CN102985097A - 包含硅酸铝和银纳米粒子作为杀菌剂的组合物 - Google Patents
包含硅酸铝和银纳米粒子作为杀菌剂的组合物 Download PDFInfo
- Publication number
- CN102985097A CN102985097A CN2011800194317A CN201180019431A CN102985097A CN 102985097 A CN102985097 A CN 102985097A CN 2011800194317 A CN2011800194317 A CN 2011800194317A CN 201180019431 A CN201180019431 A CN 201180019431A CN 102985097 A CN102985097 A CN 102985097A
- Authority
- CN
- China
- Prior art keywords
- silver
- compositions
- obtains
- kaolin
- aluminium silicate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 32
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 12
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 title claims abstract description 4
- 239000003899 bactericide agent Substances 0.000 title abstract 2
- -1 aluminum silicates Chemical class 0.000 title description 2
- 229910052782 aluminium Inorganic materials 0.000 title 1
- 239000005995 Aluminium silicate Substances 0.000 claims description 48
- 235000012211 aluminium silicate Nutrition 0.000 claims description 48
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 43
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical group O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 33
- 239000004332 silver Substances 0.000 claims description 26
- 229910052709 silver Inorganic materials 0.000 claims description 26
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 17
- 239000000725 suspension Substances 0.000 claims description 15
- 230000001105 regulatory effect Effects 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 7
- 101710134784 Agnoprotein Proteins 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 4
- 239000007900 aqueous suspension Substances 0.000 claims description 2
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 claims 4
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 abstract description 19
- 239000000843 powder Substances 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000002114 nanocomposite Substances 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000003115 biocidal effect Effects 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 241000191938 Micrococcus luteus Species 0.000 description 4
- 239000003945 anionic surfactant Substances 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 241000588724 Escherichia coli Species 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001963 growth medium Substances 0.000 description 2
- 244000144972 livestock Species 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 150000003378 silver Chemical class 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920001817 Agar Polymers 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241000192125 Firmicutes Species 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 229940041514 candida albicans extract Drugs 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 239000002054 inoculum Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 210000004962 mammalian cell Anatomy 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002417 nutraceutical Substances 0.000 description 1
- 235000021436 nutraceutical agent Nutrition 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
- 230000001717 pathogenic effect Effects 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000013207 serial dilution Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000012137 tryptone Substances 0.000 description 1
- 239000012138 yeast extract Substances 0.000 description 1
Images
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/14—Particulate form, e.g. powders, Processes for size reducing of pure drugs or the resulting products, Pure drug nanoparticles
- A61K9/141—Intimate drug-carrier mixtures characterised by the carrier, e.g. ordered mixtures, adsorbates, solid solutions, eutectica, co-dried, co-solubilised, co-kneaded, co-milled, co-ground products, co-precipitates, co-evaporates, co-extrudates, co-melts; Drug nanoparticles with adsorbed surface modifiers
- A61K9/143—Intimate drug-carrier mixtures characterised by the carrier, e.g. ordered mixtures, adsorbates, solid solutions, eutectica, co-dried, co-solubilised, co-kneaded, co-milled, co-ground products, co-precipitates, co-evaporates, co-extrudates, co-melts; Drug nanoparticles with adsorbed surface modifiers with inorganic compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K33/00—Medicinal preparations containing inorganic active ingredients
- A61K33/24—Heavy metals; Compounds thereof
- A61K33/38—Silver; Compounds thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y5/00—Nanobiotechnology or nanomedicine, e.g. protein engineering or drug delivery
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Veterinary Medicine (AREA)
- Epidemiology (AREA)
- Animal Behavior & Ethology (AREA)
- Pharmacology & Pharmacy (AREA)
- Public Health (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Agronomy & Crop Science (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
本发明涉及一种纳米复合物或纳米结构粉末的组合物,该组合物包含硅酸铝及分散在硅酸铝表面上的、尺寸小于50nm的银纳米粒子。本发明还涉及所述组合物作为杀菌剂的应用及其生产方法。
Description
技术领域
本发明涉及一种包含硅酸铝和分散在其表面上的、尺寸小于50nm的银纳米粒子的组合物,还涉及其作为杀菌剂的应用并涉及用于获得所述组合物的方法。
背景技术
众所周知,低浓度的银对于宽范围的病原体具有抗菌性,包括引发植入相关感染的常见菌株,而其对哺乳动物细胞是无毒的。大多数含银作为抗菌物质的生物材料由该金属的元素形式或阳离子形式组成,其中无机和有机母体都可以支持其阳离子形式。已研究了在含银的聚合物和生物玻璃情况下的抗菌活性,但是还没有对在纳米结构的硅酸铝-银复合物材料的情况下进行研究。
最近,对于获得高岭土与银纳米粒子的复合物的研究已发表了[Patakfalvi,P.,Dékány,I.Applied Clay Science,2004,25,pp.149–159;Patakfalvi,P.,Dékány,I.Proceeding of SPIE-The international society foroptical engineering,2003,5118,pp.657-667;Patakfalvi,P.,Oszkó,A.,Dékány,I.Colloids and Surface A:Physicochemical and Engineering Aspects,2003,220,pp.45-54]。这些文章提出了银纳米粒子在高岭土层间空间的合成,高岭土预先已通过分散(interspersing)二甲亚砜而分解(解聚,disaggregated)。所引用的案例中没有一个估算过这些材料的抗菌容量;它们只是提出了这些材料的潜在应用,如对于光敏元件、催化剂,在光催化中、表面-增强的拉曼散射光谱和化学分析中的应用。
银纳米粒子的杀生物活性受其尺寸影响:尺寸越小,抗菌活性越强,因此,纳米粒子的团聚也是影响所述活性的一个问题。
发明内容
本申请的发明人已找到通过在不同基质的表面上使用银纳米粒子来防止所述纳米粒子团聚的解决方案,特别是硅酸铝(基质),这赋予所述组合物零毒性的性质,从而使其可以应用于医药和织物领域,及其他领域。
本发明提供了一种纳米复合物或具有纳米结构的粉末组合物,所述组合物包含硅酸铝以及附着在其表面上的、尺寸小于50nm的银纳米粒子。本发明还提供了用于获得所述组合物的方法,及其作为杀菌剂的应用。
因此,本发明的第一方面涉及一种组合物(下文称本发明的组合物),该组合物包含硅酸铝以及分布在其表面上的、尺寸小于50nm的银纳米粒子。优选地,银纳米粒子的尺寸小于20nm。
在一个优选的实施方式中,将所述银纳米粒子沉积在硅酸铝的表面上,所述硅酸铝既可以是水合的也可以是非水合的。
优选地,硅酸铝选自高岭土、偏高岭土、蒙脱石、云母或其任意组合。更优选地,硅酸铝是高岭土。
在一个优选的实施方式中,相对于最终组合物,银的重量百分比范围在0.01%至15%之间。在一个更优选的实施方式中,银的重量百分比范围在0.1%至0.8%之间。
本发明的第二方面涉及用于获得本发明的组合物的方法(下文称本发明的方法),该方法包括下述步骤:
a)水性悬浮硅酸铝与表面活性剂,
b)向步骤(a)中所获得的悬浮液中加入银前体,以及
c)还原步骤(b)中所获得的产物中的银。
本发明中,“表面活性剂”理解为是指具有降低互相接触的两个表面之间的表面张力的能力的物质或产品。表面活性剂是具有一个亲水部分和一个疏水部分的分子,并且对于本领域技术人员是已知的。
在一个优选的实施方式中,本发明的方法还包括调节步骤(a)中所获得的悬浮液的pH值到6至7之间。
在一个优选的实施方式中,本发明的方法还包括步骤(b’),通过搅拌步骤(b)中所获得的悬浮液,在pH值为8至10之间沉淀银离子。
优选地,本发明还包括过滤、水洗和在温度范围为50°C至100°C之间干燥步骤(b’)中所获得的产物。
在另一个优选的实施方式中,本发明方法还包括过滤、水洗和在温度范围为50°C至100°C之间干燥步骤(c)中所获得的产物。
优选地,所述银前体是AgNO3。
在一个优选的实施方式中,所述还原是利用选自H2或NaBH4的还原剂进行的。
本发明的方法的主要优点是,相对于本领域目前的状况,由于这些银纳米粒子附着在基质,即硅酸铝上,本发明防止了银纳米粒子的团聚。
在本发明的方法的一个替换方案中,本发明是通过在硅酸铝(水合的或非水合的)的表面上沉积银纳米粒子而进行的。因此,该方法包括以下步骤:
a)制备硅酸铝的水性悬浮液,向其中加入低浓度的表面活性剂,优选阴离子表面活性剂,
b)用1M HNO3水溶液调节pH值至6到7之间,使得维持高岭土的良好分散,而这样的pH条件并不利于银前体的沉淀,
c)在无光的条件下,加入必要浓度的银前体盐的水溶液,以使在最终复合物(composite)中元素银含量相对于硅酸铝固体含量的重量百分比的范围在0.01%至8%之间,优选是1%的银,
d)剧烈搅拌悬浊液,调节pH值至9,使得Ag+阳离子以氧化物Ag2O沉淀,
e)过滤、用蒸馏水洗涤并且干燥所获得的粉末,以及
f)在温度范围为150°C–500°C,优选为350°C的条件下,在H2气氛下进行还原。
本发明另一个可替代的方法涉及银的沉积,其包括以下步骤:
a)制备带有硅酸铝粉末的水性悬浮液,向其中加入低浓度的表面活性剂,优选阴离子表面活性剂,
b)用1M HNO3水溶液调节pH值至6-7之间,使得维持高岭土良好的分散性,而这样的pH条件并不利于银前体的沉淀,
c)逐滴滴加必要量的该银前体的溶液,优选AgNO3,以使在所获得的最终复合物(composite)中Ag0的重量百分比浓度范围在0.01%至8%之间,维持激烈搅拌10分钟,优选是1%的银,
d)对银进行原位化学还原,利用任何辐射性或还原性化学试剂,优选是NaBH4,将其逐滴滴加到所述分散液中,同时持续剧烈搅拌,以及
e)过滤、用蒸馏水洗涤并且在60°C的烘箱中干燥。
本发明的第三个方面涉及上述组合物作为高效杀菌剂的应用,如在本发明的实施例中阐述的。
本发明中,“杀菌剂”理解为是指那些用来杀死(毁灭,destruction)细菌的物质。
本发明的组合物可以用于外科移植科(sector)、公用设施(卫生保健、医院、运输等)、空调设备、食品、牙科(sector)、涂料、制衣业(clothinggarments)、包装(食物、家用设备(domestic elements)、药品、医疗设备)。
本发明的组合物作为杀菌剂的另一个优点是其表现的低毒性,这是通过材料浸出(lixiviate)低于3ppm的银量证实的,且这一水平远低于毒性水平。
贯穿说明书和权利要求书中的术语“组成”及其变化形式,并不意在排除其他技术特征、添加剂、组分或步骤。对于本领域技术人员,可以部分从本发明的说明书、部分从本发明的实践中理解本发明的任何其他目的、优点及特征。以下实施例和附图是为了说明的目的,并不意在限制本发明的范围。
附图说明
图1显示通过透射电子显微镜获得的显微照片,其中,我们可以观察到由方法1获得的小于20nm的附着在高岭土表面上的银纳米粒子的近似均匀的分布。
图2显示通过透射电子显微镜获得的显微照片,其中,我们可以观察到由方法2获得的纳米复合物粉末,同样也可以观察到银纳米粒子的尺寸小于20纳米。
具体实施方式
下面,我们将通过发明人进行的实验来说明本发明,这些实验展现出包含硅酸铝和银纳米粒子的组合物作为杀菌剂的特异性和有效性,以及获得其的方法。
实施例1:获得本发明的纳米复合物粉末。用于将银沉积在高岭土或偏高岭土纳米粒子上的方法
我们描述了用于在硅酸铝(水合的或非水合的)表面上沉积银的方法,以获得本发明的纳米复合物粉末,现解释如下。
从这一点来讲,本发明的具有纳米结构的粉末利用两种方法获得。
方法1
从前体开始(例如,硝酸银),将氧化银沉积在含最佳量表面活性剂的高岭土水性分散体上。然后,在H2气氛下在炉中,将Ag+阳离子还原成Ag0,如下面所解释的:
a)制备高岭土或偏高岭土的水性悬浮液,为了使高岭土或偏高岭土实现更好的分散,引入低浓度的阴离子表面活性剂作为分散剂(相对于高岭土或偏高岭土固体浓度的1wt%);
b)用1M HNO3水溶液调节pH值至6.5,使得维持高岭土良好的分散性,而这样的pH条件并不利于银前体的沉淀;
c)避光下,加入必要浓度的该银前体水溶液,以使在所获得的最终高岭土-Ag或偏高岭土-Ag复合物中,元素Ag含量范围在0.01%至15wt%之间(相对于高岭土或偏高岭土的固体含量);
d)同时剧烈搅拌悬浊液,调节pH值至9,使得Ag+阳离子以氧化物Ag2O沉淀;
e)接下来过滤和水洗,在温度为150°C–500°C、H2气氛下进行干燥和还原。
利用偏高岭土的方法以相同方式进行。
这样,我们得到了附着在高岭土或偏高岭土表面上的小于20nm的银纳米粒子的纳米复合物粉末,近似地,具有均匀分布,如图1中可以观察到的。
方法2
将银纳米粒子,Ag0,沉积在高岭土上,或者在最佳pH值和分散条件下,将由分散在水中的银前体获得的银纳米粒子Ag0沉积在高岭土上。利用辐射或还原剂在室温下进行原位还原,如下面所解释的:
a)制备带有高岭土或偏高岭土的水性悬浮液。为了使高岭土或偏高岭土实现更好的分散,引入低浓度的阴离子表面活性剂作为分散剂(Dolapix);
b)用1M HNO3水溶液调节pH值至6.5,以使高岭土达到良好分散,同时,防止Ag+离子以Ag2O沉淀;
c)为了在最终组合物中,在所获得的最终高岭土-Ag或偏高岭土-Ag复合物中,Ag0浓度范围在0.01%至15wt%之间,加入必要量的AgNO3前体。一旦将其逐滴滴加到高岭土或偏高岭土分散液中,在进行下一步骤之前,剧烈搅拌10min。同时,一旦加入了前体,必须对加有前体的溶液和分散液进行避光处理;
d)对银进行原位化学还原,例如利用NaBH4作为还原剂,NaBH4与银以1:8(NaBH4:Ag+)摩尔比、根据以下反应式进行反应:
e)将NaBH4溶液逐滴滴加到分散液中;和
f)剧烈搅拌、过滤、用蒸馏水洗涤,最后在60°C烘箱中干燥。
利用偏高岭土的方法以相同方式进行。
这样,我们得到了本发明的纳米复合物粉末,其中可以观察到Ag纳米粒子小于20nm,如图2中所示。
实施例2:本发明的纳米复合物粉末的杀生物活性和浸出测试
杀菌实验是为了研究含银样品对不同有机体的影响而进行的:大肠杆菌JM 110(革兰氏阴性菌),藤黄微球菌(Micrococcus luteus)(革兰氏阳性菌)。将微生物接种到皮氏培养皿(Petri dish)的固体培养基中,来自Luria Bertani(LB)(含有:1%胰蛋白胨、0.5%酵母膏、1%NaCl、1.5%琼脂)。将培养皿在37°C培养24小时。之后,将每一个从上述培养皿中分离出来的微生物菌落接种至1mL的LB中,并在37℃培养5小时,以获得预培养物(precultures)。与此同时,根据方法2在水中制备300mg/ml(wt/wt)含有1%的银的悬浊液。最后,取每种微生物预培养物10μl,接种至1mL的LB中。将150μl的高岭土-纳米Ag样品加入到培养物中,使Ag的最终重量百分浓度为0.036%。此外,制备水加上营养物的混合物组成的、不含银的样品作为对照。将培养物在37°C、搅拌下培养,并收集不同培养物的等分试样,用以计算下列不同培养物的系列稀释液的活菌计数。
2.1.-利用藤黄微球菌进行的杀生物试验
制备利用方法2(AgNO3用作银前体)得到的高岭土粉末的水性悬浮液(固体的重量百分数为9%),银在最终化合物中的重量百分含量为1%(相对于高岭土的固体含量)。利用藤黄微球菌进行的测试表明,本实验的24小时的滴度<1.0×104,而对照实验是1.0×1012。
72小时后,培养介质中银浸出的浓度<3ppm。
2.2.-利用大肠杆菌进行的杀生物试验
制备利用方法2(AgNO3用作银前体)得到的高岭土粉末的水性悬浮液(固体的重量百分数为9%),银在最终化合物中的重量百分含量为1%(相对于高岭土的固体含量)。利用大肠杆菌JM 110的测试表明,本实验的24小时的滴度<1.0×104,而对照实验是2.93×1012。
72小时后,培养介质中银浸出的浓度<3ppm。
Claims (14)
1.一种组合物,所述组合物包含硅酸铝以及分散在其表面上的、尺寸小于50nm的银纳米粒子。
2.根据权利要求1所述的组合物,其中所述银纳米粒子的尺寸小于20nm。
3.根据权利要求1或2所述的组合物,其中所述硅酸铝选自高岭土、偏高岭土、蒙脱石、云母或其任意组合。
4.根据权利要求3所述的组合物,其中所述硅酸铝是高岭土。
5.根据权利要求1-4中任意一项所述的组合物,其中所述银的重量百分比范围在0.01%至15%之间。
6.根据权利要求5所述的组合物,其中所述银的重量百分比范围在0.1%至0.8%之间。
7.用于获得权利要求1-6中任意一项所述的组合物的方法,所述方法包括以下步骤:
a.水性悬浮硅酸铝以及一种表面活性剂,
b.向步骤(a)中所获得的悬浮液中加入银前体,以及
c.还原步骤(b)中所获得的产物中的银。
8.根据权利要求7所述的方法,其还包括调节步骤(a)中获得的所述悬浮液的pH值至6到7之间。
9.根据权利要求7或8所述的方法,其还包括步骤(b’),通过搅拌步骤(b)中获得的所述悬浮液,在pH值为8至10之间沉淀银离子。
10.根据权利要求7-9中任意一项所述的方法,其还包括过滤、水洗和在温度范围为50°C至100°C之间干燥步骤(b’)中获得的所述产物。
11.根据权利要求7-10中任意一项所述的方法,其还包括过滤、水洗和在温度范围为50°C至100°C之间干燥步骤(c)中获得的所述产物。
12.根据权利要求7-11中任意一项所述的方法,其中所述银前体是AgNO3。
13.根据权利要求7-12中任意一项所述的方法,其中所述还原是利用选自H2或NaBH4的还原剂进行的。
14.权利要求1-6中任意一项所述的组合物用作杀菌剂的应用。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ESP201030557 | 2010-04-16 | ||
ES201030557A ES2367387B1 (es) | 2010-04-16 | 2010-04-16 | Composición de silicatos de aluminio y nanopartículas de plata como bactericidas. |
PCT/ES2011/070272 WO2011128488A1 (es) | 2010-04-16 | 2011-04-15 | Composición de silicatos de aluminio y nanopartículas de plata como bactericidas |
Publications (1)
Publication Number | Publication Date |
---|---|
CN102985097A true CN102985097A (zh) | 2013-03-20 |
Family
ID=44798295
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN2011800194317A Pending CN102985097A (zh) | 2010-04-16 | 2011-04-15 | 包含硅酸铝和银纳米粒子作为杀菌剂的组合物 |
Country Status (6)
Country | Link |
---|---|
US (1) | US20130084339A1 (zh) |
EP (1) | EP2559436A4 (zh) |
CN (1) | CN102985097A (zh) |
CA (1) | CA2796471A1 (zh) |
ES (1) | ES2367387B1 (zh) |
WO (1) | WO2011128488A1 (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103639423A (zh) * | 2013-12-27 | 2014-03-19 | 哈尔滨理工大学 | 硅酸铝包覆银纳米核壳粒子及制备方法和用途 |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9849512B2 (en) | 2011-07-01 | 2017-12-26 | Attostat, Inc. | Method and apparatus for production of uniformly sized nanoparticles |
ES2414282B1 (es) * | 2012-01-18 | 2014-05-13 | Endeka Ceramics, S.A. | Nanocomposite de plata para tinta de piezas cerámicas, tintas bactericidas multifuncionales obtenidas a partir de los mismos, y método de preparacion |
CU24137B1 (es) | 2012-03-30 | 2015-12-23 | Ct Nac Biopreparados | Método para la detección, recuperación, identificación y enumeración simultánea de microorganismos |
CL2013002101A1 (es) * | 2013-07-23 | 2014-08-29 | Univ Chile | Aditivo que confiere propiedades biocidas a distintos materiales que comprende un material de soporte o portador modificado con un agente bacteriano que forma estructuras nanometricas sobre la superficie externa de dicho material de soporte; y metodo para preparacion de dicho aditivo. |
US20160081346A1 (en) | 2014-09-23 | 2016-03-24 | Attostat, Inc. | Antimicrobial compositions and methods |
WO2016048291A1 (en) | 2014-09-24 | 2016-03-31 | Halliburton Energy Services, Inc. | Methods and compositions for suppressing bacterial growth in a subterranean environment |
US9839652B2 (en) | 2015-04-01 | 2017-12-12 | Attostat, Inc. | Nanoparticle compositions and methods for treating or preventing tissue infections and diseases |
US11473202B2 (en) | 2015-04-13 | 2022-10-18 | Attostat, Inc. | Anti-corrosion nanoparticle compositions |
US10774429B2 (en) | 2015-04-13 | 2020-09-15 | Attostat, Inc. | Anti-corrosion nanoparticle compositions |
US10201571B2 (en) | 2016-01-25 | 2019-02-12 | Attostat, Inc. | Nanoparticle compositions and methods for treating onychomychosis |
WO2018065178A1 (en) | 2016-10-06 | 2018-04-12 | Unilever N.V. | Oligodynamic silver coated sand particles |
ES2859619T3 (es) | 2017-03-03 | 2021-10-04 | Laboratorio Jaer S A | Materiales sólidos de filosilicatos y cobre con actividad biocida |
US11018376B2 (en) | 2017-11-28 | 2021-05-25 | Attostat, Inc. | Nanoparticle compositions and methods for enhancing lead-acid batteries |
US11646453B2 (en) | 2017-11-28 | 2023-05-09 | Attostat, Inc. | Nanoparticle compositions and methods for enhancing lead-acid batteries |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090148484A1 (en) * | 2007-12-07 | 2009-06-11 | National Taiwan University | Stably-dispersing composite of metal nanoparticle and inorganic clay and method for producing the same |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006049378A1 (en) * | 2004-11-08 | 2006-05-11 | Bio Dreams Co. Ltd. | Nano-silicasilver and method for the preparation thereof |
-
2010
- 2010-04-16 ES ES201030557A patent/ES2367387B1/es active Active
-
2011
- 2011-04-15 CN CN2011800194317A patent/CN102985097A/zh active Pending
- 2011-04-15 CA CA2796471A patent/CA2796471A1/en not_active Abandoned
- 2011-04-15 US US13/640,846 patent/US20130084339A1/en not_active Abandoned
- 2011-04-15 WO PCT/ES2011/070272 patent/WO2011128488A1/es active Application Filing
- 2011-04-15 EP EP11768496.9A patent/EP2559436A4/en not_active Withdrawn
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090148484A1 (en) * | 2007-12-07 | 2009-06-11 | National Taiwan University | Stably-dispersing composite of metal nanoparticle and inorganic clay and method for producing the same |
Non-Patent Citations (2)
Title |
---|
HASMUKH A. PATEL等: "Synthesis of Highly Dispersed Gold and Silver Nanoparticles Anchored on Surfactant Intercalated Montmorillonite", 《JOURNAL OF NANOSCIENCE AND NANOTECHNOLOGY》, vol. 9, no. 10, 31 October 2009 (2009-10-31), pages 5946 - 5952, XP009171711, DOI: 10.1166/jnn.2009.1249 * |
RITA PATAKFALVI等: "Synthesis and intercalation of silver nanoparticles in kaolinite/DMSO complexes", 《APPLIED CLAY SCIENCE》, vol. 25, 22 January 2004 (2004-01-22), pages 149 - 159, XP002709946, DOI: 10.1016/J.CLAY.2003.08.007 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103639423A (zh) * | 2013-12-27 | 2014-03-19 | 哈尔滨理工大学 | 硅酸铝包覆银纳米核壳粒子及制备方法和用途 |
CN103639423B (zh) * | 2013-12-27 | 2016-06-08 | 哈尔滨理工大学 | 硅酸铝包覆银纳米核壳粒子及制备方法和用途 |
Also Published As
Publication number | Publication date |
---|---|
CA2796471A1 (en) | 2011-10-20 |
ES2367387A1 (es) | 2011-11-03 |
US20130084339A1 (en) | 2013-04-04 |
EP2559436A1 (en) | 2013-02-20 |
EP2559436A4 (en) | 2013-09-18 |
WO2011128488A1 (es) | 2011-10-20 |
ES2367387B1 (es) | 2012-09-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102985097A (zh) | 包含硅酸铝和银纳米粒子作为杀菌剂的组合物 | |
Krishnan et al. | Ag/TiO2/bentonite nanocomposite for biological applications: synthesis, characterization, antibacterial and cytotoxic investigations | |
Rahmati et al. | Ag-doped magnetic metal organic framework as a novel nanostructured material for highly efficient antibacterial activity | |
Sohrabnezhad et al. | Synthesis and characterization of CuO–montmorillonite nanocomposite by thermal decomposition method and antibacterial activity of nanocomposite | |
La Russa et al. | Testing the antibacterial activity of doped TiO2 for preventing biodeterioration of cultural heritage building materials | |
Hajipour et al. | Chemical bath synthesis of CuO-GO-Ag nanocomposites with enhanced antibacterial properties | |
Bryaskova et al. | Synthesis, characterisation and antibacterial activity of PVA/TEOS/Ag-Np hybrid thin films | |
US20140065306A1 (en) | Nanostructured calcium-silver phosphate composite powders, process for obtaining the powders and bactericidal and fungicidal applications thereof | |
Longano et al. | Synthesis and antimicrobial activity of copper nanomaterials | |
Raffi et al. | Investigations into the antibacterial behavior of copper nanoparticles against Escherichia coli | |
Grumezescu et al. | In vitro activity of the new water-dispersible Fe 3 O 4@ usnic acid nanostructure against planktonic and sessile bacterial cells | |
Jastrzębska et al. | Influence of bacteria adsorption on zeta potential of Al2O3 and Al2O3/Ag nanoparticles in electrolyte and drinking water environment studied by means of zeta potential | |
Mizwari et al. | Chitosan/metal oxide nanocomposites: synthesis, characterization, and antibacterial activity | |
SG176027A1 (en) | Nanostructural composition of biocide and process of obtaining nanostructural biocide nanocomposition | |
Jamshidi et al. | Antibacterial activity of a novel biocomposite chitosan/graphite based on zinc-grafted mesoporous silica nanoparticles | |
Thampi et al. | Functionalization of fabrics with PANI/CuO nanoparticles by precipitation route for anti-bacterial applications | |
Wang et al. | Nisin-loaded polydopamine/hydroxyapatite composites: Biomimetic synthesis, and in vitro bioactivity and antibacterial activity evaluations | |
Ramteke et al. | Synthesis and broad spectrum antibacterial activity of magnetite ferrofluid | |
Čech Barabaszová et al. | CuO and CuO/vermiculite based nanoparticles in antibacterial PVAc nanocomposites | |
Ge et al. | Development and antibacterial performance of silver nanoparticles-lecithin modified montmorillonite nanoparticle hybrid | |
Liang et al. | Development of ZnO/Ag nanoparticles supported polydopamine-modified montmorillonite nanocomposites with synergistic antibacterial performance | |
Anwar et al. | Novel synthesis and antimicrobial studies of nanoscale titania particles | |
Somaraj et al. | DNA-assisted synthesis of chitosan/\upalpha chitosan/α-Fe _ 2 O _ 3 Fe 2 O 3 nanocomposites for antioxidant and antimicrobial activities | |
Seo et al. | Ag/Al (OH) 3 mesoporous nanocomposite film as antibacterial agent | |
Matyjasik et al. | Nanohybrids of oxides nanoparticles-chitosan and their antimicrobial properties |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20130320 |