Antimicrobial formulations with pelargonic acid

Abstract

An antimicrobial composition for extending the shelf-life of water, feed or feed ingredients, comprising: water, a mixture of CrC18 organic acids, a mixture of CrC24 aldehydes, 5-25 wt. % pelargonic acid, and 5-30 wt. % trans-2-hexenal.

Claims

1. An antimicrobial composition for extending the shelf-life of water, feed or feed ingredients, comprising: water, 5-15 wt. % of pelargonic acid, 10-20 wt. % of acetic acid, 40-50 wt. % of propionic acid, 5-30 wt. % of trans-2-hexenal, and 5-30 wt. % of a C.sub.1-C.sub.24 aldehyde selected from the group consisting of, cinnamaldehyde, undecylenic aldehyde, butyraldehyde, 2,4 decadienal, and decanal.

2. A method for extending the shelf-life of water, feed or feed ingredients, comprising: spray-treating or admixing to water, feed or feed ingredients, an effective amount of a composition comprising: water, 5-15 wt. % of pelargonic acid, 10-20 wt. % of acetic acid, 40-50 wt. % of propionic acid, 5-30 wt. % of trans-2-hexenal, and 5-30 wt. % of a C.sub.1-C.sub.24 aldehyde selected from the group consisting of, cinnamaldehyde, undecylenic aldehyde, butyraldehyde, 2,4 decadienal, and decanal.

3. The method of claim 2, wherein the composition is provided in an amount that is effective against bacteria, viruses, mycoplasmas or fungi present in drinking water, feed and feed ingredients.

4. The method of claim 2, wherein the composition is spray-treated or admixed to feed or feed ingredients at a rate of 0.25 to 2 kilograms per ton of feed or feed ingredients.

Description

DESCRIPTION OF THE PREFERRED EMBODIMENTS

(1) In this specification and in the claims which follow, reference will be made to a number of terms which shall be defined to have the following meanings.

Definitions

(2) A volume percent of a component is based on the total volume of the formulation or composition in which the component is included.

(3) An organic acid of the composition can comprise formic, acetic, propionic, butyric, pelargonic, lactic and other C.sub.2 to C.sub.24 fatty acid or mono-, di-, or triglycerides containing C.sub.1 to C.sub.24 fatty acids. These fatty acids comprising small chain, medium chain, long chain fatty acids or small chain, medium chain, long chain triglycerides.

(4) The term effective amount of a compound means an amount capable of performing the function of the compound or property for which an effective amount is expressed, such as a non-toxic but sufficient amount of the compound to provide the desired antimicrobial benefits. Thus an appropriate effective amount may be determined by one of ordinary skill in the art using only routine experimentation.

(5) Formulations can vary not only in the concentration of major components i.e. organic acids, but also in the type of aldehydes and water concentration used. This invention can be modified in several ways by adding or deleting from the formulation the type of organic acid and aldehyde.

(6) By the terms synergistic effect or synergy of the composition is meant to the improved the preservative effect when the ingredients are added as a mixture rather than as individual components.

(7) Composition (s)

(8) A composition of the present invention comprises an effective amount of organic acids of 1 to 24 carbons chain and an aldehyde.

(9) The composition can comprise 1 to 100% by volume organic acids, 0 to 99% by volume acetic acid, 0 to 99% by volume propionic acid, 0 to 99% lactic acid, 0 to 99% pelargonic acid. The composition can comprise 0 to 99% water. The composition can comprise 0 to 99% of other aldehyde.

(10) Methods

(11) The present invention is effective against bacteria and fungi. The present invention is applied to water. The present invention is applied to the raw material before entering the mixer. The present invention is applied to the unmixed raw materials in the mixer. The present invention is applied during the mixing of the raw ingredients. The present invention is applied in liquid form or as a dry product mixed with a carrier. The present invention is applied is such a form that provides a uniform and homogeneous distribution of the mixture throughout the feed.

(12) One of the objectives of the present invention is to control the level of microbes in feed and feedstuffs. Several mixtures of organic acids and aldehydes resulted in several formulations that showed effectiveness against bacteria in buffer and feed. Other objective of the present invention is to formulate an antimicrobial with natural occurring compounds or safe to use compounds. All of the chemicals used in the present invention are currently approved for human uses as antimicrobials, flavor enhancers and perfumery.

(13) There were unexpected results, i.e. synergism and additive effect, when the organic acids and aldehydes were used.

(14) Throughout this application, various publications are referenced. The disclosures of these publications in their entireties are hereby incorporated by reference into this application in order to more fully describe the state of the art to which this invention pertains.

Example 1

(15) Formaldehyde and/or pelargonic acid were added to test tubes at concentrations shown in Table 1. Solutions were vortexed for 10 seconds to ensure mixing. There were three replicate tubes per treatment. A suspension of Salmonella typhimurium (10.sup.3 cfu/ml, ATCC #14028) was added to three test tubes containing each formulation. The solutions were vortexed, incubated at room temperature for 24 hours plated on SMA (Standard Methods Agar) for 24 hours before counting Salmonella colonies. The effectiveness of each formulation as a percent reduction compared to its control value is shown in the following table.

(16) TABLE-US-00001 TABLE 1 Interaction of Pelargonic acid and formaldehyde Formaldehyde Pelargonic acid Salmonella Test Product (%) (%) % reduction Control 0 0 0 Formaldehyde 0.025 0 90.8 0.0125 0 59.0 0.00625 0 39.3 0.00312 0 17.3 Pelargonic acid 0 0.0025 0 0 0.00125 0 0 0.000625 0 0 0.000312 0 HCHO: Pelargonic 0.025 0.0025 94.2 0.0125 0.0025 61.0 0.00625 0.0025 40.7 0.00312 0.0025 26.1 0.025 0.00125 92.5 0.0125 0.00125 52.5 0.00625 0.00125 38.6 0.00312 0.00125 27.8 0.025 0.000625 83.1 0.0125 0.000625 54.6 0.00625 0.000625 45.4 0.00312 0.000625 18.6 0.025 0.000312 90.2 0.0125 0.000312 57.6 0.00625 0.000312 39.7 0.00312 0.000312 22.7

(17) A dose response curve was observed with formaldehyde and the formaldehyde: pelargonic acid treatments. Pelargonic acid at the highest dose tested was not bactericidal. Pelargonic acid at 0.00125 and 0.0025% did appear to increase the effectiveness of formaldehyde.

Example 2

(18) Formaldehyde and/or pelargonic acid were added to test tubes at concentrations shown in Table 2. Solutions were vortexed for 10 seconds to ensure mixing. There were three replicate tubes per treatment. A suspension of Salmonella typhimurium (10.sup.3 cfu/ml, ATCC #14028) was added to three test tubes containing each formulation. The solutions were vortexed, incubated at room temperature for 24 hours and plated on SMA (Standard Methods Agar) for 24 hours before counting Salmonella colonies. The effectiveness of each formulation as a percent reduction compared to its control value is shown in the following table.

(19) TABLE-US-00002 TABLE 2 Interaction of pelargonic acid and formaldehyde Formaldehyde Pelargonic acid Salmonella Test Product (%) (%) % reduction Control 0 0 0 Formaldehyde 0.025 0 88.3 0.0125 0 50.5 0.00625 0 41.0 0.00312 0 17.7 Pelargonic acid 0 0.01 100 0 0.005 96.5 0 0.0025 8.8 0 0.00125 2.1 HCHO: Pelargonic 0.025 0.01 100 0.025 0.005 98.6 0.025 0.0025 97.2 0.025 0.00125 91.9 0.0125 0.01 100 0.0125 0.005 100 0.0125 0.0025 62.9 0.0125 0.00125 37.8 0.00625 0.01 100 0.00625 0.005 99.6 0.00625 0.0025 20.8 0.00625 0.00125 38.2 0.00312 0.01 100 0.00312 0.005 97.2 0.00312 0.0025 36.0 0.00312 0.00125 0.4

(20) A dose response curve was observed with formaldehyde, pelargonic acid and the formaldehyde:pelargonic acid treatments. Pelargonic acid at 0.00125% and 0.0025% did not have a significant impact on Salmonella reduction. However, when these levels of pelargonic acid were mixed with formaldehyde, the bactericidal efficacy of formaldehyde was improved.

Example 3

(21) Five formulations were prepared for in vitro studies as presented in Table 3. Formulations were added to test tubes at concentrations of 0.01% and 0.05%. Solutions were vortexed for 10 seconds to ensure mixing. There were three replicate tubes per treatment.

(22) TABLE-US-00003 TABLE 3 Chemical Composition of Product Formulas (%) Chemical 1 2 3 4 5 Acetic acid 20 20 20 20 20 Propionic acid 50 50 50 50 50 Pelargonic acid 5 10 15 20 25 Trans-2-Hexenal 25 20 15 10 5 TOTAL 100.0 100.0 100.0 100.0 100.0

(23) A suspension of Salmonella typhimurium (10.sup.4 cfu/ml) was added to three test tubes containing the different dilutions of each formulation. The tubes were vortexed, incubated at room temperature for 24 hours and then the solution was plated on SMA (Standard Methods Agar) for 48 hours before counting Salmonella colonies. The effectiveness of each formulation is reported as a percent reduction compared to its control value as is shown in the following table.

(24) TABLE-US-00004 TABLE 4 Percent Salmonella Reduction 0.01% 0.05% Treatment Dilution Dilution Formula 1 80.6 100 Formula 2 73.0 99.5 Formula 3 52.3 97.7 Formula 4 41.4 96.8 Formula 5 18.9 93.7

(25) Pelargonic acid at 10% increases the efficacy of trans-2-hexenal.

Example 4

(26) Three formulations from study 3 were chosen to test their effectiveness against Salmonella typhimurium (ATCC #14028) in feed. Poultry mash feed was amended with a meat and bone meal inoculum of Salmonella typhimurium at a level of 10.sup.3 cfu/g of feed. Contaminated feed was then treated with either 0, 1.5 or 2 kg/MT of the formulations listed below. After 24 hours, 10 g of subsamples of the untreated and treated feed were suspended in 90 ml Butterfield buffer. Dilutions were plated on XLT-4 agar and incubated at 37 C. for 48 hours before counting Salmonella colonies. Additional samples were taken at 7 days after treatment for Salmonella enumeration. The formulas used are shown in the following table.

(27) TABLE-US-00005 TABLE 5 CHEMICAL FORMULATIONS (%) Chemical 1 2 3 Acetic acid 20 20 20 Propionic acid 50 50 50 Pelargonic acid 5 10 15 Trans-2-hexenal 25 20 15 Total 100 100 100

(28) Results: The following table shows that all formulations were effective against Salmonella. Increasing the level of pelargonic acid resulted in similar efficacy as high level of hexenal.

(29) TABLE-US-00006 TABLE 6 Effect of Chemicals on Salmonella at 1 and 7 Days Post-Treatment % Reduction % Reduction Treatment Kg/MT at 1 Day at 7 Day Control 0 0 0 Formula #1 1.5 85.0 97.4 2 93.8 98.9 Formula #2 1.5 75.6 94.3 2 98.0 99.6 Formula #3 1.5 90.6 92.1 2 91.8 96.6

Example 5

(30) The five formulations used in Example 3 were chosen to test their effectiveness against Salmonella typhimurium. Poultry mash feed was amended with a meat and bone meal inoculum of Salmonella typhimurium. Contaminated feed was then treated with either 0 or 2 kg/MT of the formulations. After 24 hours, 10 g of subsamples of the treated feed were suspended in 90 ml Butterfield buffer. Dilutions were plated on XLT-4 agar and incubated at 37 C. for 48 hours before counting Salmonella colonies. Additional samples were taken 7 days after treatment for Salmonella enumeration. The following table shows that all formulations were effective against Salmonella.

(31) TABLE-US-00007 TABLE 7 Effect of Chemicals on Salmonella at 1 and 7 Days Post-Treatment % Reduction % Reduction Treatment at 24 Hours at 7 Days Control 0 0 Formula 1 90.0 96.6 Formula 2 92.6 97.6 Formula 3 86.1 91.0 Formula 4 47.3 76.5 Formula 5 55.1 66.7

(32) Equal concentration of Pelargonic acid and trans-2-hexenal resulted in similar effectiveness as high levels (25%) trans-2-hexenal.

Example 6

(33) Formula 1 from Example 3 composed of 25% trans-2-hexenal, 5% pelargonic acid and 70% aqueous organic acids was compared to trans-2-hexenal for residual activity in feed. Poultry mash feed was treated with 0.1, 0.25, 0.5 or 1.0 kg/ton of hexenal compared to 1 kg/ton of the hexenal: pelargonic acid combination product (0.25 kg/ton of hexenal), At 1, 6 and 13 days post treatment, feed was contaminated with a meat and bone meal inoculum of Salmonella typhimurium at a level of 10.sup.3 cfu/g of feed. After 24 hours, 10 g of subsamples of the untreated and treated feed were suspended in 90 ml Butterfield buffer. Dilutions were plated on XLT-4 agar and incubated at 37 C. for 48 hours before counting Salmonella colonies.

(34) The following table compares the impact of pelargonic acid on the residual activity of hexenal against Salmonella.

(35) TABLE-US-00008 TABLE 8 Evaluating the Synergism of Pelargonic acid and Hexenal on Residual Activity in Treated Feed % Reduction Treatment at 13 Days Control 0 Hexenal: pelargonic mixture 93.5 (0.25 kg/ton hexenal) 0.10 kg/ton hexenal 0 0.25 kg/ton hexenal 0 0.50 kg/ton hexenal 77.4 1.00 kg/ton hexenal 87.1

(36) The addition of pelargonic acid (5%) to trans-2-hexenal resulted in better effectiveness against Salmonella than trans-2-hexenal by itself.

Example 7

(37) Seven aldehydes (butyraldehyde, citral, undecylenic aldehyde, decadienal, cinnamaldehyde, decanal and furfural) were blended with trans-2-hexenal, pelargonic acid, propionic acid and acetic acid as presented in Table 9. A 20% (X1) and a 25% (F18) hexanal: organic acid product were included as positive controls. Formulations were added to test tube at concentration of 0.1%, 0.05%, 0.01% and 0.005%. Solutions were vortexed for 10 seconds to uniformly mix the solution. There were three replicate tubes per treatment. A suspension of Salmonella typhimurium (10.sup.4 cfu/ml) was added to three test tubes containing the different dilution of each formulation. The solutions were vortexed, incubated at room temperature for 24 hours and then plated on XLT-4 agar for 48 hours before counting Salmonella colonies.

(38) The effectiveness of each formulation as percent reduction compared to the control value is shown in the following tables.

(39) TABLE-US-00009 TABLE 9 Effect of Butyraldehyde, Hexenal and Pelargonic Acid on Salmonella FORMULAS F18 X-1 65 66 67 68 69 70 71 72 73 74 Pelargonic acid 5 10 5 5 5 5 5 10 10 10 10 10 Acetic acid (56%) 20 20 20 20 20 20 25 15 15 15 15 20 2-hexenal 25 20 20 15 10 5 0 20 15 10 5 0 Propionic acid 50 50 50 50 50 50 50 50 50 50 50 50 Butyraldehyde 5 10 15 20 20 5 10 15 20 20 100 100 100 100 100 100 100 100 100 100 100 100 % Reduction of Salmonella Growth Concentration F18 X-1 65 66 67 68 69 70 71 72 73 74 0.005% 26.7 21.2 26.7 9.1 4.2 0 0 9.1 15.2 1.2 0 0 0.01% 70.9 52.1 44.8 40.0 11.5 0 0 67.3 38.2 6.7 0 0 0.05% 100 100 100 100 94.5 69.7 0 100 99.4 95.2 77.0 0

(40) TABLE-US-00010 TABLE 10 Effect of Citral, Hexenal and Pelargonic Acid on Salmonella FORMULAS F18 X-1 75 76 77 78 79 80 81 82 83 84 Pelargonic acid 5 10 5 5 5 5 5 10 10 10 10 10 Acetic acid (56%) 20 20 20 20 20 20 25 15 15 15 15 20 2-hexenal 25 20 20 15 10 5 0 20 15 10 5 0 Propionic acid 50 50 50 50 50 50 50 50 50 50 50 50 citral 0 0 5 10 15 20 20 5 10 15 20 20 100 100 100 100 100 100 100 100 100 100 100 100 % Reduction of Salmonella Growth Concentration F18 X-1 75 76 77 78 79 80 81 82 83 84 0.005% 26.7 21.2 23.6 33.9 44.8 43.0 29.1 19.4 45.5 36.4 37.0 38.2 0.01% 70.9 52.1 70.3 63.0 63.0 77.0 33.3 68.5 60.6 60.6 53.3 30.9 0.05% 100 100 100 100 100 100 90.9 100 100 100 100 94.5

(41) TABLE-US-00011 TABLE 11 Effect of Undecylenic, Hexenal and Pelargonic Acid on Salmonella FORMULAS F18 X-1 95 96 97 98 99 100 101 102 103 104 Pelargonic acid 5 10 5 5 5 5 5 10 10 10 10 10 Acetic acid (56%) 20 20 20 20 20 20 25 15 15 15 15 20 2-hexenal 25 20 20 15 10 5 0 20 15 10 5 0 Propionic acid 50 50 50 50 50 50 50 50 50 50 50 50 undecylenic 0 0 5 10 15 20 20 5 10 15 20 20 100 100 100 100 100 100 100 100 100 100 100 100 % Reduction of Salmonella Growth Concentration F18 X-1 F95 F96 F97 F98 F99 F100 F101 F102 F103 F104 0.005% 0 0 5.9 20.1 29.6 47.2 85.1 16.1 14.7 21.5 50.6 29.6 0.01% 38.4 19.5 60.7 52.6 74.3 79.7 90.5 49.2 69.5 41.1 51.9 62.1 0.05% 100 100 99.3 100 100 100 98.6 100 100 100 99.3 89.8

(42) TABLE-US-00012 TABLE 12 Effect of Decadienal, Hexenal and Pelargonic Acid on Salmonella FORMULAS F18 X-1 85 86 87 88 89 90 91 92 93 94 Pelargonic acid 5 10 5 5 5 5 5 10 10 10 10 10 Acetic acid (56%) 20 20 20 20 20 20 25 15 15 15 15 20 2-hexenal 25 20 20 15 10 5 0 20 15 10 5 0 Propionic acid 50 50 50 50 50 50 50 50 50 50 50 50 2,4 decadieneal 0 0 5 10 15 20 20 5 10 15 20 20 100 100 100 100 100 100 100 100 100 100 100 100 % Reduction of Salmonella Growth Concentration F18 X-1 85 86 87 88 89 90 91 92 93 94 0.005% 0 0 74.3 72.9 83.1 70.2 79.7 49.2 81.7 87.8 90.5 93.9 0.01% 38.4 19.5 98.0 94.6 93.2 92.6 96.6 91.9 99.3 98.6 99.3 91.2 0.05% 100 100 100 100 100 100 100 100 100 100 100 100

(43) TABLE-US-00013 TABLE 13 Effect of Cinnamaldehyde, Hexenal and Pelargonic Acid on Salmonella FORMULAS F18 X-1 105 106 107 108 109 110 111 112 113 114 Pelargonic acid 5 10 5 10 5 5 5 10 10 10 10 10 Acetic acid (56%) 20 20 20 20 20 20 25 15 15 15 15 20 2-hexenal 25 20 20 15 10 5 0 20 15 10 5 0 Propionic acid 50 50 50 50 50 50 50 50 50 50 50 50 cinnamaldehyde 0 0 5 10 15 20 20 5 10 15 20 20 100 100 100 100 100 100 100 100 100 100 100 100 % Reduction of Salmonella Growth Concentration F18 X1 F105 F106 F107 F108 F109 F110 F111 F112 F113 F114 0.005% 50.3 29.9 31.0 39.9 26.8 5.9 21.6 31.5 24.7 22.6 37.8 23.1 0.01% 73.3 50.3 59.2 62.9 44.6 45.6 18.4 66.0 55.6 57.1 45.6 15.3 0.05% 100 100 100 100 100 100 84.8 100 100 100 100 90.6

(44) TABLE-US-00014 TABLE 14 Effect of Decanal, Hexenal and Pelargonic Acid on Salmonella FORMULAS F18 X-1 115 116 117 118 119 120 121 122 123 124 Pelargonic acid 5 10 5 10 5 5 5 10 10 10 10 10 Acetic acid (56%) 20 20 20 20 20 20 25 15 15 15 15 20 2-hexenal 25 20 20 15 10 5 0 20 15 10 5 0 Propionic acid 50 50 50 50 50 50 50 50 50 50 50 50 decanal 0 0 5 10 15 20 20 5 10 15 20 20 100 100 100 100 100 100 100 100 100 100 100 100 % Reduction of Salmonella Growth Concentration F18 X1 F115 F116 F117 F118 F119 F120 F121 F122 F123 F124 0.005% 50.3 29.9 39.9 47.2 56.6 77.5 88.5 51.9 45.1 70.7 92.7 91.6 0.01% 73.3 50.3 61.8 89.0 93.7 94.2 94.8 67.6 74.4 86.9 93.2 94.8 0.05% 100 100 100 100 100 100 97.4 100 100 100 100 97.4

(45) TABLE-US-00015 TABLE 15 Effect of Furfural, Hexenal and Pelargonic Acid on Salmonella FORMULAS F18 X-1 125 126 127 128 129 130 131 132 133 134 Pelargonic acid 5 10 5 10 5 5 5 10 10 10 10 10 Acetic acid (56%) 20 20 20 20 20 20 25 15 15 15 15 20 2-hexenal 25 20 20 15 10 5 0 20 15 10 5 0 Propionic acid 50 50 50 50 50 50 50 50 50 50 50 50 furfural 0 0 5 10 15 20 20 5 10 15 20 20 100 100 100 100 100 100 100 100 100 100 100 100 % Reduction of Salmonella Growth Concentration F18 X1 F125 F126 F127 F128 F129 F130 F131 F132 F133 F134 0.005% 50.3 29.9 33.6 40.4 41.4 34.1 41.4 28.9 29.9 39.3 24.7 47.7 0.01% 73.3 50.3 63.4 43.5 33.6 34.1 36.7 78.6 41.4 33.1 29.9 28.9 0.05% 100 100 100 97.9 95.8 81.7 0 100 100 90.6 80.1 6.4

(46) Results: 1. At 5% pelargonic acid, butyraldehyde by itself is not as effective as trans-2-hexenal. 2. At 10% pelargonic acid, 20% butyraldehyde was as effective as 20% trans-2-hexenal. 3. At both, 5% and 10% pelargonic acid, butyraldehyde can partially replace trans-2-hexenal. 4. At 5% pelargonic acid, citral by itself is not as effective as trans-2-hexenal. 5. At 10% pelargonic acid, 20% citral was as effective as 20% trans-2-hexenal. 6. At both, 5% and 10% pelargonic acid, citral can partially replace trans-2-hexenal. 7. At both, 5% and 10% pelargonic acid, undecylenic aldehyde can replace trans-2-hexenal. 8. At both, 5% and 10% pelargonic acid, decadienal aldehyde can replace trans-2-hexenal. 9. At both, 5% and 10% pelargonic acid, cinnamaldehyde can replace trans-2-hexenal. 10. At both, 5% and 10% pelargonic acid, decanal can replace trans-2-hexenal. 11. At both, 5% and 10% pelargonic acid, furfural can replace trans-2-hexenal. 12. All the formulations tested were as effective and in some instance better than a positive formula with 25% or 20% trans-2-hexenal or the formic/propionic formulation.

CONCLUSION

(47) Pelargonic acid potentiates the efficacy of each individual aldehyde and aldehyde combination. It will be apparent to those skilled in the art that variations and modifications of the invention can be made without departing from the sprit and scope of the teachings above. It is intended that the specification and examples be considered as exemplary only and are not restrictive.