CN1295965C - Inorganic mesoporous antiseptic material and its preparing method - Google Patents
Inorganic mesoporous antiseptic material and its preparing method Download PDFInfo
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- CN1295965C CN1295965C CNB2004100666663A CN200410066666A CN1295965C CN 1295965 C CN1295965 C CN 1295965C CN B2004100666663 A CNB2004100666663 A CN B2004100666663A CN 200410066666 A CN200410066666 A CN 200410066666A CN 1295965 C CN1295965 C CN 1295965C
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Abstract
The present invention relates to inorganic mesoporous antiseptic materials carrying zinc oxide (ZnO) or silver (Ag) nanometer particles and a preparing method thereof. The preparing method of the materials comprises the following processes: firstly, dissolving mesoporous materials and inorganic metallic salts in a volatile solvent, and uniformly agitating the mixture; successively, placing the mixture in air to volatilize the solvent; then, directly roasting or roasting at high temperature under the protection of nitrogen to make the metallic salts decomposed thoroughly and crystallized; finally, obtaining the required mesoporous antiseptic materials in the form of powder. The materials retain the ordered pore canal structure, the larger specific surface area and the larger pore volume of the original inorganic mesoporous materials. Compared with zinc oxide or silver nanometer particles obtained by the conventional method, the obtained zinc oxide or silver nanometer particles have the characteristics of smaller size, narrower particle diameter distribution, better sterilizing effect, etc. The lower limit of the effective bactericidal concentration of the inorganic mesoporous antiseptic materials is above two orders of magnitude lower than that of the effective bactericidal concentration of the existing reported similar materials.
Description
Technical field
The invention belongs to technical field of inorganic material, be specifically related to inorganic mesoporous antiseptic material of a kind of ZnO of being loaded with or Ag nano particle and preparation method thereof.
Technical background
Japan had taken place after the pathogenic Escherichia coli O-157 infection incident of nationwide in 1996, and the huge fear in the global range brought of SARS virus has especially in recent years started the upsurge of one research antibacterial agent and normal temperature bactericidal assay all over the world.Wherein, the inorganic metal anti-biotic material is because its lasting effectively antibacterial action has caused people's great interest again.A large amount of anti-biotic materials is applied to industries such as weaving, pottery, coating widely.Experiment showed, with organic antibacterial agent and compare, characteristics such as they have antibiotic wide spectrum, germicidal efficiency height, be difficult for developing immunity to drugs, to Escherichia coli, Pseudomonas aeruginosa, salmonella etc. have strong killing action.
Inorganic metal is combined with carrier as antibacterial agent, make the slow release anti-biotic material, compare, show huge superiority with non-slow release anti-biotic material.The slow release material can be kept permanently effective concentration of metal ions owing to can discharge metal ion lentamente in long-time, thereby has that anti-microbial property is stable, a long sterilizing time, advantage such as easy to use.In addition, because carrier material has huge surface area, and abundant pore structure, bacterium is had good adsorption capacity.So it is at present deep day by day to the research of the anti-microbial property of the anti-biotic material of various slow release zinc oxide, magnesia, calcium oxide, titanium oxide and silver etc. and antibiotic mechanism.
In the inorganic antibacterial material of support type, the size of inorganic metal (metal oxide) particle has decisive influence to its bactericidal properties.Result of study shows that particle is more little, and their bactericidal effect is just strong more.Therefore, an important channel of improving the antibacterial agent activity is to reduce and control particle grain size.But, metal (metal oxide) particle grain size that the tradition route of synthesis obtains is usually at micron number magnitude (μ m), and particle diameter distributes very wide, can not be controlled artificially, about 10nm or the synthetic method of the nano particle of littler and controllable grain size do not see report, these restrictions have directly influenced their application prospects in antibiotic field.
Summary of the invention
The objective of the invention is to propose good inorganic mesoporous antiseptic material of a kind of bactericidal effect and preparation method thereof.
The inorganic mesoporous antiseptic material that the present invention proposes, be to be inorganic carrier with meso pore silicon oxide material or meso-porous carbon material, load zinc oxide (ZnO) or silver (Ag) nano particle are formed, and the average grain diameter of ZnO or Ag nano particle is 2-12nm, and can be by the aperture adjustment of carrier material.
In the inorganic carrier that the present invention adopts, meso pore silicon oxide material makes by the surfactant templates method, SBA-15, the MCM-41 (p6mm) that comprise the bidimensional hexagonal structure, SBA-2, the FDU-1 (P63/mmc) of three-dimensional hexagonal structure, the SBA-16 of body-centered cubic structure (Im-3m), FDU-5, the KIT-6 of the co-continuous pore passage structure of three-dimensional communication, MCM-48 (Ia-3d), the SBA-1 of simple cubic structure (Pm-3m); The carbon mesoporous material is the above-mentioned various meso pore silicon oxide material mesoporous material that anti-phase filling obtains as hard template.
The preparation method of the inorganic mesoporous antiseptic material that the present invention proposes is as follows: at first will be dissolved in volatile solvent as the inorganic mesoporous material of carrier and the predecessor inorganic metal salt of zinc or silver, and stir; In air, place again, make solvent evaporates, pass through roasting direct or high-temperature roasting under nitrogen protection then, inorganic metal salt is decomposed and crystallization fully, promptly obtain desired mesoporous antiseptic material.
Among the present invention, meso-porous carbon material need pass through oxidation pre-treatment, and oxidant can adopt the concentrated sulfuric acid, red fuming nitric acid (RFNA), hydrogen peroxide and chloroazotic acid.
Among the present invention, predecessor can adopt labile inorganic zinc salt (as zinc nitrate, zinc acetate, zinc chloride, zinc citrate, zinc oxalate), with preparation ZnO nano particle; Predecessor adopts silver nitrate, with preparation Ag nano particle.
Among the present invention, the volatile solvent that disperses inorganic metal salt (being aforementioned predecessor) is the mixed solvent of ethanol, propyl alcohol, butanols, acetone, ether, acetonitrile, water one of them or they
Each preparation process further describes as follows among the present invention:
1. mesoporous material and inorganic metal salt form homodisperse solution: meso pore silicon oxide material or meso-porous carbon material and inorganic metal salt are dissolved in the volatile solvent, and the mole of inorganic metal salt and the mass ratio of mesoporous material are 10
-2-10
-5Mol/g, and on magnetic stirring apparatus, stirred 0.5-6 hour, make it even mixing.
2. the volatilization of solvent: will by the resulting solution of abovementioned steps uncovered evaporate into dried, this moment the temperature hold in range be 5-80 ℃.
3. thermal treatment: will be by the powder transfer of the resulting volatile dry of abovementioned steps to crucible or porcelain boat.There is the meso pore silicon oxide material of inorganic zinc salt (zinc source) to place Muffle furnace load, made zinc salt decompose crystallization, promptly obtain the mesopore silicon oxide anti-biotic material of loading ZnO at 350-900 ℃ of following roasting 3-10 hour; There is the meso pore silicon oxide material of silver nitrate (silver-colored source) to place tube furnace load, under nitrogen protection, made silver salt decompose crystallization, promptly obtain the mesopore silicon oxide anti-biotic material of loaded Ag at 300-500 ℃ of following roasting 3-10 hour; Have the meso-porous carbon material of inorganic zinc salt (zinc source) to place tube furnace load, nitrogen protection made zinc salt decompose crystallization at 350-900 ℃ of following roasting 3-10 hour, promptly obtained the mesoporous carbon anti-biotic material of loading ZnO; Have the meso-porous carbon material of silver nitrate (silver-colored source) to place tube furnace load, nitrogen protection made silver salt decompose crystallization at 300-500 ℃ of following roasting 3-10 hour, promptly obtained the mesoporous carbon anti-biotic material of loaded Ag.
Among the present invention, the inorganic metal source be by with the interaction of mesoporous material inner surface, effect enters the inside, duct of material by capillary condensation, and decomposes crystallization in inside.
Among the present invention, ZnO that obtains or Ag nano particle average grain diameter can be regulated in the scope of 2-12nm by the aperture of carrier.
The inorganic mesoporous antiseptic material of the present invention preparation has kept the orderly pore passage structure of carrier material, the big and aperture of homogeneous, bigger specific surface area and pore volume, and the ZnO of acquisition or Ag nanoparticle size are less and controlled, have improved the antibacterial effect of material greatly.
Among the present invention, the antibiotic property of the material for preparing adopts colony counting method to carry out quantitative assay.For microorganism, the unicellular equal of each work can be bred into a bacterium colony in the time of can thinking high dilution in theory, thereby can make each living cells grow into an independent bacterium colony, and remove to calculate remaining viable count in the sample by the clump count that grows with cultured method.
Among the present invention, the bacterial classification of employing is Escherichia coli, staphylococcus aureus, Pseudomonas aeruginosa, black-koji mould, Penicillium notatum etc.
Among the present invention, the step of the colony counting method of employing is as follows: at first with the bacterial classification constant temperature culture; In bacterium liquid, add anti-biotic material again, constant temperature culture in shaking table; Get then on the solid agar medium that bacterium liquid is coated on culture dish, in baking oven, cultivate; Write down the bacterium colony number at last, be the number of bacterium in the coated plate bacterium liquid.Here the e. coli bl21 with anti-ammonia benzyl is that bacterial classification is an example, and the concrete steps of colony counting method are described:
1. spawn culture: get 3-20 microlitre bacterial classification, 3 microlitre ammonia benzyls join in the test tube that 3 milliliters of aqua sterilisas are housed, in shaking table under the condition of 31-38 ℃, rotating speed 1000-4000 rev/min, constant temperature culture 8-12 hour.
2. the introducing of anti-biotic material: bacterium liquid that the 3-20 microlitre is obtained by step 1 and 3 microlitre ammonia benzyls join in 3 test tubes that 3 milliliters of aqua sterilisas are housed respectively, fully mix the back and add 0.01-0.5 gram anti-biotic material (1 respectively to 2 test tubes wherein
#), the non-loaded mesoporous material (2 of 0.01-0.5 gram (should with anti-biotic material uniform quality)
#), another test tube does not add any material (blank group, 3
#).In shaking table under the condition of 31-38 ℃, rotating speed 1000-4000 rev/min, constant temperature culture 8-48 hour.
3. coated plate: will by step 2 obtain 1
#Bacterium liquid evenly dilutes doubly back (not diluting usually) of 0-100 with aqua sterilisa, gets on the solid agar medium that the 0.1-1 milliliter spreads upon culture dish equably, is placed on and cultivates 12-24 hour in 37 ℃ of baking ovens.By step 2 obtain 2
#With 3
#Bacterium liquid is with the doubly back (being generally 10000) that aqua sterilisa evenly dilutes 100-10000, gets on the solid agar medium that the 0.1-1 milliliter spreads upon culture dish equably, is placed on and cultivates 12-24 hour in 37 ℃ of baking ovens.
4. counting: write down respectively that bacterium colony gets number in each culture dish that is obtained by step 3, be the number of bacterium in each coated plate bacterium liquid.
Among the present invention, the calculating principle of colony counting method is: material adsorption rate=(3
#Bacterium colony number * extension rate-2
#Bacterium colony number * extension rate) ÷ (3
#Bacterium colony number * extension rate); Material sterilizing rate=(3
#Bacterium colony number * extension rate-1
#Bacterium colony number * extension rate) ÷ (3
#Bacterium colony number * extension rate).
Among the present invention, the bactericidal effect of the material that obtains improves greatly, when load concentration is 10
-4During mol/g, this material of 0.05g is 10 for the 3mL bacterial concentration
7The adsorption rate of the colibacillary concentrated solution of CFU/mL is 15%-95%, and sterilizing rate is more than 99.99%.The same type of material of having reported for work is compared, and minimal effective concentration has descended 2 more than the order of magnitude.
Embodiment
Embodiment 1, and being loaded with the ZnO concentrations of nanoparticles is 10
-3(or 10
-4) preparation of mesopore silicon oxide (SBA-15, SBA-16, FDU-1, FDU-5) anti-biotic material of mol/g: 1g meso pore silicon oxide material (SBA-15, SBA-16, FDU-1, FDU-5) and 0.001 (or 0.0001) mol Zn (NO)
36H
2O is dissolved in the 50ml ethanol, stirs 2-3 hour.Slowly volatilization is dried down at 20 ℃.Be transferred to then in the Muffle furnace, control 550 ℃ of roastings 6 hours, promptly obtaining loading ZnO nano particles concentration is 10
-3(or 10
-4) the mesopore silicon oxide anti-biotic material of mol/g.
Embodiment 2, and being loaded with the Ag concentrations of nanoparticles is 10
-3(or 10
-4) preparation of mesopore silicon oxide (SBA-15, SBA-16, FDU-1, FDU-5) anti-biotic material of mol/g: 1g meso pore silicon oxide material (SBA-15, SBA-16, FDU-1, FDU-5) and 0.001 (or 0.0001) mol AgNO
3Be dissolved in the mixed solvent of 25ml ethanol and 25ml water, stirred 2-3 hour.20 ℃ of slowly volatilizations down.Be transferred to then in the tube furnace, 400 ℃ of roastings of control are 6 hours under nitrogen protection, and promptly obtaining the loaded Ag concentrations of nanoparticles is 10
-3(or 10
-4) the mesopore silicon oxide anti-biotic material of mol/g.
Embodiment 3, and being loaded with the ZnO concentrations of nanoparticles is 10
-3(or 10
-4) preparation of mesoporous carbon (CMK-3) anti-biotic material of mol/g: 1g meso-porous carbon material (CMK-3) and 0.001 or (0.0001) mol Zn (NO)
36H
2O is dissolved in the 50ml ethanolic solution, stirs 2-3 hour.20 ℃ of slowly volatilizations down.Be transferred to then in the tube furnace, 550 ℃ of roastings of control are 6 hours under nitrogen protection, and promptly obtaining loading ZnO nano particles concentration is 10
-3(or 10
-4) the mesoporous carbon anti-biotic material of mol/g.
Embodiment 4, and being loaded with the Ag concentrations of nanoparticles is 10
-3(or 10
-4) preparation of mesoporous carbon (CMK-3) anti-biotic material of mol/g: 1g meso-porous carbon material (CMK-3) and 0.001 (or 0.0001) mol AgNO
3Be dissolved in the mixed solvent of 25ml ethanol and 25ml water, stirred 2-3 hour.20 ℃ of slowly volatilizations down.Be transferred to then in the tube furnace, 400 ℃ of roastings of control are 6 hours under nitrogen protection, and obtaining the loaded Ag concentrations of nanoparticles is 10
-3(or 10
-4) the mesoporous carbon anti-biotic material of mol/g.
Embodiment 5, and being loaded with ZnO or Ag concentrations of nanoparticles is 10
-3Or 10
-4The mensuration of the anti-microbial property of the mesopore silicon oxide of mol/g (SBA-15, SBA-16, FDU-1, FDU-5) anti-biotic material: 10 microlitre e. coli bl21s and 3 microlitre ammonia benzyls are added 3 milliliters of aqua sterilisas, in shaking table, under the condition of 37 ℃ of constant temperature, 3000 rev/mins of rotating speeds, cultivated 8 hours.Bacterium liquid and the 3 microlitre ammonia benzyls of respectively getting 10 microlitres join in 3 test tubes that 3 milliliters of aqua sterilisas are housed, and fully mix the back and add 0.05g anti-biotic material (1 respectively to 2 test tubes wherein
#), the non-loaded mesoporous material (2 of 0.05g
#), another test tube is as blank group (3
#).Under the condition of 3000 rev/mins of 37 ℃, rotating speed, constant temperature culture is 24 hours again in shaking table.Get 0.2 milliliter 1 then
#Test tube bacterium liquid spreads upon on the solid agar medium of culture dish equably, is placed in 37 ℃ of baking ovens to cultivate 24 hours.Get 10 microlitres 2
#With 3
#Test tube bacterium liquid after 10000 times of the even dilutions of aqua sterilisa, is got 0.2 milliliter of dilution bacterium liquid, spreads upon equably on the solid agar medium of culture dish, is placed in 37 ℃ of baking ovens and cultivates 24 hours.Write down the number of bacterium colony in each culture dish.It is that the adsorption rate to bacterium of material of carrier is 97.3% that experiment draws with SBA-15, load 10
-3Sterilizing rate is 100% during mol/g Ag, load 10
-4Sterilizing rate is 100% during mol/g Ag, load 10
-3Sterilizing rate is 100% during mol/g ZnO, load 10
-4Sterilizing rate is 99.9975% during mol/g ZnO; The adsorption rate that with SBA-16 is the material of carrier is 35.3%, load 10
-3Sterilizing rate is 100% during mol/g Ag, load 10
-4Sterilizing rate is 100% during mol/g Ag, load 10
-3Sterilizing rate is 100% during mol/g ZnO, load 10
-4Sterilizing rate is 100% during mol/g ZnO; The adsorption rate that with FDU-1 is the material of carrier is 74.3%, load 10
-3Sterilizing rate is 100% during mol/g Ag, load 10
-4Sterilizing rate is 100% during mol/g Ag, load 10
-3Sterilizing rate is 100% during mol/g ZnO, load 10
-4Sterilizing rate is 99.9999% during mol/gZnO; The adsorption rate that with FUD-5 is the material of carrier is 17.4%, load 10
-3Sterilizing rate is 100% during mol/gAg, load 10
-4Sterilizing rate is 100% during mol/g Ag, load 10
-3Sterilizing rate is 100% during mol/g ZnO, load 10
-4Sterilizing rate is 100% during mol/g ZnO.
Claims (7)
1. an inorganic mesoporous antiseptic material is characterized in that with the meso pore silicon oxide material being inorganic carrier, and loading ZnO nano particles is formed, and the average grain diameter of ZnO nano particle is 2-12nm, and can be by the aperture adjustment of carrier material.
2. inorganic mesoporous antiseptic material according to claim 1, it is characterized in that described meso pore silicon oxide material is made by the surfactant templates method, be SBA-15, the MCM-41 of bidimensional hexagonal structure, SBA-2, the FDU-1 of three-dimensional hexagonal structure, the SBA-16 of body-centered cubic structure, FDU-5, KIT-6, the MCM-48 of the co-continuous pore passage structure of three-dimensional communication, the SBA-1 of simple cubic structure.
3. the preparation method of an inorganic mesoporous antiseptic material as claimed in claim 1 or 2 is characterized in that at first the predecessor inorganic metal salt of meso pore silicon oxide material and zinc is dissolved in volatile solvent, stirs; In air, place again, make solvent evaporates; Pass through roasting direct or high-temperature roasting under nitrogen protection then, slaine is decomposed and crystallization fully, promptly obtain desired inorganic mesoporous antiseptic material.
4. preparation method according to claim 3 is characterized in that described predecessor adopts labile inorganic zinc salt: zinc nitrate, zinc acetate, zinc chloride, zinc citrate, zinc oxalate, and with preparation ZnO nano particle.
5. preparation method according to claim 3, the volatile solvent that it is characterized in that dissolving inorganic metal salt is the mixed solvent of ethanol, propyl alcohol, butanols, acetone, ether, acetonitrile, water one of them or they.
6. preparation method according to claim 3, when it is characterized in that meso pore silicon oxide material and inorganic metal salt form homodisperse solution, the mole of inorganic metal salt and the mass ratio of meso pore silicon oxide material are 10
-2-10
-5Mol/g, and on magnetic stirring apparatus, stirred 0.5-6 hour, make it even mixing; During solvent evaporates, temperature remains 5-80 ℃.
7. preparation method according to claim 3, when it is characterized in that thermolysis, there is the meso pore silicon oxide material of inorganic zinc salt to place Muffle furnace load, made zinc salt decompose crystallization, promptly obtain the mesopore silicon oxide anti-biotic material of loading ZnO at 350-900 ℃ of following roasting 3-10 hour.
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| CN1295965C true CN1295965C (en) | 2007-01-24 |
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| CN101744002B (en) * | 2009-12-29 | 2012-11-21 | 浙江理工大学 | Silicon-zinc mesoporous material silver-carrying antibacterial agent and preparation method thereof |
| CN102649060B (en) * | 2011-02-24 | 2014-04-30 | 中国科学院合肥物质科学研究院 | Porous zinc oxide-silver composite nanorod, as well as preparation method and application thereof |
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| CN105350103B (en) * | 2015-12-01 | 2018-10-26 | 东华大学 | A kind of anti-biotic material and preparation method thereof |
| CN105494434B (en) * | 2016-01-25 | 2019-04-16 | 延安大学 | The preparation method of zinc oxide antimicrobial composite material |
| CN106106522B (en) * | 2016-06-23 | 2019-05-14 | 中国人民解放军军事医学科学院卫生学环境医学研究所 | A kind of nano zine oxide-load silver chitosan compound anti-bacteria agent and preparation method thereof |
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| CN111937902B (en) * | 2020-08-13 | 2021-11-30 | 河南工业大学 | Zinc oxide nano antibacterial compound and preparation method thereof |
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| CN113317324B (en) * | 2021-05-26 | 2022-05-17 | 晋大纳米科技（厦门）有限公司 | Glass silver-zinc-loaded antibacterial agent and preparation method thereof |
| CN113520997B (en) * | 2021-07-19 | 2022-09-09 | 青岛大学附属医院 | Natamycin and silver loaded nano mesoporous carbon eye drops and preparation method and application thereof |
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| CN1320378A (en) * | 2000-04-21 | 2001-11-07 | 云南大学 | High-temp inorganic antibacterial agent |
| CN1387763A (en) * | 2002-06-12 | 2003-01-01 | 骆天荣 | Composite nano germicide and its prepn |
| CN1390784A (en) * | 2002-07-30 | 2003-01-15 | 复旦大学 | Process for synthesizing macroreticular SiO2 molecular sieve containing sequential mesopores |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1320378A (en) * | 2000-04-21 | 2001-11-07 | 云南大学 | High-temp inorganic antibacterial agent |
| CN1387763A (en) * | 2002-06-12 | 2003-01-01 | 骆天荣 | Composite nano germicide and its prepn |
| CN1390784A (en) * | 2002-07-30 | 2003-01-15 | 复旦大学 | Process for synthesizing macroreticular SiO2 molecular sieve containing sequential mesopores |
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