CN102525827B - Method for preparing medical titanium material with long-acting antibacterial property and good biocompatibility - Google Patents
Method for preparing medical titanium material with long-acting antibacterial property and good biocompatibility Download PDFInfo
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Abstract
The invention discloses a method for preparing a medical titanium material with long-acting antibacterial property and good biocompatibility. The method comprises the following steps of: firstly forming a titanium dioxide nanotube array with regular and orderly height on the surface of the titanium material by anodic oxidation process; then adding a silver salt solution into the titanium dioxide nanotubes by spin-coating process, and heating at a high temperature to make the silver salt decompose into sliver nanoparticles in the titanium dioxide nanotubes; and finally modifying the material surface with a quaternary ammonium salt QAS, to obtain the final product of medical titanium material with long-acting antibacterial property and good biocompatibility. The preparation method is simple, does not need a special equipment and has a low preparation cost.
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 has the elastic modelling quantity approximate with people's bone, good corrosion resistance, good biocompatibility and processing characteristics, begins just to be widely used in dental implant, artificial joint and tooth implant frame etc. as embedded material from the seventies.It is one of modal reason of biomaterial graft failure that antibacterial infects.If be subject to severe infections, just need the taking-up implant to lay equal stress on and newly perform the operation.Therefore, desirable implant not only needs good biocompatibility, and needs lasting anti-microbial property.
Previously result of study shows, suitable nanotube caliber and pipe range can promote cell function; Titania nanotube has good anti-microbial property after adding carried with antibiotics, but because antibiotic quick release can not reach lasting antibacterial effect; Titania nanotube has more lasting antibacterial ability after loading silver nano-grain, but cell is had certain toxicity.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of medical titanium material with long acting antibiotic performance and good biocompatibility and preparation method thereof, operating process is simple, need not special installation, preparation cost is low, and products obtained therefrom has long acting antibiotic performance and good biocompatibility.
For achieving the above object, the invention provides following technical scheme:
1. have the preparation method of the medical titanium material of long acting antibiotic performance and good biocompatibility, may further comprise the steps:
A. the titanium material is cleaned and obtain clean metal surface;
B. the orderly Nano tube array of titanium dioxide of titanium material surface formation rule that adopts anodizing to obtain at step a;
C. the titanium material that obtains with the mode treatment step b of silver salt solution by spin coating enters in the titania nanotube silver salt, makes the silver salt that enters in the titania nanotube be decomposed to form silver nano-grain by high-temperature heating again;
D. irradiation under ultraviolet ray 1 ~ 3 hour is used on the titanium material surface that step c is obtained, drip dimethyl stearyl [3-(trimethoxy is silica-based) propyl group] ammonium chloride (QAS) solution on titanium material surface again, heat treated forms the QAS decorative layer, namely gets the medical titanium material with long acting antibiotic performance and good biocompatibility.
Preferably, described step a used acetone, isopropyl alcohol and methanol ultrasonic cleaning 10 ~ 20 minutes successively with the titanium material, and water cleans 2 ~ 4 times again, drying for standby.
Preferably, described step b is that the titanium material that obtains with step a is as anode, platinum is as negative electrode, with concentration be 0.25 ~ 0.30 mol/L, glycerol-water mixed liquor take volume ratio as 1:1 as the ammonium fluoride solution of solvent as electrolyte, anodic oxidation reactions is 30 ~ 60 minutes under constant voltage 30V condition; Titanium material after the processing cleans, drying for standby.
Preferred, described step b be with concentration be 0.27mol/L, glycerol-water mixed liquor take volume ratio as 1:1 as the ammonium fluoride solution of solvent as electrolyte, anodic oxidation reactions is 30 minutes under constant voltage 30V condition.
Preferably, described step c is the titanium material that obtains with the silver salt solution of the saturated concentration mode treatment step b by spin coating, and the spin coating number of times is 10 ~ 30 times, and is each first with 450 ~ 550 rev/mins of spin coatings 15 ~ 30 seconds, again with 1000 ~ 2000 rev/mins of spin coatings 10 ~ 20 seconds; Titanium material after the processing cleans, drying, heats 2 ~ 4 hours under 470 ~ 550 ℃, inert gas shielding condition again, cools off for subsequent use.
Preferred, described step c is to be that the silver nitrate solution of 1mol/L carries out spin coating with concentration, and the spin coating number of times is 30 times, and is each first with 450 rev/mins of spin coatings 18 seconds, again with 1500 rev/mins of spin coatings 12 seconds; Titanium material after the processing cleans, after the drying, heating is 3 hours under 500 ℃, argon shield condition.
Preferably, described steps d is that irradiation under ultraviolet ray 1 ~ 3 hour is used on the titanium material surface that step c obtains, drip mass fraction on titanium material surface again and be 0.4 ~ 0.6% QAS solution, 80 ℃ of heating 16-24 hour namely get the medical titanium material with long acting antibiotic performance and good biocompatibility.
Preferred, described steps d is that irradiation under ultraviolet ray 2 hours are used on the titanium material surface that step c obtains, and is 0.5% QAS solution again at titanium material surface dropping mass fraction, and 80 ℃ were heated 20 hours.
2. the product that adopts above-mentioned preparation method to make is the medical titanium material with long acting antibiotic performance and good biocompatibility.
In the above-mentioned preparation method, step b adopts anodizing 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 ammonium fluoride glycerol system, Fluohydric acid. aqueous systems and ammonium fluoride glycerol
/Water (volume ratio is 1:1) system.The result shows, prepares the Nano tube array of titanium dioxide of identical caliber pipe range with ammonium fluoride glycerol system, needs long period and high voltage; Prepare Nano tube array of titanium dioxide with the Fluohydric acid. aqueous systems, the pattern of nano-tube array is difficult to control; And use the ammonium fluoride glycerol
/Water (volume ratio is 1:1) system prepares 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 ammonium fluoride can affect the form of the titania nanotube that generates, and studies show that, adopting concentration is 0.25 ~ 0.30 ammonium fluoride electrolyte 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, the caliber of the little titania nanotube that then generates of oxidation voltage is little, be unfavorable for the loading of silver nano-grain, rising along with oxidation voltage, the caliber of titania nanotube increases, and when oxidation voltage during greater than 40V, titania nanotube is destroyed, therefore, preferential oxidation voltage of the present invention is 30V.
Step c adds silver salt solution in the titania nanotube to by spin-coating method.Spin-coating method can rely on the action of gravity of the porous tubular structured capillarity of nanotube itself and silver salt solution itself, makes silver salt enter nanotube inside, and utilizes the centrifugal force that produces when rotating that silver salt is evenly distributed in body.Affect the principal element that silver salt distributes in body silver salt solution concentration, spin coating number of times and spin speed etc. are arranged.In order effectively to load silver nano-grain in titania nanotube, silver salt solution concentration of the present invention is preferably saturated concentration.In the certain numerical value scope, the spin coating number of times is more, and the silver salt that enters body inside is more.The centrifugal force that spin speed produces too slowly is inadequate, if spin speed is very fast when just having begun, silver salt can be thrown out of and can not well be loaded in the nanotube.Result of study of the present invention shows, adopts the high concentration silver salt solution, uses first than low velocity and uses the fair speed spin coating again, and the more number of times of spin coating could effectively load silver salt to titania nanotube interior (Fig. 1).
Steps d increases first the chemical active radical on titanium material surface by ultra violet lamp, drip QAS solution again, make its under the heat treated condition with the chemical active radical reaction on titanium material surface, finally form the QAS decorative layer on titanium material surface.The QAS solution concentration is too low, titanium material surface can not be covered fully by QAS, and then affect antibacterial effect; The QAS solution concentration is too high, and then to titanium material surface, QAS is intermolecular also id reaction can to occur QAS, forms unnecessary waste except partially grafted.The present invention studies show that the mass fraction of QAS solution is preferably 0.4 ~ 0.6%, more preferably 0.5%.
Beneficial effect of the present invention is: the present invention at first by anodizing at the orderly Nano tube array of titanium dioxide of titanium material Surface Creation height rule, then by spin-coating method silver salt solution is added in the titania nanotube, high-temperature heating makes silver salt be decomposed to form silver nano-grain in nanotube, use at last quaternary ammonium salt QAS decorative material surface, made a kind of medical titanium material that has simultaneously long acting antibiotic performance and good biocompatibility, preparation method is simple, need not special installation, preparation cost is low.
Description of drawings
Fig. 1 is the field emission scanning electron microscope figure that silver loads in the titania nanotube under the different condition, wherein A is low concentration silver salt, low speed-high speed spin coating, B is high concentration silver salt, less spin coating number of times, and C is high concentration silver salt, high speed spin coating, and D is high concentration silver salt, low speed-high speed spin coating.
Fig. 2 is the field emission scanning electron microscope figure on the titanium material surface of process different disposal, wherein A is the titanium material that is untreated, B is " titania nanotube " top view, C is " titania nanotube " sectional view, D is " titania nanotube@silver " top view, E is " titania nanotube@silver@QAS " top view for " titania nanotube@silver " sectional view (arrow has been indicated the silver nano-grain in titania nanotube), F.
Fig. 3 is the energy spectrum analysis figure on the titanium material surface of process different disposal, and wherein A is " titania nanotube ", and B is " titania nanotube@silver ", and C is " titania nanotube@silver@QAS ".
Fig. 4 is rat osteoblast in the activity through the titanium material surface of different disposal, and wherein * represents and relatively p＜0.05 of titanium material of being untreated, and * * represents and relatively p＜0.01 of titanium material of being untreated, and # represents and " titania nanotube " p＜0.05 ， ﹠amp relatively; Expression is compared p＜0.05 ， ﹠amp with " titania nanotube@silver "; ﹠amp; Expression is compared p＜0.01 with " titania nanotube@silver ".
The specific embodiment
In order to make the purpose, 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 long acting antibiotic performance and good biocompatibility
A. the pretreatment of titanium material: the titanium material is used acetone, isopropyl alcohol and methanol ultrasonic cleaning 20 minutes successively, use again washed with de-ionized water 3 times, 40 ℃ of dryings, for subsequent use;
B. the structure of Nano tube array of titanium dioxide: be the glycerol-water mixed solution dissolving of 1:1 with the ammonium fluoride volume ratio, make the ammonium fluoride solution that concentration is 0.27mol/L, as electrolyte; The titanium material that step a is obtained is as anode, and platinum is set up and states in the ammonium fluoride electrolyte as negative electrode, and anodic oxidation reactions is 30 minutes under constant voltage 30V condition; Titanium material water after the processing cleans 5 times, and 40 ℃ of dryings are for subsequent use; Gained titanium material is referred to as " titania nanotube ";
C. the loading of silver nano-grain: the titanium material that step b is obtained is fixed on the spin coater (spin-coater), dripping concentration on titanium material surface is the silver nitrate solution of 1mol/L, and each 20 μ L are first with 450 rev/mins of spin coatings 18 seconds, with 1500 rev/mins of spin coatings 12 seconds, repeat spin coating 30 times again; Titanium material water after the processing cleans 5 times, drying at room temperature, and again heating 3 hours under 500 ℃, argon shield condition is cooled off for subsequent use; Gained titanium material is referred to as " titania nanotube@silver ";
D. the modification of quaternary ammonium salt: irradiation under ultraviolet ray 2 hours are used on the titanium material surface that step c obtains, drip again mass fraction on titanium material surface and be 0.5% QAS solution 20 μ L, 80 ℃ were heated 20 hours, namely get the medical titanium material with long acting antibiotic performance and good biocompatibility, referred to as " titania nanotube@silver@QAS ".
The field emission scanning electron microscope figure on gained titanium material surface as shown in Figure 2 after above steps was processed, as seen after step b processes, 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 processed, the silver nano-grain of loading had fraction 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 processed, titania nanotube was by the QAS partial coverage.
The energy spectrum analysis figure on gained titanium material surface as shown in Figure 3 after above steps was processed, as seen compare with the titanium material after the step b processing, titanium material after step c processes contains 5% the silver element of having an appointment, description of step c has loaded silver nano-grain effectively in titania nanotube inside, and the content of silicon, nitrogen and chlorine element obviously increases in the titanium material after the steps d processing, illustrates at " titania nanotube@silver " material surface successfully to have modified QAS.
A. the pretreatment of titanium material: the titanium material is used acetone, isopropyl alcohol and methanol ultrasonic cleaning 20 minutes successively, use again washed with de-ionized water 3 times, 40 ℃ of dryings, for subsequent use;
B. the structure of Nano tube array of titanium dioxide: be the glycerol-water mixed solution dissolving of 1:1 with the ammonium fluoride volume ratio, make the ammonium fluoride solution that concentration is 0.25mol/L, as electrolyte; The titanium material that step a is obtained is as anode, and platinum is set up and states in the ammonium fluoride electrolyte as negative electrode, and anodic oxidation reactions is 45 minutes under constant voltage 30V condition; Titanium material water after the processing cleans 5 times, and 40 ℃ of dryings are for subsequent use; Gained titanium material is referred to as " titania nanotube ";
C. the loading of silver nano-grain: the titanium material that step b is obtained is fixed on the spin coater (spin-coater), dripping concentration on titanium material surface is the silver nitrate solution of 1mol/L, and each 20 μ L are first with 500 rev/mins of spin coatings 30 seconds, with 1000 rev/mins of spin coatings 20 seconds, repeat spin coating 20 times again; Titanium material water after the processing cleans 5 times, drying at room temperature, and again heating 3 hours under 500 ℃, argon shield condition is cooled off for subsequent use; Gained titanium material is referred to as " titania nanotube@silver ";
D. the modification of quaternary ammonium salt: irradiation under ultraviolet ray 3 hours are used on the titanium material surface that step c obtains, drip again mass fraction on titanium material surface and be 0.6% QAS solution 20 μ L, 80 ℃ were heated 24 hours, namely get the medical titanium material with long acting antibiotic performance and good biocompatibility, referred to as " titania nanotube@silver@QAS ".
Embodiment 3. has the preparation of the medical titanium material of long acting antibiotic performance and good biocompatibility
A. the pretreatment of titanium material: the titanium material is used acetone, isopropyl alcohol and methanol ultrasonic cleaning 20 minutes successively, use again washed with de-ionized water 3 times, 40 ℃ of dryings, for subsequent use;
B. the structure of Nano tube array of titanium dioxide: be the glycerol-water mixed solution dissolving of 1:1 with the ammonium fluoride volume ratio, make the ammonium fluoride solution that concentration is 0.30mol/L, as electrolyte; The titanium material that step a is obtained is as anode, and platinum is set up and states in the ammonium fluoride electrolyte as negative electrode, and anodic oxidation reactions is 60 minutes under constant voltage 30V condition; Titanium material water after the processing cleans 5 times, and 40 ℃ of dryings are for subsequent use; Gained titanium material is referred to as " titania nanotube ";
C. the loading of silver nano-grain: the titanium material that step b is obtained is fixed on the spin coater (spin-coater), dripping concentration on titanium material surface is the silver nitrate solution of 1mol/L, and each 20 μ L are first with 550 rev/mins of spin coatings 15 seconds, with 2000 rev/mins of spin coatings 10 seconds, repeat spin coating 10 times again; Titanium material water after the processing cleans 5 times, drying at room temperature, and again heating 3 hours under 500 ℃, argon shield condition is cooled off for subsequent use; Gained titanium material is referred to as " titania nanotube@silver ";
D. the modification of quaternary ammonium salt: irradiation under ultraviolet ray 1 hour is used on the titanium material surface that step c obtains, drip again mass fraction on titanium material surface and be 0.4% QAS solution 20 μ L, 80 ℃ were heated 16 hours, namely get the medical titanium material with long acting antibiotic performance and good biocompatibility, referred to as " titania nanotube@silver@QAS ".
Experimental example 1. has the medical titanium material of long acting antibiotic performance and good biocompatibility to colibacillary inhibition ability
Get " titania nanotube " of embodiment 1 through obtaining after the different disposal, " titania nanotube@silver " and " the silver-colored@QAS of titania nanotube@" and according to embodiment 1 step a, b, d processes " the titania nanotube@QAS " material that obtains, with irradiation under ultraviolet ray sterilization in 2 hours, drip escherichia coli suspension 40 μ L at material surface, cultivate 1 respectively at 37 ℃, 7,21 and 30 days, then strongly vibrate with sterilized water 4mL and washed 5 minutes, wash the antibacterial that sticks to material surface, get cleaning mixture 100 μ L and be coated with wiping tablet, cultivated 24 hours for 37 ℃, the counting bacterium colony also calculates antimicrobial efficiency.The results are shown in Table 1, " titania nanotube@silver " and " titania nanotube@silver@QAS " this bi-material all has the long acting antibiotic performance, and along with the release approach exhaustion of silver, " titania nanotube@QAS " material still has good antibacterial ability.
The titanium material of table 1 process different disposal is to colibacillary inhibition ability
Experimental example 2. has the medical titanium material of long acting antibiotic performance and good biocompatibility to the impact of rat osteoblast activity
Get embodiment 1 " titania nanotube ", " titania nanotube silver " and " titania nanotube silver QAS " material and titanium material that is untreated (referred to as " titanium material ") through obtaining after the different disposal, at material surface inoculation neonate rat Calvarial osteoblast, inoculum density is 40000/cm
2, with containing the DMEM culture medium culturing that volume fraction is 10% new-born calf serum, changed liquid in per 2 days, cultivated respectively 4 days and 7 days, then every hole adds MTT 100 μ L, cultivates 4 hours for 37 ℃, supernatant is abandoned in suction, and every hole adds DMSO 0.5mL again, measures absorbance in wavelength 490nm place with microplate reader.The results are shown in Figure 1, the cytoactive that rat osteoblast is cultivated 4 days and 7 days at " titania nanotube@silver " material is minimum, show that this material has certain cytotoxicity, and after this material surface has been modified QAS, the cytoactive of cultivating 4 days and 7 days has all obtained significant raising, illustrate that " titania nanotube@silver@QAS " material has good biocompatibility, can promote osteoblastic growth.
Explanation is at last, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although by invention has been described with reference to the preferred embodiments of the present invention, but those of ordinary skill in the art is to be understood that, can make various changes to it in the form and details, and not depart from the spirit and scope of the present invention that appended claims limits.
Claims (6)
1. have the preparation method of the medical titanium material of long acting antibiotic performance and good biocompatibility, it is characterized in that, may further comprise the steps:
A. the titanium material is cleaned and obtain clean metal surface;
B. the titanium material that obtains with step a is as anode, platinum is as negative electrode, with concentration be 0.25 ~ 0.30mol/L, glycerol-water mixed liquor take volume ratio as 1:1 as the ammonium fluoride solution of solvent as electrolyte, anodic oxidation reactions is 30 ~ 60 minutes under constant voltage 30V condition; Titanium material after the processing cleans, drying for standby;
C. the titanium material that obtains with the silver salt solution of the saturated concentration mode treatment step b by spin coating, the spin coating number of times is 10 ~ 30 times, and is each first with 450 ~ 550 rev/mins of spin coatings 15 ~ 30 seconds, again with 1000 ~ 2000 rev/mins of spin coatings 10 ~ 20 seconds; Titanium material after the processing cleans, drying, heats 2 ~ 4 hours under 470 ~ 550 ℃, inert gas shielding condition again, cools off for subsequent use;
D. irradiation under ultraviolet ray 1 ~ 3 hour is used on the titanium material surface that step c is obtained, dripping mass fraction on titanium material surface again and be 0.4 ~ 0.6% dimethyl stearyl [3-(trimethoxy is silica-based) propyl group] ammonium chloride is QAS solution, 80 ℃ were heated 16-24 hour, and namely got the medical titanium material with long acting antibiotic performance and good biocompatibility.
2. the preparation method with medical titanium material of long acting antibiotic performance and good biocompatibility according to claim 1, it is characterized in that, described step a used acetone, isopropyl alcohol and methanol 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 long acting antibiotic performance and good biocompatibility according to claim 1, it is characterized in that, described step b be with concentration be 0.27mol/L, glycerol-water mixed liquor take volume ratio as 1:1 as the ammonium fluoride solution of solvent as electrolyte, anodic oxidation reactions is 30 minutes under constant voltage 30V condition.
4. the preparation method with medical titanium material of long acting antibiotic performance and good biocompatibility according to claim 1, it is characterized in that, described step c is to be that the silver nitrate solution of 1mol/L replaces the silver salt solution of saturated concentration to carry out spin coating with concentration, the spin coating number of times is 30 times, each first with 450 rev/mins of spin coatings 18 seconds, again with 1500 rev/mins of spin coatings 12 seconds; Titanium material after the processing cleans, after the drying, heating is 3 hours under 500 ℃, argon shield condition.
5. the preparation method with medical titanium material of long acting antibiotic performance and good biocompatibility according to claim 1, it is characterized in that, described steps d is that irradiation under ultraviolet ray 2 hours are used on the titanium material surface that step c obtains, drip again mass fraction on titanium material surface and be 0.5% QAS solution, 80 ℃ of heating 20 hours.
6. the medical titanium material with long acting antibiotic performance and good biocompatibility that adopts each described preparation method of claim 1 to 5 to make.
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| CN102758202B (en) * | 2012-08-11 | 2014-05-07 | 西北有色金属研究院 | Method for preparing biomedical titanium and titanium alloy surface antibacterial coatings |
| CN103041976B (en) * | 2012-12-25 | 2014-04-30 | 苏州大学附属第二医院 | Method for preparing argentiferous antibacterial coating on surface of CoCr alloy material for oral use |
| CN103526259B (en) * | 2013-10-08 | 2016-08-17 | 广州市健齿生物科技有限公司 | A kind of titanium alloy operating theater instruments process of surface treatment |
| CN104087966A (en) * | 2014-06-09 | 2014-10-08 | 内蒙金属材料研究所 | A preparing method of a photocatalytic electrode material for water-splitting hydrogen production |
| CN106086989B (en) * | 2016-07-20 | 2018-06-19 | 中南大学 | A kind of titania modified by Argentine nanotube composite anode and preparation method thereof |
| CN106729989A (en) * | 2016-12-23 | 2017-05-31 | 大连三生科技发展有限公司 | A kind of tooth implant preparation method of the bioactivity surface containing antibacterial peptide |
| CN108815571B (en) * | 2018-07-02 | 2020-12-18 | 河北工业大学 | Preparation method of silver modified crystal form titanium dioxide nanotube layer |
| CN109267137B (en) * | 2018-10-12 | 2020-01-17 | 厦门大学 | Preparation method of medical titanium surface gradient nano silver |
| CN111705347B (en) * | 2020-06-05 | 2021-11-30 | 西北工业大学宁波研究院 | Method for preparing titanium nanotube iodine coating by chemical vapor deposition method and application |
| CN112076348B (en) * | 2020-07-22 | 2021-09-24 | 浙江大学 | Medical metal surface anti-infection and osseointegration promotion coating, preparation method and application |
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| CN101922044A (en) * | 2010-09-11 | 2010-12-22 | 天津大学 | Method for doping nano-Ag particles in TiO2 nanotubes |
| CN102105062A (en) * | 2008-05-09 | 2011-06-22 | 国立大学法人广岛大学 | Method of fixing antibacterial agent and article obtained by the method |
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| CN101922044A (en) * | 2010-09-11 | 2010-12-22 | 天津大学 | Method for doping nano-Ag particles in TiO2 nanotubes |
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