Delivery of gas-phase antimicrobial agents via infused crystalline and porous solids

Abstract

Provided are methods and systems for injecting desired fluids, especially antimicrobial agents, into crystalline and / or porous solids, and the resulting injected crystalline and / or porous solids. The solids of the present invention that can be injected with antimicrobial agents include erythritol, flavored salt, flavored sugar, baking soda, calcium carbonate, acetic acid, ascorbic acid and marshmallows.

Description

[0001] References to Related Applications

[0002] This application claims the benefit of priority to U.S. Provisional Patent Application No. 62 / 992,133, filed on March 19, 2020, which is incorporated herein by reference in its entirety. Technical Field

[0003] The present disclosure relates generally to articles, methods, and systems for delivering antimicrobial agents, and more particularly to infusing molecules of vapor-phase antimicrobial agents into the lattice structure, grain boundaries, and fluid inclusions of crystalline solids and / or into the pores of porous solids. Background Art

[0004] The combined global consumption of just three crystalline or potentially crystalline food products – flavored salt (sodium chloride), flavored sugar (sucrose), and baking soda (sodium bicarbonate) – exceeds 300 million tons annually. Of these, flavored salt and baking soda are commonly consumed in their crystalline form; flavored sugar delivered in crystalline form is less frequent, but still well-known and common.

[0005] The crystals of a crystalline solid typically contain fluid inclusions, i.e., liquid and / or gas molecules contained within the crystals of the lattice structure and / or occupying the "gaps" or "pores" in the lattice structure. Fluids are also trapped within the boundaries between grains. The fluid contained in a crystalline solid typically represents the liquid and / or gas present in the environment when the crystalline solid crystallizes. Such fluids typically include atmospheric gases, molecular hydrogen and molecular helium, particularly when the crystals are formed in the presence of water and / or air. However, such fluids may also include any other molecules that are small enough to be contained within the crystals of the lattice structure or the pores therein, or between the boundaries between grains and / or within the fluid inclusions.

[0006] To date, the possibility of providing a method for intentionally introducing a desired liquid and / or gas into the environment of a solid prior to crystallization such that the desired liquid and / or gas is present as fluid inclusions in the crystalline solid after crystallization has not been studied or explored in any depth. Capturing desired fluids (e.g., vapor-phase antimicrobial agents) at room temperature and various pressures would be highly advantageous because they would make delivery of the desired fluid to the consumer simpler, easier, less time-consuming, and less expensive.

[0007] Similar considerations apply to non-crystalline but porous solids. As a non-limiting example, it may be advantageous to trap molecules of a desired fluid within the pores of a cotton candy or other porous solid by providing the desired fluid to bind to the solid before or during pore formation.

[0008] Therefore, there is a need in the art for a method and system for introducing a desired fluid into the lattice structure, grain boundaries and / or fluid inclusions of a crystalline solid and / or the pores of a porous solid, particularly at room temperature, and for a crystalline and / or porous solid obtained thereby. There is also a need for an article comprising such a solid that, by way of non-limiting example, can be used to enhance the properties (e.g., shelf life) of an accompanying non-crystalline and / or non-porous food product.

[0009] Ozone is the triatomic form of oxygen (O3), a gas under standard conditions, and its oxidative antimicrobial effect, even at relatively low (ppm) concentrations, has been known for at least 75 years. Consequently, ozone dissolved in water (e.g., as a rinse, mist, spray, or bath) has long been used as an antimicrobial and disinfectant, largely because it advantageously decomposes into ordinary diatomic oxygen (O2) within a very short time (usually on the order of a few minutes).

[0010] Many methods and systems for antimicrobial treatment using ozone are known, but these methods and systems generally require a large amount of energy input because they generally require strong ultraviolet radiation or ionization of the air surrounding the object, cavity, space, environment, etc. to be treated. Therefore, there is a need in the art for a simpler and cheaper ozone antimicrobial treatment method. Summary of the Invention

[0011] In one aspect of the invention, a method for producing crystals of a solid infused with a vapor-phase antimicrobial agent comprises providing a solution of the solid in a solvent; introducing the vapor-phase antimicrobial agent into the solution; and crystallizing the solid.

[0012] In some embodiments, the solid can be selected from the group consisting of erythritol, sodium chloride, magnesium sulfate, sucrose, sodium bicarbonate, potassium chloride, calcium carbonate, sugar alcohols, acetic acid, and ascorbic acid.

[0013] In some embodiments, the gas-phase antimicrobial agent can be at least one of a bactericide and a virucide. The gas-phase antimicrobial agent can be, but does not necessarily need to be, ozone.

[0014] In some embodiments, the solvent may consist essentially of water.

[0015] In some embodiments, the introducing step can include spraying the solution into a cavity containing a gas, wherein the gas contained in the cavity includes a vapor-phase antimicrobial agent. The crystallizing step can, but does not necessarily, include flowing a carrier gas through the cavity to remove residual solvent from the cavity and allow the solid to crystallize on the interior surface of the cavity. The carrier gas can, but does not necessarily, include the vapor-phase antimicrobial agent.

[0016] In another aspect of the invention, an infused crystalline solid comprises a solid lattice structure; and at least one vapor-phase antimicrobial agent molecule present within at least one of crystals of the lattice structure, pores in the lattice structure, grain boundaries between the lattice structure, and fluid inclusions of crystals of the lattice structure.

[0017] In some embodiments, the solid can be selected from the group consisting of erythritol, sodium chloride, magnesium sulfate, sucrose, sodium bicarbonate, potassium chloride, calcium carbonate, sugar alcohols, acetic acid, and ascorbic acid.

[0018] In some embodiments, the gas-phase antimicrobial agent can be at least one of a bactericide and a virucide. The gas-phase antimicrobial agent can be, but does not necessarily need to be, ozone.

[0019] In some embodiments, the solid can be prepared by the methods disclosed herein.

[0020] In another aspect of the present invention, an absorbent antimicrobial article includes an infused crystalline solid as disclosed herein.

[0021] In some embodiments, the absorbent antimicrobial article may further comprise a sheet material impregnated with the infused crystalline solid. The sheet material may, but need not necessarily, be selected from the group consisting of paper and plastic.

[0022] In another aspect of the present invention, a container for meat or ingredients comprises an absorbent antimicrobial article as disclosed herein.

[0023] In another aspect of the invention, a method for producing an ozonated crystalline solid comprises: (a) generating a gas stream comprising ozone and flowing the gas stream into or through a sealable chamber; (b) spraying a solution of a crystalline solid in a solvent into the sealable chamber; (c) removing residual solvent from the sealable chamber by flowing a first carrier gas through the sealable chamber to allow the ozonated crystalline solid to crystallize on an interior surface of the sealable chamber; and (d) removing residual ozone from the sealable chamber.

[0024] In some embodiments, the crystalline solid can be selected from the group consisting of erythritol, sodium chloride, magnesium sulfate, sucrose, sodium bicarbonate, potassium chloride, calcium carbonate, sugar alcohols, acetic acid, and ascorbic acid.

[0025] In some embodiments, the solvent may consist essentially of water.

[0026] In some embodiments, the first carrier gas can include ozone.

[0027] In some embodiments, step (a) may include the following sub-steps: (i) generating an oxygen-enriched gas stream by selectively removing nitrogen from ambient air; and (ii) converting at least a portion of the diatomic oxygen in the oxygen-enriched gas stream into ozone.

[0028] In some embodiments, when performing step (b), ozone may comprise at least about 6.0 wt. % of the total gas content of the sealable chamber.

[0029] In some embodiments, the temperature of the solution may be approximately 170°F.

[0030] In some embodiments, the solution can be pressurized to at least about 35 psi before being sprayed into the sealable chamber.

[0031] In some embodiments, step (b) can be performed at least twice.

[0032] In some embodiments, step (d) may include applying negative pressure to the sealable chamber to evacuate residual ozone from the sealable chamber.

[0033] In some embodiments, step (d) may include flowing a second carrier gas through the sealable chamber to entrain and remove at least one of residual ozone and residual solvent from the sealable chamber. The second carrier gas may, but does not necessarily, include nitrogen.

[0034] In some embodiments, the method may further comprise (e) collecting the ozonated crystalline solid from the inner surface of the sealable chamber.

[0035] In another aspect of the invention, a system for producing ozonated crystalline solids includes at least one ozone generator configured to receive an oxygen-rich gas stream and convert at least a portion of diatomic oxygen in the oxygen-rich gas stream into ozone to form an ozone-containing gas stream; a sealable chamber configured to receive the ozone-containing gas stream from the at least one ozone generator; a heat source configured to receive and heat a solution of a crystalline solid in a solvent; a pressure vessel configured to pre-pressurize the solution; an atomizer configured to receive the pre-pressurized solution from the pressure vessel, further pressurize the solution, and dispense the solution in atomized form into the sealable chamber through a nozzle; a heat tracer configured to heat a manifold and high-pressure lines of the atomizer prior to dispensing the solution into the sealable chamber; and a nitrogen source configured to flow nitrogen through the sealable chamber after dispensing the solution into the sealable chamber to remove residual ozone from the sealable chamber.

[0036] In some embodiments, the system may further include an oxygen concentrator configured to generate an oxygen-enriched gas stream by selectively removing nitrogen from ambient air.

[0037] In some embodiments, the crystalline solid can be selected from the group consisting of erythritol, sodium chloride, magnesium sulfate, sucrose, sodium bicarbonate, potassium chloride, calcium carbonate, sugar alcohols, acetic acid, and ascorbic acid.

[0038] In some embodiments, the solvent may consist essentially of water.

[0039] In another aspect of the invention, a method for antimicrobial treatment of a target object comprises: (a) providing crystals of a crystalline solid infused with a vapor-phase antimicrobial agent; and (b) placing the crystals of the crystalline solid in or on a surface of the target object, or in the environment surrounding the target object.

[0040] In some embodiments, the crystalline solid can be selected from the group consisting of erythritol, sodium chloride, magnesium sulfate, sucrose, sodium bicarbonate, potassium chloride, calcium carbonate, sugar alcohols, acetic acid, and ascorbic acid.

[0041] In some embodiments, the gas-phase antimicrobial agent can be at least one of a bactericide and a virucide. The gas-phase antimicrobial agent can be, but does not necessarily need to be, ozone.

[0042] In some embodiments, step (a) can comprise producing crystals of a crystalline solid by a method disclosed herein.

[0043] In some embodiments, in step (b), the crystals of the crystalline solid may be contained in an absorbent antimicrobial article. The absorbent antimicrobial article may, but need not, include a sheet material impregnated with the crystals of the crystalline solid. The sheet material may, but need not, be selected from the group consisting of paper and plastic.

[0044] In some embodiments, the vapor-phase antimicrobial agent can be released into the environment surrounding the target object when the crystals dissolve in a liquid present in the environment.

[0045] In some embodiments, the method may further include (c) dissolving or rendering at least a portion of the crystals non-crystalline, thereby releasing at least a portion of the vapor-phase antimicrobial agent into or onto the target object, or into the environment surrounding the target object.

[0046] In some embodiments, step (c) may include modifying at least one of a temperature of the target object, a temperature of the environment surrounding the target object, a moisture content of the target object, or a humidity of the environment surrounding the target object.

[0047] In aspects of the present disclosure, a method of infusing a vapor-phase antimicrobial agent into crystals of a food product includes providing a solution of the food product in a food-grade solvent; introducing the vapor-phase antimicrobial agent into the solution; and crystallizing the food product.

[0048] In some embodiments, the food can be selected from the group consisting of sodium chloride, magnesium sulfate, sucrose, sodium bicarbonate, potassium chloride, calcium carbonate, sugar alcohols, acetic acid, and ascorbic acid.

[0049] In some embodiments, the gas-phase antimicrobial agent can be at least one of a bactericide and a virucide. The gas-phase antimicrobial agent can be, but does not necessarily need to be, ozone.

[0050] In some embodiments, the food-grade solvent may consist essentially of water.

[0051] In aspects of the present disclosure, a method of injecting a vapor-phase antimicrobial agent into pores of a food product includes providing a liquid precursor of the food product; introducing a vapor-phase antimicrobial agent into the liquid precursor; and aerating the liquid precursor to form the food product.

[0052] In some embodiments, at least one of the following may be true: (i) the liquid precursor comprises sugar, water, and a protein source; and (ii) the food product is marshmallow. The protein source may, but need not necessarily, be selected from the group consisting of egg whites and gelatin.

[0053] In some embodiments, the gas-phase antimicrobial agent can be at least one of a bactericide and a virucide. The gas-phase antimicrobial agent is ozone.

[0054] In aspects of the present disclosure, an infused crystalline food product includes a food product crystal lattice structure; and at least one vapor-phase antimicrobial agent molecule present within at least one of crystals of the crystal lattice structure, pores in the crystal lattice structure, grain boundaries between the crystal lattice structure, and fluid inclusions of crystals of the lattice structure.

[0055] In some embodiments, the food can be selected from the group consisting of sodium chloride, magnesium sulfate, sucrose, sodium bicarbonate, potassium chloride, calcium carbonate, sugar alcohols, acetic acid, and ascorbic acid.

[0056] In some embodiments, the gas-phase antimicrobial agent can be at least one of a bactericide and a virucide. The gas-phase antimicrobial agent can be, but does not necessarily need to be, ozone.

[0057] In an aspect of the present disclosure, an infused porous food product includes a food product having a plurality of pores; and at least one gas-phase antimicrobial agent molecule present within at least one pore of the plurality of pores.

[0058] In some embodiments, the food product may be marshmallow.

[0059] In some embodiments, the gas-phase antimicrobial agent can be at least one of a bactericide and a virucide. The gas-phase antimicrobial agent can be, but does not necessarily need to be, ozone.

[0060] In aspects of the present disclosure, an absorbent antimicrobial article includes an infused crystallized food product as disclosed herein.

[0061] In some embodiments, the absorbent antimicrobial article may further include a sheet material impregnated with the infused crystallized food. The sheet material may, but does not necessarily, be selected from the group consisting of paper and plastic.

[0062] In aspects of the present disclosure, an absorbent antimicrobial article includes an infused porous food product as disclosed herein.

[0063] In some embodiments, the absorbent antimicrobial article may consist essentially of an infused porous food product.

[0064] In an aspect of the present disclosure, a container for a meat product comprises an absorbent antimicrobial article as disclosed herein. BRIEF DESCRIPTION OF THE DRAWINGS

[0065] Figure 1 A system for producing ozonated crystalline solids is shown.

[0066] Figure 2 A method for producing an ozonated crystalline solid is shown.

[0067] Figure 3 A method for antimicrobial treatment of a target object is shown. DETAILED DESCRIPTION

[0068] As used herein, unless otherwise indicated, the term "crystalline" refers to any material that can be a solid at atmospheric pressure and room temperature composed of atoms arranged in a highly ordered microstructure to form a crystalline lattice extending in all directions.

[0069] As used herein, unless otherwise indicated, the term "meat" refers to any part of the body of an animal intended for consumption by humans or domestic animals.

[0070] As used herein, unless otherwise indicated, the term "pathogen" refers to any organism that causes disease in humans or domestic animals, whether through infection by the organism or through consumption of a toxin produced by the organism.

[0071] As used herein, the term "raw material" refers to uncooked plant matter intended for consumption by humans or domestic animals.

[0072] Unless otherwise indicated, as used herein, the terms "about," "approximately," and the like, when used in conjunction with a numerical limit or range, mean that the limit or range can vary by up to 10%. As a non-limiting example, "about 750" can mean a minimum of 675 or a maximum of 825, or any value therebetween. When used in conjunction with a ratio or relationship between two or more numerical limits or ranges, the terms "about," "approximately," and the like, mean that each limit or range can vary by up to approximately 10%. As a non-limiting example, a statement that two quantities are "approximately equal" can mean that the ratio between the two quantities is at least 0.9:1.1 or at most 1.1:0.9 (or any value therebetween), while a statement that four ratios are "about 5:3:1:1" can mean that the first number in the ratio can be any value between 4.5 and 5.5, the second number in the ratio can be any value between 2.7 and 3.3, and so on.

[0073] As used herein, "at least one," "one or more," and "and / or" are open-ended expressions that are both conjunctive and disjunctive in operation. For example, each of the expressions "at least one of A, B, and C," "at least one of A, B, or C," "one or more of A, B, and C," "one or more of A, B, or C," and "A, B, and / or C" means only A, only B, only C, A and B together, A and C together, B and C together, or A, B, and C together.

[0074] It should be noted that the term "a" or "an" entity refers to one or more of the entity. Therefore, the terms "a" (or "an"), "one or more" and "at least one" can be used interchangeably herein. It should also be noted that the terms "including," "comprising," and "having" can be used interchangeably.

[0075] The embodiments and configurations described herein are neither complete nor exhaustive. It will be appreciated that other embodiments of the present invention can be realized by utilizing one or more of the features described above or described in detail below, either alone or in combination.

[0076] The present disclosure provides a method and system for injecting a gaseous antimicrobial agent into the crystals of a crystalline solid and / or the pores of a porous solid, and a crystalline and / or porous solid containing a gaseous antimicrobial agent produced according to such a method and system. The present disclosure also provides an article comprising such a crystalline and / or porous solid, so that the gaseous antimicrobial agent can be delivered or released in a desired manner and / or at a desired rate.

[0077] In an embodiment of the method of the present disclosure, the method begins by providing a solution of a potential crystalline solid in a solvent; the solution can be provided by any suitable means, including but not limited to providing a source of the solid in crystalline form and dissolving the solid in the solvent. Many solutions of crystalline solids and methods for their preparation are well known, especially when the solvent is water (e.g., saline (seasoned salt solution) and simple syrup (sucrose solution in water).

[0078] After solution is provided, the gaseous antimicrobial agent is introduced into the solution by any appropriate means. As non-limiting example, the gaseous antimicrobial agent can be introduced into the solution by bubbling the gaseous antimicrobial agent (e.g., as micron-level and / or nanometer-level bubbles) into the solution and / or by the spraying, mist, atomization spray of the solution etc. being dispersed into a certain volume of the gas that comprises the gaseous antimicrobial agent.

[0079] In some embodiments, the present invention provides the crystal of the gas phase antimicrobial of the present invention.At last, after gas phase antimicrobial is introduced in the solution, can form the solid crystal of injection, and separate and / or remove this crystal alternatively from solvent.Described crystal can form by any suitable crystallization method, include but not limited to evaporation, precipitation (for example temperature induced precipitation, introducing precipitation agent etc.) or chemical dehydration (wherein solvent is water) of solvent.The degree of fluid parcel, crystal depend on the design of crystallization kinetics and container to the volume of the gas phase antimicrobial that is included in the crystalline solid after crystalline kinetics and particle form and the crystallization.Therefore, can hold or introduce the crystallization parameter (for example temperature and pressure) in the mixing vessel of solution to control or regulate the antimicrobial content and the effect of the crystalline solid of injection by control.Can but not necessarily the crystal that has been separated and / or removed from solvent is further processed, include but not limited to bulk transportation.

[0080] Alternatively and / or additionally, crystals of the injected solid can be formed under a gas headspace by a dissolution and evaporation process, wherein the gas headspace comprises a gas phase antimicrobial agent. Such evaporation and recrystallization can be performed at room temperature to avoid affecting or catalyzing reactions that would produce undesirable by-products.

[0081] The crystalline solid can include any one or more substances that can be delivered in a crystalline form. As non-limiting examples, according to the present disclosure, solids that can be infused with a vapor-phase antimicrobial agent include flavored sugar, baking soda, flavored salt and any other chemical salts (e.g., potassium chloride), erythritol, and the like.

[0082] In some embodiments, the crystalline solid can be a sugar. Non-limiting examples of sugars that can be used to implement the present invention include sucrose, lactose, fructose, glucose, lyxose, xylose, arabinose, ribose, allose, altrose, mannose, gulose, iodose, talose, maltose, galactose, trehalose, cellobiose, isomaltose, lactulose, tulaose, maltotriose, melezitose, raffinose, stachyose and oligofructose.

[0083] In some embodiments, the crystalline solid can be a sugar alcohol. Non-limiting examples of sugar alcohols that can be used to implement the present invention include erythritol, glycerol, ethylene glycol, threitol, arabitol, xylitol, ribitol, mannitol, sorbitol, galactitol, fucitol, iditol, inositol, olemite, isomalt, maltitol, lactitol, maltotriol, maltotetraol, polyethylene glycol, acesulfame potassium, and isomaltulose.

[0084] In some embodiments, the crystalline solid can be a sugar acid. Non-limiting examples of sugar acids useful in practicing the present invention include tartaric acid, citric acid, malic acid, succinic acid, malonic acid, glutaric acid, and suberic acid.

[0085] In some embodiments, the crystalline solid can be a non-sugar carbohydrate. Non-limiting examples of non-sugar carbohydrates that can be used to implement the present invention include microcrystalline cellulose, beta glucan, inulin, resistant starch, pectin, hemicellulose, galactan, arabinoxylan, xanthan gum, agar, dextran, agarose, sepharose, gelatin, isomalto-oligosaccharides, maltodextrin, beta glucan, chitosan, dextrin, alpha-cycloglucan, beta-cycloglucan, Sephadex LH-20, Sephadex G-10, Sephadex G-15, Sephadex G-25, and Sephadex G-100.

[0086] In some embodiments, the crystalline solid may be selected from the group consisting of magnesium carbonate, magnesium bicarbonate, and carrageenan.

[0087] In some embodiments, the crystalline solid can be a salt. Non-limiting examples of salts that can be used in the practice of the present invention include sodium polyacrylate, polyacrylate, potassium hydrogen tartrate, potassium sodium tartrate tetrahydrate, potassium fluoride, sodium fluoride, cesium fluoride, rubidium fluoride, lithium fluoride, potassium acetate, sodium acetate, potassium formate, sodium formate, potassium oxalate, sodium oxalate, monopotassium phosphate, dipotassium phosphate, tripotassium phosphate, monosodium phosphate, disodium phosphate, trisodium phosphate, potassium hydrogen phosphate, sodium hydrogen phosphate, potassium dihydrogen phosphate, sodium dihydrogen phosphate, calcium sulfate, sodium sulfate, and potassium sulfate.

[0088] In other embodiments of the methods of the present disclosure, the methods begin by providing a liquid precursor of a latent porous solid in a solvent. Liquid precursors of porous solids and methods for making them are well known; a non-limiting example of such a liquid precursor is a mixture or solution of sugar, water, and a protein source (e.g., egg white or gelatin), which is a precursor to marshmallows.

[0089] After providing the liquid precursor, the gaseous antimicrobial agent is introduced into the liquid precursor by any suitable means. As non-limiting examples, the gaseous antimicrobial agent can be introduced into the liquid precursor by bubbling the gaseous antimicrobial agent (e.g., as micron- and / or nanometer-sized bubbles) into the liquid precursor and / or by dispersing a spray, mist, atomized spray, etc. of the liquid precursor into a volume of gas comprising the gaseous antimicrobial agent.

[0090] In some embodiments, the present invention provides the porous solid of the present invention.At last, after gas-phase antimicrobial agent is introduced liquid precursor, usually (but not necessarily) form porous solid by inflation.Inflation can be carried out by any appropriate means.The volume of the gas-phase antimicrobial agent that fluid wraps degree and pore morphology and is included in the porous solid after hole formation depends on the kinetics and the design of container that inflation and / or hole form.Therefore, the parameter (for example temperature and pressure) that inflation in the mixing container that can be housed with liquid precursor and / or hole formation can be controlled or regulated to control or regulate the antimicrobial content and the effect of the porous solid that injects by control.

[0091] Another parameter that can be controlled to control or regulate the antimicrobial content and effectiveness of the injected porous solid is the porosity of the porous solid. As non-limiting examples, the porous solid can have a porosity of at most about 5%, at most about 10%, at most about 15%, at most about 20%, at most about 25%, at most about 30%, at most about 35%, at most about 40%, at most about 45%, at most about 50%, at most about 55%, at most about 60%, at most about 65%, at most about 70%, at most about 75%, at most about 80%, at most about 85%, at most about 90% or at most about 95%. The porosity of the porous solid can affect the proportion of pores in which the antimicrobial agent is present, the rate at which the antimicrobial agent is released and / or diffused from the pores, etc.

[0092] Alternatively and / or in addition, the porous solid of injection can be formed by agitating the liquid precursor under the gas head space and / or by being dispersed into the gas head space that comprises the gas phase antimicrobial agent by spraying, mist, atomized spray thing etc. of solution, wherein this gas head space comprises the gas phase antimicrobial agent.This pore formation mode can be carried out at room temperature, in order to avoid affecting or catalyzing the reaction that can produce undesirable by-product.

[0093] The porous solid may include any one or more substances that can be delivered in a porous form. As a non-limiting example, a solid that can be infused with a vapor phase antimicrobial agent according to the present disclosure includes marshmallow.

[0094] The crystalline and / or porous solids of the present disclosure can be used to extend the shelf life of the food packaged therewith. In particular, the injected solids of the present disclosure (and / or articles made therefrom, such as paper or plastic liners, etc.) can be provided within or as part of a package of meat or raw materials, such as beef products, pork products, poultry products, fish products, bagged salad products, and similar raw fruit and vegetable products. In some embodiments, the injected solids (or articles comprising them) can be adapted to absorb or otherwise receive blood, concentrates, or other liquids from the meat or raw materials, so that the solids can dissolve and release antimicrobial agents into the packaging. In this way, even after packaging and transportation (such as when stored in a refrigerator at a grocery store awaiting purchase), the meat or raw materials can be treated with antimicrobial agents, thereby significantly extending the shelf life of the meat or raw materials without damage, and, in some embodiments, even improving their consumer suitability (taste, safety, nutritional content, etc.).

[0095] The antimicrobial-infused solids of the present invention can be effective against a variety of pathogenic microorganisms. As a first non-limiting example, the solids can have a bactericidal effect, i.e., are effective against pathogens such as Aeromonas caviae, Aeromonas hydrophila, Aeromonas sobria, Bacillus cereus, Brucella, Campylobacter jejuni, Clostridium botulinum, Clostridium perfringens, Corynebacterium ulcerans, Coxiella burnetii, Enterohemorrhagic Escherichia coli, Listeria monocytogenes, Pseudomonas shigelloides, Pseudomonas alternis, Pseudomonas, Salmonella, Shigella, Staphylococcus aureus, Streptococcus, Vibrio cholerae, Vibrio parahaemolyticus, Vibrio vulnificus, Yersinia enterocolitica, and Yersinia pseudotuberculosis. As a second non-limiting example, the solid can have a fungicidal effect, i.e., effective against pathogenic fungi such as Alternaria, Aspergillus flavus, Aspergillus parasiticus, Cephalosporium, Fusarium, Myrotheca, Stachybotrys, and Trichoderma. As a third non-limiting example, the solid can have a virucidal effect, i.e., effective against pathogenic viruses such as enterovirus, hepatovirus A, norovirus, hepatitis E virus A, and rotavirus, as well as coronaviruses (e.g., severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2)). As a fourth non-limiting example, the solid can have an antiparasitic effect, i.e., be effective against pathogenic parasites such as flatworms (e.g., Diphyllobothrium, Fasciola hepatica, Dwarf fluke, Taenia saginata and Taenia solium), nematodes (e.g., Anisakis, Ascaris, Gastrocystis, Trichinella and Trichuris trichiura) and protozoa (e.g., Acanthamoeba and other free-living amebas, Cryptosporidium parvum, Cyclospora, Entamoeba histolytica, Giardia lamblia, Sarcocystis hominis, Porcine cysts and Toxoplasma gondii).

[0096] Embodiments of the present disclosure include an infused solid containing ozone molecules that is incorporated into the packaging of a food product, such as marshmallows. During transportation and storage of the packaged food, ozone is gradually released from the infused solid, thereby producing an antimicrobial or antibacterial effect on the packaged food. One advantage of these embodiments is that no expensive equipment or machinery is required to perform an antimicrobial ozone treatment on the packaged food product, and the infused solid can be quickly and inexpensively placed into the package during normal manufacturing of the packaged food product.

[0097] Embodiments of the present disclosure also include articles that can encapsulate ozone and be placed in the packaging of food, such as pouches, liners, pads, etc. In some embodiments, the material of the article (e.g., paper, plastic, etc.) can be impregnated with a crystalline solid (e.g., salt or sugar) infused with ozone, thereby releasing ozone into the packaging when the article absorbs liquid (blood, condensate, etc.) and the crystalline solid is dissolved. Alternatively and / or in addition, moisture and food fluids can physically decompose the encapsulation medium containing ozone gradually or at one or more discrete times. In other embodiments, the article can include quilted or stamped materials containing voids, wherein the voids contain ozone at a higher pressure than the surrounding pressure, thereby allowing ozone to be released into the food packaging by seepage; in these embodiments, different materials and packaging media can be selected to provide controlled and / or desired seepage rates. An advantage of these embodiments is that they can advantageously utilize other materials already used in food packaging, thereby eliminating the need to modify or refurbish existing production lines or equipment.

[0098] Embodiments of the present disclosure also include a method for treating a target item with a crystal of a crystalline solid infused with an antimicrobial agent. In some embodiments, the method includes the step of directly applying the crystals infused with an antimicrobial agent to the surface of the target item (e.g., a portion of meat or raw material). In some embodiments, the method includes the step of adding the crystals infused with an antimicrobial agent in a "loose" or "bulk" form to the packaging of the target item (e.g., a container for raw meat, a bag of raw material, etc.) and / or to a shipping container (e.g., a refrigerated truck) for shipping or transporting the target item. In some embodiments, the method includes the step of placing an article (e.g., a pouch, a liner, a cushion, etc.) containing the crystals infused with an antimicrobial agent in the packaging of the target item and / or in a shipping container for shipping or transporting the target item. The mechanism by which the crystals infused with an antimicrobial agent release the antimicrobial agent to allow the target item to be treated with an antimicrobial agent when implementing these methods is described throughout this disclosure.

[0099] Should be clearly understood that antimicrobial treatment of the present invention is usually achieved by oozing out or other physical means from the solid medium or matrix of the crystalline solid that is injected with antimicrobial to release it into the surrounding atmosphere or environment. Therefore, the appropriate target item for antimicrobial treatment can be any surface, article or material in this atmosphere or environment, or in fact the atmosphere or environment itself. As a first non-restrictive example, when the crystalline solid that is injected with antimicrobial of the present invention is placed in the packaging of food, the target item for antimicrobial treatment can be the inner surface or volume of food (such as meat or raw material) and / or packaging. As a second non-restrictive example, when the crystalline solid that is injected with antimicrobial of the present invention is placed in a certain volume of liquid, the target item for antimicrobial treatment can be a certain volume of liquid itself (such as a certain volume of wastewater or possibly contaminated drinking water), a container or vessel that holds a certain volume of liquid, or any one or more of the gas head space around or adjacent to a certain volume of liquid. As a third non-limiting example, when the antimicrobial-infused crystalline solid of the present invention is placed on a surface within a room or other enclosed space, the target item for antimicrobial treatment can be the surface on which the solid is placed (e.g., a countertop or table in a bathroom, kitchen, or hospital operating room) and / or the air within the enclosed space. Thus, the antimicrobial-infused crystalline solid of the present invention can be effective against food-borne, surface-borne, water-borne (or other liquid-borne), and / or air-borne (or other gas-borne) microorganisms.

[0100] As disclosed herein, molecules of the gaseous antimicrobial agent can be present in any one or more of the crystals of the lattice structure of the crystalline solid, the pores in the lattice structure of the crystalline solid, the grain boundaries of the lattice structure of the crystalline solid, and / or the fluid inclusions of the crystals of the lattice structure of the crystalline solid. Therefore, the gaseous antimicrobial agent can be released from the lattice structure and exert an antimicrobial effect on the surrounding environment when the lattice structure is destroyed. As a non-limiting example, this destruction can be achieved by dissolving the crystalline solid in a liquid in contact with the crystalline solid (e.g., blood absorbed from meat products, moisture present in humid air, etc.) or by a phase transition of the crystalline solid from a crystalline state to an amorphous state (e.g., when the temperature is increased). Therefore, according to the method of the present invention, a crystalline solid injected with an antimicrobial agent can be manufactured under one condition (e.g., a lower temperature or lower humidity condition), and the crystalline solid can remain highly stable (i.e., the gaseous antimicrobial agent hardly diffuses or seeps out of the lattice structure) during several days, weeks, or months until it is exposed to a second condition (e.g., a higher temperature or higher humidity condition). In this way, the mechanism of release of the vapor-phase antimicrobial agent from the solid medium or matrix of the antimicrobial-infused crystalline solid can be selected or controlled to tailor the antimicrobial treatment system to the properties of the target article, atmosphere, or environment. In addition, the antimicrobial-infused crystalline solid can be manufactured and then stored for long periods of time before use.

[0101] It should be clearly understood that the biocide-infused crystalline solids of the present invention can be configured to effectively release the vapor-phase biocide under a wide range of humidity / ambient humidity conditions. More specifically, while the release of the vapor-phase biocide can be triggered or accelerated in some embodiments by applying a liquid (e.g., a solvent (e.g., water)) to the crystal and / or by increasing the humidity of the environment in which the crystal is placed, the vapor-phase biocide can still be effectively released under "dry" conditions (i.e., in a drier atmosphere without the addition of moisture or other liquids), for example, due to higher ambient temperatures and / or increased ambient temperatures.

[0102] Another relevant advantage and benefit of the compositions and methods of the present invention is that controlled and / or extended release of gas-phase antimicrobial agents can be achieved. Specifically, based on the understanding of the rates at which various crystalline solids melt, dissolve, etc. under specific temperature and humidity conditions, one of ordinary skill in the art can select a crystalline solid injected with an antimicrobial agent of the desired mass of gas-phase antimicrobial agent at the desired concentration to apply an antimicrobial effect to a target with a selected mass, volume, etc. within a selected time under specific expected temperature and / or humidity conditions. Therefore, the compositions of the present invention can advantageously be customized or designed for specific applications.

[0103] Now please refer to Figure 1, which shows a system 100 for producing ozonated crystalline solids. The system 100 includes an oxygen concentrator 101, one or more ozone generators 102, a sealable chamber 103, a heat source 104, a pressure vessel 105, an atomizer 106, a nozzle 107, an air compressor 108, a heat tracer 109, and a nitrogen source 110.

[0104] During operation of the system 100, the oxygen concentrator 101 generates an oxygen-rich gas stream 111 from ambient air (e.g., by pressure swing adsorption and / or membrane separation) and provides the oxygen-rich gas stream 111 to the ozone generator 102, which converts at least a portion of the diatomic oxygen in the oxygen-rich gas stream 111 into ozone (e.g., by corona discharge, ultraviolet light, cold plasma, and / or electrolysis). The generation of the ozone-containing gas stream 112 can be continuous, semi-continuous, or intermittent. It should be clearly understood that in embodiments of the system 100 within the scope of the present invention, the oxygen concentrator 101 can be replaced or supplemented by any suitable device that provides the oxygen-rich gas stream 111 (e.g., a gas stream having an oxygen content of at least about 40% by weight) to the ozone generator 102.

[0105] After generation, the ozone-containing gas stream 112 flows from the ozone generator 102 into the sealable chamber 103, thereby creating a positive pressure in the sealable chamber 103, which is typically between about 0.001 psi and about 2.500 psi, more typically between about 0.625 psi and about 1.875 psi, and most typically about 1.25 psi. Before any other materials are introduced into the sealable chamber 103, ozone is flowed through the sealable chamber 103 for a time sufficient to achieve a desired ozone concentration within the sealable chamber 103; typically, the desired ozone concentration can be at least about 3.0%, at least about 3.5%, at least about 4.0%, at least about 4.5%, at least about 5.0%, at least about 5.5%, at least about 6.0%, at least about 6.5%, at least about 7.0%, at least about 7.5%, at least about 8.0%, at least about 8.5%, at least about 9.0%, at least about 9.5%, or at least about 10% by weight of the total gas in the sealable chamber 103. Ozone is continuously flowed through the sealable chamber 103 throughout the production process, except when the atomized solution of the crystalline solid is introduced into the sealable chamber 103, as described in further detail below. One of ordinary skill in the art will understand how to select an appropriate flow rate and time based on the volume of the sealable chamber 103 and the desired production rate of ozonated crystalline solids; as a non-limiting example, where the volume of the sealable chamber 103 is approximately 2 cubic feet, the ozone-containing gas stream 112 can flow through the sealable chamber 103 at a rate of approximately 10 liters / minute for approximately two hours.

[0106] Heat source 104 is separately used to heat the solvent (typically, but not necessarily always, water) to a temperature sufficient to dissolve the crystalline solid in the solvent to the desired degree and / or induce the desired degree of amorphization in the crystalline solid. As a non-limiting example, if the crystalline solid is erythritol and it is desired to form a solution of two parts by weight of erythritol and one part by weight of water, heat source 104 can be used to heat the water to a temperature of approximately 170°F. One of ordinary skill in the art will understand how to select an appropriate temperature based on the selected crystalline solid and solvent, as well as the desired concentration of the crystalline solid in the resulting solution. Heat source 104 can heat the solvent before, during, and / or after the crystalline solid is added to the solvent. When the solvent reaches the appropriate temperature and the crystalline solid has dissolved therein to the desired degree, heating device 109 is activated to heat the manifold of atomizer 106 and the high-pressure line from atomizer 106 to sealable chamber 103 to reduce the degree of cooling of the solution as it passes through atomizer 106 and enters sealable chamber 103. At this point, the pressure vessel 105 and atomizer 106 may be primed, flushed (eg, with hot water or the like), and cleaned of any residual solvent or dirt.

[0107] When the solution of the crystalline solid in the solvent is complete, the oxygen concentrator 101 and the ozone generator 102 are deactivated, and the sealable chamber 103 is sealed (i.e., any input valves and / or output valves are closed). The heated crystalline solid solution 114 is then transferred from the heat source 104 to the pressure vessel 105, which is preferably preheated to prevent excessive cooling of the solution, and is pressurized to an appropriate level using an air compressor 108, typically to a pressure between about 25 psi and about 55 psi, more typically to a pressure between about 30 psi and about 50 psi, more typically to a pressure between about 35 psi and about 45 psi, and most typically to a pressure of about 40 psi. The nebulizer 106 can then be pre-filled with a portion of the heated solution before filling the nebulizer 106.

[0108] The atomizer 106, which is filled with a heated solution of the crystalline solid solution 114, then pressurizes the crystalline solid solution 114 to a high degree (e.g., to approximately 1000 psi) and dispenses an atomized spray 113 of the crystalline solid solution into the sealable chamber 103 through the nozzle 107. The nozzle 107 can be selected to deliver the crystalline solid solution into the sealable chamber 103 at an appropriate flow rate and pressure; as a non-limiting example, if the volume of the sealable chamber is approximately 2 cubic feet, the nozzle 107 can be selected to deliver the solution at a flow rate of approximately 0.06 liters per minute and a pressure of approximately 1000 psi. The atomizer 106 can then be disconnected or isolated from the sealable chamber 103. Any remaining solution in the atomizer 106 is flushed out, the atomizer 106 is cleaned (e.g., using hot water or the like), and the heat tracing device 109 is deactivated. The oxygen concentrator 101 and the ozone generator 102 are then reactivated, and the inlet and outlet valves of the sealable chamber 103 are reopened to allow ozone to flow through the sealable chamber 103 again. In this way, the ozone flow can remove moisture from the sealable chamber 103, allowing the ozonated crystalline solid to dry in the ozone-rich environment and form on the interior surface of the sealable chamber 103. Any one or more of the procedures detailed above can then be repeated to allow more production and formation of the ozonated crystalline solid on the interior surface of the sealable chamber 103.

[0109] After the desired mass of ozonated crystalline solid is produced and deposited on the inner surface of the sealable chamber 103, ozone can be flowed through the sealable chamber 103 for an additional period of time (in some embodiments, about 4 hours, but can be selected by one skilled in the art) to remove any residual moisture and cause drying and formation of a final "batch" of ozonated crystalline solid in the sealable chamber 103. The oxygen concentrator 101 and the ozone generator 102 can then be finally deactivated, whereupon the sealable chamber 103 is again sealed and allowed to stand for an appropriate period of time (in some embodiments, about 12 hours, but can be selected by one skilled in the art). The nitrogen source 110 can then be activated and a nitrogen stream 115 can be flowed through the sealable chamber 103 to purge any "free" ozone remaining in the sealable chamber 103 (i.e., ozone that has not been captured by the crystals of the ozonated crystalline solid). Finally, the sealable chamber 103 can be opened and the ozonated crystalline solid collected. The total mass of ozonated crystalline solid will depend on the level of gas flow rate, the mass of solution introduced into the sealable chamber 103, etc., but a typical total yield after two bursts 113 for a sealable chamber 103 having a volume of approximately 2 cubic feet is 25 to 30 grams.

[0110] Now please refer to Figure 2, which shows a method 200 for producing ozonated crystalline solids. The method 200 includes an ozone generation step 201, a solution distribution step 202, a drying step 203, and an ozone evacuation step 204.

[0111] In the ozone generation step 201 of method 200, a gas stream containing ozone is generated and introduced into a sealable chamber. The ozone-containing gas stream can be generated by any suitable known method, but in particular embodiments, it can be generated by first generating an oxygen-enriched gas stream from ambient air (e.g., by pressure swing adsorption and / or membrane separation) and then converting at least a portion of the diatomic oxygen in the oxygen-enriched gas stream into ozone (e.g., by corona discharge, ultraviolet light, cold plasma, and / or electrolysis). The ozone generation step 201 can be performed as a continuous process, a semi-continuous process, or a batch process, most commonly by pressurizing the sealable chamber to a positive pressure between about 0.001 psi and about 2.500 psi, more typically between about 0.625 psi and about 1.875 psi, and most typically about 1.25 psi. As part of the ozone generation step 201, before any other materials are introduced into the sealable chamber, an ozone-containing gas stream can be flowed through the sealable chamber for a sufficient period of time to achieve a desired ozone concentration in the sealable chamber; typically, the desired ozone concentration can be at least about 3.0 weight percent, at least about 3.5 weight percent, at least about 4.0 weight percent, at least about 4.5 weight percent, at least about 5.0 weight percent, at least about 5.5 weight percent, at least about 6.0 weight percent, at least about 6.5 weight percent, at least about 7.0 weight percent, at least about 7.5 weight percent, at least about 8.0 weight percent, at least about 8.5 weight percent, at least about 9.0 weight percent, at least about 9.5 weight percent, or at least about 10 weight percent of the total gas in the sealable chamber. One of ordinary skill in the art will understand how to select an appropriate flow rate and time based on the volume of the sealable chamber and the desired production rate of ozonated crystalline solids; as a non-limiting example, where the volume of the sealable chamber is approximately 2 cubic feet, the ozone-containing gas stream can flow through the sealable chamber at a rate of approximately 10 liters / minute for approximately two hours.

[0112] In the solution dispensing step 202 of method 200, a heated solution of a crystalline solid in a solvent is atomized and dispensed into a sealable chamber containing ozone. Specifically, before, during, and / or after the crystalline solid is added to the solvent, the solvent may be heated to a temperature sufficient to dissolve the crystalline solid in the solvent to a desired degree and / or induce a desired degree of amorphization in the crystalline solid; one of ordinary skill in the art will understand how to select an appropriate temperature based on the selected crystalline solid and solvent and the desired concentration of the crystalline solid in the resulting solution. After the solution of the crystalline solid in the solvent is prepared, the sealable chamber may be sealed (i.e., any input valve and / or output valve are closed) and the solution of the crystalline solid is pressurized to an appropriate degree before being dispensed into the sealable chamber via an atomized spray through a nozzle. The input and output valves of the sealable chamber may then be reopened (and, if appropriate, the apparatus used in the ozone generation step 201 may be reactivated to generate more ozone) to allow ozone to flow through the sealable chamber again, thereby removing moisture from the sealable chamber and allowing the ozonated crystalline solid to dry in the ozone-rich environment and form on the interior surfaces of the sealable chamber.

[0113] It should be expressly understood that the solution dispensing step 202 may be performed only once, or may be repeated as many times as necessary to produce the desired quality of ozonated crystalline solid.

[0114] In the drying step 203 of the method 200, ozone is flowed through the sealable chamber for an additional period of time (which may be approximately four hours in some embodiments, but may be selected by one skilled in the art) to remove any residual moisture and allow the ozonated crystalline solid to finally dry and form within the sealable chamber. After the ozone has finally flowed through the sealable chamber, the sealable chamber may be resealed and allowed to stand for an appropriate period of time (which may be approximately 12 hours in some embodiments, but may be selected by one skilled in the art).

[0115] In the ozone evacuation step 204 of the method 200, any residual ozone is removed from the sealable chamber by any suitable means. Specifically, nitrogen (and / or another non-reactive / inert carrier gas) can be flowed through the sealable chamber, and / or negative pressure / vacuum can be applied to the sealable chamber to purge and / or evacuate any "free" ozone (i.e., ozone not trapped by the crystals of the ozonated crystalline solid) remaining in the sealable chamber. This allows the sealable chamber to be opened and the ozonated crystalline solid to be collected by any suitable means.

[0116] Now please refer to Figure 3, which shows a method 300 for antimicrobial treatment of a target object. The method 300 includes a step 301 of providing an infused crystalline solid and a step 302 of applying an antimicrobial agent.

[0117] In the providing an infused crystalline solid step 301 of method 300 , any one or more of the methods and / or systems described herein may be used to provide crystals of a crystalline solid infused with a vapor-phase antimicrobial agent.

[0118] In the step 302 of applying an antimicrobial agent in method 300, a crystalline solid crystal injected with an antimicrobial agent is applied to the target item to be antimicrobially treated. It should be clearly understood that the step 302 of applying an antimicrobial agent can be carried out in any one or more of a variety of forms. In some embodiments, the step 302 of applying an antimicrobial agent can include applying the injected crystals directly to the surface of the target item (e.g., the surface or portion of meat or raw material). In some embodiments, the step 302 of applying an antimicrobial agent can include adding the injected crystals in a "loose" or "bulk" form to the packaging of the target item (e.g., a container for raw meat, a bag of raw material, etc.) and / or adding them to a shipping container (e.g., a refrigerated truck) for shipping or transporting the target item. In some embodiments, the step 302 of applying an antimicrobial agent can include placing an article (e.g., a pouch, a liner, a cushion, etc.) containing the injected crystals in the packaging of the target item and / or placing it in a shipping container for shipping or transporting the target item. In some embodiments, when the target item is a volume of liquid (e.g., a volume of wastewater or potentially contaminated drinking water), the step 302 of applying the antimicrobial agent may include placing the infused crystals in or on the surface of the volume of liquid. In some embodiments, when the target item is a room or other enclosed space or one or more solid objects or surfaces disposed therein, the step 302 of applying the antimicrobial agent may include placing the infused crystals (or an article comprising the infused crystals) in the room or other enclosed space; in certain such embodiments, the step 302 of applying the antimicrobial agent may also include selectively changing the temperature or humidity of the enclosed space, selectively changing the temperature of the crystals, and / or applying a liquid to the infused crystals so that at least a portion of the infused crystals dissolves or becomes amorphous, thereby releasing the vapor-phase antimicrobial agent into the enclosed space. The mechanism by which the crystals infused with the antimicrobial agent release ozone to allow the target item to be antimicrobially treated when implementing these methods is further described throughout this disclosure.

[0119] Figure 3A particular advantage of the illustrated method 300 and the storage stability of the biocide-infused crystalline solid of the present invention is that the step of applying the biocide 302 can be performed long after the step of providing the infused crystalline solid 301 is performed. Thus, the infused crystalline solid can be manufactured and subsequently stored or shipped over a period of days, weeks, or months before the vapor-phase biocide is released therefrom during the step of applying the biocide 302. In embodiments, the time period between the step of providing the infused crystalline solid 301 and the step of applying the biocide 302 can be at least about 1 day, at least about 2 days, at least about 3 days, at least about 4 days, at least about 5 days, at least about 6 days, at least about 7 days, at least about 8 days, at least about 9 days, at least about 10 days, at least about 11 days, at least about 12 days, at least about 13 days, at least about two weeks, at least about three weeks, at least about one month, at least about two months, at least about three months, at least about four months, at least about five months, or at least about six months.

[0120] Although explanation of the present invention concentrates on using ozone as gas phase antimicrobial agent generally, should be clearly understood that, can suitably use other gas phase antimicrobial agent, add necessary flexibility, and this is still within the scope of the present invention.The non-restrictive example of such gas phase antimicrobial agent comprises iodine and iodine compound and chlorine dioxide.In some embodiments, the gaseous material that is attached to the crystalline solid of injection of the present invention can comprise small molecule, rare and / or inert gas basically, for example, as non-restrictive example, can be helium or argon.

[0121] The present invention will be further illustrated by the following illustrative, non-limiting examples.

[0122] Example 1

[0123] This example demonstrates the use of ozonated Epsom salts prepared according to the present invention as an antimicrobial agent for a feedstock.

[0124] according to Figure 2 The method shown, using Figure 1 The system shown produces ozonated Epsom salts (ie, a plurality of magnesium sulfate crystals infused with ozone).

[0125] Four bags of raw spinach, each containing 5.5 ounces of raw spinach, were obtained from a grocery store. Of these four bags, one was left unopened and used as an experimental control; the other three bags were opened, and the raw spinach in each opened bag was inoculated with 1 million colony-forming units (1.0 × 10 6The three bags were filled with 1.1 ml of sterile deionized water. 1.1 g of ozonated Epsom salts were added to two of the three bags, while 1.1 g of conventional (non-ozonated) Epsom salts were added to the third bag. Each of the three bags was heat-sealed to create a closed environment, and the contents of the heat-sealed bags were then thoroughly mixed to ensure that the inoculated bacteria, salt, and water were substantially evenly distributed throughout each bag.

[0126] Place four bags of spinach in a refrigerator (the temperature is always maintained between 0°C and 10°C) and keep them in the refrigerator for 23 hours. After 23 hours, take out 25±0.2g of spinach samples from each bag and put them into Each sample was analyzed for S. typhimurium counts (via bioMérieux VIDAS test), E. coli counts (via 3M Petrifilm plates), and total plate counts (via 3M Petrifilm plates). The results are given in Table 1; for total plate counts and E. coli, quantitative results are reported, while for S. typhimurium, results are given as positive or negative.

[0127] Table 1

[0128]

[0129] *Due to the growth of total E. coli populations, more precise quantification was not possible.

[0130] As shown in Table 1, ozonated salts greatly inhibited the total plate counts of all bacteria (average inhibition of approximately 44%) relative to the control or non-ozonated salts. This result demonstrates the utility of ozonated Epsom salts as a broad-spectrum antimicrobial agent.

[0131] Visual inspection of the four bags of spinach showed that while the spinach in the bags with added salt wilted more than the spinach in the unopened bags, the spinach in the bags containing ozonated salt wilted less than the spinach in the bags containing non-ozonated salt. This result suggests that ozonated salt can extend the useful shelf life of ingredients such as raw spinach.

[0132] Example 2

[0133] This example demonstrates the efficacy of ozonated erythritol prepared according to the present invention as an antimicrobial agent for a raw material.

[0134] according to Figure 2 The method shown, using Figure 1 The system shown prepares ozonated erythritol (ie, a plurality of erythritol crystals infused with ozone).

[0135] In 7 25 g of bulk raw spinach was placed in each of the sample handling bags. Of the seven bags, one was immediately heat-sealed to create a closed environment and used as an uninoculated control; in each of the other six bags, one million colony-forming units (1.0×10 6 coli (ATCC 10536) containing 100 CFU of Escherichia coli. One of the six bags was then immediately heat-sealed to create a closed environment and used as an inoculation control. Of the other five inoculated bags, one bag ("Erythritol") received 1.1 ml of sterile deionized water and 1.1 g of non-ozonated erythritol; two bags ("OZ+H2O") received 1.1 ml of sterile deionized water and 1.1 g of ozonated erythritol; and two bags ("OZ") received only 1.1 g of ozonated erythritol. Each of the five inoculated and treated bags was heat-sealed to create a closed environment, and the contents of the heat-sealed bags were then thoroughly mixed to ensure that the inoculated bacteria, erythritol, and water were substantially evenly distributed in each bag. Visual observation of the OZ+H2O bag showed that the ozonated erythritol initially foamed and formed a paste-like substance when in contact with deionized water, but with additional mixing, this paste-like substance completely dissolved in the water.

[0136] The seven bags of spinach were placed in a walk-in freezer (the temperature was always maintained between 0°C and 10°C) and placed in the freezer overnight. The leaves were then taken out from each of the seven bags and tested for their water activity. The spinach in each bag was also analyzed for E. coli and total plate counts using 3M Petrifilm plates. The results are shown in Table 2.

[0137] Table 2

[0138]

[0139] *Due to the growth of total E. coli populations, more precise quantification was not possible.

[0140] As shown in Table 2, ozonated erythritol greatly inhibited the total plate count of all bacteria relative to the uninoculated control and non-ozonated erythritol treatment (on average, about 97% inhibition compared to the uninoculated control and about 98% inhibition compared to the non-ozonated erythritol treatment), and, relative to the inoculated control and non-ozonated erythritol treatment, greatly inhibited the growth of Escherichia coli (on average, about 99.8% inhibition compared to the inoculated control and about 98% inhibition compared to the non-ozonated erythritol treatment). This result demonstrates the effectiveness of ozonated erythritol as a broad-spectrum antimicrobial agent and an antimicrobial agent specifically against Escherichia coli. It should be noted that although the antimicrobial effect was enhanced in the absence of added water, ozonated erythritol maintained a significant antimicrobial effect under both "wet" and "dry" conditions.

[0141] Visual inspection of the seven bags of spinach showed that the spinach treated with erythritol had some damage to its leaf structure, compared to little damage to the leaf structure of the spinach in the control bags.

[0142] Example 3

[0143] This example demonstrates the efficacy of ozonated erythritol prepared according to the present invention as an antimicrobial agent for a raw material.

[0144] according to Figure 2 The method shown, using Figure 1 The system shown prepares ozonated erythritol (ie, a plurality of erythritol crystals infused with ozone).

[0145] In 8 25 g of bulk raw spinach was placed in each of the sample handling bags. Of the eight bags, one was immediately heat-sealed to create a closed environment and used as an uninoculated control; in each of the other seven bags, one million colony-forming units (1.0×10 6coli (ATCC 10536) containing 100 CFU of Escherichia coli (ATCC 10536). One of the seven bags was then immediately heat-sealed to create a closed environment and used as an inoculation control. In the other six inoculated bags, one bag ("erythritol") received 1.1 milliliters of sterile deionized water and 1.1 grams of non-ozonated erythritol; one ("1 / 2 erythritol") received 0.5 milliliters of sterile deionized water and 0.5 grams of non-ozonated erythritol; two bags ("OZ+H2O") received 1.1 milliliters of sterile deionized water and 1.1 grams of ozonated erythritol; and two bags ("OZ") received only 1.1 grams of ozonated erythritol. Each of the six inoculated and processed bags was heat-sealed to create a closed environment, and the contents of the heat-sealed bags were then thoroughly mixed to ensure that the inoculated bacteria, erythritol, and water were substantially evenly distributed in each bag. Visual inspection of the OZ+H2O bags indicated that the ozonated erythritol initially foamed and formed a paste-like substance upon contact with deionized water, but with additional mixing, the paste completely dissolved into the water.

[0146] The eight bags of spinach were placed in a walk-in freezer (the temperature was always maintained between 0°C and 10°C) and placed in the freezer overnight. The spinach in each bag was then analyzed for E. coli and total plate counts using 3M Petrifilm plates. The results are shown in Table 3.

[0147] Table 3

[0148]

[0149]

[0150] As shown in Table 3, ozonated erythritol significantly inhibited the total plate count of all bacteria relative to the control and non-ozonated erythritol treatments (on average, about 99.8% inhibition compared to the uninoculated control, about 99.7% inhibition compared to the inoculated control, and about 72% inhibition compared to the non-ozonated erythritol treatment), and significantly inhibited the growth of Escherichia coli relative to the inoculated control and non-ozonated erythritol treatments (on average, about 98% inhibition compared to the inoculated control and non-ozonated erythritol treatments). It should be noted that ozonated erythritol maintained a significant antimicrobial effect under both "wet" and "dry" conditions.

[0151] Visual inspection of the seven bags of spinach showed that the spinach treated with erythritol had some damage to its leaf structure, compared to little damage to the leaf structure of the spinach in the control bags. The leaves treated with ozonated erythritol also showed some slight browning.

[0152] Example 4

[0153] This example demonstrates the efficacy of ozonated erythritol prepared according to the present invention as an antimicrobial agent for a raw material.

[0154] according to Figure 2 The method shown, using Figure 1 The system shown prepares ozonated erythritol (ie, a plurality of erythritol crystals infused with ozone).

[0155] In 4 25 g of bulk raw spinach was placed in each of the sample handling bags. Of the four bags, one was immediately heat-sealed to create a closed environment and used as an uninoculated control; in each of the other three bags, one million colony-forming units (1.0×10 6 coli (ATCC 10536) containing 100 CFU of Escherichia coli (ATCC 10536). One of the three bags was then immediately heat-sealed to create a closed environment and used as an inoculation control. In the other two bags inoculated, one ("erythritol") received only 1.1 grams of non-ozonated erythritol (without water), and the other ("OZ") received only 1.1 grams of ozonated erythritol (without water). Each of the two inoculated and processed bags was heat-sealed to create a closed environment, and the contents in the heat-sealed bags were then thoroughly mixed to ensure that the inoculated bacteria, erythritol, and water were substantially evenly distributed in each bag.

[0156] The four bags of spinach were placed in a walk-in freezer (the temperature was always maintained between 0°C and 10°C) and placed in the freezer overnight. The spinach in each bag was then analyzed for E. coli and total plate counts using 3M Petrifilm plates. The results are shown in Table 4.

[0157] Table 4

[0158]

[0159] As shown in Table 4, ozonated erythritol greatly inhibited the total plate counts of all bacteria relative to the control and non-ozonated erythritol treatments (approximately 95% inhibition compared to the uninoculated control, approximately 97% inhibition compared to the inoculated control, and approximately 90% inhibition compared to the non-ozonated erythritol treatment), and greatly inhibited the growth of Escherichia coli relative to the inoculated control and non-ozonated erythritol treatments (approximately 99.4% inhibition compared to the inoculated control and 99% inhibition compared to the non-ozonated erythritol treatment).

[0160] Visual inspection of the seven bags of spinach showed that the spinach treated with erythritol had some damage to its leaf structure, compared to little damage to the leaf structure of the spinach in the control bags.

[0161] Example 5

[0162] This example demonstrates the efficacy of ozonated erythritol prepared according to the present invention as an antimicrobial agent for a raw material.

[0163] according to Figure 2 The method shown, using Figure 1 The system shown prepares ozonated erythritol (ie, a plurality of erythritol crystals infused with ozone).

[0164] In 13 25 g of bulk raw spinach was placed in each of the sample treatment bags. Of these thirteen bags, one was immediately heat-sealed to create a closed environment and used as an uninoculated control; four bags were inoculated with one million colony-forming units (1.0 × 10 6 CFU) of Staphylococcus aureus; four bags were inoculated with one million CFU of Pseudomonas aeruginosa; and four bags were inoculated with one million CFU of Escherichia coli O157:H7. For each set of four bags inoculated with a given species of bacteria, one bag was heat-sealed without further treatment and used as an inoculation control; two bags ("OZ") each received 1.1 grams of ozonated erythritol; and one bag ("Erythritol") received 1.1 grams of non-ozonated erythritol. Each of the nine inoculated and treated bags was heat-sealed to create a closed environment, and the contents of the heat-sealed bags were then thoroughly mixed to ensure that the inoculated bacteria and erythritol were substantially evenly distributed in each bag.

[0165] The thirteen bags of spinach were placed in a walk-in freezer (the temperature was always maintained between 0°C and 10°C) and kept in the freezer overnight. Subsequently, the spinach in each bag was analyzed for each of the three bacteria and the total aerobic plate count. The results are given in Table 5.

[0166] Table 5

[0167]

[0168] *Naturally contaminated with Staphylococcus and Pseudomonas species; all plates were contaminated

[0169] As shown in Table 5, ozonated erythritol greatly inhibited the growth of all three pathogenic bacteria, inhibiting Escherichia coli by about 62% (compared to the control) or 59% (compared to non-ozonated erythritol), Staphylococcus aureus by about 92% (compared to the control), and Pseudomonas aeruginosa by about 96% (compared to the control) or 91% (compared to non-ozonated erythritol).

[0170] Visual inspection of the seven bags of spinach showed that the spinach treated with erythritol had some damage to its leaf structure, compared to little damage to the leaf structure of the spinach in the control bags.

[0171] Example 6

[0172] according to Figure 2 The method shown, using Figure 1 The system shown prepares ozonated erythritol (i.e., a plurality of erythritol crystals infused with ozone) and stores them in a freezer at -5°F for five days. Then, 1 gram of ozonated erythritol is placed in each of fifteen one-ounce jars and sealed; five jars are returned to the freezer, five jars are placed in a refrigerator and maintained at 35°F, and five jars are placed in a room and maintained at 67°F. The ozone concentration of the air inside the jars is measured 24 hours after the erythritol is placed in the jars and every 48 hours thereafter. The results are given in Table 6; the peak ozone readings in parts per million (ppm) detected during the 30-second measurement period are reported.

[0173] Table 6

[0174]

[0175] As shown in Table 6, the ozone release profile of ozonated erythritol varies significantly with the temperature of the surrounding environment. At cold storage temperatures (approximately -5°F), no ozone is released into the surrounding environment. At refrigerator temperatures (approximately 35°F), ozone is slowly released over a period of at least about nine days. At ambient temperature, a large amount of ozone is released within the first 72 hours, with the concentration slowly decreasing over the next few days. Therefore, this example demonstrates that the profile of ozone release from a crystalline solid impregnated with an antimicrobial agent can be adjusted or selected based on the temperature of the environment in which the crystalline solid impregnated with the antimicrobial agent is suitable for antimicrobial treatment.

[0176] In various aspects, embodiments, and configurations, the present disclosure includes components, methods, processes, systems, and / or devices substantially as shown and described herein, including various aspects, embodiments, configurations, subcombinations, and / or subsets thereof. After understanding the present disclosure, those skilled in the art will understand how to implement and use the various aspects, embodiments, and configurations. The present disclosure, in various aspects, embodiments, and configurations, includes providing apparatus and processes in the absence of items not shown and / or described herein or in the various aspects, embodiments, and configurations of the present disclosure, including the absence of items that may have been used in previous apparatus or processes to improve performance, achieve ease of use, and / or reduce implementation costs.

[0177] The description of the disclosure hereinabove is exemplary and descriptive only. The foregoing is not intended to limit the disclosure to the forms specifically disclosed herein. For example, in the foregoing detailed description, various features of the disclosure are combined together in one or more aspects, embodiments and configurations for the purpose of simplifying the disclosure. The features of the various aspects, embodiments and configurations of the disclosure may be combined in other aspects, embodiments and / or configurations in addition to the aspects, embodiments and configurations discussed above. This method of disclosure should not be interpreted as reflecting an intention that the disclosure claimed requires more features than expressly recited in each claim. On the contrary, as reflected in the following claims, the inventive aspects are less than all the features of a single foregoing disclosed aspect, embodiment and configuration. Therefore, the following claims are hereby incorporated into the detailed description, with each claim itself representing an independent preferred embodiment of the disclosure.

[0178] Furthermore, although the description of the present disclosure has included descriptions of one or more aspects, embodiments, or configurations and certain variations and modifications, other variations, combinations, and modifications are within the scope of the present disclosure after understanding the present disclosure, such as variations and modifications within the skill and knowledge of the art. The present invention is intended to encompass, to the extent permitted, alternative aspects, embodiments, and configurations, including alternative, interchangeable, and / or equivalent structures, functions, ranges, or steps as claimed, regardless of whether such alternative, interchangeable, and / or equivalent structures, functions, ranges, or steps are disclosed herein, and is not intended to publicly dedicate any patentable subject matter.

Claims

1. A method for producing solid crystals infused with a gas phase antimicrobial agent, comprising: providing a solution of a solid in a solvent; introducing a gas-phase antimicrobial agent into the solution by spraying the solution into a cavity containing a gas, wherein the gas contained in the cavity includes the gas-phase antimicrobial agent; and The solid was crystallized.

2. The method of claim 1, wherein the solid is selected from the group consisting of sodium chloride, magnesium sulfate, sucrose, sodium bicarbonate, potassium chloride, calcium carbonate, sugar alcohols, acetic acid and ascorbic acid.

3. The method of claim 1, wherein the vapor phase antimicrobial agent is at least one of a bactericide and a virucide.

4. The method of claim 3, wherein the gas phase antimicrobial agent is ozone.

5. The method of claim 1, wherein the solvent consists essentially of water.

6. The method of claim 1, wherein the crystallizing step comprises flowing a carrier gas through the cavity to remove residual solvent from the cavity and allow the solid to crystallize on the inner surface of the cavity.

7. The method of claim 6, wherein the carrier gas comprises the gas phase antimicrobial agent.

8. A method for producing an ozonated crystalline solid, comprising: (a) generating a gas stream containing ozone and causing the gas stream to flow into or through a sealable chamber; (b) spraying a solution of a crystalline solid in a solvent into the sealable chamber; (c) removing residual solvent from the sealable chamber by passing a first carrier gas through the sealable chamber to allow the ozonated crystalline solid to crystallize on the inner surface of the sealable chamber; and (d) removing residual ozone from the sealable chamber.

9. The method of claim 8, wherein the crystalline solid is selected from the group consisting of sodium chloride, magnesium sulfate, sucrose, sodium bicarbonate, potassium chloride, calcium carbonate, sugar alcohols, acetic acid and ascorbic acid.

10. The method of claim 8, wherein the solvent consists essentially of water. The method of claim 8 , wherein the first carrier gas comprises ozone.

12. The method of claim 8, wherein step (a) comprises the following sub-steps: (i) generating an oxygen-enriched gas stream by selectively removing nitrogen from ambient air; and (ii) converting at least a portion of the diatomic oxygen in the oxygen-rich gas stream into ozone.

13. The method of claim 8, wherein: When performing step (b), ozone comprises at least 6.0 wt% of the total gas content of the sealable chamber.

14. The method of claim 8, wherein the temperature of the solution is 170°F.

15. The method of claim 8, wherein the solution is pressurized to at least 35 psi prior to being sprayed into the sealable chamber.

16. The method of claim 8, wherein step (b) is performed at least twice.

17. The method of claim 8, wherein step (d) comprises applying negative pressure to the sealable chamber to exhaust residual ozone from the sealable chamber.

18. The method of claim 8, wherein step (d) comprises flowing a second carrier gas through the sealable chamber to entrain and remove at least one of residual ozone and residual solvent from the sealable chamber. The method of claim 18 , wherein the second carrier gas comprises nitrogen.

20. The method of claim 8, further comprising: (e) collecting the ozonated crystalline solid from the inner surface of the sealable chamber.

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