CN101530633A - Antibacterial argentum-carried hydroxylapatite/carbon nanotube composite artificial bone and preparation thereof - Google Patents
Antibacterial argentum-carried hydroxylapatite/carbon nanotube composite artificial bone and preparation thereof Download PDFInfo
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- CN101530633A CN101530633A CN200910020536A CN200910020536A CN101530633A CN 101530633 A CN101530633 A CN 101530633A CN 200910020536 A CN200910020536 A CN 200910020536A CN 200910020536 A CN200910020536 A CN 200910020536A CN 101530633 A CN101530633 A CN 101530633A
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- carbon nanotube
- argentum
- hydroxylapatite
- artificial bone
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Abstract
The invention discloses an antibacterial argentum-carried hydroxylapatite/carbon nanotube composite artificial bone and a preparation method thereof. Hydroxylapatite/carbon nanotube composite powder prepared by an in situ synthesis method is used as a carrier, and argentum-carried hydroxylapatite/carbon nanotube composite powder is obtained through ion exchange and ion adsorption; and the argentum-carried hydroxylapatite/carbon nanotube composite powder is used as a raw material, and the antibacterial argentum-carried hydroxylapatite/carbon nanotube composite artificial bone is prepared by a hot pressed sintering method. The artificial bone obtained by the method has obvious antibacterial effect, and not only maintains stronger mechanical property and good biological performance of the hydroxylapatite/carbon nanotube composite artificial bone, but also can treat and prevent infection so as to avoid multiple surgeries.
Description
Technical field
The present invention relates to a kind of cmposite artificial bone and preparation method thereof, relate in particular to a kind of antibacterial argentum-carried hydroxylapatite/carbon nanotube cmposite artificial bone and preparation method thereof, belong to biomedical materials field.
Background technology
For a long time, developing ideal biomaterial substitutes and to carry out the important topic that the bone defect repair is medical science and materialogy field always from the body bone.Hydroxyapatite (Hydroxyapatite is called for short HAp) is identical with the inanimate matter composition of natural bone, and therefore structural similarity has good biological activity and biocompatibility, is widely used as bone defect repair and bone clinically and fills shaping material.Yet hydroxyapatite has the general character of such material as a kind of Inorganic Non-metallic Materials: intensity and toughness are very low.CNT has unique metal or semi-conductive electric conductivity, extremely strong mechanical strength, toughness, bigger specific surface area, can be widely used in various high-tech technical fields, is a kind of new-type functional material and structural material.Early-stage Study shows that the adding of CNT can improve the intensity of hydroxyapatite matrix greatly, obtains can be used for the bone renovating material of hard tissue substituting.
On the other hand; Have the active hydroxyapatite of good biological and also be the bacterial adhesion place of providing convenience, the infection that cause at the embedded material interface tends to cause the loosening too early of implant and come off, and the infection even the necrosis of initiation adjacent tissue and organ, cause the failure of performing the operation, also bring the misery of second operation and significant burden economically simultaneously to the patient.At present, few for the damaged Therapeutic Method of infectivity or contaminative bone clinically, take first debridement, drain usually, treat to carry out autologous bone transplanting once more after the infected wound healing.Treatment cycle is long, weak effect.Some scholars are also arranged, compound certain antibiotic of artificial bone is used for the treatment of infectivity or the contaminative bone is damaged, but it is limited because of antibiotic antimicrobial spectrum eventually, use and to make antibacterial produce antibody in about 3 days, cause protein denaturation, thereby the drug resistance phenomenon occurs, and infection is increased the weight of, be difficult to control more.This way has been proved to be one of important channel of clinical drug-resistant bacterial strain increase, is the method for running counter to rational Application antibiotics principle.
In the antibiotic property metal ion, therefore characteristics such as silver ion (Ag+) has antibiotic wide spectrum, germicidal efficiency height, be difficult for developing immunity to drugs are widely used in the inorganic antiseptic.The antibiotic mechanism of carrying silver antimicrobials be silver ion can with the sulfydryl of pheron in the thalline (-SH) combine consumingly, make some enzyme loss of activity, thereby reach sterilization functions as necessary base.But scientific research shows, excessive heavy metal element can cause body to be poisoned, even dead.Therefore, how grasping rational consumption is the content that is related to a key of personal safety.
Summary of the invention
The purpose of this invention is to provide a kind of antibacterial argentum-carried hydroxylapatite/carbon nanotube cmposite artificial bone and preparation method thereof.
Antibacterial argentum-carried hydroxylapatite/carbon nanotube cmposite artificial bone of the present invention is that a kind of ideal anti-infection property artificial bone substitutes and packing material, be adapted at the application in bone wound surgery and the shaping reconstructive surgery, this artificial bone had both kept the stronger mechanical property of hydroxylapatite/carbon nanotube composite artificial bone, good biological property, can treat again and prevention infection simultaneously, avoid repeatedly performing the operation.
Antibacterial argentum-carried hydroxylapatite/carbon nanotube cmposite artificial bone of the present invention is to be that carrier surface absorption silver ion makes with the hydroxylapatite/carbon nanotube composite artificial bone; It is characterized in that: the mass fraction of CNT is 1%～15% in the composition of described cmposite artificial bone; The mass fraction of silver ion is 1%～8%.
Further, the mass fraction preferred 5%～10% of CNT in the composition of described cmposite artificial bone; The mass fraction of silver ion preferred 3%～6%.
Wherein: above-mentioned hydroxylapatite/carbon nanotube composite artificial bone powder body adopts in-situ synthesis to make.
The preparation method of antibacterial argentum-carried hydroxylapatite/carbon nanotube cmposite artificial bone of the present invention, step is that the hydroxylapatite/carbon nanotube composite granule for preparing with in-situ synthesis is a raw material, utilize ion exchange and ion adsorption to prepare the argentum-carried hydroxylapatite/carbon nanotube composite granule, adopt hot pressed sintering to prepare the antibiotic property cmposite artificial bone then.
Further concrete preparation method, realized by following steps:
1) taking by weighing the CNT mass fraction is 1%～15% hydroxylapatite/carbon nanotube powder body, joins in the deionized water, and ultrasonic wave concussion 20～100min forms steady suspension;
2) take by weighing a certain amount of silver nitrate, it is joined in the deionized water, be made into weight percent concentration and be 1% silver nitrate solution;
3) be 1%～8% according to the silver ion mass fraction, measure corresponding step 2) silver nitrate solution of gained, under stirring condition, slowly join in the prepared suspension of step 1), be to stir 60～300min under 20～60 ℃ the condition in temperature, the precipitation that forms is centrifugal in a usual manner, alcohol is washed, drying, gets the argentum-carried hydroxylapatite/carbon nanotube composite granule;
4) with step 3) gained composite granule under nitrogen protection, with 1100 ℃ ± 30 ℃ the insulation 20min ± 5min conditions carry out hot pressed sintering, promptly get the antibacterial argentum-carried hydroxylapatite/carbon nanotube cmposite artificial bone.
In the above-mentioned method for preparing the antibacterial argentum-carried hydroxylapatite/carbon nanotube cmposite artificial bone:
CNT mass fraction preferred 5%～10% in the described hydroxylapatite/carbon nanotube powder body of step 1); Preferred 30～60min of the time of ultrasonic wave concussion.
The silver ion mass fraction preferred 3%～6% of the described silver nitrate solution of step 3).
Preferred 30～50 ℃ of the described whipping temp of step 3), the preferred 100～200min of mixing time.
The described alcohol of step 3) is washed preferred employing 75% alcoholic solution.
The programming rate of the described hot pressed sintering temperature of step 4) is 40 ℃/min preferably
In the present invention, adopt the hydroxylapatite/carbon nanotube composite granule as carrier material.Composite granule comes from the ion exchange of calcium ion in silver ion and the hydroxyapatite on the one hand for the load effect of silver ion, comes from the adsorption between CNT and the silver ion on the other hand.In the former, because two kinds of ionic charge differences, and ionic radius differs greatly, so Ag
+To Ca
2+Replacement mostly occur on the surface of carrier, be difficult to enter into intracell and go, thus its year silver-colored poor effect.Utilize high temperature action, can impel the Ag of carrier surface
+Deeply be diffused into intracell and go, thereby obtain the more stable silver-colored effect of carrying, this is the reason that high-temperature calcination can be put forward high silver supported effect.When carrying out high-temperature calcination for a common year aluminium powder, Ag
+The phenomenon that dissipation takes place is very outstanding, is unfavorable for carrying out high-temperature calcination.In the present invention, hydroxyapatite is a kind of powder body that is in nanomorphic in the gained argentum-carried hydroxylapatite/carbon nanotube composite granule, and it has very strong adsorption effect, can adsorb a large amount of Ag
+, also be in a kind of upper state simultaneously, have extremely strong reactivity.In the hot pressed sintering process,, make Ag by lattice deformability
+Be deep into intracell, reached and carried silver-colored effect preferably.
The present invention has following outstanding beneficial effect:
The present invention be directed to present infectivity and the damaged case of contaminative bone, overcome can substituting and packing material by antimicrobial artificial bone that the shortcoming of common artificial bone finds out.Because being written into of silver ion be before forming materials, so material inside and outside concentration of silver ions homogeneous relatively, can guarantee that silver ion degrades in a long time.Like this, on the one hand can play antibiotic effectively, sterilization functions, the infection once again of protecting from infection property and contaminative bone defect, on the other hand, can the sense of acceleration metachromia and the healing of contaminative bone defect.Experimental results show that further the prepared argentum-carried hydroxylapatite/carbon nanotube composite artificial bone of the present invention all reaches 100% to escherichia coli and staphylococcus aureus 24h bacteriostasis rate.
The specific embodiment
Embodiment 1
1) take by weighing 5g hydroxylapatite/carbon nanotube powder body (CNT mass fraction 5%), join in the 100mL deionized water, ultrasonic wave concussion 30min forms steady suspension;
2) take by weighing the 1g silver nitrate, join in the 100mL deionized water, be made into silver nitrate solution;
3) measure 10mL such as step 2) the gained silver nitrate solution, under mechanical agitation, slowly join in the described suspension of step 1);
4) step 3) gained suspension is stirred down 60min at 20 ℃, the gained precipitation through centrifugal, alcohol is washed, drying, obtains the argentum-carried hydroxylapatite/carbon nanotube composite granule;
5) with step 4) gained composite granule hot pressed sintering (nitrogen protection, 1100 ℃ of insulation 20min, 40 ℃ of programming rates/min), can obtain the antibacterial argentum-carried hydroxylapatite/carbon nanotube cmposite artificial bone.
Embodiment 2
1) take by weighing 5g hydroxylapatite/carbon nanotube powder body (CNT mass fraction 10%), join in the 100mL deionized water, ultrasonic wave concussion 30min forms steady suspension;
2) take by weighing the 1g silver nitrate, join in the 100mL deionized water, be made into silver nitrate solution;
3) measure 50mL such as step 2) the gained silver nitrate solution, under mechanical agitation, slowly join in the described suspension of step 1);
4) step 3) gained suspension is stirred down 60min at 30 ℃, the gained precipitation through centrifugal, 75% (v/v) ethanol is washed, drying, obtains the argentum-carried hydroxylapatite/carbon nanotube composite granule;
5) with step 4) gained composite granule hot pressed sintering (nitrogen protection, 1100 ℃ of insulation 20min, 40 ℃ of programming rates/min), can obtain the antibacterial argentum-carried hydroxylapatite/carbon nanotube cmposite artificial bone.
Embodiment 3
1) take by weighing 5g hydroxylapatite/carbon nanotube powder body (CNT mass fraction 15%), join in the 100mL deionized water, ultrasonic wave concussion 30min forms steady suspension;
2) take by weighing the 1g silver nitrate, join in the 100mL deionized water, be made into silver nitrate solution;
3) measure 20mL such as step 2) the gained silver nitrate solution, under mechanical agitation, slowly join in the described suspension of step 1);
4) step 3) gained suspension is stirred down 80min at 40 ℃, the gained precipitation through centrifugal, alcohol is washed, drying, obtains the argentum-carried hydroxylapatite/carbon nanotube composite granule;
5) with step 4) gained composite granule hot pressed sintering (nitrogen protection, 1100 ℃ of insulation 20min, 40 ℃ of programming rates/min), can obtain the antibacterial argentum-carried hydroxylapatite/carbon nanotube cmposite artificial bone.
In-situ synthesis is adopted in the preparation of the powder body of hydroxylapatite/carbon nanotube described in the foregoing description, see for details " Lu Zhihua, Sun Kangning, Zhao Zhongfan. the synthetic preparation of original position carbon nanometer tube/hydroxyapatite composite granule. 35 2 phases of volume of silicate journal .2007 ".
The resulting argentum-carried hydroxylapatite of above-mentioned 3 embodiment/magnetic nanotube cmposite artificial bone sample carries out following detection:
Analysis confirms through Rigaku D/MAX-VA-X-ray diffractometer: argentum-carried hydroxylapatite/carbon nanotube composite artificial bone is the complex of hydroxyapatite and CNT.
Energy spectrum analysis confirms through JEM-100Cx II: argentum-carried hydroxylapatite/carbon nanotube composite artificial bone contains calcium, phosphorus, oxygen and silver element.
Measure and the confirmation of bacteriostasis rate mensuration through minimal inhibitory concentration (MIC): argentum-carried hydroxylapatite/carbon nanotube composite artificial bone all has good bactericidal action to escherichia coli and staphylococcus aureus, and its 24h bacteriostasis rate all reaches 100%.
Claims (10)
1, a kind of antibacterial argentum-carried hydroxylapatite/carbon nanotube cmposite artificial bone is to be that carrier surface absorption silver ion makes with the hydroxylapatite/carbon nanotube composite artificial bone; It is characterized in that: the mass fraction of CNT is 1%～15% in the composition of described cmposite artificial bone; The mass fraction of silver ion is 1%～8%.
2, antibacterial argentum-carried hydroxylapatite/carbon nanotube cmposite artificial bone as claimed in claim 1 is characterized in that: the mass fraction of CNT is 5%～10% in the composition of described cmposite artificial bone; The mass fraction of silver ion is 3%～6%.
3, antibacterial argentum-carried hydroxylapatite/carbon nanotube cmposite artificial bone as claimed in claim 1 is characterized in that: described hydroxylapatite/carbon nanotube composite artificial bone powder body adopts in-situ synthesis to make.
4, the preparation method of claim 1 or 2 described antibacterial argentum-carried hydroxylapatite/carbon nanotube cmposite artificial bones, step is that the hydroxylapatite/carbon nanotube composite granule for preparing with in-situ synthesis is a raw material, utilize ion exchange and ion adsorption to prepare the argentum-carried hydroxylapatite/carbon nanotube composite granule, adopt hot pressed sintering to prepare the antibiotic property cmposite artificial bone then.
5, as the preparation method of antibacterial argentum-carried hydroxylapatite/carbon nanotube cmposite artificial bone as described in the claim 4, it is characterized in that: realize by following steps:
1) taking by weighing the CNT mass fraction is 1%～15% hydroxylapatite/carbon nanotube powder body, joins in the deionized water, and ultrasonic wave concussion 20～100min forms steady suspension;
2) take by weighing a certain amount of silver nitrate, it is joined in the deionized water, be made into weight percent concentration and be 1% silver nitrate solution;
3) be 1%～8% according to the silver ion mass fraction, measure corresponding step 2) silver nitrate solution of gained, under stirring condition, slowly join in the prepared suspension of step 1), be to stir 60～300min under 20～60 ℃ the condition in temperature, the precipitation that forms is centrifugal in a usual manner, alcohol is washed, drying, gets the argentum-carried hydroxylapatite/carbon nanotube composite granule;
4) with step 3) gained composite granule under nitrogen protection, with 1100 ℃ ± 30 ℃ the insulation 20min ± 5min conditions carry out hot pressed sintering, promptly get the antibacterial argentum-carried hydroxylapatite/carbon nanotube cmposite artificial bone.
6, the method for preparing the antibacterial argentum-carried hydroxylapatite/carbon nanotube cmposite artificial bone as claimed in claim 5 is characterized in that: the CNT mass fraction selects 5%～10% in the described hydroxylapatite/carbon nanotube powder body of step 1); The time of ultrasonic wave concussion is selected 30～60min.
7, the method for preparing the antibacterial argentum-carried hydroxylapatite/carbon nanotube cmposite artificial bone as claimed in claim 5 is characterized in that: the silver ion mass fraction of the described silver nitrate solution of step 3) selects 3%～6%.
8, the method for preparing the antibacterial argentum-carried hydroxylapatite/carbon nanotube cmposite artificial bone as claimed in claim 5 is characterized in that: the described whipping temp of step 3) selects 30～50 ℃, and mixing time is selected 100～200min.
9, the method for preparing the antibacterial argentum-carried hydroxylapatite/carbon nanotube cmposite artificial bone as claimed in claim 5 is characterized in that: the described alcohol of step 3) is washed and is adopted 75% alcoholic solution.
10, the method for preparing the antibacterial argentum-carried hydroxylapatite/carbon nanotube cmposite artificial bone as claimed in claim 5 is characterized in that: the programming rate of the described hot pressed sintering temperature of step 4) is 40 ℃/min.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101797399A (en) * | 2010-04-15 | 2010-08-11 | 四川大学 | Biomedical material with silver-ion-bearing hydroxyapatite coating and preparation method thereof |
| WO2011139136A1 (en) * | 2010-05-06 | 2011-11-10 | Universiti Sains Malaysia | Calcium phosphate cement composition and method of making the same |
| CN105174960A (en) * | 2015-09-06 | 2015-12-23 | 内蒙古工业大学 | Preparation method of carbon nanotube/fluorohydroxylapatite biological compound ceramic material |
| CN105561920A (en) * | 2015-09-07 | 2016-05-11 | 济南大学 | Method for preparing magnetic adsorption material with silver/multi-walled carbon nano-tubes and application of magnetic adsorption material |
| CN106942959A (en) * | 2015-12-23 | 2017-07-14 | 银未来株式会社 | Antimicrobial product and its manufacture method |
| CN109645603A (en) * | 2018-12-04 | 2019-04-19 | 广州甚多服装有限公司 | A kind of antibacterial thermal insulating polyurethane composite material and its preparation process |
| US10470463B2 (en) | 2015-12-23 | 2019-11-12 | Silver Future Co., Ltd. | Antibacterial product and method of manufacturing the same |
-
2009
- 2009-04-17 CN CN200910020536A patent/CN101530633A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101797399A (en) * | 2010-04-15 | 2010-08-11 | 四川大学 | Biomedical material with silver-ion-bearing hydroxyapatite coating and preparation method thereof |
| WO2011139136A1 (en) * | 2010-05-06 | 2011-11-10 | Universiti Sains Malaysia | Calcium phosphate cement composition and method of making the same |
| CN105174960A (en) * | 2015-09-06 | 2015-12-23 | 内蒙古工业大学 | Preparation method of carbon nanotube/fluorohydroxylapatite biological compound ceramic material |
| CN105561920A (en) * | 2015-09-07 | 2016-05-11 | 济南大学 | Method for preparing magnetic adsorption material with silver/multi-walled carbon nano-tubes and application of magnetic adsorption material |
| CN106942959A (en) * | 2015-12-23 | 2017-07-14 | 银未来株式会社 | Antimicrobial product and its manufacture method |
| US10470463B2 (en) | 2015-12-23 | 2019-11-12 | Silver Future Co., Ltd. | Antibacterial product and method of manufacturing the same |
| CN109645603A (en) * | 2018-12-04 | 2019-04-19 | 广州甚多服装有限公司 | A kind of antibacterial thermal insulating polyurethane composite material and its preparation process |
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Application publication date: 20090916 |