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.

Description:
RELATED APPLICATIONS 
       [0001]    This application claims priority to U.S. Provisional application 61/549,661, filed 20 Oct. 2011, hereby incorporated by reference. 
     
    
     BACKGROUND OF THE INVENTION 
       [0002]    1. Field of the Invention 
         [0003]    An antimicrobial formulation consisting of a mixture of organic acids and aldehydes where such combination resulted in synergistic response as compared to the addition of high levels of the other component. 
         [0004]    2. Background 
         [0005]    The Centers for Disease Control and Prevention (CDC) estimates that roughly one out of six Americans or 48 million people are sickened by food borne illnesses each year. Another 128,000 are hospitalized and approximately 3,000 die of food borne disease every year. In a 2011 report the CDC estimated that 20,000 cases of  Salmonella  resulted in hospitalization, and that 378 of these cases resulted in death. It has also estimated that  E. coli  0157:H7 causes approximately 62,000 cases of food borne disease and approximately 1,800 food borne illness-related hospitalizations in the United States. 
         [0006]    A study by the Pew Charitable Trusts of Georgetown University suggested that food borne illnesses cost the United States $152 billion in health-related expenses each year. 
         [0007]    As the world trends toward more natural and/or organic antimicrobials, the need to find them has resulted in a great amount of research, as well as increased cost for new raw materials due to the low commercial availability of these new natural/organic products. 
         [0008]    Formaldehyde has been use as an antiseptic for many years. Two patents, U.S. Pat. No. 5,547,987 and U.S. Pat. No. 5,591,467, teach the use of formaldehyde to control  Salmonella  in animal feed. These patents do not suggest that a combination of formaldehyde and an organic acid would provide a synergistic effect, as described in the present invention. 
         [0009]    New antimicrobials have been found in many plants. These antimicrobials protect plants from bacterial, fungal, viral and insect infestation. These antimicrobials, which are components of the plant essential oils, can be acidic, alcohol or aldehyde-based chemicals. 
         [0010]    One of the volatile compound used in this invention is trans-2-hexenal, which is six-carbon aldehyde with a conjugated double bond, C 6 H 10 O and MW=98.14. Aldehydes are represented by the general formula RCHO, where R is can be hydrogen or an aromatic, aliphatic or a heterocyclic group. They are moderately soluble in water and solubility decreases as the molecular weight increases. Unsaturated aliphatic aldehydes includes, propenal, trans-2-butenal, 2-methyl-2-butenal, 2-methyl-(E)-2-butenal, 2-pentenal, trans-2-hexenal, trans-2-hexen-1-ol, 2-methyl-2-pentanal, 2-isopropylpropenal, 2-ethyl-2-butenal, 2-ethyl-2-hexenal, (Z)-3-hexenal, 3,7-dimethyl-6-octenal, 3,7-dimethyl-2,6-octadienal, (2E)-3,7-dimethyl-2-6-octadienal, (2Z)-3,7-dimethyl-2,6-octadienal, trans-2-nonenal, (2E,6Z)-nonadienal, 10-undecanal, 2-dodecenal, 2,4-hexadienal and others. 
         [0011]    Trans-2-hexenal is present in many edible plants such as apples, pears, grapes, strawberries, kiwi, tomatoes, olives, etc. The use of plants and plant extracts have been successful in studies looking for new anti-microbials. For example, cashew apple was effective against  Helicobacter pylori  and  S. cholerasuis  (50-100 ug/ml). The two main components were found to be anacardic acid and trans-2-hexenal. The minimum inhibitory activity and minimum biocidal activity of trans-2-hexenal were determined to be 400 and 800 ug/ml, respectively (Kubo, J.; Lee, J. R.; Kubo, I. Anti- Helicobacter pylori  Agents from the Cashew Apple.  J. Agric. Food Chem.  1999, v. 47, 533-537; Kubo, I. And K. Fujita, Naturally Occurring Anti- Salmonella  Agents.  J. Agric. Food Chem.  2001, v. 49, 5750-5754). Kim and Shin found that trans-2-hexenal (247 mg/L) was effective against  B. cereus, S. typhimurium, V. parahaemolyticus, L. monocytogenes, S. aureus  and  E. coli  O157:H7 (Kim, Y. S.; Shin, D. H. Volatile Constituents from the Leaves of  Callicarpa japonica  Thunb. and Their Antibacterial Activities.  J. Agric. Food Chem.  2004, v. 52, 781-787). Nakamura. and Hatanaka (Green-leaf-derived C6-aroma compounds with potent antibacterial action that act on both gram-negative and gram-positive bacteria.  J. Agric. Food Chem.  2002, v. 50 no, 26, 7639-7644) demonstrated that (3E)-hexenal was effective in controlling  Staphylococcus aureus, E. coli  and  Salmonella typhimurium  at a level of 3-30 ug/ml. Trans-2-hexenal completely inhibited proliferation of both  P. syringae  pathovars (570 ug/L of air) and  E. coli  (930 micrograms/L of air) (Deng, W.; Hamilton-Kemp, T.; Nielsen, M.; Anderson, R.; Collins, G.; Hilderbrand, D. Effects of Six-Carbon Aldehydes and Alcohols on Bacterial Proliferation.  J. Agric. Food Chem.  1993, v. 41, 506-510). It was observed that trans-2-hexenal at 250 ug/ml was effective at inhibiting the growth of  Phoma  mycelium (Saniewska, S. and M. Saniewski, 2007. The effect of trans-2-hexenal and trans-2-nonenal on the mycelium growth of  Phoma narcissi  in vitro, Rocz. A R. Pozn. CCCLXXXIII,  Ogrodn . V. 41, 189-193). In a study to control mold in fruits it was found that trans-2-hexenal was not phytotoxic to apricots, but it was phytotoxic for peaches and nectarines at 40 μL/L (Neri, F., M. Mari, S. Brigati and P. Bertolini, 2007, Fungicidal activity of plant volatile compounds for controlling  Monolinia laxa  in stone fruit,  Plant Disease  v. 91, no. 1, 30-35). Trans-2-hexenal (12.5 μL/L) was effective on controlling  Penicillium expansum  that causes blue mold (Neri, F.; Mari, M.; Menniti, A.; Brigati, S.; Bertolini, P. Control of  Penicillium expansum  in pears and apples by trans-2-hexenal vapours.  Postharvest Biol. and Tech.  2006, v. 41, 101-108. Neri, F.; Mari, M.; Menniti, A. M.; Brigati, S. Activity of trans-2-hexenal against  Penicillium expansum  in ‘Conference’ pears.  J. Appl. Micrbiol.  2006, v. 100, 1186-1193). Fallik, E. et. al. (Trans-2-hexenal can stimulate  Botrytis cinerea  growth in vitro and on strawberries in vivo during storage,  J. ASHS.  1998, v. 123, no. (5, 875-881) and Hamilton-Kemp, et. al, ( J. Agric. Food Chem.  1991, v. 39, no. 5, 952-956) suggested that trans-2-hexenal vapors inhibited the germination of  Botrytis  spores and apple pollen. 
         [0012]    US Published Application No. 2007/0087094 suggests the use of at least two microbiocidally active GRAS compounds in combination with less than 50% alcohol (isopropanol or isopropanol/ethanol) as a microbicide. Trans-2-hexenal could be considered one of the GRAS compounds (Schuer. Process for Improving the Durability of, and/or Stabilizing, Microbially Perishable Products. US Published Application No. 2007/0087094). Also, Archbold et. al. observed that the use of 2-hexenal at 0.86 or 1.71 mmol (100 or 200 microliters neat compound per 1.1 L container, respectively) for 2 weeks as for postharvest fumigation of seedless table grapes showed promise for control of mold (Archbold, D.; Hamilton-Kemp, T.; Clements, A.; Collins, R. Fumigating ‘Crimson Seedless’ Table Grapes with (E)-2-Hexenal Reduces Mold during Long-term Postharvest Storage.  HortScience.  1999, v. 34, no. (4, 705-707). 
         [0013]    U.S. Pat. No. 5,698,599 suggests a method to inhibit mycotoxin production in a foodstuff by treating it with trans-2-hexenal. Trans-2-hexenal completely inhibited the growth of  A. flavus, P. notatum, A. alternate, F. oxysporum, Cladosporium  species,  B. subtilis  and  A. tumerfaciens  at a concentration of 8 ng/L air. When comparing trans-2-hexenal to citral in controlling yeast (10 5  CFU/bottle) in beverages it was found that 25 ppm of trans-2-hexenal and thermal treatment (56° C. for 20 min) was equivalent to 100-120 ppm citral. In beverages that were not thermally treated, 35 ppm of trans-2-hexenal was necessary to stabilize them (Belletti, N.; Kamdem, S.; Patrignani, F.; Lanciotti, R.; Covelli, A.; Gardini, F. Antimicrobial Activity of Aroma Compounds against  Saccharomyces cerevisiae  and Improvement of Microbiological Stability of Soft Drinks as Assessed by Logistic Regression.  AEM.  2007, v. 73, no. 17, 5580-5586). Not only has trans-2-hexenal has been used as antimicrobial but also been observed to be effective in the control of insects. Volatiles (i.e. trans-2-hexenal) were effective against beetles such as  Tibolium castaneum, Rhyzopertha dominica, Sitophilus granaries, Sitophilus orazyzae  and  Cryptolestes perrugineus  (Hubert, J.; Munzbergova, Z.; Santino, A. Plant volatile aldehydes as natural insecticides against stored-product beetles.  Pest Manag. Sci.  2008, v. 64, 57-64). U.S. Pat. No. 6,201,026 (Hammond et al. Volatile Aldehydes as Pest Control Agents) suggests of an organic aldehyde of 3 or more carbons for the control of aphides. 
         [0014]    Several patents suggest the use of trans-2-hexenal as a fragrance or perfume. U.S. Pat. No. 6,596,681 suggests the use of trans-2-hexenal as a fragrance in a wipe for surface cleaning. U.S. Pat. No. 6,387,866, U.S. Pat. No. 6,960,350 and U.S. Pat. No. 7,638,114 suggest the use of essential oil or terpenes (for example trans-2-hexenal) as perfume for antimicrobial products. U.S. Pat. No. 6,479,044 demonstrates an antibacterial solution comprising an anionic surfactant, a polycationic antibacterial and water, where an essential oil is added as perfume. This perfume could be a terpene such as trans-2-hexenal or other type of terpenes. U.S. Pat. No. 6,323,171, U.S. Pat. No. 6,121,224 and U.S. Pat. No. 5,911,915 demonstrate an antimicrobial purpose microemulsion containing a cationic surfactant where an essential oil is added as a perfume. This perfume can contain various terpenes including trans-2-hexenal. U.S. Pat. No. 6,960,350 demonstrates an antifungal fragrance where a synergistic effect was found when different terpenes were used in combinations (for example trans-2-hexenal with benzaldehyde). 
         [0015]    The mode of action of trans-2-hexenal is thought to be alteration of the cell membrane due to a reaction of the unsaturated aldehyde with sulfhydryl or cysteine residues, or the formation of Schiff bases with amino groups in peptides and proteins (Deng, W.; Hamilton-Kemp, T.; Nielsen, M.; Anderson, R.; Collins, G.; Hilderbrand, D. Effects of Six-Carbon Aldehydes and Alcohols on Bacterial Proliferation.  J. Agric. Food Chem.  1993, v. 41, 506-510). Trans-2-hexenal is reported to act as a surfactant but it likely permeates by passive diffusion across the plasma membrane. Once inside the cells, its α,β-unsaturated aldehyde moiety reacts with biologically important nucleophilic groups. This aldehyde moiety is known to react with sulphydryl groups mainly by 1,4-addition under physiological conditions (Patrignani, F.; Lucci, L.; Belletti, N.; Gardini, F.; Guerzoni, M. E.; Lanciotti, R. Effects of sub-lethal concentrations of hexanal and 2-(E)-hexenal on membrane fatty acid composition and volatile compounds of  Listeria monocytogenes, Staphylococcus aureus, Salmonella enteritidis  and  Escherichia coli. International J. Food Micro.  2008, v. 123, 1-8). 
         [0016]    It was suggested that the inhibition of  Salmonella typhimurim  and  Staphylococcus aureus  by trans-2 hexenal is due to the hydrophobic and hydrogen bonding of its partition in the lipid bilayer. The destruction of electron transport systems and the perturbation of membrane permeability have also been suggested as modes of action (Gardini, F.; Lanciotti, R.; Guerzoni, M. E. Effect of trans-2-hexenal on the growth of  Aspergillus flavus  in relation to its concentration, temperature and water activity.  Letters in App. Microbiology.  2001, v. 33, 50-55). The inhibition of  P. expansum  decay may be due to damage to fungal membranes of germinating conidia. (Neri, F.; Mari, M.; Menniti, A.; Brigati, S.; Bertolini, P. Control of  Penicillium expansum  in pears and apples by trans-2-hexenal vapours.  Postharvest Biol. and Tech.  2006, v. 41, 101-108; Neri, F.; Mari, M.; Menniti, A. M.; Brigati, S. Activity of trans-2-hexenal against  Penicillium expansum  in ‘Conference’ pears.  J. Appl. Micrbiol.  2006, v. 100, 1186-1193). 
         [0017]    Studies have been performed to compare trans-2-hexenal to similar compounds. Deng et. al. showed that unsaturated volatiles, trans-2-hexenal and trans-2-hexen-1-ol, exhibited a greater inhibitory effect than the saturated volatiles, hexanal and 1-hexanol (Deng, W.; Hamilton-Kemp, T.; Nielsen, M.; Anderson, R.; Collins, G.; Hilderbrand, D. Effects of Six-Carbon Aldehydes and Alcohols on Bacterial Proliferation.  J. Agric. Food Chem.  1993, v. 41, 506-510). Trans-2-hexenal was more active than hexanal, nonanal and trans-2-octenal against all ATCC bacterial strains (Bisignano, G.; Lagana, M. G.; Trombetta, D.; Arena, S.; Nostro, A.; Uccella, N.; Mazzanti, G.; Saija, A. In vitro antibacterial activity of some aliphatic aldehydes from  Oleo europaea  L.  FEMS Microbiology Letters.  2001, v. 198, 9-13). Others have found that (E)-2-hexenal had lower minimal fungal-growth-inhibiting concentrations than hexanal, 1-hexanol, (E)-2-hexen-1-ol, and (Z)-3-hexen-1-ol as determined for several species of molds, basically aldehydes&gt;ketones&gt;alcohols (Andersen, R. A.; Hamilton-Kemp, T.; Hilderbrand, D. F.; McCraken Jr., C. T.; Collins, R. W.; Fleming, P. D. Structure—Antifungal Activity Relationships among Volatile C 6  and C 9  Aliphatic Aldehydes, Ketones, and Alcohols.  J. Agric. Food Chem.  1994, v. 42, 1563-1568). Hexenal and hexanoic acid were more effective than hexanol in inhibiting  salmonella  (Kubo, I. And K. Fujita, Naturally Occurring Anti- Salmonella  Agents.  J. Agric. Food Chem.  2001, v. 49, 5750-5754). 
         [0018]    Muroi et al suggested that trans-2-hexenal exhibited broad antimicrobial activity but its biological activity (50 to 400 μg/mL) is usually not potent enough to be considered for practical applications (Muroi, H.; Kubo, A.; Kubo, I. Antimicrobial Activity of Cashew Apple Flavor Compounds.  J. Agric. Food Chem.  1993, v. 41, 1106-1109). Studies have shown that trans-2-hexenal can potentiate the effectiveness of certain types of antimicrobials. Several patents suggest the use of potentiators for aminoglycoside antibiotics (U.S. Pat. No. 5,663,152), and potentiators for polymyxin antibiotic (U.S. Pat. No. 5,776,919 and U.S. Pat. No. 5,587,358). These potentiators can include indol, anethole, 3-methylindole, 2-hydroxy-6-R-benzoic acid or 2-hexenal. A strong synergic effect was observed when trans-2-eptenal, trans-2-nonenal, trans-2-decenal and (E,E)-2,4-decadienal were tested together (1:1:1:1 ratio) against ATCC and clinically isolated microbial strains (Bisignano, G.; Lagana, M. G.; Trombetta, D.; Arena, S.; Nostro, A.; Uccella, N.; Mazzanti, G.; Saija, A. In vitro antibacterial activity of some aliphatic aldehydes from  Oleo europaea  L.  FEMS Microbiology Letters.  2001, v. 198, 9-13). 
         [0019]    Humans are exposed daily to trans-2-hexenal through consumption of food and beverages. Human exposures to trans-2-hexenal are ˜350 μg/kg/day, with 98% derived from natural sources and 2% from artificial flavoring. It is unlikely that trans-2-hexenal would be toxic to humans since toxic levels in rats are 30 times higher than normal intake by humans (Stout, M. D.; Bodes, E.; Schoonhoven, R.; Upton, P. B.; Travlos, G. S.; Swenberg, J. A. Toxicity, DNA Binding, and Cell Proliferation in Male F344 Rats following Short-term Gavage Exposures to Trans-2-Hexenal.  Soc. Toxicologic. Pathology  Mar. 24 2008, 1533-1601 online). In another rat study, feeding trans-2-hexenal at dietary levels of 0 (control), 260, 640, 1600 or 4000 ppm fed for 13 wk did not induce any changes in hematological parameters or organ weights. At 4000 ppm there was a reduction in body weight and intake, but it was not significant (Gaunt, I. F.; Colley, J. Acute and Short-term Toxicity Studies on trans-2-Hexenal.  Fd Cosmet. Toxicol.  1971, v. 9, 775-786). 
         [0020]    Even in fruits, twenty four hours to seven days exposure of pears and apples to trans-2-hexenal (12.5 μL/L did not affect fruit appearance, color, firmness, soluble solids content or titratable acidity. In a trained taste panel, no significant differences in the organoleptic quality of untreated and trans-2-hexenal treated “Golden Delicious” apples were observed, while maintenance of off-flavors was perceived in “Bartlett”, “Abate Fetel” and “Royal Gala” fruit (Neri, F.; Mari, M.; Menniti, A.; Brigati, S.; Bertolini, P. Control of  Penicillium expansum  in pears and apples by trans-2-hexenal vapours.  Postharvest Biol. and Tech.  2006, 41, 101-108; Neri, F.; Mari, M.; Menniti, A. M.; Brigati, S. Activity of trans-2-hexenal against  Penicillium expansum  in ‘Conference’ pears.  J. Appl. Micrbiol.  2006, v. 100, 1186-1193). 
         [0021]    Citral and cinnamaldehyde, have been found to be antifungal. The mode of action of these aldehydes is by reacting with the sulfur group (—SH) from fungi (Ceylan E and D Fung. Antimicrobial Activity of Spices.  J. Rapid Methods in Microbiology.  2004 v. 12, 1-55). 
         [0022]    U.S. Pat. No. 6,750,256 and RE 39543 suggest the use of aromatic aldehydes like α-hexyl cinnamic aldehyde for the control of ant population but does not suggest any synergistic effect of the aldehyde in combination with a organic acid to improve effectiveness or a reduction on the active ingredient or their effectiveness on bacterial control. 
         [0023]    The essential oil of  Coriandrum sativum  contains 55.5% of aldehydes which has been effective on preventing growth of gram positive and gram negative bacteria. These aldehydes include: n-octanal, nonanal, 2E-hexenal, decanal, 2E-decenal, undecenal, dodecanal, 2E-dodecenal, tridecanal, 2E-tridecene-1-al and 3-dodecen-1-al (Matasyoh, J. C., Z. C. Maiyo, R. R. Ngure and R. Chepkorir. Chemical Composition and Antimicrobial Activity of the Essential Oil of  Coriandrum sativum. Food Chemistry.  2009 v. 113, 526-529). 
         [0024]    Furfural, a cyclic aldehyde, is currently used as fungicide and nematicide but there are no reports of its use in combination with an organic acid i.e., nonanoic acid, as demonstrated in the present invention. 
         [0025]    Two aldehydes, n-decanal and nonanal were effective at controlling fungal growth (Dilantha Fernando, W. G., R. Ramaranthnam, A. Krihnamoorthy and S. Savchuck. Identification and use of potential organic antifungal volatiles in biocontrol.  Soil Biology and Biochemistry.  2005 v. 37, 955-964) 
         [0026]    The prior art has not suggested or observed that the use of aldehydes in combination with organic acids improved the antimicrobial activity of either of the components by themselves. It has suggested synergy with the combination of essential oils and as potentiators of antibiotics. 
         [0027]    Commercial mold inhibitors and bactericides are composed of single organic or a mixture of organic acids and formaldehyde. These acids are primarily propionic, benzoic acid, butyric acid, acetic, and formic acid. Organic acids have been a major additive to reduce the incidence of food borne infections. The mechanism by which small chain fatty acids exert their antimicrobial activity is that undissociated (RCOOH=non-ionized) acids are lipid permeable and in this way they can cross the microbial cell wall and dissociate in the more alkaline interior of the microorganism (RCOOH-&gt;RCOO − +H + ) making the cytoplasm unstable for survival. (Van Immerseel, F., J. B. Russell, M. D. Flythe, I. Gantois, L. Timbermont, F. Pasmans, F. Haesebrouck, and R. Ducatelle. 2006. The use of organic acids to combat  Salmonella  in poultry: a mechanistic explanation of the efficacy,  Avian Pathology . v. 35, no. 3, 182-188; Paster, N. 1979, A commercial study of the efficiency of propionic acid and acid and calcium propionate as fungistats in poultry feed, Poult. Sci. v. 58, 572-576). 
         [0028]    Pelargonic acid (nonanoic acid) is a naturally occurring fatty acid. It is an oily, colorless fluid, which at lower temperature becomes solid. It has a faint odor compared to butyric acid and is almost insoluble in water. Pelargonic acid has been used as a non-selective herbicide. Scythe (57% pelargonic acid, 3% related fatty acids and 40% inert material) is a broad-spectrum post-emergence or burn-down herbicide produced by Mycogen/Dow Chemicals. The herbicidal mode of action of pelargonic acid is due first to membrane leakage during darkness and daylight and second to peroxidation driven by radicals originating during daylight by sensitized chlorophyll displaced from the thylakoid membrane (B. Lederer, T. Fujimori., Y. Tsujino, K. Wakabayashi and P Boger, 2004. Phytotoxic activity of middle-chain fatty acids II: peroxidation and membrane effects.  Pesticide Biochemistry and Physiology  80: 151-156). 
         [0029]    Chadeganipour and Haims (2001) showed that the minimum inhibitory concentration (MIC) of medium chain fatty acids to prevent growth of  M. gypseum  was 0.02 mg/ml capric acid and for pelargonic acid 0.04 mg/ml on solid media and 0.075 mg/ml capric acid and 0.05 mg/ml pelargonic in liquid media. These acids were tested independently and not as a mixture (Antifungal activities of pelargonic and capric acid on  Microsporum gypseum ” Mycoses v. 44, no 3-4, 109-112). N. Hirazawa, et. al. (Antiparasitic effect of medium-chain fatty acids against ciliated  Crptocaryon irritans  infestation in the red sea bream  Pagrus major,  2001 , Aquaculture  v. 198, 219-228) found that nonanoic acid as well as C6 to C10 fatty acids were effective in controlling the growth of the parasite  C. irritans  and that C8, C9 and C19 were the more potent. It was found that  Trichoderma harzianum , a biocontrol for cacao plants, produces pelargonic acid as one of many chemicals, which was effective in controlling the germination and growth of cacao pathogens. (M Aneja, T. Gianfagna and P. Hebbar, 2005). 
         [0030]    Several US patents disclose the use of pelargonic acids as fungicides and bactericides: US Published Application 2004/026685 discloses a fungicide for agricultural uses that is composed of one or more fatty acids and one or more organic acids different from the fatty acid. In the mixture of the organic acids and the fatty acids, the organic acid acts as a potent synergist for the fatty acid to function as a fungicide. U.S. Pat. No. 5,366,995 discloses a method to eradicate fungal and bacterial infections in plants and to enhance the activity of fungicides and bactericides in plants through the use of fatty acids and their derivatives. This formulation contains 80% pelargonic acid or its salts for the control of plants fungi. The fatty acids used are primarily C9 to C18. U.S. Pat. No. 5,342,630 discloses a novel pesticide for plant use containing an inorganic salt that enhance the efficacy of C 8 to C22 fatty acids. One of the examples shows a powdered product with 2% pelargonic acid, 2% capric acid, 80% talc, 10% sodium carbonate and 5% potassium carbonate. U.S. Pat. No. 5,093,124 discloses a fungicide and arthropodice for plants comprising of alpha mono carboxylic acids and their salts. Preferably the fungicide consists of the C9 to C10 fatty acids, partially neutralized by active alkali metal such as potassium. The mixture described consists of 40% active ingredient dissolved in water and includes 10% pelargonic, 10% capric acid and 20% coconut fatty acids, all of with are neutralized with potassium hydroxide. U.S. Pat. No. 6,596,763 discloses a method to control skin infection comprised of C6 to C18 fatty acids or their derivatives. U.S. Pat. No. 6,103,768 and U.S. Pat. No. 6,136,856 discloses the unique utility of fatty acids and derivatives to eradicate existing fungal and bacterial infections in plants. This method is not preventive but showed effectiveness in already established infections. Sharpshooter, a commercially available product, with 80% pelargonic acid, 2% emulsifier and 18% surfactant showed effectiveness against  Penicillium  and  Botrytis  spp. U.S. Pat. No. 6,638,978 discloses an antimicrobial preservative composed of a glycerol fatty acid ester, a binary mixture of fatty acids (C6 to C18) and a second fatty acid (C6 to C18) where the second fatty acid is different from the first fatty acid for preservation of food. WO 01/97799 discloses the use of medium chain fatty acids as antimicrobials agents. It shows that an increase of the pH from 6.5 to 7.5 increased the MIC of the short chain fatty acids containing 6-8 carbons chain. 
         [0031]    Pelargonic acid is used as a component of a food contact surface sanitizing solution in food handling establishments. A product from EcoLab consist of 6.49% pelargonic acid as active ingredient to be use as a sanitizer for all food contact surfaces (12CFR178.1010 b). The FDA has cleared pelargonic acid as a synthetic food flavoring agent (21 CFR 172.515), as an adjuvant, production aid and sanitizer to be used in contact food (12 CFR 178.1010 b) and in washing or to assist in lye peeling of fruits and vegetables (12 CFR 173.315). Pelargonic acid is listed by the USDA under the USDA list of Authorized Substances, 1990, section 5.14, Fruit and Vegetable Washing Compounds. 
         [0032]    The present invention relates only to the use of some of the aldehydes extracted from plants or chemically synthesized that synergistically improve the antimicrobial capacity of these compounds by the addition of organic acids especially nonanoic acid. 
       SUMMARY OF THE INVENTION 
       [0033]    One object of the present invention is to provide a composition that synergistically improves the microbicidal effect of organic acids and aldehydes. 
         [0034]    The composition can be a solution comprising of an organic acid or a mixture of several organic acids in combination of aldehydes. 
         [0035]    The composition can further comprise a volatile aldehyde resulting from the lipoxygenase pathway. 
         [0036]    The aldehydes of the composition comprise butyraldehyde, undecylenic aldehyde, citral, decanal, decenal, 2-4-decadienal and other aldehydes from C1 to C24 carbon length or shape. 
         [0037]    The organic acids of the composition comprise organic acids of 1 to 24 carbon chain length, saturated, unsaturated, cyclic or other organic acid. 
         [0038]    The effective mixture of the invention comprising 1 to 70% by volume organic acids, 
         [0039]    The effective mixture of the invention comprising 0 to 70% by volume pelargonic acid. 
         [0040]    The effective mixture of the invention comprising 5 to 50% aldehyde. 
         [0041]    The effective mixture of the invention comprising 0 to 70% by volume water. 
         [0042]    The composition is effective against various fungi present in feed and major feed ingredients. 
         [0043]    The composition is effective against various bacteria present in feed and major feed ingredients. 
         [0044]    The composition is effective against various bacteria and fungi present in water. 
         [0045]    The composition is effective against microbes detrimental for the production of alcohol from fermentation of cellulose, starch or sugars. 
     
    
     DESCRIPTION OF THE PREFERRED EMBODIMENTS 
       [0046]    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 
       [0047]    A “volume percent” of a component is based on the total volume of the formulation or composition in which the component is included. 
         [0048]    An organic acid of the composition can comprise formic, acetic, propionic, butyric, pelargonic, lactic and other C 2  to C 24  fatty acid or mono-, di-, or triglycerides containing C 1  to C 24  fatty acids. These fatty acids comprising small chain, medium chain, long chain fatty acids or small chain, medium chain, long chain triglycerides. 
         [0049]    The term “effective amount” of a compound means anh 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. 
         [0050]    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. 
         [0051]    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. 
         [0052]    Composition (s) 
         [0053]    A composition of the present invention comprises an effective amount of organic acids of 1 to 24 carbons chain and an aldehyde. 
         [0054]    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. 
       Methods 
       [0055]    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.       
 
         [0062]    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. 
         [0063]    There were unexpected results, i.e. synergism and additive effect, when the organic acids and aldehydes were used. 
         [0064]    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 
       [0065]    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 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. 
         [0000]    
       
         
               
             
               
               
               
               
             
               
               
               
               
             
           
               
                 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 
               
               
                   
               
             
          
         
       
     
         [0066]    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 
       [0067]    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 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. 
         [0000]    
       
         
               
             
               
               
               
               
             
               
               
               
               
             
           
               
                 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 
               
               
                   
               
             
          
         
       
     
         [0068]    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 
       [0069]    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. 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                 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 
               
               
                   
                   
               
             
          
         
       
     
         [0070]    A suspension of  Salmonella typhimurium  (10 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. 
         [0000]    
       
         
               
             
               
               
               
               
             
               
               
               
               
             
           
               
                 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 
               
               
                   
                   
               
             
          
         
       
     
         [0071]    Pelargonic acid at 10% increases the efficacy of trans-2-hexenal. 
       Example 4 
       [0072]    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 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. 
         [0000]    
       
         
               
             
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                 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 
               
               
                   
                   
               
             
          
         
       
     
         [0073]    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. 
         [0000]    
       
         
               
             
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                 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 
       [0074]    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 . 
         [0000]    
       
         
               
             
               
               
               
               
             
               
               
               
               
             
           
               
                 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 
               
               
                   
                   
               
             
          
         
       
     
         [0075]    Equal concentration of Pelargonic acid and trans-2-hexenal resulted in similar effectiveness as high levels (25%) trans-2-hexenal. 
       Example 6 
       [0076]    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 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. 
         [0077]    The following table compares the impact of pelargonic acid on the residual activity of hexenal against  Salmonella . 
         [0000]    
       
         
               
             
               
               
               
             
               
               
               
             
           
               
                 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 
               
               
                   
                   
               
             
          
         
       
     
         [0078]    The addition of pelargonic acid (5%) to trans-2-hexenal resulted in better effectiveness against  Salmonella  than trans-2-hexenal by itself. 
       Example 7 
       [0079]    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% (X−1) 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 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. 
         [0080]    The effectiveness of each formulation as percent reduction compared to the control value is shown in the following tables. 
         [0000]    
       
         
               
               
             
               
               
               
               
               
               
               
               
               
               
               
               
               
             
               
               
             
               
               
               
               
               
               
               
               
               
               
               
               
               
             
           
               
                 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 
               
               
                   
               
             
          
         
       
     
         [0000]    
       
         
               
               
             
               
               
               
               
               
               
               
               
               
               
               
               
               
             
               
               
             
               
               
               
               
               
               
               
               
               
               
               
               
               
             
           
               
                 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 
                 10 
                 5 
                 5 
                 5 
                 5 
                 5 
                 5 
                 10 
                 10 
               
               
                 Acetic acid (56%) 
                 20 
                 20 
                 20 
                 20 
                 20 
                 20 
                 20 
                 20 
                 20 
                 25 
                 15 
                 15 
               
               
                 2-hexenal 
                 25 
                 20 
                 25 
                 20 
                 10 
                 20 
                 15 
                 10 
                 5 
                 0 
                 20 
                 15 
               
               
                 Propionic acid 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
               
               
                 citral 
                   
                   
                 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 
               
               
                   
               
             
          
         
       
     
         [0000]    
       
         
               
               
             
               
               
               
               
               
               
               
               
               
               
               
               
               
             
               
               
             
               
               
               
               
               
               
               
               
               
               
               
               
               
             
           
               
                 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 
                 10 
                 5 
                 5 
                 5 
                 5 
                 5 
                 5 
                 10 
                 10 
               
               
                 Acetic acid (56%) 
                 20 
                 20 
                 20 
                 20 
                 20 
                 20 
                 20 
                 20 
                 20 
                 25 
                 15 
                 15 
               
               
                 2-hexenal 
                 25 
                 20 
                 25 
                 20 
                 10 
                 20 
                 15 
                 10 
                 5 
                 0 
                 20 
                 15 
               
               
                 Propionic acid 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
               
               
                 undecylenic 
                   
                   
                 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 
               
               
                   
               
             
          
         
       
     
         [0000]    
       
         
               
               
             
               
               
               
               
               
               
               
               
               
               
               
               
               
             
               
               
             
               
               
               
               
               
               
               
               
               
               
               
               
               
             
           
               
                 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 
                 10 
                 5 
                 5 
                 5 
                 5 
                 5 
                 5 
                 10 
                 10 
               
               
                 Acetic acid (56%) 
                 20 
                 20 
                 20 
                 20 
                 20 
                 20 
                 20 
                 20 
                 20 
                 25 
                 15 
                 15 
               
               
                 2-hexenal 
                 25 
                 20 
                 25 
                 20 
                 10 
                 20 
                 15 
                 10 
                 5 
                 0 
                 20 
                 15 
               
               
                 Propionic acid 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
               
               
                 2,4 decadieneal 
                   
                   
                 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 
               
               
                   
               
             
          
         
       
     
         [0000]    
       
         
               
               
             
               
               
               
               
               
               
               
               
               
               
               
               
               
             
               
               
             
               
               
               
               
               
               
               
               
               
               
               
               
               
             
           
               
                 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 
                 5 
                 5 
                 5 
                 10 
                 10 
               
               
                 Acetic acid (56%) 
                 20 
                 20 
                 20 
                 20 
                 20 
                 20 
                 20 
                 20 
                 20 
                 25 
                 15 
                 15 
               
               
                 2-hexenal 
                 25 
                 20 
                 25 
                 20 
                 10 
                 20 
                 15 
                 10 
                 5 
                 0 
                 20 
                 15 
               
               
                 Propionic acid 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
               
               
                 cinnamaldehyde 
                   
                   
                 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 
               
               
                   
               
             
          
         
       
     
         [0000]    
       
         
               
               
             
               
               
               
               
               
               
               
               
               
               
               
               
               
             
               
               
             
               
               
               
               
               
               
               
               
               
               
               
               
               
             
           
               
                 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 
                 5 
                 5 
                 5 
                 10 
                 10 
               
               
                 Acetic acid (56%) 
                 20 
                 20 
                 20 
                 20 
                 20 
                 20 
                 20 
                 20 
                 20 
                 25 
                 15 
                 15 
               
               
                 2-hexenal 
                 25 
                 20 
                 25 
                 20 
                 10 
                 20 
                 15 
                 10 
                 5 
                 0 
                 20 
                 15 
               
               
                 Propionic acid 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
               
               
                 decanal 
                   
                   
                 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 
               
               
                   
               
             
          
         
       
     
         [0000]    
       
         
               
               
             
               
               
               
               
               
               
               
               
               
               
               
               
               
             
               
               
             
               
               
               
               
               
               
               
               
               
               
               
               
               
             
           
               
                 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 
                 5 
                 5 
                 5 
                 10 
                 10 
               
               
                 Acetic acid (56%)  
                 20 
                 20 
                 20 
                 20 
                 20 
                 20 
                 20 
                 20 
                 20 
                 25 
                 15 
                 15 
               
               
                 2-hexenal 
                 25 
                 20 
                 25 
                 20 
                 10 
                 20 
                 15 
                 10 
                 5 
                 0 
                 20 
                 15 
               
               
                 Propionic acid 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
               
               
                 furfural 
                   
                   
                 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 
               
               
                   
               
             
          
         
       
     
         [0081]    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 
       [0094]    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.