CN104141124A - Method for improving biological activity of pure titanium surface by using dopamine to be bonded with graphene oxide - Google Patents
Method for improving biological activity of pure titanium surface by using dopamine to be bonded with graphene oxide Download PDFInfo
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Abstract
本发明涉及一种利用多巴胺连接氧化石墨烯改善纯钛表面生物活性的方法。纯钛片表面粗糙度Ra不大于1μm，先后采用丙酮超声清洗，去离子水超声清洗；用硝酸对其进行酸处理、去离子水清洗后，利用氢氧化钠在40-80℃下对试样碱处理；配置多巴胺-三羟甲基氨基甲烷溶液为pH＝8.5；将处理的纯钛试样浸泡在配置的多巴胺溶液中，室温静置12h-24h；将试样取出，并用去离子水清洗，室温干燥，制备得到钛/多巴胺试样；将钛/多巴胺试样浸泡在氧化石墨烯水溶液中，室温静置12h-24h；取出后用去离子水清洗，室温干燥，制得钛/多巴胺/氧化石墨烯试样。本方法操作简单，可批量生产，且绿色无污染，为钛材料的表面改性拓宽了渠道。
The invention relates to a method for improving the biological activity of pure titanium surface by using dopamine to link graphene oxide. The surface roughness Ra of the pure titanium sheet is not greater than 1 μm, and it is ultrasonically cleaned with acetone and deionized water successively; after acid treatment with nitric acid and deionized water cleaning, the sample is treated with sodium hydroxide at 40-80°C Alkali treatment; prepare dopamine-trishydroxymethylaminomethane solution to pH = 8.5; soak the treated pure titanium sample in the prepared dopamine solution, and let it stand at room temperature for 12h-24h; take out the sample and wash it with deionized water , and dry at room temperature to prepare a titanium/dopamine sample; soak the titanium/dopamine sample in a graphene oxide aqueous solution, and let it stand at room temperature for 12h-24h; take it out, wash it with deionized water, and dry it at room temperature to obtain a titanium/dopamine/ Graphene oxide samples. The method is simple to operate, can be produced in batches, is green and pollution-free, and broadens channels for surface modification of titanium materials.
Description
Technical field
The present invention relates to the preparation method of pure titanium surface oxidation graphene layer, a kind of Dopamine HCL that utilizes connects the method that graphene oxide improves pure titanium surface bioactive specifically.
Background technology
Titanium and alloy thereof be because its density is low, and Young's modulus and bone photo have been widely used in technical field of biological material closely
[1](referring to: Liang Fanghui etc. utilize pre-calcification to process the surface bioactive [J] that improves alkali thermal treatment POROUS TITANIUM. Rare Metals Materials and engineering, 2004,33 (10): 1359-1364), become the good selection of embedded material.Yet titanium and alloy thereof are bio-inert material, after implant into body, and between bone, mostly be physical bond
[2](referring to: the .TiO2 nanotube crystal formations such as Wang little Hong are on the impact of titanium bioactive [J]. functional materials, 2013,9 (44): 1013-1018), the biological activity of titanium material itself is poor, can not realize the combination between implant and human body.For this problem, current research emphasis concentrates on implant surface and applies bioactive coating, as hydroxyapatite etc., improves the biological activity of titanium implants.
Graphene oxide (GO) is due to itself high rigidity and Young's modulus, and various oxy radical, is easy to be modified, and becomes the excellent carrier of biotic factor.Dopamine HCL is because himself is with functional groups such as phenolic hydroxyl group, amino, and can as intermediate medium, be applied to being connected of metal and organic or inorganic material etc. by auto-polymerization.Meanwhile, Dopamine HCL is the intrinsic macromolecular substance of human body, and polymerizing condition is gentle, so be widely applied in the correlative study of biomaterial.
The at present domestic research to graphene oxide is just at the early-stage, mainly concentrates on the functionalization of graphene oxide (GO) itself, and the research that is applied to metallic matrix does not also have report.From graphene oxide, can increase calcium microcosmic salt in surperficial deposition herein, promote cell to set out in the angle of material surface increment differentiation, impel the fusion of implant and human body.
Summary of the invention
The present invention relates to a kind of Dopamine HCL that utilizes and connect the method that graphene oxide improves pure titanium surface bioactive.Comprise the following steps:
1) pure titanium plate surface roughness Ra is not more than 1 μ m, successively adopts acetone ultrasonic cleaning, deionized water ultrasonic cleaning; Then with nitric acid to carrying out again after acid treatment, washed with de-ionized water, recycling sodium hydroxide under 40-80 ℃ of condition, sample is carried out to alkaline purification;
2) configuration Dopamine HCL-tris solution is pH=8.5;
3) by step 1) in the pure titanium sample processed be immersed in step 2) in the dopamine solution of configuration, the standing 12h-24h of room temperature; Sample is taken out, and by washed with de-ionized water, drying at room temperature, prepares titanium/Dopamine HCL sample.
4) titanium/Dopamine HCL sample is immersed in graphite oxide aqueous solution to the standing 12h-24h of room temperature; After taking out, by washed with de-ionized water, drying at room temperature, makes titanium/Dopamine HCL/graphene oxide sample.
Pure titanium sheet is preferably smooth through liquid honing, makes its surface roughness Ra be not more than 1 μ m;
Preferred nitric acid (HNO
3) sample is carried out to 10-30min acid treatment;
Preferably the sodium hydroxide of 5mol/L-10mol/L carries out alkaline purification to sample.
Compared with prior art, the invention has the beneficial effects as follows:
Present method is compared with the method that applies bioactive coating at titanium material surface, and its working method is more simple, can be mass, and experimentation green non-pollution, selected material is to human body nontoxicity.On the one hand, graphene oxide can promote calcium microcosmic salt deposition, and the increment differentiation of inducing cell, promotes cell to grow at implant surfaces; On the other hand, can utilize the various oxygen-containing functional group in graphene oxide surface further to modify the other biological factor, for the surface modification of titanium material has been widened channel.
Accompanying drawing explanation
Fig. 1 experimentation schematic diagram;
Pure titanium surface microstructure after Fig. 2 acid-alkali treatment;
Fig. 3 titanium/Dopamine HCL surface microstructure;
Fig. 4 titanium/Dopamine HCL/graphene oxide surface microstructure;
The Raman collection of illustrative plates of the pure titanium surface oxidation of Fig. 5 graphene layer;
The infrared spectrogram of Fig. 6 Dopamine HCL, graphene oxide, titanium/Dopamine HCL/graphene oxide;
Titanium/Dopamine HCL the sample making in the pure titanium sample of acid-alkali treatment that Fig. 7 step 1 makes, step 3, titanium/Dopamine HCL/graphene oxide sample are respectively at 37 ℃, and the surface topography soaking in SBF solution 28 days is respectively (a), (b), (c).
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
The technological line that the present invention modifies pure titanium by Dopamine HCL as intermediate medium connection graphene oxide is: the graphene oxide solution of Dopamine HCL-tris solution → dipping 2.0-3.0g/L of pre-treatment → surface preparation → dipping 2.0-3.0g/L.
Preparation method's step of the present invention's design is as follows:
1, by pure titanium sheet through liquid honing, make its surface roughness Ra be not more than 1 μ m, successively adopt acetone, deionized water ultrasonic cleaning.Adopt nitric acid (HNO
3) soak sample 10min-20min, remove oxide on surface.After washing, sample is immersed to 40-80 ℃, in the sodium hydroxide of 5-10mol/L (NaOH) solution, process 30min-45min, after taking-up, with deionized water, clean remained on surface sodium hydroxide, drying at room temperature.Make the pure titanium sample of acid-alkali treatment.
2, configuration 2.0-3.0g/L Dopamine HCL-Tutofusin tris (DA-Tris) solution.
3, the pure titanium sample of processing is first immersed in dopamine solution, the standing 12h-24h of room temperature, prepares titanium/Dopamine HCL sample.After taking-up, through washed with de-ionized water, again immerse in the graphite oxide aqueous solution of 2.0-3.0g/L the standing 12h-24h of room temperature.After taking-up, adopt washed with de-ionized water, and room temperature is dried.Make titanium/Dopamine HCL/graphene oxide sample.
Tell about by the following examples concrete preparation process of the present invention.Embodiment is for better illustrative experiment step and associated problem, is to propose take under the condition that the technology of the present invention is prerequisite.Person skilled, various replacements, variation and the modification etc. under the prerequisite that does not depart from aim of the present invention, made, all belong to protection domain of the present invention.
Embodiment 1:
1) pure titanium sample is smooth with liquid honing, make its surface roughness Ra be not more than 1 μ m, then adopt acetone, deionized water ultrasonic cleaning.Adopt nitric acid (HNO
3) (volume fraction 20%) immersion sample 10min, remove oxide on surface.After washing, sample is immersed to 40 ℃, in the sodium hydroxide of 5mol/L (NaOH) solution, process 45min, after taking-up, with deionized water, clean remained on surface sodium hydroxide, drying at room temperature.Make the pure titanium sample of acid-alkali treatment.
2) configuration of 2.0g/L Dopamine HCL-tris solution (DA-Tris): first configure pH=8.5, the Tutofusin tris of 10mmol/L (Tris) buffered soln.Get 1.21g Tutofusin tris powder dissolution in 800ml deionized water, with hydrochloric acid (HCl) the regulator solution pH=8.5 of 1mol/L, then pour solution into 1000ml volumetric flask and carry out constant volume.Then, get the solution of appropriate hydrochloric acid Dopamine HCL configuration 2.0g/L.
3) the pure titanium sample of processing is first immersed in dopamine solution, the standing 24h of room temperature, prepares titanium/Dopamine HCL sample.After taking-up, through washed with de-ionized water, then immerse in the graphite oxide aqueous solution of 2.0g/L the standing 24h of room temperature.After taking-up, adopt washed with de-ionized water, and room temperature is dried.Make titanium/Dopamine HCL/graphene oxide sample.
Experimentation as shown in Figure 1.By the sample after embodiment 1 acid-alkali treatment, under scanning electronic microscope (S4800 type), observe, from accompanying drawing 2, can see that specimen surface has formed vesicular structure.When sample is at Dopamine HCL--after soaking in tris solution (DA-Tris), as shown in Figure 3, the vesicular structure on surface disappears sample pattern originally, and specimen surface is all covered by Dopamine HCL.And after the sample after Dopamine HCL processing is immersed to graphene oxide, as shown in Figure 4, there is the pleated structure of graphene oxide feature in surface to its pattern.
Sample after subsequently titanium/Dopamine HCL/graphene oxide being processed carries out Raman (laser capture microdissection Raman DXR Microscope) and characterizes, and accompanying drawing 5 is presented at material surface and has occurred 1350cm
-1, and 1600cm
-1the class graphite characteristic peak at place, illustrate graphene oxide mortise to have arrived pure titanium surperficial.And by contrast graphene oxide raw material and titanium/Dopamine HCL/graphene oxide Raman spectrogram, find that the latter has higher fluorescence background, this has also illustrated the existence of Dopamine HCL in the latter.
Dopamine HCL, graphene oxide and titanium/Dopamine HCL/graphene oxide are done to further infrared analysis (Nicolet6700), as accompanying drawing 6.Occurred in the infrared spectrum of Dopamine HCL-NH-(1620cm-1,1504cm-1) characteristic peak, in graphene oxide collection of illustrative plates, there is C=O (1629cm-1),-OH (1462cm-1), 1390cm-1), the characteristic peak of the oxygen-containing functional groups such as C-O (1132cm-1,1096cm-1).In titanium/Dopamine HCL/graphene oxide, there is-OH (1385cm-1) ,-C-O-(1260cm-1) and-C-N-(1081cm-1), prove that Dopamine HCL and graphene oxide have formed firmly chemistry and be connected.But in titanium/Dopamine HCL/graphene oxide infrared spectrum, in graphene oxide 1462cm-1-OH characteristic peak disappears, and the oxygen-containing functional group minimizing of graphene oxide be described, graphene oxide may be by Dopamine HCL partial reduction.In Dopamine HCL, be positioned at 1504cm-1 place-NH characteristic peak disappears, this may be because of the part-NH in Dopamine HCL
2rupture, form new chemical bond with graphene oxide.In addition, titanium/Dopamine HCL/graphene oxide be positioned at 3341cm-1 place-OH characteristic peak is than graphene oxide strength degradation, this may be also because part-OH is removed caused in reaction.
By the pure titanium sample of the acid-alkali treatment of preparing in step 1, titanium/Dopamine HCL of preparing in step 3 and titanium/Dopamine HCL/graphene oxide sample is at 37 ℃, (is collocation method according to Tadashi Kokubo.How useful is SBF in predicting in vivo bone bioactivity for SBF solution? [J] .Biomaterials, 2006, 27:2907-2915.) middle immersion 28 days, its pattern is respectively if (a) in accompanying drawing 7 is (b) as shown in (c), the calcium microcosmic salt deposition that visible same time titanium/Dopamine HCL/graphene oxide surface forms at most, the calcium microcosmic salt that the pure titanium of titanium/Dopamine HCL and acid-alkali treatment surface forms is less, illustrate that graphene oxide contributes to improve the biological activity on pure titanium surface.
Embodiment 2:
1) pure titanium sample is smooth through 600,1000,2000,2500 order liquid honings, successively adopt acetone, deionized water ultrasonic cleaning.Adopt nitric acid (HNO
3) (volume fraction 20%) immersion sample 15min, remove oxide on surface.After washing, sample is immersed to 60 ℃, in 7mol/L sodium hydroxide (NaOH) solution, process 40min, after taking-up, with deionized water, clean remained on surface sodium hydroxide, drying at room temperature.Make the pure titanium sample of acid-alkali treatment.
2) configuration of 2.5g/L Dopamine HCL-tris solution (DA-Tris): the Tutofusin tris buffered soln that first configures pH=8.5.Get 1.21g Tutofusin tris powder dissolution in 800ml deionized water, with 1mol/L hydrochloric acid (HCl) regulator solution pH=8.5, then pour solution into 1000ml volumetric flask and carry out constant volume.Then, get the solution of appropriate hydrochloric acid Dopamine HCL configuration 2.0g/L.
3) the pure titanium sample of processing is first immersed in dopamine solution, the standing 12h of room temperature, prepares titanium/Dopamine HCL sample.After taking-up, through washed with de-ionized water, again immerse in the graphite oxide aqueous solution of 2.5g/L the standing 12h of room temperature.After taking-up, adopt washed with de-ionized water, and room temperature is dried.Make titanium/Dopamine HCL/graphene oxide sample.
Embodiment 3:
1) pure titanium sample is smooth through 600,1000,2000,2500 order liquid honings, successively adopt acetone, deionized water ultrasonic cleaning.Adopt nitric acid (HNO
3) (volume fraction 20%) immersion sample 20min, remove oxide on surface.After washing, sample is immersed to 80 ℃, in 10mol/L sodium hydroxide (NaOH) solution, process 30min, after taking-up, with deionized water, clean remained on surface sodium hydroxide, drying at room temperature.Make the pure titanium sample of acid-alkali treatment.
2) configuration of 3.0g/L Dopamine HCL-tris solution (DA-Tris): the Tutofusin tris buffered soln that first configures pH=8.5.Get 1.21g Tutofusin tris powder dissolution in 800ml deionized water, with 1mol/L hydrochloric acid (HCl) regulator solution pH=8.5, then pour solution into 1000ml volumetric flask and carry out constant volume.Then, get the solution of appropriate hydrochloric acid Dopamine HCL configuration 3.0g/L.
3) the pure titanium sample of processing is first immersed in dopamine solution, the standing 16h of room temperature, prepares titanium/Dopamine HCL sample.After taking-up, through washed with de-ionized water, again soak in 3.0g/L graphite oxide aqueous solution the standing 16h of room temperature.After taking-up, adopt washed with de-ionized water, and room temperature is dried.Make titanium/Dopamine HCL/graphene oxide sample.
Claims (1)
1. one kind is utilized Dopamine HCL to connect the method that graphene oxide improves pure titanium surface bioactive; It is characterized in that step is as follows
1) pure titanium plate surface roughness Ra is not more than 1 μ m, successively adopts acetone ultrasonic cleaning, deionized water ultrasonic cleaning; Then with nitric acid, it is carried out after acid treatment, washed with de-ionized water, recycling sodium hydroxide carries out alkaline purification to sample under 40-80 ℃ of condition;
2) configuration Dopamine HCL-tris solution is pH=8.5;
3) by step 1) in the pure titanium sample processed be immersed in step 2) in the dopamine solution of configuration, the standing 12h-24h of room temperature; Sample is taken out, and by washed with de-ionized water, drying at room temperature, prepares titanium/Dopamine HCL sample.
4) titanium/Dopamine HCL sample is immersed in graphite oxide aqueous solution to the standing 12h-24h of room temperature; After taking out, by washed with de-ionized water, drying at room temperature, makes titanium/Dopamine HCL/graphene oxide sample.
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| CN109440153A (en) * | 2018-11-27 | 2019-03-08 | 河北北方学院 | Microwave-electrochemical preparation method of CuHA/GO/ dopamine composite coating |
| CN111321403A (en) * | 2020-03-10 | 2020-06-23 | 河北北方学院 | Preparation method of dopamine-based zinc surface gallium-loaded graphene oxide composite coating |
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Application publication date: 20141112 |