quaternary ammonium root substitution value, molecular mass be 30000 2-hydroxypropyltrimethyl ammonium chloride chitosan be dissolved in distilled water, compound concentration is the chitosan quaternary ammonium saline solution of 0.5g/L, be placed in 4 DEG C stand-by; Be dissolved in 0.005mol/L acetic acid by liquid for a times Pedicellus et Pericarpium Trapae type i collagen, compound concentration is the collagen acetum of 0.5g/L, be placed in 4 DEG C stand-by;
2) electrolyte is prepared: by Ca (NO
3)
26H
2o is soluble in water, is mixed with the Ca (NO that calcium concentration is 80mmol/L
3)
2aqueous solution, by NH
4h
2pO
4soluble in water, being mixed with containing phosphorus concentration is the NH of 80mmol/L
4h
2pO
4aqueous solution, by Ca (NO
3)
2aqueous solution and NH
4h
2pO
4aqueous solution is uniformly mixed, and obtains solution A.Liquid for times Pedicellus et Pericarpium Trapae type i collagen, 2-hydroxypropyltrimethyl ammonium chloride chitosan solution are mixed with solution A, make the concentration of quaternary ammonium root and collagen in calcium, phosphorus, 2-hydroxypropyltrimethyl ammonium chloride chitosan be respectively 8mmol/L, 16 mmol/L, 0.08mmol/L, 0.3g/L, then be 4.4 with NaOH solution adjustment electrolyte ph;
3) using the cleaned titanium plate of surface acid as working electrode, platinum electrode is as to electrode, two electrode spacings are 1cm, getting 15ml electrolyte is placed in 37 DEG C of temperature chambers, adopt many potential steps electrochemical deposition pattern, be applied to voltage on titanium-base and the time is respectively :-1.5V (120s) ,-2.4V (180s), 2V (60s) ,-2.4V (480s), 2V (120s) ,-2.4V (720s), 2V (180s), titanium-base is taken out after deposition, for subsequent use after washed with de-ionized water;
4) prepare the BMP-2 solution of 2 μ g/mL, reconciling pH is 7, is immersed in by the titanium-base of above-mentioned preparation in 10mL BMP-2 solution.Take out after 3 days, dry in 37 DEG C of baking ovens, obtain on titanium implants surface the composite coating that nexine is loaded with the 2-hydroxypropyltrimethyl ammonium chloride chitosan/collagen of BMP-2, its pattern is shown in Fig. 1.Nexine refers to this side that composite coating directly contacts with titanium implants surface.
Embodiment 2
1) be 98% by quaternary ammonium root substitution value, molecular mass be 30000 2-hydroxypropyltrimethyl ammonium chloride chitosan be dissolved in distilled water, compound concentration is the chitosan quaternary ammonium saline solution of 0.5g/L, be placed in 4 DEG C stand-by; Be dissolved in 0.005mol/L acetic acid by liquid for a times Pedicellus et Pericarpium Trapae type i collagen, compound concentration is the collagen acetum of 0.5g/L, be placed in 4 DEG C stand-by;
2) electrolyte is prepared: by Ca (NO
3)
26H
2o is soluble in water, is mixed with the Ca (NO that calcium concentration is 80mmol/L
3)
2aqueous solution, by NH
4h
2pO
4soluble in water, being mixed with containing phosphorus concentration is the NH of 80mmol/L
4h
2pO
4aqueous solution, by Ca (NO
3)
2aqueous solution and NH
4h
2pO
4aqueous solution is uniformly mixed, and obtains solution A.Liquid for times Pedicellus et Pericarpium Trapae type i collagen, 2-hydroxypropyltrimethyl ammonium chloride chitosan solution are mixed with solution A, make the concentration of quaternary ammonium root and collagen in calcium, phosphorus, 2-hydroxypropyltrimethyl ammonium chloride chitosan be respectively 8mmol/L, 16 mmol/L, 0.08mmol/L, 0.3g/L, then be 4.4 with NaOH solution adjustment electrolyte ph.
3) using the cleaned titanium plate of surface acid as working electrode, platinum electrode is as to electrode, two electrode spacings are 1cm, getting 15ml electrolyte is placed in 37 DEG C of temperature chambers, adopt many potential steps electrochemical deposition pattern, be applied to voltage on titanium-base and the time is respectively :-2.4V (120s), 2V (60s) ,-2.4V (360s), 2V (120s) ,-2.4V (480s), 2V (180s) ,-2.4V (480s), titanium-base is taken out after deposition, for subsequent use after washed with de-ionized water;
4) prepare the BMP-2 solution of 2 μ g/mL, reconciling pH is 7, is immersed in by the titanium-base of above-mentioned preparation in 10mL BMP-2 solution.Take out after 3 days, at 37 DEG C of oven dryings, obtain on titanium implants surface the composite coating that skin is loaded with the 2-hydroxypropyltrimethyl ammonium chloride chitosan/collagen of BMP-2, its pattern is shown in Fig. 2.Skin refers to this side of composite coating and titanium implants surface non-direct contact.
Embodiment 3
1) be 98% by quaternary ammonium root substitution value, molecular mass be 30000 2-hydroxypropyltrimethyl ammonium chloride chitosan be dissolved in distilled water, compound concentration is the chitosan quaternary ammonium saline solution of 0.5g/L, be placed in 4 DEG C stand-by; Be dissolved in 0.005mol/L acetic acid by liquid for a times Pedicellus et Pericarpium Trapae type i collagen, compound concentration is the collagen acetum of 0.5g/L, be placed in 4 DEG C stand-by;
2) electrolyte is prepared: by Ca (NO
3)
26H
2o is soluble in water, is mixed with the Ca (NO that calcium concentration is 80mmol/L
3)
2aqueous solution, by NH
4h
2pO
4soluble in water, being mixed with containing phosphorus concentration is the NH of 80mmol/L
4h
2pO
4aqueous solution, by Ca (NO
3)
2aqueous solution and NH
4h
2pO
4aqueous solution is uniformly mixed, and obtains solution A.Liquid for times Pedicellus et Pericarpium Trapae type i collagen, 2-hydroxypropyltrimethyl ammonium chloride chitosan solution are mixed with solution A, make the concentration of quaternary ammonium root and collagen in calcium, phosphorus, 2-hydroxypropyltrimethyl ammonium chloride chitosan be respectively 8mmol/L, 16 mmol/L, 0.064mmol/L, 0.3g/L, then be 4.4 with NaOH solution adjustment electrolyte ph;
3) using the cleaned titanium plate of surface acid as working electrode, platinum electrode is as to electrode, two electrode spacings are 1cm, getting 15ml electrolyte is placed in 37 DEG C of temperature chambers, adopt many potential steps electrochemical deposition pattern, be applied to voltage on titanium-base and the time is respectively :-1.5V (120s) ,-2.4V (180s), 2V (60s) ,-2.4V (480s), 2V (120s) ,-2.4V (720s), 2V (180s), titanium-base is taken out after deposition, for subsequent use after washed with de-ionized water;
4) prepare the BMP-2 solution of 2 μ g/mL, reconciling pH is 7, is immersed in by the titanium-base of above-mentioned preparation in 10mL BMP-2 solution.Take out after 3 days, dry in 37 DEG C of baking ovens, obtain on titanium implants surface the composite coating that nexine is loaded with the 2-hydroxypropyltrimethyl ammonium chloride chitosan/collagen of BMP-2.
Embodiment 4
1) be 98% by quaternary ammonium root substitution value, molecular mass be 30000 2-hydroxypropyltrimethyl ammonium chloride chitosan be dissolved in distilled water, compound concentration is the chitosan quaternary ammonium saline solution of 0.5g/L, be placed in 4 DEG C stand-by; Be dissolved in 0.005mol/L acetic acid by liquid for a times Pedicellus et Pericarpium Trapae type i collagen, compound concentration is the collagen acetum of 0.5g/L, be placed in 4 DEG C stand-by;
2) electrolyte is prepared: by Ca (NO
3)
26H
2o is soluble in water, is mixed with the Ca (NO that calcium concentration is 80mmol/L
3)
2aqueous solution, by NH
4h
2pO
4soluble in water, being mixed with containing phosphorus concentration is the NH of 80mmol/L
4h
2pO
4aqueous solution, by Ca (NO
3)
2aqueous solution and NH
4h
2pO
4aqueous solution is uniformly mixed, and obtains solution A.Liquid for times Pedicellus et Pericarpium Trapae type i collagen, 2-hydroxypropyltrimethyl ammonium chloride chitosan solution are mixed with solution A, make the concentration of quaternary ammonium root and collagen in calcium, phosphorus, 2-hydroxypropyltrimethyl ammonium chloride chitosan be respectively 8mmol/L, 16 mmol/L, 0.064mmol/L, 0.3g/L, then be 4.4 with NaOH solution adjustment electrolyte ph.
3) using the cleaned titanium plate of surface acid as working electrode, platinum electrode is as to electrode, two electrode spacings are 1cm, getting 15ml electrolyte is placed in 37 DEG C of temperature chambers, adopt many potential steps electrochemical deposition pattern, be applied to voltage on titanium-base and the time is respectively :-2.4V (120s), 2V (60s) ,-2.4V (360s), 2V (120s) ,-2.4V (480s), 2V (180s) ,-2.4V (480s), titanium-base is taken out after deposition, for subsequent use after washed with de-ionized water;
4) prepare the BMP-2 solution of 2 μ g/mL, reconciling pH is 7, is immersed in by the titanium-base of above-mentioned preparation in 10mL BMP-2 solution.Take out after 3 days, at 37 DEG C of oven dryings, obtain on titanium implants surface the composite coating that skin is loaded with the 2-hydroxypropyltrimethyl ammonium chloride chitosan/collagen of BMP-2.
Embodiment 5
1) be 98% by quaternary ammonium root substitution value, molecular mass be 30000 2-hydroxypropyltrimethyl ammonium chloride chitosan be dissolved in distilled water, compound concentration is the chitosan quaternary ammonium saline solution of 0.5g/L, be placed in 4 DEG C stand-by; Be dissolved in 0.005mol/L acetic acid by liquid for a times Pedicellus et Pericarpium Trapae type i collagen, compound concentration is the collagen acetum of 0.5g/L, be placed in 4 DEG C stand-by;
2) electrolyte is prepared: by Ca (NO
3)
26H
2o is soluble in water, is mixed with the Ca (NO that calcium concentration is 80mmol/L
3)
2aqueous solution, by NH
4h
2pO
4soluble in water, being mixed with containing phosphorus concentration is the NH of 80mmol/L
4h
2pO
4aqueous solution, by Ca (NO
3)
2aqueous solution and NH
4h
2pO
4aqueous solution is uniformly mixed, and obtains solution A.Liquid for times Pedicellus et Pericarpium Trapae type i collagen, 2-hydroxypropyltrimethyl ammonium chloride chitosan solution are mixed with solution A, make the concentration of quaternary ammonium root and collagen in calcium, phosphorus, 2-hydroxypropyltrimethyl ammonium chloride chitosan be respectively 8mmol/L, 16 mmol/L, 0.048mmol/L, 0.3g/L, then be 4.4 with NaOH solution adjustment electrolyte ph;
3) using the cleaned titanium plate of surface acid as working electrode, platinum electrode is as to electrode, two electrode spacings are 1cm, getting 15ml electrolyte is placed in 37 DEG C of temperature chambers, adopt many potential steps electrochemical deposition pattern, be applied to voltage on titanium-base and the time is respectively :-1.5V (120s) ,-2.4V (180s), 2V (60s) ,-2.4V (480s), 2V (120s) ,-2.4V (720s), 2V (180s), titanium-base is taken out after deposition, for subsequent use after washed with de-ionized water;
4) prepare the BMP-2 solution of 2 μ g/mL, reconciling pH is 7, is immersed in by the titanium-base of above-mentioned preparation in 10mL BMP-2 solution.Take out after 3 days, dry in 37 DEG C of baking ovens, obtain on titanium implants surface the composite coating that nexine is loaded with the 2-hydroxypropyltrimethyl ammonium chloride chitosan/collagen of BMP-2.
Embodiment 6
1) be 98% by quaternary ammonium root substitution value, molecular mass be 30000 2-hydroxypropyltrimethyl ammonium chloride chitosan be dissolved in distilled water, compound concentration is the chitosan quaternary ammonium saline solution of 0.5g/L, be placed in 4 DEG C stand-by; Be dissolved in 0.005mol/L acetic acid by liquid for a times Pedicellus et Pericarpium Trapae type i collagen, compound concentration is the collagen acetum of 0.5g/L, be placed in 4 DEG C stand-by;
2) electrolyte is prepared: by Ca (NO
3)
26H
2o is soluble in water, is mixed with the Ca (NO that calcium concentration is 80mmol/L
3)
2aqueous solution, by NH
4h
2pO
4soluble in water, being mixed with containing phosphorus concentration is the NH of 80mmol/L
4h
2pO
4aqueous solution, by Ca (NO
3)
2aqueous solution and NH
4h
2pO
4aqueous solution is uniformly mixed, and obtains solution A.Liquid for times Pedicellus et Pericarpium Trapae type i collagen, 2-hydroxypropyltrimethyl ammonium chloride chitosan solution are mixed with solution A, make the concentration of quaternary ammonium root and collagen in calcium, phosphorus, 2-hydroxypropyltrimethyl ammonium chloride chitosan be respectively 8mmol/L, 16 mmol/L, 0.048mmol/L, 0.3g/L, then be 4.4 with NaOH solution adjustment electrolyte ph.
3) using the cleaned titanium plate of surface acid as working electrode, platinum electrode is as to electrode, two electrode spacings are 1cm, getting 15ml electrolyte is placed in 37 DEG C of temperature chambers, adopt many potential steps electrochemical deposition pattern, be applied to voltage on titanium-base and the time is respectively :-2.4V (120s), 2V (60s) ,-2.4V (360s), 2V (120s) ,-2.4V (480s), 2V (180s) ,-2.4V (480s), titanium-base is taken out after deposition, for subsequent use after washed with de-ionized water;
4) prepare the BMP-2 solution of 2 μ g/mL, reconciling pH is 7, is immersed in by the titanium-base of above-mentioned preparation in 10mL BMP-2 solution.Take out after 3 days, at 37 DEG C of oven dryings, obtain on titanium implants surface the composite coating that skin is loaded with the 2-hydroxypropyltrimethyl ammonium chloride chitosan/collagen of BMP-2.
Comparing embodiment 1 is to embodiment 6, and Fig. 3 is shown in nexine and the contrast of outer carrying BMP-2 ability of composite coating.
Embodiment 7
1) be 20% by quaternary ammonium root substitution value, molecular mass be 100000 2-hydroxypropyltrimethyl ammonium chloride chitosan be dissolved in distilled water, compound concentration is the chitosan quaternary ammonium saline solution of 0.5g/L, be placed in 4 DEG C stand-by; Be dissolved in 0.005mol/L acetic acid by liquid for a times Pedicellus et Pericarpium Trapae type i collagen, compound concentration is the collagen acetum of 0.5g/L, be placed in 4 DEG C stand-by;
2) electrolyte is prepared: by CaCl
2soluble in water, be mixed with the Ca (NO that calcium concentration is 80mmol/L
3)
2aqueous solution, by NaH
2pO
4soluble in water, being mixed with containing phosphorus concentration is the NaH of 80mmol/L
2pO
4aqueous solution, by CaCl
2aqueous solution and NaH
2pO
4aqueous solution is uniformly mixed, and obtains solution A.Liquid for times Pedicellus et Pericarpium Trapae type i collagen, 2-hydroxypropyltrimethyl ammonium chloride chitosan solution are mixed with solution A, make the concentration of quaternary ammonium root and collagen in calcium, phosphorus, 2-hydroxypropyltrimethyl ammonium chloride chitosan be respectively 8mmol/L, 16 mmol/L, 0.08mmol/L, 0.3g/L, then be 4.4. with NaOH solution adjustment electrolyte ph
3) using the cleaned titanium plate of surface acid as working electrode, platinum electrode is as to electrode, two electrode spacings are 1cm, getting 15ml electrolyte is placed in 37 DEG C of temperature chambers, adopt many potential steps electrochemical deposition pattern, be applied to voltage on titanium-base and the time is respectively :-2.4V (120s), 2V (60s) ,-2.4V (360s), 2V (120s) ,-2.4V (480s), 2V (180s) ,-2.4V (480s), titanium-base is taken out after deposition, for subsequent use after washed with de-ionized water;
4) prepare the BMP-2 solution of 2 μ g/mL, reconciling pH is 7, is immersed in by the titanium-base of above-mentioned preparation in 10mL BMP-2 solution.Take out after 3 days, at 37 DEG C of oven dryings, obtain on titanium implants surface 2-hydroxypropyltrimethyl ammonium chloride chitosan/collagen composite coating that skin is loaded with BMP-2.
Embodiment 8
1) be 98% by quaternary ammonium root substitution value, molecular mass be 30000 2-hydroxypropyltrimethyl ammonium chloride chitosan be dissolved in distilled water, compound concentration is the chitosan quaternary ammonium saline solution of 0.5g/L, be placed in 4 DEG C stand-by; Be dissolved in 0.005mol/L acetic acid by liquid for a times Pedicellus et Pericarpium Trapae type i collagen, compound concentration is the collagen acetum of 0.5g/L, be placed in 4 DEG C stand-by;
2) electrolyte is prepared: by Ca (NO
3)
26H
2o is soluble in water, is mixed with the Ca (NO that calcium concentration is 20mmol/L
3)
2aqueous solution, by NH
4h
2pO
4soluble in water, being mixed with containing phosphorus concentration is the NH of 20mmol/L
4h
2pO
4aqueous solution, by Ca (NO
3)
2aqueous solution and NH
4h
2pO
4aqueous solution is uniformly mixed, and obtains solution A.Liquid for times Pedicellus et Pericarpium Trapae type i collagen, 2-hydroxypropyltrimethyl ammonium chloride chitosan solution are mixed with solution A, make the concentration of quaternary ammonium root and collagen in calcium, phosphorus, 2-hydroxypropyltrimethyl ammonium chloride chitosan be respectively 4mmol/L, 8 mmol/L, 0.08mmol/L, 0.3g/L, then be 4.3 with NaOH solution adjustment electrolyte ph.
3) using the cleaned magnesium plate of surface acid as working electrode, platinum electrode is as to electrode, two electrode spacings are 1cm, getting 15ml electrolyte is placed in 37 DEG C of temperature chambers, adopt many potential steps electrochemical deposition pattern, be applied to voltage on magnesium substrate and the time is respectively :-2.4V (120s), 2V (60s) ,-2.4V (360s), 2V (120s) ,-2.4V (480s), 2V (180s) ,-2.4V (480s), magnesium substrate is taken out after deposition, for subsequent use after washed with de-ionized water;
4) prepare the BMP-2 solution of 2 μ g/mL, reconciling pH is 7, is immersed in by the magnesium substrate of above-mentioned preparation in 10mL BMP-2 solution.Take out after 3 days, at 37 DEG C of oven dryings, obtain at magnesium implant surfaces 2-hydroxypropyltrimethyl ammonium chloride chitosan/collagen composite coating that skin is loaded with BMP-2.
Embodiment 9
1) be 98% by quaternary ammonium root substitution value, molecular mass be 30000 2-hydroxypropyltrimethyl ammonium chloride chitosan be dissolved in distilled water, compound concentration is the chitosan quaternary ammonium saline solution of 0.5g/L, be placed in 4 DEG C stand-by; Be dissolved in 0.005mol/L acetic acid by liquid for a times Pedicellus et Pericarpium Trapae type i collagen, compound concentration is the collagen acetum of 0.5g/L, be placed in 4 DEG C stand-by;
2) electrolyte is prepared: by Ca (NO
3)
26H
2o is soluble in water, is mixed with the Ca (NO that calcium concentration is 100mmol/L
3)
2aqueous solution, by NH
4h
2pO
4soluble in water, being mixed with containing phosphorus concentration is the NH of 100mmol/L
4h
2pO
4aqueous solution, by Ca (NO
3)
2aqueous solution and NH
4h
2pO
4aqueous solution is uniformly mixed, and obtains solution A.Liquid for times Pedicellus et Pericarpium Trapae type i collagen, 2-hydroxypropyltrimethyl ammonium chloride chitosan solution are mixed with solution A, make the concentration of quaternary ammonium root and collagen in calcium, phosphorus, 2-hydroxypropyltrimethyl ammonium chloride chitosan be respectively 8mmol/L, 16 mmol/L, 0.016mmol/L, 0.3g/L, then be 4.3 with NaOH solution adjustment electrolyte ph.
3) using the cleaned tantalum plate of surface acid as working electrode, platinum electrode is as to electrode, two electrode spacings are 2cm, getting 15ml electrolyte is placed in 37 DEG C of temperature chambers, adopt many potential steps electrochemical deposition pattern, be applied to voltage on tantalum substrate and the time is respectively :-2.4V (120s), 2V (60s) ,-2.4V (360s), 2V (120s) ,-2.4V (480s), 2V (180s) ,-2.4V (480s), tantalum substrate is taken out after deposition, for subsequent use after washed with de-ionized water;
4) prepare the BMP-6 solution of 2 μ g/mL, reconciling pH is 3, is immersed in 10mLBMP-6 solution by the tantalum substrate of above-mentioned preparation.Take out after 1 day, at 37 DEG C of oven dryings, obtain at tantalum implant surfaces 2-hydroxypropyltrimethyl ammonium chloride chitosan/collagen composite coating that skin is loaded with BMP-6.
Embodiment 10
1) be 98% by quaternary ammonium root substitution value, molecular mass be 30000 2-hydroxypropyltrimethyl ammonium chloride chitosan be dissolved in distilled water, compound concentration is the chitosan quaternary ammonium saline solution of 0.5g/L, be placed in 4 DEG C stand-by; Be dissolved in 0.005mol/L acetic acid by liquid for a times Pedicellus et Pericarpium Trapae type i collagen, compound concentration is the collagen acetum of 0.5g/L, be placed in 4 DEG C stand-by;
2) electrolyte is prepared: by Ca (NO
3)
26H
2o is soluble in water, is mixed with the Ca (NO that calcium concentration is 80mmol/L
3)
2aqueous solution, by NH
4h
2pO
4soluble in water, being mixed with containing phosphorus concentration is the NH of 80mmol/L
4h
2pO
4aqueous solution, by Ca (NO
3)
2aqueous solution and NH
4h
2pO
4aqueous solution is uniformly mixed, and obtains solution A.Liquid for times Pedicellus et Pericarpium Trapae type i collagen, 2-hydroxypropyltrimethyl ammonium chloride chitosan solution are mixed with solution A, make the concentration of quaternary ammonium root and collagen in calcium, phosphorus, 2-hydroxypropyltrimethyl ammonium chloride chitosan be respectively 8mmol/L, 16 mmol/L, 0.08mmol/L, 0.3g/L, then be 4.4 with NaOH solution adjustment electrolyte ph.
3) using the cleaned titanium plate of surface acid as working electrode, platinum electrode is as to electrode, two electrode spacings are 1cm, getting 15ml electrolyte is placed in 37 DEG C of temperature chambers, adopt many potential steps electrochemical deposition pattern, be applied to voltage on titanium-base and the time is respectively :-2V (60s) ,-2.5V (120s), 2.3V (120s) ,-2.5V (480s), 2.3V (120s) ,-2.5V (720s), 2.3V (180s), titanium-base is taken out after deposition, for subsequent use after washed with de-ionized water;
4) prepare the BMP-2 solution of 2 μ g/mL, reconciling pH is 10, is immersed in by the titanium-base of above-mentioned preparation in 10mL BMP-2 solution.Take out after 3 days, at 37 DEG C of oven dryings, obtain on titanium implants surface 2-hydroxypropyltrimethyl ammonium chloride chitosan/collagen composite coating that nexine is loaded with BMP-2.
Embodiment 11
1) be 98% by quaternary ammonium root substitution value, molecular mass be 30000 2-hydroxypropyltrimethyl ammonium chloride chitosan be dissolved in distilled water, compound concentration is the chitosan quaternary ammonium saline solution of 0.5g/L, be placed in 4 DEG C stand-by; Be dissolved in 0.005mol/L acetic acid by liquid for a times Pedicellus et Pericarpium Trapae type i collagen, compound concentration is the collagen acetum of 0.5g/L, be placed in 4 DEG C stand-by;
2) electrolyte is prepared: by Ca (NO
3)
26H
2o is soluble in water, is mixed with the Ca (NO that calcium concentration is 80mmol/L
3)
2aqueous solution, by NH
4h
2pO
4soluble in water, being mixed with containing phosphorus concentration is the NH of 80mmol/L
4h
2pO
4aqueous solution, by Ca (NO
3)
2aqueous solution and NH
4h
2pO
4aqueous solution is uniformly mixed, and obtains solution A.Liquid for times Pedicellus et Pericarpium Trapae type i collagen, 2-hydroxypropyltrimethyl ammonium chloride chitosan solution are mixed with solution A, make the concentration of quaternary ammonium root and collagen in calcium, phosphorus, 2-hydroxypropyltrimethyl ammonium chloride chitosan be respectively 8mmol/L, 16 mmol/L, 0.08mmol/L, 0.3g/L, then be 4.4. with NaOH solution adjustment electrolyte ph
3) using the cleaned titanium plate of surface acid as working electrode, platinum electrode is as to electrode, two electrode spacings are 1cm, getting 15ml electrolyte is placed in 37 DEG C of temperature chambers, adopt many potential steps electrochemical deposition pattern, be applied to voltage on titanium-base and the time is respectively :-1.5V (240s) ,-2.4V (360s), 2V (180s) ,-2.4V (720s), 2V (180s), titanium-base is taken out after deposition, for subsequent use after washed with de-ionized water;
4) prepare the BSA solution of 2 μ g/mL, reconciling pH is 7, is immersed in 10mLBSA solution by the titanium-base of above-mentioned preparation.Take out after 3 days, at 37 DEG C of oven dryings, obtain on titanium implants surface 2-hydroxypropyltrimethyl ammonium chloride chitosan/collagen composite coating that nexine is loaded with BSA.
Embodiment 12
1) be 98% by quaternary ammonium root substitution value, molecular mass is the N of 30000, and N, N-N-trimethyl chitosan TMC quaternary ammonium salt is dissolved in distilled water, and compound concentration is the chitosan quaternary ammonium saline solution of 0.5g/L, be placed in 4 DEG C stand-by; Be dissolved in 0.005mol/L acetic acid by liquid for a times Pedicellus et Pericarpium Trapae type i collagen, compound concentration is the collagen acetum of 0.5g/L, be placed in 4 DEG C stand-by;
2) electrolyte is prepared: by CaCl
2soluble in water, be mixed with the Ca (NO that calcium concentration is 60mmol/L
3)
2aqueous solution, by NH
4h
2pO
4soluble in water, being mixed with containing phosphorus concentration is the NH of 60mmol/L
4h
2pO
4aqueous solution, by CaCl
2aqueous solution and NH
4h
2pO
4aqueous solution is uniformly mixed, and obtains solution A.By liquid for times Pedicellus et Pericarpium Trapae type i collagen, N, N, N-N-trimethyl chitosan TMC quaternary ammonium salt solution mixes with solution A, make calcium, phosphorus, N, N, in N-N-trimethyl chitosan TMC quaternary ammonium salt, the concentration of quaternary ammonium root and collagen is respectively 8mmol/L, 16 mmol/L, 0.08mmol/L, 0.3g/L, then is 4.4 with NaOH solution adjustment electrolyte ph.
3) using the cleaned titanium plate of surface acid as working electrode, platinum electrode is as to electrode, two electrode spacings are 1cm, getting 15ml electrolyte is placed in 37 DEG C of temperature chambers, adopt many potential steps electrochemical deposition pattern, be applied to voltage on titanium-base and the time is respectively :-1.5V (120s) ,-2.4V (180s), 2V (60s) ,-2.4V (480s), 2V (120s) ,-2.4V (720s), 2V (180s), titanium-base is taken out after deposition, for subsequent use after washed with de-ionized water;
4) prepare the BMP-2 solution of 2 μ g/mL, reconciling pH is 7, is immersed in by the titanium-base of above-mentioned preparation in 10mL BMP-2 solution.Take out after 3 days, at 37 DEG C of oven dryings, obtain on titanium implants surface 2-hydroxypropyltrimethyl ammonium chloride chitosan/collagen composite coating that nexine is loaded with BMP-2.
Embodiment 13
Be 98% by quaternary ammonium root substitution value, molecular mass is the N of 30000, and N, N-N-trimethyl chitosan TMC quaternary ammonium salt is dissolved in distilled water, and compound concentration is the chitosan quaternary ammonium saline solution of 0.5g/L, be placed in 4 DEG C stand-by; Be dissolved in 0.005mol/L acetic acid by liquid for a times Pedicellus et Pericarpium Trapae type i collagen, compound concentration is the collagen acetum of 0.5g/L, be placed in 4 DEG C stand-by;
Preparation electrolyte: by Ca (NO
3)
26H
2o is soluble in water, is mixed with the Ca (NO that calcium concentration is 80mmol/L
3)
2aqueous solution, by NH
4h
2pO
4soluble in water, being mixed with containing phosphorus concentration is the NH of 80mmol/L
4h
2pO
4aqueous solution, by Ca (NO
3)
2aqueous solution and NH
4h
2pO
4aqueous solution is uniformly mixed, and obtains solution A.By liquid for times Pedicellus et Pericarpium Trapae type i collagen, N, N, N-N-trimethyl chitosan TMC quaternary ammonium salt solution mixes with solution A, make calcium, phosphorus, N, N, in N-N-trimethyl chitosan TMC quaternary ammonium salt, the concentration of quaternary ammonium root and collagen is respectively 8mmol/L, 16 mmol/L, 0.08mmol/L, 0.3g/L, then is 4.4 with NaOH solution adjustment electrolyte ph.
3) using the cleaned tantalum plate of surface acid as working electrode, platinum electrode is as to electrode, two electrode spacings are 1cm, getting 15ml electrolyte is placed in 37 DEG C of temperature chambers, adopt many potential steps electrochemical deposition pattern, be applied to voltage on tantalum substrate and the time is respectively :-1.5V (120s) ,-2.4V (180s), 2V (60s) ,-2.4V (480s), 2V (120s) ,-2.4V (720s), 2V (180s), tantalum substrate is taken out after deposition, for subsequent use after washed with de-ionized water;
4) prepare the BMP-2 solution of 2 μ g/mL, reconciling pH is 7, is immersed in by the tantalum substrate of above-mentioned preparation in 10mL BMP-2 solution.Take out after 3 days, at 37 DEG C of oven dryings, obtain at tantalum implant surfaces 2-hydroxypropyltrimethyl ammonium chloride chitosan/collagen composite coating that nexine is loaded with BMP-2.
Claims (6)
1. the preparation method of medical metal implant surfaces chitosan quaternary ammonium salt/collagen composite coating, is characterized in that comprising the following steps:
1) be dissolved in distilled water by chitosan quaternary ammonium salt, compound concentration is the chitosan quaternary ammonium saline solution of 0.5g/L, be placed in 4 DEG C stand-by; Be dissolved in by type i collagen in 0.005mol/L acetic acid, compound concentration is the collagen acetum of 0.5g/L, be placed in 4 DEG C stand-by;
2) prepare electrolyte: calcium containing compound is soluble in water, be mixed with the calcic aqueous solution that concentration is 10mmol/L ~ 100mmol/L; Phosphorus-containing compound is soluble in water, be mixed with the phosphorous aqueous solution that concentration is 10mmol/L ~ 100mmol/L; Calcic aqueous solution and phosphorous aqueous solution are uniformly mixed, obtain solution A, by step 1) obtained type i collagen acetum and chitosan quaternary ammonium saline solution mix with solution A, make the quaternary ammonium root concentration of calcium in mixed liquor, phosphorus, collagen, chitosan quaternary ammonium salt be respectively 4 ~ 8mmol/L, 8 ~ 16 mmol/L, 0.3g/L, 0.32 ~ 0.016mmol/L, adjustment electrolyte ph is 4.3 ~ 4.6;
3) electrolyte is placed in the temperature chamber that temperature is 37 DEG C, using platinized platinum as to electrode, the metal basal board crossed using sour cleaning treatment is as working electrode, and the spacing of two electrodes is 1 ~ 2cm, adopts many potential steps pattern to carry out electrochemical deposition, the positive voltage applied on metallic substrates is 2.0 ~ 2.8V, negative voltage is-1.5 ~-2.5V, and step hop count is 3 ~ 7 sections, and every section of sedimentation time is 1-20min, take out metal basal board, with stand-by after washed with de-ionized water;
4) prepare the biotic factor solution of 0.1 ~ 2 μ g/mL, the pH regulating biotic factor solution is 3 ~ 10, by 3) metal basal board prepared is immersed in biotic factor solution, takes out after 1-3 days, dry at 37 DEG C.
2. the preparation method of medical metal implant surfaces chitosan quaternary ammonium salt/collagen composite coating according to claim 1, it is characterized in that described chitosan quaternary ammonium salt be quaternary ammonium root substitution value is 20% ~ 99%, molecular mass be 1000 ~ 100000 2-hydroxypropyltrimethyl ammonium chloride chitosan or quaternary ammonium root substitution value be 20% ~ 99%, molecular mass is the N of 1000 ~ 100000, N, N-N-trimethyl chitosan TMC quaternary ammonium salt.
3. the preparation method of medical metal implant surfaces chitosan quaternary ammonium salt/collagen composite coating according to claim 1, is characterized in that described type i collagen is for the liquid collagen of times Pedicellus et Pericarpium Trapae.
4. the preparation method of medical metal implant surfaces chitosan quaternary ammonium salt/collagen composite coating according to claim 1, is characterized in that described biotic factor to be pH is that 3 ~ 10 with BMP-2, BMP-6 or BSA of negative charge.
5. the preparation method of medical metal implant surfaces chitosan quaternary ammonium salt/collagen composite coating according to claim 1, is characterized in that described calcium containing compound is Ca (NO
3)
26H
2o or CaCl
2.
6. the preparation method of medical metal implant surfaces chitosan quaternary ammonium salt/collagen composite coating according to claim 1, is characterized in that described phosphorus-containing compound is NH
4h
2pO
4or NaH
2pO
4.
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