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WO2006078786A1 - Objets susceptibles de désorber un gaz antimicrobien - Google Patents

Objets susceptibles de désorber un gaz antimicrobien Download PDF

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Publication number
WO2006078786A1
WO2006078786A1 PCT/US2006/001847 US2006001847W WO2006078786A1 WO 2006078786 A1 WO2006078786 A1 WO 2006078786A1 US 2006001847 W US2006001847 W US 2006001847W WO 2006078786 A1 WO2006078786 A1 WO 2006078786A1
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WO
WIPO (PCT)
Prior art keywords
article
gas
polymeric material
antimicrobial
chlorine dioxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2006/001847
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English (en)
Inventor
Landon Merrill
Gary O'neill
John Warner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Selective Micro Technologies LLC
Original Assignee
Selective Micro Technologies LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Selective Micro Technologies LLC filed Critical Selective Micro Technologies LLC
Publication of WO2006078786A1 publication Critical patent/WO2006078786A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
    • A61L2/20—Gaseous substances, e.g. vapours
    • 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
    • A01N25/08—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 solids as carriers or diluents
    • A01N25/10—Macromolecular compounds
    • 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
    • A01N25/18—Vapour or smoke emitting compositions with delayed or sustained release
    • 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
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23B—PRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
    • A23B2/00—Preservation of foods or foodstuffs, in general
    • A23B2/70—Preservation of foods or foodstuffs, in general by treatment with chemicals
    • A23B2/704—Preservation of foods or foodstuffs, in general by treatment with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23B—PRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
    • A23B7/00—Preservation of fruit or vegetables; Chemical ripening of fruit or vegetables
    • A23B7/14—Preserving or ripening with chemicals not covered by group A23B7/08 or A23B7/10
    • A23B7/144—Preserving or ripening with chemicals not covered by group A23B7/08 or A23B7/10 in the form of gases, e.g. fumigation; Compositions or apparatus therefor
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
    • A61L2/23—Solid substances, e.g. granules, powders, blocks, tablets
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L9/00—Disinfection, sterilisation or deodorisation of air
    • A61L9/015—Disinfection, sterilisation or deodorisation of air using gaseous or vaporous substances, e.g. ozone

Definitions

  • the invention relates generally to gas desorbing articles, and. more specifically to polymeric materials impregnated with an antimicrobial gas, and methods for making and employing the same to remediate microbial life.
  • gas for retarding, controlling, killing or preventing microbiological contamination (e.g., bacteria, fungi, viruses, mold spores, algae and protozoa); retarding, preventing, or controlling biochemical decomposition; controlling respiration, deodorizing and/or retarding and preventing chemotaxis to name a few, is known.
  • microbiological contamination e.g., bacteria, fungi, viruses, mold spores, algae and protozoa
  • Such gases include, but are not limited to, chlorine dioxide, sulfur dioxide, nitrogen dioxide, nitric oxide, nitrous oxide, carbon dioxide, hydrogen sulfide, hydrocyanic acid, and dichlorine monoxide.
  • chlorine dioxide has been found to be useful as a. disinfectant, antiseptic and sanitizer. It is used, e.g., to disinfect drinking water, various water supplies and food items.
  • chlorine dioxide finds use as a bleaching agent for flour, fats and textiles.
  • the present invention involves the impregnation of polymeric materials with an antimicrobial gas for use in a variety of purposes including sterilization, disinfection, deodorization, bleaching and sanitization.
  • the present invention provides a gas desorbing article including a polymeric material impregnated with an antimicrobial gas and methods of making and using the article.
  • the articles and methods of trie present invention are readily applicable to a number of applications where microbial remediation is desired, e.g.
  • the present invention is directed to a gas desorbing article including a polymeric material such as polystyrene impregnated with an antimicrobial gas (for example, chlorine dioxide).
  • the article is a container (e.g. , a food container) such as a vial, a bottle, or a clam sliell.
  • the article is in the form of a packaging material (e.g., a food packaging material), a pellet, a fiber, a liner or a sheet.
  • the article is substantially saturated with the antimicrobial gas and/ or the article is sanitized, disinfected or sterilized.
  • the article is impregnated with antimicrobial gas such that it is capable of desorbing antimicrobial gas for at least 10 minutes, 20 minutes, 30 minutes, 2 hours, 1 day or 5 days.
  • an item including, but not limited to, a food item, an agricultural product, a medical instrument, medical waste, a fruit, a vegetable, a flower, a bar sink, a mop bucket, and a dental instrument, is disposed within or exposed to the article.
  • the item may be disinfected, sterilized or sanitized, and, in certain embodiments, may remain as such for at least 10 minutes, 20 minutes, 30 minutes, 2 hours, 1 day or 5 days.
  • the article is disposed within a substantially gas impermeable package such that a substantial amount of antimicrobial gas remains impregnated within the polymeric material, hi yet another embodiment, the article further includes a gas impermeable material.
  • the article can be formed, at least in part, of a multilayer sheet including a gas impermeable layer and a layer including the impregnated polymeric material.
  • the invention is directed to a package including this multilayer sheet, where the gas impermeable layer impedes the release of antimicrobial gas from the package.
  • the invention is directed to methods of remediating microbial life in an environment by enclosing the environment with these articles or packages, such that the gas impermeable material impedes the release of the antimicrobial gas from the environment and microbial life is remediated within the environment.
  • the present invention is directed to a method for remediating microbial life by exposing an environment to an article as described herein, such that microbial life is remediated in the environment.
  • the environment may be defined by the article or, alternatively, may be immediately adjacent to the article.
  • the environment may include an item selected from the group consisting of a food item, an agricultural product, a medical instrument, medical waste, a fruit, a vegetable, a flower, a bar sink, a mop bucket, and a dental instrument, hi one embodiment, the environment is sanitized, sterilized, and/or disinfected, hi another embodiment, the gas is released over a period of at least about 10 minutes, 20 minutes, 1 hour, or 5 days, hi certain embodiments, the gas maybe released from the article to maintain a concentration of antimicrobial gas from about 0.10 ppm to about 20 ppm and/or to obtain an initial concentration of antimicrobial gas from about 0.10 ppm to about 20 ppm.
  • the present invention is directed to a method of making an article of the present invention by exposing a polymeric material to the antimicrobial gas (for example, a solution comprising the antimicrobial gas), hi certain embodiments, the polymeric material is exposed to the solution for at least about 10 minutes, 20 minutes, 1 tiour, 2 hours or 4 hours.
  • the solution may have a concentration of antimicrobial gas from about 50 ppm to about 600 ppm chlorine dioxide, from about 50 ppm to about 150 ppm chlorine dioxide, or from about 450 ppm to about 550 ppm chlorine dioxide.
  • Figure 1 is a graph illustrating the impregnation of a polystyrene vial with clilorine dioxide gas over time in accordance with the present invention.
  • Figure 2 is a graph illustrating desorption of chlorine dioxide from a polystyrene vial impregnated with chlorine dioxide in accordance with the present invention.
  • Figure 3 graphically depicts impregnation of a polystyrene vial with chlorine dioxide over time upon exposure to a 100 ppm chlorine dioxide solution.
  • Figure 4 graphically depicts the impregnation of a polystyrene vial with chlorine dioxide over time upon exposure to a 500 ppm chlorine dioxide solution.
  • Figure 5 graphically depicts desorption of chlorine dioxide into water from a ⁇ n impregnated polystyrene vial over time, following impregnation of the polystyrene v ⁇ al by exposure to a 100 ppm chlorine dioxide solution.
  • Figure 6 graphically depicts desorption of chlorine dioxide into water from axi impregnated polystyrene vial over time, following impregnation of the polystyrene vial by exposure to a 500 ppm chlorine dioxide solution.
  • the present invention is based, at least in part, on the discovery that polymeric materials can be impregnated with an antimicrobial gas and can subsequently desorb "the gas in a manner that is useful.
  • Such impregnated polymeric material can be employed to remediate microbial life, e.g., to sterilize, disinfect or sanitize desired items, such as food items, raw agricultural products, or medical or dental instruments by desorption of the antimicrobial gas from the polymeric material.
  • the present invention provides gas desorbing articles generally including pory ⁇ neric material impregnated with an antimicrobial gas, e.g., chlorine dioxide.
  • an antimicrobial gas e.g., chlorine dioxide.
  • the invention provides methods for employing such articles to remediate microbial life, e.g., to extend the life of fruits and vegetables or to remediate medical or laboratory equipment prior to ixse.
  • the invention further provides methods of making gas desorbing articles, and kits for making gas desorbing articles, e.g., at the point of use.
  • One advantage of the present invention is that the articles and polymeric materials of the present invention allow for convenient, efficient and safe remediation using antimicrobial gas.
  • the articles and methods of the present invention provide a means to disinfect, sanitize and/or sterilize an article or its contents, without the production or presence of residual byproducts and/or unused reactants. Additionally, the methods and articles of the present invention provide a convenient means of microbial remediation without additional steps, for example, the need to add any volume to the interior of the article, for example, by the addition of reactants, and, without the need for, for example, an on-site gas generating device. Yet another advantage is that the article can desorb gas over a period of time, thus providing timed release of microbial gas such that microbial life is remediated over time.
  • imppregnate generally refer to the association of a gas with a polymeric material by permeation or diffusion into the polymeric material (e.g., on the surface and/or into openings or insterstices of the polymeric material). Without wishing to be bound to any particular theory, it is believed that the gas is soluble in the polymeric material and accordingly, is absorbed by the polymeric material. However, various associations of gas into and onto polymeric material, including, but not limited to, absorption, adsorption, electrostatic and/ or ionic, are intended to be encompassed by the teachings of the present invention.
  • Impregnation can be achieved by exposing the polymeric article to the gas (e.g., chlorine dioxide in solution), for a desired length of time.
  • the gas e.g., chlorine dioxide in solution
  • the terms "desorb,” desorbing,” “desorption” and the like refer generally to the removal, release or diffusion of impregnated antimicrobial gas from a polymeric material. Desorption includes removal, release or diffusion of the gas from the polymeric material, whether the gas is associated with the polymeric material by any of a variety of mechanisms, including, but not limited to, absorption, adsorption, electrostatic and/ or ionic. Accordingly, a “gas desorbing article” refers to an article capable of desorption of impregnated gas.
  • remediating when used in the context of remediating microbes, refer to reducing, eliminating, retarding, controlling, killing and/or preventing the growth or presence of microbes; retarding, preventing, or controlling biochemical decomposition; controlling respiration, deodorizing and/or retarding and preventing chemotaxis of microbial life and/or growth; and the like.
  • Remediation can include, but is not limited to, sanitization, disinfection and sterilization of the article itself (e.g., for use in laboratory equipment) or its environment (e.g., for use in packing fruits and vegetables or controlling microbial life in a refrigerated case).
  • Remediation also can include antiseptic and germicidal activity.
  • the terms "sanitize,” “sanitizing” and the like, refer generally to the reduction, but not necessarily the elimination, of microbial life.
  • infectious refers generally to the destruction or inactivation of microbial life (e.g., infectious fungi and bacteria) but not necessarily the elimination, e.g., viable spores may remain.
  • sterilize refers to the destruction or elimination of microbial life, including vegetative bacteria, bacterial spores, fungi, fungal spores, and viruses. Sterilization is critical to infection control and is widely used in hospitals on medical and surgical instruments and equipment.
  • Antiseptic and “germicide” generally refer to the prevention of infection and/or decay by inhibiting the growth of microorganisms on or in living animals, including humans.
  • the present invention provides a gas desorbing article that generally includes a polymeric material impregnated with an antimicrobial gas.
  • the articles and/or items with respect to which it is desired to remediate microbial life can include any article including polymeric material capable of impregnation of antimicrobial gas, or item where remediation is desired.
  • surfaces e.g., countertops and lab benches
  • meat processing and packaging equipment e.g., dental and medical instruments and devices (e.g., syringes, scalpels, implantable devices
  • Commonly used devices made of polymeric material may be imbued with antimicrobial activity so as to, for example, sterilize, disinfect and sanitize its contents.
  • impregnated containers such as clam shells, or impregnated sheets may be manufactured and sold to farmers for packaging food items or agricultural products.
  • the antimicrobial gas would release into the interior volume of the container and serve to remediate, for example, sterilize, disinfect or sanitize, microbial life associated with the contents.
  • the containers can be used in the field upon or after collection of the food items or agricultural products and/or for repackaging prior to sale of the products.
  • polymeric materials impregnated with an antimicrobial gas such as chlorine dioxide for example, in the form of one or more pellets, beads, sheets, linings or fibers can serve to remediate microbial life and sanitize, disinfect or sterilize the article and items in the surrounding environment.
  • an antimicrobial gas such as chlorine dioxide
  • the articles can be placed within a closed environment, such as a shipping or storage container, such that the gas can desorb into the volume of the container and serve to remediate microbial life and sanitize, disinfect or sterilize the container and/or its contents.
  • the container is closed or enclosed within further packaging (e.g., shrink wrap) so as to prevent the release of the gas into the external environment, thereby enhancing the antimicrobial effect.
  • the articles can be placed in a closed shipping box or in a refrigerated case, such as a deli case or a refrigerated transport container.
  • the container is not enclosed, such as, for example, a cut flower container or a box having openings that is impregnated with gas and/or gas impregnated beads in a cut flower container wherein the gas remediates microbial life thereby increasing the shelf life of the flowers.
  • a cut flower container or a box having openings that is impregnated with gas and/or gas impregnated beads in a cut flower container wherein the gas remediates microbial life thereby increasing the shelf life of the flowers is another example.
  • the gas desorbing articles of the present invention can be employed to remediate microbial life, for example, to sterilize, disinfect or sanitize, the article itself, an item exposed to the environment about the article or contained within the article, or an environment exposed to or contained within the article.
  • the microbe may be present within the article, for example, a container, or alternatively may be adjacent to the article, e.g., fruit packaged with antimicrobial gas-impregnated packing materials.
  • the item to be subject to microbial remediation may be contained within an environment defined by the article, for example, ⁇ vithin the article itself, or alternatively may be adjacent to or near the article, for example, such that the item is exposed to the article.
  • the impregnated polymeric material is placed in an environment that is free or substantially free of the antimicrobial gas, thereby promoting desorption of the gas from the polymeric material into the surrounding environment.
  • the gas can exhibit its antimicrobial properties, for example, by killing mold, microorganisms, pathogens, bacteria or viruses present in the environment or on or in the item.
  • Trie gas can selectively exhibit antimicrobial properties, as desired, by, for example, varying the original concentration of the antimicrobial solution and/or by varying the exposure time of the contaminated item to the impregnated polymeric material.
  • Trie methods and articles of the present invention additionally provide a means for so-called '"last-step" antimicrobial remediation, for example, sanitization, disinfection and sterilization.
  • the methods of the present invention provide a means for remediating the contents of a package after the contents have been packaged.
  • the present invention provides for time release of antimicrobial gas into the surrounding environment or into solution, hi some embodiments, the gas desorbs from the polymeric material over time. Accordingly, the present invention provides a time release or residual effect for the antimicrobial gas. This property of continued release renders the present invention particularly suitable for use in various applications including, but not limited to, holding and packaging food items, such as fresh cut fruit and vegetables, raw agricultural products and cut flowers.
  • the present invention provides an apparatus and method for the controlled release of gas from an environment.
  • the polymeric material can enclose an environment containing a gas, and, optionally a gas generating device, and thereby mediate ⁇ e.g., control) the release of the gas from the enclosed environment.
  • gas contained and/or produced in the enclosed environment can be impregnated into the polymeric material, and subsequently desorbed to the external environment.
  • the system can be designed so as to achieve a desired release profile of said gas into the external environment.
  • the nature of the polymeric material, the concentration of the gas, the rate of gas generation, the volume of the enclosed environment and other factors can be manipulated by one skilled in the art to achieve a desired controlled release profile.
  • the antimicrobial gas is released from the polymeric materials over the course of about 120, 96, 72, 64, 56, 48, 44, 40, 36, 32, 28, 24, 22, 20, 18, 16, 14, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1 or 0.5 hours.
  • the antimicrobial gas is released over a period from about 30 minutes to about 5 days.
  • the polymeric material is impregnated with antimicrobial gas such that it is capable of desorbing antimicrobial gas for at least 10 minutes, 20 minutes, 30 minutes, 45 minutes, 1 hour, 2 hours, 6 hours, 8 hours, 12 hours, 1 day, 2 days or 5 days.
  • Ranges of values and minimum values using a combination of any of the above recited values as upper and/or lower limits are intended to be included as embodiments of the present invention.
  • the ability of an antimicrobial gas such as chlorine dioxide to release over a period of time is dependent on various factors readily known and/or determinable by one skilled in the art, including, but not limited to, the nature of the polymeric material and the concentration of the chlorine dioxide within the polymeric material and the surrounding environment.
  • Trie desorption time can be dependent on a number of factors, including the initial concentration desired, the concentration that is desired to be maintained and the length of time over -which it is desirable to continue to desorb gas.
  • a number of modifications can be made that are within the scope of the present invention, including for example, employing at least two polymeric materials that have varying sorption and desorption capabilities and rates.
  • microbial life remains substantially remediated for at least 10 minutes, 20 minutes, 30 minutes, 45 minutes, 1 hour, 2 hours, 6 hours, 8 hours, 12 hours, 1 day, 2 days or 5 days. Ranges of values and minimum values using a combination of any of the above recited values as upper and/or lower limits are intended to be included as embodiments of the present invention.
  • this controlled release property renders the present invention suitable for use with various devices, including bar sinks, mop buckets and humidifiers.
  • a bar sink made of impregnatable polymeric material may be impregnated with chlorine dioxide (for example, by filling the bar sink with a chlorine dioxide solution), thereby allowing for convenient sterilization of the sink and its contents, for example, upon the addition of water.
  • a mop bucket may be impregnated with chlorine dioxide, thereby allowing for convenient sterilization of the mop bucket, and/or for the production of chlorine dioxide solution for cleaning, for example, by the addition of water.
  • a humidifier can involve the impregnation of a separate compartment (of the water tank) made of a gas-desorbing polymeric material.
  • the separate compartment inay have a screw cap made of a non-diffusible polymer. Accordingly, the chlorine dioxide impregnated within the polymeric material will desorb through the compartment walls and into the humidifier solution, thereby sanitizing the humidifier solution and/or the humidifier itself.
  • impregnated filters may be utilized in accordance with the methods of the present invention.
  • Further embodiments include impregnated trash bags, medical waste bags or liners or packing for trash, medical waste and the like.
  • Such articles can be used, e.g., in remediating microbes, e.g., odor-causing bacteria, mold or viruses, within and/or in the immediate vicinity of the articles.
  • kits include laboratory supplies (e.g., vials, pipettes, and syringes), food containers (e.g., baby bottles), and the like (e.g., sponges and wipes) on which microbial life has been remediated " by impregnation of antimicrobial gas.
  • food containers e.g., baby bottles
  • the like e.g., sponges and wipes
  • Such bottles or other food containers could be shipped with gas impregnated or, alternatively, the article can be impregnated on-site and optionally sealed until used.
  • the invention could be particularly useful where on-site impregnation is not practicable or desired (e.g., a field hospital or in home).
  • the invention provides a method of providing a remediated item, by exposing the item to an article of the present invention, such that the item is remediated, for example, disinfected, sanitized and/or sterilized.
  • the article can be remediated on-site according to the methods of the present invention prior to or after use.
  • a gas impregnated vial can be removed from a gas impermeable package, and used in a non-sterile environment (e.g., a hospital), but remain remediated and/or returned to remediated conditions as a result of gas desorbing from the vial over time.
  • an item after use, an item can be placed in a gas impermeable or substantially impermeable container or returned to such a container so as to facilitate or enhance the remediation of microbial life.
  • remediated equipment can be packaged in such articles so that they can be shipped, stored and used in remediated condition, e.g., medical devices and equipment such as stents, scalpels, catheters, and the like. Such equipment also could be returned to the package for remediation as the gas desorbs over time, thus remediating the article for safe disposal or re-use of the article.
  • the article may include a gas impermeable material in addition to the impregnated polymeric material.
  • the article is formed of a first zone including a gas impermeable material and a second zone including an impregnated polymeric material.
  • the article may be of any form, including, but not limited to, a multilayer sheet, film, lining or packaging material, that includes a gas impermeable layer and an impregnated polymeric material layer. Accordingly, the article can be used to remediate an environment, optionally, one that contains an item to be remediated.
  • the article may enclose an environment such that the impregnated polymeric material releases antimicrobial gas into the enclosed environment so as to remediate the interior environment and the contents contained therein.
  • the gas impermeable layer would be positioned, for example, disposed on the external surface of the package, so as to impede or prevent the release of gas from the enclosed environment, thereby enhancing the remediating effect.
  • the invention provides a method for impregnating an article and related systems therefor.
  • Various aseptic packaging systems for example, from Bosch Inc. (Minneapolis, MN)
  • Bosch Inc. Minneapolis, MN
  • a packaging system can be designed or adjusted such that ttrultilayer sheets with a gas impermeable layer and a gas soluble polymeric material are exposed to antimicrobial gas so as to impregnate the gas soluble polymeric material.
  • the present invention provides a method of retrofitting a package system by providing a bath, chamber and/ or a gas generating device. Such features may be activated so as to produce the desired antimicrobial gas and to expose the impregnatable material thereto.
  • Gas generating devices include, but are not limited to, those described in U.S. Patent Application Publication No. 2004/0022676 (Hamilton et al), U.S. Patent Nos. 6,607,696 (Hamilton et al.) and 6,602,466 (Hamilton et al), International Publication Nos.
  • WO03/051407 (Hamilton et al), WO04/07375 (Hamilton et al.) and WO04/113224 (Warner et al.).
  • the invention further provides for assemblies and/or articles for retrofitting packaging systems, such as a bath, chamber, and/or gas generating devices.
  • the methods and articles of the present invention provide a safe and convenient means for transporting antimicrobial gas.
  • the impregnated polymeric material may be sealed within a gas impermeable package, which can be conveniently and safely transported without release of the gas into the atmosphere.
  • the methods and articles of the present invention may provide a means for deactivating microorganisms or enzymes in a sample without significant structural damage to cells and microorganisms present within the sample. Accordingly, the present invention provides an improved means of analysis of samples, for example, environmental samples, by creating a sample substantially similar to its natural state while minimizing the changes to the properties of the sample.
  • the article of the present invention includes or is formed, at least substantially, of polymeric material.
  • the polymeric material should be gas permeable so as to allow for the impregnation of antimicrobial gas into the polymeric material, and the subsequent desorption of the gas from the polymeric material.
  • Polymeric materials will vary in terms of their ability to be impregnated by an antimicrobial gas such as chlorine dioxide and in terms of their ability to release the gas. Release rates of particular polymeric materials can be readily determined by one skilled in the art, for example, as described in Example 3.
  • a desired impregnated polymeric material and/ or a desired release profile including, but not limited to, the nature of polymeric material, the solubility of the gas in the polymeric material, the concentration of antimicrobial gas, for example, in solution, to which the material is exposed and the loading time for which the material is exposed.
  • the amount of gas that can be impregnated and desorbed in a polymeric material, and the concentration of the gas in an exposed environment can be determined by any number of known methods, including those described in the instant application, e.g., in the examples.
  • the article and polymeric materials of the present invention may be prepared by exposing the polymeric material to the antimicrobial gas, for example, a chlorine dioxide solution, vapor or gas.
  • the polymeric material may be submerged within an antimicrobial gas solution under conditions that promote the impregnation of the gas into the polymeric material. Accordingly, the gas is impregnated into the polymeric material. Upon removal of the external source of gas, the gas will remain sorbed or impregnated in the polymeric material.
  • the present invention further contemplates use of other gases.
  • gases include, but are not limited to, sulfur dioxide, nitrogen dioxide, nitric oxide, nitrous oxide, carbon dioxide, hydrogen sulfide, hydrocyanic acid and dichlorine monoxide.
  • Chlorine dioxide and other gases maybe produced by techniques and devices well known in the art, for example, as described in U.S. Patent Application Publication No. 2004/0022676 (Hamilton et al), U.S. Patent Nos. 6,607-, 696 (Hamilton et al.) and 6,602,466 (Hamilton et al), International Publication Nos. WO03/051407 (Hamilton et al), WO04/07375 (Hamilton et al) and WO04/113224 (Warner et al).
  • the polymeric material is exposed to the gas for 48, 44, 40, 36, 32, 28, 24, 22, 20, 18, 16, 14, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1 or 0.5 hours.
  • the polymeric material is exposed to the antimicrobial gas for a period from about 30 mirrutes to about 5 days. Ranges of values using a combination of any of the above recited values as upper and/or lower limits are intended to be included as embodiments of the present invention.
  • the polymeric material is saturated; in another embodiment, the polymeric material is substantially saturated with, antimicrobial gas.
  • the polymeric material is exposed to a gas ⁇ e.g., in air or in solution) at a concentration of about 1000, 950, 900, 850, 800, 750, 700, 650, 600, 550, 500, 450, 400, 350, 300, 250, 200, 150, 100, 50, 25 and 10 ppm.
  • the polymeric material is exposed to a solution, of about 50 to about 6O0 ppm, 50 to about 150 ppm, or about 450 to about 550 ppm of, for example, chlorine dioxide solution. Ranges of values using a combination of any of the above recited values as upper and/or lower limits are intended to be inclixded as embodiments of the present invention.
  • a polymeric material can be chosen with a desired release profile.
  • Polymeric materials suitable for use in the present invention include, but are not limited to, ethylene vinyl acetate, polyanhydrides, polyglycolic acid, collagen, polyorthoesters, polylactic acid (PLA), polyethylene, polypropylene, polyvinyl chloride, polyvinyl acetate, methacrylic acid, polyacetylene, polyphenylene, polypyrrole, polythiophene, hydroxyethyl cellulose, hydroxypropyl cellulose, polyethylene glycol (PEG), polyethylene oxide, ethylene oxide- propylene oxide, and co-polymers thereof.
  • the polymeric material is polystyrene.
  • any polymeric material or combination of polymeric material can be readily determined, e.g., by using the methods described in the examples. Accordingly, a desired concentration of released antimicrobial gas, for example, in the exposed environment or solution, can be achieved.
  • the article produces a concentration ⁇ e.g., produces an initial concentration or maintains a concentration) of antimicrobial gas of about 50, 45, 40, 35, 30, 25, 20, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5 or 0.1 ppm in air of antimicrobial gas.
  • the article produces a concentration of antimicrobial gas of about 0.1 to about 50 ppm, of about 1 to about 40 ppm, of about 5 to about 30 ppm, or about 10 to about 20 ppm in air of antimicrobial gas. In a particular embodiment, the article produces a concentration of antimicrobial gas of about 0.1 to about 20 ppm of chlorine dioxide gas in air.
  • the article can produce a concentration ⁇ e.g., produces an initial concentration or maintains a concentration) of antimicrobial gas in solution of a.foout 500, 475, 450, 425, 400, 375, 350, 325, 300, 275, 250, 225, 200, 175, 150, 125, 100, 90, 80, 70, 60, 50, 45, 40, 35, 30, 25, 20, 1 5, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5 or 0.1 ppm.
  • the article produces a concentration of antimicrobial gas in solution of about 0.1 to about 500 ppm, about 0.5 to about 250 ppm, about 1 to about 100 ppm, and about 5 to about 50 ppm.
  • the article produces a concentration of antimicrobial gas of about 0.1 to about 20 ppm of chlorine dioxide gas in solution.
  • concentration of antimicrobial gas of about 0.1 to about 20 ppm of chlorine dioxide gas in solution.
  • the article of the present invention may be any device that can exhibit the desired antimicrobial activity.
  • the article may be, but is not limited to, a container such as a vial, a bottle or a clam shell container.
  • the article may be a container used to collect and transport food items or agricultural products, such as a clam shell.
  • the device may be of sufficient size to hold and remediate microbial life on the desired item.
  • the article may define a volume capable of holding the desired item.
  • the article may further define an opening, for example into the volume of the article.
  • the article may further include a device to enclose the opening, for example, a. cap, cover or lid that encloses the opening and the internal volume of the article.
  • the device to enclose the opening maybe a separate object, such as a cap, cover or lid, or may be structured as part of the article such tbiat the article is capable of sealing itself.
  • the ability of the article to enclose the opening and the internal volume of the article can serve to enhance the antimicrobial remediating capabilities of the article.
  • the antimicrobial gas that diffuses into the article will be substantially prevented from escaping the internal volume of the article. Accordingly, the gas will remain in a high concentration, thereby sterilizing, disinfecting or sanitizing the object contained therein.
  • the article can also be in the form of a packing material, lining, pellets, slheets or fibers.
  • the polymeric material has a high surface area and/ o>r mass.
  • the polymeric material may be self-sealing by, for example, pressure fit, zip lock, snap fit, tongue and groove or threaded fit techniques, thereby to impede or prevent the escape of " antimicrobial gas and to ultimately enhance the sterilizing effect.
  • the article can. include packing materials, e.g., for fruits or vegetables.
  • the polymeric material may be in the form of a pellet.
  • the pellet may be enclosed within a gas impermeable package, for example, so as to allow for the convenient transportation of chlorine dioxide.
  • the packaging material for example, a closed cardboard box, retards permeation of tfcie antimicrobial gas.
  • the polymeric material or article maybe enclosed within a gas impermeable or a substantially gas impermeable material so as to impede or prevent the antimicrobial gas from escaping the environment.
  • the gas can serve to remediate microbial life on the contents of the gas impermeable material.
  • the polymeric material maybe in the form of a pellet contained within a gas impermeable material.
  • the article may be a multilayer device with an impregnated polymeric material and an impermeable material, preferably surrounding the impregnated polymeric material, to retard or eliminate release of the gas.
  • articles in accordance with the present invention are packed in gas impermeable packaging such that a substantial amount of the gas remains impregnated within the polymeric material.
  • Advantages of this embodiment include that the articles can be prepared, then stored and/or shipped to the point of use, so that the articles are ready to remediate microbial life upon removing the gas impermeable material or packaging.
  • clam shell containers can be impregnated with chlorine dioxide gas and enclosed in shrink wrap for shipment to where agricultural products are packed.
  • Another exemplary embodiment is the impregnation and packaging of laboratory supplies such as pipettes and vials, so that they are ready for use at a later time without having to talce the additional step of sterilizing the item.
  • Impermeable material refers to a material that substantially" binders or prevents the passage of solids, gases and liquids and/or in which a gas has little to no solubility.
  • Impermeable materials can be constructed from various materials, including polymeric material, glass, metal, metallized polymeric material and/or coated papexs. Suitable impermeable or barrier materials include, but are not limited to, metals, polymeric materials and/or coated papers.
  • Oth.er suitable materials include polymeric layers constructed from, e.g., polyester, polyvinyl chloride, polyvinylidene chloride, acrylobutylstyrene and/or polytetrafluoroethylene, polyacrylate, acrylic, polycarbonate, poly(acrylonitrile, butadiene, styrene), and polyacetal.
  • metallized layers e.g., any of the above polymeric layers that have been metallized.
  • metallic foils such as aluminum, foils.
  • Various other impermeable materials can be used to form the barrier film as well, svich as glass or ceramics.
  • any item to be, for example, sanitized, sterilized or disinfected may be introduced within the interior volume of the article, may be surrounded by the polymeric material generally, or may be adjacent to the items.
  • the item may be a food item, including, but not limited, to fruits (such as berries and, in particular, strawberries) and vegetables, raw agricultural products, cut flowers, and medical and dental instruments.
  • the article is adjacent to the items, such as liners, spacers, or other articles adjacent to the item and used, for example, for storage or shipping.
  • a sample such as a biological, environmental or chemical sanr/ple
  • the sample may be remediated, for example, sanitized, disinfected or sterilized, as necessary to achieve the desired result.
  • an environmental sample may be introduced into an impregnated vial to allow for deactivation of microorganisms or to retain the sterility of the sample.
  • water may be introduced within the article, for example, a spray bottle,, to allow for the production of a chlorine dioxide solution for use in various other applications, such as decontamination of medical devices.
  • kits of the present invention may be reused by the methods of the present invention.
  • the polymeric material may be exposed to antimicrobial gas such that the gas is re-impregnated within the material, thereby rendering the article suitable for further use.
  • the present invention provides kits and methods for using kits that can be employed to make and use gas desorbing articles.
  • a kit includes a reactant and/or device for the production of an antimicrobial gas (e.g., chlorine dioxide in solution).
  • the kit incLudes instructions or other useful information, (e.g., a chart providing guidance for generating desired concentrations of chlorine dioxide solutions).
  • the kit may further include at least one of a polymeric material, an article including a polymeric material, or a gas impermeable membrane.
  • the kit includes a substantially gas impermeable packaging material for use in retaining the antimicrobial gas impregnated or substantially impregnated within the polymeric material.
  • Example 1 Administration of a Contaminated Solution to an Impregnated Vial
  • Polystyrene vials and glass containers (as a control) were each exposed to chlorine dioxide solutions in water having a concentration of about 193 ppm. The concentration of the gas in the solution did not significantly cliange upon exposure of the glass vials to the solution.
  • FIG. 1 is a graph depicting the amount of gas impregnated in a 6.45 g polystyrene vial over time. As shown in Figure 1, in 8 hrs, a 6.45 g vial of polystyrene was impregnated with 1.77 mg of chlorine dioxide.
  • Example 3 Release of Chlorine Dioxide from Impregnated Polvsiryrene
  • Example 4 Impregnation of Common Containers and Packing Materials Certain containers and packing materials, including polystyrene clamshell containers,
  • PLA clamshell containers expanded polystyrene or expanded polyethylene pack materials, were impregnated with chlorine dioxide by exposure to chlorine dioxide solution.
  • Each of the containers upon exposure to chlorine dioxide exhibited a greenish tinge, indicating the impregnation of chlorine dioxide within the walls of the materials.
  • Chlorine dioxide solution was removed from each vial prepared in Example 5. After the vials were allowed to air dry, the vials were filled with deionized water to allow for desorption of the chlorine dioxide from the vial into the water. In order to determine the amount of chlorine dioxide desorbed from the vials over time, the concentration, of the chlorine dioxide for a sample from each category of vial was measured at 30, 6O and 90 minutes. The desorption of ClO 2 over time from polystyrene vials previously exposed to 100 ppm chlorine dioxide solution is shown in Figure 5. As expected, the ClO 2 concentration in solution increased over time and was greater for those vials with greater initial exposure times to ClO 2 .

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Abstract

La présente invention décrit des objets susceptibles de désorber un gaz, lesdits objets incluant généralement des matériaux polymères imprégnés d'un gaz antimicrobien, par exemple le dioxyde de chlore. La présente invention décrit également des méthodes d'emploi de tels articles dans la lutte contre les micro-organismes tels que les champignons, les bactéries et les moisissures. La présente invention décrit en outre des méthodes d'élaboration de tels objets ainsi que de kits s'y rapportant.
PCT/US2006/001847 2005-01-18 2006-01-18 Objets susceptibles de désorber un gaz antimicrobien Ceased WO2006078786A1 (fr)

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WO2009036571A1 (fr) * 2007-09-21 2009-03-26 Enox Biopharma, Inc. Tubes antimicrobiens libérant un gaz pour drainer l'oreille

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WO2009036571A1 (fr) * 2007-09-21 2009-03-26 Enox Biopharma, Inc. Tubes antimicrobiens libérant un gaz pour drainer l'oreille
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