CN102560598A - Method for preparing medical titanium material with high anti-cancer and antibacterial properties - Google Patents
Method for preparing medical titanium material with high anti-cancer and antibacterial properties Download PDFInfo
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Abstract
The invention relates to a method for preparing a medical titanium material with high anti-cancer and antibacterial properties. The method comprises the following steps of: firstly, generating highly regular and ordered titanium dioxide nanotube arrays on the surface of the titanium material by an anodic oxidation method; secondly, generating selenium nanoparticles in titanium dioxide nanotubes in situ by an electrochemical deposition method; and finally, modifying multi-layer chitosan on the surface of the titanium material by a spin-coating method to obtain the medical titanium material with high anti-cancer and antibacterial properties. The method is easy to operate and low in cost, special equipment is not needed, and tests prove that the obtained product can inhibit the growth of bone tumor cells for a long time and promote the growth of normal osteoblasts simultaneously and has high antibacterial property.
Description
Technical field
The invention belongs to field of medical materials, relate to a kind of preparation method of functionalization titanium material.
Background technology
Titanium or titanium alloy is the medical metal material of using always; Because it has and the proximate Young's modulus of people's bone, good solidity to corrosion, excellent biological compatibility and processing characteristics, just is used widely at aspects such as dental implant, tooth implant frame, bone planting body and joint prosthesises from the seventies.The method of treating osteocarcinoma clinically normally substitutes the bone of canceration with the bone planting body.Owing to possibly still have the cancer cells that is not removed fully near the bone planting body that implant the operation back; And bacterial inflammatory reaction causes the implantation back loosening easily; Therefore, a kind of bone implant material with good anticancer and anti-microbial property of exploitation is quite important.
Previously result of study shows, suitable nanotube caliber and pipe range can promote cell function; Titania nanotube can be used as pharmaceutical carrier, has shown good antimicrobial property after making titania nanotube add carried with antibiotics through lyophilization, but because antibiotic snap-out release can not reach persistent antibacterial effect.
Summary of the invention
In view of this; The object of the present invention is to provide a kind of medical titanium material and preparation method thereof with good anticancer anti-microbial property, simple to operate, need not specific installation; Cost is low; Products obtained therefrom can suppress the growth of cells of tumorous bone in a long time, promotes normal osteoblastic growth simultaneously, also has good antimicrobial property.
For achieving the above object, the present invention provides following technical scheme:
1. have the preparation method of the medical titanium material of good anticancer anti-microbial property, may further comprise the steps:
A. the titanium material is cleaned and obtain clean metallic surface;
B. adopt anonizing at the orderly Nano tube array of titanium dioxide of step a gained titanium material surface formation rule;
C. adopt electrochemical deposition method original position in the titania nanotube on step b gained titanium material surface to generate the selenium nano particle;
D. adopt spin-coating method at 5 ~ 15 layers of chitosan of step c gained titanium material finishing, promptly get medical titanium material with good anticancer anti-microbial property.
Preferably, said step a used acetone, Virahol and methyl alcohol ultrasonic cleaning 10 ~ 20 minutes successively with the titanium material, and water cleans 2 ~ 4 times again, drying for standby.
Preferably; Said step b is that the titanium material that obtains with step a is as anode; Platinum is as negative electrode, to use concentration be 0.25 ~ 0.30 mol/L, with volume ratio as USP Kosher-water mixed liquid of 1:1 as the ammonium fluoride solution of solvent as electrolytic solution, anodic oxidation reactions is 30 ~ 60 minutes under constant voltage 30V condition; Titanium material after the processing cleans, drying for standby.
Preferred, said step b be use concentration as 0.27mol/L, with volume ratio as USP Kosher-water mixed liquid of 1:1 as the ammonium fluoride solution of solvent as electrolytic solution, anodic oxidation reactions is 30 minutes under constant voltage 30V condition.
Preferably, said step c be the titanium material that obtains with step b as negative electrode, platinum is as anode, with concentration be the selenous acid aqueous solution of 1 ~ 3mmol/L as electrolytic solution, galvanic deposit is 0.5 ~ 2 hour under constant voltage 1 ~ 2V condition; Titanium material after the processing cleans, drying for standby.
Preferred, said step c be with concentration be the selenous acid aqueous solution of 1mmol/L as electrolytic solution, galvanic deposit is 1 hour under constant voltage 1.5V condition.
Preferably, the titanium material that the mode treatment step c that said steps d is that to use massfraction be 0.4 ~ 0.6% chitosan solution through spin coating obtains, the spin coating number of times is 5 ~ 15 times, at every turn with 400 ~ 600 rev/mins of spin coatings 10 ~ 20 seconds.
The titanium material preferred, that the mode treatment step c that said steps d is that to use massfraction be 0.5% chitosan solution through spin coating obtains, the spin coating number of times is 10 times, at every turn with 500 rev/mins of spin coatings 15 seconds, makes 10 layers of chitosan in the finishing of titanium material.
2. the product that adopts above-mentioned preparation method to make is the medical titanium material with good anticancer anti-microbial property.
In above-mentioned preparation method, step b adopts anonizing to prepare Nano tube array of titanium dioxide.In anode oxidation process, many factors can influence the formation of nano-tube array, for example electrolyte system, oxidation voltage etc., and different preparation conditions possibly obtain having the nano-tube array of different-shape characteristic.The present invention investigates electrolyte system, comprises Neutral ammonium fluoride USP Kosher system, hydrofluoric acid aqueous systems and Neutral ammonium fluoride USP Kosher
/Water (volume ratio is 1:1) system.The result shows, prepares the Nano tube array of titanium dioxide of identical caliber pipe range with Neutral ammonium fluoride USP Kosher system, needs long period and high voltage; Prepare Nano tube array of titanium dioxide with the hydrofluoric acid aqueous systems, the pattern of nano-tube array is difficult to control; And use the Neutral ammonium fluoride USP Kosher
/Water (volume ratio is 1:1) preparation Nano tube array of titanium dioxide can more easily be controlled the caliber pipe range of nanotube through changing approach such as oxidation voltage; Therefore, electrolyte system preferred fluorinated ammonium USP Kosher of the present invention
/Water (volume ratio is 1:1) system.The concentration of Neutral ammonium fluoride can influence the form of the titania nanotube that is generated, and research shows, adopting concentration is 0.25 ~ 0.30 Neutral ammonium fluoride electrolytic solution of 0.27 mol/L particularly, and prepared titania nanotube has good form.The present invention also investigates oxidation voltage, is respectively 5,10,15,20,25,30,40V.The result shows that the caliber of the little titania nanotube that then generates of oxidation voltage is little, is unfavorable for the loading of selenium nano particle; Rising along with oxidation voltage; The caliber of titania nanotube increases, and when oxidation voltage during greater than 40V, titania nanotube is destroyed; Therefore, the preferred oxidation voltage of the present invention is 30V.
Steps d is passed through spin-coating method at titanium material finishing multilayered shell glycan.Chitosan solution concentration is too low, and titanium material surface can not be covered by chitosan fully, and then influences the shutoff and the antibacterial effect of nanotube; The chitosan solution excessive concentration can influence the release of cancer-resisting substance selenium in the initial stage nanotube, and then influence anticancer effect.The present invention studies demonstration, and the massfraction of chitosan solution is preferably 0.4 ~ 0.6%, and more preferably 0.5%.
Beneficial effect of the present invention is: the present invention at first generates highly regular Nano tube array of titanium dioxide through anonizing on titanium material surface; Generate the selenium nano particle through electrochemical deposition method original position in titania nanotube then, pass through spin-coating method at last, made a kind of medical titanium material with good anticancer anti-microbial property at titanium material finishing multilayered shell glycan; Simple to operate; Need not specific installation, cost is low, and products obtained therefrom confirms to suppress in a long time the growth of cells of tumorous bone through test; Promote normal osteoblastic growth simultaneously, also have good antimicrobial property.
Description of drawings
Fig. 1 is the field emission scanning electron microscope figure on the titanium material surface of process different treatment; Wherein A is the titanium material that is untreated; B is " titania nanotube " vertical view, and C is " titania nanotube " sectional view, and D is " titania nanotube selenium " vertical view; E is " titania nanotube selenium " sectional view (arrow has been pointed out the selenium nano particle in titania nanotube), and F is " titania nanotube selenium chitosan " vertical view.
Fig. 2 is a cells of tumorous bone in the activity through the titanium material surface of different treatment, wherein * * represent be untreated the titanium material relatively p 0.01, and * * * represent be untreated the titanium material relatively p < 0.001 ， && representes and " titania nanotube silver " p < 0.01 relatively.
Fig. 3 is the activity of rat osteoblast on the titanium material surface of process different treatment, and wherein * * representes and the relatively p < 0.01 of titanium material that is untreated.
Embodiment
In order to make the object of the invention, technical scheme and advantage clearer, will combine accompanying drawing that the preferred embodiments of the present invention are carried out detailed description below.
Embodiment 1. has the preparation of the medical titanium material of good anticancer anti-microbial property
A. the pre-treatment of titanium material: the titanium material is used acetone, Virahol and methyl alcohol ultrasonic cleaning 20 minutes successively, use washed with de-ionized water again 3 times, 40 ℃ of dryings, subsequent use;
B. the structure of Nano tube array of titanium dioxide: use volume ratio to process the solution of concentration Neutral ammonium fluoride, as electrolytic solution as 0.27mol/L as USP Kosher-water mixed liquid dissolving of 1:1; The titanium material that step a is obtained is as anode, and platinum is put in the above-mentioned Neutral ammonium fluoride electrolytic solution as negative electrode, and anodic oxidation reactions is 30 minutes under constant voltage 30V condition; Titanium material after the processing is with washed with de-ionized water 5 times, and 40 ℃ of dryings are subsequent use; Gained titanium material abbreviates " titania nanotube " as;
C. the loading of selenium nano particle: use deionized water dissolving to process the aqueous solution of concentration selenous acid, as electrolytic solution as 1.0mmol/L; The titanium material that step b is obtained is as negative electrode, and platinum is put in the above-mentioned selenous acid electrolytic solution as anode, and galvanic deposit is 1 hour under the condition of constant voltage 1.5V; Titanium material after the processing is with washed with de-ionized water 5 times, and 40 ℃ of dryings are subsequent use; Gained titanium material abbreviates " titania nanotube selenium " as;
D. the modification of chitosan: with viscosity be 20cP, it is deacetylated that to use volume(tric)fraction greater than 85% chitosan (purchasing the company in sigma) be that to process massfraction be 0.5% solution for 2% acetic acid soln dissolving; The titanium material that step c is obtained is fixed on the spin coater (spin-coater), drips above-mentioned chitosan solution 40 μ L at every turn, with 500 rev/mins of rotations 15 seconds, repeats spin coating 10 times, makes 10 layers of chitosan in the finishing of titanium material; Titanium material after the processing is dry, promptly gets the medical titanium material with good anticancer anti-microbial property, abbreviates " titania nanotube selenium chitosan " as.
The field emission scanning electron microscope figure on gained titanium material surface sees Fig. 1 after above-mentioned each step process; It is thus clear that after step b handles; Vertical arrangement, regular Nano tube array of titanium dioxide have been formed on titanium material surface, the about 110nm of the caliber of titania nanotube wherein, the about 900nm of pipe range; After step c handled, the selenium nano particle of loading had small portion to be present between the surface and tube and tube of nanotube, and major part is present in titania nanotube inside; After steps d was handled, titania nanotube was covered by chitosan fully.
Embodiment 2. has the preparation of the medical titanium material of good anticancer anti-microbial property
A. the pre-treatment of titanium material: the titanium material is used acetone, Virahol and methyl alcohol ultrasonic cleaning 20 minutes successively, use washed with de-ionized water again 3 times, 40 ℃ of dryings, subsequent use;
B. the structure of Nano tube array of titanium dioxide: use volume ratio to process the solution of concentration Neutral ammonium fluoride, as electrolytic solution as 0.25mol/L as USP Kosher-water mixed liquid dissolving of 1:1; The titanium material that step a is obtained is as anode, and platinum is put in the above-mentioned Neutral ammonium fluoride electrolytic solution as negative electrode, and anodic oxidation reactions is 45 minutes under constant voltage 30V condition; Titanium material after the processing is with washed with de-ionized water 5 times, and 40 ℃ of dryings are subsequent use; Gained titanium material abbreviates " titania nanotube " as;
C. the loading of selenium nano particle: use deionized water dissolving to process the aqueous solution of concentration selenous acid, as electrolytic solution as 2mmol/L; The titanium material that step b is obtained is as negative electrode, and platinum is put in the above-mentioned selenous acid electrolytic solution as anode, and galvanic deposit is 2 hours under the condition of constant voltage 1V; Titanium material after the processing is with washed with de-ionized water 5 times, and 40 ℃ of dryings are subsequent use; Gained titanium material abbreviates " titania nanotube selenium " as;
D. the modification of chitosan: with viscosity be 20cP, it is deacetylated that to use volume(tric)fraction greater than 85% chitosan (purchasing the company in sigma) be that to process massfraction be 0.4% solution for 2% acetic acid soln dissolving; The titanium material that step c is obtained is fixed on the spin coater (spin-coater), drips above-mentioned chitosan solution 40 μ L at every turn, with 400 rev/mins of rotations 10 seconds, repeats spin coating 15 times, makes 15 layers of chitosan in the finishing of titanium material; Titanium material after the processing is dry, promptly gets the medical titanium material with good anticancer anti-microbial property, abbreviates " titania nanotube selenium chitosan " as.
Embodiment 3. has the preparation of the medical titanium material of good anticancer anti-microbial property
A. the pre-treatment of titanium material: the titanium material is used acetone, Virahol and methyl alcohol ultrasonic cleaning 20 minutes successively, use washed with de-ionized water again 3 times, 40 ℃ of dryings, subsequent use;
B. the structure of Nano tube array of titanium dioxide: use volume ratio to process the solution of concentration Neutral ammonium fluoride, as electrolytic solution as 0.30mol/L as USP Kosher-water mixed liquid dissolving of 1:1; The titanium material that step a is obtained is as anode, and platinum is put in the above-mentioned Neutral ammonium fluoride electrolytic solution as negative electrode, and anodic oxidation reactions is 60 minutes under constant voltage 30V condition; Titanium material after the processing is with washed with de-ionized water 5 times, and 40 ℃ of dryings are subsequent use; Gained titanium material abbreviates " titania nanotube " as;
C. the loading of selenium nano particle: use deionized water dissolving to process the aqueous solution of concentration selenous acid, as electrolytic solution as 3mmol/L; The titanium material that step b is obtained is as negative electrode, and platinum is put in the above-mentioned selenous acid electrolytic solution as anode, and galvanic deposit is 0.5 hour under the condition of constant voltage 2V; Titanium material after the processing is with washed with de-ionized water 5 times, and 40 ℃ of dryings are subsequent use; Gained titanium material abbreviates " titania nanotube selenium " as;
D. the modification of chitosan: with viscosity be 20cP, it is deacetylated that to use volume(tric)fraction greater than 85% chitosan (purchasing the company in sigma) be that to process massfraction be 0.6% solution for 2% acetic acid soln dissolving; The titanium material that step c is obtained is fixed on the spin coater (spin-coater), drips above-mentioned chitosan solution 40 μ L at every turn, with 600 rev/mins of rotations 20 seconds, repeats spin coating 5 times, makes 5 layers of chitosan in the finishing of titanium material; Titanium material after the processing is dry, promptly gets the medical titanium material with good anticancer anti-microbial property, abbreviates " titania nanotube selenium chitosan " as.
Experimental example 1. has the medical titanium material of good anticancer anti-microbial property to colibacillary inhibition ability
Get embodiment 1 " titania nanotube ", " titania nanotube selenium " and " titania nanotube selenium chitosan " material,, drip intestinal bacteria suspension 40 μ L at material surface with UV-irradiation sterilization in 2 hours through obtaining after the different treatment; Respectively at 37 ℃ of overnight cultures; Vibrate strongly with sterilized water 4mL then and washed 5 minutes, wash the bacterium that sticks to material surface, get washings 100 μ L and smear flat board; Cultivated 24 hours for 37 ℃, the counting bacterium colony also calculates antimicrobial efficiency.The result shows that the antimicrobial efficiency of " titania nanotube " is 20.5%; After loading the selenium nano particle, the antimicrobial efficiency of " titania nanotube selenium " is 22.2%, has by a small margin to improve; And after chitosan-modified, the antimicrobial efficiency of " titania nanotube selenium chitosan " increases substantially greater than 99.9%, has good antibacterial ability.
Experimental example 2. has the medical titanium material of good anticancer anti-microbial property to cells of tumorous bone and the normal active influence of scleroblast
Get " titania nanotube ", " titania nanotube selenium " and " titania nanotube selenium chitosan " material and the be untreated titanium material (abbreviate " titanium material ") of embodiment 1 respectively through obtaining after the different treatment; Inoculate human osteosarcoma cell 143B and neonate rat skull scleroblast respectively at material surface, inoculum density is 40000/cm
2, use that to contain volume(tric)fraction be that the DMEM substratum of 10% NBCS was cultivated respectively 4 days and 7 days, changed liquid in per 2 days; Every then hole adds MTT 100 μ L, cultivates 4 hours for 37 ℃, inhales and abandons supernatant; Every again hole adds DMSO 0.5mL, measures absorbancy in wavelength 490nm place with ELIASA.The titanium material to cells of tumorous bone active influence see Fig. 2; It is thus clear that cultivating the cytoactive of 4 days and 7 days on " titania nanotube selenium " and " titania nanotube selenium chitosan " these two kinds of materials, cells of tumorous bone all is lower than other control group; Show that these two kinds of materials all can effectively suppress the growth of cells of tumorous bone; And because " titania nanotube selenium chitosan " is further to have covered the multilayered shell glycan on " titania nanotube selenium " surface; Make the rate of release of selenium nano particle slow down, therefore, the growth that " titania nanotube selenium chitosan " material can more persistent inhibition cells of tumorous bone.The titanium material to normal scleroblast active influence see Fig. 3; It is thus clear that the cytoactive that healthy scleroblast was cultivated 7 days on " titania nanotube selenium chitosan " material is significantly higher than other group, shows that this material can effectively promote healthy osteoblastic growth.
Explanation is that above embodiment only is used to explain technical scheme of the present invention, does not constitute the restriction to content of the present invention at last.Although the present invention has been done comparatively detailed giving an example through the foregoing description; But those skilled in the art still can be according to summary of the invention part and the described technology contents of embodiment part; In form with on the details it is made various changes, and the spirit and scope of the present invention that do not depart from appended claims and limited.
Claims (9)
1. have the preparation method of the medical titanium material of good anticancer anti-microbial property, it is characterized in that, may further comprise the steps:
A. the titanium material is cleaned and obtain clean metallic surface;
B. adopt anonizing at the orderly Nano tube array of titanium dioxide of step a gained titanium material surface formation rule;
C. adopt electrochemical deposition method original position in the titania nanotube on step b gained titanium material surface to generate the selenium nano particle;
D. adopt spin-coating method 5 ~ 15 layers of chitosan in the finishing of step c gained titanium material, promptly get medical titanium material with good anticancer anti-microbial property.
2. the preparation method with medical titanium material of good anticancer anti-microbial property according to claim 1 is characterized in that, said step a used acetone, Virahol and methyl alcohol ultrasonic cleaning 10 ~ 20 minutes successively with the titanium material, and water cleans 2 ~ 4 times again, drying for standby.
3. the preparation method with medical titanium material of good anticancer anti-microbial property according to claim 1; It is characterized in that; Said step b is that the titanium material that obtains with step a is as anode; Platinum is as negative electrode, to use concentration be 0.25 ~ 0.30mol/L, with volume ratio as USP Kosher-water mixed liquid of 1:1 as the ammonium fluoride solution of solvent as electrolytic solution, anodic oxidation reactions is 30 ~ 60 minutes under constant voltage 30V condition; Titanium material after the processing cleans, drying for standby.
4. the preparation method with medical titanium material of good anticancer anti-microbial property according to claim 3; It is characterized in that; Said step b be use concentration as 0.27mol/L, with volume ratio as USP Kosher-water mixed liquid of 1:1 as the ammonium fluoride solution of solvent as electrolytic solution, anodic oxidation reactions is 30 minutes under constant voltage 30V condition.
5. the preparation method with medical titanium material of good anticancer anti-microbial property according to claim 1; It is characterized in that; Said step c is that the titanium material that obtains with step b is as negative electrode; Platinum is as anode, with concentration be the selenous acid aqueous solution of 1 ~ 3mmol/L as electrolytic solution, galvanic deposit is 0.5 ~ 2 hour under constant voltage 1 ~ 2V condition; Titanium material after the processing cleans, drying for standby.
6. the preparation method with medical titanium material of good anticancer anti-microbial property according to claim 5 is characterized in that, said step c be with concentration be the selenous acid aqueous solution of 1mmol/L as electrolytic solution, galvanic deposit is 1 hour under constant voltage 1.5V condition.
7. the preparation method with medical titanium material of good anticancer anti-microbial property according to claim 1; It is characterized in that; The titanium material that the mode treatment step c that said steps d is that to use massfraction be 0.4 ~ 0.6% chitosan solution through spin coating obtains; The spin coating number of times is 5 ~ 15 times, at every turn with 400 ~ 600 rev/mins of spin coatings 10 ~ 20 seconds; Titanium material after the processing cleans, drying, promptly gets the medical titanium material with good anticancer anti-microbial property.
8. the preparation method with medical titanium material of good anticancer anti-microbial property according to claim 7; It is characterized in that; The titanium material that the mode treatment step c that said steps d is that to use massfraction be 0.5% chitosan solution through spin coating obtains; The spin coating number of times is 10 times, at every turn with 500 rev/mins of spin coatings 15 seconds, makes 10 layers of chitosan in the finishing of titanium material.
9. the medical titanium material that adopts each said preparation method of claim 1 to 8 to make with good anticancer anti-microbial property.
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| CN108744047A (en) * | 2018-06-11 | 2018-11-06 | 浙江理工大学 | A kind of preparation method of titanium nanometer/fibroin albumen/hydroxyapatite composite medical titanium coating |
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| CN108853606A (en) * | 2018-07-11 | 2018-11-23 | 北京大学口腔医学院 | A method of using Polyethylene glycol chitosan Gel Treatment dental material surface |
| CN108853606B (en) * | 2018-07-11 | 2019-04-23 | 北京大学口腔医学院 | A method of using Polyethylene glycol chitosan Gel Treatment dental material surface |
| CN113456896A (en) * | 2021-05-20 | 2021-10-01 | 宁波市医疗中心李惠利医院 | Selenium-doped titanium dioxide nanotube array orthopedic anti-tumor implant |
| US11825847B2 (en) | 2021-08-02 | 2023-11-28 | Board Of Regents, The University Of Texas System | Antimicrobial coating comprising chalcogenide nano-particles capped by chitosan |
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