CN102560598B - 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 conventional medical metal material, because it has the Young's modulus approximate with people's bone, good solidity to corrosion, good biocompatibility and processing characteristics, from the seventies, just at aspects such as dental implant, tooth implant frame, bone planting body and joint prosthesises, be used widely.The method for the treatment of clinically osteocarcinoma normally substitutes the bone of canceration with bone planting body.Owing to may still having the cancer cells not removed completely near the bone planting body of implanting after operation, and bacterial inflammatory reaction easily causes implanting rear loosening, therefore, develop a kind of bone implant material with good anticancer and anti-microbial property 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, but due to antibiotic quick release, can not reach lasting antibacterial effect by lyophilization.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of medical titanium material with high anti-cancer anti-microbial property and preparation method thereof, simple to operate, without 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 invention provides following technical scheme:
1. the preparation method with the medical titanium material of high anti-cancer anti-microbial property, comprises the following steps:
A. titanium material is cleaned and obtains 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 selenium nano particle;
D. adopt spin-coating method at 5 ~ 15 layers of chitosan of step c gained titanium material finishing, must there is the medical titanium material of high anti-cancer anti-microbial property.
Preferably, described step a uses acetone, Virahol and methyl alcohol ultrasonic cleaning 10 ~ 20 minutes successively by titanium material, then water cleans 2 ~ 4 times, drying for standby.
Preferably, described step b is usingd titanium material that step a obtains as anode, platinum is as negative electrode, with concentration be 0.25 ~ 0.30 mol/L, the volume ratio of the usining glycerol-water mixed solution that is 1:1 the ammonium fluoride solution that is solvent is as electrolytic solution, under constant voltage 30V condition, anodic oxidation reactions is 30 ~ 60 minutes; Titanium material after processing cleans, drying for standby.
Preferred, described step b be with concentration be 0.27mol/L, the volume ratio of the usining glycerol-water mixed solution that is 1:1 the ammonium fluoride solution that is solvent is as electrolytic solution, under constant voltage 30V condition, anodic oxidation reactions is 30 minutes.
Preferably, described step c is usingd titanium material that step b obtains as negative electrode, and platinum is as anode, and the selenous acid aqueous solution that the concentration of usining is 1 ~ 3mmol/L is as electrolytic solution, and under constant voltage 1 ~ 2V condition, galvanic deposit is 0.5 ~ 2 hour; Titanium material after processing cleans, drying for standby.
Preferred, described step c is usingd the selenous acid aqueous solution that concentration is 1mmol/L as electrolytic solution, and under constant voltage 1.5V condition, galvanic deposit is 1 hour.
Preferably, the titanium material that the mode treatment step c of the chitosan solution that described steps d is is 0.4 ~ 0.6% with massfraction by spin coating obtains, spin coating number of times is 5 ~ 15 times, at every turn with 400 ~ 600 revs/min of spin coatings 10 ~ 20 seconds.
The titanium material preferred, the mode treatment step c of the chitosan solution that described steps d is is 0.5% with massfraction by spin coating obtains, spin coating number of times is 10 times, at every turn with 500 revs/min 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 high anti-cancer anti-microbial property.
In above-mentioned preparation method, step b adopts anonizing to prepare Nano tube array of titanium dioxide.In anode oxidation process, factors can affect the formation of nano-tube array, such as electrolyte system, oxidation voltage etc., and different preparation conditions may obtain having the nano-tube array of different-shape feature.The present invention investigates electrolyte system, comprises Neutral ammonium fluoride glycerol system, hydrofluoric acid aqueous systems and Neutral ammonium fluoride glycerol
/water (volume ratio is 1:1) system.Result shows, prepares the Nano tube array of titanium dioxide of identical caliber pipe range by Neutral ammonium fluoride glycerol system, needs long period and high voltage; By hydrofluoric acid aqueous systems, prepare Nano tube array of titanium dioxide, the pattern of nano-tube array is difficult to control; And use Neutral ammonium fluoride glycerol
/water (volume ratio is 1:1) is prepared Nano tube array of titanium dioxide, can control relatively easily the caliber pipe range of nanotube by changing the approach such as oxidation voltage; Therefore, electrolyte system preferred fluorinated ammonium glycerol of the present invention
/water (volume ratio is 1:1) system.The concentration of Neutral ammonium fluoride can affect the form of generated titania nanotube, 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.Result shows, the caliber of the little titania nanotube generating of oxidation voltage is little, be unfavorable for the loading of selenium nano particle, rising along with oxidation voltage, the caliber of titania nanotube increases, and when oxidation voltage is greater than 40V, titania nanotube is destroyed, therefore, preferential oxidation voltage of the present invention is 30V.
Steps d by spin-coating method at titanium material finishing multilayered shell glycan.Chitosan solution concentration is too low, can make titanium material surface do not covered completely by chitosan, and then affects shutoff and the antibacterial effect of nanotube; Chitosan solution excessive concentration, can affect the release of cancer-resisting substance selenium in initial stage nanotube, and then affect anticancer effect.The present invention studies show that, the massfraction of chitosan solution is preferably 0.4 ~ 0.6%, more preferably 0.5%.
Beneficial effect of the present invention is: the present invention first by anonizing at the orderly Nano tube array of titanium dioxide of titanium material Surface Creation height rule, then by electrochemical deposition method original position in titania nanotube, generate selenium nano particle, finally by spin-coating method at titanium material finishing multilayered shell glycan, made a kind of medical titanium material with high anti-cancer anti-microbial property, simple to operate, without specific installation, cost is low, 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 there is good antimicrobial property.
Accompanying drawing explanation
Fig. 1 is the field emission scanning electron microscope figure on the titanium material surface through different treatment, wherein A is untreated titanium material, B is " titania nanotube " vertical view, C is " titania nanotube " sectional view, 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 that cells of tumorous bone is in the activity on the titanium material surface through different treatment, wherein * * represents to compare p<0.01 with untreated titanium material, * * represents to compare p<0.001 with untreated titanium material, and & & represents to compare p<0.01 with " titania nanotube@silver ".
Fig. 3 is rat osteoblast in the activity on the titanium material surface through different treatment, and wherein * * represents and untreated titanium material p<0.01 relatively.
Embodiment
In order to make the object, technical solutions and advantages of the present invention clearer, below in conjunction with accompanying drawing, the preferred embodiments of the present invention are described in detail.
embodiment 1. has the preparation of the medical titanium material of high anti-cancer anti-microbial property
A. the pre-treatment of titanium material: titanium material is used to acetone, Virahol and methyl alcohol ultrasonic cleaning 20 minutes successively, then use washed with de-ionized water 3 times, 40 ℃ dry, standby;
B. the structure of Nano tube array of titanium dioxide: the glycerol-water mixed solution that is 1:1 by volume ratio by Neutral ammonium fluoride dissolves makes the solution that concentration is 0.27mol/L, as electrolytic solution; The titanium material that step a is obtained is as anode, and platinum, as negative electrode, is set up and states in Neutral ammonium fluoride electrolytic solution, and under constant voltage 30V condition, anodic oxidation reactions is 30 minutes; Washed with de-ionized water 5 times of titanium material after processing, 40 ℃ are dry, standby; Gained titanium material is referred to as " titania nanotube ";
C. the loading of selenium nano particle: selenous acid is made to the aqueous solution that concentration is 1.0mmol/L with deionized water dissolving, as electrolytic solution; The titanium material that step b is obtained is as negative electrode, and platinum, as anode, is set up and states in selenous acid electrolytic solution, and under the condition of constant voltage 1.5V, galvanic deposit is 1 hour; Washed with de-ionized water 5 times of titanium material after processing, 40 ℃ are dry, standby; Gained titanium material is referred to as " titania nanotube@selenium ";
D. the modification of chitosan: viscosity is 20cP, is deacetylatedly greater than acetic acid solution that 85% chitosan (being purchased from sigma company) is 2% by volume fraction and dissolves that to make massfraction be 0.5% solution; It is upper that the titanium material that step c is obtained is fixed on spin coater (spin-coater), drips above-mentioned chitosan solution 40 μ L at every turn, with 500 revs/min of rotations 15 seconds, repeats spin coating 10 times, makes 10 layers of chitosan in the finishing of titanium material; Titanium material after processing is dry, must have the medical titanium material of high anti-cancer anti-microbial property, referred to as " titania nanotube@selenium@chitosan ".
The field emission scanning electron microscope figure that above steps is processed rear gained titanium material surface is shown in Fig. 1, it is visible after step b processes, vertical arrangement, regular Nano tube array of titanium dioxide on titanium material surface, have been formed, the about 110nm of the caliber of titania nanotube wherein, the about 900nm of pipe range; After step c processes, the selenium nano particle of loading has 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 is processed, titania nanotube is covered completely by chitosan.
embodiment 2. has the preparation of the medical titanium material of high anti-cancer anti-microbial property
A. the pre-treatment of titanium material: titanium material is used to acetone, Virahol and methyl alcohol ultrasonic cleaning 20 minutes successively, then use washed with de-ionized water 3 times, 40 ℃ dry, standby;
B. the structure of Nano tube array of titanium dioxide: the glycerol-water mixed solution that is 1:1 by volume ratio by Neutral ammonium fluoride dissolves makes the solution that concentration is 0.25mol/L, as electrolytic solution; The titanium material that step a is obtained is as anode, and platinum, as negative electrode, is set up and states in Neutral ammonium fluoride electrolytic solution, and under constant voltage 30V condition, anodic oxidation reactions is 45 minutes; Washed with de-ionized water 5 times of titanium material after processing, 40 ℃ are dry, standby; Gained titanium material is referred to as " titania nanotube ";
C. the loading of selenium nano particle: selenous acid is made to the aqueous solution that concentration is 2mmol/L with deionized water dissolving, as electrolytic solution; The titanium material that step b is obtained is as negative electrode, and platinum, as anode, is set up and states in selenous acid electrolytic solution, and under the condition of constant voltage 1V, galvanic deposit is 2 hours; Washed with de-ionized water 5 times of titanium material after processing, 40 ℃ are dry, standby; Gained titanium material is referred to as " titania nanotube@selenium ";
D. the modification of chitosan: viscosity is 20cP, is deacetylatedly greater than acetic acid solution that 85% chitosan (being purchased from sigma company) is 2% by volume fraction and dissolves that to make massfraction be 0.4% solution; It is upper that the titanium material that step c is obtained is fixed on spin coater (spin-coater), drips above-mentioned chitosan solution 40 μ L at every turn, with 400 revs/min of rotations 10 seconds, repeats spin coating 15 times, makes 15 layers of chitosan in the finishing of titanium material; Titanium material after processing is dry, must have the medical titanium material of high anti-cancer anti-microbial property, referred to as " titania nanotube@selenium@chitosan ".
embodiment 3. has the preparation of the medical titanium material of high anti-cancer anti-microbial property
A. the pre-treatment of titanium material: titanium material is used to acetone, Virahol and methyl alcohol ultrasonic cleaning 20 minutes successively, then use washed with de-ionized water 3 times, 40 ℃ dry, standby;
B. the structure of Nano tube array of titanium dioxide: the glycerol-water mixed solution that is 1:1 by volume ratio by Neutral ammonium fluoride dissolves makes the solution that concentration is 0.30mol/L, as electrolytic solution; The titanium material that step a is obtained is as anode, and platinum, as negative electrode, is set up and states in Neutral ammonium fluoride electrolytic solution, and under constant voltage 30V condition, anodic oxidation reactions is 60 minutes; Washed with de-ionized water 5 times of titanium material after processing, 40 ℃ are dry, standby; Gained titanium material is referred to as " titania nanotube ";
C. the loading of selenium nano particle: selenous acid is made to the aqueous solution that concentration is 3mmol/L with deionized water dissolving, as electrolytic solution; The titanium material that step b is obtained is as negative electrode, and platinum, as anode, is set up and states in selenous acid electrolytic solution, and under the condition of constant voltage 2V, galvanic deposit is 0.5 hour; Washed with de-ionized water 5 times of titanium material after processing, 40 ℃ are dry, standby; Gained titanium material is referred to as " titania nanotube@selenium ";
D. the modification of chitosan: viscosity is 20cP, is deacetylatedly greater than acetic acid solution that 85% chitosan (being purchased from sigma company) is 2% by volume fraction and dissolves that to make massfraction be 0.6% solution; It is upper that the titanium material that step c is obtained is fixed on spin coater (spin-coater), drips above-mentioned chitosan solution 40 μ L at every turn, with 600 revs/min of rotations 20 seconds, repeats spin coating 5 times, makes 5 layers of chitosan in the finishing of titanium material; Titanium material after processing is dry, must have the medical titanium material of high anti-cancer anti-microbial property, referred to as " titania nanotube@selenium@chitosan ".
experimental example 1. has the medical titanium material of high anti-cancer anti-microbial property to colibacillary inhibition ability
Get " titania nanotube ", " titania nanotube@selenium " and " titania nanotube@selenium@chitosan " material that embodiment 1 obtains after different treatment, with UV-irradiation sterilization in 2 hours, at material surface, drip intestinal bacteria suspension 40 μ L, respectively at 37 ℃ of overnight incubation, then with sterilized water 4mL, strongly vibrate and wash 5 minutes, wash down the bacterium that sticks to material surface, get washings 100 μ L and be coated with wiping tablet, cultivate 24 hours for 37 ℃, counting bacterium colony also calculates antimicrobial efficiency.Result demonstration, the antimicrobial efficiency of " titania nanotube " is 20.5%; Load after selenium nano particle, the antimicrobial efficiency of " titania nanotube@selenium " is 22.2%, has by a small margin and improves; And after chitosan-modified, the antimicrobial efficiency of " titania nanotube@selenium@chitosan " is greater than 99.9%, increase substantially, there is good antibacterial ability.
experimental example 2. has the medical titanium material of high anti-cancer anti-microbial property to cells of tumorous bone and the normally impact of osteoblast activity
Get respectively " titania nanotube ", " titania nanotube@selenium " and " titania nanotube@selenium@chitosan " material and untreated titanium material (referred to as " titanium material ") that embodiment 1 obtains after different treatment, at material surface, inoculate respectively human osteosarcoma cell 143B and neonate rat Calvarial osteoblast, inoculum density is 40000/cm
2, with containing volume fraction, be that the DMEM substratum of 10% new-born calf serum is cultivated respectively 4 days and 7 days, within every 2 days, change liquid, then every hole adds MTT 100 μ L, cultivates 4 hours for 37 ℃, inhales and abandons supernatant liquor, every hole adds DMSO 0.5mL again, measures absorbancy by microplate reader in wavelength 490nm place.Titanium material is shown in Fig. 2 to the impact of cells of tumorous bone activity, visible cells of tumorous bone is cultivated the cytoactive of 4 days and 7 days all lower than other control group on " titania nanotube@selenium " and " titania nanotube@selenium@chitosan " this bi-material, show that this bi-material all can effectively suppress the growth of cells of tumorous bone, and on " titania nanotube@selenium " surface, further covered multilayered shell glycan because " titania nanotube@selenium@chitosan " is, the rate of release of selenium nano particle is slowed down, therefore, " titania nanotube@selenium@chitosan " material can be more lasting the growth of inhibition cells of tumorous bone.Titanium material is shown in Fig. 3 to the impact of normal osteoblast activity, the cytoactive that visible healthy scleroblast is cultivated 7 days on " titania nanotube@selenium@chitosan " material is significantly higher than other group, shows the effectively osteoblastic growth of promotion health of this material.
Finally explanation, above embodiment only, for technical scheme of the present invention is described, does not form the restriction to content of the present invention.Although the present invention has been done to comparatively detailed exemplifying by above-described embodiment, 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 the form and details it is made to various changes, and do not depart from the spirit and scope of the present invention that appended claims limits.
Claims (6)
1. the preparation method with the medical titanium material of high anti-cancer anti-microbial property, is characterized in that, comprises the following steps:
A. titanium material is cleaned and obtains clean metallic surface;
B. adopt anonizing at the orderly Nano tube array of titanium dioxide of step a gained titanium material surface formation rule: the titanium material that the step a of usining obtains is as anode, platinum is as negative electrode, with concentration be 0.25 ~ 0.30mol/L, the volume ratio of the usining glycerol-water mixed solution that is 1:1 the ammonium fluoride solution that is solvent is as electrolytic solution, under constant voltage 30V condition, anodic oxidation reactions is 30 ~ 60 minutes; Titanium material after processing cleans, drying for standby;
C. adopt electrochemical deposition method original position in the titania nanotube on step b gained titanium material surface to generate selenium nano particle: the titanium material that the step b of usining obtains is as negative electrode, platinum is as anode, the selenous acid aqueous solution that the concentration of usining is 1 ~ 3mmol/L is as electrolytic solution, and under constant voltage 1 ~ 2V condition, galvanic deposit is 0.5 ~ 2 hour; Titanium material after processing cleans, drying for standby;
D. adopt spin-coating method 5 ~ 15 layers of chitosan in the finishing of step c gained titanium material: the titanium material that the mode treatment step c of the chitosan solution that is 0.4 ~ 0.6% with massfraction by spin coating obtains, spin coating number of times is 5 ~ 15 times, at every turn with 400 ~ 600 revs/min of spin coatings 10 ~ 20 seconds; Titanium material after processing cleans, is dried, and must have the medical titanium material of high anti-cancer anti-microbial property.
2. the preparation method with the medical titanium material of high anti-cancer anti-microbial property according to claim 1, is characterized in that, described step a uses acetone, Virahol and methyl alcohol ultrasonic cleaning 10 ~ 20 minutes successively by titanium material, then water cleans 2 ~ 4 times, drying for standby.
3. the preparation method with the medical titanium material of high anti-cancer anti-microbial property according to claim 1, it is characterized in that, described step b be with concentration be 0.27mol/L, the volume ratio of the usining glycerol-water mixed solution that is 1:1 the ammonium fluoride solution that is solvent is as electrolytic solution, under constant voltage 30V condition, anodic oxidation reactions is 30 minutes.
4. the preparation method with the medical titanium material of high anti-cancer anti-microbial property according to claim 1, is characterized in that, described step c is usingd the selenous acid aqueous solution that concentration is 1mmol/L as electrolytic solution, and under constant voltage 1.5V condition, galvanic deposit is 1 hour.
5. the preparation method with the medical titanium material of high anti-cancer anti-microbial property according to claim 1, it is characterized in that, the titanium material that the mode treatment step c of the chitosan solution that described steps d is is 0.5% with massfraction by spin coating obtains, spin coating number of times is 10 times, with 500 revs/min of spin coatings 15 seconds, make 10 layers of chitosan in the finishing of titanium material at every turn.
6. the medical titanium material with high anti-cancer anti-microbial property that described in employing claim 1 to 5 any one, preparation method makes.
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| US9903035B2 (en) * | 2012-12-03 | 2018-02-27 | The Regents Of The University Of California | Devices, systems and methods for coating surfaces |
| CN105088313A (en) * | 2015-09-14 | 2015-11-25 | 江西洪都航空工业集团有限责任公司 | Titanium alloy activation technological method |
| CN105343941B (en) * | 2015-11-04 | 2018-06-22 | 中国科学院上海硅酸盐研究所 | A kind of surface modification biological Nickel-titanium alloy for medical purpose and its preparation method and application |
| CN106729964A (en) * | 2016-12-02 | 2017-05-31 | 江苏师范大学 | It is a kind of to have promoting bone growing concurrently and suppress titania nanotube of bone resorption and preparation method thereof |
| US11076599B2 (en) | 2017-03-28 | 2021-08-03 | The Board Of Regents Of The University Of Texas System | Antimicrobial coating comprising chalcogenide nano-particles capped by chitosan |
| CN107693843B (en) * | 2017-04-01 | 2020-09-04 | 华东理工大学 | Surface modification method of biomedical active titanium and alloy implant material thereof |
| CN108744047B (en) * | 2018-06-11 | 2021-08-13 | 浙江理工大学 | Preparation method of titanium nano/silk fibroin/hydroxyapatite composite medical titanium coating |
| 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 |
| CN113456896B (en) * | 2021-05-20 | 2022-11-11 | 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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| CN101766838B (en) * | 2009-12-31 | 2012-10-24 | 东南大学 | Functionalized artificial joint with selenium-loaded nanotube array surface and preparation method thereof |
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