Compositions and composites for forming nitric oxide

Abstract

Provided herein is a composite article. The composite article includes a source layer and an activation layer overlying the source layer. The source layer includes a nitric oxide precursor and the activation layer includes a thiol-containing compound. The nitric oxide precursor and the thiol-containing compound are capable of reacting in the presence of a solvent to form nitric oxide.

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application is an international application claiming priority to Provisional Patent Application No. 63 / 271,103, filed October 22, 2021, the entire contents of which are incorporated by reference in their entirety.

[0002] FIELD OF THE DISCLOSURE The present disclosure generally relates to compositions and composite articles including a source layer and an activation layer capable of forming nitric oxide for food preservation and sanitization. [Background technology]

[0003] Various products and articles, such as medical instruments, devices, and equipment, must be sterilized before use to prevent biocontamination of wound sites, samples, organisms, etc. Many sterilization processes are used that involve contacting the product or article with a sterilant. Examples of such sterilants include nitrogen tetroxide, nitric oxide, water vapor, ethylene oxide, hydrogen peroxide, dry heat, etc. Traditional methods for forming nitric oxide use catalytic and enzymatic generation of nitric oxide from nitrite.

[0004] There is a need to create long-term nitric oxide-releasing materials that are highly stable, temperature-insensitive, and light-insensitive. Temperature insensitivity allows for the use of several manufacturing techniques (e.g., extrusion, heat curing, etc.) that are incompatible with nearly all currently used nitric oxide-generating materials. Furthermore, temperature and light insensitivity open up the potential uses of nitric oxide-releasing materials to a wide range of potential applications where nitric oxide release may be desired to reduce microbial loads, such as those that cause odors, spoil food, and sustain mold and fungal growth.

[0005] Thus, there remains an opportunity for improved compositions and composites capable of forming nitric oxide for food preservation and sanitization. Summary of the Invention

[0006] Provided herein is a composite article. The composite article includes a source layer and an activation layer overlying the source layer. The source layer includes a nitric oxide precursor, and the activation layer includes a thiol-containing compound. The nitric oxide precursor and the thiol-containing compound are capable of reacting to form nitric oxide in the presence of a solvent.

[0007] The inventors contemplate composite articles comprising a nitric oxide precursor and a thiol-containing compound that react to form gas-phase nitric oxide in a controllable manner, allowing for the tailoring of nitric oxide release depending on the particular desired application. Nitrosothiols (RSNOs) are formed in a polymer matrix under extremely mild conditions and then reduced to form nitric oxide. In particular, the inventors contemplate composite articles or compositions that achieve thermally stable and photostable nitric oxide-releasing materials. In various embodiments, the composite articles or compositions comprise a carrier, a nitric oxide precursor, a thiol-containing compound, a catalyst, and various functional layers that can be utilized depending on the particular application (e.g., food packaging for meat, poultry, fish, fruits, vegetables, etc.).

[0008] From another perspective, a solvent (e.g., HCl) is absorbed into the composite article or composition. The solvent solubilizes a nitric oxide precursor (e.g., sodium nitrite). The nitric oxide precursor then mobilizes in the solvent and flows over a thiol-containing compound (e.g., reduced glutathione). The nitric oxide precursor and the thiol-containing compound react in situ to form an unstable S-nitrosothiol (e.g., S-nitrosoglutathione), which is then reduced to form nitric oxide. The nitric oxide diffuses out of the composite article and interacts with microorganisms in the area surrounding the composite article.

[0009] Control over the composite release characteristics of this material can be achieved through many aspects of the system, which will affect the size of the source layer, the rate at which the source layer is solubilized, the concentration and identity of the thiol-containing compound, the properties of the metering layer, the number and arrangement of layers that serve each purpose, the solvent uptake of the various layers present, and the presence of additives such as acids, reducing / oxidizing agents, etc.

[0010] Additionally, the presence of a catalyst (e.g., a transition metal) influences the rate of reduction of RSNOs. Furthermore, control of water uptake and layer thickness can be used to modulate nitric oxide release. Other solvents, such as methanol, ethanol, ethyl acetate, acetone, THF, brine, etc., can also be used in combination with or instead of water to solubilize nitric oxide precursors.

[0011] In one exemplary embodiment, a carrier (e.g., cellulose or ethylene vinyl acetate) is saturated with an aqueous solution containing sodium nitrite to form a source layer. A second carrier (e.g., cellulose or ethylene vinyl acetate) is saturated with an aqueous solution containing reduced glutathione to form an activated layer. When these layers are stacked on top of each other to form a composite article and the composite article is exposed to water, nitric oxide is produced by the reduction of S-nitrosoglutathione, which then rapidly decomposes to release nitric oxide.

[0012] In another exemplary embodiment, the activation layer further comprises trace zinc chloride. The presence of a transition metal alters the rate and release profile of nitric oxide production. The trace zinc chloride may be combined with glutathione in the activation layer or may be present in a separate catalyst layer.

[0013] In yet another embodiment, sodium nitrite is mixed into an uncured silicone sealant that also contains glutathione in the same carrier. The sodium nitrite may be incorporated directly into the sealant, or may be incorporated into vessels, micelles, or capsules within the sealant. A catalyst, such as a transition metal (e.g., zinc chloride) or a reducing agent (e.g., ascorbic acid), may be combined with the sealant. Once the sealant is applied and cured, exposure to water solubilizes the sodium nitrite, which can then promote reaction with thiol-containing compounds to form S-nitrosothiols, which are reduced to form nitric oxide. Nitric oxide can prevent mildew formation on the sealant. [Brief explanation of the drawings]

[0014] [Figure 1] FIG. 1 illustrates a non-limiting embodiment of a composite article. [Figure 2] FIG. 2 illustrates a non-limiting embodiment of a composite article. [Figure 3] FIG. 3 illustrates a non-limiting embodiment of a composite article. [Figure 4] FIG. 4 illustrates a non-limiting embodiment of a composite article. [Figure 5] FIG. 5 illustrates a non-limiting embodiment of a composite article. [Figure 6] FIG. 6 illustrates a non-limiting embodiment of a composite article. [Figure 7] FIG. 7 illustrates a non-limiting embodiment of a composite article. [Figure 8] FIG. 8 illustrates a non-limiting embodiment of a composite article. [Figure 9] FIG. 9 illustrates a non-limiting embodiment of a composite article.

[0015] [Figure 10] FIG. 10 is a diagram illustrating nitric oxide formation by a non-limiting embodiment of the composite article of FIGS.

[0016] [Figure 11] FIG. 11 is another diagram showing nitric oxide formation by a non-limiting embodiment of the composite article of FIGS. DETAILED DESCRIPTION OF THE INVENTION

[0017] Except in the examples or where expressly indicated, all numerical values ​​herein expressing amounts of ingredients or conditions of reaction and / or use should be understood to be modified by the word "about" in the broadest sense of the present disclosure. In various embodiments, the terms "about" and "approximately," when referring to specific measurable values ​​(e.g., parameters, amounts, temporal durations, etc.), are meant to encompass the particular value as well as variations therefrom, e.g., variations of + / - 10% or less, or + / - 5% or less, or + / - 1% or less, or + / - 0.1% or less, of the particular value, to the extent that such variations are appropriate in the disclosed embodiment. Accordingly, values ​​to which the modifiers "about" and "approximately" refer are themselves specifically disclosed.

[0018] Practice within the stated numerical limits is generally preferred. Similarly, unless expressly stated to the contrary: percents, "parts," and ratio values ​​are by weight; the description of a group or class of materials as suitable or preferred for a given purpose in connection with the present invention means that mixtures of any two or more members of the group or class are equally suitable or preferred; the description of components in chemical terms refers to the components at the time of addition in any combination specified in the specification and does not necessarily exclude chemical interactions between the components of the mixture once mixed; the initial definition of an acronym or other abbreviation applies to all subsequent uses of the same abbreviation herein, applying mutatis mutandis to normal grammatical variations of the initially defined abbreviation; and unless expressly stated to the contrary, measurements of properties are determined by the same techniques as those earlier or later referred to for the same property.

[0019] It should also be noted that as used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. For example, reference to a component in the singular is intended to include plural components.

[0020] As used herein, "embodiment" means that a particular feature, structure, or characteristic is included in at least one manifestation, example, or implementation of the invention. Moreover, as would be apparent to one of ordinary skill in the art, particular features, structures, or characteristics can be combined in any suitable manner. All combinations of features from different embodiments are intended to be within the scope of the invention, without the need to explicitly list every possible permutation by example. Thus, any of the claimed embodiments can be used in any combination.

[0021] As used herein, the term "weight percent" (and therefore the related abbreviation "wt. %") refers to percent by weight, typically expressed in terms of the weight of dry matter. It should therefore be understood that weight percent can be calculated based on the total weight of the composition, or can be calculated from the ratio between two or more components / portions of a mixture (e.g., total weight of dry matter).

[0022] As used herein, the term "substantially" refers to the complete or near-complete extent or degree of an action, characteristic, property, state, structure, item, or result. As a given example, an object that is "substantially" encapsulated would mean that the object is completely encapsulated, or so nearly completely encapsulated that it has the same overall result as if the object were completely encapsulated.

[0023] The drawings are semi-schematic and not to scale; in particular, some dimensions are shown exaggerated in the drawings for clarity of presentation. Similarly, while figures in the drawings for ease of explanation generally show similar orientations, this representation in the drawings is arbitrary. In general, composite articles can be handled in any orientation. As used herein, when a first component or layer is described as being "over," "overlying," "under," or "underlying" a second component or layer, it will be understood that the first component or layer may be directly on (directly in contact with) the second component or layer, or there may be intervening components or layers where a straight line can be drawn through and between the overlapping features. When a first component or layer is described as being "on" a second component or layer, the first component or layer is directly on and in contact with the second component or layer. Additionally, spatially relative terms, such as "upper," "over," "lower," "under," etc., may be used herein for ease of description to describe the relationship of one component or feature to another component(s) or feature(s) shown in the figures. It will be understood that the above spatially relative terms are intended to encompass different orientations of the composite article in use or handling, in addition to the orientation shown in the figures. For example, if a composite article in the figures were turned over, a component described as being "under" another component or feature would now be oriented "above" the other component or feature. Thus, the exemplary term "under" can include either an "above" or "under" orientation. The composite article can be otherwise oriented (rotated 90 degrees or to another orientation), and the spatially relative descriptors used herein can likewise be interpreted accordingly.

[0024] Throughout this disclosure, where publications are cited, the disclosures of these publications in their entireties are hereby incorporated by reference into this disclosure in order to more fully describe the state of the art to which this disclosure pertains.

[0025] The following detailed description is merely exemplary in nature and is not intended to limit the subject matter or application of the embodiments and uses of such embodiments. Furthermore, there is no intention to be bound by any expressed or implied theory presented in the preceding technical field, background, brief summary or the following detailed description.

[0026] Provided herein are composite articles 10 and compositions capable of forming nitric oxide. In various embodiments, a mixture of nitric oxide and air reacts to produce a mixture containing many different nitrogen oxides. Specifically, the addition of nitric oxide to air, or air to nitric oxide, results in the formation of nitrogen dioxide when the nitric oxide reacts with oxygen in the air. The concentration of each nitric oxide species present in the mixture can vary depending on the temperature, pressure, and initial concentration of nitric oxide.

[0027] Nitric oxide is lipid-soluble and has the ability to disrupt the lipid membranes of microorganisms. Furthermore, nitric oxide can inactivate thioproteins, thereby destroying functional proteins in microorganisms. Nitric oxide is more water-soluble than nitric oxide. Finally, nitric oxide and nitrogen dioxide are potent disruptors of DNA, causing strand breaks and other damage that results in the inability of cells to function.

[0028] As used herein, the term "nitric oxide" or "NO" refers to the NO free radical or NO xAs used herein, the term NOx is an abbreviation for nitrogen oxides or oxides of nitrogen, which are oxides formed by nitrogen, where nitrogen indicates each of its positive oxidation states from +1 to +5. As used herein, the terms "nitrogen oxides" and "oxides of nitrogen" and "NO x " means a gas having one or more of the following gases, all of which contain varying amounts of nitrogen and oxygen: nitric oxide (NO), nitrogen dioxide (NO), nitrogen trioxide (NO), dinitrogen trioxide (NO), dinitrogen tetroxide (NO), dinitrogen pentoxide (NO), and nitrous oxide (NO). As used herein, the phrase "nitric oxide precursor" refers to a gas having one or more of the following gases, all of which contain varying amounts of nitrogen and oxygen: nitric oxide (NO), nitrogen dioxide (NO), nitrogen trioxide (NO), dinitrogen tetroxide (NO), dinitrogen pentoxide (NO), and nitrous oxide (NO). As used herein, the phrase "nitric oxide precursor" refers to a gas having one or more of the following gases: NO, NO, and NO. x By "antibody" is meant a compound or composition capable of producing or releasing

[0029] In view of the above, the inventors contemplate utilizing composite article 10 and compositions to form nitric oxide for a variety of applications. Non-limiting examples of suitable applications for composites or compositions capable of forming nitric oxide include food packaging for preserving foodstuffs (e.g., meat, fruits, vegetables, cheese, ingredients thereof, etc.); vehicle components for sanitizing vehicles (e.g., headliners, seat cushion liners, carpet liners, etc.); hygiene containers for sanitizing hygiene devices (e.g., toothbrushes, mouth / bite guards, CPAP masks, face masks, etc.); medical device containers for sanitizing medical devices (e.g., stethoscopes, otoscopes, etc.), medical devices (e.g., portable ultrasound machines, communication devices, etc.); components of devices exposed to moisture (e.g., washing machines, boat compartments, etc.) for resisting mold or mildew growth; liners for sports equipment bags for sanitizing sports equipment (e.g., shoes, hockey equipment, ski equipment, face masks, goggles, helmets, etc.); and sealants for resisting mold or mildew growth (e.g., window sealants, shower / bath sealants, etc.).

[0030] 1-9 illustrate a non-limiting embodiment of a composite article 10. Composite article 10 includes, consists essentially of, or consists of a source layer 12 and an activation layer 14 overlying source layer 12. Source layer 12 includes, consists essentially of, consists of, or is a nitric oxide precursor. Activation layer 14 includes, consists essentially of, consists of, or is a thiol-containing compound. The nitric oxide precursor and the thiol-containing compound can react to form nitric oxide in the presence of a solvent (e.g., water).

[0031] As introduced above, compositions are also provided herein. The compositions include a source portion and an activating portion, consist essentially of a source portion and an activating portion, consist of a source portion and an activating portion, or are a source portion and an activating portion. The source portion includes, consists essentially of, consists of, or is a nitric oxide precursor. The activating portion includes, consists essentially of, consists of, or is a thiol-containing compound. Again, the nitric oxide precursor and the thiol-containing compound can react in the presence of a solvent (e.g., water) to form nitric oxide.

[0032] In particular, in certain embodiments, a nitric oxide precursor and a thiol-containing compound can react in the presence of a solvent to form a nitrosothiol, which is generally unstable and capable of decomposing to form nitric oxide. To this end, in an exemplary embodiment, a solvent (e.g., water moisture from the environment) is absorbed into composite article 10 to solubilize at least the nitric oxide precursor. The nitric oxide precursor is then mobilized in the solvent and migrates through source layer 12 to activated layer 14. However, it should be understood that the solvent may solubilize the thiol-containing compound, thereby mobilizing the thiol-containing compound in the solvent so that it migrates through activated layer 14 to source layer 12. The nitric oxide precursor and the thiol-containing compound then react to form an unstable S-nitrosothiol in situ, which rapidly decomposes to release nitric oxide. The nitric oxide then exits composite article 10 and sanitizes the area adjacent to composite article 10, for example, through interaction with microorganisms in the area. Importantly, in various embodiments, nitric oxide can be formed (a) at temperatures between -50°C and 150°C, (b) in the presence or absence of visible light, or (c) a combination thereof.

[0033] As introduced above, the source layer 12 overlies the activation layer 14. It should be understood that the term "overlying" should not be construed to limit the composite article in any way, such as by limiting the composite article to a particular configuration or by limiting the method of formation. Furthermore, as would be understood by one of ordinary skill in the art, the source layer 12 may overlie or be disposed on any portion(s) of the activation layer 14. For example, the source layer 12 may overlie or be disposed on one face or side of the activation layer 14. Furthermore, for example, the source layer 12 may be disposed on only a portion of one face or side of the activation layer 14. In certain embodiments, the source layer 12 and the activation layer 14 are in direct contact. In other words, there is no intervening layer between the source layer 12 and the activation layer 14. In other embodiments, composite article 10 includes other layers in various configurations relative to source layer 12 and activation layer 14, as described in more detail below.

[0034] The nitric oxide precursor of source layer 12 may be associated with source layer 12 in any manner known in the art. In some embodiments, the nitric oxide precursor is disposed substantially uniformly throughout source layer 12. In other embodiments, the nitric oxide precursor is included in source layer 12 in a gradient (e.g., a higher concentration adjacent to at least one of the faces of source layer 12, or a higher concentration adjacent to the center of source layer 12). In yet other embodiments, the nitric oxide precursor is a coating on source layer 12. In yet other embodiments, the nitric oxide precursor is source layer 12.

[0035] Depending on the design constraints of the desired application of the composite article 10 or composition, there are a wide variety of potential nitric oxide precursors that can be used. Nitric oxide precursors include, but are not limited to, SNAP-PDMS and other nitric oxide-donating polymers that utilize different nitric oxide moieties and different polymer base materials. The nitric oxide donor can be covalently attached to the polymer or mixed into the polymer. Separate nitric oxide donors can also be used in solid, liquid, or gel form. Non-limiting examples of this include one or more of S-nitroso-N-acetyl-D-penicillamine (SNAP), nitrite, S-nitrosocysteine, S-nitrosoglutathione, diazeniumdiolate compounds, enzymatic generation of NO from arginine, or biological sources such as organitrite, macrophage generation, etc. Non-limiting examples of suitable S-nitroso-N-acetyl-D-penicillamine and other photosensitive S-nitrosothiols covalently attached to polymers are described in U.S. Pat. No. 9,884,943 B2 and International Publication No. WO 2020 / 018488 A1, which are incorporated by reference in their entireties. Non-limiting examples of other suitable nitric oxide precursors are described in U.S. Patent Application Publication No. 2021 / 0220523 A1, which is incorporated by reference in its entirety.

[0036] Other non-limiting examples of nitric oxide precursors include one or more of polymers, acidified nitrites or nitrates, gas phase delivery from nitric oxide donating molecules such as diazeniumdiolates, nitrosothiols, nitrosyl compounds, or other methods of NO generation, such as enzymatic generation of nitric oxide, chemical generation of nitric oxide from ascorbic acid or metal catalysts, electrochemical generation of nitric oxide, photolytic cleavage of a bond to release nitric oxide, direct delivery of nitric oxide gas, and the like.

[0037] In certain embodiments, the nitric oxide precursor may include a nitrite, which may be selected from the group consisting of sodium nitrite, calcium nitrite, potassium nitrite, tetrabutylammonium nitrite, dicyclohexylammonium nitrite, butyl nitrite, isobutyl nitrite, t-butyl nitrite, amyl nitrite, pentyl nitrite, nitrite salts, ion pair nitrites, silver nitrite, zinc nitrite, iron nitrite, copper nitrite, transition metal nitrite compounds, and combinations thereof.

[0038] The nitric oxide precursor can be present in source layer 12 in any amount suitable for forming nitric oxide. In certain embodiments, the nitric oxide precursor is present in source layer 12 in an amount from about 0.01 to about 100 weight percent, optionally from about 0 to about 99 weight percent, or optionally from about 0.01 to about 99 weight percent, based on the total weight of source layer 12. Additional subranges of the foregoing endpoints and other points in between are also contemplated.

[0039] Returning to reference to source layer 12, source layer 12 can be in solid or semi-solid form. In various embodiments, source layer 12 is in solid form. Source layer 12 can be thermoplastic or thermoset. Source layer 12 can be any shape and size, each typically selected based on the intended use of composite article 10. Source layer 12 can have an average thickness of from about 0.01 to about 100 mils, optionally from about 0.1 to about 40 mils, or optionally from about 0.01 to about 4 mils.

[0040] In various embodiments, source layer 12 includes a carrier material. The carrier material may be thermoplastic or thermosetting. Non-limiting examples of suitable thermoplastic materials include polyvinyl chloride ("PVC"), polyethylene terephthalate ("PET"), glycol-modified polyethylene terephthalate ("PETG"), polypropylene ("PP"), polyethylene ("PE"), polyamides such as nylon, and combinations thereof. Non-limiting examples of suitable thermosetting materials include UV-curable materials, thermosetting materials, chemically curable materials such as free radicals, room-temperature curable materials, and low-temperature curable materials.

[0041] In certain embodiments, the carrier material of source layer 12 may be formed from cellulose, polyvinyl chloride, polyurethane, carbosil, polydimethylsiloxane, acrylic polymer, polyester, poly(lactic acid), poly(lactic-co-glycolic acid), poly(vinyl acetate), ethylene vinyl acetate, tecothane, pellethane, hydrogel, polytetrafluoroethylene, copolymers thereof, or combinations thereof. In one exemplary embodiment, the carrier material is formed from cellulose. In another exemplary embodiment, the carrier material is formed from a hydrogel selected from the group consisting of polymacron, polyacrylamide, collagen, agarose, hyaluronic acid, poly(organophosphazene), chitosan, poly(ethylene glycol), poly(vinyl alcohol), and combinations thereof. Non-limiting examples of suitable hydrogels are described in the journal article entitled "S-Nitrosothiol Detection via Amperometric Nitric Oxide Sensor with Surface Modified Hydrogel Layer Containing Immobilized Organoselenium Catalyst," cited as Langmuir 2006, 22, 25, 10830-10836, which is incorporated by reference in its entirety.

[0042] In other exemplary embodiments, the carrier material of source layer 12 includes a substrate. The substrate can include polytetrafluoroethylene in the form of a mesh or fiber. However, it should be understood that any type of material and any form of substrate can be utilized. In these and other embodiments, the carrier material is disposed within the substrate and further includes a material formed from cellulose, polyvinyl chloride, polyurethane, carbocyl, polydimethylsiloxane, acrylic polymer, polyester, poly(lactic acid), poly(lactic-co-glycolic acid), poly(vinyl acetate), ethylene vinyl acetate, tecothane, pellethane, hydrogel, another polytetrafluoroethylene, a copolymer thereof, or a combination thereof.

[0043] In certain embodiments, source layer 12 has a permeability in accordance with ASTM E2945-14(2021) in an amount of at least 0.001 g / (m·s·Pa), optionally at least 0.1 g / (m·s·Pa), optionally at least g / (m·s·Pa), optionally at least 1 g / (m·s·Pa), or optionally at least 5 g / (m·s·Pa) to allow at least one of the nitric oxide precursor or the solvent to migrate through source layer 12 to activation layer 14.

[0044] In various embodiments, source layer 12 has a water content of less than about 20 parts by weight, less than about 15 parts by weight, less than about 10 parts by weight, less than about 5 parts by weight, less than about 1 part by weight, or nearly 0 parts by weight per 100 parts by weight of source layer 12. Excessive moisture prior to use of composite article 10 can prematurely allow nitric oxide precursors to migrate through source layer 12 to activation layer 14, initiating the formation of nitric oxide.

[0045] Referring now to the thiol-containing compound of activated layer 14, the thiol-containing compound can be associated with activated layer 14 in any manner known in the art. In some embodiments, the thiol-containing compound is substantially uniformly distributed throughout activated layer 14. In other embodiments, the thiol-containing compound is included in activated layer 14 in a gradient (e.g., a higher concentration adjacent to at least one of the faces of activated layer 14, or a higher concentration adjacent to the center of activated layer 14). In yet other embodiments, the thiol-containing compound is a coating on activated layer 14. In still other embodiments, the thiol-containing compound is activated layer 14.

[0046] There are a wide variety of potential thiol-containing compounds that can be used depending on the design constraints of the desired application of the composite article 10 or composition, which may include, but are not limited to, one or more of 1,2-ethanedithiol, 2,3-dimercaptopropanol, pyrithione, dithioerythritol, 3,4-dimercaptotoluene, 2,3-butanedithiol, 1,3-propanedithiol, 2-hydroxypropanethiol, 1-mercapto-2-propanol, dithioerythritol, and dithiothreitol. Other exemplary thiol-containing compounds include alpha-lipoic acid, methanethiol (CHSH [m-mercaptan]), ethanethiol (CHSH [e-mercaptan]), 1-propanethiol (CHSH [nP-mercaptan]), 2-propanethiol (CHCH(SH)CH [2C-mercaptan]), butanethiol (CHSH([n-butyl mercaptan]), tert-butyl mercaptan (C(CH)SH [t-butyl mercaptan]), pentanethiol (CH 11SH [pentyl mercaptan]), coenzyme A, lipoamide, glutathione, cysteine, cystine, 2-mercaptoethanol, dithiothreitol, dithioerythritol, 2-mercaptoindole, transglutaminase, (11-mercaptoundecyl)hexa(ethylene glycol), (11-mercaptoundecyl)tetra(ethylene glycol), (11-mercaptoundecyl)tetra(ethylene glycol)-functionalized gold nanoparticles, 1,1′,4′,1″-terphenyl-4-thiol, 1,11-undecanedithiol, 1,16 -Hexadecanedithiol, 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-benzenedimethanethiol, 1,4-butanedithiol, 1,4-butanedithiol diacetate, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, 1,9-nonanedithiol, adamantanethiol, 1-butanethiol, 1-decanethiol, 1-dodecanethiol, 1-heptanethiol, 1-heptanethiol, 1-hexadecanethiol, 1-hexanethiol, 1-mercapto-(triethyl)- ethylene glycol), 1-mercapto-(triethylene glycol) methyl ether functionalized gold nanoparticles, 1-mercapto-2-propanol, 1-nonanethiol, 1-octadecanethiol, 1-octanethiol, 1-octanethiol, 1-pentadecanethiol, 1-pentanethiol, 1-propanethiol, 1-tetradecanethiol, 1-tetradecanethiol, 1-undecanethiol, 11-(1H-pyrrol-1-yl)undecane-1-thiol, 11-amino-1-undecanethiol hydrochloride, 11-bromo-1-undecanethiol 11-mercapto-1-undecanol, 11-mercapto-1-undecanol, 11-mercaptoundecanoic acid, 11-mercaptoundecanoic acid, 11-mercaptoundecyl trifluoroacetate, 11-mercaptoundecyl phosphate, 12-mercaptododecanoic acid, 12-mercaptododecanoic acid, 15-mercaptopentadecanoic acid, 16-mercaptohexadecanoic acid, 16-mercaptohexadecanoic acid, 1H,1H,2H,2H-perfluorodecanethiol, 2,2′-(ethylenedioxy)diethanethiol, 2,3-Butanedithiol, 2-Butanethiol, 2-Ethylhexanethiol, 2-Methyl-1-propanethiol, 2-Methyl-2-propanethiol, 2-Phenylethanethiol, 3,3,4,4,5,5,6,6,6-Nonafluoro-1-hexanethiol, 3-(Dimethoxymethylsilyl)-1-propanethiol, 3-Chloro-1-propanethiol, 3-Mercapto-1-propanol, 3-Mercapto-2-butanol, 3-Mercapto-N-nonylpropionamide, 3-Mercapto Isopropionic acid, 3-mercaptopropyl-functionalized silica gel, 3-methyl-1-butanethiol, 4,4′-bis(mercaptomethyl)biphenyl, 4,4′-dimercaptostilbene, 4-(6-mercaptohexyloxy)benzyl alcohol, 4-cyano-1-butanethiol, 4-mercapto-1-butanol, 6-(ferrocenyl)hexanethiol, 6-mercapto-1-hexanol, 6-mercaptohexanoic acid, 8-mercapto-1-octanol, 8-mercaptooctanoic acid, 9-mercapto-1-octanol, 10-mercapto-1-octanol, 11-mercapto-1-octanol, 12-mercapto-1-octanol, 13-mercapto-1-octanol, 14-mercapto-1-octanol, 15-mercapto-1-octanol, 16-mercapto-1-octanol, 17-mercapto-1-octanol, 18-mercapto-1-octanol, 19 ... Dodecanethiol-1-nonanol, biphenyl-4,4'-dithiol, butyl 3-mercaptopropionate, copper(I) 1-butanethiolate, cyclohexanethiol, cyclopentanethiol, decanethiol-functionalized silver nanoparticles, dodecanethiol-functionalized gold nanoparticles, dodecanethiol-functionalized silver nanoparticles, hexa(ethylene glycol) mono-11-(acetylthio)undecyl ether, mercaptosuccinic acid, methyl 3-mercaptopropionate, octanethiol-functionalized gold nanoparticles, PEG dithiolate Examples of suitable mercaptans include thiophenol, S-(11-bromoundecyl)thioacetate, S-(4-cyanobutyl)thioacetate, thiophenol, triethylene glycol mono-11-mercaptoundecyl ether, trimethylolpropane tris(3-mercaptopropionate), [11-(methylcarbonylthio)undecyl]tetra(ethylene glycol), m-carborane-9-thiol, p-terphenyl-4,4"-dithiol, tert-dodecyl mercaptan, and tert-nonyl mercaptan.

[0047] In certain embodiments, the thiol-containing compound includes cysteine ​​or a derivative thereof, a thiol-derivatized polymer or bulking agent, or a combination thereof. In embodiments where cysteine ​​or a derivative thereof is used, the cysteine ​​or derivative thereof can be selected from the group consisting of cysteine, glutathione, acetylcysteine, penicillamine, acetylpenicillamine, S-nitroso-n-acetylpenicillamine, bucillamine, and combinations thereof. It should be understood that the thiol-containing compound can be included as part of a peptide, polymer, copolymer, or other macromolecule. In embodiments where cysteine ​​or a derivative thereof is used as part of a peptide, the peptide can include any combination of amino acids, as long as the peptide includes cysteine ​​or a derivative thereof as at least one of the peptide components. Non-limiting examples of suitable cysteine ​​or derivatives thereof are described in the journal article entitled "S-Nitrosothiol Detection via Amperometric Nitric Oxide Sensor with Surface Modified Hydrogel Layer Containing Immobilized Organoselenium Catalyst," cited as Langmuir 2006, 22, 25, 10830-10836, which is incorporated by reference in its entirety.

[0048] The thiol-containing compound can be present in activated layer 14 in any amount suitable for forming nitric oxide. In certain embodiments, the thiol-containing compound is present in activated layer 14 in an amount from about 0.1 to about 100 weight percent, optionally from about 5 to about 10 weight percent, or optionally from about 20 to about 50 weight percent, based on the total weight of activated layer 14. Additional subranges of the foregoing endpoints, and other intermediate points, are also contemplated.

[0049] Returning to reference to activation layer 14, activation layer 14 may be in solid or semi-solid form. In various embodiments, activation layer 14 is in solid form. Activation layer 14 may be thermoplastic or thermoset. Activation layer 14 may be of any shape and size, each typically selected based on the intended use of composite article 10. Activation layer 14 may have an average thickness of about 0.01 to about 100 mils, optionally about 0.1 to about 2 mils, or optionally about 1 to about 4 mils. In various embodiments, activation layer 14 comprises a carrier material as described above for source layer 12. However, it should be understood that the carrier material may be different for each of the layers described herein.

[0050] In certain embodiments, activation layer 14 has a permeability in an amount of at least 0.001 g / (m·s·Pa), optionally at least 0.1 g / (m·s·Pa), optionally at least 1 g / (m·s·Pa), or optionally at least 5 g / (m·s·Pa), according to ASTM E2945-14(2021), to allow migration of at least one of the nitric oxide precursor or the solvent through activation layer 14, or in alternative embodiments, to allow migration of at least one of the thiol-containing compound or the solvent through activation layer 14 to source layer 12.

[0051] In various embodiments, activated layer 14 has a water content of less than about 20 parts by weight, less than about 15 parts by weight, less than about 10 parts by weight, less than about 5 parts by weight, less than about 1 part by weight, or nearly zero parts by weight per 100 parts by weight of activated layer 14. Excessive moisture prior to use of composite article 10 may prematurely allow at least one of the nitric oxide precursor or thiol-containing compound to migrate through source layer 12 to activated layer 14, or in alternative embodiments, through activated layer 14 to source layer 12, initiating the formation of nitric oxide.

[0052] Proceeding further, the composite article 10 or composition can further include a catalyst. The inventors contemplate that the catalyst can modulate the reduction of S-nitrosothiols to nitric oxide (e.g., increase the reaction rate, decrease the reaction rate, etc.). The catalyst can include a transition metal, a nonmetal, or a combination thereof. However, it should be understood that the catalyst can include any compound known in the art that can modulate the reduction of S-nitrosothiols to nitric oxide. In some embodiments, the catalyst includes a transition metal selected from the group consisting of copper (Cu), zinc (Zn), silver (Ag), gold (Au), lead (Pb), platinum (Pt), iron (Fe), magnesium (Mg), manganese (Mn), cobalt (Co), nickel (Ni), and combinations thereof. Non-limiting examples of suitable copper (Cu) catalysts are described in International Publication No. WO 2005 / 094913 A1, U.S. Pat. No. 8,168,423 B2, and the journal article entitled "Spontaneous Catalytic Generation of Nitric Oxide from S-Nitrosothiols at the Surface of Polymer Films Doped with Lipophilic Copper(II) Complex," cited in J. Am. Chem. Soc. 2003, 125, 32, 9552-9553, which are incorporated by reference in their entireties. In an exemplary embodiment, the catalyst is zinc chloride.

[0053] In other embodiments, the catalyst includes a non-metal selected from the group consisting of selenium (Se), tellurium (Te), organometallic compounds, and combinations thereof. In exemplary embodiments, the catalyst is selenium, organoselenium, or a combination thereof. Non-limiting examples of suitable organoselenium catalysts are described in the journal article entitled "S-Nitrosothiol Detection via Amperometric Nitric Oxide Sensor with Surface Modified Hydrogel Layer Containing Immobilized Organoselenium Catalyst," cited as Langmuir 2006, 22, 25, 10830-10836, which is incorporated by reference in its entirety.

[0054] The catalyst may be associated with any layer of the composite article 10 in any manner known in the art. In some embodiments, the catalyst is substantially uniformly disposed throughout at least one of the layers. In other embodiments, the catalyst is included in at least one of the layers in a gradient (e.g., a higher concentration adjacent to at least one of the faces of the layer, or a higher concentration adjacent to the center of the layer). In still other embodiments, the catalyst is a coating on at least one of the layers. In still other embodiments, the catalyst is a layer in its own right.

[0055] The catalyst may be present in source layer 12, activation layer 14, catalyst layer 16 (described in more detail below), or a combination thereof. In certain embodiments, the catalyst is present in at least one of source layer 12, activation layer 14, or catalyst layer 16 in an amount from about 0.1 to about 100 weight percent, optionally from about 0.02 to about 0.5 weight percent, or optionally from about 1 to about 10 weight percent, based on the total weight of each layer including the catalyst. Additional subranges of the foregoing endpoints, and other intermediate points, are also contemplated.

[0056] Composite article 10 may further include a catalyst layer 16. Catalyst layer 16 may overlie any of the layers of composite article 10 or may be disposed between any of the layers of composite article 10. In certain embodiments, catalyst layer 16 may be (a) disposed between source layer 12 and activation layer 14, (b) disposed on source layer 12 and optionally spaced apart from activation layer 14, (c) disposed on activation layer 14 and optionally spaced apart from source layer 12, or (d) a combination thereof.

[0057] Catalyst layer 16 may be in solid or semi-solid form. In various embodiments, catalyst layer 16 is in solid form. Catalyst layer 16 may be thermoplastic or thermoset. Catalyst layer 16 may be any shape and size, each typically selected based on the intended use of composite article 10. Catalyst layer 16 may have an average thickness of about 0.01 to about 100 mils, optionally about 0.1 to about 1 mil, or optionally about 1 to about 5 mils. In various embodiments, catalyst layer 16 comprises a support material as described above for source layer 12. However, it should be understood that the support material may vary for each of the layers described herein.

[0058] In certain embodiments, catalyst layer 16 has a permeability according to ASTM E2945-14(2021) in an amount of at least 0.001 g / (m·s·Pa), optionally at least 0.1 g / (m·s·Pa), optionally at least g / (m·s·Pa), optionally at least 1 g / (m·s·Pa), or optionally at least 5 g / (m·s·Pa) to allow movement of a component of composite material XX through catalyst layer 16.

[0059] Proceeding further, composite article 10 may further include a metering layer 18 capable of regulating the movement of at least one of the nitric oxide precursor or solvent to or through activation layer 14, or alternatively, the movement of at least one of the thiol-containing compound or solvent to or through source layer 12. Metering layer 18 may overlie any of the layers of composite article 10 or may be disposed between any of the layers of composite article 10. In certain embodiments, metering layer 18 may be (a) disposed between source layer 12 and activation layer 14, (b) disposed on source layer 12 and optionally spaced apart from activation layer 14, (c) disposed on activation layer 14 and optionally spaced apart from source layer 12, or (d) a combination thereof. In an exemplary embodiment, metering layer 18 is disposed on activation layer 14 and spaced apart from source layer 12. In these and other embodiments, the metering layer 18 only partially overlaps the active layer 14 such that a portion of the active layer 14 is free of the metering layer 18 .

[0060] The metering layer 18 may be in a solid or semi-solid form. In various embodiments, the metering layer 18 is in a solid form. The metering layer 18 may be thermoplastic or thermoset. The metering layer 18 may be any shape and size, each typically selected based on the intended use of the composite article 10. The metering layer 18 may have an average thickness of about 0.01 to about 100 mils, optionally about 0.1 to about 1 mil, or optionally about 1 to about 5 mils. In various embodiments, the metering layer 18 comprises a carrier material as described above for the source layer 12. However, it should be understood that the carrier material may be different for each of the layers described herein.

[0061] The metering layer can have a permeability that is different from the permeability of at least one of the source layer 12 or the activation layer 14. In certain embodiments, the metering layer 18 has a permeability that is less than the permeability of at least one of the source layer 12 or the activation layer 14, but in an amount of at least 0.001 g / (m·s·Pa), optionally at least 0.1 g / (m·s·Pa), optionally at least g / (m·s·Pa), optionally at least 1 g / (m·s·Pa), or optionally at least 5 g / (m·s·Pa), according to ASTM E2945-14(2021), to allow for controlled movement of components of the composite article 10 through the metering layer 18.

[0062] The composite article 10 or composition may further include various additives, such as, but not limited to, ascorbates, reducing equivalents, oxidizing equivalents, acids, bases, pH buffers, ionophores, enzymes, any agent that may affect the formation and stability of thiols (e.g., disulfide formation or disulfide bond cleavage), nitrosothiols (e.g., acid / base, ion mobility, gas permeability, reaction / buffering of NO gas), plasticizers, surfactants, colorants, fillers, or combinations thereof.

[0063] The plasticizer may include plasticizers that can be used to modify various properties, such as, but not limited to, permeability, hydrophobicity modification, tensile strength, elongation, etc. Plasticizers include, but are not limited to, phthalates, trimellitates, benzoates, adipates, sebacates, maleates, citrates, epoxidized vegetable oils, sulfonamides, organic phosphates, glycol / polyethers, polymeric plasticizers, and polybutanes, or combinations thereof. However, it should be understood that the plasticizer may include any other plasticizer understood in the art, so long as the plasticizer is compatible with the components or composition of the composite article 10.

[0064] The plasticizer may be an ester plasticizer. Examples of suitable ester plasticizers include, but are not limited to, dioctyl phthalate (DOP), n-hexyl-n-decyl phthalate (NHDP), n-octyl-decyl phthalate (NODP), di(isononyl) phthalate (DINP), di(isodecyl) phthalate (DIDP), diundecyl phthalate (DUP), di(isotridecyl) phthalate (DTDP), di-2-ethylhexyl adipate (DOA), di-n-octyl-n-decyl adipate (DNODA), diisononyl adipate (DINA), di-2-ethylhexyl azelate (DOZ), di-2-ethylhexyl sebacate (DOS), trioctyl trimellitate (TOTM), trioctyl phosphate (TOP), tricresyl phosphate (TCP), aliphatic polyester plasticizers, aliphatic polyol plasticizers, or combinations thereof. In certain embodiments, the plasticizer component includes trioctyl trimellitate (TO™). It should be understood that the plasticizer can include any phthalate known in the art, so long as it is compatible with the composite article 10 or composition.

[0065] The surfactant component may include an anionic surfactant, a nonionic surfactant, a cationic surfactant, a zwitterionic surfactant, or a combination thereof, although it should be understood that the surfactant component may include any other surfactant understood in the art so long as the surfactant is compatible with the components or compositions of composite article 10.

[0066] Examples of suitable anionic surfactants include, but are not limited to, fatty alcohol sulfates, alkylphenol sulfates, fatty alcohol ether sulfates, alkylphenol ether sulfates, alkylbenzene sulfonic acids, alkyl ether carboxylic acids and their salts, alkyl sulfosuccinates, alkyl sulfosuccinamates, phosphate esters, α-olefin sulfonates, or combinations thereof. Examples of suitable nonionic surfactants include, but are not limited to, alcohol ethoxylates, alkylphenol ethoxylates, polyethylene oxide / polyethylene oxide block copolymers, polyvinyl alcohol, polyvinylpyrrolidone, sorbitan fatty acid esters, sorbitan ester ethoxylates, or combinations thereof. Examples of suitable cationic surfactants include, but are not limited to, alkyldimethylamines, quaternary ammonium compounds, or combinations thereof. In certain embodiments, the surfactant component comprises a nonionic surfactant. The nonionic surfactant may include an acetylene glycol surfactant, 2-ethylhexanol, or a combination thereof.

[0067] The filler may include any filler that can be used for various purposes, such as, but not limited to, cost containment, rheology control, lubricity modification, and preventing seizing or galling. The filler component may include an inorganic filler. Examples of suitable inorganic fillers include, but are not limited to, powdered nickel, copper, zinc, and aluminum. Suitable mineral fillers include, but are not limited to, talc, calcium carbonate, silicates such as mica, wollastonite, titanium dioxide, quartz, fumed silica, precipitated silica, graphite, boron nitride, or combinations thereof.

[0068] Other components that may be present in the composite article 10 or composition include trace amounts of antioxidants, inhibitors, antifoaming agents, dispersing aids, heat stabilizers, UV stabilizers, etc., such as one or more of the components described in U.S. Patent Application Publication No. 2004 / 0258922 A1, U.S. Patent No. 9,404,015 B2, and U.S. Patent No. 10,214,668 B2, the disclosures of which are incorporated herein by reference in their entireties. In various embodiments, one or more of such additives are individually present in the composite article 10 or composition in an amount of less than about 5 wt.%, based on the total weight of the composite article 10 or composition.

[0069] Also provided herein is a food packaging article capable of forming nitric oxide to preserve a food product. The food packaging article includes a source layer 12 and an activation layer 14 overlying the source layer 12, as described above. The food packaging article further includes a contact layer 20 overlying the activation layer 14. The contact layer may have a permeability according to ASTM E2945-14(2021) in an amount of at least 0.001 g / (m·s·Pa), optionally at least 0.1 g / (m·s·Pa), optionally at least g / (m·s·Pa), optionally at least 1 g / (m·s·Pa), or optionally at least 5 g / (m·s·Pa) to allow nitric oxide to migrate therethrough. The contact layer 20 may be substantially impermeable to ions. The food packaging article may further include a barrier layer 22. Source layer 12 is disposed on barrier layer 22, which is spaced apart from activation layer 14. Barrier layer 22 has a permeability of less than 0.01 g / (m·s·Pa) according to ASTM E2945-14(2021) to prevent migration of nitric oxide therethrough. The food packaging may be in the form of a rigid container, wrapper, bag, bottle, or tube. In various embodiments, poultry contained in the food packaging exhibits reduced spoilage after 96 hours at 23° C. compared to poultry contained in a container that does not contain at least one of a nitric oxide precursor or a thiol-containing compound.

[0070] A vehicle headliner for a vehicle capable of forming nitric oxide to sanitize the vehicle is also provided. The vehicle headliner includes, as described above, a source layer 12 and an activation layer 14. The vehicle headliner further includes a woven fabric layer overlying the activation layer 14.

[0071] A washing machine component capable of forming nitric oxide to resist mold or mildew growth is also provided. The washing machine component includes a source portion and an activator portion. In certain embodiments, the washing machine component is a gasket or a liner.

[0072] Also provided is a sealant composition capable of forming nitric oxide to resist mold or mildew growth. The sealant composition includes a source portion and an activator portion. The sealant composition further includes a sealant material. In certain embodiments, the sealant material is selected from the group consisting of silicone, epoxy, polyurethane, polysulfide, latex, and combinations thereof.

[0073] Composite article 10 can be formed using conventional techniques understood in the art. In an exemplary formation method, the method includes providing a first support material and a second support material. The method further includes combining a nitric oxide precursor with water to form a first solution. The method further includes combining a thiol-containing compound with water to form a second solution. The method further includes disposing and applying the first solution to the first support material to form source layer 12. The method further includes applying the second solution to the second support material to form activated layer 14. The method further includes disposing activated layer 14 on source layer 12 to form composite article 10.

[0074] The carrier material may be formed by various methods understood in the art. For example, the carrier material may be extruded, cast, laminated, etc. The solution may be applied to the carrier by various methods understood in the art. For example, the solution may be sprayed onto the carrier, the carrier may be immersed in the solution, or the carrier and solution may be combined and then extruded or cast to form a layer. It should be understood that any other method known in the art for forming a composite article may be utilized, so long as the method is compatible with the components of composite article 10.

[0075] The composition can be formed using conventional techniques understood in the art. In an exemplary method of formation, the method includes combining a carrier material, a nitric oxide precursor, and a thiol-containing compound to form the composition. In embodiments where the composition is a sealant, the combining step can further include a sealant material. [Example]

[0076] The following examples are included to illustrate various embodiments contemplated herein. It should be understood by those of skill in the art that the techniques disclosed in the examples which follow represent techniques found by the inventor(s) to function well in the practice of the invention, and therefore can be considered to constitute preferred modes for its practice. However, those of skill in the art should, in light of the present disclosure, understand that many changes can be made in the specific embodiments which are disclosed and still obtain like or similar results without departing from the spirit and scope of the invention. Unless otherwise indicated, all percentages are by weight and all measurements are made at 23°C.

[0077] Exemplary Formulations of Combination Products Exemplary formulations of the combination products are provided below. [Table 1]

[0078] Carrier I is commercially available cellulose.

[0079] Carrier II is commercially available ethylene vinyl acetate.

[0080] Nitric oxide precursor I is commercially available sodium nitrite.

[0081] Thiol-containing compound I is commercially available glutathione.

[0082] Catalyst I is commercially available zinc chloride.

[0083] Exemplary Formulations of the Compositions Exemplary formulations of the compositions are provided below. [Table 2]

[0084] Carrier I is commercially available cellulose.

[0085] Carrier II is commercially available ethylene vinyl acetate.

[0086] Nitric oxide precursor I is commercially available sodium nitrite.

[0087] Thiol-containing compound I is commercially available glutathione.

[0088] Catalyst I is commercially available zinc chloride.

[0089] Example I: Composite Article A cellulose support was saturated with an aqueous solution containing sodium nitrite. Another cellulose support was saturated with an aqueous solution containing reduced glutathione. The two layers were stacked on top of each other to form a composite. The composite was then exposed to water, generating nitric oxide through the formation of S-nitrosoglutathione, which rapidly decomposes to release nitric oxide (see Figure 10). Neither layer produced nitric oxide by itself. Furthermore, without exposure to water, the layers together did not produce nitric oxide. However, when both layers were in contact with each other and exposed to water, nitric oxide was produced.

[0090] Example II: Composite Article A cellulose support was saturated with an aqueous solution containing sodium nitrite. Another cellulose support was saturated with an aqueous solution containing reduced glutathione and zinc chloride. The two layers were stacked on top of each other to form a composite. The composite was then exposed to water, generating nitric oxide by forming S-nitrosoglutathione, which rapidly decomposes to release nitric oxide (see Figure 10). Neither layer produced nitric oxide by itself. Furthermore, without exposure to water, the layers together did not produce nitric oxide. However, when both layers were in contact with each other and exposed to water, nitric oxide was produced.

[0091] Example III: Composite Article An ethylene vinyl acetate carrier was saturated with sodium nitrite. Another ethylene vinyl acetate carrier was saturated with reduced glutathione. The two layers were stacked on top of each other to form a composite. The composite was then exposed to water, generating nitric oxide by forming S-nitrosoglutathione, which rapidly decomposes to release nitric oxide (see Figure 11). Neither layer produced nitric oxide by itself. Furthermore, without exposure to water, the layers together did not produce nitric oxide. However, when both layers were in contact with each other and exposed to water, nitric oxide was produced.

[0092] It should be understood that the scope of the appended claims is not limited to the language and specific compounds, compositions, or methods described in the detailed description, but may vary among specific embodiments falling within the scope of the appended claims. With respect to any Markush group relied upon herein to describe particular properties or aspects of various embodiments, different, special, and / or unexpected results can be obtained from each member of the respective Markush group, independent of all other Markush members. Each member of a Markush group may be relied upon individually and / or in combination to provide sufficient support for specific embodiments within the scope of the appended claims.

[0093] Furthermore, any ranges and subranges relied upon in describing various embodiments of the present invention are understood to individually and collectively fall within the scope of the appended claims and to describe and contemplate all ranges, including whole and / or fractional values ​​therein, even if such values ​​are not expressly written herein. Those skilled in the art will readily recognize that the recited ranges and subranges fully describe and enable various embodiments of the present invention, and that such ranges and subranges may be further expressed into related halves, thirds, quarters, fifths, etc. As merely an example, a range "from 0.1 to 0.9" may be further expressed into a lower third, i.e., 0.1 to 0.3, a middle third, i.e., 0.4 to 0.6, and an upper third, i.e., 0.7 to 0.9, which, individually and collectively, are within the scope of the appended claims and may be relied upon individually and / or collectively to provide sufficient support for particular embodiments within the scope of the appended claims. Furthermore, with respect to terms defining or modifying ranges, such as "at least," "greater than," "less than," "less than or equal to," etc., it should be understood that such terms encompass subranges and / or upper or lower limits. As another example, the range "at least 10" inherently encompasses subranges of at least 10 to 35, at least 10 to 25, 25 to 35, etc., each of which may be relied upon individually and / or collectively to provide sufficient support for particular embodiments within the scope of the appended claims. Finally, individual numbers within the disclosed ranges may be relied upon to provide sufficient support for particular embodiments within the scope of the appended claims. For example, the range "from 1 to 9" encompasses various individual integers, such as 3, as well as individual numbers including decimal points (or fractions), such as 4.1, which may be relied upon to provide sufficient support for particular embodiments within the scope of the appended claims.

[0094] The present invention has been described herein in an illustrative manner, and it should be understood that the terminology used is intended to be in the nature of words of description rather than words of limitation. Many modifications and variations of the present invention are possible in light of the above teachings. The invention may be practiced otherwise than as specifically described, within the scope of the appended claims. The subject matter of all combinations of independent aspects and dependent aspects, both singly and multiply dependent, is expressly contemplated herein. Aspects of the present disclosure include the following. [1] a source layer comprising a nitric oxide precursor; and an activation layer overlying the source layer and comprising a thiol-containing compound; A composite article comprising: A composite article, wherein the nitric oxide precursor and the thiol-containing compound are capable of reacting in the presence of a solvent to form nitric oxide. [2] 2. The composite article of claim 1, wherein the nitric oxide precursor and the thiol-containing compound are capable of reacting in the presence of a solvent to form a nitrosothiol, and the nitrosothiol is capable of decomposing to form the nitric oxide. [3] 3. The composite article of any one of claims 1 to 2, wherein the nitric oxide precursor comprises a nitrite. [4] 4. The composite article of claim 3, wherein the nitrite is selected from the group of sodium nitrite, sodium nitrite, calcium nitrite, potassium nitrite, tetrabutylammonium nitrite, dicyclohexylammonium nitrite, butyl nitrite, isobutyl nitrite, t-butyl nitrite, amyl nitrite, pentyl nitrite, nitrite salts, ion pair nitrites, silver nitrite, zinc nitrite, iron nitrite, copper nitrite, transition metal nitrite compounds, and combinations thereof. [5] Aspect 5. The composite article of any one of aspects 1-4, wherein the thiol-containing compound comprises cysteine ​​or a derivative thereof, a thiol-derivatized polymer or bulking agent, or a combination thereof. [6] 6. The combination article of any one of Aspects 1 to 5, wherein the cysteine ​​or derivative thereof is selected from the group consisting of cysteine, glutathione, acetylcysteine, penicillamine, acetylpenicillamine, S-nitroso-n-acetylpenicillamine, bucillamine, and combinations thereof. [7] 7. The composite article of any one of embodiments 1 to 6, further comprising a catalyst. [8] 8. The composite article of embodiment 7, wherein the catalyst comprises a transition metal, a non-metal, or a combination thereof. [9] 9. The composite article of embodiment 8, wherein the catalyst comprises a transition metal selected from the group of copper (Cu), zinc (Zn), silver (Ag), gold (Au), lead (Pb), platinum (Pt), iron (Fe), magnesium (Mg), manganese (Mn), cobalt (Co), nickel (Ni), and combinations thereof.

[10] 10. The composite article of embodiment 9, wherein the catalyst is zinc chloride.

[11] 9. The composite article of embodiment 8, wherein the catalyst comprises a non-metal selected from the group of selenium (Se), tellurium (Te), organometallic compounds, and combinations thereof.

[12] 12. The composite article of embodiment 11, wherein the catalyst is selected from the group of selenium, organoselenium, and combinations thereof.

[13] 13. The composite article of any one of embodiments 7 to 12, wherein the activation layer further comprises the catalyst.

[14] 13. The composite article of any one of aspects 7 to 12, wherein the composite article further comprises a catalyst layer, the catalyst layer comprising the catalyst.

[15] The catalyst layer comprises: (a) disposed between the source layer and the activation layer; (b) disposed on the source layer and optionally spaced apart from the activation layer; (c) disposed on the activation layer and optionally spaced apart from the source layer; or (d) a combination thereof; 15. The composite article of embodiment 14.

[16] 16. The composite article of any one of the preceding aspects, wherein at least one of the source layer or the activation layer comprises a carrier material formed from cellulose, polyvinyl chloride, polyurethane, carbocyl, polydimethylsiloxane, an acrylic polymer, polyester, poly(lactic acid), poly(lactic-co-glycolic acid), poly(vinyl acetate), ethylene vinyl acetate, tecothane, pellethane, a hydrogel, polytetrafluoroethylene, a copolymer thereof, or a combination thereof.

[17] 17. The composite article of embodiment 16, wherein the carrier material is formed from cellulose.

[18] 17. The composite article of embodiment 16, wherein the carrier material is formed from a hydrogel selected from the group consisting of polymacron, polyacrylamide, collagen, agarose, hyaluronic acid, poly(organophosphazene), chitosan, poly(ethylene glycol), poly(vinyl alcohol), and combinations thereof.

[19] The carrier material comprises: a support comprising polytetrafluoroethylene in the form of a mesh or fiber; and A material disposed in the support and formed from cellulose, polyvinyl chloride, polyurethane, carbosil, polydimethylsiloxane, acrylic polymer, polyester, poly(lactic acid), poly(lactic-co-glycolic acid), poly(vinyl acetate), ethylene vinyl acetate, tecothane, pellethane, hydrogel, another polytetrafluoroethylene, copolymers thereof, or combinations thereof. 19. The composite article of any one of aspects 16 to 18, comprising:

[20] 20. The composite article of any one of the preceding aspects, wherein at least one of the source layer or the activation layer has a permeability according to ASTM E2945-14(2021) in an amount of at least 0.001 g / (m·s·Pa) to allow movement of at least one of the nitric oxide precursor or the solvent into or through the activation layer.

[21] 21. The composite article of embodiment 20, further comprising a metering layer capable of regulating the movement of at least one of the nitric oxide precursor or the solvent into or through the activation layer.

[22] The metering layer is (a) disposed between the source layer and the activation layer; (b) disposed on the source layer and optionally spaced apart from the activation layer; (c) disposed on the activation layer and optionally spaced apart from the source layer; or (d) a combination thereof; 22. The composite article of embodiment 21.

[23] 23. The composite article of claim 22, wherein the metering layer is disposed on the activation layer and spaced apart from the source layer, and the metering layer only partially overlaps the activation layer such that a portion of the activation layer is free of the metering layer.

[24] 24. The composite article of any one of embodiments 21 to 23, wherein the metering layer has a permeability that is different from the permeability of at least one of the source layer or the activation layer.

[25] 25. The composite article of claim 24, wherein the metering layer has a permeability according to ASTM E2945-14(2021) of at least 0.001 g / (m·s·Pa) but less than the permeability of at least one of the source layer or the activated layer.

[26] 26. The composite article of any one of embodiments 1 to 25, wherein the source layer and the activation layer are in direct contact.

[27] 27. The composite article of any one of aspects 1 to 26, wherein the solvent comprises water.

[28] 28. The composite article of any one of embodiments 1 to 27, further comprising an additive selected from the group consisting of a transition metal, ascorbic acid, a pH control layer, and a buffer component.

[29] 29. The composite article of embodiment 28, wherein at least one of the source layer or the activated layer comprises one or more of the additives.

[30] The nitric oxide comprises: (a) At temperatures between 0°C and 100°C; (b) in the presence or absence of visible light; or (c) a combination of these 30. The composite article of any one of embodiments 1 to 29, which is capable of being formed.

[31] 1. A food packaging article capable of forming nitric oxide to preserve food products, comprising: a source layer containing a nitric oxide precursor; an activation layer overlying the source layer and comprising a thiol-containing compound; and a contact layer overlying the activation layer; Including, The food packaging article, wherein the nitric oxide precursor and the thiol-containing compound are capable of reacting in the presence of a solvent to form nitric oxide.

[32] 32. The food packaging of claim 31, wherein the contact layer has a permeability according to ASTM E2945-14(2021) in an amount of at least 0.001 g / (m·s·Pa) to allow migration of nitric oxide through the contact layer.

[33] 33. The food packaging of claim 32, wherein the contact layer is substantially impermeable to ions.

[34] 34. The food packaging of any one of Aspects 31-33, wherein the food packaging further comprises a barrier layer, the sauce layer disposed on the barrier layer, and the barrier layer spaced apart from the activation layer.

[35] 35. The food packaging of claim 34, wherein the barrier layer has a permeability according to ASTM E2945-14(2021) of less than 0.01 g / (m·s·Pa) to prevent migration of nitric oxide through the barrier layer.

[36] 36. The food packaging of any one of aspects 31 to 35, wherein the food packaging is in the form of a rigid container, a wrapper, a bag, a bottle, or a tube.

[37] 37. The food packaging of any one of aspects 31 to 36, wherein the poultry contained in the food packaging exhibits reduced spoilage after 96 hours at 23°C compared to poultry contained in a container that does not contain at least one of the nitric oxide precursor or the thiol-containing compound.

[38] 1. A vehicle headliner for a vehicle capable of forming nitric oxide to sanitize the vehicle, comprising: a source layer containing a nitric oxide precursor; an activation layer overlying the source layer and comprising a thiol-containing compound; and a woven fabric layer overlying the activation layer; Including, A vehicle headliner, wherein the nitric oxide precursor and the thiol-containing compound are capable of reacting in the presence of a solvent to form nitric oxide.

[39] a source portion comprising a nitric oxide precursor; and an activating portion comprising a thiol-containing compound; A composition comprising: A composition, wherein the nitric oxide precursor and the thiol-containing compound are capable of reacting in the presence of a solvent to form nitric oxide.

[40] 1. A washing machine component capable of forming nitric oxide to resist mold or mildew growth, comprising: a source portion comprising a nitric oxide precursor; and an activating portion comprising a thiol-containing compound; Including, A washing machine component, wherein the nitric oxide precursor and the thiol-containing compound are capable of reacting in the presence of a solvent to form nitric oxide.

[41] 41. The washing machine component of claim 40, wherein the washing machine component is a gasket or a liner.

[42] 1. A sealant composition capable of forming nitric oxide to resist mold or mildew growth, comprising: a source portion containing a nitric oxide precursor; an activating portion comprising a thiol-containing compound; and sealant materials; Including, A sealant composition, wherein the nitric oxide precursor and the thiol-containing compound are capable of reacting in the presence of a solvent to form nitric oxide.

[43] A sealant composition according to aspect 42, wherein the sealant material is selected from the group of silicone, epoxy, polyurethane, polysulfide, latex, and combinations thereof.

Claims

1. a source layer comprising a nitric oxide precursor; and an activation layer overlying the source layer and comprising a thiol-containing compound; A composite article comprising: A composite article, wherein the nitric oxide precursor and the thiol-containing compound are capable of reacting in the presence of a solvent to form nitric oxide.

2. 2. The composite article of claim 1, wherein the nitric oxide precursor and the thiol-containing compound are capable of reacting in the presence of a solvent to form a nitrosothiol, and the nitrosothiol is capable of decomposing to form the nitric oxide.

3. 3. The composite article of claim 1 or 2, wherein the nitric oxide precursor comprises a nitrite.

4. 4. The composite article of claim 3, wherein the nitrite is selected from the group consisting of sodium nitrite, sodium nitrite, calcium nitrite, potassium nitrite, tetrabutylammonium nitrite, dicyclohexylammonium nitrite, butyl nitrite, isobutyl nitrite, t-butyl nitrite, amyl nitrite, pentyl nitrite, nitrite salts, ion pair nitrites, silver nitrite, zinc nitrite, iron nitrite, copper nitrite, transition metal nitrite compounds, and combinations thereof.

5. 3. The composite article of claim 1 or 2, wherein the thiol-containing compound comprises cysteine ​​or a derivative thereof, a thiol-derivatized polymer or bulking agent, or a combination thereof.

6. 6. The composite article of claim 5, wherein the cysteine ​​or derivative thereof is selected from the group consisting of cysteine, glutathione, acetylcysteine, penicillamine, acetylpenicillamine, S-nitroso-n-acetylpenicillamine, bucillamine, and combinations thereof.

7. 3. The composite article of claim 1 or 2, further comprising a catalyst.

8. 8. The composite article of claim 7, wherein the catalyst comprises a transition metal, a non-metal, or a combination thereof.

9. 9. The composite article of claim 8, wherein the catalyst comprises a transition metal selected from the group of copper (Cu), zinc (Zn), silver (Ag), gold (Au), lead (Pb), platinum (Pt), iron (Fe), magnesium (Mg), manganese (Mn), cobalt (Co), nickel (Ni), and combinations thereof.

10. 10. The composite article of claim 9, wherein the catalyst is zinc chloride.

11. 9. The composite article of claim 8, wherein the catalyst comprises a non-metal selected from the group consisting of selenium (Se), tellurium (Te), organometallic compounds, and combinations thereof.

12. 12. The composite article of claim 11, wherein the catalyst is selected from the group of selenium, organoselenium, and combinations thereof.

13. The composite article of claim 7 , wherein the activation layer further comprises the catalyst.

14. The composite article of claim 7 , wherein said composite article further comprises a catalyst layer, said catalyst layer comprising said catalyst.

15. The catalyst layer comprises: (a) disposed between the source layer and the activation layer; (b) disposed on the source layer and optionally spaced apart from the activation layer; (c) disposed on the activation layer and optionally spaced apart from the source layer; or (d) a combination thereof; 15. The composite article of claim 14.

16. 3. The composite article of claim 1 or 2, wherein at least one of the source layer or the activation layer comprises a carrier material formed from cellulose, polyvinyl chloride, polyurethane, carbosil, polydimethylsiloxane, acrylic polymer, polyester, poly(lactic acid), poly(lactic-co-glycolic acid), poly(vinyl acetate), ethylene vinyl acetate, tecothane, pellethane, hydrogel, polytetrafluoroethylene, copolymers thereof, or combinations thereof.

17. 17. The composite article of claim 16, wherein the carrier material is formed from cellulose.

18. 17. The composite article of claim 16, wherein the carrier material is formed from a hydrogel selected from the group consisting of polymacron, polyacrylamide, collagen, agarose, hyaluronic acid, poly(organophosphazene), chitosan, poly(ethylene glycol), poly(vinyl alcohol), and combinations thereof.

19. The carrier material comprises: A support comprising polytetrafluoroethylene in the form of a mesh or fiber; and A material disposed in the support and formed from cellulose, polyvinyl chloride, polyurethane, carbosil, polydimethylsiloxane, acrylic polymer, polyester, poly(lactic acid), poly(lactic-co-glycolic acid), poly(vinyl acetate), ethylene vinyl acetate, tecothane, pellethane, hydrogel, another polytetrafluoroethylene, copolymers thereof, or combinations thereof.

17. The composite article of claim 16, comprising:

20. 3. The composite article of claim 1 or 2, wherein at least one of the source layer or the activation layer has a permeability in an amount of at least 0.001 g / (m·s·Pa) according to ASTM E2945-14(2021) to allow movement of at least one of the nitric oxide precursor or the solvent into or through the activation layer.

21. 21. The composite article of claim 20, further comprising a metering layer capable of regulating the movement of at least one of the nitric oxide precursor or the solvent into or through the activation layer.

22. The metering layer is (a) disposed between the source layer and the activation layer; (b) disposed on the source layer and optionally spaced apart from the activation layer; (c) disposed on the activation layer and optionally spaced apart from the source layer; or (d) a combination thereof; 22. The composite article of claim 21.

23. 23. The composite article of claim 22, wherein the metering layer is disposed on the activation layer and spaced apart from the source layer, and the metering layer only partially overlaps the activation layer such that a portion of the activation layer is free of the metering layer.

24. 22. The composite article of claim 21, wherein the metering layer has a permeability that is different from the permeability of at least one of the source layer or the activation layer.

25. 25. The composite article of claim 24, wherein the metering layer has a permeability according to ASTM E2945-14(2021) of at least 0.001 g / (m·s·Pa) but less than the permeability of at least one of the source layer or the activated layer.

26. 3. The composite article of claim 1 or 2, wherein the source layer and the activation layer are in direct contact.

27. 3. The composite article of claim 1 or 2, wherein the solvent comprises water.

28. 3. The composite article of claim 1 or 2, further comprising an additive selected from the group consisting of a transition metal, ascorbic acid, a pH control layer, and a buffer component.

29. 30. The composite article of claim 28, wherein at least one of the source layer or the activated layer comprises one or more of the additives.

30. The nitric oxide is: (a) at temperatures between 0°C and 100°C; (b) in the presence or absence of visible light; or (c) a combination of these 3. The composite article of claim 1 or 2, which is capable of being formed.

31. 1. A food packaging article capable of forming nitric oxide to preserve food products, comprising: a source layer comprising a nitric oxide precursor; an activation layer overlying the source layer and comprising a thiol-containing compound; and a contact layer overlying the activation layer; Including, The food packaging article, wherein the nitric oxide precursor and the thiol-containing compound are capable of reacting in the presence of a solvent to form nitric oxide.

32. 32. The food packaging of claim 31, wherein the contact layer has a permeability in an amount of at least 0.001 g / (m·s·Pa) according to ASTM E2945-14(2021) to allow migration of nitric oxide through the contact layer.

33. 33. The food packaging of claim 32, wherein the contact layer is substantially impermeable to ions.

34. 34. The food packaging of claim 31, further comprising a barrier layer, the sauce layer disposed on the barrier layer, and the barrier layer spaced apart from the activation layer.

35. 35. The food packaging of claim 34, wherein the barrier layer has a permeability in an amount less than 0.01 g / (m·s·Pa) according to ASTM E2945-14(2021) to prevent migration of nitric oxide through the barrier layer.

36. 34. The food packaging of any one of claims 31 to 33, wherein the food packaging is in the form of a rigid container, a wrapper, a bag, a bottle, or a tube.

37. 34. The food packaging of any one of claims 31 to 33, wherein the poultry contained in the food packaging exhibits reduced spoilage after 96 hours at 23°C compared to poultry contained in a container that does not contain at least one of the nitric oxide precursor or the thiol-containing compound.

38. 1. A vehicle headliner for a vehicle capable of forming nitric oxide to sanitize the vehicle, comprising: a source layer comprising a nitric oxide precursor; an activation layer overlying the source layer and comprising a thiol-containing compound; and a woven fabric layer overlying the activation layer; Including, A vehicle headliner, wherein the nitric oxide precursor and the thiol-containing compound are capable of reacting in the presence of a solvent to form nitric oxide.

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