CN100508757C - Kernel-shell structured rare-earth nanometer antibiotic agent, prepn. method and application thereof - Google Patents
Kernel-shell structured rare-earth nanometer antibiotic agent, prepn. method and application thereof Download PDFInfo
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Abstract
A nano-class RE antibacterial agent with core-shell structure for plastics, paine and ceramics is prepared from binary RE-heterocyclic compound match composed of RE ions chosen from La, Ce, Pr, Nd, Sm, Er, Eu, Y, Dy and Gd and the heterocyclic compound (imidazole or benzimidazole), and the carrier chosen from spherical SiO2 or spherical meta-porous SiO2. Its preparing process is also disclosed.
Description
Technical field
The invention belongs to rare earth nano material technical field and depollution of environment field, particularly relate to a kind of rare-earth nanometer antibiotic agent and its production and application.
Background technology
Along with the growth of human material wealth and comprehensive progress of society, people more and more are concerned about environmental problem, and the negative effect to human health and quality of life that is caused by environment especially receives publicity.Therefore, reduce and prevent that effectively bacterium alleviates the common recognition that the bad results such as courses of infection, poisoning and disease that cause thus become society gradually to human lives's influence and harm among the human settlement, make people strong day by day the demand of anti-biotic material.
General anti-biotic material can be divided into according to forming: inorganic antibacterial material, organic anti-bacterial material and natural antibacterial material three parts, and natural antibacterial material is mainly the extract of natural plants, is subjected to the restriction of resource, and application has certain difficulty; The applicating history of organic anti-bacterial material existing three more than ten years though its sterilizing power is strong, effective, exists that safety is relatively poor, chemical stability is bad, poor heat resistance, easily produces drug resistance and can cause secondary pollution problems; Inorganic antibacterial material is generally by containing metal cation components such as silver, zinc, copper and inorganic carrier and form, play antibacterial effect by slow releasing function, have advantages such as safety, warm tolerance, persistence, the serial anti-biotic material of silver is present modal inorganic antibacterial material, but the silver particles chemical property is active, variable color easily under effects such as illumination, heat, and discoloration problem has seriously restricted its application.
Common antibacterial agent product form often is in a kind of nature of anti-biotic material at present, is generally powder, Powdered crystallite or liquid, and the antibacterial agent by special structural design in the practical application is comparatively rare.The structure of antibacterial agent has important effect to compatibility, the use antibacterial agent of performance, antibacterial agent and the sill of the anti-microbial property of antibacterial agent to the influence of material physical property, mechanical property, optical property, therefore can obviously improve the efficient of antibacterial agent by the antibacterial agent structural design, and the anti-biotic material of antibacterial agent and the physical and chemical performance of antibacterial product have been used in expansion, form the personalization of different field antibacterial agent, and can expand the application of antibacterial agent to a great extent.
Rare earth is a brand-new field in the application of medicine and pharmacology and agricultural, the depollution of environment, rare earth ion has unique plysiochemical character, rare-earth salts can be used as anticorrosion and bactericidal agent or little fertilizer, also can be used as the feed addictive and the bait of domestic animal, fishes and shrimps etc., rare earth ion can also disclose the function of metal ions such as Na, K, Ca in the organism as probe, make people's growing interest rare earth to ecotope and health effects, experimental results show that rare earth ion has the strong unique property that is penetrated in the organism; Azole is a kind of heterocyclic compound with sterilization, anti-inflammatory ability; About the synthetic of the complex of rare earth and azole material with use existing people's report, but its synthetic method adopts crystallization mode to obtain product, its post processing is comparatively complicated, and is subject to the influence of external environment and reduces productive rate even can not get product, has therefore limited its extensive use.Have not yet to see the report for preparing rare-earth nanometer antibiotic agent by the design of nucleocapsid structure.
Summary of the invention
Technical problem to be solved
Technical problem to be solved by this invention provides rare-earth nanometer antibiotic agent of a kind of nucleocapsid structure and its production and application, lack special structural design to overcome existing antibacterial agent, the anti-microbial property of anti-biotic material can not be given full play to, the compatibility of antibacterial agent and sill is poor, the physical property of anti-biotic material, mechanical property, optical property be because the defective that its particle diameter and structural reason can not extensively be suitable for.
Technical scheme
One of technical scheme of the present invention provides a kind of rare-earth nanometer antibiotic agent of nucleocapsid structure, and particle size range is 60～200nm, is made up of carrier and antibacterial active compounds, and antibacterial active compounds is a rare earth heterocycle two-element match, and rare earth ion is La
3+, Ce
3+, Pr
3+, Nd
3+, Sm
3+, Er
3+, Eu
3+, Y
3+, Dy
3+Or Gd
3+In one or more, heterocyclic compound is the azole heterocyclic compound, carrier is preparing spherical SiO 2 or sphericity mesoporous silicon dioxide.
One of preferred version of above-mentioned rare-earth nanometer antibiotic agent is that said anti-biotic material component is a rare-earth nanometer antibiotic agent, accounts for 2～60% of gross mass.
Two of the preferred version of above-mentioned rare-earth nanometer antibiotic agent is that said heterocyclic compound is imidazoles or benzimidazole.
Three of the preferred version of above-mentioned rare-earth nanometer antibiotic agent is that said rare earth ion is from rare earth chloride salt or nitric acid rare earth salt.
Four of the preferred version of above-mentioned rare-earth nanometer antibiotic agent is, said carrier is spherical oxide or spherical mesoporous oxide, and particle size range is 50～100nm.
Five of the preferred version of above-mentioned rare-earth nanometer antibiotic agent is that said spherical oxide or spherical mesoporous oxide are preparing spherical SiO 2 or sphericity mesoporous silicon dioxide.
Six of the preferred version of above-mentioned rare-earth nanometer antibiotic agent is that said sphericity mesoporous silicon dioxide specific surface area is 600～1500m
2/ g, the aperture is 2.0～5.0nm.
Two of technical scheme of the present invention provides a kind of preparation method of above-mentioned preparing spherical SiO 2 rare-earth nanometer antibiotic agent, comprises the steps:
(1) ammoniacal liquor and ethanol are mixed under 40～100 ℃, drip ethyl orthosilicate, when solution becomes is muddy, stop to drip, drip ethyl orthosilicate after 0.2～1 hour, drip and finish back continuation reaction 2～8 hours, the room temperature ageing is spent the night, centrifugation 40～80 ℃ of following vacuum dryings 4～18 hours, gets the preparing spherical SiO 2 carrier;
(2) rare-earth salts and imidazoles or benzimidazole are that the ratio of 1:6 feeds intake with the mol ratio, add absolute ethyl alcohol, stir down at 40～80 ℃, transfer pH=6～8, continue to stir 5～8 hours, decompression distillation, and fully wash with ether and water, 40～80 ℃ of following vacuum drying 8～12 hours, rare earth heterocycle two-element match;
(3) get carrier and the antimicrobial compound that mass ratio is 1:0.01～1:0.6, mixed 2～10 hours with alcoholic solution, ageing 8～20 hours, suction filtration, 40～80 ℃ of following vacuum drying 4～10 hours obtains the rare-earth nanometer antibiotic agent of said nucleocapsid structure.
Three of technical scheme of the present invention provides the preparation method of another kind of sphericity mesoporous silicon dioxide rare-earth nanometer antibiotic agent, comprises the steps:
(1) mixes softex kw solution and concentrated ammonia liquor down at 70-90 ℃, stir, transfer pH=8～13, drip ethyl orthosilicate, when solution becomes is muddy, stop to drip, drip ethyl orthosilicate after 0.2～1 hour, drip and finish back continuation reaction 2～8 hours, the room temperature ageing is spent the night, and centrifugation was 40～80 ℃ of following vacuum dryings 4～10 hours, 500～700 ℃ of following roastings 2～6 hours, get the sphericity mesoporous silicon dioxide carrier;
(2) rare-earth salts and imidazoles or benzimidazole are that the ratio of 1:6 feeds intake with the mol ratio, add absolute ethyl alcohol, stir down at 40～80 ℃, transfer pH=6～8, continued stir about 5～8 hours, decompression distillation is fully washed with ether and water, 40～80 ℃ of following vacuum drying 8～12 hours, rare earth heterocycle two-element match;
(3) get carrier and the antimicrobial compound that mass ratio is 1:0.01～1:0.6, in alcohol solution, mixed 2～10 hours, ageing 8～20 hours, suction filtration, 40～80 ℃ of following vacuum drying 4～10 hours obtains the rare-earth nanometer antibiotic agent of said nucleocapsid structure.
Four of technical scheme of the present invention provides the application of above-mentioned rare-earth nanometer antibiotic agent in antibiotic, and the responsive bacterial classification of said antibacterial agent is Escherichia coli, staphylococcus aureus, bacillus wax, Bacillus megatherium or Candida albicans.
Beneficial effect
Antibacterial agent of the present invention passes through special structural design, rare earth heterocycle two-element match and nanometer spherical silica or sphericity mesoporous silicon dioxide are made up, produced significant antibacterial effect, and to Escherichia coli, staphylococcus aureus, bacillus wax, Bacillus megatherium or Candida albicans have inhibition and killing action preferably, the MIC value reaches 130～350ppm, and (wherein MIC is the minimal inhibitory concentration of antibacterial agent, MIC Zhi ≦ the 800ppm of country's antibiotic center of industry regulation anti-biotic material, ppm is its unit, be generally mg/litre, be abbreviated as ppm), be much better than national standard.Preparation method provided by the present invention has simple to operate, the output height, and preparation process does not produce advantages such as environmental pollution.
Antibacterial agent particle diameter of the present invention is in nanoscale, because the size of general germ or bacterium is about about the 0.5-5 micron, therefore, the antibacterial agent that the present invention has nano-scale can make the active easier bacterium inside that enters mutually, make the membranolysis of bacterium, and kill effectively and suppress bacterium, have efficient, fast, the characteristics of lasting and broad-spectrum antiseptic.Secondly, the bulk effect of nano particle uniqueness can improve active distribution consistency degree mutually greatly with surface-area effects, increases its contact surface with bacterium and amasss, thereby further improve antimicrobial efficiency; Utilize the quantum size effect of nano particle and macro quanta tunnel effect etc. can improve its electronics and level structure characteristic, improve antibacterial ability.In addition, nano-silicon dioxide particle has characteristics such as surface atom coordination degree of unsaturation height and The adsorbed hydroxyl content height, can be organic with majority and inorganic material (as textile, coating, leather, paper, printing ink, resin etc.) evenly mix, and produce stronger adsorption bond, not only adding the fashionable quality and the service life that can not influence product, and it is long-acting, high temperature resistant and not easy to change, have common antibacterial agent photostability and the heat endurance that can not compare, be particularly suitable for the health and the epidemic prevention demand of Public Goods and facility.
Description of drawings
Fig. 1 is the TEM photo of the rare-earth nanometer antibiotic agent of nucleocapsid structure of the present invention.
Fig. 2 is the TEM photo of preparing spherical SiO 2 carrier.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
The experimental technique of unreceipted actual conditions in the following example, usually according to normal condition, as the chemical products handbook, or the condition of advising according to manufacturer.Wherein used bacterial classification: Escherichia coli (8099), staphylococcus aureus (ATCC6538P), bacillus wax, Bacillus megatherium and Candida albicans are provided by Shanghai Pharmaceutical Inst., Chinese Academy of Sciences.All inorganic chemical reagents and organic solvent are available from Shanghai chemical reagent factory.
Embodiment 1
With 10g softex kw and 200g water 80 ℃ of following mixing and stirring, the concentrated ammonia liquor that adds 37ml then, continue to stir, transfer its pH value in the 8-13 scope, be added dropwise to ethyl orthosilicate 5ml with suitable speed then, when solution becomes is muddy, stop to drip, drip remaining ethyl orthosilicate 6ml with suitable speed after half an hour approximately, drip and finish, continue reaction 2-8 hour, the room temperature ageing is spent the night, centrifugation is at 40-80 ℃ of following vacuum drying 4-18 hour, then 550 ℃ of following roastings 5 hours, get the carrier sphericity mesoporous silicon dioxide, particle diameter is white powder between 50-100nm, specific surface area is 600-1500m
2/ g, the aperture is 2.0-5.0nm.
Lanthanum chloride and imidazoles are that the ratio of 1:6 feeds intake with the mol ratio, add a certain amount of absolute ethyl alcohol, stir down at 40-80 ℃, transfer its pH value between 6-8, continued stir about 5-8 hour, decompression distillation, and fully wash with ether and water, 40-80 ℃ following vacuum drying 8-10 hour, lanthanum imidazoles two-element match, its color is a white powder, and particle diameter is between 20-80nm.
Get the carrier of above-mentioned 2g and the antibacterial activity composition of 0.2g, add an amount of pure aqueous solvent, magnetic agitation 2-10 hour, ageing 8-20 hour, suction filtration, 40-80 ℃ following vacuum drying 4-10 hour, obtain the rare earth nano rare earth antibacterial agent that this has nucleocapsid structure.
Embodiment 2
4g water, 12ml concentrated ammonia liquor and 65ml absolute ethyl alcohol are mixed with certain proportion, abundant 50-100 ℃ of following water-bath heated and stirred, be added dropwise to the 6ml ethyl orthosilicate with suitable speed then, when solution becomes is muddy, stop to drip, drip remaining 7ml ethyl orthosilicate with suitable speed after half an hour approximately, drip and finish, continue reaction 2-8 hour, the room temperature ageing is spent the night, centrifugation, at 40-80 ℃ of following vacuum drying 4-18 hour, get the carrier preparing spherical SiO 2, particle diameter is white powder between 50-100nm.
Cerium chloride and imidazoles are that the ratio of 1:6 feeds intake with the mol ratio, add the 50ml absolute ethyl alcohol, stir down at 40-80 ℃, transfer its pH value between 6-8, continued stir about 5-8 hour, decompression distillation, and fully wash with ether and water, 40-80 ℃ following vacuum drying 4-10 hour, cerium imidazoles two-element match, its color is a white powder, and particle diameter is between 20-80nm.
Get above-mentioned a certain amount of carrier and antibacterial activity composition, add an amount of pure aqueous solvent, magnetic agitation 2-5 hour, ageing 8-20 hour, suction filtration, 40-80 ℃ following vacuum drying 4-10 hour, obtain the rare-earth nanometer antibiotic agent that this has nucleocapsid structure.
Embodiment 3
With 5.8g hexadecyltrimethylammonium chloride and 186g water 80 ℃ of following mixing and stirring, the sodium hydroxide that adds 0.3 mole then, continue to stir, transfer its pH value in the 8-13 scope, be added dropwise to ethyl orthosilicate 2.4ml with suitable speed then, when solution becomes is muddy, stop to drip, drip remaining ethyl orthosilicate 3ml with suitable speed after half an hour approximately, drip and finish, continue reaction 2-8 hour, the room temperature ageing is spent the night, centrifugation is at 40-80 ℃ of following vacuum drying 4-10 hour, then 550 ℃ of following roastings 5 hours, get the carrier sphericity mesoporous silicon dioxide, particle diameter is white powder between 50-100nm, specific surface area is 600-1500m
2/ g, the aperture is 2.0-5.0nm.
Neodymium chloride and imidazoles are that the ratio of 1:6 feeds intake with the mol ratio, add the 60ml absolute ethyl alcohol, stir down at 40-80 ℃, transfer its pH value between 6-8, continued stir about 5-8 hour, decompression distillation, and fully wash with ether and water, 40-80 ℃ following vacuum drying 8-10 hour, neodymium imidazoles two-element match, its color is the purple powder, and particle diameter is between 20-80nm.
Get above-mentioned a certain amount of carrier and antibacterial activity composition, add an amount of pure aqueous solvent, magnetic agitation 2-10 hour, ageing 8-20 hour, suction filtration, 40-80 ℃ following vacuum drying 4-18 hour, obtain the rare-earth nanometer antibiotic agent that this has nucleocapsid structure.
Embodiment 4-10
Replace neodymium chloride among the embodiment 3 respectively with the villaumite of praseodymium, samarium, europium, erbium, yttrium, dysprosium and gadolinium, the remaining reaction condition is with embodiment 3, the rare-earth nanometer antibiotic agent of preparation nucleocapsid structure.It should be noted that if substitute the villaumite of rare earth ion, also can prepare the rare-earth nanometer antibiotic agent of the nucleocapsid structure of same physical chemical property with identical method with the nitrate of above rare earth ion.
Embodiment 11-20
With the imidazoles among the benzimidazole replacement embodiment 1-10, the remaining reaction condition prepares the rare-earth nanometer antibiotic agent of nucleocapsid structure with embodiment 2.
Embodiment 21
The rare-earth nanometer antibiotic agent of the prepared various nucleocapsid structures of embodiment 1-36 is cultivated altogether with Escherichia coli (8099), staphylococcus aureus (ATCC6538P), bacillus wax, Bacillus megatherium or Candida albicans respectively, continued antibacterial test.The result shows that the MIC value scope of each antibacterial agent is 130-350ppm, is better than national defined standard 800ppm (effect such as table 1, wherein, Im is an imidazoles, Benlm is a benzimidazole).
The different antibacterial agents of table 1 are to colibacillary MIC pH-value determination pH result
| Title | La-Im/SiO 2 | Ce-Im/SiO 2 | Pr-Im/SiO 2 | Nd-Im/SiO 2 |
| MIC | 200 | 180 | 195 | 260 |
| Title | Eu-Im/SiO 2 | Y-Im/SiO 2 | Gd-Im/SiO 2 | Dy-Im/SiO 2 |
| MIC | 300 | 350 | 290 | 260 |
| Title | Sm-Im/SiO 2 | Er-Im/SiO 2 | La-Benlm/SiO 2 | Ce-Benlm/SiO 2 |
| MIC | 280 | 270 | 180 | 130 |
| Title | Eu-Benlm/SiO 2 | Y-Benlm/SiO 2 | Gd-Benlm/SiO 2 | Dy-Benlm/SiO 2 |
| MIC | 280 | 330 | 270 | 200 |
| Title | Pr-Benlm/SiO 2 | Nd-Benlm/SiO 2 | Sm-Benlm/SiO 2 | Er-Benlm/SiO 2 |
| MIC | 140 | 220 | 250 | 210 |
Claims (8)
1. the rare-earth nanometer antibiotic agent of a nucleocapsid structure, particle size range is 60～200nm, is made up of carrier and antibacterial active compounds, and antibacterial active compounds is a rare earth heterocycle two-element match, and rare earth ion is La
3+, Ce
3+, Pr
3+, Nd
3+, Sm
3+, Er
3+, Eu
3+, Y
3+,, Dy
3+Or Gd
3+In one or more, heterocyclic compound is imidazoles or benzimidazole, carrier is preparing spherical SiO 2 or sphericity mesoporous silicon dioxide.
2. rare-earth nanometer antibiotic agent according to claim 1 is characterized in that, said antibacterial active compounds is 2.0～60% of a rare-earth nanometer antibiotic agent gross mass.
3. rare-earth nanometer antibiotic agent according to claim 1 is characterized in that, said rare earth composition is rare earth chloride salt or nitric acid rare earth salt.
4. rare-earth nanometer antibiotic agent according to claim 1 is characterized in that, said carrier is preparing spherical SiO 2 or sphericity mesoporous silicon dioxide, and particle size range is 50～100nm.
5. rare-earth nanometer antibiotic agent according to claim 4 is characterized in that, said sphericity mesoporous silicon dioxide specific surface area is 600～1500m
2/ g, the aperture is 2～5nm.
6. the preparation method of the described preparing spherical SiO 2 rare-earth nanometer antibiotic agent of claim 1 comprises the steps:
(1) ammoniacal liquor and ethanol are mixed under 40～100 ℃, drip ethyl orthosilicate, when solution becomes is muddy, stop to drip, drip ethyl orthosilicate after 0.2～1 hour, drip and finish back continuation reaction 2～8 hours, the room temperature ageing is spent the night, centrifugation 40～80 ℃ of following vacuum dryings 4～18 hours, gets the preparing spherical SiO 2 carrier;
(2) rare-earth salts and imidazoles or benzimidazole are that the ratio of 1:6 feeds intake with the mol ratio, add absolute ethyl alcohol, stir down at 40～80 ℃, transfer pH=6～8, continue to stir 5～8 hours, decompression distillation, and fully wash with ether and water, 40～80 ℃ of following vacuum drying 4～10 hours, rare earth heterocycle two-element match;
(3) get carrier and the antimicrobial compound that mass ratio is 1:0.02～1:0.6, in alcohol solution, mixed 2～10 hours, ageing 8～20 hours, suction filtration, 40～80 ℃ of following vacuum drying 4～10 hours obtains said rare-earth nanometer antibiotic agent.
7. the preparation method of the described sphericity mesoporous silicon dioxide rare-earth nanometer antibiotic agent of claim 1 comprises the steps:
(1) mixes softex kw solution and concentrated ammonia liquor down at 70-90 ℃, stir, transfer pH=8～13, drip ethyl orthosilicate, when solution becomes is muddy, stop to drip, 0.2 drip ethyl orthosilicate after～1 hour, drip and finish back continuation reaction 2～8 hours, the room temperature ageing is spent the night, centrifugation, 40～80 ℃ of following vacuum dryings 4～10 hours, 500～700 ℃ of following roastings 2～6 hours, get the sphericity mesoporous silicon dioxide carrier, specific surface area is 600～1500m
2/ g, the aperture is 2～5nm;
(2) rare-earth salts and imidazoles or benzimidazole are that the ratio of 1:6 feeds intake with the mol ratio, add absolute ethyl alcohol, stir down at 40～80 ℃, transfer pH=6～8, continue to stir 5～8 hours, decompression distillation is fully washed with ether and water, 40～80 ℃ of following vacuum drying 4～10 hours, rare earth heterocycle two-element match;
(3) get carrier and the antimicrobial compound that mass ratio is 1:0.2～1:0.6, in alcohol solution, mixed 2～10 hours, ageing 8～20 hours, suction filtration, 40～80 ℃ of following vacuum drying 4～10 hours obtains said rare-earth nanometer antibiotic agent.
8. the application of the described rare-earth nanometer antibiotic agent of claim 1 in antibiotic, it is characterized in that the responsive bacterial classification of said antibacterial agent is Escherichia coli (Escherichia coli), staphylococcus aureus (Staphyloccocus aureus), bacillus megaterium (Bacillus megatherium) or Candida albicans (Monilia albican).
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| CN105145568B (en) * | 2015-09-16 | 2017-07-07 | 浙江理工大学 | A kind of renewable SiO2The preparation method of/PAM nucleocapsid composite nano anti-biotic particles |
| CN107821446A (en) * | 2017-11-25 | 2018-03-23 | 安徽正丰农业科技有限公司 | A kind of rice breeding bactericide specially containing Lanthanide complex |
| CN108329215B (en) * | 2018-04-10 | 2020-09-11 | 新昌县勤勉生物医药科技有限公司 | Preparation method of styryl diphenylamine antioxidant |
| CN108623250A (en) * | 2018-04-19 | 2018-10-09 | 铜仁市万山区建辉新型环保建材有限公司 | A kind of environmentally friendly construction smart coatings |
| WO2021132643A1 (en) * | 2019-12-26 | 2021-07-01 | 東レ株式会社 | Cerium oxide nanoparticles, dispersion, oxidant, antioxidant and method for producing cerium oxide nanoparticles |
| JPWO2021132628A1 (en) * | 2019-12-26 | 2021-07-01 | ||
| CN114276582A (en) * | 2020-09-27 | 2022-04-05 | 合肥杰事杰新材料股份有限公司 | Antibacterial agent, preparation method thereof and antibacterial composition containing antibacterial agent |
| CN113273580A (en) * | 2021-06-07 | 2021-08-20 | 广东顾纳凯材料科技有限公司 | Antibacterial agent and preparation method thereof, antibacterial polyolefin composite material and preparation method thereof |
| CN114736222A (en) * | 2022-03-30 | 2022-07-12 | 厦门稀土材料研究所 | Rare earth-based complex antibacterial agent and preparation method thereof |
| CN116212091B (en) * | 2023-05-09 | 2023-08-01 | 天津包钢稀土研究院有限责任公司 | Composite antibacterial agent, human-friendly medical antibacterial dressing and preparation method thereof |
| CN116606491B (en) * | 2023-05-16 | 2024-03-19 | 广东诚和信新材料有限公司 | Anti-aging PE material and synthesis process thereof |
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| CN1454481A (en) * | 2003-05-29 | 2003-11-12 | 四川大学 | Rare-earth-carrying nano titanium dioxide antibacterial agent and preparation method thereof |
| CN1582665A (en) * | 2004-06-01 | 2005-02-23 | 中国农业大学 | Rare-earth organic composite bactericidal agent and its preparation |
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| CN1454481A (en) * | 2003-05-29 | 2003-11-12 | 四川大学 | Rare-earth-carrying nano titanium dioxide antibacterial agent and preparation method thereof |
| CN1582665A (en) * | 2004-06-01 | 2005-02-23 | 中国农业大学 | Rare-earth organic composite bactericidal agent and its preparation |
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