Improved chlorine dioxide biocides

Abstract

A biocide comprising: (i) chlorine dioxide or salt thereof, (ii) one or more sugar oxidation products, and (iii) at least one of the compounds selected from the group consisting of organic acids, augmenters and solvents. A method of disinfecting a surface comprising applying to the surface a biocide composition comprising: (i) chlorine dioxide or salt thereof, (ii) one or more sugar oxidation products, and (iii) at least one of the compounds selected from the group consisting of organic acids, augmenters and solvents.

Description

IMPROVED CHLORINE DIOXIDE BIOCIDESCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims benefit and priority of U.S. provisional patent application Serial No 63 / 684,223 filed August 16, 2024, and entitled “CHLORINE DIOXIDE BIOCIDES,” which is hereby incorporated herein by reference in its entirety for all purposes.STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

[0002] Not applicable.TECHNICAL FIELD

[0003] The present disclosure relates generally to biocides. More particularly, the present disclosure relates to oxidizing biocides. Still more particularly, the present disclosure relates to stabilized chlorine dioxide compositionsBACKGROUND

[0004] Biocidal products are a broad group of chemicals that contain or generate active ingredients that give them antibacterial, antimicrobial, disinfecting or sanitizing properties. They destroy, make harmless or control harmful organisms such as bacteria or viruses by means other than mere physical or mechanical action. Biocides are intended for non-plant uses and include products such as disinfectants, wood preservatives, rodenticides, insecticides, and antifouling agents. In many areas of our daily life, biocidal active substances are used to ensure personal hygiene, disinfect surfaces, control insects and preserve a wide range of non-durable goods.

[0005] Chlorine dioxide is an example of a potent biocide that is characterized as a very effective quick acting, oxidizing disinfectant. However, due to the low stability of this compound it is also characterized by a short window of efficacy. An ongoing need exists for chlorine dioxide based biocidal compositions that can address one or more of the challenges associated with the existing formulations.BRIEF SUMMARY OF THE DISCLOSURE

[0006] Disclosed herein is a biocide comprising (i) chlorine dioxide or salt thereof, (ii) one or more sugar oxidation products, and (iii) at least one of the compounds selected from the group consisting of organic acids, augmenters and solvents.

[0007] Also disclosed herein is a method of disinfecting a surface comprising applying to the surface a biocide composition comprising (i) chlorine dioxide or salt thereof, (ii) one or more sugar oxidation products, and (iii) at least one of the compounds selected from the group consisting of organic acids, augmenters and solvents.

[0008] Also disclosed herein is a method of preparing a biocide comprising combining (i) chlorine dioxide or salt thereof, (ii) one or more sugar oxidation products, and (iii) at least one of the compounds selected from the group consisting of organic acids, augmenters and solvents to form a biocide the one or more sugar oxidation products in the biocide composition; and maintaining the chlorine dioxide or salt thereof in solution based on the acidification of the one or more sugar oxidation products.

[0009] Aspects described herein comprise a combination of features and characteristics intended to address various shortcomings associated with certain prior devices, systems, and methods. The foregoing has outlined rather broadly the features and technical characteristics of the disclosed aspects in order that the detailed description that follows may be better understood. The various characteristics and features described above, as well as others, will be readily apparent to those skilled in the art upon reading the following detailed description, and by referring to the accompanying drawings. It should be appreciated that the conception and the specific aspects disclosed may be readily utilized as a basis for modifying or designing other structures for carrying out the same purposes as the disclosed aspects. It should also be realized that such equivalent constructions do not depart from the spirit and scope of the principles disclosed herein.BRIEF DESCRIPTION OF THE DRAWINGS

[0010] For a detailed description of various exemplary aspects, reference will now be made to the accompanying drawings in which:

[0011] Figure 1 depicts the equations for interconversion of gluconic acid to its corresponding lactones.

[0012] Figure 2 depicts the equation for interconversion of glucaric acid to its corresponding lactone and dilactone forms.

[0013] Figure 3 is a plot of pH for the indicated organic acid as a function of time.DETAILED DESCRIPTION

[0014] The following discussion is directed to various exemplary aspects. However, one skilled in the art will understand that the examples disclosed herein have broadapplication, and that the discussion of any aspect is meant only to be exemplary of that aspect, and not intended to suggest that the scope of the disclosure, including the claims, is limited to that aspect.

[0015] Certain terms are used throughout the following description and claims to refer to particular features or components. As one skilled in the art will appreciate, different persons may refer to the same feature or component by different names. This document does not intend to distinguish between components or features that differ in name but not function. The drawing figures are not necessarily to scale. Certain features and components herein may be shown exaggerated in scale or in somewhat schematic form and some details of conventional elements may not be shown in interest of clarity and conciseness.

[0016] Unless the context dictates the contrary, all ranges set forth herein should be interpreted as being inclusive of their endpoints, and open-ended ranges should be interpreted to include only commercially practical values. In addition, with respect to all ranges disclosed herein, such ranges are intended to include any combination of the mentioned upper and lower limits even if the particular combination is not specifically listed. All lists of values should be considered as inclusive of intermediate values unless the context indicates the contrary. Where numerical ranges or limitations are expressly stated, such express ranges or limitations should be understood to include iterative ranges or limitations of like magnitude falling within the expressly stated ranges or limitations (e.g., from about 1 to about 10 includes, 2, 3, 4, etc.; greater than 0.10 includes 0.11 , 0.12, 0.13, etc.).

[0017] In the following discussion and in the claims, the terms “including” and “comprising” are used in an open-ended fashion, and thus should be interpreted to mean “including, but not limited to... .” As used herein, the phrases “consist(s) of’ and “consisting of” are used to refer to exclusive components of a composition, meaning only those expressly recited components are included in the composition; whereas the phrases “consist(s) essentially of’ and “consisting essentially of” are used to refer to the primary components of a composition, meaning that only small or trace amounts of components other than the expressly recited components (e.g., impurities, byproducts, etc.) may be included in the composition. For example, a composition consisting of X and Y refers to a composition that only includes X and Y, and thus, does not include any other components; and a composition consisting essentially of X and Yrefers to a composition that primarily comprises X and Y, but may include small or trace amounts of components otherthan X and Y. In aspects described herein any such small or trace amounts of components otherthan those expressly recited following the phrase “consist (s) essentially of” or “consisting essentially of’ preferably represent less than 5.0 wt.% of the composition, more preferably less than 4.0 wt.% of the composition even more preferably less than 3.0 wt.% of the composition, and still more preferably less than 1.0 wt.% of the composition. Use of broader terms such as comprises, includes, having, etc. should be understood to provide support for narrower terms such as consisting of, consisting essentially of, comprised substantially of, etc. Use of the term "optionally" with respect to any element of a claim is intended to mean that the subject element is required, or additionally or alternatively , is not required. Both alternatives are intended to be within the scope of the claim. As used herein, the terms “approximately,” “about,” “substantially,” and the like mean within 10% (i.e., plus or minus 10%) of the recited value. Thus, for example, a recited angle of “about 80 degrees” refers to an angle ranging from 72 degrees to 88 degrees.

[0018] Disclosed herein are biocide compositions comprising (i) a biocide and a (ii) one or more sugar oxidation products. In an aspect, the biocide comprises chlorine dioxide, salts thereof or derivatives thereof. Hereinafter a biocide composition of the type disclosed herein is characterized by a biocidal activity that displays increased stability and is termed an improved biocidal composition, IBC.

[0019] In an aspect, the IBC comprises chlorine dioxide. Chlorine dioxide can be obtained from any suitable source. For example, chlorine can be reacted with water to form hypochlorous acid and hydrochloric acid which are then reacted with sodium chlorite to produce chlorine dioxide water and sodium chloride. These reaction equations are presented below.NaOCl + HCl -► HOCl + NaCl2NaClO2+ NaOCl + 2HCI -> 2CIO2+ 3 NaCl + H2O Combined:5NaClO2+ 4HCI -> 4CIO2+ 5NaCl + 2H2O

[0020] In one or more aspects, the IBC comprises chlorine dioxide or a salt thereof present in an amount of about 0.1 weight percent (wt.%), additionally or alternatively about 0.25 wt.%, or about 0.5 wt.%, or about 0.75 wt.%, or about 1 wt.%, or about 1.25wt.%, or about 1 .5 wt.%, or about 1 .75 wt.%, or about 2 wt.%, or about 2.25 wt.%, or about 2.5 wt.%, or about 2.75 wt.%, or about 3 wt.%, or about 3.25 wt.%, or about 3.5 wt.%, or about 3.75 wt.%, or about 4 wt.%, or about 4.25 wt.%, or about 4.5 wt.%, or about 4.75 wt.%, or about 5 wt.%, or about 10 wt.%, or about 12.5 wt.%, or about 15 wt.%, or about 17.5 wt.%, or about 20 wt.%, or about 22.5 wt.%, or about 25 wt.%, or about 27.5 wt.%, or about 30 wt.%, or about 32.5 wt.%, or about 35 wt.%, or about 37.5 wt.%, or about 40 wt.%, or about 42.5 wt.%, or about 45 wt.%, or about 47.5 wt.%, or about 50 wt.%, or about 52.5 wt.%, or about 55 wt.%, or about 57.5 wt.%, or about 60 wt.%, or about 62.5 wt.%, or about 65 wt.%, or about 67.5 wt.%, or about 70 wt.%, or about 72.5 wt.%, or about 75 wt.%, or about 77.5 wt.%, or about 80 wt.%, or about 82.5 wt.%, or about 85 wt.%, or about 87.5 wt.%, or about 90 wt.%, or about 92.5 wt.%, or about 95 wt.%, or about 97.5 wt.%, or about 100 wt.%, additionally or alternatively 0.1 wt.% to about 99 wt.%, additionally or alternatively about 1 wt.% to about 95 wt.%, additionally or alternatively about 5 wt.% to about 90 wt.%, additionally or alternatively about 10 wt.% to about 90 wt.%, additionally or alternatively about 15 wt.% to about 85 wt.%, additionally or alternatively about 20 wt.% to about 80 wt.%, additionally or alternatively about 25 wt.% to about 75 wt.%, additionally or alternatively about 40 wt.% to about 60 wt.%, additionally or alternatively about 50 wt.%, additionally or alternatively about 0.1 wt.% to about 10 wt.%, additionally or alternatively about 1 wt.% to about 20 wt.%, additionally or alternatively about 5 wt.% to about 50 wt.% based on the total weight of the IBC. In some aspects, the biocide has chlorine dioxide present in an amount between any of the end points listed herein.

[0021] In some aspects, the IBC comprises one or more sugar-derived molecules. For example, the IBC can comprise one or more sugar oxidation products. In an aspect, the one or more sugar oxidation products comprise aldonic acid, uronic acid, aldaric acid, or combinations thereof.

[0022] Additionally, or alternatively, in one or more aspects, the one or more sugar oxidation products comprise glucaric acid, gluconic acid, gluconate, glucuronic acid, glucose oxidation products, gluconic acid oxidation products or combinations thereof.

[0023] Additionally, or alternatively, in one or more aspects, the one or more sugar oxidation products comprise galactonic acid, galactaric acid, an oxidation product comprising predominantly (e.g., greater than about 50 weight percent) galactonic acid and / or galactaric acid with minor component species of n-keto-acids, C2 to Cs diacidsor combinations thereof. Additionally, or alternatively, in one or more aspects, the one or more sugar oxidation products comprise glutamic acid.

[0024] In an aspect, the one or more sugar oxidation products comprise a glucose oxidation product, a gluconic acid oxidation product, glucaric acid, an oxidized glucuronolactone, a uronic acid oxidation product or combinations thereof. Additionally, or alternatively, the one or more sugar oxidation products comprises a buffered glucose oxidation product, a buffered gluconic acid oxidation product or combinations thereof. In some such aspects, the buffered glucose oxidation product, the buffered gluconic acid oxidation product, or combinations thereof.

[0025] In an aspect, the one or more sugar oxidation products comprise glucaric acid, lactones of glucaric acid, gluconic acid, lactones of gluconic acid, galactonic acid, lactones of galactonic acid, galactaric acid, lactones of galactaric acid, galactonic acid, glucoheptonic acid, lactones of glucoheptonic acid, or combinations thereof.

[0026] In an aspect, the IBC comprises a mixture of gluconic acid and glucaric acid. In such aspects, the ratio of gluconic acid:glucaric acid may range from about 0.1 :10 to about 10:0.1 , alternatively about 0.15:10, or about 0.5:10, about 1 :10, about 1 :5, about 1 :4, about 1 :3, about 1:2, about 1 :1 , about 10:0.1 , about 10:0.5, about 10:1 , about 5:1 , about 4:1 , about 3:1 , or about 2:1 .

[0027] In one or more aspects, the IBC has one or more sugar oxidation products present in an amount of about 0.1 wt.%, or about 0.25 wt.%, or about 0.5 wt.%, or about 0.75 wt.%, or about 1 wt .%, or about 1 .25 wt.%, or about 1 .5 wt.%, or about 1 .75 wt.%, or about 2 wt.%, or about 2.25 wt.%, or about 2.5 wt.%, or about 2.75 wt.%, or about 3 wt.%, or about 3.25 wt.%, or about 3.5 wt.%, or about 3.75 wt.%, or about 4 wt.%, or about 4.25 wt.%, or about 4.5 wt.%, or about 4.75 wt.%, or about 5 wt.%, or about 10 wt.%, or about 12.5 wt.%, or about 15 wt.%, or about 17.5 wt.%, or about 20 wt.%, or about 22.5 wt.%, or about 25 wt.%, or about 27.5 wt.%, or about 30 wt.%, or about 32.5 wt.%, or about 35 wt.%, or about 37.5 wt.%, or about 40 wt.%, or about 42.5 wt.%, or about 45 wt.%, or about 47.5 wt.%, or about 50 wt.%, or about 52.5 wt.%, or about 55 wt.%, or about 57.5 wt.%, or about 60 wt.%, or about 62.5 wt.%, or about 65 wt.%, or about 67.5 wt.%, or about 70 wt.%, or about 72.5 wt.%, or about 75 wt.%, or about 77.5 wt.%, or about 80 wt.%, or about 82.5 wt.%, or about 85 wt.%, or about 87.5 wt.%, or about 90 wt.%, or about 92.5 wt.%, or about 95 wt.%, or about 97.5 wt.%, or about 100 wt.%, additionally or alternatively about 0.1 wt.% to about 99 wt.%, additionally or alternatively about 1 wt.% to about 95 wt.%, additionally or alternatively about 5 wt.% toabout 90 wt.%, additionally or alternatively about 10 wt.% to about 90 wt.%, additionally or alternatively about 15 wt.% to about 85 wt.%, additionally or alternatively about 20 wt.% to about 80 wt.%, additionally or alternatively about 25 wt.% to about 75 wt.%, additionally or alternatively about 40 wt.% to about 60 wt.%, additionally or alternatively about 50 wt.%, additionally or alternatively about 0.1 wt.% to about 10 wt.%, additionally or alternatively about 1 wt.% to about 20 wt.%, additionally or alternatively about 5 wt.% to about 50 wt.% based on the total weight of the IBC. On some aspects, the IBC has one or more sugar oxidation products present in an amount between any of the end points listed herein.

[0028] In some aspects, the IBC comprises an organic acid. For example, the IBC may comprise at least one acid selected from the group consisting essentially of citric acid, lactic acid, hydrochloric acid, malic acid, acetic acid, formic acid, propionic acid, butyric acid, sorbic acid, fumaric acid, tartaric acid, benzoic acid, succinic acid, ascorbic acid, adipic acid, quinic acid, isocitric acid, shikimic acid, maleic acid and combinations thereof. The organic acid may be present in the IBC in an amount of from about 0.1 wt.% to about 99 wt.%, additionally or alternatively about 1 wt.% to about 95 wt.%, additionally or alternatively about 5 wt.% to about 90 wt.%, additionally or alternatively about 10 wt.% to about 90 wt.%, additionally or alternatively about 15 wt.% to about 85 wt.%, additionally or alternatively about 20 wt.% to about 80 wt.%, additionally or alternatively about 25 wt.% to about 75 wt.%, additionally or alternatively about 40 wt.% to about 60 wt.%, additionally or alternatively about 50 wt.%, additionally or alternatively about 0.1 wt.% to about 10 wt.%, additionally or alternatively about 1 wt.% to about 20 wt.%, additionally or alternatively about 5 wt.% to about 50 wt.% based on the total weight of the IBC.

[0029] In one or more aspects, the IBC further comprises an augmenter which is a material that functions to improve the biocidal activity of the IBC. Nonlimiting examples of augmenters include aldehydes, quaternary ammonium compounds, active halogen compounds such as brominated organic compounds, phosphonium salts, oxidizers such as hydrogen peroxide, peracetic acid, bleach, organosulfur compounds, phenolics, organometallics, isothiazolinone, isothiazolothione, derivatives thereof or combinations thereof. The IBC may comprise an augmenter singularly or in combination in an amount ranging from about 0.5 wt.% to about 20 wt.%; additionally or alternatively from about 2 wt.% to about 15 wt.%; additionally or alternatively from about 5 wt.% to about 10 wt.%; additionally or alternatively an amount of about 0.1 wt.%, or about 0.25 wt.%, or about0.5 wt.%, or about 0.75 wt.%, or about 1 wt.%, or about 1 .25 wt.%, or about 1 .5 wt.%, or about 1.75 wt.%, or about 2 wt.%, or about 2.25 wt.%, or about 2.5 wt.%, or about 2.75 wt.%, or about 3 wt.%, or about 3.25 wt.%, or about 3.5 wt.%, or about 3.75 wt.%, or about 4 wt.%, or about 4.25 wt.%, or about 4.5 wt.%, or about 4.75 wt.%, or about 5 wt.%, or about 10 wt.%, or about 12.5 wt.%, or about 15 wt.%, or about 17.5 wt.%, or about 20 wt.% based on the total weight of the IBC.

[0030] In some aspects, the IBC comprises a solvent. Nonlimiting examples of solvents that may be included in the IBC are water, glycols, alcohols or combinations thereof. In one or more aspects, the solvent comprises the remainder of the IBC when all other components are accounted for.

[0031] In one or more aspects, a biocide of the type disclosed herein addresses one or more of the challenges associated with the use of conventional chlorine dioxide biocides. The addition of a sugar oxidation product of the type disclosed herein is expected to produce a slower, longer lasting generation of chlorine dioxide. Without wishing to be limited by theory, the sugar oxidation products disclosed herein are in equilibrium with their lactone forms. The sugar oxidation products may function as slow- acidulants, providing long lasting preservation effects with slow acidification. As seen in Figure 1 and Figure 2, gluconic and glucaric acid act as slow acidulants via a mechanism that other organic acids or inorganic acids lack.

[0032] The IBCs disclosed herein are able to generate chlorine dioxide for various sanitizing and oxidizing applications with unexpected performance advantages. The IBCs of the present disclosure are more efficient for a longer period of time when compared to chlorine dioxide compositions including inorganic acids such as hydrochloric acid. In one or more aspects, the IBC excludes a mineral acid.

[0033] Without wishing to be limited by theory, use of the presently disclosed biocide compositions may advantageously address the current challenges of chlorine dioxide stability by modifying the release kinetics of the chlorine dioxide. In addition, these disclosed novel biocides (i.e., IBC) have applicability to disinfectant and sanitizing formulations that are applicable to cleaning applications. Other relevant applications for these novel IBCs can include but are not limited to: insect repellent, antimicrobial, attractant, sterilizer, bleach, disinfectant, sanitizer, deodorizer, detoxifier, fungicide, nematocide, fumigant, herbicide, defoliant, desiccant, antifoulant, insecticide, rodenticide, algaecide, preservative, molluscicide and water purifier. In one or more aspects, a method of disinfecting a surface comprises applying to the surface a biocidecomposition comprising (i) chlorine dioxide or salt thereof (ii) one or more sugar oxidation products and at least one of the compounds selected from the group consisting of organic acids, augmenters and solvents.

[0034] In one or more aspects, an IBC finds utility in any application where control of microorganism growth is desired. For example, a biocide of the present disclosure may be useful in applications such as, water treatment, agriculture, food processing, personal care, animal feed, and aquaculture.The biocide disclosed herein may also function as an oxidizer and will have similar benefits to the use of organic acids instead of or in conjunction with inorganic acids can lead to a long lasting effect of chlorine dioxide.

[0035] The IBC can also be incorporated with other ingredients to form a variety of disinfectant and sterilant products. Nonlimiting examples of disinfectant products include but are not limited to hand cleansers, mouthwashes, surgical scrubs, body splashes, hand sanitizer gels and foams, disinfectant wipes, and similar personal care products. Additional types of products include disinfectant foams, creams, mousses, and the like, and compositions containing organic and inorganic filler materials, such as emulsions, lotions, creams, pastes, and the like. The compositions further can be used as an antibacterial cleanser for hard surfaces, for example, sinks and countertops in hospitals, food service areas, and meat processing plants. The disinfectant compositions can also be used as disinfectant fogs and disinfectant mists. The various products in which the disinfectants are used may also include fragrances, depending on the nature of the product. For example, a pine or lemon fragrance may be desirable for use for kitchen cleaning wipes because of their appealing association with cleanliness to many consumers. The IBC of the present disclosure can be used for sterilization of semi-critical and critical surfaces and I or equipment and non-critical surfaces.

[0036] In one or more aspects, an IBC is prepared by the contacting of chlorine dioxide, or a salt thereof, one or more sugar oxidation products (e.g., GOGA) and a at least one of the compounds selected from the group consisting of organic acids, augmenters and solvents of the type disclosed herein. The method may further comprise acidifying the one or more sugar oxidation products wherein acidification of the one or more sugar oxidation products allows for longer stability of the chlorine dioxide present in the IBC. For example, the half-life of the IBC may be increased by from about 10% to about 90%;additionally or alternatively from about 20% to about 75%; additionally or alternatively from about 30% to about 50%.ADDITIONAL DISCLOSURE

[0037] The following are additional nonlimiting exemplary aspects of the presently disclosed subject matter

[0038] A first aspect which is a biocide comprising (i) chlorine dioxide or salt thereof, (ii) one or more sugar oxidation products, and (iii) at least one of the compounds selected from the group consisting of organic acids, augmenters and solvents.

[0039] A second aspect which is the biocide of the first aspect wherein chlorine dioxide or salt thereof is present in an amount of from about 0.1 wt.% to about 99 wt.% based on the total weight of the biocide.

[0040] A third aspect which is a biocide of any of the first through second aspects wherein the one or more sugar oxidation products comprise aldonic acid, uronic acid, aldaric acid, or combinations thereof.

[0041] A fourth aspect which is the biocide of any of the first through third aspects wherein the one or more sugar oxidation products comprise a glucose oxidation product, a gluconic acid oxidation product, glucaric acid, an oxidized glucuronolactone, a uronic acid oxidation product or combinations thereof.

[0042] A fifth aspect which is the biocide of any of the first through fourth aspects wherein the one or more sugar oxidation products comprise glucaric acid, lactones of glucaric acid, gluconic acid, lactones of gluconic acid, galactonic acid, lactones of galactonic acid, galactaric acid, lactones of galactaric acid, galactonic acid, glucoheptonic acid, lactones of glucoheptonic acid, or combinations thereof.

[0043] A sixth aspect which is the biocide of any of the first through fifth aspects wherein the one or more sugar oxidation products comprise a mixture of gluconic acid and glucaric acid.

[0044] A seventh aspect which is the biocide of the sixth aspect wherein the ratio of gluconic acid:glucaric acid may range from about 0.1 :10 to about 10:0.1 .

[0045] An eighth aspect which is the biocide of any of the first through seventh aspects wherein the one or more sugar oxidation products is present in an amount of from about 0.1 wt.% to about 99 wt.% based on the total weight of the biocide.

[0046] A ninth aspect which is the biocide of any of the first through eighth aspects wherein the organic acid is selected from the group consisting essentially of citric acid, lactic acid, hydrochloric acid, malic acid, acetic acid, formic acid, propionic acid, butyricacid, sorbic acid, fumaric acid, tartaric acid, benzoic acid, succinic acid, ascorbic acid, adipic acid, quinic acid, isocitric acid, shikimic acid, maleic acid and combinations thereof.

[0047] A tenth aspect which is the biocide of any of the first through ninth aspects wherein the organic acid is present in an amount from about 0.1 wt.% to about 99 wt.% based on the total weight of the biocide.

[0048] An eleventh aspect which is the biocide of any of the first through tenth aspects wherein the augmenter comprises aldehydes, quaternary ammonium compounds, active halogen compounds, phosphonium salts, oxidizers, hydrogen peroxide, peracetic acid, bleach, organosulfur compounds, phenolics, organometallics, isothiazolinone, isothiazolothione, derivatives thereof or combinations thereof.

[0049] A twelfth aspect which is the biocide of any of the first through eleventh aspects wherein the augmenter is present in an amount of from about 0.5 wt.% to about 20 wt.% based on the total weight of the biocide.

[0050] A thirteenth aspect which is the biocide of any of the first through twelfth aspects excluding a mineral acid.

[0051] A fourteenth aspect which is a method of disinfecting a surface comprising applying to the surface a biocide composition comprising: (i) chlorine dioxide or salt thereof, (ii) one or more sugar oxidation products, and (iii) at least one of the compounds selected from the group consisting of organic acids, augmenters and solvents.

[0052] A fifteenth aspect which is the method of the fourteenth aspect wherein the one or more sugar oxidation products comprise aldonic acid, uronic acid, aldaric acid, or combinations thereof.

[0053] A sixteenth aspect which is the method of any of the fourteenth through fifteenth aspects wherein the organic acid is selected from the group consisting essentially of citric acid, lactic acid, hydrochloric acid, malic acid, acetic acid, formic acid, propionic acid, butyric acid, sorbic acid, fumaric acid, tartaric acid, benzoic acid, succinic acid, ascorbic acid, adipic acid, quinic acid, isocitric acid, shikimic acid, maleic acid and combinations thereof

[0054] A seventeenth aspect which is the method of any of the fourteenth through sixteenth aspects wherein the augmenter comprises aldehydes, quaternary ammonium compounds, active halogen compounds, phosphonium salts, oxidizers, hydrogen peroxide, peracetic acid, bleach, organosulfur compounds, phenolics, organometallics, isothiazolinone, isothiazolothione, derivatives thereof or combinations thereof.

[0055] An eighteenth aspect which is the method of any of the fourteenth through seventeenth aspects wherein the surface comprises sinks, countertops, food service areas, meat processing plants, medical equipment or combinations thereof.

[0056] A nineteenth aspect which is a disinfectant comprising the biocide of the first aspect.

[0057] A twentieth aspect which is the disinfectant of the nineteenth aspect wherein the disinfectant comprises hand cleansers, mouthwashes, surgical scrubs, body splashes, hand sanitizer gels, hand sanitizer foams, disinfectant wipes, emulsions, lotions, creams, pastes, or combinations thereof.

[0058] A twenty-first aspect which is a method of preparing a biocide comprising combining (i) chlorine dioxide or salt thereof, (ii) one or more sugar oxidation products, and (iii) at least one of the compounds selected from the group consisting of organic acids, augmenters and solvents to form a biocide composition; acidifying the one or more sugar oxidation products in the biocide composition; and maintaining the chlorine dioxide or salt thereof in solution based on the acidification of the one or more sugar oxidation products.EXAMPLES

[0059] The presently disclosed subject matter having been generally described, the following examples are given as particular aspects of the subject matter and to demonstrate the practice and advantages thereof. It is understood that the examples are given by way of illustration and are not intended to limit the specification or the claims in any manner.EXAMPLE 1Slow Acidification of Organic Acids

[0060] A 1% active solution of samples of gluconic acid lactone(GDL), glucaric acid lactone, citric acid, or acetic acid were compared to monitor how “gentle” the acidification process was. Specifically, the extent to which the solution pH for each sample decreased as a function of time was monitored and the results are presented in Figure 3. With reference to Figure 3, the 1 % solution of glucaric acid provided similar endpoint pH results and displayed a gradual decrease in pH, indicative of a slower proton donor effect. Gluconic acid lactone displayed a similar effect. The results demonstrate that the biocide compositions of the present disclosure (i.e. , IBCs) which are associated with sugar acids (e.g., gluconic acid, glucaric acid) led to an increased longevity of chlorine dioxide generation.EXAMPLE 2

[0061] The biocidal / disinfecting power of a biocide of the present disclosure (i.e. , IBCs) was investigated. The minimum inhibitory concentration (MIC) of the indicated biocide compositions were determined using either acid-producing bacteria (APB) or sulfatereducing bacteria. For both bacterial samples, the MIC for chlorine dioxide is 1000 ppm. The MIC test results with wild strain acid producing bacteria (APB) or sulfate reducing bacteria (SRB) proved the compositions disclosed herein are characterized by a synergistic effect in the biocidal activity when using an APB model.If K<1 , the biocides are considered to be synergistic.If K=1 , the biocides are considered to be additive.If K>1 , the biocides are considered to be antagonistic.

[0062] The subject matter having been shown and described, modifications thereof can be made by one skilled in the art without departing from the spirit and teachings of the subject matter. The aspects described herein are exemplary only and are not intended to be limiting. Many variations and modifications of the subject matter disclosed herein are possible and are within the scope of the disclosed subject matter. Where numerical ranges or limitations are expressly stated, such express ranges or limitations should be understood to include iterative ranges or limitations of like magnitude falling within the expressly stated ranges or limitations (e.g., from about 1 to about 10 includes, 2, 3, 4,etc.; greater than 0.10 includes 0.11 , 0.12, 0.13, etc.). Use of the term "optionally" with respect to any element of a claim is intended to mean that the subject element is required, or additionally or alternatively , is not required. Both alternatives are intended to be within the scope of the claim. Use of broader terms such as comprises, includes, having, etc. should be understood to provide support for narrower terms such as consisting of, consisting essentially of, comprised substantially of, etc.

[0063] Accordingly, the scope of protection is not limited by the description set out above but is only limited by the claims which follow, that scope including all equivalents of the subject matter of the claims. Each and every claim is incorporated into the specification as an aspect of the present disclosure. Thus, the claims are a further description and are an addition to the aspects of the present invention. The discussion of a reference herein is not an admission that it is prior art to the presently disclosed subject matter, especially any reference that may have a publication date after the priority date of this application. The disclosures of all patents, patent applications, and publications cited herein are hereby incorporated by reference, to the extent that they provide exemplary, procedural or other details supplementary to those set forth herein.

Claims

CLAIMSWhat is claimed is:1 . A biocide comprising:(i) chlorine dioxide or salt thereof;(ii) one or more sugar oxidation products; and(iii) at least one of the compounds selected from the group consisting of organic acids, augmenters, and solvents.

2. The biocide of claim 1 , wherein chlorine dioxide or salt thereof is present in an amount of from about 0.1 wt.% to about 99 wt.% based on the total weight of the biocide.

3. The biocide of claim 1 , wherein the one or more sugar oxidation products comprise aldonic acid, uronic acid, aldaric acid, or combinations thereof.

4. The biocide of claim 1 , wherein the one or more sugar oxidation products comprise a glucose oxidation product, a gluconic acid oxidation product, glucaric acid, an oxidized glucuronolactone, a uranic acid oxidation product or combinations thereof.

5. The biocide of claim 1 , wherein the one or more sugar oxidation products comprise glucaric acid, lactones of glucaric acid, gluconic acid, lactones of gluconic acid, galactonic acid, lactones of galactonic acid, galactaric acid, lactones of galactaric acid, galactonic acid, glucoheptonic acid, lactones of glucoheptonic acid, or combinations thereof.

6. The biocide of claim 1 , wherein the one or more sugar oxidation products comprise a mixture of gluconic acid and glucaric acid.

7. The biocide of claim 6, wherein the ratio of gluconic acid:glucaric acid may range from about 0.1 : 10 to about 10:0.1.

8. The biocide of claim 1 , wherein the one or more sugar oxidation products is present in an amount of from about 0.1 wt.% to about 99 wt.% based on the total weight of the biocide.

9. The biocide of claim 1 , wherein the organic acid is selected from the group consisting essentially of citric acid, lactic acid, hydrochloric acid, malic acid, acetic acid, formic acid, propionic acid, butyric acid, sorbic acid, fumaric acid, tartaric acid, benzoic acid, succinic acid, ascorbic acid, adipic acid, quinic acid, isocitric acid, shikimic acid, maleic acid and combinations thereof.

10. The biocide of claim 1 , wherein the organic acid is present in an amount from about 0.1 wt.% to about 99 wt.% based on the total weight of the biocide.11 . The biocide of claim 1 , wherein the augmenter comprises aldehydes, quaternary ammonium compounds, active halogen compounds, phosphonium salts, oxidizers, hydrogen peroxide, peracetic acid, bleach, organosulfur compounds, phenolics, organometallics, isothiazolinone, isothiazolothione, derivatives thereof or combinations thereof.

12. The biocide of claim 1 , wherein the augmenter is present in an amount of from about 0.5 wt.% to about 20 wt.% based on the total weight of the biocide.

13. The biocide of claim 1 , excluding a mineral acid.

14. A method of disinfecting a surface, the method comprising: applying to the surface a biocide composition comprising:(i) chlorine dioxide or salt thereof;(ii) one or more sugar oxidation products; and(iii) at least one of the compounds selected from the group consisting of organic acids, augmenters, and solvents.

15. The method of claim 14, wherein the one or more sugar oxidation products comprise aldonic acid, uronic acid, aldaric acid, or combinations thereof.

16. The method of claim 14, wherein the organic acid is selected from the group consisting essentially of citric acid, lactic acid, hydrochloric acid, malic acid, acetic acid, formic acid, propionic acid, butyric acid, sorbic acid, fumaric acid, tartaric acid, benzoicacid, succinic acid, ascorbic acid, adipic acid, quinic acid, isocitric acid, shikimic acid, maleic acid and combinations thereof17. The method of claim 14, wherein the augmenter comprises aldehydes, quaternary ammonium compounds, active halogen compounds, phosphonium salts, oxidizers, hydrogen peroxide, peracetic acid, bleach, organosulfur compounds, phenolics, organometallics, isothiazolinone, isothiazolothione, derivatives thereof or combinations thereof.

18. The method of claim 14, wherein the surface comprises sinks, countertops, food service areas, meat processing plants, medical equipment or combinations thereof.

19. A disinfectant comprising the biocide of claim 1 .

20. The disinfectant of claim 19, wherein the disinfectant comprises hand cleansers, mouthwashes, surgical scrubs, body splashes, hand sanitizer gels, hand sanitizer foams, disinfectant wipes, emulsions, lotions, creams, pastes, or combinations thereof.21 . A method of preparing a biocide, the method comprising: combining (i) chlorine dioxide or salt thereof, (ii) one or more sugar oxidation products, and (iii) at least one of the compounds selected from the group consisting of organic acids, augmenters and solvents to form a biocide composition; acidifying the one or more sugar oxidation products in the biocide composition; and maintaining the chlorine dioxide or salt thereof in solution based on the acidification of the one or more sugar oxidation products.

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