CN101884807B - Preparation method for borate antibacterial glass coating with bioactivity and application thereof - Google Patents
Preparation method for borate antibacterial glass coating with bioactivity and application thereof Download PDFInfo
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- CN101884807B CN101884807B CN 201010209082 CN201010209082A CN101884807B CN 101884807 B CN101884807 B CN 101884807B CN 201010209082 CN201010209082 CN 201010209082 CN 201010209082 A CN201010209082 A CN 201010209082A CN 101884807 B CN101884807 B CN 101884807B
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Abstract
The invention belongs to the technical field of biological materials, and in particular relates to a preparation method for a borate antibacterial glass coating with bioactivity and application thereof. The preparation method comprises the following steps of: preparing sterilization ion-containing borate glass; smashing and screening the glass; uniformly coating the glass powder onto the surface of an implanted device; performing thermal treatment to make the glass powder have viscosity; and forming an antibacterial coating covered on the surface of the implanted device. The preparation method has the characteristics of simple equipment, easy operation and low cost. The coating of the invention has the bioactivity, can be coated on the surface of the implanted device firmly, and can effectively improve the bioactivity and the antibacterial property of conventional implanted materials.
Description
Technical field
The invention belongs to technical field of biological materials, be specifically related to a kind of preparation method and application thereof with bioactive borate antibacterial glass coating.
Background technology
Titanium alloy (Ti6A14V) is used as load-bearing embedded material, for example blade plate widely due to its good mechanical property and biocompatibility.The shortcoming of materials is there is no direct bonding with human bone, and due to the existence of v element, makes to have certain toxicity.Simultaneously, take blade plate as example, thereby the main method of at present treatment fracture is implanted exactly blade plate and is carried out internal fixation of fracture.Yet there is the situation of a large amount of postoperative infection in internal fixation of fracture, and according to bibliographical information, its infection rate is about 5%～20%.Wherein pin track infection more can cause the serious consequences such as screw loosening, brings great pain to sufferer.
As seen, take present blade plate as example, there is obvious defective in the implantation equipment of many types.They do not have antibiotic property usually, can not adapt to the requirement of operation fully, and people are in the urgent need to its improvement.
Summary of the invention
Purpose of the present invention is overcoming above-mentioned deficiency, and a kind of preparation method that can have the borate glass coating of biological activity and anti-microbial property is provided.
The preparation method of the borate glass coating with biological activity and anti-microbial property that the present invention proposes, concrete steps are as follows:
(1) add the salt that contains the ion of sterilizing in borate glass, after ground and mixed is even, adopt high-temperature melting method to make glass blocks; The glass blocks that gained is contained the ion of sterilizing crushes and screens and obtains uniform particle diameter, mean diameter less than the glass dust of 50um; Described sterilization ion is heavy metal ion, in silver ion, zinc ion or copper ion any; The addition of sterilization ion is the 0.1wt%-15wt% of borate glass quality; Described borate glass Network former is B
2O
3, do not contain or contain on a small quantity SiO
2/ or contain P
2O
5, B wherein
2O
3Content is greater than SiO
2/ P
2O
5Content, total molecule ratio of Network former is 30～90mol%; Network outer body contains CaO, and also contains Na
2O, K
2O alkali metal oxide and MgO, the SrO alkaline earth oxide; Total molecule ratio of network-modifying ion oxide is 5～80mol%; Wherein the molecule ratio of CaO and SrO is respectively 5～60mol%;
(2) by sonic oscillation, step (1) gained glass dust is dispersed in solvent, then along with the volatilization of solvent, glass dust just is deposited on the implantation equipment surface; Or the employing spraying process, the binding agent that will contain glass dust is sprayed on the implantation equipment surface; Or the employing czochralski method, the binding agent that will contain glass dust sticks to the implantation equipment surface;
(3) implantation equipment that step (2) has been deposited glass powder or sticked glass powder is put in Muffle furnace, burns the cinder binding agent at 350-400 ℃ of temperature, is incubated 2-30min under 600～1000 ℃, namely gets required antimicrobial coating.
Utilize the inventive method to obtain having the application of borate glass coating on bone reparation implant of biological activity and anti-microbial property.
Utilize the inventive method to obtain having the borate glass coating of biological activity and anti-microbial property in the application that stimulates on bone cell growth.
Utilize the inventive method to obtain having the borate glass coating application in animal body of biological activity and anti-microbial property.
The present invention be in can regulate by the consumption of glass dust the thickness of gained coating, thereby regulates the content of sterilization ion in coating.Regulate the bond strength of gained coating and implantation equipment by heat treated temperature and time.Regulate the rate of release of sterilization ion in the gained coating by the composition of the sterilization incorporation of ion or glass carrier, thus biological activity and the antibacterial effect of the coating of regulating.By the composition of glass dust, the ratio of various oxides can be regulated biological activity and the biological degradability of glass coating, and to the stimulation of bone cell growth.
The present invention adopts the method for ion sterilization, combine the good mechanical property of traditional implantation equipment and borate glass good biological activity and special construction, and the sterilization ion, silver ion for example, its antimicrobial efficiency is high, little to harm, the advantage of has a broad antifungal spectrum, process equipment is simple, easily operation, with low cost, can effectively reduce in operation by bacterial disease, be applied to simultaneously bone and repair on implant, the effect of obvious stimulation bone cell growth is arranged.
Description of drawings
Fig. 1. the cytocompatibility property testing of the blade plate of argentiferous borate glass coating, measure it to the result of Rat Osteoblast Induced by the MTT colorimetry, illustrate that glass coating has good biocompatibility.
The test of the cytositimulation bone cell growth of the blade plate of Fig. 2 argentiferous borate glass coating is surveyed its cell proliferation quantity by alkali phosphatase (ALP) method, illustrates that glass coating has excellent biological activity, can stimulate bone cell growth.
The blade plate of Fig. 3 argentiferous borate glass coating is imbedded the rabbit tibia after near 10 weeks, the material phase analysis of the surperficial formation of blade plate, and prompting shows that the inorganic mineral that has formed osseous tissue on blade plate forms, hydroxyapatite.The function that this blade plate has stimulates bone cell growth is described.
The specific embodiment
Further illustrate the present invention below by embodiment.
The preparation of embodiment 1 argentiferous borate glass coating
(1) preparation of the borate glass of silver content 1.0%
Take respectively the 2.926g natrium carbonicum calcinatum, 7.107g Anhydrous potassium carbonate, 4.995g basic magnesium carbonate, 10.294g calcium carbonate, 5.694g strontium carbonate, 6.951g silicon dioxide, 29.473g boric acid, 3.419g sodium dihydrogen phosphate, 0.529g silver phosphate.After grinding, fully mix, obtain original ingredient.
Batching is packed into after platinum crucible, put into 1150 ℃ and be incubated 120min, then the fining glass liquid of gained is poured on the steel plate of preheating and obtains glass blocks.
Glass blocks is crushed and screened, obtain mean diameter at the glass particle of 2-50um left and right.
(2) preparation of coating is adopted in following method any:
(1) after the glass particle clean dry of gained in step (), take 0.15g and pack in the 100ml small beaker.
The blade plate of cleaning equally is placed on beaker bottom, then measures the 10ml dehydrated alcohol and pour in small beaker.
Make by sonic oscillation 15min that glass dust is even must be dispersed in ethanol, then beaker is put into 80 ℃ of baking oven dried overnight, obtain the blade plate that surface uniform has precipitated one deck glass dust.
Above-mentioned blade plate is put into 600 ℃ of Muffle furnaces, the rear taking-up in insulation 20min, the glass coating that obtains being evenly distributed.
(2) after the glass particle clean dry with gained in step (), take 4.0g and pack in the 100ml small beaker.Measure 20ml ethanol, take the 1.2g ethyl cellulose.Pour together ball milling 30min in ball grinder after stirring into, make slurry.
Then the blade plate of cleaning is immersed in slurry, lifts out from slurry with the speed of 1cm/min, air-dry after, obtain the blade plate that surface uniform has sticked one deck glass dust.
Above-mentioned blade plate is put into Muffle furnace, be warming up to 460 ℃ with the speed of 2.5 ℃/min with stove, then insulation 1h is warming up to 660 ℃ with 10 ℃/min speed, and insulation 15min takes out the glass coating that obtains being evenly distributed from stove.
(3) standby after the glass particle clean dry with gained in step ().Ethanol is mixed according to the ratio of 1: 3 with water, then the ratio according to 0.1g/ml adds glass dust in solution, together putting into atomization box atomizes, carried through shower nozzle by carrier gas subsequently and be sprayed onto equably the blade plate surface, after air-dry, the blade plate of one deck glass dust that obtained surface uniform deposition.
Above-mentioned blade plate is put into 600 ℃ of Muffle furnaces, the rear taking-up in insulation 20min, the glass coating that obtains being evenly distributed.
Embodiment 2: the anti-microbial property of the coating of argentiferous borate glass coating
According to embodiment 1 method, in formula, add respectively 0.265g, 0.529g at glass, 0.794g the silver phosphate of 1.058g makes respectively that to contain AgO be 0.5,1.0,1.5 and four kinds of glass blocks of 2.0wt%, obtain the lixiviating solution of four kinds of glass coating pieces according to embodiment 2 methods.Separately put escherichia coli ATCC259, staphylococcus aureus ATCC25923 transferred species before test on blood agar plate, is hatched 18h for 35 ℃, and then difference picking escherichia coli and 2～3 bacterium colonies of staphylococcus aureus are in meat soup on blood plate, and 35 ℃ of ovum are educated 2h.Get a certain amount of bacterium liquid with micro sample adding appliance and add successively in the lixiviating solution of being arranged to high concentration by low concentration, result is observed, and is its bacteriostasis property to this bacterium (MIC) without the minimum lixiviating solution concentration of naked eyes visible growth.A certain amount of bacterium liquid of dilution by a certain percentage is inoculated on 2 blood plates, is coated with 35 ℃ and hatches 18h.Calculate the bacterium colony number on blood plate, take the mean and calculate initial quantity of microorganism inoculated.The bacterium colony number is its (going out) bacterium ability (MBC) of killing to this bacterium lower than 0.1% minimum lixiviating solution concentration of initial quantity of microorganism inoculated.
Result shows, the bacteriostasis property of Antibacterial borosilicate glass coating is stronger than the parent glass ability of sterilizing, and does not mix the less antibacterial ability that there is no of silver or silver content.The coating of silver content 2% is all relatively good to the antibacterial and bactericidal effect of escherichia coli and staphylococcus aureus, silver content 1% and 0.75% coating are apparent in view to colibacillary fungistatic effect, but to the killing effect of staphylococcus aureus with regard to weaker (seeing Table 1).Along with the increase of silver content, sterilization effect significantly increases.
Sterilization effect contrast when table 1 silver content is 1.5wt%
Embodiment 3: cupric and contain the bacteriostasis property of zinc-borate glass coating
According to the described method of embodiment 1, in glass formula, change silver phosphate into copper sulfate, add respectively 6.818g, 13.636g, 20.454g CuSO4, make respectively three kinds of borate glasses that copper content is different, and and then to make the copper ion mass percent be 5%, 10%, 15% cupric borate glass coating.Use same method, add respectively zinc oxide 2.172g in glass batch, 4.344g, 6.516g, use the same method make three kinds of zinc ion mass percents be 5%, 10%, 15% contain the zinc-borate glass coating.
Adopt in sterile petri dish to add sterilized ordinary nutrient agar culture medium, make it to cover whole culture dish bottom, thick approximately 2.5mm, more evenly to be coated with concentration be 10
7The escherichia coli of cfu/ml (Escherichia coli) bacterium liquid forms the bacterium liquid film.Cut six 10*10*0.5mm
3Blade plate, wherein upper surface has applied respectively above-mentioned six clock glass coatings, and it is lain against in ware, cultivates 24h under 37 ℃, observes bacterial growth situation around coating sample, measures inhibition zone.
The result demonstration, along with the increase of copper content, inhibition zone enlarges, and bacteriostasis property is strengthened.The bacteriostasis property that contains the zinc-borate glass coating is along with the increase of zinc content is also strengthened, and rule is similar to copper ion, but its bacteriostasis property is a little less than the copper ion gained coating (seeing Table 2) of same mass percentage content.
Table 2
| Antibiotic ion | Addition (mass percent %) | Antibacterial circle diameter (mm) |
| Cu 2+ | 5 | 23 |
| |
10 | 32 |
| Cu 2+ | 15 | 39 |
| Zn 2+ | 5 | 18 |
| |
10 | 27 |
| Zn 2+ | 15 | 35 |
Embodiment 4: the biocompatibility of Antibacterial borosilicate glass coating
According to embodiment 1 method, in formula, add respectively 0.397g, 0.529g, 1.058g silver phosphate, make respectively that to contain AgO be 0.75,1.0 and three kinds of glass coating pieces of 2.0wt%, the glass coating piece of three kinds of different silver contents of gained is immersed in respectively in ethanol 24 hours, uses afterwards washed with de-ionized water 3 times.Then according to 1.25cm
2The ratio of the corresponding 1ml solution of surface area with glass immersion in DMEM cell culture medium or α-MEM cell culture medium.After 24 hours, remove glass blocks, obtain the lixiviating solution of three kinds of glass, and to replenish therein volume ratio be 10% hyclone and 1% mycillin.
Then introduce MC3T3E1 type osteoblast in lixiviating solution, with cell strain with the density plantation in 0.2ml/ hole to the culture dish in 96 holes.Then osteoblast is cultivated in α-MEM culture medium, added 10% hyclone, 100U/ml penicillin, the streptomycin of 100ug/ml in culture medium.Do not add the culture medium of glass lixiviating solution as a control group.All cells is all cultivated under 37 ℃, 5%CO
2In environment.Through the cultivation of 24 hours, estimate the growing state of cell by the MTT colorimetry.
Result shows along with the raising of silver content in borate glass is larger to primary cellular defect, and the borate glass lixiviating solution of silver content 1% and 0.75% is less to the toxicity of cell, and the borate glass lixiviating solution of silver content 2% also (is seen Fig. 1) within the scope that can bear.
Embodiment 5: the stimulation bone cell growth performance of Antibacterial borosilicate glass coating
Make three kinds of different borate glasses of silver content according to embodiment 4, and obtain the lixiviating solution of three kinds of corresponding glass coating pieces.MC3T3-E1 type osteoblast kind in 24 hole culture dishs, is cultivated in blank culture medium or in having added the culture medium of argentiferous borate glass lixiviating solution.Through the cultivation of 48 hours, clean cell twice with PBS, then be placed on 500ul concentration and be in 1% Triton X-100 phosphate buffer, utilize freeze-thaw cycle (80/37 ℃) with cytolysis.The lysate of equal portions is contained in respectively and utilizes its ALP of metric measurement active in the culture dish in 96 holes.
Result shows, having added silver content to be respectively the α-MEM of four groups of borate glass lixiviating solution of 0%, 0.75%, 1.0%, 2.0% and blank α-MEM culture medium affects difference little (seeing Fig. 2) to what the osteoblast performance caused.The result demonstration, these three kinds of silver-containing glass coating blocks all have excellent biological activity, can stimulate the propagation of osteocyte.
Embodiment 6: the effect in animal body of Antibacterial borosilicate glass coating:
According to embodiment 1, get to be made by sedimentation and scribble the borate glass coating blade plate (20x2x0.5mm) that contains silver oxide 1wt%, be embedded to the surface of the tibia of 10 rabbits, then inject near the tibia of rabbit and contain 0.1 milliliter of staphylococcus aureus ATCC25923 milkiness solution, manufacturing contains germy animal model.Imbed the experimental session of rabbit at blade plate, 10 rabbits are not found inflammatory symptom.Take out the blade plate of imbedding in the rabbit body after 10 weeks, do not find bone necrosis's sign, illustrate that the blade plate coating has antibacterial functions; Separate the surperficial formation of blade plate, carry out XRD surface analysis (seeing Fig. 3), prompting shows that this surface formation contains inorganic mineral in osseous tissue, and hydroxyapatite illustrates that the blade plate in the rabbit body has certain stimulation to bone cell growth.
Claims (2)
1. preparation method with borate glass coating of biological activity and anti-microbial property is characterized in that concrete steps are as follows:
(1) add the salt that contains the ion of sterilizing in borate glass, after ground and mixed is even, adopt high-temperature melting method to make glass blocks; The glass blocks that gained is contained the ion of sterilizing crushes and screens and obtains uniform particle diameter, mean diameter less than the glass dust of 50um; Described sterilization ion is heavy metal ion, in silver ion, zinc ion or copper ion any; The addition of sterilization ion is the 0.1wt%-15wt% of borate glass quality; Described borate glass Network former is B
2O
3, do not contain or contain on a small quantity SiO
2/ or contain P
2O
5, B wherein
2O
3Mol% content is greater than SiO
2/ P
2O
5Mol% content, total molecule ratio of Network former is 30～90mol%; Network outer body contains CaO, and also contains Na
2O, K
2O alkali metal oxide and MgO, the SrO alkaline earth oxide; Total molecule ratio of network-modifying ion oxide is 5～80mol%; Wherein the molecule ratio of CaO and SrO is 5～60mol%;
(2) by sonic oscillation, step (1) gained glass dust is dispersed in solvent, then along with the volatilization of solvent, glass dust just is deposited on the implantation equipment surface; Or the employing spraying process, the binding agent that will contain glass dust is sprayed on the implantation equipment surface; Or the employing czochralski method, the binding agent that will contain glass dust sticks to the implantation equipment surface;
(3) implantation equipment that step (2) has been deposited glass powder or sticked glass powder is put in Muffle furnace, burns the cinder binding agent at 350-400 ℃ of temperature, is incubated 2-30min under 600～1000 ℃, namely gets required antimicrobial coating.
One kind as claimed in claim 1 method prepare borate glass coating with biological activity and anti-microbial property and repair application on implant at bone.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140033028A (en) * | 2011-03-28 | 2014-03-17 | 코닝 인코포레이티드 | Antimicrobial action of copper in glass |
| CN102380127A (en) * | 2011-11-09 | 2012-03-21 | 同济大学 | Preparation method and application of antibacterial glass coating of antibacterial bone fracture plate |
| CN103285425B (en) * | 2012-03-01 | 2015-01-07 | 中国科学院上海硅酸盐研究所 | Bio-coating with good anti-degradation property and antibacterial property, and preparation method thereof |
| US9622483B2 (en) | 2014-02-19 | 2017-04-18 | Corning Incorporated | Antimicrobial glass compositions, glasses and polymeric articles incorporating the same |
| US11039620B2 (en) | 2014-02-19 | 2021-06-22 | Corning Incorporated | Antimicrobial glass compositions, glasses and polymeric articles incorporating the same |
| US11039621B2 (en) | 2014-02-19 | 2021-06-22 | Corning Incorporated | Antimicrobial glass compositions, glasses and polymeric articles incorporating the same |
| CN106999622A (en) * | 2014-12-04 | 2017-08-01 | 3M创新有限公司 | Antimicrobial compositions comprising bio-vitric |
| US9789228B2 (en) * | 2014-12-11 | 2017-10-17 | Covidien Lp | Antimicrobial coatings for medical devices and processes for preparing such coatings |
| CN111919857A (en) * | 2020-08-12 | 2020-11-13 | 高时(厦门)石业有限公司 | Preparation method of sterilization powder, sterilization powder and antibacterial inorganic artificial stone using sterilization powder |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4478904A (en) * | 1981-04-08 | 1984-10-23 | University Of Florida | Metal fiber reinforced bioglass composites |
| CN1539512A (en) * | 2003-10-31 | 2004-10-27 | 中国科学院上海硅酸盐研究所 | Biological living being in medical use for Embeded to human body, and preparation method |
| CN1982504A (en) * | 2005-12-16 | 2007-06-20 | 中国科学院金属研究所 | Production of titanium and titanium-alloy glass ceramic coating |
-
2010
- 2010-06-24 CN CN 201010209082 patent/CN101884807B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4478904A (en) * | 1981-04-08 | 1984-10-23 | University Of Florida | Metal fiber reinforced bioglass composites |
| CN1539512A (en) * | 2003-10-31 | 2004-10-27 | 中国科学院上海硅酸盐研究所 | Biological living being in medical use for Embeded to human body, and preparation method |
| CN1982504A (en) * | 2005-12-16 | 2007-06-20 | 中国科学院金属研究所 | Production of titanium and titanium-alloy glass ceramic coating |
Non-Patent Citations (2)
| Title |
|---|
| 硼酸盐玻璃在生物材料领域中的应用;肖伟 等;《中国组织工程研究与临床康复》;20090820;第13卷(第34期);第6741-6744页 * |
| 肖伟 等.硼酸盐玻璃在生物材料领域中的应用.《中国组织工程研究与临床康复》.2009,第13卷(第34期),第6741-6744页. |
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