WO2025019172A1

WO2025019172A1 - Antimicrobial extractant formed from copper-containing source

Info

Publication number: WO2025019172A1
Application number: PCT/US2024/037024
Authority: WO
Inventors: Johnathan David Culpepper Jr.
Original assignee: Corning Inc
Current assignee: Corning Inc
Priority date: 2023-07-20
Filing date: 2024-07-08
Publication date: 2025-01-23
Anticipated expiration: 2026-01-20

Abstract

Aspects of the disclosure relate to a method of preparing an antimicrobial extractant. In the method, a mixture including a source of Cu¹⁺ ions, a ligand configured to form a coordination complex with the Cu¹⁺ ions, and a solvent is prepared. The mixture is reacted for a time sufficient to form Cu¹⁺ coordination complexes, and the source is separated from the mixture to form the antimicrobial extractant.

Description

ANTIMICROBIAL EXTRACTANT FORMED FROM COPPER-CONTAINING SOURCE

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority to U.S. Provisional Patent Application No. 63/527,982, filed on July 20, 2023, which is hereby incorporated herein by reference in its entirety for all purposes.

BACKGROUND

[0002] The disclosure relates to an antimicrobial extractant and, more particularly, to an extractant formed from a mixture of a copper-containing source, a ligand, and a solvent.

[0003] Various objects can be exposed to undesired contaminants such as bacteria, viruses, mildew, mold, fungi, algae, and the like. Exposure to these contaminants can render the objects visually unattractive or unsuitable for a particular purpose, or even present a health hazard. Therefore, it can be desirable to mitigate the ability of the undesired contaminants to thrive once in contact with the surface of the object.

SUMMARY

[0004] A first aspect of the disclosure relates to a method of preparing an antimicrobial extractant. In the method, a mixture including a source of Cu¹⁺ ions, a ligand configured to form a coordination complex with the Cu¹⁺ ions, and a solvent is prepared. The mixture is reacted for a time sufficient to form Cu¹⁺ coordination complexes, and the source is separated from the mixture to form the antimicrobial extractant.

[0005] A second aspect of the disclosure relates to an antimicrobial extractant prepared according to the method of the first aspect. The antimicrobial extractant includes a solvent and a coordination complex of a Cu¹⁺ ion and a ligand.

[0006] A third aspect of the disclosure relates to an antimicrobial composition that includes a solvent and a coordination complex of a Cu¹⁺ ion and a ligand.

[0007] A fourth aspect of the disclosure relates to an antimicrobial material that includes a carrier and the antimicrobial extractant according to the second aspect or the antimicrobial composition according to the second aspect dispersed in the carrier [0008] Additional features and advantages will be set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art from that description or recognized by practicing the aspects as described herein, including the detailed description which follows, the claims, as well as the appended drawings.

[0009] It is to be understood that both the foregoing general description and the following detailed description are merely exemplary and are intended to provide an overview or framework to understanding the nature and character of the claims. The accompanying drawings are included to provide a further understanding and are incorporated in and constitute a part of this specification.

BRIEF DESCRIPTION OF THE DRAWINGS

[0010] The accompanying drawings incorporated in and forming a part of the specification illustrate several aspects of the present invention and, together with the description, serve to explain the principles of the invention. In the drawings:

[0011] FIG. 1 depicts a flow diagram of a method of forming an antimicrobial extractant according to one or more aspects of the present disclosure;

[0012] FIG. 2 depicts the antimicrobial material disposed within a carrier, according to an exemplary aspect,

[0013] FIG. 3 depicts a graph of the average log-kill for various samples of paint containing water-based and alcohol-based antimicrobial extractant;

[0014] FIG. 4 depicts a graph of average log-kill for various samples of paint containing antimicrobial extractants with a ligand and base;

[0015] FIG. 5 depicts a graph of average log-kill for various samples of paint containing antimicrobial extractants considering the effect of ligand concentration and use of neutralizer;

[0016] FIG. 6 depicts a graph of average log-kill for various samples of paint containing antimicrobial extractants having amino alcohol ligands; and

[0017] FIG. 7 depicts a chart of total copper contained in extractants formed from mixtures having various amounts of copper ion source. [0018] FIG. 8 depicts a graph of average log-kill for films of latex paint containing an extractant prepared from a Tris buffer solution.

DETAILED DESCRIPTION

[0019] Reference will now be made in detail to various aspects of an antimicrobial extract (also called “extractant” interchangeably herein) configured to impart antimicrobial properties to a carrier material. According to some aspects of the present disclosure, the antimicrobial extractant is prepared from a mixture of a source of Cu¹⁺ ions, a ligand, and a solvent. In some aspects, a base, in particular a Lewis base, is also added to the mixture. The mixture is allowed sufficient time to react to form coordination complexes between the Cu¹⁺ ions of the source and the ligands, and then, if desired, the source of Cu¹⁺ ions is removed from the mixture, leaving the extractant. In some aspects, the source of Cu¹⁺ ions is not removed from the mixture. The extractant can then be added to a carrier, such as a coating (e.g., paint) or plastic, to form an antimicrobial material. In some aspects, the mixture (i.e., in which the source is not removed after the reaction) can then be added to a carrier, such as a coating (e.g., paint) or plastic, to form an antimicrobial material. According to certain aspects and while other solvents are also suitable for use, the extractant exhibited the strongest antimicrobial behavior in the tests performed when a solvent comprising water was used as the solvent for extraction. In such aspects, the antimicrobial extractant does not significantly contribute to the release of volatile chemicals from the carrier during manufacture or curing. Additionally, the antimicrobial extractant produces a low color change when added to a carrier, such as paint and coatings. As used herein, when used as nouns, the terms “extract” and “extractant” are used interchangeably. These and other aspects and advantages of the antimicrobial extractant and method of forming the same will be described in relation to the aspects provide below and depicted in the figures. These aspects are presented by way of illustration and not by way of limitation.

[0020] FIG. 1 depicts a flow diagram of a method 100 of forming an antimicrobial extractant according to one or more aspects of the present disclosure. In a first step 101 of the method, a mixture of at least one source of Cu¹⁺ ions, at least one ligand, a solvent, and optionally at least one base is prepared. The source of Cu¹⁺ ions can be any of a variety of substances that are or contain monovalent Cu compounds. In one or more aspects, the source is or contains only monovalent Cu compounds, and in one or more other aspects, the source contains at least one monovalent Cu compound among other, e.g., nonvalent, divalent, trivalent, or tetravalent Cu compounds. In one or more aspects, the source is a glass, a glass ceramic, an oxide, or a salt. According to one or more aspects, a particularly suitable source of Cu¹⁺ ions is Guardiant® glass or glass-ceramic powder available from Coming Incorporated, Corning, NY. In one or more aspects, the salt is a copper(I) salt. In one or more aspects, the salt is a copper halide, such as CuBr, Cui, or CuCl. In one or more aspects, the oxide is or comprises cuprous oxide and/or cuprite, both of which have the formula CU2O.

[0021] In one or more aspects, the composition of the glass or glass-ceramic powder (such as Guardiant®) includes Cu selected from among Cu¹⁺, Cu°, and/or Cu²⁺. The combined total of the Cu species in the composition may be about 10 wt% or more. Desirably, the amount of Cu²⁺ is minimized or is reduced such that the copper-containing glass is substantially free of Cu²⁺. The Cu¹⁺ ions may be present on or in the surface and/or the bulk of the powder particles. In one or more aspects, the Cu¹⁺ ions are present in a glass network and/or a glass matrix of the composition. Where the Cu¹⁺ ions are present in the glass network, the Cu ¹⁺ ions are atomically bonded to the atoms in the glass network. Where the Cu¹⁺ ions are present in the glass matrix, the Cu¹⁺ ions maybe present in the form of Cu¹⁺ crystals that are dispersed in the glass matrix. In some aspects, the Cu¹⁺ crystals include cuprite (CU2O). In such aspects, where Cu¹⁺ crystals are present, the glass may also be referred to as a glass-ceramic, which is intended to refer to a specific type of glass with crystals that may or may not be subjected to a traditional ceramming process by which one or more crystalline phases are introduced and/or generated in the composition. Where a material is substantially free of or does not contain a crystalline phase, such as when the Cu¹⁺ ions and other species are present in a noncrystalline form, the material may be referred to as a glass. In some aspects, both Cu ¹⁺ crystals and Cu¹⁺ ions not associated with a crystal may be present in the glass compositions described herein. Cu¹⁺ ions can also be present in amorphous form as cuprous oxide.

[0022] In one or more aspects, the glass or glass-ceramic powder may be formed from a glass composition that can include, in mole percent, SiCh in the range from about 30 to about 70, AI2O3 in the range from about 0 to about 20, a copper-containing oxide in the range from about 10 to about 50, CaO in the range from about 0 to about 15, MgO in the range from about 0 to about 15, P2O5 in the range from about 0 to about 25, B2O3 in the range from about 0 to about 25, K2O in the range from about 0 to about 20, ZnO in the range from about 0 to about 5, Na2O in the range from about 0 to about 20, and/or Fe2O3 in the range from about 0 to about 5. In such aspects, the amount of the copper-containing oxide is greater than the amount of AI2O3. In some aspects, the glass composition may include a content of R2O, where R may include K, Na, Li, Rb, Cs and combinations thereof. Further, in some aspects, the glass composition includes at least one of B2O3, P2O5, and R2O.

[0023] In one or more aspects, the glass composition includes SiCh in an amount, in mole percent, in the range from about 30 to about 70, from about 30 to about 69, from about 30 to about 68, from about 30 to about 67, from about 30 to about 66, from about 30 to about 65, from about 30 to about 64, from about 30 to about 63, from about 30 to about 62, from about 30 to about 61, from about 30 to about 60, from about 40 to about 70, from about 45 to about 70, from about 46 to about 70, from about 48 to about 70, from about 50 to about 70, from about 41 to about 69, from about 42 to about 68, from about 43 to about 67 from about 44 to about 66 from about 45 to about 65, from about 46 to about 64, from about 47 to about 63, from about 48 to about 62, from about 49 to about 61 , from about 50 to about 60 and all ranges and sub-ranges therebetween.

[0024] In one or more aspects, the glass composition includes AI2O3 an amount, in mole percent, in the range from about 0 to about 20, from about 0 to about 19, from about 0 to about 18, from about 0 to about 17, from about 0 to about 16, from about 0 to about 15, from about 0 to about 14, from about 0 to about 13, from about 0 to about 12, from about 0 to about 11 from about 0 to about 10, from about 0 to about 9, from about 0 to about 8, from about 0 to about 7, from about 0 to about 6, from about 0 to about 5, from about 0 to about 4, from about 0 to about 3, from about 0 to about 2, from about 0 to about 1, from about 0.1 to about 1, from about 0.2 to about 1, from about 0.3 to about 1 from about 0.4 to about 1 from about 0.5 to about 1, from about 0 to about 0.5, from about 0 to about 0.4, from about 0 to about 0.3 from about 0 to about 0.2, from about 0 to about 0.1 and all ranges and sub-ranges therebetween. In some aspects, the glass composition is substantially free of AI2O3. As used herein, the phrase “substantially free” with respect to the components of the glass composition and/or resulting glass means that the component is not actively or intentionally added to the glass compositions during initial batching or subsequent post processing, but may be present as an impurity. For example, a glass composition, may be describe as being substantially free of a component, when the component is present in an amount of less than about 0.01 mol%.

[0025] The amount of AI2O3 may be adjusted to serve as a glass-forming oxide and/or to control the viscosity of molten glass compositions. However, excess AI2O3 has been found to promote the formation of Cu²⁺ ions, instead of the desired Cu¹⁺ ions. [0026] In one or more aspects, the glass composition includes a copper-containing oxide in an amount, in mole percent, in the range from about 10 to about 50, from about 10 to about 49, from about 10 to about 48, from about 10 to about 47, from about 10 to about 46, from about 10 to about 45, from about 10 to about 44, from about 10 to about 43, from about 10 to about 42, from about 10 to about 41 , from about 10 to about 40, from about 10 to about 39, from about 10 to about 38, from about 10 to about 37, from about 10 to about 36, from about 10 to about 35, from about 10 to about 34, from about 10 to about 33, from about 10 to about 32 , from about 10 to about 31 , from about 10 to about 30, from about 10 to about 29 , from about 10 to about 28, from about 10 to about 27, from about 10 to about 26, from about 10 to about 25, from about 10 to about 24, from about 10 to about 23, from about 10 to about 22, from about 10 to about 21, from about 10 to about 20, from about 11 to about 50, from about 12 to about 50, from about 13 to about 50, from about 14 to about 50, from about 15 to about 50, from about 16 to about 50, from about 17 to about 50, from about 18 to about 50, from about 19 to about 50, from about 20 to about 50, from about 10 to about 30, from about 11 to about 29, from about 12 to about 28, from about 13 to about 27, from about 14 to about 26, from about 15 to about 25, from about 16 to about 24, from about 17 to about 23, from about 18 to about 22, from about 19 to about 21 and all ranges and sub-ranges therebetween. In one or more specific aspects, the copper-containing oxide may be present in the glass composition in an amount of about 20 mole percent, about 25 mole percent, about 30 mole percent or about 35 mole percent. In one or more aspects, the copper-containing oxide may include CuO, CU2O, or combinations thereof, and such oxides may comprise a crystalline phase (e.g., cuprite, tenorite, or a combination thereof).

[0027] The copper-containing oxides in the glass composition form the Cu¹⁺ ions present in the resulting glass or glass-ceramic. Copper may be present in the glass composition and/or the glasses including the glass composition in various forms including Cu°, Cu¹⁺, and Cu²⁺. Copper in the Cu° or Cu¹⁺ forms provide antimicrobial activity. However, forming and maintaining these states of antimicrobial copper are difficult and often, in known glass compositions, Cu²⁺ ions are formed instead of the desired Cu° or Cu¹⁺ ions.

[0028] In one or more aspects, the amount of copper-containing oxide is greater than the amount of AI2O3 in the glass composition. Without being bound by theory, it is believed that an about equal amount of copper-containing oxides and AI2O3 in the glass composition results in the formation of tenorite (CuO) instead of cuprite (CU2O). The presence of tenorite decreases the amount of Cu¹⁺ in favor of Cu²⁺ and thus leads to reduced antimicrobial activity. Moreover, when the amount of copper-containing oxides is about equal to the amount of AI2O3, aluminum prefers to be in a four- fold coordination and the copper in the glass composition and resulting glass remains in the Cu²⁺ form so that the charge remains balanced. Where the amount of copper-containing oxide exceeds the amount of AI2O3, then it is believed that at least a portion of the copper is free to remain in the Cu¹⁺ state, instead of the Cu²⁺ state, and thus the presence of Cu¹⁺ ions increases.

[0029] The glass composition of one or more aspects includes P2O5 in an amount, in mole percent, in the range from about 0 to about 25, from about 0 to about 22, from about 0 to about 20, from about 0 to about 18, from about 0 to about 16, from about 0 to about 15, from about 0 to about 14, from about 0 to about 13, from about 0 to about 12, from about 0 to about 11 , from about 0 to about 10, from about 0 to about 9, from about 0 to about 8, from about 0 to about 7, from about 0 to about 6, from about 0 to about 5, from about 0 to about 4, from about 0 to about 3, from about 0 to about 2, from about 0 to about 1 , from about 0.1 to about 1, from about 0.2 to about 1, from about 0.3 to about 1 from about 0.4 to about 1 from about 0.5 to about 1, from about 0 to about 0.5, from about 0 to about 0.4, from about 0 to about 0.3 from about 0 to about 0.2, from about 0 to about 0.1 and all ranges and sub-ranges therebetween. In some aspects, the glass composition includes about 10 mole percent or about 5 mole percent P2O5 or, alternatively, may be substantially free of P2O5.

[0030] The glass composition of one or more aspects includes B2O3 in an amount, in mole percent, in the range from about 0 to about 25, from about 0 to about 22, from about 0 to about 20, from about 0 to about 18, from about 0 to about 16, from about 0 to about 15, from about 0 to about 14, from about 0 to about 13, from about 0 to about 12, from about 0 to about 11 , from about 0 to about 10, from about 0 to about 9, from about 0 to about 8, from about 0 to about 7, from about 0 to about 6, from about 0 to about 5, from about 0 to about 4, from about 0 to about 3, from about 0 to about 2, from about 0 to about 1, from about 0.1 to about 1, from about 0.2 to about 1, from about 0.3 to about 1 from about 0.4 to about 1 from about 0.5 to about 1, from about 0 to about 0.5, from about 0 to about 0.4, from about 0 to about 0.3 from about 0 to about 0.2, from about 0 to about 0.1 and all ranges and sub-ranges therebetween. In some aspects, the glass composition includes a non-zero amount of B2O3, which may be, for example, about 10 mole percent or about 5 mole percent. The glass composition of some aspects may be substantially free of B2O3. [0031] The glass composition of one or more aspects includes one or more alkali oxides (R2O) (e.g., Li2O, Na2O, K2O, Rb2O and/or CS2O). In some aspects, the alkali oxides modify the melting temperature and/or liquidus temperatures of such glass compositions. In one or more aspects, the amount of alkali oxides may be adjusted to provide a glass composition exhibiting a low melting temperature and/or a low liquidus temperature.

[0032] In one or more aspects, the glass composition may include one or more divalent cation oxides, such as alkaline earth oxides and/or ZnO. Such divalent cation oxides may be included to improve the melting behavior of the glass compositions.

[0033] In one or more aspects, the glass composition includes CaO in an amount, in mole percent, in the range from about 0 to about 15, from about 0 to about 14, from about 0 to about 13, from about 0 to about 12, from about 0 to about 11 , from about 0 to about 10, from about 0 to about 9, from about 0 to about 8, from about 0 to about 7, from about 0 to about 6, from about 0 to about 5, from about 0 to about 4, from about 0 to about 3, from about 0 to about 2, from about 0 to about 1 , from about 0.1 to about 1 , from about 0.2 to about 1, from about 0.3 to about 1 from about 0.4 to about 1 from about 0.5 to about 1, from about 0 to about 0.5, from about 0 to about 0.4, from about 0 to about 0.3 from about 0 to about 0.2, from about 0 to about 0.1 and all ranges and sub-ranges therebetween. In some aspects, the glass composition is substantially free of CaO.

[0034] In one or more aspects, the glass composition includes MgO in an amount, in mole percent, in the range from about 0 to about 15, from about 0 to about 14, from about 0 to about 13, from about 0 to about 12, from about 0 to about 11 , from about 0 to about 10, from about 0 to about 9, from about 0 to about 8, from about 0 to about 7, from about 0 to about 6, from about 0 to about 5, from about 0 to about 4, from about 0 to about 3, from about 0 to about 2, from about 0 to about 1 , from about 0.1 to about 1 , from about 0.2 to about 1, from about 0.3 to about 1 from about 0.4 to about 1 from about 0.5 to about 1, from about 0 to about 0.5, from about 0 to about 0.4, from about 0 to about 0.3 from about 0 to about 0.2, from about 0 to about 0.1 and all ranges and sub-ranges therebetween. In some aspects, the glass composition is substantially free of MgO.

[0035] The glass composition of one or more aspects may include ZnO in an amount, in mole percent, in the range from about 0 to about 5, from about 0 to about 4, from about 0 to about 3, from about 0 to about 2, from about 0 to about 1 , from about 0.1 to about 1 , from about 0.2 to about 1, from about 0.3 to about 1 from about 0.4 to about 1 from about 0.5 to about 1, from about 0 to about 0.5, from about 0 to about 0.4, from about 0 to about 0.3 from about 0 to about 0.2, from about 0 to about 0.1 and all ranges and sub-ranges therebetween In some aspects, the glass composition is substantially free of ZnO.

[0036] The glass composition of one or more aspects may include Fe2O3, in mole percent, in the range from about 0 to about 5, from about 0 to about 4, from about 0 to about 3, from about 0 to about 2, from about 0 to about 1, from about 0.1 to about 1, from about 0.2 to about 1, from about 0.3 to about 1 from about 0.4 to about 1 from about 0.5 to about 1 , from about 0 to about 0.5, from about 0 to about 0.4, from about 0 to about 0.3 from about 0 to about 0.2, from about 0 to about 0.1 and all ranges and sub-ranges therebetween. In some aspects, the glass composition is substantially free of Fe20s.

[0037] In one or more aspects, the glass composition may include one or more colorants. Examples of such colorants include NiO, TiCE, Fe20s, CT2O3, CO3O4 and other known colorants. In some aspects, the one or more colorants may be present in an amount in the range up to about 10 mol%. In some instances, the one or more colorants may be present in an amount in the range from about 0.01 mol% to about 10 mol%, from about 1 mol% to about 10 mol%, from about 2 mol% to about 10 mol%, from about 5 mol% to about 10 mol%, from about 0.01 mol% to about 8 mol%, or from about 0.01 mol% to about 5 mol%. In some aspects, the colorant employed in the particles is selected to match the color of the matrix and/or bulk element employed in the antimicrobial article.

[0038] In one or more aspects, the glass composition may include one or more nucleating agents. Exemplary nucleating agents include TiCE, ZrCE and other known nucleating agents in the art. The glass composition can include one or more different nucleating agents. The nucleating agent content of the glass composition may be in the range from about 0.01 mol% to about 1 mol%. In some instances, the nucleating agent content may be in the range from about 0.01 mol% to about 0.9 mol%, from about 0.01 mol% to about 0.8 mol%, from about 0.01 mol% to about 0.7 mol%, from about 0.01 mol% to about 0.6 mol%, from about 0.01 mol% to about 0.5 mol%, from about 0.05 mol% to about 1 mol%, from about 0.1 mol% to about 1 mol%, from about 0.2 mol% to about 1 mol%, from about 0.3 mol% to about 1 mol%, or from about 0.4 mol% to about 1 mol%, and all ranges and subranges therebetween.

[0039] The copper-containing glasses formed from the glass compositions as described may include a plurality of Cu¹⁺ ions. In some aspects, such Cu¹⁺ ions form part of the glass network and may be characterized as a glass modifier. Without being bound by theory, where Cu¹⁺ ions are part of the glass network, it is believed that during typical glass formation processes, the cooling step of the molten glass occurs too rapidly to allow crystallization of the copper- containing oxide (e.g., CuO and/or CU2O). Thus, the Cu¹⁺ remains in an amorphous state and becomes part of the glass network. In some cases, the total amount of Cu¹⁺ ions, whether they are in a crystalline phase or in the glass matrix, may be even higher, such as up to 40 mol%, up to 50 mol%, or up to 60 mol%.

[0040] In one or more aspects, the copper-containing glasses formed form the glass compositions disclosed herein include Cu¹⁺ ions that are dispersed in the glass matrix as Cu¹⁺ crystals. In one or more aspects, the Cu¹⁺ crystals may be present in the form of cuprite. The cuprite present in the copper-containing glass may form a phase that is distinct from the glass matrix or glass phase. The Cu¹⁺ crystals may have an average major dimension of about 9 pm or less, about 8 pm or less, about 7 pm or less, about 6 pm or less, about 5 pm or less, 4 pm or less, 3 pm or less, 2 pm or less, about 1.9 pm or less, about 1.8 pm or less, about 1.7 pm or less, about 1.6 pm or less, about 1.5 pm or less, about 1.4 pm or less, about 1.3 pm or less, about 1.2 pm or less, about 1.1 pm or less, 1 pm or less, about 0.9 pm or less, about 0.8 pm or less, about 0.7 pm or less, about 0.6 pm or less, about 0.5 pm or less, about 0.4 pm or less, about 0.3 pm or less, about 0.2 pm or less, about 0.1 pm or less, about 0.05 pm or less, and all ranges and subranges therebetween. As used herein and with respect to the phrase "average major dimension", the word "average" refers to a mean value and the word "major dimension" is the greatest dimension of the particle as measured by SEM. In some aspects, the cuprite phase may be present in the copper-containing glass in an amount of at least about 10 wt%, at least about 15 wt%, at least about 20 wt%, at least about 25 wt% and all ranges and subranges therebetween of the copper-containing glass.

[0041] In some aspects, the copper content of the copper-containing glass may include about 70 wt% Cu¹⁺ or more and about 30 wt% of Cu²⁺ or less. The Cu²⁺ ions may be present in tenorite form and/or in the glass (i.e., not as a crystalline phase).

[0042] In some aspects, the total amount of Cu by wt% in the copper-containing glass may be in the range from about 10 to about 30, from about 15 to about 25, from about 11 to about 30, from about 12 to about 30, from about 13 to about 30, from about 14 to about 30, from about 15 to about 30, from about 16 to about 30, from about 17 to about 30, from about 18 to about 30, from about 19 to about 30, from about 20 to about 30, from about 10 to about 29, from about 10 to about 28, from about 10 to about 27, from about 10 to about 26, from about 10 to about 25, from about 10 to about 24, from about 10 to about 23, from about 10 to about 22, from about 10 to about 21 , from about 10 to about 20, from about 16 to about 24, from about 17 to about 23, from about 18 to about 22, from about 19 to about 21 and all ranges and subranges therebetween.

[0043] In one or more aspects, the ratio of Cu¹⁺ ions to the total amount Cu in the copper- containing glass is about 0.5 or greater, 0.55 or greater, 0.6 or greater, 0.65 or greater, 0.7 or greater, 0.75 or greater, 0.8 or greater, 0.85 or greater, 0.9 or greater or even up to 1, and all ranges and sub-ranges therebetween. Further, in one or more aspects, the copper-containing glass may exhibit a greater amount of Cu¹⁺ and/or Cu° than Cu²⁺. The amount of Cu and the ratio of Cu°, Cu¹⁺, and Cu²⁺ ions to total Cu may be determined by inductively coupled plasma (ICP) techniques known in the art or by using x-ray photoluminescence spectroscopy (XPS) techniques known in the art.

[0044] In one or more aspects, the glass or glass-ceramic may be formed in low cost melting tanks that are typically used for melting glass compositions, such as for melting soda lime silicate. The copper-containing glass or glass-ceramic may be formed into a sheet using forming processes known in the art, such as float glass processes and down-draw processes (e.g., fusion draw and slot draw).

[0045] In one or more aspects, the powder is formed from the sheets by size-reducing the glass or glass-ceramic sheets into the powder or particulate form, such as by grinding. In one or more aspects, the glass is ground using a milling technique, such as attrition milling, jet milling, ball milling, or centrifuge milling, among others.

[0046] In one or more aspects, the at least one ligand is any of a variety of compounds configured to form coordination complexes with Cu¹⁺ ions.

[0047] In one or more aspects, the ligand is a phosphorus-based compound, such as phosphate, phosphite, phosphonate, or phosphine.

[0048] In one or more aspects, the ligand comprises a phosphate ((R¹O)3)P=O) of formula (I) below:

[0049] In one or more such aspects, each R¹ is independently one of hydrogen, a C1-C20 alkyl (or Ci-Cis alkyl) optionally fluorosubstituted, a phenyl (which can be further substituted with a C1-C6 alkyl, a halide (e.g., F, Cl, Br, I), a hydroxyl, or any combination thereof), and a benzyl; with at least one of the three R¹ groups being hydrogen. In particular, in one or more aspects, R¹ is independently one of hydrogen, a C1-C13 alkyl (or Ci-Cs alkyl, or Ci-Ce alkyl, or C2-C5 alkyl, or C2-C4 alkyl), phenyl, and benzyl. Examples of suitable phosphates include diphenyl phosphate, 2-ethylhexyl phosphate, dibenzyl phosphate, dibutyl phosphate, potassium tripolyphosphate, and sodium hexametaphosphate, or any combination thereof.

[0050] In one or more aspects, the ligand comprises a phosphite (P(R²O)s) of formula (II) below:

[0051] In one or more such aspects, each R² is independently a C1-C20 alkyl (or Ci-Cis alkyl) or a C1-C20 (or Ci-Cis alkyl) fluorosubstituted alkyl. In particular, in one or more such aspects, each R² is independently a Ci-Ce alkyl (or a C1-C5 alkyl, or C2-C5 alkyl, or C2-C4 alkyl), optionally fluorosubstituted. Examples of suitable phosphites include trimethyl phosphite, triethyl phosphite, tributyl phosphite, tridecyl phosphite, and trioctadecyl phosphite, or any combination thereof.

[0052] In one or more aspects, the ligand comprises a phosphine (R3P) of formula (III) below:

[0053] In one or more aspects, each R³ is independently a C1-C20 alkyl (or Ci-Cis alkyl) optionally fluorosubstituted, optionally substituted with a hydroxy group. In particular, in one or more aspects, each R³ is independently a Ci-Ce alkyl (or a Ci-Ce alkyl, or C2-C5 alkyl, or C2-C4 alkyl), optionally substituted with a hydroxy group. Examples of suitable phosphines include triphenylphosphine, trioctylphosphine, ethylenebis(diphenylphosphine), tributylphosphine (e.g., tri-n-butylphosphine), tri(2-furyl)phosphine, tri ethylphosphine, triethylphosphine, and isopropyldiphenylphosphine, or any combination thereof.

[0054] In one or more aspects, the ligand comprises a phosphonate. Phosphonates generally have the formula (IV) below, in which R⁴ and R⁵ independently can be selected from R¹, R², or R³, as defined elsewhere herein, including hydrogen, C1-C20 alkyl, or any of the other variables disclosed herein for R¹, R², or R³.

[0055] In some aspects, the phosphonate is diethylphosphonate, in which each R⁴ is ethyl, and R⁵ is hydrogen. For clarity, note that the literature sometimes incorrectly refers to diethylphosphonate as diethylphosphite, which is a misnomer and is incorrect. As used herein, diethylphosphonate means (R⁴O)2PR⁵, in which each R⁴ is ethyl, and R⁵ is hydrogen, and diethylphosphite is a compound of formula (II), i.e., (P(R²O)s), in which two R² groups are ethyl, and the third R² group is hydrogen.

[0056] In some aspects, some ligands comprising phosphorus at least partially hydrolyze in water, or in the present of water, to a hydrolyzed product. For example, in some aspects, phosphite may at least partially hydrolyze in water, or in the presence of water, to provide a phosphonate. For example, in some aspects, tri ethyl phosphite at least partially hydrolyzes in water, or in the presence of water, to diethylphosphonate. In some aspects, in the presence of coper (e.g., Cu¹⁺), a ligand comprising phosphorous (e.g., phosphite) is at least partially prevented from hydrolyzing in water, or in the presence of water. Without wishing to be bound by theory, it is believed the coordination to copper (e.g., Cu¹⁺) may prevent or hinder hydrolysis of the ligand comprising phosphorus due to complexation of the ligand to the copper. Accordingly, in some aspects, some ligands comprising phosphorus (e.g., phosphite) may at least partially hydrolyze in water, or in the presence of water, such that the composition may contain one or more of the original ligand, a hydrolyzed product of the ligand, or both.

[0057] In one or more aspects, the ligand is an amino alcohol. In one or more embodiments, the amino alcohol includes an alcohol functional group and an amine functional group in the form of -NH2, -NHR, or -NR2, the amine is non-sterically hindered. Examples of suitable amino alcohols include 2-amino-2 -m ethyl- 1 -propanol, N-butyldiethanolamine, D-leucinol, DL-phenylalaninol, DL-phenylglycinol, D-phenylalaninol, D-(-)-valinol, L-isoleucinol, L- leucinol, L-(-)-methioninol, L-phenylalaninol, L-tryptophanol, L-(+)-valinol, N(alpha)-Boc- D-tryptophanol, N-benzyloxycarbonyl-D-alaninol, N-benzyloxycarbonyl-L-alaninol, N-Boc- D-alaninol, N-Boc-D-alpha-phenylglycinol, N-Boc-D-cyclohexylglycinol, N-Boc-D-leucinol, N-Boc-D-phenylalaninol, N-Boc-D-valinol, N-Boc-L-alaninol, N-Boc-L-alpha- phenylglycinol, N-Boc-L-isoleucinol, N-Boc-L-leucinol, N-Boc-L-phenylalaninol, N-Boc-L- tryptophanol, N-Boc-L-valinol, N-Fmoc-D-threoninal, N-Fmoc-L-alaninol, N-Fmoc-L- phenylalaninol, N-Fmoc-L-threoninol, N-Fmoc-L-valinol, (R)-(-)-2-phenylglycinol, and (S)- (+)-2-phenylglycinol, among others.

[0058] In one or more aspects, the antimicrobial extractant or antimicrobial composition comprises at least one base, in particular a Lewis base. In one or more aspects, the at least one base is an organic base. In some aspects, the antimicrobial extractant or antimicrobial composition does not contain a base as will be demonstrated in certain examples below. In one or more aspects, the base is one of the amino alcohols listed elsewhere herein. In one or more other aspects, the base is a hydroxide compound, such as sodium hydroxide (NaOH), potassium hydroxide (KOH), ammonium hydroxide (NH4OH), or any combination thereof.

[0059] In one or more aspects, the mixture includes the source of Cu¹⁺ ions in an amount of at least 0.5 wt%, at least 1 wt%, at least 2 wt%, at least 4 wt%, or at least 5 wt%. In one or more aspects, the mixture includes the source of Cu¹⁺ ions in an amount of up to up to 20 wt%, up to 30 wt%, up to 40 wt%, up to 50 wt%, or up to 60 wt%. In one or more aspects, the mixture includes the source of Cu¹⁺ ions in an amount in a range from 0.5 wt% to 60 wt%, in particular from 1 wt% to 50 wt%, and most particularly from 2 wt% to 40 wt%.

[0060] In one or more aspects, the mixture includes the ligand in an amount of at least 0.1 wt%, at least 0.5 wt%, at least 1 wt%, at least 2 wt%, or at least 5 wt%. In one or more aspects, the mixture includes the ligand in an amount of up to 10 wt%, up to 20 wt%, up to 30 wt%, or up to 40 wt%. In one or more aspects, the mixture includes the ligand in an amount in a range from 0.1 wt% to 40 wt%, in particular from 0.5 wt% to 30 wt%, and most particularly from 1 wt% to 20 wt%. In one or more aspects, the amount of ligand is selected based on the amount of accessible Cu ions in the source. For example, when the source of Cu¹⁺ ions is glass or glass-ceramic powder, the accessible Cu (total copper ions, including Cu¹⁺ ions) are located at or near (e.g., in a degradable phase) the surface of the powder particles, and for powder having a mean particle size (d50) of about 3.8 pm and about 28 wt% Cu, the accessible Cu is about 30%. Thus, the amount of ligand may be selected to react with the accessible Cu of the source, not necessarily the total amount of Cu in the source. For example, the molar equivalent of ligand used in the mixture may be from one to five times, in particular from one to three times, the molar equivalent of accessible Cu.

[0061] As used herein, “accessible copper” (also called “accessible Cu”) of a copper source means the maximum amount of copper that is determined to be present in a given copper source according to the following iterative measurement technique. (1) When the copper-source is in solid form, such as a copper-containing glass-ceramic powder, 1 g of the copper source is combined with 2 mL of 30 wt.% citric acid (can be diluted to up to 10 mL of 30 wt.% citric acid for ease of handling) and allowed to sit for 1 hour. The mixture is then centrifuged and the supernatant analyzed for copper content using ICP. (2) When the copper source is a liquid composition, first, 0.1 g of hydroxylamine hydrochloride is added to a 10 g aliquot of composition, thoroughly mixed, and then the mixture is left to sit for 1 hr. The mixture is then centrifuged to separate solids from supernatant and the supernatant analyzed using inductively coupled plasma (ICP) for copper content (providing moles of copper per grams of composition, which can be readily converted to weight percent). To determine if the result corresponds to the maximum amount of copper that can be extracted, a different aliquot of 10 g of composition is then mixed with an increased amount (e.g., 0.125 g) of hydroxylamine hydrochloride and the same procedure repeated. If the same amount of copper is determined to be present using the increased amount of hydroxylamine hydrochloride compared to the procedure using 0.1 g hydroxylamine hydrochloride, then the amount of measured copper represents the “accessible copper” of the copper source. However, if more copper is extracted with the increased amount (e.g., 0.125 g) of hydroxylamine hydrochloride, then the amount of hydroxylamine hydrochloride is iteratively increased again and added to new 10 g aliquots of composition until the amount of copper measured is the same between successive aliquots. Such a plateaued amount of measured copper represents the “accessible copper” of the copper source. One of ordinary skill in the art would understand how to perform such a procedure, and would be cognizant that two or more repeat measurements should be performed to confirm the result.

[0062] In one or more aspects, the mixture includes less than 1 wt% of the base. In one or more aspects, the mixture includes the base in a range from 100 ppm to 1000 ppm, in particular from 100 ppm to 750 ppm, and most particularly from 100 ppm to 500 ppm.

[0063] In one or more aspects, the mixture includes the remainder of solvent, which may be up to 90 wt%, up to 92 wt%, up to 94 wt%, up to 96 wt%, up to 98 wt%, or up to 99 wt%. In one or more aspects, the mixture includes the solvent in an amount of at least 25 wt%, at least 35 wt%, at least 45 wt%, or at least 50 wt%. In one or more aspects, the mixture includes the solvent in the range of from 25 wt% to 99 wt%, in particular from 35 wt% to 98 wt%, and most particularly from 50 wt% to 90 wt%. Suitable solvents for use according to the present disclosure include water, tetrahydrofuran, methyl ethyl ketone, dimethyl sulfoxide, 1,4- dioxane, and diethyl ether. In one or more particular aspects where it is desirable to reduce the evolution of volatile organic compounds, water is used as the solvent. In some aspects, the solvent comprises water, in which the solvent is a buffer solution, such as a buffer solution comprising tris(hydroxymethyl)aminomethane (commonly referred to in the art as “Tris” buffer).

[0064] In a second step 102 of the method 100, the mixture is allowed to react for a time sufficient to form Cu¹⁺ coordination complexes. In the mixture, the source of Cu¹⁺ ions, the ligand, and optionally the base are dispersed in water, and, without wishing to be bound by theory, it is believed that the base operates with the ligand to enhance the ligand’s ability to form coordination complexes with the Cu¹⁺ ions of the source. Specifically, in the context of phosphate ligands, it is believed that the base deprotonates the phosphate to facilitate the forming of coordination complexes. While coordination complexes formed with Cu¹⁺ ions are desired for their antimicrobial activity and color staying properties, other coordination complexes with any available copper (e.g., Cu° or Cu²⁺) may also be formed. In one or more aspects, the mixture is allowed to react for a time of at least 30 min, at least 1 hour, or at least 2 hours. In one or more aspects, the mixture is allowed to react for up to 24 hours. For example, the mixture may be allowed to react to form the Cu¹⁺ coordination complexes for a time in a range of 2 hours to 24 hours, in particular 2 hours to 12 hours, and more particularly 2 hours to 6 hours. As will be discussed below, it was determined that long reaction times did not result in appreciably greater extraction of Cu¹⁺ coordination complexes than short reaction times, e.g., of around 2 hours. However, if desired, longer reaction times than 24 hours can be employed if there is no urgency in performing the extraction.

[0065] In a third step 103 of the method 100, the source is separated from the mixture, leaving the antimicrobial extractant. The source can be separated from the mixture in a variety of suitable ways. For example, in one or more aspects, the source is separated through centrifuging and/or filtering, such as through vacuum filtration, gravity filtration, or syringe filtration, amongst other possibilities. In one or more aspects, the extractant is in the form of a liquid. In one or more other aspects, the extractant is in the form of a gel. In such aspects, the gel form may be desirable as a concentrated solution for reducing the required storage space and shipping costs. The gel may be resuspended in the solvent by adding solvent to the gel at a ratio of solvent to gel in a range from 1 :0.5 to 0.5: 1, in particular in a arrange from 1 :0.7 to 07: 1. [0066] Prior to and/or after separation of the source, in some aspects, the antimicrobial extractant includes a coordination complex formed from a Cu¹⁺ ion and a ligand along with the base (if provided) and water. In one or more aspects, the antimicrobial extractant has a pH in a range from 5.5 to 8. Notwithstanding, when the ligand is an amino alcohol, the pH of the antimicrobial extractant may be as high as about 12. In one or more aspects, the antimicrobial extractant is incorporated into a carrier to form an antimicrobial material. As will be described more fully below, the carrier is a coating (such as paint) or a plastic.

[0067] FIG. 2 depicts an exemplary aspect of an antimicrobial material 200. The antimicrobial material 200 includes a carrier 202 into which the antimicrobial extractant 204 is added and which, in some aspects, may be dispersed homogeneously or inhomogeneously. As shown in FIG. 2, the antimicrobial material 200 is a coating (e.g., a direct-to-metal coating, a clear coat, a reactive coating (such as a polyurethane including a 1- or 2-part polyurethane, or such as an epoxy resin including a 1- or 2-part epoxy resin), or a paint, among others) on a substrate 210. In some aspects, the coating is a UV cured or UV curable coating. In one or more such aspects, the substrate 210 has an exterior surface 212, and the antimicrobial material 200 is applied over the exterior surface 212 in a variety of suitable ways, such as by brush, roller, and/or spray. In this regard, the carrier 202 may be a curable compound (e.g., UV curable, heat curable, drying curable, or any combination thereof), and the antimicrobial material 200 may be stored in an uncured state with the antimicrobial extractant 204 dispersed in a liquid carrier 202. Upon application, the antimicrobial material 200 may become a solid coating or film in which the antimicrobial extractant 204 is dispersed in a solid carrier 202.

[0068] Further, in one or more aspects, the antimicrobial material 200 may be free-standing, i.e., not applied to a substrate 210. For example, the antimicrobial material 200 may include a plastic carrier 202 into which the antimicrobial extractant 204 is added. The plastic carrier 202 may be molded or shaped into an article, and the antimicrobial extractant 204 is dispersed (e.g., homogeneously or inhomogeneously) throughout the article or in proximity to a surface of the article.

[0069] In one or more aspects, the carrier 202 does not possess any notable antimicrobial characteristics, and the inclusion of the antimicrobial extractant 204 imparts the antimicrobial properties to the antimicrobial material 200.

[0070] Because the antimicrobial extractant 204 is added to the carrier 202 for the purpose of imparting antimicrobial activity, the antimicrobial extractant 204 desirably does not have any other substantial effect on the carrier 202, such as imparting of color. Thus, the antimicrobial extractant 204 is added in an amount required to impart the desired level of antimicrobial activity while minimizing color change.

[0071] In one or more aspects, the color effect in an antimicrobial material is measured under the CIE L*a*b* colorimetry system. L*, a*, and b* are the Cartesian coordinates for the CIE color scale, and C* (chroma) and h° (hue) are polar coordinates that are functions of a* and b*. In one or more aspects, the antimicrobial material exhibits a color shift AE of 4 or less, 3 or less, 2 or less, or 1 or less over time, e.g., from a first time (tl) upon storage or curing to a second time (t2) 2 days, 7 days, 28 days, 56 days, 100 days, 200 days, 300 days, or 1 year after curing. As used herein, the color shift AE is equal to ((Lt2*-L_t2*)²+(at2*-ati*)²+(bt2*-bti*)²).

[0072] The L*, a*, and b* values described herein are measured at normal incidence using a standard illuminant as determined by the CIE, including an A illuminant (representing tungsten-filament lighting), B illuminant (representing daylight simulating illuminants), C illuminant (representing daylight simulating illuminants), D illuminant (representing natural daylight), and F illuminant (representing various types of fluorescent lighting). In some aspects, the L*, a*, and b* values described herein are measured under CIE D65 of F2 illuminant.

[0073] The antimicrobial extractant 204, and an antimicrobial material containing the antimicrobial extractant, is “antimicrobial” in the sense that, when included as part of an antimicrobial material 200, the material or a surface thereof will kill or inhibit the growth of microbes including bacteria, viruses and/or fungi. The term as used herein does not mean the material or the surface of the material will kill or inhibit the growth of all species microbes within such families, but that it will kill or inhibit the growth or one or more species of microbes from such families.

[0074] The antimicrobial effect is measured using “log reduction.” As used herein the term “log reduction” means -log(Ca/C_c), where C_a = the colony form unit (CFU) number of the antimicrobial surface and C_c = the colony form unit (CFU) of the control surface that is not an antimicrobial surface. As an example, a log reduction of 3 equals about 99.9% of the microbes killed and a log reduction of 5 equals 99.999% of the microbes killed.

[0075] The antimicrobial extractant, or an antimicrobial material containing the antimicrobial extractant, of one or more aspects may exhibit a log reduction of 2 or greater (e.g., 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5 and all ranges and sub-ranges therebetween) in a concentration of at least one of Staphylococcus aureus, Enterobacter aerogenes, Pseudomomas aeruginosa, methicillin-resistant Staphylococcus aureus (MRSA), and E. coli, under the U.S. Environmental Protection Agency “Test Method for Efficacy of Copper Alloy as a Sanitizer” (2009) testing conditions (“the EPA Test”). In some instances, the antimicrobial extractant, or an antimicrobial material containing the antimicrobial extractant, exhibits at least a log reduction of 4, a log reduction of 5, or even a log reduction of 6 in the concentration of at least one of Staphylococcus aureus, Enterobacter aerogenes, Pseudomomas aeruginosa bacteria, MRSA, and E. coli under the EPA Test. Unless otherwise specified, all logarithmic reduction information disclosed herein employs the EPA Test.

[0076] The antimicrobial extractant 204, or an antimicrobial material containing the antimicrobial extractant, described herein according to one or more aspects may exhibit a log reduction of 4 or greater (e.g., log reduction of 5 or greater) in a concentration of at least one of Staphylococcus aureus, Enterobacter aerogenes, Pseudomomas aeruginosa bacteria, MRSA, and E. coli, under JIS Z 2801 (2000) testing conditions. One or more aspects of the antimicrobial extractant 204, or an antimicrobial material containing the antimicrobial extractant, described herein also exhibit a log reduction of 4 or greater (e.g., log reduction of 5 or greater) in a concentration of at least one of Staphylococcus aureus, Enterobacter aerogenes, Pseudomomas aeruginosa, MRSA, and E. coli, under the Modified JIS Z 2801 Test for Bacterial. As used herein, Modified JIS Z 2801 Test for Bacteria includes evaluating the bacteria under the standard JIS Z 2801 (2000) test with modified conditions comprising heating the glass or article to a temperature of about 23 °C to about 37 °C at a humidity of about 38% to about 42% for about 6 hours.

[0077] In one or more aspects described herein, the antimicrobial extractant 204, or an antimicrobial material containing the antimicrobial extractant, exhibits a log reduction of 2 or greater, a log reduction of 3 or greater, a log reduction of 4 or greater, or a log reduction of 5 or greater in Murine Norovirus under a Modified JIS Z 2801 for Viruses test. The Modified JIS Z 2801 (2000) Test for Viruses includes the following procedure. For each material (e.g., the antimicrobial extractant, an antimicrobial material containing the antimicrobial extract,, control materials, and any comparative compositions or materials) to be tested, three samples of the material (contained in individual sterile petri dishes) are each inoculated with a 20 pL aliquot of a test virus (where antimicrobial activity is measured) or a test medium including an organic soil load of 5% fetal bovine serum with or without the test virus (where cytotoxicity is measured). The inoculum is then covered with a film and the film is pressed down so the test virus and/or or test medium spreads over the film, but does not spread past the edge of the film. The exposure time begins when each sample was inoculated. The inoculated samples are transferred to a control chamber set to room temperature (about 20 °C) in a relative humidity of 42% for 2 hours. Exposure time with respect to control samples are discussed below. Following the 2-hour exposure time, the film is lifted off using sterile forceps and a 2.00 mL aliquot of the text virus and/or test medium is pipetted individually onto each sample of material and the underside of the film (or the side of the film exposed to the sample) used to cover each sample. The surface of each sample is individually scraped with a sterile plastic cell scraper to collect the test virus or test medium. The test virus and/or test medium is collected (at 10'² dilution), mixed using a vortex type mixer and serial 10-fold dilutions are prepared. The dilutions are then assayed for antimicrobial activity and/or cytotoxicity.

[0078] To prepare a control sample for testing antimicrobial activity (which are also referred to as “zero-time virus controls”) for the Modified JIS Z 2801 Test for Viruses, three control samples (contained in individual sterile petri dishes) are each inoculated with a 20 pL aliquot of the test virus. Immediately following inoculation, a 2.00 mL aliquot of test virus is pipetted onto each control sample. The surface of each sample was individually scrapped with a sterile plastic cell scraper to collect test virus. The test virus is collected (at 10'² dilution), mixed using a vortex type mixer, and serial 10-fold dilutions were prepared. The dilutions are assayed for antimicrobial activity.

[0079] To prepare controls samples for cytotoxicity (which are also referred to as “2 hour control virus") for the Modified JIS Z 2801 Test for Viruses, one control sample (contained in an individual sterile petri dish) is inoculated with a 20 pL aliquot of a test medium containing an organic soil load (5% fetal bovine serum), without the test virus. The inoculum is covered with a film and the film is pressed so the test medium spreads over the film but does not spread past the edge of the film. The exposure time begins when each control sample is inoculated. The control sample is transferred to a controlled chamber set to room temperature (20 °C) in a relative humidity of 42% for a duration of 2 hours exposure time. Following this exposure time, the film is lifted off using sterile forceps and a 2.00 mL aliquot of the test medium is pipetted individually onto each control sample and the underside of the film (the side exposed to the sample). The surface of each sample is individually scrapped with a sterile plastic cell scraper to collect the test medium. The test medium is collected (at 10'² dilution), mixed using a vortex type mixer, and serial 10-fold dilutions were prepared. The dilutions were assayed for cytotoxicity. [0080] The antimicrobial extractant 204, or an antimicrobial material containing the antimicrobial extractant, of one or more aspects may exhibit the log reduction described herein for long periods of time. In other words, the antimicrobial extractant 204, or an antimicrobial material containing the antimicrobial extractant, may exhibit extended or prolonged antimicrobial efficacy. For example, in some aspects, the antimicrobial extractant 204, or an antimicrobial material containing the antimicrobial extractant, may exhibit the log reductions described herein under the EPA Test, the JIS Z 2801 (2000) testing conditions, the Modified JIS Z 2801 Test for Bacteria and/or the Modified JIS Z 2801 Test for Viruses for up to 1 month, up to 3 months, up to 6 months or up to 12 months after the antimicrobial extractant is formed or after the antimicrobial extractant is combined with a carrier (e.g., polymers, monomers, binders, solvents and the like) to form an antimicrobial material. These time periods may start at or after the antimicrobial extractant 204 is formed or combined with a carrier 202.

[0081] In some aspects, the antimicrobial extractant, or an antimicrobial material containing the antimicrobial extractant, exhibits longevity in antimicrobial efficacy. For example, in some aspects, when the antimicrobial extractant, or an antimicrobial material containing the antimicrobial extractant, is formed into a coating (for example, a dry film) or an article within one day of preparing the antimicrobial extractant or antimicrobial material containing same, and the coating or article is stored at ambient conditions for 7 days or at least 7 days (for example, 10 days or at least 10 days, 15 days or at least 15 days, 20 days or at least 20 days, 25 days or at least 25 days, 30 days or at least 30 days, 40 days or at least 40 days, 50 days or at least 50 days, 60 days or at least 60 days, 75 days or at least 75 days, 90 days or at least 90 days, 100 days or at least 100 days, 120 days or at least 120 days, 150 days or at least 150 days, 180 days or at least 180 days, 365 days or at least 365 days, 2 years or at least 2 years, 3 years or at least 3 years, 4 years or at least 4 years, 5 years or at least 5 years, or 6 years or at least 6 years; alternatively, or additionally, less than 6 years, less than 5 years, less than 4 years, less than 3 years, less than 2 years, less than 365 days, less than 180 days, less than 150 days, less than 120 days, less than 100 days, less than 90 days, less than 75 days, less than 60 days, less than 50 days, less than 40 days, less than 30 days, less than 25 days, less than 20 days, less than 15 days, or less than 10 days) to form a stored coating or stored article, the stored coating or article exhibits greater than 1 logarithmic reduction (for example, greater than 2.5 logarithmic reduction, greater than 3 logarithmic reduction, greater than 3.5 logarithmic reduction, greater than 4 logarithmic reduction, greater than 4.5 logarithmic reduction, or greater than 5 logarithmic reduction; alternatively, or additionally, less than 6 logarithmic reduction, less than 5.5 logarithmic reduction, less than 5 logarithmic reduction, less than 4.5 logarithmic reduction, less than 4 logarithmic reduction, less than 3.5 logarithmic reduction, less than 3 logarithmic reduction, less than 2.5 logarithmic reduction, less than 2 logarithmic reduction, or less than

1.5 logarithmic reduction) in the concentration of microbe selected from the group consisting of Staphylococcus aureus, Enterobacter aerogenes, Pseudomonas aeruginosa, Methicillin Resistant Staphylococcus aureus, E. coli, SARS-Cov-2, and mixtures thereof. Generally, and without wishing to be bound by theory, it is believed that the above feature shows the longevity of antimicrobial efficacy of a coating (for example, dry film) or article including the biocidal composition over time. Antimicrobial efficacy can be measured as described elsewhere herein, such as by using the EP A Test.

[0082] As used herein, the term “for X days” or “for X years” in which X is a number, means that the longevity of a specified property lasts minimally for X days (or for X years). The longevity of the specified property may last for a longer period of time, and after such longer period of time the specified property (e.g., log reduction or color value) may begin to decrease; however, “for X days” (or “for X years”) is met if the specified property was present at X days (or X years). In this regard, the terms “for X days” and the term “for at least X days” are meant to be synonymous terms.

[0083] In some aspects, when the antimicrobial extractant, or an antimicrobial material containing the antimicrobial extractant, is stored as a liquid (for example, aqueous or organic solvent based) composition or suspension at ambient conditions for a period of 7 days or at least 7 days (for example, 10 days or at least 10 days, 15 days or at least 15 days, 20 days or at least 20 days, 25 days or at least 25 days, 30 days or at least 30 days, 40 days or at least 40 days, 50 days or at least 50 days, 60 days or at least 60 days, 75 days or at least 75 days, 90 days or at least 90 days, 100 days or at least 100 days, 120 days or at least 120 days, 150 days or at least 150 days, 180 days or at least 180 days, 365 days or at least 365 days (1 year), 2 years or at least 2 years, 3 years or at least 3 years, 4 years or at least 4 years, 5 years or at least 5 years, or 6 years or at least 6 years; alternatively, or additionally, less than 6 years, less than 5 years, less than 4 years, less than 3 years, less than 2 years, less than 365 days, less than 180 days, less than 150 days, less than 120 days, less than 100 days, less than 90 days, less than 75 days, less than 60 days, less than 50 days, less than 40 days, less than 30 days, less than 25 days, less than 20 days, less than 15 days, or less than 10 days) to form a stored liquid composition or suspension, a coating or article prepared from the stored liquid composition or suspension within one day exhibits greater than 1 logarithmic reduction (for example, greater than 2.5 logarithmic reduction, greater than 3 logarithmic reduction, greater than 3.5 logarithmic reduction, greater than 4 logarithmic reduction, greater than 4.5 logarithmic reduction, or greater than 5 logarithmic reduction; alternatively, or additionally, less than 6 logarithmic reduction, less than 5.5 logarithmic reduction, less than 5 logarithmic reduction, less than 4.5 logarithmic reduction, less than 4 logarithmic reduction, less than 3.5 logarithmic reduction, less than 3 logarithmic reduction, less than 2.5 logarithmic reduction, less than 2 logarithmic reduction, or less than 1.5 logarithmic reduction) in the concentration of microbe selected from the group consisting of Staphylococcus aureus, Enterobacter aerogenes, Pseudomonas aeruginosa, Methicillin Resistant Staphylococcus aereus, E. coli, SARS-Cov-2, and mixtures thereof. Generally, and without wishing to be bound by theory, it is believed that the above feature shows the antimicrobial efficacy of a coating (for example, dry film) or article after the antimicrobial extractant, or an antimicrobial material containing the antimicrobial extractant, has been stored in liquid (for example, aqueous or organic solvent based) form (for example, a can of paint stored on a shelf, a masterbatch awaiting extrusion, and so forth) for a certain time period. Antimicrobial efficacy may be measured as described elsewhere herein, such as by using the EP A Test.

[0084] As discussed above, the antimicrobial extractant 204 is dispersed in a carrier 202. In one or more aspects, the carrier 202 includes polymers, monomers, binders, solvents, or a combination thereof. In a specific aspect, the carrier 202 is a paint formulation that is used for application to surfaces (which may include interior or exterior surfaces).

[0085] The polymer used in the aspects described herein can include a thermoplastic polymer, a polyolefin, a cured polymer, an ultraviolet- or UV-cured or curable polymer, a polymer emulsion, a solvent-based polymer, and combinations thereof. Examples of suitable polymers include, without limitation: thermoplastics including polystyrene (PS), high impact PS, polycarbonate (PC), nylon (sometimes referred to as polyamide (PA)), poly(acrylonitrile- butadiene-styrene) (ABS), PC-ABS blends, polybutyleneterephthlate (PBT) and PBT copolymers, polyethyleneterephthalate (PET) and PET co-polymers, polyolefins (PO) including polyethylenes (PE), polypropylenes (PP), cyclicpolyolefins (cyclic-PO), modified polyphenylene oxide (mPPO), polyvinylchloride (PVC), acrylic polymers including polymethyl methacrylate (PMMA), thermoplastic elastomers (TPE), thermoplastic urethanes (TPU), poly etherimide (PEI) and blends of these polymers with each other. Suitable injection moldable thermosetting polymers include epoxy, acrylic, styrenic, phenolic, melamine, urethanes, polyesters and silicone resins. In other aspects, the polymers may be dissolved in a solvent or dispersed as a separate phase in a solvent and form a polymer emulsion, such as a latex (which is a water emulsion of a synthetic or natural rubber, or plastic obtained by polymerization and used especially in coatings (as paint) and adhesives. Polymers may include fluorinated silanes or other low friction or anti-frictive materials. The polymers can contain impact modifiers, flame retardants, UV inhibitors, antistatic agents, mold release agents, fillers including glass, metal or carbon fibers or particles (including spheres), talc, clay or mica and colorants. Specific examples of monomers include catalyst curable monomers, thermally- curable monomers, radiation-curable monomers and combinations thereof.

[0086] In one or more aspects, the carrier 202 is a paint or coating. In one or more such aspects, the antimicrobial extractant 204 is dispersed in the paint carrier 202 at a dosage sufficient to provide, on a weight basis, Cu in an amount of at least 100 ppm, at least 500 ppm, at least 1000 ppm, at least 5000 ppm, or at least 10,000 ppm of the antimicrobial material 200. In one or more aspects, the antimicrobial extractant 204 is dispersed in the paint carrier 202 at a dosage sufficient to provide, on a weight basis, Cu in an amount up to 50,000 ppm, up to 75,000 ppm, or up to 100,000 ppm of the antimicrobial material 200. In one or more aspects, the antimicrobial extractant 204 is dispersed in the paint carrier 202 at a dosage sufficient to provide, on a weight basis, Cu in an amount in a range from 100 ppm to 100,000 ppm, in particular in a range from 500 ppm to 75,000 ppm, and more particularly in a range from 1000 ppm to 50,000 ppm.

[0087] In one or more aspects, the carrier 202 is a plastic. In one or more such aspects, the antimicrobial extractant 204 is dispersed in the plastic carrier 202 at a dosage sufficient to provide, on a weight basis, Cu in an amount of at least 100 ppm, at least 500 ppm, at least 1000 ppm, at least 5000 ppm, or at least 10,000 ppm of the antimicrobial material 200. In one or more aspects, the antimicrobial extractant 204 is dispersed in the plastic carrier 202 at a dosage sufficient to provide, on a weight basis, Cu in an amount up to 50,000 ppm, up to 75,000 ppm, or up to 100,000 ppm of the antimicrobial material 200. In one or more aspects, the antimicrobial extractant 204 is dispersed in the paint carrier 202 at a dosage sufficient to provide, on a weight basis, Cu in an amount in a range from 100 ppm to 100,000 ppm, in particular in a range from 500 ppm to 75,000 ppm, and more particularly in a range from 1000 ppm to 50,000 ppm of the antimicrobial material 200. [0088] Various aspects are contemplated herein, several of which are set forth in the paragraphs below. It is explicitly contemplated that any aspect or portion thereof may be combined to form a combination.

[0089] Aspect 1 relates to a method of preparing an antimicrobial extractant. In the method, a mixture including a source of Cu¹⁺ ions, a ligand configured to form a coordination complex with the Cu¹⁺ ions, and a solvent is prepared. The mixture is reacted for a time sufficient to form Cu¹⁺ coordination complexes, and the source is separated from the mixture to form the antimicrobial extractant.

[0090] Aspect 2 relates to the method of Aspect 1, or any preceding aspect, in which the source of Cu¹⁺ ions is a glass, a glass-ceramic, an oxide, or a salt of Cu¹⁺.

[0091] Aspect 3 relates to the method of Aspect 2, or any preceding aspect, in which the glass or glass-ceramic includes 30 mol% to 70 mol% of SiCh; 0 mol% to 20 mol% of AI2O3;

10 mol% to 50 mol% of one or more copper-containing oxides; 0 mol% to 15 mol% of CaO; 0 mol% to 15 mol% of MgO; 0 mol% to 25 mol% P2O5; 0 mol% to 25 mol% of B2O3; 0 mol% to 20 mol% of K2O; 0 mol% to 20 mol% of Na2O; 0 mol% to 5 mol% of ZnO; and 0 mol% to 5 mol% of Fe2O3. Further, an amount of the one or more copper-containing oxides is greater than the amount of AI2O3.

[0092] Aspect 4 relates to the method of Aspect 3, or any preceding aspect, in which the glass or glass-ceramic includes at least one of B2O3, P2O5, and R2O, wherein R is any one or more of K, Na, Li, Rb, and Cs.

[0093] Aspect 5 relates to the method of Aspect 3, or any preceding aspect, in which the one or more copper-containing oxides include copper ions and in which at least 50% of the copper ions are Cu¹⁺.

[0094] Aspect 6 relates to the method of Aspect 3 or Aspect 4, or any preceding aspect, in which the one or more copper-containing oxides includes at least 50 mol% cuprite and/or cuprous oxide.

[0095] Aspect 7 relates to the method of Aspect 2, or any preceding aspect, in which the salt includes a copper halide.

[0096] Aspect 8 relates to the method of Aspect 2, or any preceding aspect, in which the oxide comprises cuprite and/or cuprous oxide.

[0097] Aspect 9 relates to the method of any one of Aspects 1-8 in which the ligand includes at least one of a phosphate, a phosphite, a phosphine, a phosphonate, or an amino alcohol. [0098] Aspect 10 relates to the method of Aspect 9, or any preceding aspect, in which the phosphate is in a form of ((R¹O)3)P=O in which each R¹ group is independently one of hydrogen, a C1-C20 alkyl, a phenyl, or a benzyl, and at least one of the R¹ groups is hydrogen. [0099] Aspect 11 relates to the method of Aspect 9 or Aspect 10, or any preceding aspect, in which the phosphate is selected from a group consisting of diphenyl phosphate, 2-ethylhexyl phosphate, dibenzyl phosphate, dibutyl phosphate, potassium tripolyphosphate, sodium hexametaphosphate, or any combination thereof.

[00100] Aspect 12 relates to the method of Aspect 9, or any preceding aspect, in which the phosphite is in a form of P(R²O)s in which each R² group is independently a C1-C20 alkyl or a C1-C20 fluoro-substituted alkyl.

[00101] Aspect 13 relates to the method of Aspect 9 or Aspect 12, or any preceding aspect, in which the phosphite is selected from a group consisting of triethyl phosphite, trimethyl phosphite, tributyl phosphite, trioctadecyl phosphite, tridecyl phosphite, or any combination thereof.

[00102] Aspect 14a relates to the method of Aspect 9, or any preceding aspect, in which the phosphine is in a form of (R³)sP in which each R³ group is independently a C1-C20 alkyl or a C1-C20 alkyl substituted with a hydroxy group.

[00103] Aspect 14b relates to the method of Aspect 9, or any preceding aspect, in which the phosphine is selected from a group consisting of triphenylphosphine, trioctylphosphine, ethylenebis(diphenylphosphine), tributylphosphine (e.g., tri-n-butylphosphine), tri(2- furyl)phosphine, triethylphosphine, triethylphosphine, and isopropyldiphenylphosphine, or any combination thereof.

[00104] Aspect 15 relates to the method of Aspect 9, or any preceding aspect, in which the amino alcohol is selected from a group consisting of 22-amino-2-methyl-l-propanol, N- butyldiethanolamine, D-leucinol, DL-phenylalaninol, DL-phenylglycinol, D-phenylalaninol, D-(-)-valinol, L-isoleucinol, L-leucinol, L-(-)-methioninol, L-phenylalaninol, L-tryptophanol, L-(+)-valinol, N(alpha)-Boc-D-tryptophanol, N-benzyloxycarbonyl-D-alaninol, N- benzyloxycarbonyl-L-alaninol, N-Boc-D-alaninol, N-Boc-D-alpha-phenylglycinol, N-Boc-D- cyclohexylglycinol, N-Boc-D-leucinol, N-Boc-D-phenylalaninol, N-Boc-D-valinol, N-Boc- L-alaninol, N-Boc-L-alpha-phenylglycinol, N-Boc-L-isoleucinol, N-Boc-L-leucinol, N-Boc- L-phenylalaninol, N-Boc-L-tryptophanol, N-Boc-L-valinol, N-Fmoc-D-threoninal, .N-Fmoc- L-alaninol, N-Fmoc-L-phenylalaninol, N-Fmoc-L-threoninol, N-Fmoc-L-valinol, (R)-(-)-2- phenylglycinol, and (S)-(+)-2-phenylglycinol, and combinations thereof. [00105] Aspect 16 relates to the method of any one of Aspects 1-15 in which the mixture further includes a base.

[00106] Aspect 17 relates to the method of Aspect 16, or any preceding aspect, in which the base is an inorganic base.

[00107] Aspect 18 relates to the method of Aspect 17, or any preceding aspect, in which the inorganic base is sodium hydroxide or ammonium hydroxide.

[00108] Aspect 19 relates to the method of Aspect 17, or any preceding aspect, in which the base is an organic base.

[00109] Aspect 20 relates to the method of Aspect 19, or any preceding aspect, in which the organic base is an amino alcohol.

[00110] Aspect 21 relates to the method of any one of Aspect 1-20 in which the solvent comprises water (e.g., a buffer solution), tetrahydrofuran, methyl ethyl ketone, dimethyl sulfoxide, 1,4-di oxane, diethyl ether, and combinations thereof.

[00111] Aspect 22 relates to the method of any one of Aspects 1-21 in which the mixture comprises from 0.5 wt% to 60 wt% of the source of Cu¹⁺ ions.

[00112] Aspect 23 relates to the method of any one of Aspects 1-22 in which the time of reacting the mixture is at least 2 hours and no more than 24 hours.

[00113] Aspect 24 relates to the method of any one of Aspects 1-23 in which separating includes filtering, centrifuging, or both filtering and centrifuging.

[00114] Aspect 25 relates to an antimicrobial extractant prepared according to the method of any one of Aspects 1-24. The antimicrobial extractant includes a solvent and a coordination complex of a Cu¹⁺ ion and a ligand.

[00115] Aspect 26 relates to the antimicrobial extractant of Aspect 25, or any preceding aspect, including a pH in a range from 5.5 to 12.

[00116] Aspect 27 relates to an antimicrobial composition that includes a solvent and a coordination complex of a Cu¹⁺ ion and a ligand.

[00117] Aspect 28 relates to the antimicrobial composition of Aspect 27, or any preceding aspect, in which the ligand comprises at least one of a phosphate, a phosphite, a phosphine, a phosphonate, or an amino alcohol.

[00118] Aspect 29 relates to the antimicrobial composition of Aspect 28, or any preceding aspect, in which the phosphate is in a form of ((R¹O)3)P=O in which each R¹ group is independently one of hydrogen, a C1-C20 alkyl, a phenyl, or a benzyl, and in which at least one of the R¹ groups is hydrogen. [00119] Aspect 30 relates to the antimicrobial composition of Aspect 28 or Aspect 29, or any preceding aspect, in which the phosphate is selected from a group consisting of diphenyl phosphate, 2-ethylhexyl phosphate, dibenzyl phosphate, dibutyl phosphate, potassium tripolyphosphate, sodium hexametaphosphate, and combinations thereof.

[00120] Aspect 31 relates to the antimicrobial composition of Aspect 28, or any preceding aspect, in which the phosphite is in a form of P(R²O)s in which each R² group is independently a C1-C20 alkyl or a C1-C20 fluoro-substituted alkyl.

[00121] Aspect 32 relates to the antimicrobial composition of Aspect 28 or Aspect 31, or any preceding aspect, in which the phosphite is selected from a group consisting of triethyl phosphite, trimethyl phosphite, tributyl phosphite, trioctadecyl phosphite, tridecyl phosphite, and combinations thereof.

[00122] Aspect 33 relates to the antimicrobial composition of Aspect 28, or any preceding aspect, in which the phosphine is in a form of (R³)sP in which each R³ group is independently a C1-C20 alkyl or a C1-C20 alkyl substituted with a hydroxy group.

[00123] Aspect 34 relates to the antimicrobial composition of Aspect 28, or any preceding aspect, in which the amino alcohol is selected from a group consisting of 22-amino-2-methyl- 1 -propanol, N-butyldi ethanolamine, D-leucinol, DL-phenylalaninol, DL-phenylglycinol, D- phenylalaninol, D-(-)-valinol, L-isoleucinol, L-leucinol, L-(-)-methioninol, L-phenylalaninol, L-tryptophanol, L-(+)-valinol, N(alpha)-Boc-D-tryptophanol, N-benzyloxycarbonyl-D- alaninol, N-benzyloxycarbonyl-L-alaninol, N-Boc-D-alaninol, N-Boc-D-alpha- phenylglycinol, N-Boc-D-cyclohexylglycinol, N-Boc-D-leucinol, N-Boc-D-phenylalaninol, N-Boc-D-valinol, N-Boc-L-alaninol, N-Boc-L-alpha-phenylglycinol, N-Boc-L-isoleucinol, N-Boc-L-leucinol, N-Boc-L-phenylalaninol, N-Boc-L-tryptophanol, N-Boc-L-valinol, N- Fmoc-D-threoninal, .N-Fmoc-L-alaninol, N-Fmoc-L-phenylalaninol, N-Fmoc-L-threoninol, N-Fmoc-L-valinol, (R)-(-)-2-phenylglycinol, and (S)-(+)-2-phenylglycinol, and combinations thereof.

[00124] Aspect 35 relates to the antimicrobial composition of any one of Aspects 27-34, or any preceding aspect, further including a base.

[00125] Aspect 36 relates to the antimicrobial composition of Aspect 35, or any preceding aspect, in which the base is an inorganic base.

[00126] Aspect 37 relates to the antimicrobial composition of Aspect 36, or any preceding aspect, in which the inorganic base is sodium hydroxide or ammonium hydroxide. [00127] Aspect 38 relates to the antimicrobial composition of Aspect 35, or any preceding aspect, in which the base is an organic base.

[00128] Aspect 39 relates to the antimicrobial composition of Aspect 38, or any preceding aspect, in which the organic base is an amino alcohol.

[00129] Aspect 40 relates to an antimicrobial material that includes a carrier and the antimicrobial extractant according to Aspect 25 or Aspect 26, or any preceding aspect, or the antimicrobial composition according to any one of Aspects 27-39, or any preceding aspect, dispersed in the carrier.

[00130] Aspect 41 relates to the antimicrobial material of Aspect 40, or any preceding aspect, in which the antimicrobial material exhibits a log reduction of 3 or greater in a concentration of Staphylococcus aureus under the EPA Test Method for Efficacy of Copper Alloy as a Sanitizer testing conditions.

[00131] Aspect 42 relates to the antimicrobial material of Aspect 40 or Aspect 41, or any preceding aspect, in which the carrier is a coating.

[00132] Aspect 43 relates to the antimicrobial material of Aspect 42, or any preceding aspect, wherein the coating is a paint.

[00133] Aspect 44 relates to the antimicrobial material of Aspect 43, or any preceding aspect, including at least 100 ppm of copper.

[00134] Aspect 45 relates to the antimicrobial material of any one of Aspects 40-44, or any preceding aspect, in which the antimicrobial material exhibits a color change AE* according to the CIE L*a*b* color system from a first time to a second time of 4 or less, in which the first time (tl) is upon formation of the antimicrobial material through curing after application to a surface and the second time (t2) is after at least 2 days, the antimicrobial material being stored at room temperature in ambient indoor conditions, and in which AE equals ((L_t2*-

[00135] Aspect 46 relates to the antimicrobial material of Aspect 45, or any preceding aspect, in which at the second time, the color change AE* is 2 or less.

[00136] Aspect 47 relates to the antimicrobial material of Aspect 42, or any preceding aspect, in which the coating is a direct-to-metal coating, a clear coat, or a reactive coating. [00137] Aspect 48 relates to the antimicrobial material of Aspect 40 or Aspect 41, or any preceding aspect, in which the carrier is a plastic.

[00138] Aspect 49 relates to the antimicrobial material of Aspect 48, or any preceding aspect, in which the plastic is a thermoplastic polymer selected from a group consisting of a polystyrene, a polycarbonate, a polyamide, a poly(acrylonitrile-butadiene-styrene), a polybutylene terephthalate, a polyethylene terephthalate, a polyolefin, a polymethyl methacrylate, a thermoplastic urethane, a polyetherimide, and combinations thereof. [00139] Aspect 50 relates to the antimicrobial material of Aspect 48, or any preceding aspect, in which the plastic is a thermosetting polymer selected from a group consisting of an epoxy resin, an acrylic resin, a styrenic resin, a phenolic resin, a melamine resin, a urethane resin, a polyester resin, and combinations thereof.

[00140] Aspect 51 relates to a combination of any two or more preceding aspects, or any portion(s) thereof, to form an aspect.

EXAMPLES

[00141] Table 1 describes various mixtures (Samples 1-20) from which antimicrobial extractant was prepared. The samples were analyzed using ³¹P NMR spectroscopy. These samples are discussed in relation to Examples 1-5, below.

Table 1. Compositions of Mixtures for ³¹P NMR Spectroscopy Investigations

[00142] In Table 1, for each of the samples that included glass powder, the glass powder used was Guardiant®. In Sample 9, the source of Cu¹⁺ ions was cuprite (CU2O), and in Samples 15 and 16, the source of Cu¹⁺ ions was CuBr. In Samples 1, 5, 7-9, and 11-16, the ligand was diphenyl phosphate (“DPP”). In Samples 17-20, the ligand was 2-ethylhexyl phosphate (“2- EHP”) mixture of esters. In Samples 5-7, 12, and 15, an inorganic base was used. For Samples 5-7 and 15, the inorganic base was sodium hydroxide (NaOH), and for Sample 12, the inorganic base was ammonium hydroxide. In Sample 3, the acid used was ascorbic acid, and in Sample 4, the acid used was citric acid. In Example 15, 2-IPA refers to 2-propanol. In Samples 1 and 17, CeDe refers to deuterated benzene. In Samples 8-11, 16, 18, and 20, the organic base was 2-amino-2-methyl-l -propanol (“AMP”). In Sample 10, the organic base, being an amino alcohol, operated as a ligand for the Cu ions of the Guardiant® powder. In Sample 13, the organic neutralizer was N-butyldiethanolamine, and in Sample 14, the organic neutralizer was 2-dimethylamino-2-methyl-l -propanol (“DMAMP-80”).

[00143] EXAMPLE 1

[00144] In conducting the ³¹P NMR spectroscopy, Sample 1 (DPP in CeDe) was used as a control to determine the chemical shift for DPP. Samples 3 and 4 were also used to determine the effect of the ascorbic acid and citric acid dissolved in water for promoting the release of the Cu in Guardiant®. In particular, Guardiant® has a dissolvable phase in water, and the ascorbic acid and citric acid were selected to facilitate dissolution of the dissolvable phase, which may include such elements as boron, aluminum, phosphorus, and potassium. However, no chemical shift peaks were detected using ³¹P NMR spectroscopy, indicating that minimal or no phases were dissolved (as might be evidenced by detected phosphorus). Sample 12, which contained DPP and an inorganic base (NH4OH) in water, exhibited peak shift and peak broadening, demonstrating that the DPP reacted with the inorganic base QSIH fPl^PCU']). Sample 5, which contained DPP and another inorganic base (NaOH) in water, also exhibited peak shift, demonstrating that the DPP reacted with the second inorganic base (Na⁺[Ph2PO4-]). Sample 6, which contained Guardiant® powder and the second inorganic base in water, exhibited two minor, broad peak shifts, possibly indicating that some of the dissolvable phase of the Guardiant® powder entered solution. Sample 7, containing Guardiant® powder, DPP, and the second inorganic base in water, exhibited a large peak, shifted as compared to the control Sample 1. Sample 7 also included the two minor, broad peak shifts of Sample 6, again possibly demonstrating the dissolvable phase of the Guardiant® powder in solution along with the coordination complex. This series of ³¹P NMR spectroscopy analyses demonstrates that DPP in water formed coordination complexes with the Cu ions in the glass powder.

[00145] EXAMPLE 2

[00146] Further ³¹P NMR spectroscopy investigations were undertaken. Sample 8 (DPP and AMP in water) exhibited a peak shift, indicating that the AMP reacted with the DPP. In Sample 9, CU2O, DPP, and AMP were reacted in water, and the peak was slightly shifted and broadened as compared to Sample 8, indicating some possible formation of some coordination complexes with the Cu ions of CU2O. Sample 2 (Guardiant® powder and water) exhibited no peak shifts, indicating that the dissolvable phase of the Guardiant® powder did not enter solution in the reaction time. Sample 10, which further included AMP, also exhibited substantially no peak shifts; however, as demonstrated below, higher concentrations of AMP in the mixture did result in the extraction of Cu ions and resultant antimicrobial activity. Sample 11, which further included DPP, exhibited a peak shift and broadening relative to the control (Sample 1) and relative to the DPP and AMP sample (Sample 8), indicating the formation of coordination complexes between the Guardiant® powder and the DPP. In Samples 15 and 16, the source of Cu¹⁺ ions was changed from Guardiant® powder to CuBr. In Sample 15, the solvent included 2-IPA in addition to water, and an inorganic base (NaOH) was used. In Sample 16, the solvent was just water, and an organic base (AMP) was used. In comparison, Sample 15 had a minimal peak shift and broadening from the DPP control (Sample 1), whereas Sample 16 exhibited a larger peak shift and significant broadening, demonstrating the formation of coordination complexes between the DPP and Cu¹⁺ ions of the CuBr in the presence of AMP and in water as a solvent.

[00147] EXAMPLE S

[00148] Additional ³¹P NMR spectroscopy investigations were conducted to determine the effect of the organic base. Samples 11 and 13 included AMP and N-butyldi ethanolamine, respectively. These samples exhibited significant broadening, demonstrating the formation of coordination complexes with the Cu¹⁺ ions of the Guardiant® powder. By contrast, Sample 14, which included DMAMP-80, did not exhibit peak shift or broadening relative to Sample 8 (DPP and AMP), indicating that coordination complexes were not formed. It is believed that the nitrogen of the amine group of DMAMP-80 was too crowded to facilitate formation of the coordination complexes between the DPP and Cu¹⁺ ions.

[00149] EXAMPLE 4

[00150] ³¹P NMR spectroscopy was used to determine whether coordination complexes could be formed using 2-EHP. Sample 17 was the 2-EHP control sample (containing just 2-EHP and CeDe) exhibited two characteristic peak shifts. When AMP was added (Sample 18), the peaks were shifted and were slightly increased in width, and a new peak was resolved. When Guardiant® powder was added (Sample 20), the peaks were again shifted and were significantly broadened. Thus, 2-EHP in water was able to form coordination complexes with the Cu¹⁺ ions of Guardiant® powder in the presence of AMP.

[00151] EXAMPLE S

[00152] Several samples as shown below in Table 2 were allowed to react for a time of up to 90 minutes. Each sample included a phosphate except a control sample (Sample 29), and each sample included a source of Cu¹⁺ ions except two other control samples (Samples 21 and 22). After preparing the extractant according to Samples 21-29, the extractants were each added to about 25 g of paint to determine the effect on the color of the paint.

Table 2. Extractant Samples Prepared to Determine Color Change in Paint

[00153] The phosphates used in the samples varied. In Samples 21-24, the phosphate was DPP. In Sample 25, the phosphate was dibenzyl phosphate (“DBzP”), and in Sample 26, the phosphate was dibutyl phosphate. In Sample 27, the phosphate was potassium tripolyphosphate (“KTPP”), and in Sample 28, the phosphate was sodium hexametaphosphate (“SHMP”). Over time, the samples transitioned from substantially clear or cloudy to various different colors, such as yellow, blue, and purple as shown in Table 2. The source of Cu¹⁺ ions was separated from the extractant using syringe filters, and the extractant was injected into white paint. Despite the color of the extractant, the color of the paint was not visibly changed after mixing the extractant into the paint.

[00154] EXAMPLE 6

[00155] Table 3 includes samples of paint including extractant formed from mixtures containing Guardiant® powder. The powder was added to the mixture at 1 wt% of the paint sample.

Table 3. Samples of Paint including Antimicrobial Extractant

[00156] For each of the samples, the mixture of water or ethanol, glass powder, and any additives was allowed to react for under 2 hours. Thereafter, the glass powder was separated from the mixture using a syringe filter, and the extractant was injected into the paint. As shown in Table 3, Samples 30 and 31 were control samples for water and ethanol, respectively. Samples 32 and 33 used phosphite as a ligand (specifically triethyl phosphite (“TEP”)) in an amount of 3 molar equivalents of TEP (3X TEP) to the moles of accessible Cu of the glass powder. Sample 34 used the phosphate DPP as the ligand in an amount of 1 molar equivalent of DPP (IX DPP) to the moles the accessible Cu of the glass powder, and Sample 34 also included AMP. Sample 35 used l-butyl-3-methlimidazolium bromide ([BMIM]Br) as the ligand in an amount of 1 molar equivalent of [BMIM]Br (IX [BMIM]Br) to the moles of accessible Cu of the glass powder. The dosage of each of these samples on the basis of glass powder in the mixture relative to the volume of paint was 50 g/gal.

[00157] FIG. 3 provides a graph of Log-kill for Samples 30-35. The standard for determining full-kill was copper metal, which exhibited a log-kill of greater than 5 in this trial. As can be seen from the graph, Samples 30 and 31, which did not include a ligand, exhibited a log-kill below 1. Sample 35 included [BMIM]Br, and the log-kill was approximately 1. Sample 33 included TEP as the ligand in a solvent of ethanol had an increased log-kill of approximately 2. Samples 32 and 34 used water as the solvent with ligands of TEP and DPP, respectively. As can be seen from FIG. 3, the log-kill for each is above 3. Sample 32 had a log-kill of about 4, and Sample 34 had a log-kill of about 4.5. These samples demonstrate that water is a better solvent for the extractant than ethanol.

[00158] EXAMPLE ?

[00159] Table 4 includes samples of paint including extractant formed from mixtures containing Guardiant® powder. The powder was added to the mixture at 2 wt% of the paint sample.

Table 4. Samples of Paint including Antimicrobial Extractant

[00160] For each of the samples of Table 4, the mixture of water, glass powder, and any additives was allowed to react for 24 hours. Thereafter, the glass powder was separated from the mixture using a syringe filter, and the extractant was injected into the paint. As shown in Table 4, Sample 36 was a control sample for Guardiant® powder in water. Sample 37 used phosphite as a ligand (TEP) in an amount of 3 molar equivalents (3X TEP) to moles of accessible Cu of the glass powder. Sample 38 included AMP as a ligand. Sample 39 used the phosphate DPP as the ligand in an amount of 1 molar equivalent (IX DPP) to moles of accessible Cu of the glass powder. Sample 39 also included AMP, which acted as a base in this mixture to enhance the ability of DPP to form coordination complexes. The dosage of each of these samples on the basis of glass powder in the mixture relative to the volume of paint was 100 g/gal.

[00161] FIG. 4 provides a graph of Log-kill for Samples 36-39. The standard for determining full-kill was copper metal, which exhibited a log-kill of greater than 5 in this trial. As can be seen from the graph, Sample 36 (control) had a log-kill of less than 3. Sample 38 had a logkill of about 2.5, indicating that an increased amount of AMP for use as a ligand may improve the antimicrobial activity. Sample 37, which included the ligand TEP, exhibited a log-kill of greater than 3. However, Sample 39, which included both the ligand (DPP) and base (AMP) achieved the greatest log-kill of over 4. These samples demonstrate that the antimicrobial performance may be better when the ligand is used in conjunction with a base, especially where the ligand is a phosphate.

[00162] EXAMPLE S

[00163] Table 5 includes samples of paint including extractant formed from mixtures containing Guardiant® powder. The powder was added to the mixture at 2 wt% of the paint sample.

Table 5. Samples of Paint including Antimicrobial Extractant

[00164] For each of the samples of Table 5, the mixture of water, glass powder, and any additives was allowed to react for 2 hours or less. Thereafter, the glass powder was separated from the mixture using centrifugation at 5000 RPM for ten to twenty minutes, and the extractant was injected into the paint. As shown in Table 5, Sample 40 was a control sample for Guardiant® powder in water. Samples 41 and 42 included a ligand (TEP and DPP, respectively) without a base. Sample 43 included an amino alcohol ligand (AMP). Samples 44 and 45 included a ligand (TEP and DPP, respectively) along with a base (AMP). Samples 46 and 47 included another ligand (DBzP) without and with a base (AMP), respectively. Finally, Sample 48 included a mix of ligands (TEP and DPP) along with a base (AMP). The dosage of each of these samples on the basis of glass powder in the mixture relative to the volume of paint was 100 g/gal.

[00165] FIG. 5 provides a graph of Log-kill for Samples 40-48. The standard for determining full-kill was copper metal, which exhibited a log-kill of greater than 5 in this trial. As can be seen from the graph, Samples 40 (control), Sample 43 (small amount of amino alcohol ligand), and Sample 46 (phosphate with no base) each had a log-kill of less than 3. Samples 41 and 42 demonstrate that a high concentration of ligand (such as TEP or DPP) in the mixture is able to extract sufficient Cu¹⁺ to achieve a log-kill of greater than 3 even without a base. Indeed, each of these samples exhibited a log-kill of greater than 4 and close to full-kill.

[00166] Sample 44 included a ligand (DPP) and base (AMP) and was able to achieve a logkill of greater than 3. Sample 45 demonstrates that increasing the concentration of ligand with the base further improves the log-kill performance, in particular to full kill in this case.

[00167] Samples 46 and 47 involve a different phosphate ligand (DBzP), and these examples demonstrate that the inclusion of a base can improve the performance of the phosphate ligand. In particular, Sample 46, which included DBzP without a base, did not achieve a log-kill of greater than 3. When the base was added in Sample 47, the log-kill was greatly increased to over 4, even for the same concentration of phosphate ligand.

[00168] Sample 48 included a mix of ligands (TEP and DPP) along with a base, and as can be seen in FIG. 5, this Sample exhibited a full-kill level of antimicrobial activity.

[00169] Samples 40-48 demonstrate (1) that increasing the concentration of the ligand can improve antimicrobial activity, (2) that including a base can improve antimicrobial activity for a ligand at a given concentration, and (3) that the time the mixture is allowed to react does not significantly affect the antimicrobial performance. Regarding the third point, when compared to Samples 36-39, which were allowed to react for 24 hours, Samples 40-48 performed similarly despite only reacting for around 2 hours.

[00170] EXAMPLE 9

[00171] Table 6 includes samples of extractant formed from mixtures containing Guardiant® at different concentrations along with a ligand of amino alcohol (specifically AMP) alone or in conjunction with other phosphorus-based ligands.

Table 6. Samples of Extractant formed from Mixtures with Varying Amounts of Amino Alcohol Ligand and Copper Source

[00172] For Samples 49-55, the total mass of the solution was 6 g. For Sample 49, the mass of the mixture including the glass powder (Guardiant®) was 6.25 g, and for Samples 50-55, the mass of the mixture was 6.51 g. Thus, for Samples 49-55, the weight percentage of amino alcohol in the solution was 15 wt%, 5 wt%, 10 wt%, 15 wt%, 30 wt%, 15 wt%, and 15 wt%, respectively. For Samples 56-58, the total mass of the solution was 10.54 g, and the total mass of the mixture including the glass powder (Guardiant®) was 15.58 g. For Samples 56-58, the weight percentage of amino alcohol in the solution was 15 wt% for each. After reacting, the glass powder was removed from the mixture, and each of Samples 49-58 was combined with 50 g of paint. The equivalent dosage of glass powder to paint was 25 g/gal (Sample 49) 50 g/gal (Samples 50-55), and 500 g/gal (Samples 56-58), which corresponds to 0.5 wt%, 1 wt%, and 10 wt%, respectively, of glass powder in paint.

[00173] FIG. 6 depicts a graph of log-kill for Samples 49-58. The standard for determining full-kill was copper metal, which exhibited a log-kill of about 5 in this trial. Each of the samples exhibited a log-kill of greater than 3, and Samples 51-58 exhibited full-kill. Thus, Samples 49-58 demonstrate that an amino alcohol can be used as the ligand when provided in sufficient quantity. That is, when included at less than 1 wt% in certain of the samples discussed above, the amino alcohols did not demonstrate significant formation of coordination complexes. When included at those low levels, the amino alcohols did interact with the phosphate ligands to enhance the ability of the phosphate ligands to form coordination complexes with the Cu ions of the source. When included at the higher levels, such as 5 wt% of the extractant solution or higher, the ability of the amino alcohols to operate as a ligand to form coordination complexes with the Cu ions of the source in the extractant solution is enhanced.

[00174] EXAMPLE 10

[00175] Table 7 includes samples of extractant formed from mixtures containing Guardiant® powder at different concentrations.

Table 7. Samples of Extractant formed from Mixtures with Varying Amounts of Copper

Source

[00176] For each of the samples of Table 7, the mixture of water, glass powder, 2-ethyl hexyl phosphate (2 -EHP), and neutralizer (AMP) was allowed to react for about 2 hours. Thereafter, the glass powder was separated from the mixture by centrifugation at 5000 RPM for ten to twenty minutes. The samples were then investigated to determine the amount of Cu contained in the extractant using neocuproine test with UV-vis spectroscopy.

[00177] FIG. 7 depicts a graph of the amount of copper (ppm, number basis) of all species contained in each of Samples 59-64. As can be seen from FIG. 7, the copper extracted from the Guardiant® powder in the mixture increased with increasing concentration of the Guardiant® powder in the mixture up to 20wt%. However, after 20 wt%, the copper extracted decreased, with the 40 wt% sample (Sample 64) being lower than the 12 wt% sample (Sample 62). It was also observed that Sample 64 gelled. It was determined that the gelled sample was able to be resuspended in water. In particular, water was added to the gel at a ratio of 1 :0.7 (i.e., 1 ml of water was added to 700 pl of gel. In certain aspects, a gel may be desirable to provide a concentrated product requiring less storage space and shipping costs, and the concentrated product can be diluted by the end user when ready for incorporation into a carrier to form an antimicrobial material.

[00178] Another set of samples was prepared similar to Samples 59-64 of Table 7 with the exception that the 2-EHP was replaced with DPP. The extractants formed from these mixtures gelled at Guardiant® glass powder dosage levels of 10 wt% and higher. A further set of samples was prepared similar to Samples 59-64 of Table 7 with the exception that the 2-EHP was replaced with TEP. None of the extractants formed from these mixtures gelled, but at 12 wt% and higher of Guardiant® glass powder dosages, the extractant thickened and coated the container. The samples prepared from mixtures including TEP were also tested for antimicrobial activity, and each sample exhibited a log-kill of about 4 or greater. By comparison, full-kill for this test was established as about 5.5 for Cu metal.

[00179] EXAMPLE 11

[00180] Another sample, Sample 65, was prepared from a mixture of 146.2 mg cuprite (CU2O), 350.5 pl of TEP, and 10 ml of water. The extractant was separated from the mixture and added to 50 g of paint. The paint was investigated to determine log-kill, and it was determined that Sample 65 exhibited full-kill relative to the copper metal standard. Thus, Sample 65 demonstrates that a copper-containing oxide, such as cuprite (CU2O) can be used as the source of copper ions.

[00181] EXAMPLE 12

[00182] Several of the paint samples described above were analyzed to determine color change after the paint sample was applied to a surface and cured. The CIE L*a*b* color system coordinates were measured at a first time (tl) after curing and at a second time (t2) at least 2 days later. During that time, the samples were stored at room temperature in ambient indoor conditions. From the CIE L*a*b* coordinates measured at each time, the color change AE was determined according to the equation ((Lt2*-L_t2*)²+(at2*-ati*)²+(bt2*-bti*)²). It was found that all of the samples prepared from mixtures having 2 wt% or less of Guardiant® powder relative to the paint dosage exhibited a color change AE of about 4 or less. Certain samples, such as those having 2 wt% or less of Guardiant® and a phosphite ligand, exhibited a color change AE of about 1 or less. Further, two samples prepared from mixtures having up to 10 wt% of Guardiant® powder exhibited a color change AE of about 4. Thus, the antimicrobial extractant can used in various amounts to achieve desired antimicrobial activity while also limiting color change of the paint.

[00183] EXAMPLE 13

[00184] This example demonstrates that Cu¹⁺ ion extraction from a glass-ceramic can be performed with selected buffered solutions to achieve >5.0 log kill AM efficacy after addition to a latex paint.

[00185] Tris buffer solutions were prepared at 10, 20, 30 and 50 mM in water. 20 g of glassceramic powder was added to 10 ml of each buffered solution, and then 4.6 ml of triethyl phosphite (TEP) was added. The reaction mixture was rolled/mixed overnight, and the liquid copper extract was isolated by centrifugation. A 500 pL aliquot of each extract was then added to 50g of latex paint and cured as a film for 7 days before AM log kill was measured on 1 x 1 coupons. The results are shown in Table 8 and FIG. 8. In FIG. 8, “G” represents the glassceramic, and the Cu metal bar represents “full kill” using a copper metal coupon.

Table 8. Antimicrobial efficacy results for a latex paints containing aqueous extractants prepared from extraction of glass-ceramic powder with a buffer solution containing triethyl phosphite

[00186] Unless otherwise expressly stated, it is in no way intended that any method set forth herein be construed as requiring that its steps be performed in a specific order. Accordingly, where a method claim does not actually recite an order to be followed by its steps or it is not otherwise specifically stated in the claims or descriptions that the steps are to be limited to a specific order, it is in no way intended that any particular order be inferred. In addition, as used herein, the article "a" is intended to include one or more than one component or element, and is not intended to be construed as meaning only one.

[00187] It will be apparent to those skilled in the art that various modifications and variations can be made without departing from the spirit or scope of the disclosed aspects. Since modifications, combinations, sub-combinations and variations of the disclosed aspects incorporating the spirit and substance of the aspects may occur to persons skilled in the art, the disclosed aspects should be construed to include everything within the scope of the appended claims and their equivalents.

Claims

What is claimed is:

1. A method of preparing an antimicrobial extractant, the method comprising: preparing a mixture comprising a source of Cu¹⁺ ions, a ligand configured to form a coordination complex with the Cu¹⁺ ions, and a solvent; reacting the mixture for a time sufficient to form Cu¹⁺ coordination complexes; separating the source from the mixture to form the antimicrobial extractant.

2. The method of claim 1, wherein the source of Cu¹⁺ ions is a glass, a glass-ceramic, an oxide, or a salt of Cu¹⁺.

3. The method of claim 2, wherein the glass or glass-ceramic comprises:

30 mol% to 70 mol% of SiCh;

0 mol% to 20 mol% of AI2O3;

10 mol% to 50 mol% of one or more copper-containing oxides;

0 mol% to 15 mol% of CaO;

0 mol% to 15 mol% of MgO;

0 mol% to 25 mol% P2O5;

0 mol% to 25 mol% of B2O3;

0 mol% to 20 mol% of K2O;

0 mol% to 20 mol% of Na2O;

0 mol% to 5 mol% of ZnO; and

0 mol% to 5 mol% of Fe2O3; wherein an amount of the one or more copper-containing oxides is greater than the amount of AI2O3.

4. The method of claim 3, wherein the glass or glass-ceramic comprises at least one of B2O3, P2O5, and R2O, wherein R is any one or more of K, Na, Li, Rb, and Cs.

5. The method of claim 3, wherein the one or more copper-containing oxides comprise copper ions, wherein at least 50% of the copper ions are Cu¹⁺.

6. The method of claim 3 or claim 4, wherein the one or more copper-containing oxides comprises at least 50 mol% cuprite.

7. The method of claim 2, wherein the salt comprises a copper halide.

8. The method of claim 2, wherein the oxide comprises cuprite.

9. The method of any one of claims 1-8, wherein the ligand comprises at least one of a phosphate, a phosphite, a phosphine, a phosphonate, or an amino alcohol.

10. The method of claim 9, wherein the phosphate is in a form of ((R¹O)3)P=O in which each R¹ group is independently one of hydrogen, a C1-C20 alkyl, a phenyl, or a benzyl, wherein at least one of the R¹ groups is hydrogen.

11. The method of claim 9 or claim 10, wherein the phosphate is selected from a group consisting of diphenyl phosphate, 2-ethylhexyl phosphate, dibenzyl phosphate, dibutyl phosphate, potassium tripolyphosphate, sodium hexametaphosphate, or any combination thereof.

12. The method of claim 9, wherein the phosphite is in a form of P(R²O)s in which each R² group is independently a C1-C20 alkyl or a C1-C20 fluoro-substituted alkyl.

13. The method of claim 9 or claim 12, wherein the phosphite is selected from a group consisting of triethyl phosphite, trimethyl phosphite, tributyl phosphite, trioctadecyl phosphite, tridecyl phosphite, or any combination thereof.

14. The method of claim 9, wherein: the phosphine is in a form of (R³)sP in which each R³ group is independently a C1-C20 alkyl or a C1-C20 alkyl substituted with a hydroxy group; and/or the phosphine is selected from the group consisting of triphenylphosphine, trioctylphosphine, ethylenebis(diphenylphosphine), tributylphosphine (e.g., tri-n- butylphosphine), tri(2-furyl)phosphine, triethylphosphine, tri ethylphosphine, and isopropyldiphenylphosphine, or any combination thereof.

15. The method of claim 9, wherein the amino alcohol is selected from a group consisting of 22-amino-2-methyl-l -propanol, N-butyldiethanolamine, D-leucinol, DL-phenylalaninol, DL-phenylglycinol, D-phenylalaninol, D-(-)-valinol, L-isoleucinol, L-leucinol, L-(-)- methioninol, L-phenylalaninol, L-tryptophanol, L-(+)-valinol, N(alpha)-Boc-D-tryptophanol, N-benzyloxycarbonyl-D-alaninol, N-benzyloxycarbonyl-L-alaninol, N-Boc-D-alaninol, N- Boc-D-alpha-phenylglycinol, N-Boc-D-cyclohexylglycinol, N-Boc-D-leucinol, N-Boc-D- phenylalaninol, N-Boc-D-valinol, N-Boc-L-alaninol, N-Boc-L-alpha-phenylglycinol, N-Boc- L-isoleucinol, N-Boc-L-leucinol, N-Boc-L-phenylalaninol, N-Boc-L-tryptophanol, N-Boc-L- valinol, N-Fmoc-D-threoninal, .N-Fmoc-L-alaninol, N-Fmoc-L-phenylalaninol, N-Fmoc-L- threoninol, N-Fmoc-L-valinol, (R)-(-)-2-phenylglycinol, and (S)-(+)-2-phenylglycinol, and combinations thereof.

16. The method of any one of claims 1-15, wherein the mixture further comprises a base.

17. The method of claim 16, wherein the base is an inorganic base.

18. The method of claim 17, wherein the inorganic base is sodium hydroxide or ammonium hydroxide.

19. The method of claim 17, wherein the base is an organic base.

20. The method of claim 19, wherein the organic base is an amino alcohol.

21. The method of any one of claims 1-20, wherein the solvent comprises water, tetrahydrofuran, methyl ethyl ketone, dimethyl sulfoxide, 1,4-di oxane, diethyl ether, and combinations thereof.

22. The method of any one of claims 1-21, wherein the mixture comprises from 0.5 wt% to 60 wt% of the source of Cu¹⁺ ions.

23. The method of any one of claims 1-22, wherein the time of reacting the mixture is at least 2 hours and no more than 24 hours.

24. The method of any one of claims 1-23, wherein separating comprises filtering, centrifuging, or both filtering and centrifuging.

25. An antimicrobial extractant prepared according to the method of any one of claims 1- 24, comprising: a coordination complex of a Cu¹⁺ ion and a ligand; and a solvent.

26. The antimicrobial extractant of claim 25, comprising a pH in a range from 5.5 to 12.

27. An antimicrobial composition, comprising: a coordination complex of a Cu¹⁺ ion and a ligand; and a solvent.

28. The antimicrobial composition of claim 27, wherein the ligand comprises at least one of a phosphate, a phosphite, a phosphine, a phosphonate, or an amino alcohol.

29. The antimicrobial composition of claim 28, wherein the phosphate is in a form of ((R¹0)3)P=0 in which each R¹ group is independently one of hydrogen, a C1-C20 alkyl, a phenyl, or a benzyl, wherein at least one of the R¹ groups is hydrogen.

30. The antimicrobial composition of claim 28 or claim 29, wherein the phosphate is selected from a group consisting of diphenyl phosphate, 2-ethylhexyl phosphate, dibenzyl phosphate, dibutyl phosphate, potassium tripolyphosphate, sodium hexametaphosphate, and combinations thereof.

31. The antimicrobial composition of claim 28, wherein the phosphite is in a form of P(R²O)S in which each R² group is a C1-C20 alkyl or a C1-C20 fluoro-substituted alkyl.

32. The antimicrobial composition of claim 28 or claim 31, wherein the phosphite is selected from a group consisting of triethyl phosphite, trimethyl phosphite, tributyl phosphite, trioctadecyl phosphite, tridecyl phosphite, and combinations thereof.

33. The antimicrobial composition of claim 28, wherein: the phosphine is in a form of (R³)sP in which each R³ group is independently a C1-C20 alkyl or a C1-C20 alkyl substituted with a hydroxy group; and/or the phosphine is selected from the group consisting of triphenylphosphine, trioctylphosphine, ethylenebis(diphenylphosphine), tributylphosphine (e.g., tri-n- butylphosphine), tri(2-furyl)phosphine, triethylphosphine, tri ethylphosphine, and isopropyldiphenylphosphine, or any combination thereof.

34. The antimicrobial composition of claim 28, wherein the amino alcohol is selected from a group consisting of 22-amino-2-methyl-l -propanol, N-butyldiethanolamine, D- leucinol, DL-phenylalaninol, DL-phenylglycinol, D-phenylalaninol, D-(-)-valinol, L- isoleucinol, L-leucinol, L-(-)-methioninol, L-phenylalaninol, L-tryptophanol, L-(+)-valinol, N(alpha)-Boc-D-tryptophanol, N-benzyloxycarbonyl-D-alaninol, N-benzyloxycarbonyl-L- alaninol, N-Boc-D-alaninol, N-Boc-D-alpha-phenylglycinol, N-Boc-D-cyclohexylglycinol, N-Boc-D-leucinol, N-Boc-D-phenylalaninol, N-Boc-D-valinol, N-Boc-L-alaninol, N-Boc-L- alpha-phenylglycinol, N-Boc-L-isoleucinol, N-Boc-L-leucinol, N-Boc-L-phenylalaninol, N- Boc-L-tryptophanol, N-Boc-L-valinol, N-Fmoc-D-threoninal, .N-Fmoc-L-alaninol, N-Fmoc- L-phenylalaninol, N-Fmoc-L-threoninol, N-Fmoc-L-valinol, (R)-(-)-2-phenylglycinol, and (S)-(+)-2-phenylglycinol, and combinations thereof.

35. The antimicrobial composition of any one of claims 27-34, further comprising a base.

36. The antimicrobial composition of claim 35, wherein the base is an inorganic base.

37. The antimicrobial composition of claim 36, wherein the inorganic base is sodium hydroxide or ammonium hydroxide.

38. The antimicrobial composition of claim 35, wherein the base is an organic base.

39. The antimicrobial composition of claim 38, wherein the organic base is an amino alcohol.

40. An antimicrobial material, comprising: a carrier; and the antimicrobial extractant according to claim 25 or claim 26 or the antimicrobial composition according to any one of claims 27-39 dispersed in the carrier.

41. The antimicrobial material of claim 40, wherein the antimicrobial material exhibits a log reduction of 3 or greater in a concentration of Staphylococcus aureus under the EPA Test Method for Efficacy of Copper Alloy as a Sanitizer testing conditions.

42. The antimicrobial material of claim 40 or claim 41, wherein the carrier is a coating.

43. The antimicrobial material of claim 42, wherein the coating is a paint.

44. The antimicrobial material of claim 43, comprising at least 100 ppm of copper.

45. The antimicrobial material of any one of claims 40-44, wherein the antimicrobial material exhibits a color change AE* according to the CIE L*a*b* color system from a first time to a second time of 4 or less, wherein the first time (tl) is upon formation of the antimicrobial material through curing after application to a surface and the second time (t2) is after at least 2 days, the antimicrobial material being stored at room temperature in ambient indoor conditions, and wherein AE equals ((Lt2*-Lt2*)²+(at2*-ati *)²+(bt2*-bti *)²).

46. The antimicrobial material of claim 45, wherein at the second time, the color change AE* is 2 or less.

47. The antimicrobial material of claim 42, wherein the coating is a direct-to-metal coating, a clear coat, or a reactive coating.

48. The antimicrobial material of claim 40 or claim 41, wherein the carrier is a plastic.

49. The antimicrobial material of claim 48, wherein the plastic is a thermoplastic polymer selected from a group consisting of a polystyrene, a polycarbonate, a polyamide, a poly(acrylonitrile-butadiene-styrene), a polybutylene terephthalate, a polyethylene terephthalate, a polyolefin, a polymethyl methacrylate, a thermoplastic urethane, a poly etherimide, and combinations thereof.

50. The antimicrobial material of claim 48, wherein the plastic is a thermosetting polymer selected from a group consisting of an epoxy resin, an acrylic resin, a styrenic resin, a phenolic resin, a melamine resin, a urethane resin, a polyester resin, and combinations thereof.