WO2022201200A1 - Broad-spectrum antimicrobial formulations prepared from electrolytically generated metal ions and methods of preparation - Google Patents
Broad-spectrum antimicrobial formulations prepared from electrolytically generated metal ions and methods of preparation Download PDFInfo
- Publication number
- WO2022201200A1 WO2022201200A1 PCT/IN2022/050295 IN2022050295W WO2022201200A1 WO 2022201200 A1 WO2022201200 A1 WO 2022201200A1 IN 2022050295 W IN2022050295 W IN 2022050295W WO 2022201200 A1 WO2022201200 A1 WO 2022201200A1
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- WIPO (PCT)
- Prior art keywords
- acid
- formulation
- silver
- antimicrobial
- formulations
- Prior art date
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- 239000010452 phosphate Substances 0.000 description 1
- 229940096992 potassium oleate Drugs 0.000 description 1
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000001243 protein synthesis Methods 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- BSWGGJHLVUUXTL-UHFFFAOYSA-N silver zinc Chemical compound [Zn].[Ag] BSWGGJHLVUUXTL-UHFFFAOYSA-N 0.000 description 1
- 230000037394 skin elasticity Effects 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000009182 swimming Effects 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000000699 topical effect Effects 0.000 description 1
- 230000014616 translation Effects 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 description 1
- 235000019352 zinc silicate Nutrition 0.000 description 1
Classifications
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- 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
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- 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
- A01N25/02—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 containing liquids as carriers, diluents or solvents
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- 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
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- 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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/185—Acids; Anhydrides, halides or salts thereof, e.g. sulfur acids, imidic, hydrazonic or hydroximic acids
- A61K31/19—Carboxylic acids, e.g. valproic acid
-
- 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
- A61K33/242—Gold; 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
- A61K33/243—Platinum; 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
- A61K33/30—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
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- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/042—Electrodes formed of a single material
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Abstract
The present invention relates to light insensitive and thermally stable antimicrobial formulations of electrolytically generated transition metal ions. The specific combination of metal ions gives it a broad spectrum anti-microbial ability against potentially pathogenic bacteria, virus, fungi, mold, mildew and antibiotic resistant species. The low viscosity formulations of the present invention are easy to be dosed, stand alone preservatives, providing a big change in the cosmetics and food industry. These eco-friendly formulations are effective alternatives to formaldehyde donors and parabens, with high bioavailability in water and oily phases. The alcohol and surfactants free formulations are effective in very small doses. Since, no organometallics or salts are used as the metal source in the present invention, this makes the formulations safe for sensitive applications such as in the cosmetics and food industry.
Description
BROAD-SPECTRUM ANTIMICROBIAL FORMULATIONS PREPARED FROM ELECTROLYTICALLY GENERATED METAL IONS AND METHODS OF PREPARATION
FIELD OF THE INVENTION:
[001] The present invention broadly relates to non-toxic environment friendly disinfectants. More particularly, the invention relates to antimicrobial formulations of electrolytically generated metal ions and method of preparing the same.
BACKGROUND OF THE INVENTION
[002] General state of the art demonstrates the use of silver and copper ions in aqueous solutions for use as disinfectant. In a typical electrochemical set-up, electric potential is applied across copper and silver electrodes thereby generating copper and silver ions in an electrolytic solution. The solution emanating from the ion chamber comprises of copper and silver ions generated by the copper and silver electrodes within the ion chamber is used as a disinfectant in water systems such as cooling towers, swimming pools, hot water systems in hospitals, potable water systems, spa pools and the like.
[003] In general, cosmetics are water based or hydrous solutions, thus in order to extend its shelf life and inhibit the consequent contamination by microorganisms such cosmetics require the addition of antimicrobial agents. Although preservatives can be added to solve the contamination problems, but such chemicals can lead to unwanted adverse effects such as allergies and other irritations on the skin on topical use apart from hormonal disruption and carcinogenic disposition.
[004] Similarly food contact surfaces such as the variety of kitchen appliances used in the kitchen including equipments used for processing, manufacturing, cooking, and storing foods are prone to contamination and therefore, sterilization
of tools or eating utensils is also becoming very important. However, in the disinfection and disinfection of kitchen appliances, the disinfectant or disinfectant residues may also adversely affect the human body. Further, due to the nature of the sterilizing and disinfecting material, it is not suitable for disinfecting the utensils/appliances due to pH or other ingredients, and there is a drawback in that it causes problems such as corrosion. Considering these factors, there is the need of non-toxic, non-acidic formulations which can effectively neutralize microorganisms while maintaining the characteristics of the other formulation matrices.
[005] References have been made to the following literature:
[006] US5503840 relates to an antimicrobial composition of titanium dioxide, barium sulfate, zinc oxide particles, and mixtures thereof having successive coatings of silver, in some cases a coating of zinc and/or copper compounds such as zinc oxide, copper (II) oxide and zinc silicate; silicon dioxide; alumina; and a dispersion aid such as dioctyl azelate. However the formulation is a complex mixture comprising a number of chemicals which might be unsafe for the cosmetics and food industry.
[007] US6197814 discloses a disinfectant formulated by electrolytically generated silver ions in the presence of citric acid referred to as electrolytically generated silver citrate. As the potential is applied across the electrodes, silver ion tends to migrate towards the cathode & gets deposited thereon thus leaving lesser number of silver ions in the electrolyte to form a complex with the acid. Owing to the same, the concentration of silver citrate complex formation is lesser thereby requiring much more time to reach the desired concentration.
[008] US7732486 discloses anhydrous silver dihydrogen citrate compositions comprising silver dihydrogen citrate and citric acid, where preparation method of liquid SDC (Silver dihydrogen citrate) involves applying a D.C potential across the electrodes. The anhydrous composition is prepared by freeze-drying. The document further discloses application of a reversible current to prevent
deposition of silver on the cathode. The inventions described in the literature typically use alcohol and detergents as additives and the concentrations of silver and citric acid is very low, thereby very less silver content in the final formulation.
[009] It is evident that despite the widespread use of copper and silver ions in making the antimicrobials, these ions have a limited stable ionic life and therefore, limited shelf life. Accordingly, there is a need to create stable metal ionic formulations which may be generated in a high concentration within a short duration of time.
[0010] The information disclosed in this background of the disclosure section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
SUMMARY OF THE INVENTION:
[0011] The present invention attempts to overcome the problems faced in the prior arts, and discloses formulations which can effectively neutralize microorganisms while not altering the characteristics of future formulations by providing for a stabilized, non-toxic, aqueous antimicrobial formulations based on electrolytically generated transition metal ions such as silver, zinc, gold, platinum, rhodium and copper for cosmetic and therapeutic use. The resultant formulation is colourless, odourless, tasteless, and non-caustic and formulates well with other compounds, thereby enabling safe usage on human skin, without adverse side effects.
[0012] In an embodiment, the present invention relates to antimicrobial formulations of electrolytically generated metal ions as stabilized ionic disinfectant where the specific combination of metal ions gives it the ability to be effective and work in a broad spectrum against potentially pathogenic bacteria, virus, fungi, mold, mildew and antibiotic resistant species. As no salts are used in
the process, thus no counter ions are generated which in turn makes it safer for the sensitive applications such as cosmetics and food industry.
[0013] In an exemplary embodiment, the present invention relates to a method for generating aqueous antimicrobial formulation, comprising the steps of a) preparing an electrolytic solution by adding measured amount of electrolyte (2- 40% w/v) in water in an electrochemistry vessel; b) applying potential difference across at least one anode and at least one cathode electrode in the electrolytic solution obtained from step (a) in the electrochemistry vessel to drive a current, wherein at least one anode electrode is selected from a group comprising transition metals and at least one cathode electrode is selected from a group comprising conductive materials; c) applying controlled volumes of pressurized inert gas in the electrolytic solution by an air sparger; d) collecting the final formulation from the outlet; f) gently heating the formulation at 50-60°C from step (d) to increase the concentration of the active ions in the formulation.
[0014] In another embodiment of the present invention, the electrolyte is selected from a group comprising of neutral salts such as that of zinc chloride or sodium sulphate or of acids selected from a group of carboxylic acids such as citric acid or long chain carboxylic acids/fatty acid such as oleic acid, lactic acid, mild acids, acetic acid, formic acid, oxalic acid, uric acid, maleic acid, tartaric acid, malonic acid, propionic acid, palmitic acid, linoleic acid, beheneic acid, and their salts, ascorbic acid and combinations thereof.
[0015] In a preferred embodiment, the transition metals, used for at least one anode electrode is selected from a group comprising silver, zinc, gold, rhodium, platinum and copper, and combinations thereof. Further, the cathode electrode is selected from a group comprising stainless steel, mild steel, boron, diamond, graphite, platinum, silver, copper and combinations thereof. Further, the present invention discloses a process of preparing an antimicrobial formulation wherein the electrolytically generated transition metal ions comprise of ions in the concentration of 0 % to 2 % by volume.
[0016] In another embodiment of the present invention, the cathode and anode electrodes may be of same or different material and can be interchanged in a sequential manner to generate a formulation with combination of antimicrobial metal ions.
[0017] In yet another embodiment of the present invention, the anode to cathode ratio is in the range of 1:10 to 10:1. Having this flexibility in the anode to cathode ratio enables the control of the discharge of the metal ions, such as, a larger anode to cathode ratio helps dissolve the metal ion faster but then the reaction has to be balanced. Besides, the cathode is the inert electrode and anode can be changed as per the requirement of the polarity so that metal of interest comes from the positively charged anode. The polarity can be reversed if the metal that is deposited on the cathode needs to be dissolved back in the solution.
[0018] In still another embodiment of the present invention, the electrolytic medium in the electrochemistry vessel comprises the skin friendly acid at pH 3-9.
[0019] In another embodiment of the present invention, the air sparging is with inert gas selected from a group comprising argon gas or nitrogen gas for enhancing the rate of reaction.
[0020] In another preferred embodiment of the present invention, the potential difference of 2-30 V is applied on to the electrodes and the reaction is continued for at least 20 minutes - 4 hour.
[0021] In an exemplary embodiment, the present invention relates to an electrolytically generated aqueous antimicrobial formulation, comprising of electrolytically generated transition metal ions 0.1-2% (w/v) and an electrolyte 2- 40% (w/v), in an aqueous electrolytic medium, with the pH of the antimicrobial formulation in the range of 3- 9.
[0022] In another embodiment, the transition metal is selected from a group of metals comprising gold, silver, copper, zinc, rhodium, platinum, titanium, cobalt, nickel, zirconium, molybdenum, tin and combinations thereof.
[0023] In yet another embodiment, the formulation after the generation of the metal complex is neutralized in the ratio of 1:1 with sodium or potassium carboxylate salts to obtain a resulting formulation that is near neutral pH.
[0024] In another preferred embodiment of the present invention, the formulation may be in the form of a tablet or capsule containing the antimicrobial powder, or antimicrobial solutions in the form as aerosols, infusions, sprays, mist, drops, or one or more liquids formulations or spray dried to generate a powdered form, but not limited to.
[0025] In another embodiment, the formulations of the present invention are broad spectrum antimicrobials with low viscosity, water & fat soluble formulations, alternate to the harmful chemicals (parabens, HCHO Donors, phenoxy ethanol, Isothiazolines, etc.)
[0026] The foregoing summary is illustrative only and is not intended to be in any way limiting. In addition to the illustrative aspects, embodiments, and features described above, further aspects, embodiments, and features will become apparent by reference to the drawings and the following detailed description.
BRIEF DESCRIPTION OF THE DRAWINGS
[0027] It is to be noted, however, that the appended drawings illustrate only typical embodiments of the present invention and are therefore not to be considered for limiting of its scope, for the invention may admit to other equally effective embodiments. The detailed description is described with reference to the accompanying figures. In the figures, the left-most digit(s) of a reference number identifies the figure in which the reference number first appears. The same numbers are used throughout the figures to reference like features and
components. Some embodiments of system or methods in accordance with embodiments of the present invention are now described, by way of example, and with reference to the accompanying figures, in which:
[0028] Fig. 1 illustrates diagrammatic view of electrochemical set-up, in accordance with an embodiment of the present invention.
[0029] The figure depicts embodiments of the present invention for the purposes of illustration only. A person skilled in the art will easily recognize from the following description that alternative embodiments of the structures and methods illustrated herein may be employed without departing from the principles of the disclosure described herein.
DESCRIPTION OF THE PREFERRED EMBODIMENTS:
[0030] While the embodiments of the disclosure are subject to various modifications and alternative forms, specific embodiments thereof have been shown by way of example in the figures and will be described below. It should be understood, however, that it is not intended to limit the disclosure to the particular forms disclosed, but on the contrary, the disclosure is intended to cover all modifications, equivalents, and alternatives falling within the scope of the disclosure. Further, the phraseology and terminology employed in the description is for the purpose of description only and not for the purpose of limitation.
[0031] The terms “comprises”, “comprising”, or any other variations thereof used in the disclosure, are intended to cover a non-exclusive inclusion, such that a device, apparatus, system, assembly, method that comprises a list of components or a series of steps that does not include only those components or steps but may include other components or steps not expressly listed or inherent to such apparatus, or assembly, or device. In other words, one or more elements or steps in a system or device or process proceeded by “comprises... a” or “comprising of’ does not, without more constraints, preclude the existence of other elements or
additional elements or additional steps in the system or device or process as the case may be.
[0032] The present invention relates to antimicrobial formulation of electrolytically generated metal ions and method of preparing the same. The said formulation is in the form of a stabilized ionic disinfectant wherein the specific combination of transition metal ions provides the ability of being extremely broad spectrum, which can work against potentially pathogenic bacteria, virus, fungi, mold, mildew and antibiotic resistant species. The said formulation is colorless, odorless, non-caustic and formulates well in different matrices. It is also available in a powder form and is effective against a wide range of microorganisms without the need of parabens, formaldehyde, halogens or quaternary ammonium compounds. As no salts are used in the process, thus no spectator counter ions are generated which in turn makes it safer for the sensitive applications such as cosmetics and food industry.
[0033] In accordance with an embodiment of the present invention, the metal ions in the composition are enveloped by a protective layer of carrier molecules such as citrate, oleate and others of the type to prevent the aggregation of ions. The carrier molecules slowly release metallic ions and the active metallic ions then neutralize the evolving micro-organisms in next generation antimicrobial formulations by mechanisms such as disruption of cell wall, perforation and disruption of cell membrane, inhibiting the protein synthesis and interfering with DNA replication etc. The highly water soluble antimicrobial formulation can be easily incorporated into the aqueous phase of gels, surfactants and emulsions produced in a cold process or hot process.
[0034] Reference may be made to Figure 1 illustrating the diagrammatic view of the electrochemical set-up in accordance with an embodiment of the present invention. In the Electrochemical setup for the generation of ions, the electrolysis process entails the steps of using neutral salts or carboxylic acids selected from a group of citric acid, oleic acid and long chain carboxylic acids/fatty acids as an
electrolytic solution and transition metal selected from a group of zinc, copper and silver metals as electrodes. The said electrodes (both cathode and anode) are preferably formed from 99.99 percent pure metal having impurities lesser than 100 ppm. The anode is spaced apart from the cathode at a distance of around 0.1 mm-100 cm. An electric potential of 2-30 V was applied on to the electrodes. An air sparger having a hollow metal ring with a hose coupled thereto is introduced into the solution for introducing controlled amount of pressurized gas in the form of air bubbles. When direct current is applied onto the electrodes, metal ions were generated which react with the electrolytic solution to form metal complexes. The sparging procedure by breaking the diffusion layer around the electrodes, improves the reaction rate and allows the formation of metal complexes of citrate, malonate, propionate, oleate, palmate, linolate, behenate etc. depending on the type of electrolytes used.
[0035] In an embodiment the present invention relates to a method for generating aqueous antimicrobial formulation, comprising the steps of a) preparing an electrolytic solution by adding measured amount of electrolyte (2-40% w/v) in water in an electrochemistry vessel; b) applying potential difference across at least one anode and at least one cathode electrode in the electrolytic solution obtained from step (a) in the electrochemistry vessel to drive a current, wherein at least one anode electrode is selected from a group comprising transition metals and at least one cathode electrode is selected from a group comprising conductive materials; c) applying controlled volumes of pressurized inert gas in the electrolytic solution by an air sparger; d) collecting the final formulation from the outlet; f) gently heating the formulation at 50-60°C from step (d) to increase the concentration of the active ions in the formulation.
[0036] In another embodiment of the present invention the electrolyte is selected from a group comprising of acids selected from a group of carboxylic acids such as citric acid or long chain carboxylic acids/fatty acid such as oleic acid, lactic acid, mild acids, acetic acid, formic acid, oxalic acid, uric acid, maleic acid, tartaric acid, malonic acid, propionic acid, palmitic acid, linoleic acid, beheneic
acid, dilute phosphoric acid, and their salts, ascorbic acid and combinations thereof.
[0037] In a preferred embodiment, the transition metals, used for at least one anode electrode is selected from a group comprising silver, zinc, gold, rhodium, platinum and copper, and combinations thereof. Further, the cathode electrode is selected from a group comprising stainless steel, mild steel, boron, diamond, graphite, platinum, silver, copper and combinations thereof. The cathode and anode electrodes may be of same or different material and can be interchanged in a sequential manner to generate a formulation with combination of antimicrobial metal ions.
[0038] In yet another embodiment of the present invention, the anode to cathode ratio is in the range of 1:10 to 10:1 to allow the fine tuning of the metal active concentration as required. Having this flexibility in the anode to cathode ratio enables the control of the discharge of the metal ions, such as, a larger anode to cathode ratio helps dissolve the metal ion faster but then the reaction has to be balanced. Besides, the cathode is the inert electrode and anode can be changed as per the requirement of the polarity so that metal of interest comes from the positively charged anode. The polarity can be reversed if the metal that is deposited on the cathode needs to be dissolved back in the solution.
[0039] In still another embodiment of the present invention, the electrolytic medium in the electrochemistry vessel comprises the skin friendly acid at pH 3-9.
[0040] In another embodiment of the present invention, the air sparging is with inert gas selected from a group comprising argon gas or nitrogen gas for enhancing the rate of reaction. The sparging procedure by breaking the diffusion layer around the electrodes, improves the reaction rate and allows the formation of metal complexes of citrate, malonate, propionate, oleate, palmate, linolate, behenate etc. depending on the type of electrolytes used.
[0041] In another preferred embodiment of the present invention, the potential difference of 2-30 V is applied on to the electrodes and the reaction is continued for at least 30 minutes to 4 hours.
[0042] In an exemplary embodiment, the present invention relates to an electrolytically generated aqueous antimicrobial formulation, comprising of electrolytically generated transition metal ions 0.1-2% (w/v) and an eletrolyte 2- 40% (w/v), in an aqueous electrolytic medium, with the pH of the antimicrobial formulation in the range of 3- 9.
[0043] In another embodiment, the transition metal is selected from a group of metals comprising gold, silver, copper, zinc, rhodium, platinum, titanium, cobalt, nickel, zirconium, molybdenum, tin and combinations thereof.
[0044] In yet another embodiment, the formulation after the generation of the metal complex is neutralized in the ratio of 1:1 with sodium or potassium carboxylate salts to obtain a resulting formulation in near neutral pH.
[0045] In another preferred embodiment of the present invention, the formulation may be in the form of a tablet or capsule containing the antimicrobial powder, or antimicrobial solutions in the form as aerosols, infusions, sprays, mist, drops, or one or more liquids formulations or spray dried to generate a powdered form, but not limited to.
Examples:
[0046] Example 1: Electrochemical setup for the generation of ions:
[0047] A typical electrolysis process of the present invention entails the steps of using neutral salts or carboxylic acids selected from a group of citric acid, oleic acid and long chain carboxylic acids/fatty acids as an electrolytic solution and using electrodes made of transition metal selected from a group of zinc, copper and silver metals. The said electrodes (both cathode and anode) are preferably formed from 99.99 percent pure metal having impurities lesser than 100 ppm. The
anode is spaced apart from the cathode at a distance of around 0.1 mm- 100 cm. An electric potential of 2-30 V is applied on to the electrodes for 20 minutes - 4 hours. An air sparger having a hollow metal ring with a hose coupled thereto is introduced into the solution for introducing controlled amount of pressurized gas in the form of air bubbles (Figure 1). When direct current is applied onto the electrodes, metal ions are generated which react with the electrolytic solution to form metal complexes. The sparging procedure by breaking the diffusion layer around the electrodes, improves the reaction rate and allows the formation of metal complexes of citrate, malonate, propionate, oleate, palmate, linolate, behenate etc. depending on the type of electrolytes used. Generation of a desired concentration of ions is also possible by application of specific voltage for a fixed duration of time. Generally, after the generation of the metal complex the formulation is neutralized in the ratio of 1 : 1 with sodium or potassium carboxylate salts so that the resulting formulation is near neutral in pH. This is one of the unique features of the present invention.
[0048] Example 2: Microbiological studies:
[0049] The zone of inhibition antimicrobial study was done to test the efficacy of the formulations. In Figure 2, S. aureus (ATCC 6538) species was used and the formulation P-14 was generated using a silver anode and a SS cathode. The current flowed for about 20 minutes and the media used in this case was citric acid. The zone of inhibition was recorded as almost 30 mm in this case and the amount of free silver in this particular formulation was found to be 76.6 ppm, (in this case < 0.01 %) using atomic absorption spectrometry methods.
[0050] Table 1: Table showing the Zone of Inhibition and anti microbial activity data of different formulations.
[0051] With respect to formulation P-15 with silver and Zinc combination, a silver zinc electrolyte was prepared by an electrochemical process using zinc and silver anodes sequentially and Stainless Steel as cathode. The flow of current in this electrochemical set up was for 4 hours and an electrolytic precipitate having free silver and zinc ions was generated. The zone of inhibition recorded with the formulation was almost 21 mm and the amount of free silver in this particular formulation was found to be 8 ppm and zinc ions as 1000 ppm using atomic absorption spectrometry methods. It is to be noted that the control electrolyte containing only zinc ions in similar concentrations showed a zone of only around 18.43 mm (P16).
[0052] Formulations with potassium oleate and / or oleic acid in aqueous solution as electrolyte and Silver or Copper as the active electrodes resulted in the release of free silver and copper ions, showing broad-spectrum antimicrobial activity.
[0053] Example 3: With respect to a formulation with silver and phosphate combination, a silver phosphate electrolyte was prepared by an electrochemical process using dilute phosphoric acid electrolyte with a silver anode and Stainless Steel cathode. The flow of current in this electrochemical set up was for 4 hours and an electrolytic precipitate having free silver ions was generated. The microbial cell count for the formulation was less than 30 CFU/g indicating a strong antimicrobial property of the formulation. (Table 2)
[0054] Table 2: Microbiological analysis of silver phosphate formulation
[0055] Example 4: 0.2 % of silver citrate: a formulation with silver and citric acid combination, was prepared by an electrochemical process using citric acid electrolyte with a silver anode and Stainless Steel cathode. The flow of current in this electrochemical set up was for 1 hour and an electrolytic precipitate having
silver citrate was generated. This formulation was added at a percentage of 0.2 % by volume to a skin lotion, where the lotion was devoid of any other anti microbial additive. The microbial cell count for the formulation was less than 10 CFU/g indicating towards the strong antimicrobial property of the formulation. (Table 3)
[0056] Table 3: Microbiological analysis of silver citrate formulation
[0057] Example 5: Silver lactate formulation, a formulation with silver and lactic acid combination, was prepared by an electrochemical process using lactic acid electrolyte with a silver anode and Stainless Steel cathode. The flow of current in this electrochemical set up was for 1 hour and an electrolytic precipitate having silver lactate was generated. The microbial cell count for the formulation was less than 10 CFU/g indicating towards the strong antimicrobial property of the formulation. (Table 4). Besides, after concentrating the formulation to half the original volume by gentle heating methods, the zone with S. Aureus was 27.04 mm, which confirms the strong antimicrobial potential of the formulation.
[0058] Table 4: Microbiological analysis of silver lactate formulation
[0059] Electrolytic formulations obtained by following the process of the present invention, such as those described in the examples above having free silver and zinc ions, thus, can kill bacteria, viruses and fungus that evolve in the cosmetic formulations, on contact due to the antimicrobial properties of silver and zinc ions. The formulations can be further utilized on food contact surfaces as efficient
surface disinfectant. The antimicrobial formulations being gentle enough to be used in child care environments provide an unparalleled combination of high efficiency and low toxicity with instant kill and long term efficacy.
[0060] In accordance with advantages of the present invention as compared with the existing formulations, the present invention is to provide a big change in the cosmetics industry. This is a low viscosity, easy to be dosed stand alone preservative, for many formulations. It is an effective alternative to formaldehyde donors and parabens, with high bioavailability in the water phase. The highly water-soluble antimicrobial formulation can be incorporated into the aqueous phase of gels, surfactants and emulsions produced in a cold process. In emulsions produced by hot processes, the antimicrobial active must be added to the final formulation after the emulsion has cooled down. Further, as organic acids are used as electrolyte, these formulations are oil soluble and thus can be used in essential oil based formulations as well. In the current invention, as the only solvent is water and the organic acid is used up to 40 weight percent so that a large concentration of the metal ions and their combinations can be extracted. This enables a very small volume percentage of the actual formulation to be needed for the cosmetic composition as mandated by various regulations.
[0061] Advantages:
• Silver lactate a formulation obtained by using the method of the present invention comprising the silver and lactic acid combination is an active ingredient that prevents infections and for intimate hygiene
• Formulations made using the process of the present invention containing gold and platinum are useful for luxury cosmetics. Further gold additives have other useful properties, such as reduce the loss of collagen, increase skin elasticity and brightens complexion. Further, platinum ions also work deeply with cellular DNA to reverse degenerative conditions. This is in contrast of using metallic gold and platinum, as these are not that active. Whereas the one added in the form of formulations of electrolytically
generated process of the present invention are well dispersed and in readily available ionic forms.
• The formulation can be used for the anti microbial cosmetic formulations such as, deodorant & foot-care, oral care, hair care (dandruff), skin care (acne, atopic), intimate hygiene, preservatives, wet wipes
• Light insensitive, thermally stable formulation needed to be added in very small amount to have the effect
• Since, no organometallics or salts are used for the metal source in the present invention, thus no spectator counter ions, which makes it safe for sensitive applications such as in the cosmetics and food industry.
Alcohol and surfactants free formulations.
• A simple and cost effective process
• Eco-friendly formulations [0062] It will be further appreciated that functions or structures of a plurality of components or steps may be combined into a single component or step, or the functions or structures of one-step or component may be split among plural steps or components. The present invention contemplates all of these combinations. Unless stated otherwise, dimensions and geometries of the various structures depicted herein are not intended to be restrictive of the invention, and other dimensions or geometries are possible. In addition, while a feature of the present invention may have been described in the context of only one of the illustrated embodiments, such feature may be combined with one or more other features of other embodiments, for any given application. It will also be appreciated from the above that the fabrication of the unique structures herein and the operation thereof also constitute methods in accordance with the present invention. The present invention also encompasses intermediate and end products resulting from the practice of the methods herein. The use of “comprising” or “including” also
contemplates embodiments that “consist essentially of’ or “consist of’ the recited feature.
[0063] Although embodiments for the present invention have been described in language specific to structural features, it is to be understood that the present invention is not necessarily limited to the specific features described. Rather, the specific features and methods are disclosed as embodiments for the present invention. Numerous modifications and adaptations of the system/component of the present invention will be apparent to those skilled in the art, and thus it is intended by the appended claims to cover all such modifications and adaptations which fall within the scope of the present invention.
Claims
1. A method for generating aqueous antimicrobial formulation, comprising the steps: a) preparing an electrolytic solution by adding measured amount of electrolyte (2-40% w/v) in water in an electrochemistry vessel; b) applying potential difference across at least one anode and at least one cathode electrode in the electrolytic solution obtained from step (a) in the electrochemistry vessel to drive a current, wherein at least one positive electrode is selected from a group comprising transition metals and at least one negative electrode is selected from a group comprising conductive materials; c) applying controlled volumes of pressurized inert gas in the electrolytic solution by an air sparger; d) collecting the final formulation from the outlet; f) gently heating the formulation at 50-60°C from step (d) to increase the concentration of the active ions in the formulation.
2. The method as claimed in claim 1, wherein the electrolyte is selected from mild acids selected from a group of carboxylic acids such as citric acid or long chain carboxylic acids/fatty acid such as oleic acid, lactic acid, mild acids, acetic acid, formic acid, oxalic acid, uric acid, maleic acid, tartaric acid, malonic acid, propionic acid, palmitic acid, linoleic acid, beheneic acid, dilute phosphoric acid and their salts, ascorbic acid and combinations thereof.
3. The method as claimed in claim 1, wherein the transition metals, used for at least one positive electrode is selected from a group comprising silver, zinc, gold, rhodium, platinum and copper, and combinations thereof.
4. The method as claimed in claim 1, wherein the negative electrode is selected from a group comprising stainless steel, mild steel, boron, diamond, graphite, platinum, silver, copper and combinations thereof.
5. The method as claimed in claim 1, wherein the cathode and anode electrode is of same or different material and can be interchanged in a
sequential manner to generate a formulation with combination of antimicrobial metal ions.
6. The method as claimed in claim 5, wherein the anode to cathode ratio is in the range of 1:10 to 10:1.
7. The method as claimed in claim 5, wherein the cathode is the inert electrode and anode can be changed as per the requirement of the polarity so that metal of interest comes from the positively charged anode.
8. The method as claimed in claim 1, wherein the electrolytic medium in the electrochemistry vessel comprises the skin friendly acid at pH 3-9.
9. The method as claimed in claim 1, wherein the air sparging is with inert gas selected from a group comprising argon gas or nitrogen gas for enhancing the rate of reaction.
10. The method as claimed in claim 1, wherein a potential difference of 2-30 V is applied on to the electrodes and the reaction is continued for at least 20 minutes- 4 hours.
11. An electrolytically generated aqueous antimicrobial formulation, comprising: a. electrolytically generated transition metal ions 0.1-2 % (w/v); b. an electrolyte 2-40% (w/v); in an aqueous electrolytic medium, wherein the pH of the antimicrobial formulation is 3- 9.
12. The antimicrobial formulation as claimed in claim 11, wherein the transition metal is selected from a group of metals comprising gold, silver, copper, zinc, rhodium, platinum, titanium, cobalt, nickel, zirconium, molybdenum, tin and combinations thereof.
13. The anti microbial formulation as claimed in claim 11, wherein the formulation after the generation of the metal complex is neutralized in the ratio of 1:1 with sodium or potassium carboxylate salts to obtain a resulting formulation in near neutral pH.
14. An anti-microbial formulation generated by the process as claimed in claim 1 , wherein the formulation may be in the form of a tablet or capsule
containing the antimicrobial powder, or antimicrobial solutions in the form as aerosols, infusions, sprays, mist, drops, or one or more liquid formulations or spray dried to generate a powdered form, and combinations thereof.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999018790A1 (en) * | 1997-10-10 | 1999-04-22 | Nvid International, Inc. | Disinfectant and method of making |
| NZ518845A (en) * | 1997-10-10 | 2004-02-27 | Innovative Medical Services | Disinfectant and method of making |
| WO2005041861A2 (en) * | 2003-08-28 | 2005-05-12 | Pure Bioscience | Anhydrous silver dihydrogen citrate compositions |
| WO2008149104A1 (en) * | 2007-06-07 | 2008-12-11 | Aguacure Limited | An antimicrobial composition comprising an aqueous solution of silver and copper |
-
2022
- 2022-03-24 WO PCT/IN2022/050295 patent/WO2022201200A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999018790A1 (en) * | 1997-10-10 | 1999-04-22 | Nvid International, Inc. | Disinfectant and method of making |
| NZ518845A (en) * | 1997-10-10 | 2004-02-27 | Innovative Medical Services | Disinfectant and method of making |
| WO2005041861A2 (en) * | 2003-08-28 | 2005-05-12 | Pure Bioscience | Anhydrous silver dihydrogen citrate compositions |
| WO2008149104A1 (en) * | 2007-06-07 | 2008-12-11 | Aguacure Limited | An antimicrobial composition comprising an aqueous solution of silver and copper |
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