WO2021107800A1 - Copper-gold alloy nanoparticles and their manufacturing method - Google Patents
Copper-gold alloy nanoparticles and their manufacturing method Download PDFInfo
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 45
- 229910001020 Au alloy Inorganic materials 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- QRJOYPHTNNOAOJ-UHFFFAOYSA-N copper gold Chemical compound [Cu].[Au] QRJOYPHTNNOAOJ-UHFFFAOYSA-N 0.000 title description 4
- 239000003353 gold alloy Substances 0.000 title description 2
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 16
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 14
- 150000002500 ions Chemical class 0.000 claims abstract description 13
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- 239000012873 virucide Substances 0.000 claims abstract description 5
- 239000003899 bactericide agent Substances 0.000 claims abstract description 4
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract 8
- 239000000243 solution Substances 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 229910052737 gold Inorganic materials 0.000 claims description 12
- 229910001868 water Inorganic materials 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 229910045601 alloy Inorganic materials 0.000 claims description 8
- 239000000956 alloy Substances 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
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- 238000003760 magnetic stirring Methods 0.000 claims description 4
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- 229940124561 microbicide Drugs 0.000 claims description 2
- 239000002855 microbicide agent Substances 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 6
- 238000000265 homogenisation Methods 0.000 claims 2
- 230000007774 longterm Effects 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 238000005202 decontamination Methods 0.000 abstract description 3
- 230000003588 decontaminative effect Effects 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- 238000002059 diagnostic imaging Methods 0.000 abstract description 2
- 230000005693 optoelectronics Effects 0.000 abstract description 2
- 239000010931 gold Substances 0.000 description 34
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 21
- 239000010949 copper Substances 0.000 description 14
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 10
- 230000008569 process Effects 0.000 description 8
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- 239000003638 chemical reducing agent Substances 0.000 description 7
- 239000000084 colloidal system Substances 0.000 description 7
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
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- 241000894006 Bacteria Species 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 241000589517 Pseudomonas aeruginosa Species 0.000 description 3
- 241000191967 Staphylococcus aureus Species 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
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- 238000002360 preparation method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- NZDXSXLYLMHYJA-UHFFFAOYSA-M 4-[(1,3-dimethylimidazol-1-ium-2-yl)diazenyl]-n,n-dimethylaniline;chloride Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1N=NC1=[N+](C)C=CN1C NZDXSXLYLMHYJA-UHFFFAOYSA-M 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- -1 hydroxyl radicals Chemical class 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 230000005865 ionizing radiation Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
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- 239000000203 mixture Substances 0.000 description 2
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- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000003608 radiolysis reaction Methods 0.000 description 2
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- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 229910002708 Au–Cu Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical class [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000194029 Enterococcus hirae Species 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 238000002083 X-ray spectrum Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
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- 239000007792 gaseous phase Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
- B01J2/02—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops
- B01J2/06—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops in a liquid medium
-
- 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
- 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
- A01N59/20—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/081—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing particle radiation or gamma-radiation
- B01J19/082—Gamma-radiation only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- B01J19/122—Incoherent waves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
Definitions
- the invention refers to Cu-Au bimetallic alloy nanoparticles and Au nanoparticles with controllable properties (size, narrow dimensional dispersion and high stability) with high antimicrobial activity, as well as to their manufacturing method
- Such types of materials are used in various applications, such as optoelectronics, sensors, renewable energy technologies and catalysts, medical imaging, biomedical devices, antimicrobial agents, etc.
- Np Metal nanoparticles
- Metal nanoparticles can be obtained in gaseous, solid and liquid phase [2].
- the nanoparticles are either chemically or biologically synthesized as colloids starting from solutions of precursors, i.e. soluble metal salt, reducing agent and optionally coating agents (stabilizer) [3].
- Some disadvantages of this type of methods are related to the frequently use as reducing agents of toxic and/or high biologic risk (health or environmentally harmful) compounds, long-time and multi-step synthesis procedures, the need of elevated temperatures and/or pressures, significant amounts of byproducts with environmental impact, etc. [4-6].
- Other disadvantages of classical syntheses consist in difficulty of obtaining metal nanoparticles with controllable properties (size, narrow dispersion and high stability), enabling of reproducible conditions, limitation to obtaining of small amounts of nanoparticles, leading to elevated costs of the synthesis process [7].
- the proposed synthesis method is based on the radiolysis of aqueous solutions, ionizing radiation transferring to the irradiated material a very large amount of energy, much higher than the average energy required to break any chemical bond, hence the energy transfer is non-selective [8].
- the principle of the proposed method is based on the interaction of ionizing radiation with the aqueous solution of Cu and Au ions which result in ionization and excitation of the water molecules and leads to the formation of radiation-induced species with high reducing capacity, especially hydrated electrons (e aq ) and atoms of H ⁇ .
- the aims of the present invention are to eliminate the above-mentioned disadvantages, by: (i) preparing Cu-Au alloy nanoparticles, in a single step, in aqueous solutions, at ambient temperature and pressure, with small sizes, narrow dimensional distribution and high stability in time; (ii) obtaining colloidal solutions based on copper-gold bimetallic alloy and gold nanoparticles, with high microbicide activity (simultaneously high efficiency against bacteria, fungi and viruses) used as surface decontamination agents, especially in the medical area; (iii) a process which ensures a reasonable consumption of raw materials, low losses, high yield and high selectivity (no wastes, no by-products and no unreacted raw materials); (iv) a process which does not involves the use of toxic or environmentally harmful reagents.
- the technical problem solved by the present invention is to obtain small-sized Cu-Au alloy nanoparticles with narrow dimensional distribution, high stability and high biocide activity (bactericide, fungicide and virucide), in conditions of efficient consumption of raw materials (involving high yield and high selectivity of the ionic precursor transformation).
- metal precursors either a mixture of soluble copper and Au salts, or soluble Au salt, respectively
- the proposed methods for obtaining Cu-Au alloy and Au nanoparticles are simple, fast and can be performed at ambient pressure and temperature;
- the synthesis of nanoparticles according to the present invention takes place in aqueous solution, which allows precise control of the parameters at any point of the reactor (concentration, temperature, dose), ensuring the reproducibility of the process;
- the synthesis does not involve toxic or high biological risk chemicals as reducing agents, the main reducing agent in the absence of oxygen being the hydrated electron which has a very high reduction potential;
- the Cu-Au alloy and Au Np, prepared according to the invention are uniform dispersions with high stability over time (of the order of months);
- the synthesis process according to the invention enables the manufacture of large amounts of Cu-Au or Au Np with controllable size and structure, with high reproducibility; it can be applied at industrial scale;
- the average size of the nanoparticles and the dimensional distribution prepared according to the invention depend critically on a small number of parameters that can be easily controlled, namely: (i) the irradiation dose, (ii) concentrations of the stabilizing agent (iii) the concentrations of Cu and Au ions and (iv) the molar ratio of Cu/Au;
- the dispersions of Cu-Au Np, prepared according to the invention present high antimicrobial activity: bactericide against Gram-positive and Gram-negative bacteria, fungicide and virucide effects; - the dispersions o Cu-Au Np, prepared according to the invention, are aseptic and can be used as professional disinfectants in surface decontamination applications in the medical field.
- Fig. 2 UV-Vis spectrum of the colloidal Cu/Au/SDS/EG system (molar ratio Cu/Au
- Fig. 4 UV-Vis spectra of the colloidal Cu Au SDS/EG system at different concentrations of Cu 2+ (different Cu Au ratios);
- - preparation of the aqueous solution of the stabilizing agent (either SDS, PVP, PVA): established amounts of water and soluble polymer (either SDS, PVA or PVP) are mixed together at 80 °C using a magnetic stirrer till the solution becomes clear; then, heating is stopped and the solution is left to chill naturally at room temperature; the weighted precursors (either Cu 2+ or Au 3+ , as appropriate) are added under stirring at room temperature;
- reaction mixture consists in mixing established volumes of solutions A and B/ or B with a compound R(OH)x; the dissolution of compound R(OH)x is performed at ambient temperature, after cooling the polymer solution, with a magnetic stirrer for 30 min.,
- the characterization is performed by specific, known measurements, such as UV-vis spectroscopy (maximum plasmonic wavelength), DLS, XRD, Zeta potential as well as by antimicrobial activity tests.
- Cu-Au nanoparticle solutions showed a high bactericidal efficiency characterized by Log 5 reduction of the microbial load (destroys 99.999% of the initial number of germs) against Staphylococcus aureus, Pseudomonas aeruginosa, Enterococcus hirae ) and, also, high fungicide and virucide activities.
- reaction mixture was obtained using different volume ratios between solution A and solution B (see Table 1), to obtain different concentrations of Cu ions in the solution. 15 % (v/v) of ethylene glycol (EG) are added to this solution; deaeration was performed with Ar for 30 minutes at a flow rate of 50 ml / minute;
- EG ethylene glycol
- the stability of the bimetallic alloy nanoparticle system was tested by measuring the absorbance of the solutions over a period of approx. 2 months (Fig. 5), the UV-Vis spectra remained practically unchanged during this period.
- the prepared solutions showed antimicrobial activity against E. coli, Pseudomonas aeruginosa and Staphylococcus Aureus, with inhibition zones between 4 and 15 mm, depending on the degree of dilution of the initial solution of Cu-Au alloy nanoparticles (Table 2) ⁇
- reaction mixture was obtained using 15 ml of solution A, 15 ml of solution B and 4 ml of isopropyl alcohol (IP A); deaeration was performed with Ar for 30 minutes at a flow rate of 50 ml / minute;
- the obtained solutions showed antimicrobial activity when tested against Pseudomonas aeruginosa and Staphylococcus Aureus, with inhibition zones between 5 and 13 mm, depending on the degree of dilution of the initial solution of Cu-Au alloy nanoparticles (Table 3).
Abstract
The invention refers to Cu-Au alloy and Au nanoparticles, with narrow dimensional dispersion obtained by radiochemical synthesis and to a method for manufacturing these materials with applications in optoelectronics, sensors, renewable energy technologies and catalysts, medical imaging, surface decontamination agents in the medical field etc. Narrow-dimensional Cu-Au alloy nanoparticles, are obtained in one-step eco-friendly synthesis by γ-radiation exposure (at doses between 15-75 kGy) of systems consisting in salt-precursors containing Cu2+ and Au3+ ions and a couple of coating and stabilizing agents on water-soluble polymer base; the resulted nanoparticles present absorption SPR maxima between 528-550 nm, average size between 1-30 nm, with high stability over time, with high bactericide, fungicide and virucide activities. Narrow-dimensional Au nanoparticles, are obtained in one-step eco-friendly synthesis by γ-radiation exposure (at doses between 15-75 kGy) of a system consisting in salt-precursor containing Au3+ ions and a couple of water- soluble polymer-based coating and stabilizing agents; the resulted Au nanoparticles present absorption SPR maxima between 520-532 nm, with average dimensions bellow 20 nm, with high stability over time.
Description
COPPER-GOLD ALLOY NANOPARTICLES AND THEIR MANUFACTURING
METHOD
The invention refers to Cu-Au bimetallic alloy nanoparticles and Au nanoparticles with controllable properties (size, narrow dimensional dispersion and high stability) with high antimicrobial activity, as well as to their manufacturing method
Such types of materials are used in various applications, such as optoelectronics, sensors, renewable energy technologies and catalysts, medical imaging, biomedical devices, antimicrobial agents, etc.
It is known that an important aspect in establishing the properties of these nanomaterials is the control of particle size, particle distribution and shape. Consequently, there is a growing interest in the development of methods enabling controlled synthesis of nanoparticles.
Metal nanoparticles (Np) are characterized by different chemical composition, shape, size and size-dispersion. To modify these characteristics, three main types of synthesis methods are known: chemical, physical and biological [1].
Metal nanoparticles can be obtained in gaseous, solid and liquid phase [2]. In the liquid phase, the nanoparticles are either chemically or biologically synthesized as colloids starting from solutions of precursors, i.e. soluble metal salt, reducing agent and optionally coating agents (stabilizer) [3].
Some disadvantages of this type of methods are related to the frequently use as reducing agents of toxic and/or high biologic risk (health or environmentally harmful) compounds, long-time and multi-step synthesis procedures, the need of elevated temperatures and/or pressures, significant amounts of byproducts with environmental impact, etc. [4-6]. Other disadvantages of classical syntheses consist in difficulty of obtaining metal nanoparticles with controllable properties (size, narrow dispersion and high stability), enabling of reproducible conditions, limitation to obtaining of small amounts of nanoparticles, leading to elevated costs of the synthesis process [7].
Numerous examples concerning the synthesis of nanometric structures based on Cu and other metals, especially core-shell structures, obtained by chemical synthesis, are cited in literature [see for example 4,5]. By far, the main drawbacks of many of these methods are the use of chemical reducing agents (hydrazine, sodium borohydride) known to be toxic [5-6] or the use of high temperatures [4].
The process proposed in the paper [6], in which Au-Cu bimetallic alloy nanospheres were obtained by chemical synthesis and the use of sodium borohydride as a reducing agent and PVP as a nanoparticle stabilizing agent at high temperatures, has the mentioned drawbacks.
The proposed synthesis method is based on the radiolysis of aqueous solutions, ionizing radiation transferring to the irradiated material a very large amount of energy, much higher than the average energy required to break any chemical bond, hence the energy transfer is non-selective [8]. The principle of the proposed method is based on the interaction of ionizing radiation with the aqueous solution of Cu and Au ions which result in ionization and excitation of the water molecules and leads to the formation of radiation-induced species with high reducing capacity, especially hydrated electrons (e aq) and atoms of H·.
These species are strong reducing agents with redox potentials (normal hydrogen electrode): Eo (H20/eaq) = -2,87 V and Eo (H+/H*) = -2,3 V [9] and can reduce Cu and Au ions from the solution to zero-valent Cu and Au particles.
The hydroxyl radicals (OH*), induced by water radiolysis, having a redox potential Eo (OH'/thO) = +2,8 V [9] can oxidize ions or atoms at high oxidation states. To avoid this process, a hydroxyl radical scavenger (such as primary or secondary alcohols) shall be present; it is added to the precursor solution.
The aims of the present invention are to eliminate the above-mentioned disadvantages, by: (i) preparing Cu-Au alloy nanoparticles, in a single step, in aqueous solutions, at ambient temperature and pressure, with small sizes, narrow dimensional distribution and high stability in time; (ii) obtaining colloidal solutions based on copper-gold bimetallic alloy and gold nanoparticles, with high microbicide activity (simultaneously high efficiency against bacteria, fungi and viruses) used as surface decontamination agents, especially in the medical area; (iii) a process which ensures a reasonable consumption of raw materials, low losses, high yield and high selectivity (no wastes, no by-products and no unreacted raw materials); (iv) a process which does not involves the use of toxic or environmentally harmful reagents.
The technical problem solved by the present invention is to obtain small-sized Cu-Au alloy nanoparticles with narrow dimensional distribution, high stability and high biocide activity (bactericide, fungicide and virucide), in conditions of efficient consumption of raw materials (involving high yield and high selectivity of the ionic precursor transformation).
According to the present invention, either Cu-Au alloy or pure Au nanoparticles are obtained by gamma-irradiation of an aqueous solution containing (i) metal precursors (either a mixture of soluble copper and Au salts, or soluble Au salt, respectively), (ii) coating and stabilizing agents consisting of a soluble polymer (such as PVA, PVP, SDS) and (iii) free radical scavenger agent with general formula R(OH)x (where R = alkyl or iso-alkyl, substituted phenyl and x = 1, 2) soluble or partially soluble in water, preventing so the oxidation of the resulted nanoparticles.
The present invention has the following advantages:
- the proposed methods for obtaining Cu-Au alloy and Au nanoparticles are simple, fast and can be performed at ambient pressure and temperature;
- the synthesis of nanoparticles according to the present invention takes place in aqueous solution, which allows precise control of the parameters at any point of the reactor (concentration, temperature, dose), ensuring the reproducibility of the process;
- the synthesis does not involve toxic or high biological risk chemicals as reducing agents, the main reducing agent in the absence of oxygen being the hydrated electron which has a very high reduction potential;
- the Cu-Au alloy and Au Np, prepared according to the invention, are uniform dispersions with high stability over time (of the order of months);
- the synthesis process according to the invention enables the manufacture of large amounts of Cu-Au or Au Np with controllable size and structure, with high reproducibility; it can be applied at industrial scale;
- the average size of the nanoparticles and the dimensional distribution prepared according to the invention, depend critically on a small number of parameters that can be easily controlled, namely: (i) the irradiation dose, (ii) concentrations of the stabilizing agent (iii) the concentrations of Cu and Au ions and (iv) the molar ratio of Cu/Au;
- the dispersions of Cu-Au Np, prepared according to the invention, present high antimicrobial activity: bactericide against Gram-positive and Gram-negative bacteria, fungicide and virucide effects;
- the dispersions o Cu-Au Np, prepared according to the invention, are aseptic and can be used as professional disinfectants in surface decontamination applications in the medical field.
The following are 4 embodiments of the invention, in connection with Figures 1-7, which represent:
Fig. 1 - Technological scheme of the process for obtaining Cu-Au alloy nanoparticles and Au nanoparticles
Fig. 2 - UV-Vis spectrum of the colloidal Cu/Au/SDS/EG system (molar ratio Cu/Au
1/1)
Fig. 3 - The zeta potential of Cu/Au/SDS/EG system (Cu Au molar ratio of 1/1)
Fig. 4 - UV-Vis spectra of the colloidal Cu Au SDS/EG system at different concentrations of Cu2+ (different Cu Au ratios);
Fig. 5 - Stability over time of the colloidal Cu-Au alloy system (depending on the concentration of Cu2+ (different Cu Au ratios)
Fig. 6 - UV-Vis spectra of the colloidal Cu Au PVP/IPA system (Cu Au molar ratio
2/1)
Example 1
For the purpose of radiochemical synthesis according to the invention, the following general sequence of operations is used (Fig. 1):
- preparation of the aqueous solution of the stabilizing agent (either SDS, PVP, PVA): established amounts of water and soluble polymer (either SDS, PVA or PVP) are mixed together at 80 °C using a magnetic stirrer till the solution becomes clear; then, heating is stopped and the solution is left to chill naturally at room temperature; the weighted precursors (either Cu2+ or Au3+, as appropriate) are added under stirring at room temperature;
- preparation of the reaction mixture consists in mixing established volumes of solutions A and B/ or B with a compound R(OH)x; the dissolution of compound R(OH)x is performed at ambient temperature, after cooling the polymer solution, with a magnetic stirrer for 30 min.,
- deaeration (removal of oxygen by bubbling N2 or Ar) is performed under magnetic stirring for another 30 min.;
- exposure to irradiation (dose rate: 0.7 kGy/h) of the reaction mixture is performed in a hermetically sealed glass container wrapped in aluminum foil;
- dimensional characterization and biocidal activity assessment of the resulted product. The characterization is performed by specific, known measurements, such as UV-vis spectroscopy (maximum plasmonic wavelength), DLS, XRD, Zeta potential as well as by antimicrobial activity tests.
Example 2
Using the procedure generally described in Example 1, prepare:
- 250 ml of solution (A) by dissolving a quantity of copper salt corresponding to a concentration of 2 -103 mol / 1 Cu2+ in a solution of 0.8% SDS in deionized water;
- 250 ml of solution (B) by dissolving an amount of Au3+ salt (chloroauric acid - H [AuCU]) corresponding to a concentration of 2-103 mol / 1 Au3+ in a solution of 0,8% SDS in deionized water;
- the reaction mixture was obtained using 212.5 ml of solution A, 212.5 ml of solution B (corresponding to a molar ratio Cu/Au = 1/1) and 75 ml of ethylene glycol (EG) by mixing at room temperature under magnetic stirrer, for 30 min., followed by deaeration under magnetic stirring and Ar (flow rate: 50 ml/min) for another 30 min.;
- exposure to irradiation was made at a total dose of 30 kGy.
After irradiation, a colloidal system of ruby-red color (visual analysis) Cu-Au alloy nanoparticles (from X-ray spectra), with average particle size of 5 nm (from DLS), at a concentration of 261 ppm, is obtained. The solution presented a pH of 2.84. UV-Vis spectra showed a characteristic maximum SPR absorption at approx. 532 nm (Fig. 2). The zeta potential of -44,4 mV (Fig. 3) suggests high stability of the alloy nanoparticles system.
Cu-Au nanoparticle solutions showed a high bactericidal efficiency characterized by Log 5 reduction of the microbial load (destroys 99.999% of the initial number of germs) against Staphylococcus aureus, Pseudomonas aeruginosa, Enterococcus hirae ) and, also, high fungicide and virucide activities.
Example 3
Using the procedure described in Examples 1 and 2, prepare:
- 100 ml of solution (A) with a concentration of 2 -103 mol/1 Cu2+ in a solution of 0.8% SDS in deionized water;
- 100 ml solution (B) with a concentration of 2 TO 3 mol/1 Au3+ (chloroauric acid - H [AuCL]) in a solution of 0.8% SDS in deionized water;
- the reaction mixture was obtained using different volume ratios between solution A and solution B (see Table 1), to obtain different concentrations of Cu ions in the solution. 15 % (v/v) of ethylene glycol (EG) are added to this solution; deaeration was performed with Ar for 30 minutes at a flow rate of 50 ml / minute;
- exposure to irradiation was made at a total dose of 30 kGy.
After irradiation, stable colloidal systems of spherical nanoparticles of Cu-Au bimetallic alloy, with color varying from red-ruby to light pink, depending on the initial concentration of Cu2+ ions (the solution became lighter with increasing concentration of Cu2+) were obtained. The optical properties of these solutions are illustrated in Fig. 4, with UV-vis spectra which show that the maximum SPR (Surface Plasmon Resonance) is between 532 nm (0% Cu; a stable colloidal system of Gold nanoparticles is formed) and 550 nm (at 90% Cu). DLS measurements showed average nanoparticle sizes of less than 10 nm (Table 1).
Table 1 - Characteristics of Cu-Au bimetallic alloy nanoparticles obtained according to Examples 1 and 2
The stability of the bimetallic alloy nanoparticle system was tested by measuring the absorbance of the solutions over a period of approx. 2 months (Fig. 5), the UV-Vis spectra remained practically unchanged during this period.
The prepared solutions showed antimicrobial activity against E. coli, Pseudomonas aeruginosa and Staphylococcus Aureus, with inhibition zones between 4 and 15 mm, depending on the degree of dilution of the initial solution of Cu-Au alloy nanoparticles (Table 2)·
Table 2 - Antimicrobial efficiency of the colloidal system of Cu-Au nanoparticles
Example 4
Using the procedure described in examples 1 and 2 prepare:
- 100 ml of solution (A) by dissolving a quantity of copper salt corresponding to a concentration of 2-103 mol/1 Cu2+ in a solution of 3.5% polyvinylpyrrolidone (PVP) in deionized water;
- 100 ml solution (B) by dissolving an amount of Au3+ salt (chloroauric acid - H [AuCU]) corresponding to a concentration of 1-103 mol/1 Au3+ in a solution of 3.5% polyvinylpyrrolidone (PVP) in water deionized water;
- the reaction mixture was obtained using 15 ml of solution A, 15 ml of solution B and 4 ml of isopropyl alcohol (IP A); deaeration was performed with Ar for 30 minutes at a flow rate of 50 ml / minute;
- exposure to irradiation was made at a total dose of 30 kGy.
After irradiation, colloidal systems of ruby-red color Cu-Au alloy nanoparticles were obtained. The UV-Vis spectra showed a characteristic maximum absorption of SPR at approx. 530 nm (Fig. 6).
The obtained solutions showed antimicrobial activity when tested against Pseudomonas aeruginosa and Staphylococcus Aureus, with inhibition zones between 5 and 13 mm, depending on the degree of dilution of the initial solution of Cu-Au alloy nanoparticles (Table 3).
Table 3 - Antimicrobial efficiency of the colloidal system of Cu-Au nanoparticles/PVP/IPA
REFERENCES
[1] Yashiro K. Microbial Synthesis of Noble Metal Nanoparticles Using Metal Reducing Bacteria. Journal of the Society of Powder Technology. 43 (7), 515-521 (2006)
[2] Madou MJ. Fundamentals of Microfabrication and Nanotechnology: From MEMS to Bio- MEMS and Bio-Nems: manufacturing techniques and applications. Boca Raton, FL: CRC Presslnc (2011)
[3] Abedini A, Daud A.R., Hamid M.A.A., Othman N. K., Saion E. A review on radiation- iduced nucleation and growth of colloidal metallic nanoparticles. Nanoscale Research Letters, 8, 474-484 (2013)
[4] Lauterbach JA, Hattrick-Simpers JR, Wen C. One-step synthesis of monodisperse transition metal core-shell nanoparticles with solid solution shells. US patent 9205410B2 (2013)
[5] Preparation method of nuclear shell structured nano-gold copper powder. China patent 1299865C (2005)
[6] Preparation method for gold-copper bimetal nanospheres. China patent 102728847A
(2011)
[7] A.A Alkhedhairy, J. Mussarat. Methods for producing silver nanoparticles. US 2011/0274736, 10 Nov. 2011
[8] Fiti M.B. Dozimetria chimica a radiatiilor ionizante. Ed. Academiei, Bucure§ti (1973)
[9] Rojas J., Castano C. Production of palladium nanoparticles supported on multiwalled carbon nanotubes by gamma irradiation. Radiat. Phys. Chem. 81, 16-21 (2012)
Claims
1. Dispersion of bimetallic Cu-Au alloy nanoparticles, characterized in that they are obtained by exposure to irradiation of systems consisting in a salt-precursor containing Cu and Au ions and a couple of coating and stabilizing agents consisting in (a) a water-soluble polymer (SDS, PVA, PVP) and (b) an alcohol with general formula R(OH)x (where R = alkyl or iso-alkyl, or substituted phenyl and x = 1, 2) soluble or partially soluble in water, the latter acting as a free radical scavenger preventing the oxidation of the resulted nanoparticles, which present maxima of plasmon absorption between 528-550 nm, controlled average size between 1-30 nm, with narrow dispersion, long term stability and high microbicide activity (including bactericide, fungicide and virucide).
2. Dispersion of Au nanoparticles, characterized in that they are obtained by exposure to irradiation of a system consisting of a salt-precursor containing Au ions and a couple of water-soluble polymer-based coating and a stabilizing agent (SDS, PVP, PVA) and an alcohol with general formula R(OH)x (where R = alkyl or iso-alkyl, or substituted phenyl, and x = 1, 2) soluble or partially soluble in water, the latter acting as a free radical scavenger preventing the oxidation of the resulted nanoparticles, which present plasmon absorption maximum between 520-532 nm, average particle size bellow 20 nm and narrow size dispersion, and long term stability.
3. Method of radiochemical synthesis of Cu-Au bimetallic alloy nanoparticles according to Claim 1, characterized in that systems consisting of the salt-precursor of Cu and Au ions and a pair of coating and stabilizing agents based on water-soluble polymer (SDS, PVA, PVP) and an alcohol with general formula R(OH) x (where R = alkyl or iso-alkyl, substituted phenyl and x = 1, 2) soluble or partially soluble in water, the latter acting as a free radical scavenger preventing the oxidation of the nanoparticles formed and consists in obtaining aqueous solutions of Cu and Au ions (concentrations between 105 and 103 mol/1) by magnetic stirring at ambient temperature, its introduction into an aqueous solution consisting of a water-soluble polymer (SDS 0.8%, PVP 3.5%) obtained by mixing at 80 0 C with a magnetic stirrer and an alcohol with general formula R(OH) x (where R = alkyl or isoalkyl, substituted phenyl, and x = 1, 2) soluble or partially soluble in water, in different concentrations, homogenization of the resulting solution with magnetic stirrer at room temperature, for 30 min., deaeration of the solution with N2 or Ar to remove O2, for another 30 minutes, followed by irradiation at a dose rate between 0.4 and 1.1 kGy / h, at integral doses between 15-75 kGy.
4. Method for obtaining Au nanoparticles by radiochemical synthesis according to Claim 2, characterized in that systems consisting of Au ion precursor salt and a pair of coating and stabilizing agents based on water-soluble polymers (SDS, PVA, PVP) and an alcohol with general formula R(OH) x (where R = alkyl or iso-alkyl, substituted phenyl and x = 1, 2) soluble or partially soluble in water, the latter acting as free radical scavenger preventing the oxidation of nanoparticles formed and consists in obtaining aqueous solutions of Au ions by magnetic stirring at ambient temperature, introducing it into an aqueous solution consisting of a water-soluble polymer (SDS 0.8%, PVP 3, 5%) obtained by mixing at 80 0 C with a magnetic stirrer and an alcohol with general formula R(OH) x (where R = alkyl or iso-alkyl, substituted phenyl and x = 1, 2) soluble or partially soluble in water, in different concentrations, homogenization of the resulting solution with magnetic stirrer at room temperature, for 30 min, deaeration of the solution with N2 or Ar to remove O2, for another 30 minutes, followed by irradiation at a dose rate between 0.4- 1.1 kGy /h, at integral doses between 15-75 kGy.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1299865C (en) | 2005-04-26 | 2007-02-14 | 黄德欢 | Preparation method of nuclear shell structured nano-gold copper powder |
| US20110274736A1 (en) | 2010-05-10 | 2011-11-10 | King Saud University | Methods for producing silver nanoparticles |
| CN102728847A (en) | 2011-04-02 | 2012-10-17 | 中国科学院大连化学物理研究所 | Preparation method for gold-copper bimetal nanospheres |
| US9205410B2 (en) | 2012-04-03 | 2015-12-08 | University Of South Carolina | One-step synthesis of monodisperse transition metal core-shell nanoparticles with solid solution shells |
-
2019
- 2019-11-27 RO ROA201900801A patent/RO134945B1/en unknown
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2020
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1299865C (en) | 2005-04-26 | 2007-02-14 | 黄德欢 | Preparation method of nuclear shell structured nano-gold copper powder |
| US20110274736A1 (en) | 2010-05-10 | 2011-11-10 | King Saud University | Methods for producing silver nanoparticles |
| CN102728847A (en) | 2011-04-02 | 2012-10-17 | 中国科学院大连化学物理研究所 | Preparation method for gold-copper bimetal nanospheres |
| US9205410B2 (en) | 2012-04-03 | 2015-12-08 | University Of South Carolina | One-step synthesis of monodisperse transition metal core-shell nanoparticles with solid solution shells |
Non-Patent Citations (12)
| Title |
|---|
| A.A ALKHEDHAIRYJ. MUSSARAT, METHODS FOR PRODUCING SILVER NANOPARTICLES |
| ABEDINI ADAUD A.R.HAMID M.A.A.OTHMAN N. K.SAION E.: "A review on radiation-iduced nucleation and growth of colloidal metallic nanoparticles", NANOSCALE RESEARCH LETTERS, vol. 8, 2013, pages 474 - 484 |
| AHMAD SHAHRUL IZWAN BIN ET AL: "A Study on Gamma Irradiation Synthesis of Copper Nanoparticles", AIP CONFERENCE PROCEEDINGS, 1 January 2009 (2009-01-01), pages 186 - 190, XP055798235, DOI: 10.1063/1.3160127 * |
| FITI M.B.: "Dozimetria chimica a radiatiilor ionizante", 1973 |
| FREITAS DE FREITAS LUCAS ET AL: "An Overview of the Synthesis of Gold Nanoparticles Using Radiation Technologies", NANOMATERIALS, vol. 8, no. 11, 15 November 2018 (2018-11-15), pages 939, XP055798233, DOI: 10.3390/nano8110939 * |
| HORI TATSURO ET AL: "Synthesis of Cu nanoparticles using gamma-ray irradiation reduction method", JAPANESE JOURNAL OF APPLIED PHYSICS, vol. 53, no. 5S1, 17 April 2014 (2014-04-17), JP, pages 05FC05, XP055798236, ISSN: 0021-4922, Retrieved from the Internet <URL:http://stacks.iop.org/1347-4065/53/i=5S1/a=05FC05?key=crossref.b8cb45992c984c4a4d0509c8671e2558> DOI: 10.7567/JJAP.53.05FC05 * |
| LAUTERBACH JAHATTRICK-SIMPERS JRWEN C, ONE-STEP SYNTHESIS OF MONODISPERSE TRANSITION METAL CORE-SHELL NANOPARTICLES WITH SOLID SOLUTION SHELLS |
| LUNGULESC EDUARD-MARIUS ET AL: "GAMMA ASSISTED SYNTHESIS OF COLLOIDAL COPPER BASED NANOPARTICLES", 19TH INTERNATIONAL BALKAN WORKSHOP ON APPLIED PHYSICS, CONSTANTA [RO], 16 July 2019 (2019-07-16), pages 119 - 120, XP055798227, Retrieved from the Internet <URL:DOI:10.13140/RG.2.2.24955.67369> * |
| MADOU MJ: "Fundamentals of Microfabrication and Nanotechnology: From MEMS to Bio-MEMS and Bio-Nems: manufacturing techniques and applications", 2011, CRC PRESSLNC |
| NILANJAL MISRA ET AL: "Gamma radiation induced synthesis of gold nanoparticles in aqueous polyvinyl pyrrolidone solution and its application for hydrogen peroxide estimation", RADIATION PHYSICS AND CHEMISTRY, ELSEVIER, AMSTERDAM, NL, vol. 81, no. 2, 12 October 2011 (2011-10-12), pages 195 - 200, XP028112338, ISSN: 0969-806X, [retrieved on 20111025], DOI: 10.1016/J.RADPHYSCHEM.2011.10.014 * |
| ROJAS J.CASTANO C.: "Production of palladium nanoparticles supported on multiwalled carbon nanotubes by gamma irradiation", RADIAT. PHYS. CHEM., vol. 81, 2012, pages 16 - 21, XP028325513, DOI: 10.1016/j.radphyschem.2011.08.010 |
| YASHIRO K: "Microbial Synthesis of Noble Metal Nanoparticles Using Metal Reducing Bacteria", JOURNAL OF THE SOCIETY OF POWDER TECHNOLOGY, vol. 43, no. 7, 2006, pages 515 - 521 |
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