WO2008140469A2

WO2008140469A2 - Antimicrobial compositions, methods and systems

Info

Publication number: WO2008140469A2
Application number: PCT/US2007/021941
Authority: WO
Inventors: Mervyn L. De Souza; Jill Louise Zullo; James C. Anderson; Richard L. Pederson; Yann Schrodi
Original assignee: Elevance Renewable Sciences Inc
Current assignee: Elevance Renewable Sciences Inc
Priority date: 2006-10-13
Filing date: 2007-10-15
Publication date: 2008-11-20
Anticipated expiration: 2009-04-13
Also published as: WO2008140469A3

Abstract

Antimicrobial compositions comprising a combination of a first antimicrobial agent of Formula I and a second antimicrobial agent of Formula IV are reported. The antimicrobial compositions including a combination of antimicrobial agents of Formula (I) and Formula (IV) are effective as an antimicrobial agent with MIC levels of about 0.1% or less against certain fungi. Also reported are antimicrobial products such as consumer products, industrial preparations, and food and feed formulations.

Description

ANTIMICROBIAL COMPOSITIONS, METHODS AND SYSTEMS

CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U.S. Provisional Application having

Serial No. 60/851,472, filed October 13, 2006, and entitled ANTIMICROBIAL COMPOSITIONS, METHODS AND SYSTEMS, the disclosure of which is incorporated herein by reference.

BACKGROUND Many types of substrates and water-containing compositions and formulations, when exposed to common environmental conditions, are prone to attack, spoilage and various kinds of destruction by a variety of species of microorganisms, including fungi, yeast, bacteria and algae. As a result, there has long been a great need for effective and economical means to protect, for extended periods of time, commercial compositions and formulations from the deterioration and destruction caused by such microorganisms.

Materials that can benefit from protection against such microorganisms include, for example, materials such as paints and other coating formulations, surfactants, emulsions and resins, wood, adhesives, caulks, sealants, leather, textiles, and the like. Other important commercial materials such as polymer dispersions or aqueous latex paints, clay and mineral suspensions and metalworking fluids (MWF), are also prone to degradation by the action of objectionable microorganisms that can spoil and significantly impair the usefulness of such compositions. Such degradation may produce, for example, changes in pH values, gas formation, discoloration, the formation of objectionable odors, and/or changes in rheological properties.

Antimicrobials can also be useful during the processing of materials. For example, animal skins are susceptible to attack by microorganisms both prior to and after the tanning process. Prior to the tanning process, bactericides can be used in the brine solutions to prevent bacteria from damaging the hide grain. After the tanning process, the so called wet blue hides can be subject to fungal attack during storage or transport, and fungicides can be used to inhibit this fungal growth. Antimicrobials can also be used in the fat liquors and leather finishing products to prevent the growth of bacteria, fungi and yeast.

A great deal of effort has gone into developing a wide variety of materials which, to various degrees, are effective in retarding or preventing the growth of, and accompanying destruction caused by, such microorganisms in a variety of circumstances. Such antimicrobial materials include halogenated compounds, organometallic compounds, quaternary ammonium compounds, phenolics, metallic salts, heterocyclic amines, formaldehyde adducts, organosulfur compounds, and the like. When selecting antimicrobial agents for a particular application, an initial consideration is efficacy. Antimicrobial efficacy can be assessed in various ways, including spectrum of activity (e.g., effectiveness in controlling growth of bacteria, fungi and the like), rate of kill of microorganisms, residual antimicrobial effect, and the like. The specific requirements for antimicrobial agents can vary according to the intended application (e.g., sanitizer, disinfectant, sterilant, aseptic packaging treatment, etc.) and the applicable public health requirements.

In addition to efficacy, other limitations can restrict the usefulness of certain antimicrobial agents. For example, the stability, physical properties, toxicological profile, regulatory considerations, economic considerations or environmental concerns can render a particular antimicrobial agent unsuitable for a particular use.

Many known antimicrobial agents (such as iodophors, peracids, hypochlorites, chlorine dioxide, ozone, and the like) have a broad spectrum of antimicrobial properties. However, these agents sometimes have inadequate activity against fungi. Killing, inactivating, or otherwise reducing the active population of fungi on surfaces or within formulations can be particularly difficult. The unique chemical composition of fungal cells, especially mold spores, makes them more resistant to chemical and physical agents than are other microorganisms. This resistance can be particularly troublesome when the spores or fungi are located on surfaces or in formulations that come in contact with food and/or beverages. In addition, this resistance can be troublesome when the fungi are contained within products that come in direct contact with a consumer (e.g., personal care products). Certain fatty acids and polyol esters have been identified as possessing some antimicrobial activity. See, Kabara, J.J., et al., "Antimicrobial Lipids: Natural and Synthetic Fatty Acids and Monoglycerides," Lipids, 12(9) 753-759 (1977). Kabara et al. noted that the majority of fatty acids and derivatives were most effective against Gram positive bacteria and yeasts, but not against Gram negative bacteria. Moreover, the authors reported that the saturated Cn fatty acids tested were more active than the unsaturated derivatives.

Therefore, a continuing need exists for new antimicrobial compositions that can be added to the arsenal of weapons used to fight the proliferation of microbes on and in consumer and industrial products.

SUMMARY

The invention provides antimicrobial compositions that comprise a combination of a first antimicrobial agent of Formula I and a second antimicrobial agent of Formula IV:

(I)

(IV)

In some aspects, the first antimicrobial agent and second antimicrobial agent are present in a ratio of 1 : 1 by weight within the composition. In some embodiments, the first antimicrobial agent and second antimicrobial agent are present in the composition in a combined amount in the range of 0.01% to 0.1% by weight of said composition. The antimicrobial composition can be provided with a pH in the range of 5 to 9. In accordance with aspects of the invention, the antimicrobial compositions can be formed by metathesis.

In some aspects, the antimicrobial compositions including a combination of antimicrobial agents of Formula (I) and Formula (IV) are effective as an antimicrobial agent with MIC levels of about 0.1% or less, against fungi selected from Aspergillus parasiticus, Trichoderma virens, Aureobasidium pullulans, Aspergillus flavus, Cladosporium cladosporiodes, Aspergillus flavus, Aspergillus oryzae, Aspergillus parasiticus, Ulocladium atrum, Candida albicans, Alternaria alternata, Stachybotrys chartarum, Aspergillus niger, and combinations thereof. In additional aspects, the invention provides antimicrobial products comprising the compositions described herein. The antimicrobial products can include consumer products, industrial preparations, or a food or feed formulations.

In further aspects, the invention provides antimicrobial compositions comprising a combination of a first antimicrobial agent and a second antimicrobial agent. The first antimicrobial agent can be selected from antimicrobial agents of Formula I, Formula II, Formula III, or a combination of any two or more of these. The second antimicrobial agent can be selected from antimicrobial agents of Formula IV, Formula V, Formula VI, or a combination of any two or more of these. In other embodiments, the second antimicrobial agent can be selected from known antimicrobial agents.

In additional aspects, the invention provides industrial preparations comprising an effective amount of an antimicrobial composition comprising 9- undecenoic acid, a salt of 9-undecenoic acid, an ester of 9-undecenoic acid, or a combination thereof. In some embodiments, the industrial preparations can be formed by metathesis.

It has been surprisingly discovered that certain embodiments of the invention can provide antimicrobial agents having efficacy against a broad spectrum of microorganisms, even at pH levels well above the neutral range, such as 8 and higher. This is significant, since many conventional antimicrobial agents lose efficacy at neutral pH levels and higher.

In method aspects, the invention provides methods for controlling bacterial growth in an environment, the method comprising contacting the environment with an effective amount of an antimicrobial composition that comprises a combination of a first antimicrobial agent of Formula I and a second antimicrobial agent of Formula IV. The environment can be selected from consumer products, industrial preparations, and food or feed formulations. In additional method aspects, the invention provides methods for controlling bacterial growth in an environment comprising contacting the environment with a composition comprising a first antimicrobial agent of Formula I and a second antimicrobial agent of Formula IV as active ingredients in a ratio of 1 : 1 by weight. In some aspects, the bacterial growth comprises Gram positive bacteria and Gram negative bacteria.

In further method aspects, the invention provides methods for controlling fungal growth in an environment comprising contacting the environment with a composition comprising a first antimicrobial agent of Formula I and a second antimicrobial agent of Formula IV as active ingredients in a ratio of 1 : 1 by weight. BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate several aspects of the invention and together with the description of the preferred embodiments, serve to explain the principles of the invention. A brief description of the drawings is as follows: FIGS. 1-13 are graphs illustrating antimicrobial properties for compositions in accordance with aspects of the invention, wherein composition identification and concentration (% by weight) are represented on the X-axis, and percentage fungal coverage (%) is represented on the Y-axis.

FIG. 14 is a graph illustrating antimicrobial properties for compositions in accordance with aspects of the invention, and compared to sodium benzoate, wherein time (days) is represented on the X-axis, and microbial reduction (Logi₀) is represented on the Y-axis.

DETAILED DESCRIPTION

The embodiments of the invention described below are not intended to be exhaustive or to limit the invention to the precise forms disclosed in the following detailed description. Rather, the embodiments are chosen and described so that others skilled in the art can appreciate and understand the principles and practices of the invention.

Throughout the specification and claims, percentages are weight/volume and temperatures in degrees Celsius unless otherwise indicated.

The present invention relates to antimicrobial compositions, methods and systems that comprise one or more linear, monounsaturated fatty acids or derivatives thereof. Advantageously, the antimicrobial compositions can be produced by metathesis of naturally occurring oils such as soybean or canola oils. More particularly, in one aspect, the invention relates to antimicrobial compositions comprising 9-undecenoic acid (also known as 9-hendecenoic acid, 9-undecylenic acid, and sometimes referred to herein as "9-UDA"), salts of 9-undecenoic acid, esters of 9-undecenoic acid, or a combination of any of these.

In other aspects, the invention relates to antimicrobial compositions comprising a first antimicrobial agent selected from 9-undecenoic acid, a salt of 9- undecenoic acid, an ester of 9-undecenoic acid, or a combination of any two or more of these, and a second antimicrobial agent selected from 9-decenoic acid (also known as caproleic acid and sometimes referred to herein as 9-DA), a salt of 9- decenoic acid, an ester of 9-decenoic acid, or a combination of any two or more of these. In some embodiments, the antimicrobial composition can comprise 9- undecenoic acid and 9-decenoic acid. In one illustrative embodiment, the antimicrobial composition can comprise 9-undecenoic acid and 9-decenoic acid in a 1 : 1 ratio.

It has been discovered that 9-undecenoic acid, salts of 9-undecenoic acid, and esters of 9-undecenoic acid have unexpected antimicrobial activity. Under standard antimicrobial tests, these agents have been found to inhibit the growth of and/or eliminate various Gram-positive bacteria and fungi, and, surprisingly, Gram- negative bacteria. As will be apparent upon review of this disclosure, the antimicrobial agents can be formulated to provide a variety of antimicrobial compositions as end products. The antimicrobial compositions can be in concentrated form or from a container, from an aerosol container, or from a container as a crystal, powdered or otherwise semi-solid or solid form, or as a liquid. The antimicrobial compositions can be applied in various formulations such as, but not limited to, solutions, gels, creams, lotions, stick, balm, sprays, powders, granules, emulsions, and the like in either aqueous or nonaqueous vehicles. The antimicrobial agents and compositions thus have utility in a wide variety of industrial and consumer applications.

In one compositional aspect, the antimicrobial agent can be a monounsaturated fatty acid of 1 1 carbon atoms that can be provided as an acid, salt or ester. In some embodiments, the antimicrobial agent is 9-undecenoic acid having the structure shown in Formula (I):

(I)

Generally, 9-undecenoic acid (also known as 9-hendecenoic acid or 9- undecylenic acid) has a molecular weight of approximately 184, and a boiling point of approximately 129°C/1 mm Hg. 9-undecenoic acid has been found to be particularly effective as an antimicrobial agent, with a broad spectrum of efficacy. Further, 9-undecenoic acid exhibits low toxicity to humans and can be synthesized utilizing naturally-occurring starting materials.

In some embodiments, the antimicrobial agent can be a salt of 9-undecenoic acid having the structure shown in Formula (II): κ⁺ⁿ [Rr]_n

where Rl^" is ; n is an integer, for example, ranging from 1 to 4; and K⁺" is a +n charged cation.

When n=l, representative examples include group IA cations (such as Li⁺, Na⁺, K⁺, and Ag⁺), and a variety of ammonium salts, such as those including ammonium (NH₄ ⁺) or quaternary ammonium (NR₄ ⁺) as cations. When n=2, representative examples include Ca²⁺, Mg²⁺, Zn²⁺, Cu²⁺, and Fe²⁺. When n=3, representative examples include Al³⁺, Fe³⁺ and Ce³⁺. When n=4, representative examples include Ce⁴⁺. In still further embodiments, the anion/cation pair (K⁺ⁿ [Rl^" ]_n) can bind a known antimicrobial agent, such as those described elsewhere herein as useful for the second antimicrobial agent and/or known antimicrobial agent. In some embodiments, the anion/cation pair can serve a dual role, such as, for example, as antimicrobial agent and emulsifier or compatibility aid.

In some embodiments, the antimicrobial agent can be an ester of 9- undecenoic acid having the structure shown in Formula (III):

(III)

where — R3 is an organic group. As used herein, "organic group" can be an aliphatic group, an alicyclic group, or an aromatic group. Organic groups can include heteroatoms (such as O, N, or S atoms), as well as functional groups (such as carbonyl groups). In the context of the invention, the term "aliphatic group" means a saturated or unsaturated, linear or branched, hydrocarbon group. This term is used to encompass alkyl, alkenyl, and alkynyl groups, for example. The term "alkyl group" means a monovalent, saturated, linear or branched, hydrocarbon group. The term "alkenyl group" means a monovalent, saturated, linear or branched, hydrocarbon group with one or more carbon-carbon double bonds. The term "alkynyl group" means a monovalent, unsaturated, linear or branched, hydrocarbon group with one or more carbon-carbon triple bonds. An alicyclic group is an aliphatic group arranged in one or more closed ring structures. The term is used to encompass saturated (such as cycloparaffϊns) or unsaturated (cycloolefins or cycloacetylenes) groups. An aromatic group or aryl group is an unsaturated cyclic hydrocarbon having a conjugated ring structure. Included within aromatic or aryl groups are those possessing both an aromatic ring structure and an aliphatic group or an alicyclic group. In some aspects,

— R3 can be selected to serve a dual role as an antimicrobial agent and emulsifier or compatibility aid. For example, embodiments where — R3 is a C₈ to C_]6 alkyl group may provide emulsification properties.

In some embodiments, — R3 is an alkyl group, for example, a Ci to Ci₈ alkyl group or a Ci to C₆ alkyl group. Representative examples include methyl, ethyl, propyl (n-propyl or i-propyl) butyl (n-butyl or t-butyl), heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, and the like. In other embodiments, -R3 is an alkenyl group, for example, a C₉ alkenyl group, such as, -CH₂-CH₂-CH₂-CH₂-CH₂-CH₂-CH₂- CH₂=CH₂.

In still further embodiments, — R3 can comprise a known antimicrobial agent, such as (but not limited to) antimicrobial agents described elsewhere herein as useful as first antimicrobial agents and/or known antimicrobial agents.

In still further embodiments, — R3 can be selected such that the structure of formula (III) is a monoglyceride, diglyceride, triglyceride, or a phospholipid. For example, in some embodiments — R3 is -CH₂-CHOR'-CH₂OR", where R' and R" are, independently, selected from fatty acids, phosphate groups, or hydrogen. The choice of a first antimicrobial agent from Formulae (I), (II) and/or (III) will depend upon the end use of the composition, including formulation considerations, target microorganisms, and the like. It will be readily appreciated that some combination of 9-undecenoic acid and salt can occur within a composition by virtue of the pH level of the composition. In some aspects, the invention contemplates use of antimicrobial compositions composed of the agents of Formulae (I), (II) and/or (III) alone. In these aspects, antimicrobial properties are provided primarily by the agent of Formulae (I), (II) and/or (III). To the extent any additional ingredients are included in the antimicrobial composition, such additional ingredient(s) do not contribute a significant antimicrobial property to the composition as a whole.

Alternatively, the inventive antimicrobial compositions can comprise a combination of a first antimicrobial agent and a second antimicrobial agent, wherein the first antimicrobial agent is selected from antimicrobial agents of Formulae (I), (II) and/or (III). In accordance with these aspects, the second antimicrobial agent can be selected from 9-decenoic acid, salts of 9-decenoic acid, and/or esters of 9- decenoic acid. In still further aspects, antimicrobial compositions that comprise a combination of agents can include more than one of the first antimicrobial agents and/or second antimicrobial agents. These combinational aspects will now be described.

In some aspects, the second antimicrobial agent can be a monounsaturated fatty acid of 10 carbon atoms that can be provided as an acid, salt or ester. In some embodiments, the antimicrobial agent is 9-decenoic acid having the structure shown in Formula (IV):

(IV)

Generally, 9-decenoic acid is a colorless liquid having a molecular weight of approximately 170, boiling point of approximately 269⁰C to 271°C/760 mm, specific gravity of 0.912 to 0.920 at 25⁰C, and refractive index of 1.44 to 1.45 at 2O⁰C. Generally, 9-decenoic acid is soluble in water at biocidal levels, and soluble in alcohol.

In some embodiments, the second antimicrobial agent is an ester of 9- decenoic acid having the structure shown in Formula V:

(V)

where — R is an organic group. As used herein, "organic group" can be an aliphatic group, an alicyclic group, or an aromatic group. Organic groups can include heteroatoms (such as O, N, or S atoms), as well as functional groups (such as carbonyl groups). In the context of the invention, the term "aliphatic group" means a saturated or unsaturated, linear or branched, hydrocarbon group. This term is used to encompass alkyl, alkenyl, and alkynyl groups, for example. The term "alkyl group" means a monovalent, saturated, linear or branched, hydrocarbon group. The term "alkenyl group" means a monovalent, saturated, linear or branched, hydrocarbon group with one or more carbon-carbon double bonds. The term "alkynyl group" means a monovalent, unsaturated, linear or branched, hydrocarbon group with one or more carbon-carbon triple bonds. An alicyclic group is an aliphatic group arranged in one or more closed ring structures. The term is used to encompass saturated (such as cycloparaffins) or unsaturated (cycloolefms or cycloacetylenes) groups. An aromatic group or aryl group is an unsaturated cyclic hydrocarbon having a conjugated ring structure. Included within aromatic or aryl groups are those possessing both an aromatic ring structure and an aliphatic group or an alicyclic group. In some aspects, — R can be selected to serve a dual role as an antimicrobial agent and emulsifier or compatibility aid. For example, embodiments where — R is a C₈ to Ci₆ alkyl group may provide emulsification properties.

In some embodiments, — R is an alkyl group, for example, a Ci to Ci₈ alkyl group or a Ci to C₆ alkyl group. Representative examples include methyl, ethyl, propyl (n-propyl or i-propyl) butyl (n-butyl or t-butyl), heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, and the like. In other embodiments, -R is an alkenyl group, for example, a C₉ alkenyl group, such as, -CH₂-CH₂-CH₂-CH₂-CH₂-CH₂-CH₂- CH₂=CH₂.

In still further embodiments, — R can comprise a known antimicrobial agent, such as (but not limited to) antimicrobial agents described elsewhere herein as useful as first antimicrobial agents and/or known antimicrobial agents.

In some aspects, utilization of a 9-decenoic acid ester, as described in Formula (V), can be advantageous, as these compounds can be pH independent in various formulations. In some embodiments of the invention, the second antimicrobial agent is a salt of 9-decenoic acid having the structure shown in Formula (VI):

K⁺ⁿ [RT]_n (VI)

where R2^' is

n is an integer, for example, ranging from 1 to 4; and K⁺" is a +n charged cation.

When n=l, representative examples include group IA cations (such as Li⁺, Na⁺, K⁺, and Ag⁺), and a variety of ammonium salts, such as those including ammonium (NH₄ ⁺) or quaternary ammonium (NR₄ ⁺) as cations. When n=2, representative examples include Ca²⁺, Mg²⁺, Zn²⁺, Cu²⁺, and Fe²⁺. When n=3, representative examples include Al³⁺, Fe³⁺ and Ce³⁺. When n=4, representative examples include Ce⁴⁺. In still further embodiments, the anion/cation pair (K⁺" [R2^~ ]_n) can bind a known antimicrobial agent, such as those described elsewhere herein as useful for the second antimicrobial agent. In some embodiments, the anion/cation pair can serve a dual role, such as, for example, as antimicrobial agent and emulsifier or compatibility aid.

In some aspects, utilization of a salt of 9-decenoic acid, as described in Formula (VI) can be advantageous, for example, by being more soluble in aqueous systems, less volatile, and/or easier to handle as compared to the acid or ester forms of 9-decenoic acid. The choice of an antimicrobial agent from Formulae (IV), (V) and/or (VI) will depend upon the end use of the composition, including formulation considerations, target microorganisms, and the like.

It will be readily appreciated that some combination of 9-decenoic acid and salt can occur within a composition by virtue of the pH level of the composition. For example, at calculated pKa of about 4.78 (± 0.1), a composition will be composed of approximately equal amounts of 9-decenoic acid and salt of 9-decenoic acid (50/50 9-deceonic acid/salt). In some embodiments, presence of 9-decenoic acid (at some levels in the composition) can be particularly advantageous. It has been surprisingly found that antimicrobial compositions comprising a combination of a first antimicrobial agent of Formula (I), (II) and/or (III) and a second antimicrobial agent of Formulae (IV), (V) and/or (VI) provide antimicrobial compositions having superior activity against a wide range of microorganisms, including Gram-positive bacteria and fungi, as well as Gram-negative bacteria. These antimicrobial compositions can, in some aspects, provide special value in a broad range of industrial and consumer applications due to their low oral, skin, eye and aquatic toxicity as well as low irritation properties. This ability to deliver efficacious antimicrobial activity while providing low toxicity and irritation properties can be particularly valuable in applications such as consumer products, where toxicity and environmental effects can be a concern. Further, in some aspects, the antimicrobial compositions can be synthesized by metathesis from natural products, thereby providing a synthesis route involving renewable resources as starting materials. In still further aspects, the invention can provide antimicrobial compositions comprising a combination of any one or more of the antimicrobial agents of Formula (I), (II) and/or (III), and a second antimicrobial agent that comprises one or more known antimicrobial agents. In these combination aspects, the invention can provide commercial products with significantly lower toxicity than current products that include the known antimicrobial agent(s) alone. In this discussion, the term "toxicity" is used in its broadest sense. It may mean toxicity to people per se, harm or damage to the environment, indirect harm to people via environmental damage, and/or simply skin or mucous membrane irritation. In other words, the antimicrobial agents of Formula (I), (II) and/or (III) can replace at least a portion of the known antimicrobial agent, thus providing lower toxicity of the overall product. It is known that products such as Kathon™, Triclosan™ and others can have toxicity effects in current formulations. Thus, by replacing at least a portion of these substances with the antimicrobial agent of Formula (I), (II) and/or (III), an end product with lower overall toxicity can be achieved. In some aspects, this lower toxicity can be accomplished while maintaining efficacy of the antimicrobial agents as a whole.

Any antimicrobial agent that is compatible with the antimicrobial agent of Formula I, II and/or III can be utilized as a known antimicrobial agent in accordance with these embodiments. By "compatible" is meant the antimicrobial agents can be mixed together without adversely affecting one or more useful properties of the individual antimicrobial agents, for example, the ability of the antimicrobial agents to be formulated into a stable composition, such that the individual antimicrobial agents remain in the composition without separating out over time (such as by precipitation).

In these aspects, the antimicrobial composition can provide one or more of the following benefits: broadened spectrum of activity; use of lower concentrations of individual antimicrobial agents, thus minimizing irritancy potential; reduced risk of the development of microbial resistance; synergistic effect, giving greater than the anticipated simple additive effect; potentiation, or activity of an antimicrobial agent^' is enhanced by combination with a microbiologically inactive or weakly active agent such as EDTA or Monolaurin; and/or improved long-term stability of product by combining a labile, strongly biocidal agent with a stable longer-acting agent. In some embodiments, when the known antimicrobial agent exhibits higher oral, acute, or aquatic toxicity or higher irritation, formulating a composition that includes a reduced amount of the known antimicrobial agent can provide significant toxicity and/or environmental benefit.

Illustrative known antimicrobial agents include, but are not limited to: phenol derivatives (such as halogenated phenols, for example 3,5-dichlorophenol, 2,5-dichlorophenol, 3,5-dibromophenol, 2,5-dibromophenol, 2,5- or 3,5-dichloro-4- bromophenol, 3,4,5-trichlorophenol, 3,4,5-tribromophenol, phenylphenol, 4-chloro- 2-phenylphenol, 4-chloro-2-benzylphenol); dichlorophene, hexachlorophene; aldehydes (such as formaldehyde, glutaraldehyde, salicylaldehyde); alcohols (such as phenoxyethanol); antimicrobial carboxylic acids and derivatives thereof such as parabens, including methyl, propyl and benzyl parabens, and the like; organometallic compounds (such as tributyl tin derivatives); iodine compounds (such as iodophors, idonium compounds); quaternary ammonium compounds (such as benzyldimethyldodecylammonium chloride, dimethyldidecylammonium chloride, benzyl-di-(2-hydroxyethyl)-dodecylammonium chloride, dimethyldidecylammonium chloride, benzyl-di-(2-hydroxyethyl)- dodecylammonium chloride)); sulfonium and phosphonium compounds; mercapto compounds and the alkali metal, alkaline earth metal and heavy metal salts thereof, such as 2-mercaptopyridine-N-oxide and the sodium, zinc and copper salts thereof, 3-mercaptopyridazine-2-oxide, 2-mercaptoquinoxaline-l -oxide, 2- mercaptoquinoxaline-di-N-oxide, and also the symmetrical disulfides of these mercapto compounds; ureas (such as tribromocarbanilide or trichlorocarbanilide); dichlorotrifluoromethyldiphenylurea; tribromosalicylanilide; 2-bromo-2-nitro- l,3dihydroxypropane; dichlorobenzoxazolone; chlorohexidine; isothiazolone and benzisothiazolone derivatives. Further illustrative second antimicrobial agents include Triclosan™ (2,4,4'-trichloro-2'-hydroxydiphenyl ether, also known as 5- chloro-2-(2,4-dichlorophenoxy)phenol) and Kathon™ (methyl chloroisothiazolinone and methyl isothiazolinone in various ratios).

Typically, when an antimicrobial agent of Formula (I), (II) and/or (III) is combined with a known antimicrobial agent, the chemical reactivity of the ingredients is taken into consideration during formulation of the product. For example, the agent of Formula I can, in some instances (for example, 9-undecenoic acid) be incompatible with a certain known antimicrobial agent, but in other instances (for example, when formulated as a salt) will mix well.

For each of the applications described herein, an "antimicrobial agent content" will be described. The antimicrobial agent content is the total amount of antimicrobial agent (or agents), based on total weight of the composition, provided in the product. For example, when only one antimicrobial agent is selected from the agents defined in Formulae (I), (II) and/or (III), then the antimicrobial agent content is the amount of the agent included in the product, based on total weight of the product. In another example, if a combination of two antimicrobial agents (A and B) is provided in a composition, then the antimicrobial agent content is the total of A + B in the composition.

In some aspects, the invention provides antimicrobial compositions that include a combination of any two or more of the antimicrobial agents of Formulae (I), (II) and/or (III). In these aspects, the relative amounts of each antimicrobial agent can be selected to provide an overall antimicrobial effect. In some aspects, a combination of acid and salt can occur by virtue of the formulation parameters. In some embodiments, when the antimicrobial composition comprises a combination of two antimicrobial agents, the antimicrobial agents can be provided in a 1 : 1 ratio. In some aspects, when the antimicrobial composition comprises a combination of two antimicrobial agents, the antimicrobial agents can be provided in a ratio in the range of about 1 : 10 to about 10: 1, or in the range of about 1 :5 to about 5: 1, or in the range of about 1 : 1 to about 3: 1. Synthesis

Embodiments of the antimicrobial agents of Formulae (I)-(VI) may be prepared, for example, by the cross-metathesis of propylene with a fatty acid, a fatty ester, a glyceride (e.g., triglyceride) or a mixture thereof. The 9-undecenoic acid (or salt or ester thereof) and/or 9-decenoic acid (or salt or ester thereof) can be separated from the starting material and other components using known techniques for separation, including, for example, distillation or chromatography. A useful synthetic route is reported, for example, in U.S. Provisional Patent Application 60/851,693, filed October 13, 2006, and entitled "SYNTHESIS OF TERMINAL ALKENES FROM INTERNAL ALKENES VIA OLEFIN METATHESIS",

Schrodi, et al). In some aspects, the antimicrobial agents can be produced by cross metathesis of propylene with a naturally occurring oil such as soybean or canola oil. In some embodiments the antimicrobial composition comprises 9-undecenoic acid (or salt or ester thereof) and 9-decenoic acid (or salt or ester thereof) in weight ratio of about 0.2: 1 to about 2: 1. In other embodiments, the antimicrobial composition comprises 9-undecenoic acid (or salt or ester thereof) and 9-decenoic acid (or salt or ester thereof) in a weight ratio of about 1 : 1.

In some embodiments, the metathesis reaction product comprises a mixture of 9-undecenoic acid (or a salt thereof) and a second antimicrobial agent selected from 9-decenoic acid, a salt of 9-decenoic acid, an ester of 9-decenoic acid, or a mixture thereof. In these cases, separation of the product mixture is not required.

Non-metathesis routes to the production of 9-decenoic acid include, for example, the method reported by Black et al., in Unsaturated Fatty Acids. Part I. The Synthesis of Erythrogenic (Isantic) and Other Acetylenic Acids; Journal of the Chemical Society, Abstracts (1953) at pp. 1785-93. As reported by Black, a solution of chromium trioxide (19.0 g) in water (20 cc) was added over 1.5 hours with vigorous stirring to a solution of 1 : 1 diphenylundeca-l : 10-diene (25.0 g) in glacial acetic acid (250 cc) at 35°C. After an additional 0.5 hour stirring, acetic acid (70 cc) was removed under reduced pressure, and 2N sulphuric acid (500 cc) was added to the residue. Extraction of the product with benzene and isolation of the acidic fraction yielded 9-decenoic acid (8.5 g). 9-decenoic acid can also be obtained commercially, for example, from

Pyrazine Specialties, Inc. (Athens, GA). Whether produced by metathesis or another technique, 9-decenoic acid may be converted to its esters (see, formula V) and salts (see, formula VI) according to known synthetic techniques for converting carboxylic acid compounds into esters or salts, respectively. Formulation

Antimicrobial compositions in accordance with the invention can be formulated by mixing or dispersing the active ingredients in a selected proportion with a vehicle (e.g., liquid) for dissolving or suspending the active components. The vehicle may contain a diluent, an emulsifϊer, a wetting agent or the like, as typically used in formulation of antimicrobial compositions.

Illustrative uses of the antimicrobial compositions of the invention include the protection of paint, coatings, adhesives, aqueous industrial products, leather, wood products, inks, sealants, caulkings, metalworking fluids, petroleum applications, water treatments, textiles, polymer emulsions, and the like. Additional exemplary uses include personal care products (such as cosmetics and toiletries) and food or feed applications. The compositions of the invention can be provided as wettable powders, liquid mixtures such as dispersions, emulsions, microemulsions or in any other suitable product form that is desirable or most useful for a particular application. When preparing formulations of the invention for specific applications, the composition also will likely be provided with adjuvants conventionally employed in compositions intended for such applications, such as organic binding agents, additional fungicides, auxiliary solvents, processing additives, fixatives, plasticizers, UV stabilizers or stability enhancers, water soluble or water insoluble dyes, color pigments, siccatives, corrosion inhibitors, antisettlement agents, anti-skinning agents, extenders, fillers, thickeners, driers, plasticizers, wetting agents, emulsifiers, free-thaw stabilizers, coalescents, dispersants, defoamers, and the like. These adjuvants can be included in the amounts ordinarily used for these purposes.

In another aspect, the invention provides methods for controlling bacterial and/or fungal growth in an environment, the method comprising contacting the environment with an effective amount of an antimicrobial comprising 9-undecenoic acid, a salt of 9-undecenoic acid, or a combination thereof. The environment can comprise a consumer product, industrial preparation, and/or food or feed formulation.

The "effective amount" of antimicrobial composition that is desirable in a given consumer product, industrial preparation, or food or feed formulation can be determined by one of skill in the art using various known techniques and methods. Performance of a given antimicrobial composition in a product, preparation or formulation can be evaluated, for example, as described below.

The antimicrobial compositions of the invention can provide preservative, antiseptic, sanitizing, and/or disinfectant features to a wide variety of end products. Some illustrative common applications that can benefit from the antimicrobial properties described herein (whether they be preservative, antiseptic, sanitizing or disinfectant properties) include industrial and consumer applications, as well as food and feed (i.e., livestock feed) applications. According to the invention, antimicrobial compositions including 9- undecenoic acid, a salt of 9-undecenoic acid, and/or an ester of 9-undecenoic acid are useful in controlling microbial growth. As discussed herein, control of microbial growth can involve preventing propagation of microbes within an environment, and/or elimination of many or all pathogenic microorganisms in an environment. For instance, 9-undecenoic acid, salts of 9-undecenoic acid and/or esters of 9- undecenoic acid can be incorporated into compositions to protect the compositions themselves from microbial attack (i.e., as preservatives). In these embodiments, 9- undecenoic acid, salts of 9-undecenoic acid and/or esters of 9-undecenoic acid can be utilized as an auxiliary agent within the composition to be preserved and/or protected from microbial attack and/or spoilage.

Furthermore, 9-undecenoic acid, salts of 9-undecenoic acid and/or esters of 9-undecenoic acid can be employed as a disinfectant. In these embodiments, 9- undecenoic acid, salts of 9-undecenoic acid and/or esters of 9-undecenoic acid can be incorporated as an active ingredient in a variety of cleansing agent products for household and industrial use. As used herein, the term "disinfect" shall mean the elimination of many or all pathogenic microorganisms in an environment with the possible exception of bacterial endospores. As used herein, the term "sanitize" shall mean the reduction of contaminants in the inanimate environment to levels considered safe according to public health ordinance, or that reduces the bacterial population by significant numbers where public health requirements have not been established. An at least 99% reduction in bacterial population within a 24 hour time period is deemed "significant."

In some aspects, the invention provides antimicrobial compositions having utility in industrial applications. Some illustrative industrial applications include wood preservation (e.g., prevention or reduction in slime formation and/or wood rotting), preservation of polymer emulsions, surface coating applications (e.g., paints and coatings), metalworking fluids (MWF), petroleum production and preservation (oil well simulation, crude oil production, jet fuels), industrial water treatment systems (e.g., cooling water), pulp and paper production, leather production, and textile production and protection. For purposes of illustration, some industrial applications will be described with, some detail. One of skill in the art will readily be able to apply the principles of these exemplary embodiments to other industrial applications, given the teachings herein. Surface Coatings

In some aspects, the invention provides methods for protecting surface coating compositions (such as water-based paint or coating) from in-can spoilage or film degradation due to the action of microorganisms. The method comprises incorporating into the surface coating composition an antimicrobial composition comprising 9-undecenoic acid, a salt of 9-undecenoic acid, an ester of 9-undecenoic acid, or a combination thereof. In other aspects, the method comprises incorporating into the surface coating composition an antimicrobial composition comprising 9- undecenoic and, a salt of 9-undecenoic acid, an ester of 9-undecenoic acid, or a combination thereof, in combination with a second antimicrobial agent. The second antimicrobial agent can comprise 9-decenoic acid, a salt of 9-decenoic acid, an ester of 9-decenoic acid, or a combination thereof, and/or a known antimicrobial agent.

In some embodiments, the methods protect the surface coating composition from in-can spoilage from the action of microorganisms. In other embodiments, the methods protect the surface coating composition from film degradation due to the action of microorganisms. In an exemplary embodiment, the methods protect the surface coating composition from both in-can spoilage and film degradation from the action of microorganisms. Film degradation typically takes the form of discoloration, dulling, loss of integrity, increased dirt retention, and/or loss of adhesion of the film.

The amount of antimicrobial composition that is desirable in a given surface coating formulation can be determined by one of skill in the art using various known techniques and methods. Performance of a given antimicrobial composition in a composition may be evaluated, for example, as described below. An antimicrobial for many coatings applications (such as paint) desirably provides protection against both fungal and algal growth. The fact that an antimicrobial composition is known to possess fungicidal activity, however, does not mean that it will necessarily be effective in inhibiting mold growth on exterior surfaces for long periods of time. For example, certain antimicrobial compositions may lose their fungicidal activity prior to being applied in a dried film. Other antimicrobial compositions may prevent deterioration by anaerobic microorganisms in a sealed can, but may fail to prevent the formation of mold or mildew by aerobic microorganisms on a surface exposed to air. In addition, the activity of the antimicrobial composition may be impaired by the weathering environment to which many exterior coatings are exposed.

In one technique, the minimum inhibitory concentration (MIC) of the antimicrobial composition in a coating composition is determined. MIC refers to the concentration of a given antimicrobial composition below which growth of microorganisms is not inhibited. MIC may be determined using a dilution series to identify the amount of antimicrobial agent that is required to inhibit microbial growth under defined laboratory conditions. In this test, efficacy is determined against a selected grouping of fungal and/or algal species that are often found on coated surfaces. Representative organisms include, for example, fungi, such as Alternaria alter nata, Aspergillus species, Aureobasidium pullulans, Cladosporium species, Penicillium species, Phoma violacea, Stachybotrys chararum; and algae, such as Oscillatoria spp., Chlorella spp., Trentepholia spp., Nostoc spp., and Pleurococcus spp. MIC values are often presented in parts per million (ppm) required to inhibit the growth of a target organism or group of target organisms. A lower MIC value indicates increased efficacy.

Accelerated laboratory exposure may also be used to evaluate the desired amount of antimicrobial composition in a coating formulation. This test typically involves placing panels painted with an antimicrobial composition-containing coating formulation into a test chamber having a humid atmosphere. One or more test microorganisms are added directly to the coating or are introduced into the chamber. The high humidity promotes rapid microbial growth and the painted samples are monitored over time to determine the effectiveness of the antimicrobial composition at the formulated level in inhibiting growth of the test organism(s). A representative accelerated exposure protocol is reported in ASTM D3273 "Standard Test Method for Resistance to Growth of Mould on the Surface of Interior Coatings in an Environmental Chamber."

In another method, field trials can be conducted in order to determine how an antimicrobial performs in a coating when exposed to outdoor conditions. In such tests, the coating containing antimicrobial composition is applied to a test panel and is exposed at a fixed orientation and angle. The panels are monitored over time and are rated for the extent of microbial growth. Performance of the antimicrobial composition is measured as the time (e.g., in months or years) that the antimicrobial composition prevents microbial growth form reaching a predetermined level. A representative field trial protocol is reported in ASTM D3456 "Standard Practice for Determining by Exterior Exposure Tests the Susceptibility of Paint Films to Microbiological Attack."

Performance of an antimicrobial composition for efficacy against in-can spoilage may be evaluated, for example, as described below.

In one technique, the antimicrobial composition is evaluated to determine the MIC of the antimicrobial composition for in-can spoilage of a coating formulation. The MlC may be determined using a dilution series to identify the amount of antimicrobial composition that is required to inhibit in-can microbial growth under defined laboratory conditions. Suitable MIC procedures are discussed elsewhere herein. Another method for evaluating an antimicrobial composition for in-can preservation of a coating composition is a challenge test. In a challenge test, microorganisms are deliberately added to a sample of the coating formulation containing an antimicrobial composition. The survival of the microorganisms as a function of time is then monitored. In some test protocols, the sample is challenged several times. A representative protocol for evaluating antimicrobial composition efficacy is ASTM 2574 "Standard Test Method for Resistance of Emulsion Paints in the Container to Attack by Microorganisms."

Typically, the antimicrobial composition can be incorporated into the surface coating formulations using conventional techniques. In some aspects, two or more (for example, 2, 3, 4 or more) antimicrobial agents are used in a surface coating formulation in order to provide, for example, a broader spectrum of activity, lower toxicity, and/or lower cost. For example, two or more of: 9-undecenoic acid, salts of 9-undecenoic acid and/or esters of 9- undecenoic acid can be used together in a surface coating formulation in accordance with the invention. In some embodiments, one or more of 9-undecenoic acid, a salt of 9-undecenoic acid or an ester of 9-undecenoic acid can be used with one or more second antimicrobial agents. The second antimicrobial agent(s) can comprise an antimicrobial agent having Formulae (IV), (V) and/or (VI)), and/or one or more known antimicrobial agents. Representative examples of in-can preservatives include 4,4- dimethyloxazolidine; 3,4,4, -trimethyloxazolidine; l,2-dibromo-2,4-dicyanobutane; 2[(hydroxymethyl)-amino]ethanol; 2[(hydroxymethyl)-amino]propanol; 1 -(3- chlorallyl)-3,5,7-triaza-l-azoniaadamantane chloride; l,2-benzisothiazolin-3-one; 5- chloro-2-methyl-4-isothiazolin-3-one; 2-methyl-4-isothiazolin-3-one; 5- hydroxymethoxy-methyl-l-aza-Sjy-dioxa-bicyclo-p.S.OJoctane; 5-hydroxymethyl- l-aza-3,7-dioxabicyclo-[3.3.0]octane; 5-hydroxypolymethyl-l-aza-3,7- dioxabicyclo[3.3.0]-octane; hexahydro-1 ,3,5-triethyl-s-triazine; 2-hydroxymethyl-2- nitro-1,3 propanediol; chloroacetamide; methyl chloroisothiazolinone; methylisothiazolinone (methyl chloroisothiazolinone and methylisothiazolinone are available under the trade designation "KATHON"); 2,4,4' trichloro-2- hydroxydiphenyl ether (available under the trade designation "TRICLOSAN") ; metal salts (e.g., silver chloride or copper nitrate); glycols (e.g., phenoxyethanol); alcohols (e.g., benzylalcohol); quaternary ammonium salts (e.g., benzalkonium chloride); and phenol derivatives (e.g., ortho-phenyl-phenol).

Representative examples of dry film preservatives include tetrachloroisophthalonitrile, 2-iodo-2-propynyl butyl carbamate, 2-n-octyl-4- isothiazolin-3-one, diiodomethyl-p-tolylsulphone, n-(trimethylthio)phthalimide, carbendazim, dichloro-octylisothiazolinone, zinc pyrithione, thiuram and barium meta-borate. Combinations may be used to gain broad-spectrum efficacy. In some embodiments, the first antimicrobial agent and the second antimicrobial agent are present in ratios ranging from about 1 : 10 to about 10: 1. In other embodiments, the first antimicrobial agent is added to the coating formulation in an amount ranging from about 0.01% weight to about 5% weight based on the total weight of the coating composition (e.g., about 0.1% to about 1% weight based on the total weight of the coating composition), and the second antimicrobial agent is added to the coating formulation in an amount ranging from about 0.01% weight to about 5% weight based on the total weight of the coating composition (e.g., about 0.1% to about 1% weight based on the total weight of the coating composition). In some embodiments, surface coatings of the invention comprise water- based latex paint compositions comprising a latex binder, water, and an antimicrobial agent comprising 9-undecenoic acid, an ester of 9-undecenoic acid, a salt of 9-undecenoic acid, or a combination thereof. In addition, the surface coating compositions may contain various auxiliary materials, such as pigments, extenders, fillers, thickeners, driers, plasticizers, wetting agents, emulsifying agents, freeze- thaw stabilizers, coalescents, dispersants, anti-settling agents, defoamers, solvents, and the like in the amounts ordinarily used for these purposes. In some embodiments, a second in-can or dry film antimicrobial agent may be added.

The manufacture of a latex paint typically occurs in two steps, commonly referred to as the grind (step 1) and the letdown (step 2). In the grind, one or more of the liquid components (e.g., water) are mixed together followed by the addition of the dry pigments. The dry pigments are dispersed in the liquid components under high shear. In the letdown stage, the latex binder and other ingredients are added, typically under low speed mixing to form the latex paint composition. A biocidally effective amount of the antimicrobial agent(s) may be added at either the grind stage or the letdown stage, and may be preblended with a component of the composition or may be added directly. In an exemplary embodiment, the antimicrobial agent(s) is added in the letdown stage. Metalworking fluids applications In further aspects, the invention provides methods for protecting metalworking fluids (MWF) from undesirable microbial growth. The method comprises incorporating into the MWF an antimicrobial composition comprising 9- undecenoic acid, a salt of 9-undecenoic acid, an ester of 9-undecenoic acid, or a combination thereof. In other aspects, the method comprises incorporating into the surface coating composition an antimicrobial composition comprising 9-undecenoic and, a salt of 9-undecenoic acid, an ester of 9-undecenoic acid, or a combination thereof, in combination with a second antimicrobial agent. The second antimicrobial agent can comprise 9-decenoic acid, a salt of 9-decenoic acid, an ester of 9-decenoic acid, or a combination thereof, and/or a known antimicrobial agent. In some embodiments, the methods protect the MWF from spoilage from the action of microorganisms. In accordance with these aspects, the antimicrobial composition can be added to the MWF during formulation, prior to storage and/or during storage. In other embodiments, the methods protect the MWF during use from degradation due to the action of microorganisms. In an exemplary embodiment, the methods protect the MWF from both spoilage and degradation during use from the action of microorganisms. MWF degradation typically takes the form of loss of emulsion stability, pH changes, viscosity changes, loss of lubrication properties, discoloration, production of unpleasant odors and growth of slimes and other biomass deposits. The growth of slimes and other biomass deposits can be particularly undesirable because they can clog up the pipes, filters and screens used in MWF handling systems. Anaerobic bacteria, specifically the sulfate reducers, may produce hydrogen sulfide and other disagreeable and toxic gases. More importantly, the microbial contaminants may result in adverse health effects in workers exposed to MWF aerosols.

Desirably, the antimicrobial compositions are thermostable, to accommodate the elevated temperature ranges of the MWF. When formulating an antimicrobial composition for MWF applications, it is desirable to consider bacteria that may be present in biofilms. Commonly, bacteria are not only present in the flowing fluids of MWF, but are also present in large numbers in biofilms. In addition, it is desirable that the antimicrobial compositions are effective at pH ranges commonly found in MWF. MWF are used in metal processing operations such as cutting, drilling, tapping, grinding, milling, rolling, metal drawing, stamping and turning operations. The primary function of the MWF is to provide cooling and lubrication to the metal and tools used in the processing operations. MWF are also used to protect metals and metal working tools against corrosion and rust formation, as temporary surface coatings to protect newly machined articles such as coils and springs, as quenching fluids and as casting fluids.

Because the main purpose of MWF is typically to reduce heat from friction when cutting metal, the temperature of these fluids tends to be warm. Generally, MWF have a pH of about 3 to about 10, or about 7 to about 10, or about 6 to about 9 and are organized into four categories, namely, straight oils, soluble oils, semisynthetic fluids, and synthetic fluids. The distinguishing feature among the fluids is the amount of highly refined oil. Straight oils are 60-100% oil and synthetic fluids contain no oil. The two largest classes, the soluble oils, and semisynthetic fluids, contain 5-85% oil. While these are often split into two categories, their only distinguishing feature is that semi-synthetic fluids contain less oil than the soluble oils.

The inventive antimicrobial compositions can be utilized in straight oil MWF, soluble oil (emulsifiable oil) MWF, semi-synthetic MWF, synthetic MWF, quenching fluids, water-soluble corrosion products, casting fluids, and the like. Although efforts have been undertaken to reduce microbial contamination of

MWF, one risk of incorporating biocides into MWF is the emergence of biocide- resistant strains. Antimicrobial agents can be incorporated as components in foπnulated MWF or added to MWF before and during use to prevent microbial growth. Illustrative commonly used biocides for MWF include nitroalcohols such as tris(hydroxymethyl) nitromethane (Tris Nitro™); s-triazines such as hexahydro- l,3,5-tris(2-hydroxyethyl)-S-triazine (Grotan™, Onyxide™ 200, Busan™ 1060, Bioban™ GK, Triadine™ 3) and hexahydro-l,3,5-triethyl-S-triazine (Vancide TH); l-(3-chloroallyl)-3,5,7-triaza-l-azonia adamantane chloride (Dowicil 75); 4-(2- nitrobutyl)moφholine-4,4-(2-ethyl-2-nitrotrimethylene) dimoφholine (Bioban™ P- 1487); o-phenyl phenol (Dowicide™ -1); sodium 2-pyridinethiol-l -oxide (Sodium Omdanie™); l,2-benzisothiazolin-3-one (1 , 2-BIT, Proxel™ MW 300 or MW 200); 5-chloro-2-methyl-4-isothiazolin-3-one-2-methyl-4-isothiazolin-3-one (Kathon™ 886); 6-acetoxy-2,4-dimethyl-m-dioxane (Givgard™ DNX); 2,2-dibromo-3- nitrilopropionamide (Dow XD-8254, DBNPA); p-chloro-m-xylenol (PCMX); 2-n- octyl-4-isothiazolin-3-one (Kathon™ 893 MW); a mixture of 5-chloro-2-methyl-4- isothiazolin-3-one and 2-methyl-4-isothiazonlin-3-one (Kathon™ MWC); 3-iodo-2- propynyl-N-n-butyl carbamate (Troysan™).

Other known antimicrobial agents for MWF include quaternary ammonium compounds; urea derivatives; antimicrobial amino compounds such as dodecylamine or 2-[(hydroxymethyl)-amino]ethanol; antimicrobial imidazole derivatives; antimicrobial nitrile compounds such as 2-bromo-2-bromomethyl-glutaronitrile; antimicrobial thiocyanate derivatives such as methylene(bis)thiocyanate; isothiazolin-3-ones such as 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4- isothiazolin-3-one, 4,5-dichloro-2-methylisothiazolin-3-one 2-n-octylisothiazolin-3- one, 4,5-trimethylene4-isothiazolin-3-one and 2-methyl-4,5-trimethylene-4- isothiazolin-3-one and mixtures thereof; thiazole derivatives; antimicrobial nitro compounds; iodine compounds such as 3-iodo-2-propynyl-N-n-butyl carbamate; aldehydes and aldehyde release agents such as glutaraldehyde (pentanediol), formaldehyde or glyoxal; amides such as chloracetamide; guanidine derivatives; antimicrobial thiones; antimicrobial triazine derivatives such as hexahydro- 1,3, 5- tris(2-hydroxyethyl)triazine and hexahydro- 1, 3, 5-triethyltriazine; oxazolidine and derivatives thereof; furan and derivatives thereof; antimicrobial carboxylic acids and the salts and esters thereof; phenol and derivatives thereof; salts and complexes of 2- pyridinethione-1 -oxide, especially alkali metal salts, for example sodium pyridine-2- thiol-1 oxide and the 2: 1 zinc complex of 1 -hydroxy-pyridine-2-thione; antimicrobial sulphone derivatives; imides; thioamides; azole fungicides and strobilurin fungicides.

Some microbiocidal or microbiostatic activities of the known MWF antimicrobial agents occur through the release of formaldehyde. Formaldehyde releasers are usually soluble in water rather than oil and are more effective against bacteria than fungi. Tris(hydroxym ethyl) nitromethane and hexahydro-1,3,5, tris(2- hydroxyethyl)-s-triazine are examples of formaldehyde-releasing antimicrobial agents. Formaldehyde is an airway irritant and recognized cause of occupational asthma. Further, studies have suggested that exposure to certain known antimicrobial agents can cause allergic or irritant contact dermatitis. Concerns have been raised about the potential carcogenicity of some of these known antimicrobial agents because of their formaldehyde-releasing action.

Non-formaldehyde-releasing antimicrobial agents are generally more effective against fungi than formaldehyde releasers but are also effective against bacteria. The phenolic compounds are oil soluble, and the antimicrobial agent derivatives of morpholine and the dioxanes are partially soluble in oil and water. Sodium 2-pyridinethiol-l -oxide and o-phenyl phenol are examples of non- formaldehyde-releasing biocides. Nitrated antimicrobial agents such as Bronopol (2-bromo-2-nitro 1,3- propanediol), 2-methyl-2-nit.ro- 1,3 -propanediol, and 5-methyl-5-nitro-l ,3-dioxane, which have been shown to release nitrite, can act as nitrosating agents in MWF. Bioban P- 1487, which is composed of 70% 4-(2-nitrobutyl) morpholine and 30% 4,4-(2-ethyl-2-nitrotrimethylene) dimorpholine, can dissociate to form nitrite ions. Bioban P- 1487 added to metalworking fluid concentrate can directly form N- nitrosomorpholine (NMOR, an animal carcinogen), which can increase in concentration over time.

Thus, known antimicrobial agents for use in MWF can have disadvantages, as noted above. In accordance with the invention, the inventive antimicrobial compositions can be used in substitution of these known metalworking fluid antimicrobial agents. In other aspects of the invention, the inventive antimicrobial compositions can be used in combination with any one or more of these known metalworking fluid antimicrobial agents, thereby reducing the amount of the known antimicrobial agent required for preservative or biocidal effect. This, in turn, can reduce the potential hazards noted herein for these known metalworking fluid antimicrobial agents. MWF can be prepared as a concentrate that is diluted with water prior to use.

When preparing formulations of the invention for specific applications, the composition also will likely be provided with additives conventionally employed in compositions intended for such applications. For example, the MWF can include such additives as water, mineral oil, emulsifying agents, surfactants (which can be cationic, anionic or non-ionic), chelating agents, coupling agents, viscosity modifiers, detergent, plasticizer, anti-mist agents, anti-weld agents, oiliness agents, surfactant wetting agents, dispersants, passivators, anti-foam ing agents, alkaline reserves, dyes, odorants, corrosion inhibitors, oxidation inhibitors, and extreme pressure additives. These additives can be included in the amounts ordinarily used for these purposes.

The inventive antimicrobial compositions can be added directly to the MWF, or the antimicrobial composition can be formulated with a carrier for ease of handling and dosing. When formulated with a carrier, the carrier can be a solid or a liquid medium (thereby forming a solution, suspension, emulsion or micro- emulsion). When the carrier is a liquid, it is generally selected so that the formulation is compatible with the MWF to be protected. For example, if the MWF is a straight oil, the carrier is preferably a solvent, especially a non-polar solvent. When the MWF is an aqueous based formulation such as a synthetic, semi-synthetic or soluble oil, the carrier is preferably water or a water-miscible organic solvent or mixture thereof.

If the antimicrobial composition formulation is in the form of a suspension or emulsion, it preferably also contains a surface active agent to produce a stable dispersion or to maintain the discontinuous phase uniformly distributed throughout the continuous phase. Any surface active agent that does not have a significant adverse effect on the antimicrobial activity of the antimicrobial agent can be utilized. Suitable surface active agents include emulsifiers, surfactants, and mixtures thereof. The emulsifiers/surfactants may be non-ionic, anionic, or a mixture thereof. Suitable anionic emulsifiers and surfactants include alkylarylsulfonates (e.g., calcium dodecylbenzensulfonate), alkylsulfates (e.g., sodium dodecyl sulfate), sulfosuccinates (e.g., sodium dioctylsulfosuccinate), alkyletheresulfates, alkylaryletheresulfates, alkylether carboxylates, alkylaryletherecarboxylates, lignin sulfonates or phosphate esters. Suitable non-ionic emulsifiers and surfactants include fatty acid ethoxylates, ester ethoxylates, glyceride ethoxylates (e.g., castor oil ethoxylate), alkylaryl polygylcol ethers (e.g., nonylphenol ethoxylates), alcohol ethoxylates, propylene oxide-ethylene oxide condensation products, amine ethoxylates, amide ethoxylates, amine oxides, alkyl polyglucosides, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylenesorbitol esters or alcohol ethoxy carboxylates (e.g., those obtainable from Ci₂-_I4 alcohols). The amount of antimicrobial composition that is desirable in a given MWF formulation can be determined by one of skill in the art using various known techniques and methods. Performance of a given antimicrobial composition in a composition may be evaluated, for example, as described below.

In one technique, performance of an antimicrobial composition for efficacy against spoilage of MWF is evaluated, for example, as described in ASTM E2169- 01 "Standard Practice for Selecting Antimicrobial Pesticides Use in Water-Miscible Metalworking Fluids." Another method for assessment of performance of an antimicrobial composition for efficacy against microorganisms can be based on ASTM E686-91 : "Standard Test Method for Evaluation of Antimicrobial Agents in Aqueous Metal Working Fluids." In one illustrative test methodology, the MWF is selected, and the test microorganisms (bacteria, fungi) are gradually acclimatised to the MWF. The organisms are grown in biocide-free MWF (containing 50% (v/v) minimal broth) with aeration at 25⁰C until microbial count reaches 10⁹ cfu/ml. Every seven (7) days each microorganism is subcultured into 90 ml (10 ml inoculum) and re-incubated. Subculturing can be done for three cycles before use.

To 1 L French square bottles, 900 ml of MWF is added at use concentration (diluted to 5% with water of 125 ppm calcium hardness). Next, 100 ml of inoculum is added and mixed (100 ml of total quantity is removed and discarded). The MWF is allowed to sit undisturbed for 64 hours. The MWF is mixed and sampled for microbiological testing.

Bacteria and fungi are enumerated by streaking an aliquot onto nutrient or malt agar as appropriate. The mixtures are aerated using capillary tubing to bubble air into the bottom of the bottle (introduced by means of a multi-valve air manifold). Antifoam is also added. After 5 days, the aeration is stopped and volume replaced with sterile distilled water. The mixture is allowed to sit for 64 hours and then mixed. 10 ml of inoculum is used to re-inoculate and all losses are replaced with antimicrobial composition containing MWF. The pH of the MWF is measured at the start of the test and every 7 days. The physical condition of the MWF is also noted at the start of the test and every 7 days. Aeration is resumed and the regime repeated for a minimum of 6 weeks or until failure.

Some biocide suppliers provide MIC data for specific microorganisms. The MlC is the lowest treatment dose that will prevent a laboratory test culture population from proliferating, or otherwise contributing to biodeteri oration.

Typically, for MWF, a kill dose is about two to six times greater than the MIC dose. Personal Care Products

In other aspects, the invention provides methods for protecting consumer products. Illustrative consumer products include cleansing agents and personal care products (such as cosmetics and toiletries).

In some aspects, the invention provides methods for protecting personal care products from spoilage or degradation during use due to the action of microorganisms. The method comprises incorporating into the personal care product an antimicrobial composition comprising 9-undecenoic acid, a salt of 9- undecenoic acid, an ester of 9-undecenoic acid, or a combination thereof. In other aspects, the method comprises incorporating into the personal care product an antimicrobial composition comprising 9-undecenoic and, a salt of 9-undecenoic acid, an ester of 9-undecenoic acid, or a combination thereof, in combination with a second antimicrobial agent. The second antimicrobial agent can comprise 9- decenoic acid, a salt of 9-decenoic acid, an ester of 9-decenoic acid, or a combination thereof, and/or a known antimicrobial agent. The amount of antimicrobial composition added to a given personal care product can be determined by one of skill in the art using various known techniques and methods.

In some aspects, two or more (for example, 2, 3, 4 or more) antimicrobial agents are used in a personal care product, in similar manner to that described above for surface coating formulations.

Illustrative second antimicrobial agents that are known personal care antimicrobial agents include: phenol derivatives (such as halogenated phenols, for example 3,5-dichlorophenol, 2,5-dichlorophenol, 3,5-dibromophenol, 2,5- dibromophenol, 2,5- or 3,5-dichloro-4-bromophenol, 3,4,5-trichlorophenol, 3,4,5- tribromophenol, phenylphenol, 4-chloro-2-phenylphenol, 4-chloro-2-benzylphenol); dichlorophene, hexachlorophene; aldehydes (such as formaldehyde, glutaraldehyde, salicylaldehyde); alcohols (such as phenoxyethanol); antimicrobial carboxylic acids and derivatives thereof such as parabens, including methyl, propyl and benzyl parabens, and the like; organometallic compounds (such as tributyl tin derivatives); iodine compounds (such as iodophors, idonium compounds); quaternary ammonium compounds (such as benzyldimethyldodecylammonium chloride, dimethyldidecylammonium chloride, benzyl-di-(2-hydroxyethyl)- dodecylammonium chloride, dimethyldidecylammonium chloride, benzyl-di-(2- hydroxyethyl)-dodecylammonium chloride)); sulfonium and phosphonium compounds; mercapto compounds and the alkali metal, alkaline earth metal and heavy metal salts thereof, such as 2-mercaptopyridine-N-oxide and the sodium, zinc and copper salts thereof, 3-mercaptopyridazine-2-oxide, 2-mercaptoquinoxaline-l- oxide, 2-mercaptoquinoxaline-di-N-oxide, and also the symmetrical disulfides of these mercapto compounds; ureas (such as tribromocarbanilide or trichlorocarbanilide); dichlorotrifluoromethyldiphenylurea; tribromosalicylanilide; 2-bromo-2-nitro- 1 ,3dihydroxypropane; dichlorobenzoxazolone; chlorohexidine; isothiazolone and benzisothiazolone derivatives. Further illustrative second antimicrobial agents include Triclosan™ (2,4,4'-trichloro-2'-hydroxydiphenyl ether, also known as 5-chloro-2-(2,4-dichlorophenoxy)phenol) and Kathon™ (methyl chloroisothiazolinone and methyl isothiazolinone in various ratios).

In some embodiments, the phenol derivatives suitable as second antimicrobial agent do not include phenolic compounds having antioxidant properties. Examples of such compounds include BHT, BHA, TBHQ and natural analogues with similar anti-oxidant properties such as tocopherols, cinnamic acid compounds and compounds described as flavins or flavinoids. In some embodiments, the antimicrobial carboxylic acids suitable as second antimicrobial agents do not include short chain organic acids that are water soluble, such as lactic, acetic, citric, malic, succinic, natural amino acids, formic, propionic, butyric, and the like. Illustrative short chain organic acids of this type have four or fewer carbon atoms in the carbon backbone and can also contain other substituent groups such as -OH, NH₂, and the like. In some embodiments, alcohols suitable as second antimicrobial agents do not include short chain alcohols, such as Ci-C₄ alcohols such as methanol, ethanol, propanol, butanol. In these aspects, the antimicrobial agents of Formulae (I), (II) and (III) can be effective in low concentrations without combining with these particular second antimicrobial agents. Illustrative household cleansing agents include dishwashing cleaners, detergents, hard surface cleaners, glass cleaner, appliance cleaner, floor cleaner, bath and kitchen cleaners, auto cleaning and polishing products, water treatment (including cleaners for humidifiers and water softeners), and the like. As used herein, the term "hard surface" includes, but is not limited to, bathroom surfaces (e.g., floor, tub, shower, mirror, toilet, bidet, bathroom fixtures), kitchen surfaces (e.g., counter tops, stove, oven, range, sink, refrigerator, microwave, appliances, tables, chairs, cabinets, drawers, floor), furniture surfaces (e.g., tables, chairs, entertainment centers, libraries, cabinets, desks, doors, shelves, couches, beds, television, stereo, pool table, ping pong table), windows, window ledges, tools, utility devices (e.g., telephones, radios, CD players, digital sound devices, palm computers, laptop computers), toys, writing implements, watches, framed picture or paintings, books).

In addition, the antimicrobial compositions can be utilized in connection with personal care cleansing agents. Illustrative personal care cleansing agents in accordance with these aspects include, but are not limited to, skin lotions and creams, soap bars, liquid hand and body lotions, liquid hand soaps, bath salts, ointments, face lotions, hair shampoo and conditioning products, hair tonics, skin oils, powders, sunscreen creams, contact lens storage and/or cleansing solution, and the like. The antimicrobial compositions can also find utility in connection with cosmetics.

In further aspects, the inventive antimicrobial compositions have utility in food or feed formulations, as well as potable water-contacting applications. Illustrative water-contacting applications include water treatment systems.

The inventive antimicrobial compositions possess a broad spectrum of efficacy against Gram negative bacteria, fungi, and even Gram positive bacteria. Thus, the antimicrobial compositions in accordance with the invention can find wide application in industrial products, consumer products, and food/feed applications. Table 1 summarizes some relevant microorganisms and applications that relate to some of these microorganisms.

Table 1 : Microorganisms Relevant for Various Applications

As illustrated in the Examples herein, the antimicrobial compositions in accordance with the invention provide a broad spectrum of antimicrobial efficacy. This broad spectrum encompasses Gram positive bacteria, fungi, and even Gram negative bacteria. Moreover, embodiments of the antimicrobial compositions can exhibit antimicrobial efficacy even at pH levels about neutral. This expanded efficacy can provide significant benefits and broaden the applications of these antimicrobial agents significantly over known antimicrobial agents.

The invention will now be described with reference to the following non- limiting Examples. EXAMPLES Example 1:

The efficacy of antimicrobial compositions in accordance with aspects of the invention against the following organisms was determined as follows. The following organisms were incubated in the presence of varying concentrations of 9- decenoic acid (9-DA), 9-undecenoic acid (9-UDA), or a combination of 9-decenoic acid and 9-undecenoic acid (9-DA/9-UDA) on an agar surface: Aspergillus parasiticus (ATCC 56857), Trichoderma virens (ATCC 9645;, Aureobasidium pullulans (ATCC 12536), Aspergillus flavus (ATCC 96045), Cladosporium cladosporiodes (ATCC 16022), Aspergillus flavus (ATCC 5917), Aspergillus oryzae (ATCC 10124), Aspergillus parasiticus (ATCC 13539), Ulocladium atrum (ATCC 52426), Candida albicans (ATCC 1 165 U Alternaria alternata (ATCC 52170;, Stachybotrys chartarum (ATCC 16026;, Aspergillus niger (ATCC 1 1414/

The minimum inhibitory concentration (MIC) was defined as the least concentration tested that completely inhibited growth of the organism.

Fungal spores were hydrated in 0.1% Tween 80 and then plated onto Potato Dextrose Agar (PDA) (Difco # 213400; Becton, Dickinson and Company, Sparks, MD) and incubated at 25-30°C for six (6) days. The spores were washed from the surface with 5 ml of 0.1% Tween 80 and enumerated. PDA plates were prepared according to the manufacturer's instructions through sterilization. The agar was tempered to approximately 50°C and filter sterilized. Antimicrobial compositions (9-DA, 9-UDA or 9-DA/9-UDA) were added by percent weight to molten autoclaved PDA media, with consideration of specific gravity (0.915g/mL for 9-DA and 0.9179g/mL for 9-UDA) and purity (98% for 9- DA and 97% for 9-UDA). In a 9-DA/9-UDA mix, the antimicrobial agents were added in equal proportion. For example, a 1.0% 9-DA/9-UDA solution would contain 0.5% 9-DA and 0.5% 9-UDA. The agar was thoroughly mixed and poured into sterile petri plates and allowed to solidify.

The pH of all concentrations of 9-DA, 9-UDA, and 9-DA/9-UDA percentages in PDA media used was as follows: Table 2.

The MIC for 9-DA, 9-DA/9-UDA and 9-UDA are shown in Table 3 below:

Table 3. MIC for Antimicrobial Compositions.

The agar plates were inoculated with the spore solution to achieve 10² spores/plate. The plates were incubated at 25-30°C in Ziploc bags with a wet paper towel to keep the moisture level high. The plates were examined for growth at 1, 2, 3, 4, 8, 1 1, 15, 17, 23, 29 and 31 days. The percent coverage of growth on the agar surface was recorded at each sample point.

For all thirteen fungal strains tested above, both 9-DA and 9-UDA were observed to be effective antimicrobial agents with MICs in the ranges of 0.01% to 0.05% and 0.01% to 0.1% respectively. In the case of Aspergillus parasiticus ATCC 56857, Trichoderma virens ATCC 9645, Aspergillus parasiticus ATCC 13539, Candida albicans ATCC 1 1651, Alternaria alternata ATCC 52170, Stachybotrγs chartarum ATCC 16026, and Aspergillus niger ATCC 1 1414, a synergistic effect was observed when using a 9-DA/9-UDA (50:50) mixture. The MIC when using the 9-DA/9-UDA (50:50) mixture was lower than would be expected for a comparable amount of either 9DA or 9UDA by itself.

Results are illustrated in Figures 1-13, wherein antimicrobial composition is represented on the X-axis, and percentage fungal coverage is represented on the Y- axis. Example 2:

Efficacy of 9-UDA against several microorganisms was measured based on percent reduction in comparison to growth of the controls. The growth inhibition due to 9-UDA was determined for the following organisms: Enterobacter aerogenes (ATCC 13048), Escherichia coli (ATCC 1 1229), Escherichia coli (ATCC 8739), Bacillus subtilis (ATCC 6051), Bacillus cereus (ATCC 14579), Pediococcus acidolactici (ATCC 8042), and Lactobacillus casei (ATCC 334).

Stock cultures of each organism were transferred into MRS liquid medium. MRS medium (Difco 288130) was purchased from Becton, Dickinson and Company, Sparks, MD.

The efficacy of 0.25% and 0.5% 9-UDA (free acid) to inhibit the growth of various microorganisms of interest indicated above was tested as follows. The pH of MRS media with various concentrations of 9-UDA was measured to ensure that there were not significant variations in pH due to addition of the 9-UDA.

Table 4. Measured pH of all concentrations of 9UDA used in study in MRS media.

The selected organisms were incubated overnight in 5 ml of MRS medium at 35°C and 250 rpm. A 0.25 and 0.50% 9-UDA in MRS medium were prepared, along with a control of straight media (no 9-UDA). The concentrated 9-UDA was diluted with the appropriate media required for the respective microorganisms, to reach the required concentrations for the studies as indicated below. The antimicrobial (9-UDA) was added by weight / volume percent to the media. The specific gravity (0.9179g/mL) and purity (97%) of the compounds were taken into account. The pH of the medium was not adjusted. The target for initial cell density was 10⁵ to 10⁶ cfu/ml. According to the McFarland standard, 0.01 OD_OOO is equivalent to approximately 10 cfu/ml. To achieve the proper dilution, 30 μl of overnight culture diluted to 0.01 OD_6O0 was added to the 3 ml of media in each tube. The tubes were incubated at 35⁰C. Treatments were all done in duplicate. All strains were shaken at 250 rpm, with the exception of Lactobacillus (because it is anaerobic). OD₆₀₀ readings were taken at 0, 24, and 48 hours.

"Percent reduction in comparison with control" was defined as (1- abs. of treatment / abs. of control) X 100. Results are shown below in Table 5. Table 5: (Free acid 9-UDA)

Bold indicates complete inhibition of growth n=2 for all treatments

In the case of Bacillus subtilis 6051, both 0.25% and 0.5% 9-UDA resulted in a complete reduction when compared with the control culture that was grown in MRS medium the absence of any antimicrobial agent. At a concentration of 0.5%, 9-UDA resulted in a complete reduction when compared with the control culture that was grown in the absence of any antimicrobial compound for E. coli 8739, Bacillus subtilis 6051, Bacillus cereus 14579, Pediococcus acidolactici 8042, and Lactobacillus casei 334. It is worthwhile to note that 0.5% 9-UDA resulted in a complete inhibition of E.coli 8739. This is surprising, since it was previously reported that most Gram negative bacteria are not sensitive to lipophilic agents. See Kabara, J.J., et al., "Antimicrobial Lipids: Natural and Synthetic Fatty Acids and Monoglycerides," Lipids, 12(9) 753-759 (1977). Example 3:

Efficacy of potassium salts of 9-DA and 9-UDA were determined through incubation of the following organisms in the presence of varying concentrations of the potassium salt: Serratia marcescens A TCC 990, Pseudomonas straminea A TCC 33636, Bacillus subtilis ATCC 6051, Bacillus licheniformis ATCC 14580, Bacillus cereus ATCC 14579, Pediococcus acidilactici ATCC 8042, and Lactobacillus casei ATCC 334 .

The efficacy of different levels of potassium salts of 9-DA and 9-UDA (K-9- DA and K-9-UDA) were tested depending on the organism to inhibit the growth of various microorganisms indicated above. The selected organisms were incubated overnight in 5 ml of MRS medium at

35⁰C and 250 rpm. MRS media with K-9-DA or K-9-UDA were prepared, along with a control of straight media (no antimicrobial added). The concentrated antimicrobial agents were diluted with the appropriate media required for the respective microorganisms, to reach the required concentrations for the studies as indicated below. The antimicrobial agents were added by weight / volume percent on an 'as 9-DA' or 'as 9-UDA' basis to the media. The purity of the antimicrobial agent (99% for K-9-DA and 96% for K-9-UDA) was taken into account. The pH of the medium was not adjusted. The target for initial cell density was 10⁵ to 10⁶ cfu/ml. According to the McFarland standard, 0.01 OD₆₀₀ is equivalent to approximately 10 cfu/ml. To achieve the proper dilution, 30 μl of overnight culture diluted to 0.01 OD₆₀₀ was added to the 3 ml of media in each tube. The tubes were incubated at 35°C. Treatments were all done in duplicate. All strains were shaken at 250 rpm, with the exception of Lactobacillus (because it is anaerobic). OD_6O0 readings were taken at 0, 4, 17, 23 and 47 hours.

"Percent reduction in comparison with control" was defined as (1- abs. of treatment / abs. of control) X 100. Results are illustrated in the Table 6 below:

Table 6.

All grown in MRS n=2 for all

Within the above table, complete growth inhibition is highlighted in bold font for the particular microorganisms and composition tested. In addition, it can be seen that with the exception of Serrαtiα mαrcescens, and Bacillus licheniformis, all concentrations of the potassium salts of 9-DA and 9-UDA resulted in at least a 95% reduction in growth when compared to the appropriate controls cultivated in MRS medium in the absence of any antimicrobial compound. In the case of Serratia marcescens, the potassium salt of 9-DA appeared to be more effective than 9-UDA under the conditions tested. In the case of B. licheniformis, 0.075% potassium 9-DA resulted in an 88.63% reduction in growth when compared with the appropriate control as described above.

It should be noted that MRS medium is considered to be a rich medium by those skilled in the art and one would expect the potassium salts of 9-DA and 9- UDA to be even more effective in sub-optimal culture conditions for the various microorganisms tested. Thus it is expected that even greater reductions in growth when compared with growth could be observed with even lower concentrations of the antimicrobial compounds that those listed above. Example 4: Efficacy of potassium salts of 9-DA and 9-UDA was tested at various pH levels against the following: E.coli ATCC 8739, Serratia marcescens ATCC 990, Bacillus cereus ATCC 14579, Bacillus licheniformis ATCC 14580, Bacillus subtilis ATCC 6051, Pediococcus acidolactici ATCC 8042, Pseudomonas straminea ATCC 33636, Pseudomonas stutzeri ATCC 17588, Pseudomonas oleovorans ATCC 8062 and Lactobacillus casei ATCC 334. Stock cultures of each organism were transferred into MRS liquid medium. MRS medium (Difco 288130) was purchased from Becton, Dickinson and Company, Sparks, MD.

The efficacy of potassium salts of 9-DA and 9-UDA (K-9-DA and K-9- 5 UDA) was tested at different concentrations and pH levels, including 6.75 (unadjusted), 7.5, 8, 8.5, and 9.

The selected organisms were incubated overnight in 5 ml of MRS medium at 35°C and 250 rpm. MRS media with K-9-DA or K-9-UDA were prepared, along with a control of straight media (no antimicrobial added). The antimicrobial agents

10 were added by weight / volume percent to the media. The purity, 99% for K-9-DA and 96% for K-9-UDA, were taken into account. The pH adjustments to 7.5, 8, 8.5 and 9 were done with 50% potassium hydroxide. Filter sterilization was used instead of autoclaving to prevent adverse chemical reactions at higher pH and temperature. The target for initial cell density was 10⁵ to 10 cfu/ml. According to

15 the McFarland standard, 0.01 OD₆₀₀ is equivalent to approximately 10⁸ cfu/ml. To achieve the proper dilution, 30 μl of overnight culture diluted to 0.01 OD_60O was added to the 3 ml of media in each tube. The tubes were incubated at 35°C with the exception of Pseudomonas strains which were incubated at 30°C. Treatments were all done in duplicate. All strains were shaken at 250 rpm, with the exception of

20 Lactobacillus (because it is anaerobic). OD₆₀₀ readings were taken at 0, 19, 25.5, 42.5 and 49 hours.

"Percent reduction in growth vs. control" was defined as (1- abs. of treatment / abs. of control) X 100. Results are illustrated in the Tables 7-12 below: Table 7.

Table 8.

Table 9.

Table 10.

Tablell.

Table 12.

Results indicated that in the case of all organisms tested in Tables 7-11 and at the respective concentrations of the antimicrobial agent used (indicated in the tables above), the potassium salt of 9-UDA resulted in a 96 % to 100 % reduction in growth at pH 7.5 when compared with the appropriate control organisms grown at the same pH. The potassium salt of 9-UDA resulted in a 88 % to 100 % reduction in growth at pH 8.5 when compared with the appropriate control organisms grown at the same pH, with the exception of Bacillus cereus. Results further indicated that in the case of all organisms tested above, in Tables 7-1 1, with the exception ofSerratia marcescens, at the concentrations of the antimicrobial agent used (indicated in the table above), the various concentrations of potassium salt of 9-DA tested, resulted in a 92 % to 96 % reduction in growth at pH 7.5 when compared with the appropriate control organisms grown at the same pH. Various concentrations of the potassium salt of 9-DA tested resulted in a 94 % to 98 % reduction in growth at pH 8.5 when compared with the appropriate control organisms grown at the same pH, with the exception of Serratia marcescens.

Based on the observations in Tables 7-11, it is expected that increasing the potassium 9-UDA or 9-DA concentrations would be required for complete inhibition of growth of those microorganisms that did not show complete growth inhibition at the concentrations of antimicrobial used in this study. The results in Table 12, indicate that for Bacillus cereus, when comparing the results from Tables 9, as expected when a higher concentration of potassium 9-UDA was used, 100% reduction in growth vs. the control was observed at pH 8.0 and pH 9.0.

It should also be noted that these studies were performed in rich media under optimal growth conditions for the various microorganisms. Therefore in some cases the use of lower amounts of the antimicrobial could be efficacious in various products or applications where inhibition of specific microbes is desired. Further, it is surprising that the potassium salts of 9-UDA and 9-DA exhibited significant antimicrobial activity at pH levels of 8 and higher. Typically, it has been observed that effectiveness for conventional antimicrobial agents fails around neutral pH levels. Thus, in accordance with some aspects of the invention, the antimicrobial compositions can provide significant benefits over known antimicrobial agents, in light of this additional pH range of efficacy. Example 5:

The efficacy of potassium salts of 9-DA and 9-UDA in food applications was determined through the comparison at equimolar equivalence to 1000 to 500 concentrations (ppm) of potassium sorbate (control). Efficacy was determined against the following microorganisms: Lactobacillus plantarwn-WMtype from Dressing, Listeria innocua ATCC 32293, Pseudomonas putida ATCC 12633, Bacillus cereus F3802A184, E. coli ATCC 1 1229, and Saccharomyces cerevisiae ATCC 32167.

Each organism was grown in 10 ml APT broth at a pH of 6.5 and was incubated at 21⁰C for 3 days, except for yeast and mold at 5 days. A 1,000-ppm (0.1%) and 500-ppm (0.05%) concentration for Potassium 9-Decenoic Acid Salt (K9DA), Potassium 9-Undecenoic Acid Salt (K9UDA) and Potassium Sorbate (K Sorbate) were made as indicated below. A 1000-ppm K Sorbate, purity 99%, solution was made using 1.0 Ig salt into 50ml-distilled water; filter sterilized and added to sterile 950 ml APT broth. A 500-ppm K Sorbate, purity 99%, solution was made using 0.5Og salt into 50ml-distilled water; filter sterilized and added to sterile 950 ml APT broth. 9-DA or 9-UDA were tested at equimolar levels to 500 ppm or 100 ppm potassium sorbate as indicated in Table 13 below.

Table 13: Conversion to same molarity as potassium sorbate

Each solution was checked for a final pH (6.5 +/- 0.05) and dispensed into properly numbered tubes necessary for 5 testing periods in duplicate. Each tube was inoculated with about 100-1000 microbes per ml. For each organism, the inoculum was plated on APT agar and incubated at 2O⁰C for 3 days, with the exception of yeast and mold at 5 days to act as a positive control. In addition, sets of non- inoculated tubes were used as negative controls.

At Plate time 0, two tubes per condition were plated onto APT agar at pH (6.5 +/- 0.05), using appropriate dilutions (-1, -2, -3). Plates were incubated at 2O⁰C for 3 days, with the exception of yeast and mold at 5 days. Plating was repeated for remaining 4 test periods (Day 1, Day 4, Day 7, Day 14). Tubes that became turbid over time were not plated and reported as >7 logs. Tubes that stayed clear were then plated to include direct counts. After incubation, typical colonies were counted and multiplied according to appropriate dilutions to get a final count per gram (cfu/g). Results are illustrated in Tables 14-16 below:

Table 14.

Table 16.

All results are an average from duplicate samples ND = Not determined since bacterial counts were high 0.70 equals < lO cfu/g -0.30 equals , lcfu/g

Results indicate that the potassium salts of 9-UDA and 9-DA have antimicrobial activity against several potential spoilage microorganisms and were very effective against Saccharomyces cerevisiae ATCC 32167. While the potassium salts of 9-DA were not effective antimicrobial agents, at the concentrations used, against Listeria innocua ATCC 32293, the potassium salts of 9-UDA were very effective antimicrobial agents. Results indicate that the potassium salt of 9-UDA was very effective at concentrations equimolar with 1 OOOppm and 500 ppm potassium sorbate. While the potassium salts of 9-UDA and 9-DA were not effective antimicrobial agents at the concentrations used, against Lactobacillus plantarum-VJildtype from Dressing, Pseudomonas putida ATCC 12633, or E. coli ATCC 1 1229, it is expected that higher concentrations could be still be effective. While the potassium salts of 9-DA were not effective antimicrobial agents, at the concentrations used, against Listeria innocua ATCC 32293, the potassium salts of 9-UDA were very effective antimicrobial agents. Under the conditions of the test above, the potassium salts of 9-UDA and 9-DA were effective antimicrobial agents and demonstrated superior antimicrobial activity than potassium sorbate as a control at equimolar amounts under the same conditions. Example 6: The efficacy of potassium salts of 9-DA and 9-UDA was studied against an

Alicyclobacillus cocktail consisting of four different species. Alicyclobacillus is a common juice spoilage organism. Potassium salts of 9-DA and 9-UDA at equimolar equivalence respectively to 500 ppm and 100 ppm sodium benzoate were found to be more effective than the control sodium benzoate. Other concentrations of the potassium salts of 9-DA and 9-UDA were found to be as effective as the equimolar amount of sodium benzoate.

Alicyclobacillus acidoterrestris ATCC 49025 and wildtype A. acidoterrestris from orange juice, Alicyclobacillus acidocaldarius ATCC 27009 and wildtype A. acidocaldarius from orange juice were enriched on 5 Yeast, Starch, and Glucose (YSG) spread plates for each culture. Plated cultures were incubated at 46⁰C for 7 days to produce spores. Plates were incubated in a plastic bag to avoid moisture loss.

The following concentrations of potassium 9-DA and potassium 9-UDA were prepared: 500-ppm (0.05%) and 100-ppm (0.01%) concentration solutions for Potassium 9-Decenoic Acid Salt (K9DA), Potassium 9-Undecenoic Acid Salt (K9UDA) and Sodium Benzoate. The antimicrobial agents were tested at two temperatures points (46⁰C and 32⁰C). For 500-ppm Sodium Benzoate, purity 99%, 0.5 Ig of salt was added to 50 ml distilled water, the mixture was filter-sterilized, and the sterilized mixture was added to sterile 950 ml YSG broth. For 100-ppm Sodium Benzoate, purity 99%, 0.1 Og of salt was added to 50 ml distilled water, the mixture was filter-sterilized, and the sterilized mixture was added to sterile 950 ml YSG broth.

9-DA or 9-UDA were tested at equimolar levels to 500 ppm or 100 ppm sodium benzoate as indicated in the table below. Table 17: Molar equivalent for 50-1000 ppm Sodium benzoate (144.11 MW)

Each solution was checked for a final pH (3.7 +/- 0.1) and dispensed into properly numbered tubes necessary for 5 testing periods in triplicate. After 7 days incubation, cultures were examined under a microscope using a wet mount for spores. If spores were present, sterile distilled water was used to produce inoculum. The samples were heat shocked at 80⁰C for 10 minutes. Time was not counted until solutions reached 80⁰C. Each YSG tube was inoculated with approximately 100-1000 microbes per ml. Then the inoculum was plated on YSG agar and incubated at 46⁰C for 5 days for a positive control. Plates were incubated in a plastic bag to avoid moisture loss, hi addition, 5 non-inoculated YSG tubes per condition were included to act as negative controls. Samples were tested in triplicate except for the negative controls.

At plate time 0, three tubes per condition were plated onto YSG agar at pH (3.7 +/- 0.1), using appropriate dilutions (-1, -2, -3). Plates were incubated at 46⁰C and 32⁰C for 5 days in a bag. Plating was repeated for remaining 4 test periods (Day 4, Day 7, Day 14, Day 21) as described above. Tubes that became turbid over time were not plated and were reported as >7 logs. Tubes that appeared clear needed plating and in some cases required direct plating. The two principal spoilage species, A. acidocalderius (more thermophilic) and A acidoterrestris (less thermophilic) have different temperature growth ranges hence the choice of two different incubation temperatures. After incubation, typical colonies were counted and multiplied according to appropriate dilution factor to get a final count per gram (cfu/g). Results are indicated in the Table 18 below and are graphically represented in FIG. 14: Table 18: 9-Decenoic Acid Potassium Salt Study Against Λlicyclobaccillus species with Comparison to Sodium Benzoate as a control

n = 3 for all treatments -0.30 equals <lcfu/g 0.70 equals <10cfu/g

Alicyclobacillus sp. are bacterial spore formers that are sometimes called^{^} acidophilic thermophilic bacteria (ATB). These bacteria cause spoilage of many shelf-stable juice products, resulting in off-flavor and off-odor in these products.

10 Results demonstrated that the potassium salts of both 9-UDA and 9-DA were much more effective as antimicrobial agents against an Alicyclobacillus cocktail when compared at equimolar amounts to 500 ppm (0.05%) sodium benzoate under similar test conditions of incubation at 46⁰C. Potassium salts of 9-DA and 9-UDA at equimolar equivalence to 100 ppm sodium benzoate were found to be as effective as

15 the control sodium benzoate under the test incubation conditions of 46⁰C. Potassium salts of 9-DA and 9-UDA at equimolar equivalence to 500ppm and 100 ppm sodium benzoate were found to have similar efficacy as the control sodium benzoate under the test incubation conditions of 32°C.

The following procedures are applicable to Examples 7- 10.

General Procedure for Metathesis Reactions To a Fisher Porter tube containing metathesis catalyst and degassed internal olefin (e.g., SBO, methyl canola or methyl soyate) is added terminal olefin (e.g., 1-propene or 1-butene). A Fisher Porter tube pressure rated for 225 psi is used. Temperature, catalyst loading and pressure of alpha olefin are indicated in the tables. Metathesis catalyst is removed as described below. Products (e.g., methyl 9-decenoate and methyl 9- undecenoate) are isolated, after trans-esterification in the case of SBO, by fractional vacuum distillation. Excess 1-propene is optionally recovered and recycled in another metathesis reaction.

Catalyst Removal Procedure A 1.0 M solution of tris(hydroxymethyl)phosphine (THMP) in IPA ( 25 mol equiv of THMP per mole of metathesis catalyst) is added to the metathesized oil and the mixture is heated at 70 ⁰C for 6 hours under an atmosphere of argon (R. L. Pederson; I. M. Fellows; T.A. Ung; H. Ishihara; S.P Hajela Adv. Syn. Cat. 2002, 344, 728). Hexanes is added if needed to form a second phase; the mixture is washed 3 times with water. The organic phase is dried with anhydrous Na₂SO₄, filtered and analyzed by GC analysis.

Alternative Catalyst Removal Procedure A 1.0 M solution of tris(hydroxymethyl)phosphine (THMP) in IPA ( 25 mol equiv of THMP per mole of metathesis catalyst) is added to the metathesized oil and the mixture is heated at 70 ⁰C for 6 hours under an atmosphere of argon (R.L. Pederson; LM. Fellows; T.A. Ung; H. Ishihara; S.P Hajela Adv. Syn. Cat. 2002, 344, 728). IPA is then removed via rotary evaporator (also removing in part the volatile terminal olefins). Bleaching clay (Pure Flow B80 CG, 5 wt% to product) is added to the crude reaction mixture, which is then stirred overnight under argon at 70 ⁰C. The crude product mixture containing the clay is subsequently filtered through a packed bed of sand (10 g), celite (5 g), bleaching clay (12.5 g), and sand (10 g). The filtered oil is analyzed by GC analysis.

Example Procedure for the Transesterification of Metathesized SBO A glass 3 -necked round bottom flask containing a magnetic stirrer and fitted with a condenser, temperature probe, and gas adapter was charged with crude metathesized SBO product (~ 2 L) and 1% w/w NaOMe in MeOH. The resulting light yellow heterogeneous mixture was stirred at 60 ⁰C for 1 hr. Towards the end of the hour, the mixture turned a homogeneous orange color. Esterified products were transferred into a separatory funnel and extracted with 2.0 L DI-H₂O. The aqueous layer was then extracted with 2 x 2.0 L Et₂O. The combined organic extracts were dried over anhydrous Na₂SO₄ (300 g) for 20 hours. The solution of esterified products was filtered and the filtrate was stripped of solvent via rotary evaporator.

Vacuum Distillation A glass 2.0 L 3-necked round bottom flask with a magnetic stirrer, packed column, distillation head, and temperature controller was charged with methyl ester products and placed in a heating mantle. The flask was attached to a 2-inch x 36-inch glass distillation packed column contain 0.16" Pro- Pak™ stainless steel saddles. The distillation column was adapted to a fractional distilling head, which was connected to a vacuum line. A 500 mL pre-weighed round bottom flask was used for collecting the fractions. Vacuum on this system was <1 mmHg.

GC Analysis Conditions The products were analyzed using an Agilent 6890 gas chromatography (GC) instrument with a flame ionization detector (FID). The following conditions and equipment were used:

Column: Rtx-5, 30m x 0.25mm (ID) x 0.25μm film thickness. Manufacturer: Restek

GC and column conditions: Injector temperature: 250°C

Detector temperature: 280°C

Oven temperature: Starting temperature: 100°C, hold time: 1 minute. Ramp rate 10°C/min to 25O⁰C, hold time: 12 minutes. Carrier gas: Helium Mean gas velocity: 31.3 ± 3.5% cm/sec (calculated)

Split ratio: -50: 1

The products were characterized by comparing peaks with known standards, in conjunction with supporting data from mass spectrum analysis (GCMS-Agilent 5973N). GCMS analysis was accomplished with a second Rtx-5, 30m x 0.25mm (ID) x 0.25μm film thickness GC column, using the same method as above. Table 19 provides GC retention times used for identifying compounds in the examples provided below. Table 19 also provides compound abbreviations that are used throughout the examples.

Table 19. GC Analysis of Products from the Cross Metathesis of Seed Oils with 1-Propene and 1-Butene.

Retention Compound Compound

Time Abbreviation

(min)

2.039 1-Decene IC₁₀

2.907 E-2-Undecene E-2C, ,

3.001 Z-2-Undecene Z-2C,,

5.298 Methyl 9-Decenoate 9C₁₀O₂Me (9DA)

6.708 Methyl E-9-Undecenoate E-9CnO₂Me (9UDA)

6.852 Methvl Z-9-Undecenoate Z-9CπCbMe f9UDAΪ

Example 7:

Propenolysis of SBO

SBO (source: Cargill, lot # F5L19) was reacted according to the general metathesis procedure provided above. Catalyst 827 and propene (130 psi) were used, and the reaction was performed at 60 ⁰C. The results are provided in Table 20.

Table 20. Propenolysis of SBO¹

Exp. # Amt. Time IC₁₀ E-2C,i + 9DA 9UDA Yield TON₉DA

Catalyst (h) (%) Z-2C_n (%) (%) (%)

(PPm) (%) 3-1 12A 75 2 7.14 6.13 12.72 9.49 35.74 1696 3-1 12B 75 4 6.63 4.74 16.76 10.95 39.08 2234 3-1 13A 50 2 7.52 5.55 15.97 10.80 39.84 3194 3-1 13B 50 4 8.99 5.38 21.61 12.30 48.29 4322 3-1 14A 25 1 7.65 6.01 18.51 14.50 46.64 7403 3-1 14B 25 2 7.31 6.33 18.70 16.05 48.39 7482 3-1 14C 25 3 8.71 6.58 20.69 15.56 51.54 8275 3-1 14D 25 4 8.91 6.60 21.52 15.82 52.86 8609 3-1 16B 10 1 2.91 2.92 4.71 4.73 15.27 4705 3-1 16C 10 2 5.68 4.77 9.50 8.35 28.30 9501 3-1 16D 10 3 7.82 5.84 14.21 10.63 38.51 1421493-1 16E 10 4 7.89 5.40 15.59 10.89 39.77 1559393-1 16F 10 6 9.53 6.42 16.42 10.74 43.1 1 16423

Percentages correspond to GC area

Example 8:

Propenolysis of Methyl Soyate

Methyl soyate (source: Chemol) was reacted according to the general metathesis procedure provided above. Catalyst 827 and propene (130 psi, unless specified otherwise) were used, and the reaction was performed at 60 ⁰C. The results are provided in Table 21.

Table 21. Propenolysis of Methyl Soyate'

Exp. # Amt. Time IC₁₀ E-2C,, 9DA 9UDA Yield TON_9DA

Catalyst (h) (%) + Z- (%) (%) (%)

(ppm) 2C₁₁

(%) 93-107² 75 4 5.60 4.79 9.96 8.15 28.23 129293-109 75 4 6.82 5.56 1 1.89 8.84 33.1 1 1585 3-1 HA 25 1 10.51 7.73 22.39 15.68 56.30 8955 3-1 H B 25 2 10.78 7.51 22.51 15.10 55.90 9006 3-1 H C 25 3 1 1.06 7.35 23.72 14.89 57.01 9486 3-1 H D 25 4 1 1.47 7.40 23.68 14.88 57.42 9470 3-1 15A 10 0.5 8.67 6.42 16.36 1 1.54 42.99 16359 3-1 15B 10 1 9.78 6.40 18.90 12.13 47.21 18898 3-1 15C 10 2 10.08 6.43 19.87 12.33 48.71 19871 3-1 15D 10 3 10.20 6.41 20.00 12.32 48.92 20001 3-1 15E 10 4 10.17 6.43 20.13 12.36 49.10 20134 3-1 15F 10 6 10.12 6.45 20.35 12.39 49.31 20347 3-1 17A 5 1.5 0.76 0.92 1.01 0.53 3.22 2020 3-1 17B 5 4 0.82 0.99 1.07 1.01 3.89 2140 3-1 18A 2.5 1.5 0.18 0.23 0.22 0.21 0.84 880 3-1 18B 2.5 4 0.21 .027 0.27 1.01 1.76 1080

Percentages correspond to GC area. 2 Reaction performed with 100 psi propene.

Example 9: Propenolysis of FAMEs

Fatty acid methyl esters (FAMEs) were reacted according to the general metathesis procedure provided above. Canola FAME (source: Cognis, Lot # MF-CNF6C27), SBO FAME (source: Chemol, Lot # IF-24298), and Sun FAME (source: Nu Chek, Lot # "Special") were used. Catalyst 827 (5 ppm) and propene (130 psi) were used, and the reaction was performed at 60 ⁰C. The results are provided in Table 22.

Table 22. Propenolysis of Various FAMEs'

Exp. # Seed Oil Time IC₁₀ 2C₁₁ 9DA 9UDA Yield TON₉₀A

(h) (%) (%) (%) (%) (%)

129- Canola 2 10.53 7.59 16.75 1 1.39 46.26 33500

018A FAME

129- Canola 4 10.42 7.56 16.93 1 1.47 46.38 33860

018B FAME

129- Canola 2 10.9 7.64 16.97 1 1.38 46.89 33940

019A FAME

129- Canola 4 1 1.09 7.85 17.82 1 1.85 48.61 35640

019B FAME

129- SBO 2 0.77 0.98 0.98 0.94 3.67 1960

021A FAME

129- SBO 4 0.72 0.95 0.96 0.92 3.55 1920

021 B FAME

129- Sun 2 0.51 0.61 0.56 0.61 2.29 1 120

022A FAME

129- Sun 4 0.5 0.6 0.55 0.62 2.27 1 100

022B FAME

129- Sun 2 3.1 3.21 3.3 3.16 12.77 6600

023A FAME

129- Sun 4 2.79 3.02 3.21 3.14 12.16 6420

023 B FAME

¹ Percentages correspond to GC area.

Example 10: Propenolysis of FAMEs

Fatty acid methyl esters (FAMEs) were reacted according to the general metathesis procedure provided above. Canola FAME (source: Cognis), SBO FAME (source: Cognis), and Sun FAME (source: Nu Chek) were used. Propene (130 psi) was used as the terminal olefin, and the reaction was performed at 60 ⁰C for 4 hours. The results are provided in Table 23.

Table 23. Propenolysis of FAMEs¹

129-012B Sun C827 18.65 13.65 21.32 15.16 68.78 8528

FAME (25)

129-014B Canola C827 13.19 9.63 20.78 14.91 58.51 8312

FAME (25)

129-013B Sun C827 15.45 10.64 23.95 14.63 64.67 23950

FAME (10)

129-015B Canola C827 13.41 8.69 20.72 13.48 56.3 20720

FAME (10)

129-018B Canola C827 10.42 7.56 16.93 11.47 46.38 33860

FAME (5)

129-019B Canola C827 11.09 7.85 17.82 11.85 48.61 35640

FAME (5)

129-006B² SBO C848 8.67 4.38 27.52 13.39 53.96 11008

FAME (25)

129-009B² Canola C848 15.19 9.65 25.74 15.68 66.26 10296

Other embodiments of this invention will be apparent to those skilled in the art upon consideration of this specification or from practice of the invention disclosed herein. Variations on the embodiments described herein will become apparent to those of skill in the relevant arts upon reading this description. The inventors expect those of skill to use such variations as appropriate, and intend to the invention to be practiced otherwise than specifically described herein. Accordingly, the invention includes all modifications and equivalents of the subject matter recited in the claims as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the invention unless otherwise indicated. All patents, patent documents, and publications cited herein are hereby incorporated by reference as if individually incorporated. In case of conflict, the present specification, including definitions, will control.

Claims

WHAT IS CLAIMED IS:

1. An antimicrobial composition comprising a combination of a first antimicrobial agent of Formula 1 and a second antimicrobial agent of Formula IV.

2. The antimicrobial composition according to claim 1 , wherein the antimicrobial agent and second antimicrobial agent are present in a ratio in the range of about 1 :5 to about 2: 1.

3. The antimicrobial composition according to claim 1, wherein the antimicrobial agent and second antimicrobial agent are present in a ratio of about 1 : 1.

4. The antimicrobial composition according to claim 1, wherein the antimicrobial composition is formed by metathesis.

5. The antimicrobial composition according to claim 4, wherein the antimicrobial composition is formed by the cross-metathesis of propylene with a fatty acid, a fatty ester, a glyceride, or a mixture thereof.

6. The antimicrobial composition according to claim 1 , wherein said composition is effective as an antimicrobial agent with MIC levels of about 0.1% or less, against fungi selected from Aspergillus parasiticus, Trichoderma virens, Aureobasidium pullulans, Aspergillus flavus, Cladosporium cladosporiodes, Aspergillus flavus, Aspergillus oryzae,

Aspergillus parasiticus, Ulocladium atrum, Candida albicans, Alternaria alternata, Stachybotrys chartarum, Aspergillus niger, and combinations thereof.

7. The antimicrobial composition according to claim 1, wherein said composition comprises the first antimicrobial agent and second antimicrobial agent in a combined amount in the range of 0.01% to 0.1% by weight of said composition.

8. The antimicrobial composition according to claim 1, wherein said composition is provided with a pH in the range of 5 to 9.

9. An antimicrobial product comprising the composition of claim 1.

10. The antimicrobial product according to claim 9, wherein said product is a consumer product, industrial preparation, or a food or feed formulation.

1 1. The antimicrobial product according to claim 10, wherein the industrial preparation is a surface coating composition.

12. The antimicrobial product according to claim 1 1 , wherein the surface coating composition is a paint, varnish, stain, concrete coating, or anti-graffiti coating.

13. The antimicrobial product according to claim 10, wherein the industrial preparation is a metalworking fluid.

14. An antimicrobial composition comprising a combination of a first antimicrobial agent selected from antimicrobial agents of Formula I, Formula II, Formula III, or a combination of any two or more of these, and a second antimicrobial agent selected from antimicrobial agents of Formula IV, Formula V, Formula VI, or a combination of any two or more of these.

15. An industrial preparation comprising an effective amount of an antimicrobial composition comprising 9-undecenoic acid, a salt of 9-undecenoic acid, an ester of 9-undecenoic acid, or a combination thereof.

16. The industrial preparation according to claim 15, wherein the antimicrobial composition is antibacterial.

17. The industrial preparation according to claim 15, wherein the antimicrobial composition comprises 9-undecenoic acid, and wherein the industrial preparation is a surface coating composition.

18. The industrial preparation according to claim 15, wherein the antimicrobial composition comprises 9-undecenoic acid, and wherein the industrial preparation is a metalworking fluid.

19. The industrial preparation according to claim 15, wherein the antimicrobial composition comprises 9-undecenoic acid, and wherein the industrial preparation is a preparation for wood preservation.

20. The industrial preparation according to claim 15, wherein the antimicrobial composition comprises 9-undecenoic acid, and wherein the industrial preparation is a preparation for pulp and paper treatment.

21. The industrial preparation according to claim 15, wherein the antimicrobial composition comprises 9-undecenoic acid, and wherein the industrial preparation is a preparation for adhesives.

22. The industrial preparation according to claim 15, wherein the antimicrobial composition comprises 9-undecenoic acid, and wherein the industrial preparation is a preparation for water treatment.

23. The industrial preparation according to claim 15, wherein the antimicrobial composition is a salt of 9-undecenoic acid according to Formula (II):

K⁺" [Rr]_n

where R I^" is ; n is an integer, for example, ranging from 1 to 4; and K⁺" is a +n charged cation.

24. The industrial preparation according to claim 23, wherein K⁺ⁿ is selected from Li⁺, Na⁺, K⁺, Ag⁺, NH₄ ⁺, and quaternary ammonium.

25. The industrial preparation according to claim 24, wherein the antimicrobial composition exhibits significant antimicrobial activity at pH levels of 8.

26. The industrial preparation according to claim 23, wherein K⁺ⁿ is selected from Ca⁺², Mg⁺², Cu⁺², and Fe⁺².

27. The industrial preparation according to claim 23, wherein K⁺" is selected from Al³⁺, Fe³⁺ and Ce³⁺.

28. The industrial preparation according to claim 15, wherein the antimicrobial composition is an ester of 9-undecenoic acid according to Formula (III):

(III) where — R3 is an organic group.

29. The industrial preparation according to claim 15, wherein the antimicrobial composition is formed by metathesis.

30. A dried film comprising the industrial preparation according to claim 15.

31. A method for controlling bacterial growth in an environment, the method comprising contacting the environment with an effective amount of an antimicrobial composition of claim 1.

32. The method according to claim 31 , wherein the environment is selected from consumer products, industrial preparations, and food or feed formulations.

33. A method for controlling bacterial growth in an environment comprising contacting the environment with a composition comprising a first antimicrobial agent of Formula I and a second antimicrobial agent of Formula IV as active ingredients in a ratio of 1 : 1 by weight.

34. The method according to claim 33, wherein said bacterial growth comprises Gram positive bacteria and Gram negative bacteria.

35. A method for controlling bacterial growth in an environment, the method comprising contacting the environment with an effective amount of an antimicrobial composition comprising 9-undecenoic acid, a salt of 9- undecenoic acid, an ester of 9-undecenoic acid, or a combination thereof.

36. The method according to claim 35, wherein the environment is selected from consumer products, industrial preparations, and food or feed formulations.

37. The method according to claim 35, wherein said bacterial growth comprises Gram positive bacteria and Gram negative bacteria.