WO2011033040A2 - Particules antibactériennes et leur synthèse - Google Patents

Particules antibactériennes et leur synthèse Download PDF

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WO2011033040A2
WO2011033040A2 PCT/EP2010/063646 EP2010063646W WO2011033040A2 WO 2011033040 A2 WO2011033040 A2 WO 2011033040A2 EP 2010063646 W EP2010063646 W EP 2010063646W WO 2011033040 A2 WO2011033040 A2 WO 2011033040A2
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zno
nanoparticles
copper
reaction mixture
antibacterial
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WO2011033040A3 (fr
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Vesna Aleksandrovic
Charis Rabea Schlundt
Katja Werner
Marie Woost
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Centrum Für Angewandte Nanotechnologie (Can) Gmbh
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Publication of WO2011033040A3 publication Critical patent/WO2011033040A3/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
    • 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
    • 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
    • A61K33/06—Aluminium, calcium or magnesium; Compounds thereof, e.g. clay
    • 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
    • A61K33/30—Zinc; Compounds thereof
    • 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
    • A61K33/34—Copper; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K45/00—Medicinal preparations containing active ingredients not provided for in groups A61K31/00 - A61K41/00
    • A61K45/06—Mixtures of active ingredients without chemical characterisation, e.g. antiphlogistics and cardiaca
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/27—Zinc; Compounds thereof
    • 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
    • A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
    • A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
    • A61K9/51—Nanocapsules; Nanoparticles
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/04—Antibacterial agents
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/005—Antimicrobial preparations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/02—Oxides; Hydroxides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/44—Oxides or hydroxides of elements of Groups 2 or 12 of the Periodic Table; Zincates; Cadmates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41—Particular ingredients further characterized by their size
    • A61K2800/413—Nanosized, i.e. having sizes below 100 nm
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/60—Particulates further characterized by their structure or composition
    • A61K2800/65—Characterized by the composition of the particulate/core
    • A61K2800/651—The particulate/core comprising inorganic material
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C01P2002/54—Solid solutions containing elements as dopants one element only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

Definitions

  • the field of the invention relates to a method for the manufacture of an antibacterial nanoparticle and its use.
  • Nanoparticles as antibacterial agents are relevant for many industrial sectors like environmental, healthcare, medical care, food, synthetic textiles etc..
  • ZnO nanoparticles due to their antibacterial characteristics and physical stability have been used as antibacterial material in textile industry, medicine, and cosmetics.
  • the antibacterial activity of the ZnO nanoparticles increases with decreasing nanoparticle size (Zhang, L et al., Journal of Nanoparticle Research 2007, 9, 479; Yamamoto, O.; International Journal of Inorganic Materials 2001, 3, 643).
  • Copper as an antibacterial agent has been known for a long time. Copper ions (Cu 2+ ) are soluble in water and function at low concentration as bacteriostatic substances and fungicides.
  • the copper can be used as an anti-germ surface that can add to the antibacterial and antimicrobial features of buildings, such as hospitals.
  • the advantage of the copper is the low toxicity that is useful in antibacterial treatments.
  • the syntheses of copper nanoparticles is usually time consuming and very expensive, and often the particle agglomeration is a problem.
  • some groups used the deposition of the Cu on supporting substrates as, for example, silica glass or silica nanoparticles (Y.H.Kim, D.K. Lee, J Phys. Chem.
  • US Patent Application Number US 2006/0222586 Al discloses the syntheses of ZnO nanoparticles smaller or equal to 15 nm, starting with zinc chloride or zinc chloride hydrate and an inorganic alkali, both dissolved in ethylene glycol. Afterwards the precipitated ZnO particles are thermally aged.
  • ZnO nanoparticles with a diameter of 13 nm showed a complete inhibition of E. coli growth at concentrations of 3.4 mM, whereas growth of S. aureus was completely inhibited with 1 mM of nanoparticles.
  • the specific role of size scale, surface capping, and the aspect ratio of ZnO nanoparticles on toxicity toward prokaryotic and eukaryotic cells is reported by Shantikumar and colleagues (Shantikumar et al., J.Mater.Sei.Mater.Med. 2008).
  • the ZnO nanoparticles that were PEG-capped were increasingly antibacterial in nature as the size was reduced from the micro-scale to the nano-scale and at increasing concentrations.
  • the antibacterial activity was less towards Gram-positive bacteria than towards Gram- negative bacteria, but the functional dependence on particle size was the same.
  • starch capping of the nanoparticles appeared to provide greater protection to bacteria, possibly due to the OH-related quenching of positive charges on the ZnO nanoparticle surface.
  • the WO 2006/019008 Al discloses polymer-modified nanoparticles, which are stably present over long time without aggregating. This document refers to metal sulphide nanoparticles with particles stabilised with polymers that start to grow directly from the nanoparticle surface.
  • None of the prior art discloses a simple method for the manufacture of ZnO particles doped with copper or magnesium as disclosed herein for the manufacture of new antibacterial material with low toxicity and higher antibacterial effect than ZnO particles.
  • the present disclosure provides a method for the synthesis of antibacterial nanoparticles based on ZnO doped with copper or magnesium, and investigation of their antibacterial activity on Escherichia Coli (E. Coli) DH5a and Pseudomonas aeruginosa (P aeruginosa) as a representative of gram- negative bacteria and Staphylococcus Carnosus (S. Carnosus), staphylococcus aureus (S. aureus) and bacillus subtilis (B. subtilis) as a representative of gram-positive bacteria.
  • Escherichia Coli E. Coli
  • Pseudomonas aeruginosa Pseudomonas aeruginosa
  • S. Carnosus Staphylococcus Carnosus
  • Staphylococcus aureus S. aureus
  • Bacillus subtilis Bacillus subtilis
  • the present disclosure teaches the synthesis of ZnO particles by a wet procedure in methanol as a reaction media, and during the syntheses, the ZnO particles were doped with various amount of copper or magnesium.
  • the shape of the particles was varied from spherical via rice-shape to elongated, rod like particles.
  • the particle size varied from a few nanometres up to 100 nm.
  • the invention provides a method for the manufacture of colloidal ZnO particles doped with Cu or Mg comprising:
  • precursor Zn(Ac) 2 x 2H 2 0 and Cu(Ac) 2 x H 2 0 or Mg(N0 3 ) 2 x 6H 2 0 can be used.
  • a solution of Cu(Ac) 2 x H 2 0 dissolved in an alcohol at room temperature can be injected prior to heating the reaction mixture. It is further intended to use 0.5 to 15 mol % of copper precursor calculated on the amount of Zn(Ac) 2 .
  • the temperature of the reaction mixture is heated to 64°C followed by cooling to 40°C for 10 to 30 min before injecting the solution of Cu(Ac) 2 x H 2 0.
  • the alcoholic solution used in the disclosed method comprises methanol or ethanol as solvent. It is also within the scope of the invention that the alcoholic solution comprises other solvents, for instance water.
  • the basic solution comprises a solution of an alkali in an alcoholic solution, for example methanol.
  • alkali shall be understood as alkali metal or earth alkali metal hydroxide and a basic solution shall be a solution comprising an alkali, like the basic solution of KOH or Ba(OH) 2 .
  • the reaction mixture of the Zn and Cu or Mg salts may be heated to a temperature in the range of 60 to 65 °C and the final heating of the reaction mixture can be done for at least 22 h at 64°C.
  • the size and/or shape of the resulting particles may be adjusted by the amount of copper or magnesium precursor, since there is a dependency between these parameters.
  • a further object of the invention is a particle consisting of ZnO doped with copper. The size of such a particle may be in the range of 3 to 10 nm for spherical particles and 3 mm in one dimension and up to 100 nm in the other dimension for rod like shaped particles.
  • the disclosed particle shall comprise up to 10 % of incorporated copper.
  • Another object of the disclosure of this invention is an antibacterial composition
  • a composition comprising ZnO/Cu and /or ZnO/Mg particles manufactured according to one of the disclosed methods above.
  • Such a composition may be a pharmaceutical, cosmetic or medicine product.
  • the disclosed particles and the composition may be further used as disinfectant, antibacterial coating or as an additive in cosmetic, medicine or pharmaceutical products.
  • the disclosed particles may be used for the manufacture of textiles or fibres for the manufacture of textiles with antibacterial properties.
  • the syntheses of the nanoparticles based on ZnO doped with copper or magnesium is performed by a wet procedure in methanol as reaction media, starting form different salts of Zn and Cu or Mg as a precursor. Mixture of the different salts added in certain ratios was stirred at 64°C until a clear solution was formed. Then a solution of alkali in methanol was added drop by drop at room temperature under vigorous stirring. Formed nanoparticles were heated for a minimum of 22 hours at 64°C. Particle size was varied from few nanometres up to 100 nm. Additionally, shape of the particles was varied from spherical via rise-shape until elongated, rod like particles by changing a precursor ratio in reaction mixture.
  • the present disclosure describes a method for the manufacture of antibacterial nanoparticles and its use.
  • the disclosed method comprises a defined sequence of procedural steps, which is critical for obtaining nanoparticles with the described properties as described below.
  • the US 2005/260122 Al discloses reaction conditions indicating broad ranges for reaction, for example a reaction temperature from at least about 30° C to about 80° C. It is obvious for a person skilled in the art, that the indicated range is very general and is not suitable to specify new and inventive reaction conditions. Although this document mentions copper as a dopant, the antibacterial properties of nanoparticals doped with copper is not disclosed. Besides this, the description of the US 2005/260122 Al does not support the use of other metal oxides as zinc oxide, since the described method is limited to zinc oxides.
  • the claimed process of the US 2005/260122 Al differs from the process of the present disclosure, because it claims the formation of an alcohol-based solution and maintaining the pH greater than 7 before adding the metal oxide precursor.
  • the method claimed within the present disclosure starts with dissolving the metal oxide precursor in an alcohol solution followed by heating and stirring of the reaction, before a basic solution is added drop wise. It seems to be important according to paragraphs 67 and 68 process of the US 2005/260122 Al that the metal oxide precursors are added to a solution with a pH above 7, while this is in contrast no prerequisite for performing the method described within the context of the present disclosure.
  • ZnO/Cu Cu-3%) nanoparticles at different concentrations and of ZnO (ZnO-RZOl) nanoparticles.
  • Fig. 9 SEM images of E.Coli: (a) E.Coli before treatment; (b) E.Coli after treatment with ZnO/Cu (Cu-3%) at 1.5 mg/mL for 4h).
  • High quality crystalline copper doped ZnO nanoparticles were synthesized by procedures as described in the examples below.
  • the shape of the synthesized ZnO/Cu nanoparticles can be controlled from spheres to rods, depending on the copper precursor concentration and on the time of a copper precursor addition.
  • the formation of ZnO/Cu rods is based on an oriented attachment of preformed quasi-spherical nanoparticles.
  • the length of nanoparticles synthesized with different copper concentrations is shown in Figure 1. The nanoparticles were heated at 64 °C for 22 hours.
  • the length of the rods decreases with the copper concentration until a concentration limit (1.5 mol %) is reached, where the oriented attachment of semi- spherical particles formed at the beginning is avoided. If the Cu(Ac) 2 amount exceeds 1.5 mol % calculated on amount of Zn(Ac) 2 , the formed the ZnO/Cu nanoparticles have a spherical shape. By usage of higher amount of copper precursors than the 1.5 mol % the nanoparticles became smaller and spherical. Two typical samples of nanoparticles synthesized starting from 10 and 0.5 mol % of copper precursor are shown in the TEM images in Fig 2.
  • a decrease of the copper concentration leads to an increase of the elongation of the nanoparticles along the c axis.
  • the nanoparticles are rods with a length of 30 nm and a diameter of 8 nm - calculated based on TEM image ( Figure 2 (b)).
  • the rod formation along the c axis was confirmed by XRD diffractogram (Fig. 3 (b)) that shows much sharper 002 reflection than the other reflections.
  • Amount of Cu atoms present in synthesized nanoparticles was determined by energy-dispersive X-ray analysis (EDX). The obtained results are summarized in table 1.
  • Table 1 Influence of the amount of Cu precursor in reaction mixture on ZnO/Cu nanoparticle shape, size and photoluminescence (PL).
  • PL photoluminescence
  • the bacteria used for the antibacterial study were E. Coli DH5 , Gram-negative and S.Carnosus TM300. S. Carnosus as a typical gram-positive bacterium. Antibacterial tests were performed with a solution of nanoparticles in distilled water.
  • the ZnO/Cu nanoparticles synthesized with 15 , 10 % and 5 % of the copper precursor were used for the antibacterial study.
  • the average size of the ZnO/Cu nanoparticles was from 7 to 5 nm and the fraction of the copper (in mol) ranges from 2 to 4 %.
  • the ZnO nanoparticles synthesized according to the method of Pacholsky et al. (C. Pacholski, A. Kornowski, H. Weller Angew. Chem 2002 114 7 1234). was used as comparison. Their average size was 7 nm that is in the same range as investigated ZnO/Cu nanoparticles.
  • E. Coli and S. Carnosus bacteria were tested with different concentrations of the nanoparticles in order to observe the effect of nanoparticle concentration on bacterial growth.
  • the final concentration of the ZnO and ZnO/Cu nanoparticles in the bacterial cultures ranged from 0.300 to 0.070 mg/ml.
  • samples were used the same solvent as for the nanoparticles and LB medium.
  • the growth curves of the E.Coli DH5a and S. Carnosus TM300 bacteria are shown on Figure 5 and 6, respectively.
  • the bacteria growth was determined by measuring the time evolution of the optical density (OD) of the sample at 600 nm. As the value of the OD at 600 nm represents the absorbance of the bacteria, an increase of the number of the bacteria implies more light being absorbed by the bacteria.
  • the control sample containing the solvent showed no antibacterial activity.
  • the results shows in Fig.6 indicate an increase of the antibacterial activity with increase of the nanoparticle concentration in the medium.
  • the ZnO/Cu nanoparticles containing 3% copper are antibacterial against the E.Coli bacteria above a concentration of 0.09 mg/ml while the ZnO nanoparticles show the antibacterial effect only above 0.13 mg/ml. Similar results was obtained with S. Carnosus ( Figure 6.). Thus the results demonstrate that the ZnO/Cu nanoparticles have a higher antibacterial activity than the ZnO nanoparticles.
  • the results indicate a small increase in the antibacterial activity of the ZnO/Cu nanoparticles with a decrease of the copper percentage. All of the ZnO/Cu nanoparticles show the antibacterial activity against the E.Coli bacteria above a concentration of 0.09 mg/ml, which remains higher than the antibacterial activity of the ZnO nanoparticles.
  • Figure 10 shows the results of a growth test using S. carnosus with nanoparticle/polymer coated flasks, wherein the nanoparticles were doped with ZnO or ZnO:Cu. For both kinds of doped nanoparticles different concentrations were used as indicated in order to determine whether an effect is depending on the nanoparticle concentration.
  • the growth of the bacteria in the solution was determined by measuring the optical density (OD) of the solution at 600 nm at the beginning and after 2, 4, 6 and 8 h after incubation.
  • the results of the negative controls are depicted on the left and right side of figure 10.
  • the negative control comprising medium only with bacteria (left side of fig. 10) shows the typical growth curve for cultured bacteria. The same applies for the negative control with added polymer but without nanoparticles (right side of fig. 10).
  • the use of a nanoparticle-covered polymer results in a clear inhibition of bacteria proliferation.
  • the growth of the bacteria is more or less static, while the use of a higher concentration of doped nanoparticles results in a slightly better inhibition of bacteria growth as can be observed in the results using 1 mg/ml with more or less in a constant amount of bacteria in the medium.
  • the observed effects can be traced back to the nanoparticle/polymer coating of the flask, which is quite surprising and demonstrates that the coating of material with a doped nanoparticle -polymer according to the disclosure is appropriate for producing a bactericide surface.
  • Figure 11 shows the results of a growth test with S. carnosus, wherein the nanoparticles were directly added to the medium.
  • the control experiment shows the expected exponential growth of the bacteria within 24 hours.
  • the addition of nanoparticles doped with ZnO in a concentration of 0.2 mg/ml or 0.1 mg/ml resulted in a clear inhibition of any bacteria growth.
  • the addition of the doped nanoparticles to the medium seems to cause a slightly stronger effect than coating a surface with a nanoparticle-coated polymer.
  • the results depicted in fig. 11 demonstrate that adding nanoparticles according to the disclosure is very efficient with regard to the inhibition of bacteria growth in a solution.
  • Figures 12 to 16 show further experiments performed with different bacteria or yeasts as indicated on top of each figure.
  • the nanoparticles were added directly into the growth medium in a concentraion of 0.5 mg/ml and at the beginning, after 3, 16 and 24 h the optical density (OD) was determined at a wavelength of 600 nm in order to measure the bacteria concentration.
  • Table 2 summarizes the particles, which were added to the respective sample.
  • Table 2 Overview of samples and added substances.
  • FIG 12 shows the results of growth experiments with B. subtilis.
  • the bacteria growths is clearly inhibited by the addition of doped nanoparticles according to the present disclosure, independently whether they were coated with ZnO, ZnO:Mg or ZnO:Cu.
  • P. aeruginosa was used and an anti-bacterial effect can be observed, although the added nanoparticles are less efficient in reducing or preventing growth of P. aeruginosa.
  • colloidal ZnO/Cu nanoparticles and ZnO/Mg nanoparticles were synthesized from zinc acetate dehydrate (Zn(Ac) 2 x 2H 2 0) with copper acetate monohydrate (Cu(Ac) 2 x H 2 0) and magnesium chloride or nitrate (Mg(N0 3 ) 2 x 6 H 2 0) hexahydrate, respectively, in an alcohol solution under basic conditions. In order to improve solubility of Cu(Ac) 2 it will be solved in diluted hydrochlorid acid.
  • the synthesis is a modification of the method developed by Pacholsky et al. (C. Pacholski, A. Kornowski, H. Weller Angew. Chem. 2002 114 7 1234). The shape and size of the colloidal nanoparticles was varied from spheres to rods depending on the concentration of copper precursor in reaction mixture, wherein copper can be used in an amount of up to 15 % w/v.
  • Example 1 3.0 g of Zn(Ac) 2 x 2H 2 0 and 0.27 g of Cu(Ac) 2 x H 2 0 were dissolved in 18 ml of methanol to form a reaction mixture. The reaction mixture was heated at 64°C in a three-neck flask until a clear solution was formed. To produce the nanoparticles, a solution of 1.5 g of KOH dissolved in 6.5 ml of methanol at room temperature was added drop by drop into the three-neck flask under vigorous stirring. After the addition the reaction mixture was heated for minimum 22 hours at 64°C.
  • Example 2 3.0 g of Zn(Ac) 2 x 2H 2 0 and 0.4 g of Cu(Ac) 2 x H 2 0 were dissolved in 18 ml of methanol to form a reaction mixture. The reaction mixture was heated to 64°C in a three-neck flask until a clear solution was formed. To produce the nanoparticles, a solution of 1.5 g of KOH dissolved in 6.5 ml of methanol at room temperature was added drop by drop into the three-neck flask under vigorous stirring. After the addition the reaction mixture was heated for minimum 22 hours at 64°C.
  • Example 3 3.0 g of Zn(Ac) 2 x 2H 2 0 was dissolved in 18 ml of methanol to form a reaction mixture. The reaction mixture was heated to 64°C in a three-neck flask until a clear solution was formed. A solution of 1.5 g of KOH dissolved in 6.5 ml of methanol at room temperature was added drop by drop into the three-neck flask under vigorous stirring. After 1.5 hours a Solution of 0.27 g of Cu(Ac) 2 x H 2 0 dissolved in 7.5 ml methanol at room temperature was injected into the three-neck flask. After the injection the reaction mixture was heated for minimum 22 hours at 64°C.
  • Example 4 3.0 g of Zn(Ac) 2 x 2H 2 0 and 0.36 g of Mg(N0 3 ) 2 x 6H 2 0 were dissolved in 18 mL of methanol to form a reaction mixture. The reaction mixture was heated to 64°C in a three-neck flask until a clear solution was formed. To produce the nanoparticless, a solution of 1.5 g of KOH dissolved in 6.5 mL of methanol at room temperature was added drop by drop into the three-neck flask under vigorous stirring. After the addition the reaction mixture was heated for minimum 22 hours at 64°C.
  • Example 5 3.0 g of Zn(Ac) 2 x 2H 2 0 and 0.14 g of MgCl 2 were dissolved in 18 mL of methanol to form a reaction mixture. The reaction mixture was heated to 64°C in a three-neck flask until a clear solution was formed. To produce the nanoparticles, a solution of 1.5 g of KOH dissolved in 6.5 mL of methanol at room temperature was added drop by drop into the three-neck flask under vigorous stirring. After the addition the reaction mixture was heated for minimum 22 hours at 64°C.
  • US Patent US 6710091 Bl discloses the synthesis of ZnO nanoparticles having an average particle diameter of less than or equal to 15 nm, which are redispersible in organic solvents and/or water by basic hydrolysis of at least one Zn-compound in alcohol or an alcohol/water mixture.
  • US 6,710,091 does not disclose the synthesis of larger particles, or rods, and no doping of the ZnO nanoparticles with other metals.
  • the synthesized nanoparticles were characterized by low and high-resolution transmission electron microscopy (TEM), electron diffraction, and X-ray diffraction.
  • TEM samples were prepared by dropping diluted aqueous solutions of the ZnO/Cu nanoparticles onto 400-mesh carbon-coated copper grids with excess solvent immediately evaporated.
  • the optical properties of the nanoparticles have been characterized by electronic absorption and fluorescence spectroscopy. Absorption spectra were obtained using a Cary 50 spectrophotometer. Photoluminescence measurements were performed at room temperature using a Cary 50 spectrofluorimeter.
  • Escherichia Coli E. Coli
  • DH5a and Staphylococcus Carnosus S. Carnosus
  • TM300 bacteria were used for the antibacterial tests.
  • the bacteria were cultured in an LB medium at 37 °C on a shaker.
  • the bacterial culture was suspended in a sterile LB medium
  • CFU cm Cold-Colony Forming Unit
  • the antibacterial activity of the nanoparticles was assessed by measuring the growth curve of the bacteria.
  • 1.5 ml of the ZnO/Cu nanoparticles solution was diluted in 14.7 ml LB medium with 300 ⁇ bacteria.
  • the bacterial cultures incubated with the nanoparticles were grown at 37°C under an agitation condition.
  • the growth curve was determined by measuring the time evolution of the optical density (OD) of the sample at 600 nm.
  • OD optical density

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Abstract

Le domaine de l'invention concerne un procédé pour la fabrication d'une nanoparticule antibactérienne et son utilisation. La présente invention porte sur un procédé pour la synthèse de nanoparticules antibactériennes à base de ZnO dopé par du cuivre ou du magnésium et l'étude de leur activité antibactérienne sur Escherichia Coli (E. Coli) DH5α en tant que représentant des bactéries à gram négatif et sur Staphylococcus Carnosus (S. Carnosus) en tant que représentant des bactéries à gram positif.
PCT/EP2010/063646 2009-09-16 2010-09-16 Particules antibactériennes et leur synthèse WO2011033040A2 (fr)

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US9247734B2 (en) 2014-05-23 2016-02-02 Robert Sabin Potentiation of fixed coppers and other pesticides containing copper and supplementing plant nutrition
US9271502B2 (en) 2014-05-23 2016-03-01 Robert Sabin Potentiation of fixed coppers and other pesticides containing copper and supplementing plant nutrition
EP2994413A1 (fr) * 2013-05-06 2016-03-16 Bar-Ilan University Nanoparticules d'oxyde métallique dopées et utilisations associées
US9487453B2 (en) 2014-05-23 2016-11-08 Robert Sabin Potentiation of fixed coppers and other pesticides containing copper and supplementing plant nutrition
US9586871B2 (en) 2014-05-23 2017-03-07 Robert Sabin Potentiation of fixed coppers and other pesticides containing copper and supplementing plant nutrition
US9718739B2 (en) 2014-05-23 2017-08-01 Robert Sabin Potentiation of fixed coppers and other pesticides containing copper and supplementing plant nutrition
CN111109291A (zh) * 2019-12-13 2020-05-08 佛山欧神诺陶瓷有限公司 一种陶瓷砖抗菌剂及其制备方法
CN113287635A (zh) * 2021-05-12 2021-08-24 湘潭大学 用于抗菌、防霉的掺杂金属氧化物纳米颗粒、分散体或粉体的制备方法
CN113476640A (zh) * 2021-06-11 2021-10-08 中南大学 一种含异种离子掺杂金属硫化物的抗菌水凝胶敷料的制备方法

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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
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DE102011119332A1 (de) 2011-11-25 2013-05-29 Centrum Für Angewandte Nanotechnologie (Can) Gmbh Verwendung von über radikalische Emulsionspolymerisation erhältlichen Polymeren als Verdicker für Reinigungsmittel
EP2994413A1 (fr) * 2013-05-06 2016-03-16 Bar-Ilan University Nanoparticules d'oxyde métallique dopées et utilisations associées
EP2994413A4 (fr) * 2013-05-06 2017-05-03 Bar-Ilan University Nanoparticules d'oxyde métallique dopées et utilisations associées
US9586871B2 (en) 2014-05-23 2017-03-07 Robert Sabin Potentiation of fixed coppers and other pesticides containing copper and supplementing plant nutrition
US9487453B2 (en) 2014-05-23 2016-11-08 Robert Sabin Potentiation of fixed coppers and other pesticides containing copper and supplementing plant nutrition
US9271502B2 (en) 2014-05-23 2016-03-01 Robert Sabin Potentiation of fixed coppers and other pesticides containing copper and supplementing plant nutrition
US9247734B2 (en) 2014-05-23 2016-02-02 Robert Sabin Potentiation of fixed coppers and other pesticides containing copper and supplementing plant nutrition
US9717251B2 (en) 2014-05-23 2017-08-01 Robert Sabin Potentiation of fixed coppers and other pesticides containing copper and supplementing plant nutrition
US9718739B2 (en) 2014-05-23 2017-08-01 Robert Sabin Potentiation of fixed coppers and other pesticides containing copper and supplementing plant nutrition
CN111109291A (zh) * 2019-12-13 2020-05-08 佛山欧神诺陶瓷有限公司 一种陶瓷砖抗菌剂及其制备方法
CN113287635A (zh) * 2021-05-12 2021-08-24 湘潭大学 用于抗菌、防霉的掺杂金属氧化物纳米颗粒、分散体或粉体的制备方法
CN113476640A (zh) * 2021-06-11 2021-10-08 中南大学 一种含异种离子掺杂金属硫化物的抗菌水凝胶敷料的制备方法
CN113476640B (zh) * 2021-06-11 2022-10-21 中南大学 一种含异种离子掺杂金属硫化物的抗菌水凝胶敷料的制备方法

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