Beltran, Joan Baptista Urgell (Barcelona, ES)
Bonaventura, Joan Seguer (L'Hospitalet de Llobregat/Barcelona, ES)

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08/05/2008

10/25/2001

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Laboratorios Miret, S.A. (Barcelona, ES)

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Hendricks, Keith D.

Chawla, Jyoti

Renner, Otto, Boisselle & Sklar, LLP

The invention claimed is:

1. A food product containing a cationic preservative which is the ethyl ester of lauramide of arginine hydrochloride, derived from the condensation of fatty acids and esterified dibasic amino acids, said ethyl ester of lauramide of arginine hydrochloride having the following formula: wherein said cationic preservative is present in the food product in an amount from about 0.006% to about 0.015% by weight.

2. The food product according to claim 1, wherein said cationic preservative is present in the food product in an amount from 0.008% to 0.015% by weight.

3. A method of preservation of a food product comprising the step of adding a cationic preservative which is the ethyl ester of lauramide of arginine hydrochloride, derived from the condensation of fatty acids and esterified dibasic amino acids, said ethyl ester of lauramide of arginine hydrochloride having the following formula: wherein said cationic preservative is added to the food product as a solution, dispersion or solid before, during and/or after the manufacture of the food product at a concentration of from about 0.006% to about 0.015% by weight.

4. The method of claim 3 wherein the food product comprises fish, crustaceans, fish substitutes or crustacean substitutes.

5. The method of claim 3 wherein the food product comprises meat, meat substitutes or poultry products.

6. The method of claim 3 wherein the food product comprises vegetables, greens, sauces or emulsions.

7. The method of claim 3 wherein the food product comprises beverages, juices, wines or beers.

8. The method of claim 3 wherein the food product comprises dairy, egg-based, jam, jelly, bakery or confectionary products.

9. The method of claim 3 wherein the food product comprises pre-cooked meal or ready-to-serve meal products.

10. The method according to claim 3, wherein said ethyl ester of lauramide of arginine hydrochloride is added to the food product to provide a concentration of from 0.008% to 0.015% by weight.

11. A method of preservation of food products, wherein a cationic preservative which is the ethyl ester of lauramide of arginine hydrochloride, derived from the condensation of fatty acids and esterified dibasic amino acids, said ethyl ester of lauramide of arginine hydrochloride having the following formula: wherein said cationic preservative is applied by surface treatment before, during and/or after the manufacture of the food product at a concentration of from about 0.006% to about 0.015% by weight.

12. A method according to claim 11, wherein the cationic preservative is applied by spraying.

This application is a national phase of International Application No. PCT/EP01/12358 filed Oct. 25, 2001 and published in the English language.

This invention relates to a novel use of cationic preservatives and preparations according to this novel use.

Despite the food industry must avoid the use of preservative products by means of good manufacture practices as it is described in the national and international regulations, it is often necessary to warrant the needed storage capability of the produced food-stuff but never to hide defective effects of a manipulation or manufacture technique.

A cationic preservative derived from lauric acid and arginine, in particular, the ethyl ester of the lauramide of the arginine monohydrochloride, hereafter named LAE, could be used for the protection against the growth of the microorganisms. The chemical structure is described in the following formula:

The preparation of this product has been described in Spanish patent application ES-A-512643.

Biological studies carried out at different research centres under supervision of the present applicant showed LAE to act mainly over the external and cytoplasmatic membrane of the microorganisms and, also, into the cytoplasmatic media, preventing their proliferation. Its action depends on the kind of microorganism and on the exposure time.

Besides, its metabolism in rats has been studied showing a fast absortion and metabolisation into naturally-occurring amino acids and the fatty acid lauric acid, which are eventually excreted as carbon dioxide and urea. Toxicological studies have demonstrated, that LAE is completely harmless to animals and humans.

Therefore, LAE and related compounds are particularly suitable to be used in the preservation of all perishable food products.

This compound is remarkable for its inhibitory action over the proliferation of different microorganisms, such as bacteria, fungi and yeasts. The minimum inhibitory concentrations of LAE are shown in the following table 1.

TABLE 1
Kind	Microorganism	M.I.C. (ppm)
Gram + Bacteria	Arthrobacter oxydans ATCC 8010	64
	Bacillus cereus var mycoide ATCC 11778	32
	Bacillus subtilis ATCC 6633	16
	Clostridium perfringens ATCC 77454	16
	Listeria monocytogenes ATCC 7644	10
	Staphylococcus aureus ATCC 6538	32
	Micrococcus luteus ATCC 9631	128
	Lactobacillus delbrueckii ssp lactis CECT 372	16
	Leuconostoc mesenteroides CETC 912	32
Gram − Bacteria	Alcaligenes faecalis ATCC 8750	64
	Bordetella bronchiseptica ATCC 4617	128
	Citrobacter freundii ATCC 22636	64
	Enterobacter aerogenes CECT 689	32
	Escherichia coli ATCC 8739	32
	Escherichia coli 0157H7	20
	Klebsiella pneumoniae var pneumoniae CECT 178	32
	Proteus mirabilis CECT 170	32
	Pseudomonas aeruginosa ATCC 9027	64
	Salmonella typhimurium ATCC16028	32
	Serratia marcenses CECT 274	32
	Mycobacterium phlei ATCC 41423	2
Fungi	Aspergillus niger ATCC14604	32
	Aureobasidium pullulans ATCC 9348	16
	Gliocadium virens ATCC 4645	32
	Chaetonium globosum ATCC 6205	16
	Penicillium chrysogenum CECT 2802	128
	Penicillium funiculosum CECT 2914	16
Yeast	Candida albicans ATCC 10231	16
	Rhodotorula rubra CECT 1158	16
	Saccharomyces cerevisiae ATCC 9763	32

The use of the invention relates to cationic preservatives derived from the condensation of fatty acids and esterified dibasic amino acids, according to the following formula:

where:

• X ⁻ is Br ⁻ , Cl ⁻ , or HSO ₄ ⁻
• R1: is a linear alkyl chain from a saturated fatty acid or hydroxyacid from 8 to 14 atoms of carbon bonded to the α-amino acid group through an amidic bond.
• R ₂ : is a linear or branched alkyl chain from 1 to 18 carbon atoms or an aromatic group.
• R ₃ : is:
  • —NH ₃

and n can be from 0 to 4.

The most preferred compound of the above class of compounds is LAE.

It is preferred to dissolve the compound directly before use in one of the following preferred solvents of food grade: water, ethanol, propylene glycol, isopropyl alcohol, other glycols, mixtures of glycols and mixtures of glycols and water. If the treatment shall be performed at a specific pH value the use of a corresponding buffer solution may be recommendable.

The composition optionally comprises auxiliary components and excipients. Such auxiliary components and excipients can be thickening agents (e.g. xanthan gum, guar gum, modified starches), anti-foam agents (e.g. dimethylpolysiloxane, silicon dioxide), products to obtain the optimal pH value (e.g. phosphates, tartrates, citrates, lactates), colouring agents (e.g. curcumin, tartrazine, erythrosine), and aroma products. It is preferred, that the preservative composition comprises LAE in an amount of from 0,0001% to 1% by weight relative to the whole weight of the preservative composition.

It is particularly preferred to use the inventive composition for the preservation of meat products, like for instance meat, poultry products, fish, crustaceans, vegetables, greens, emulsions, sauces, confectionery, bakery, pre-cooked meals, ready-to-serve meals, dairy products, egg-based products, jams, jellies, beverages, juices, wines and beers.

Moreover, the intended use relates to: wine-based flavoured drinks including products; non-alcoholic flavoured drinks; liquid tea concentrates and liquid fruit and herbal infusion concentrates; Barley Water; fruit and citric juices; Capilé Groselha; grape juices, unfermented, for sacramental use; wines, alcohol-free wines, fruit wines (including alcohol-free), alcoholic drinks with fruit; made wines, fruit sparkling wines, ciders, beers and perries (including alcohol-free); fermentation vinager; sod, saft; mead; spirits with less than 15% alcohol by volume; fillings of ravioli and similar products; quince, jams, jellies, marmelades and other fruit based spreads, candied, crystallized and glacé fruit and vegetables; sugar, glucose syrup, molasses and other sugars; transformed and dried fruits and vegetables, Frugtgrod and Rote Grütze, fruit and vegetable preparations (including fruit-based sauces); vegetable flesh; shell fruits; mousse, compote; salads, fruits and similar products, canned or bottled; Mostarda Di Fruta; Mascarpone; fruit based cake fillings; fruit gelling extracts and liquid pectine; vegetables and fruits in vinegar, brine or oil; rehydrated dried fruits; dressed dried fruits; sweetcorn canned in vacuum; potato dough and pre-fried, sliced, transformed, frozen, deep-frozen and peeled potatoes; dehydrated potato flakes and granulated (?); gnocchi; polenta; olives and olive-based preparations; jelly coating of meat products (cooked, cured or dried); burger meat; heat-treated meat products, sausages, breakfast sausages, pickled porks, pates, Foie Gras, Foie Gras Entier, Blocs de Foie Gras; Sagu; Mehu and Makeutettu; Ostkaka; Pasha; Semmelknodelteig; Polsebrod and bollery Dansk; canned Flutes; gelatine; collagen based covers with a water activity of more than 0.6; salted meats, cured placenta, dried meat products; semi-preserved fish products including fish roe products, pickling, salted, dried fish, shrimps, cooked, Crangon crangon and Crangon vulgaris cooked; fresh, cooked, frozen and deep-frozen crusteacean; cheese, pre-packed, sliced, unripened and cured cheese, processed cheese, layered cheese and cheese with added foodstuffs; superficial treatment of cheese, fruits and vegetables; cheese substitute, meat substitute, fish substitute, crusteacean substitute; non-heat-treated dairy-based desserts, curdled milk, semolina and tapioca based desserts; liquid egg (white, yolk or whole egg), dehydrated, concentrated, frozen and deep-frozen egg products; pre-packed and sliced bread and rye-bread; partially baked, pre-packed bakery wares intended for retail sale, fine bakery wares with a water activity of more than 0.65; low-energetic bread; dry-biscuits; cereal- or potato-based snacks and coated nuts; batters, confectionery, glucose syrup based confectionery, flour based confectionery with a water activity of more than 0.65, chewing gum; Christmas pudding, nougats and marzipans; clotted cream; toppings (syrups for pancakes, flavoured syrups for milkshakes and ice cream, similar products), fat emulsions, dressing salads, emulsified sauces, non-emulsified sauces; prepared salads, mustard, seasonings and condiments; liquid soups and broths; aspic, liquid dietary food supplements; pearl barley; dietetic foods intended for special medical purposes and starches; dietetic formulae for weight control intended to replace total daily food intake or an individual meal; and other food products where the use of preservatives became necessary and allowed by law.

The cationic preservative may be added to a final stage of the product to be preserved or it may be added to a initial stage which would have the advantage of treating the food product, whereby it may be added as dry product to the product to be preserved, or in the form of a solution or dispersion.

The food products according to the invention are prepared according to the techniques which are well known to a person skilled in the art.

Procedures to Determine the Microbiological Population and Preservative Effect

The determination of the microbiological population is carried out according to the ISO standards.

The samples are treated by dilution in buffer peptone with the appropriate neutralising agent of the preservative. The culture media used for counting the microorganisms are: Soya triptone agar (32-35° C., 48 hours) for the determination of mesophilic bacteria; Sabouraud agar with chloramfenicol (25° C., 3-5 days) for fungi and yeast; Violet red bile glucose agar (32-35° C., 24 hours) for enterobacteria; Soya triptone agar (17° C., 5 days) for psychrotrophic bacteria.

EXAMPLES

Different examples of food products and formulations are shown where the product has been assayed. These examples are a part of the preparations and formulations assayed.

Example 1

This example shows the use of LAE in semi-preserved codfish in oil (table 2). The sample LAE was added to the oil assayed at a concentration of 100 ppm and its microbiological evolution at 4° C. was compared against a control.

	TABLE 2
	Time (days)
	0	14	43
	Microorganism
		Aerobe	Mould &	Aerobe	Mould &	Aerobe	Mould &
		Bacteria	yeast	Bacteria	yeast	Bacteria	yeast
Sample	Control (cfu/g)	3.4 · 10 3	4.0 · 10 2	3.8 · 10 5	2.0 · 10 4	2.7 · 10 8	1.2 · 10 7
	With LAE (cfu/g)	7.6 · 10 3	3.0 · 10 2	1.0 · 10 4	5.4 · 10 3	8.5 · 10 4	8.2 · 10 3

Example 2

This example shows the use of IAE in a chicken product (table 3). The sample LAE was added to at a concentration of 150 ppm and the evolution of aerobe and psychrotrophic bacteria at 10° C. was compared against a control.

	TABLE 3
	Time (days)
	0	14	43
	Microorganism
		Aerobe	Psychro.	Aerobe	Psychro.	Aerobe	Psychro.
		Bacteria	Bacteria	Bacteria	Bacteria	Bacteria	Bacteria
Sample	Control (cfu/g)	3.1 · 10 5	2.4 · 10 4	9.8 · 10 5	6.5 · 10 5	7.5 · 10 8	4.2 · 10 8
	With LAE (cfu/g)	1.2 · 10 5	3.0 · 10 4	4.2 · 10 5	7.1 · 10 4	6.1 · 10 5	6.8 · 10 4

Example 3

This example shows the use of LAE in a carbonated orange beverage (table 4). The sample LAE was added to at a concentration of 100 ppm and its micobiological evolution at 17° C. was compared against a control.

	TABLE 4
	Time (days)
	0	14
	Microorganism
		Aerobe	Mould &	Aerobe	Mould &
		Bacteria	yeast	Bacteria	yeast
Sample	Control (cfu/g)	4.0 · 10 2	<10	6.5 · 10 4	1.7 · 10 3
	With LAE	4.3 · 10 2	<10	1.0 · 10 2	<10
	(cfu/g)

Example 4

This example shows the use of LAE in a blackberry juice (table 5). The sample LAE was added to at a concentration of 60 ppm and its micobiological evolution at 34° C. was compared against a control.

	TABLE 5
	Time (days)
	0	14
	Microorganism
		Aerobe	Mould &	Aerobe	Mould &
		Bacteria	yeast	Bacteria	yeast
Sample	Control (cfu/g)	5.1 · 10 2	<10	2.5 · 10 5	3.7 · 10 4
	With LAE	4.0 · 10 2	<10	2.4 · 10 3	<10
	(cfu/g)

Example 5

This example shows the use of LAE in custard (table 6). The sample LAE was added to at a concentration of 100 ppm and its micobiological evolution at 25° C. was compared against a control.

	TABLE 6
	Time (days)
	0	5
	Microorganism
		Aerobe	Anaerobe	Aerobe	Anaerobe
		Bacteria	Bacteria	Bacteria	Bacteria
Sample	Control (cfu/g)	<10	<10	9.1 · 10 7	3.4 · 10 7
	With LAE (cfu/g)	<10	<10	1.1 · 10 3	4.1 · 10 2

Example 6

This example shows the use of LAE in fairy cakes (table 7). The sample LAE was added to at a concentration of 80 ppm and its micobiological evolution at 25° C. was compared against a control.

	TABLE 7
	Time (months)
	0	3
	Microorganism
		Aerobe	Mould &	Aerobe	Mould &
		Bacteria	yeast	Bacteria	yeast
Sample	Control (cfu/g)	<10	<10	9.1 · 10 4	3.4 · 10 3
	With LAE (cfu/g)	<10	<10	1.1 · 10 2	<10

Example 7

This example shows the use of LAE in veal stew (table 8). The sample LAE was added to at a concentration of 100 ppm and its microbiological evolution at 10° C. was compared against a control.

	TABLE 8
	Time (days)
	0	14
	Microorganism
		Aerobe	Mould	Entero-	Aerobe	Mould	Entero-
		Bacteria	& yeast	bacteria	Bacteria	& yeast	bacteria
Sample	Control (cfu/g)	<10	<10	<10	9.1 · 10 4	3.4 · 10 3	1.1 · 10 2
	With LAE (cfu/g)	<10	<10	<10	<10	<10	<10

Example 8

This example shows the use of LAE in ketchup (table 9). The sample LAE was added to at a concentration of 100 ppm and its microbiological evolution at 25° C. was compared against a control.

	TABLE 9
	Time (days)
	0	14
	Microorganism
		Aerobe	Mould	Entero-	Aerobe	Mould	Entero-
		Bacteria	& yeast	bacteria	Bacteria	& yeast	bacteria
Sample	Control (cfu/g)	<10	<10	<10	1.2 · 10 6	4.3 · 10 2	1.4 · 10 3
	With LAE (cfu/g)	<10	<10	<10	2.2 · 10 3	1.4 · 10 1	<10