EP4250953A1

EP4250953A1 - Method for pasteurizing and preserving drinks

Info

Publication number: EP4250953A1
Application number: EP21806774.2A
Authority: EP
Inventors: Jens Bitzer; Thomas Henkel; Marcus Taupp
Original assignee: Lanxess Deutschland GmbH
Current assignee: Lanxess Deutschland GmbH
Priority date: 2020-11-27
Filing date: 2021-11-19
Publication date: 2023-10-04
Also published as: CO2021015657A1; AR124124A1; WO2022112132A1; CN116507218A

Abstract

The invention relates to a method for pasteurizing and preserving drinks by means of specific glycolipids and dialkyl dicarbonates in specific weight ratios, the preserved drinks thereby produced, and the use of specific glycolipids to pasteurize and preserve drinks.

Description

Method of sterilizing and preserving beverages

The invention relates to a method for sterilizing and preserving beverages using specific glycolipids and dialkyl dicarbonates in specific weight ratios, the preserved beverages produced and the use of specific glycolipids for sterilizing and preserving beverages.

Bacteria and fungi cause food and beverages, personal care and home care products, and other consumer goods to spoil, thereby shortening the shelf life or useful life of such products or commodities. Food and personal care products therefore need good protection against microbiological contamination; and antimicrobial activity is desired for certain household and pharmaceutical products. Numerous efforts have been made to reduce the harmful effects of microbial contamination in food and beverage, personal care, household care and pharmaceuticals.

Food preservatives such as salt, sugar, and vinegar have been used for generations, and while they are relatively safe to use, their preservative effects are limited in both how long they last and the types of foods and beverages they can be used on. In addition, preservatives, such as salt and vinegar, in higher concentrations can affect the taste and health effects of the product.

Antimicrobial agents such as quaternary ammonium compounds, alcohols, chlorinated phenols, parabens and paraben salts, imidazolidinyl urea, phenoxyethanol, p-hydroxybenzoate, and small carboxylic acids such as benzoic acid, sorbic acid, salicylic acid, and lactic acid are among the commonly used preservatives with antimicrobial activity for body care and sometimes also in food , formic acid, propionic acid or corresponding salts. Formaldehyde releasers and isothiazolinones can also be used.

However, these substances are often incompatible or, for example in the case of formaldehyde, even toxic and even carcinogenic, or they can trigger allergies or food intolerances. In addition, some microorganisms, particularly among spoilage yeasts, have acquired resistance or tolerance to one or more of the commonly used preservatives. In particular, the formation of spores by the spoilage pathogens entails risks, since they enable regrowth even after thorough hygienic treatment of the consumer products mentioned. Another preservative with antimicrobial activity that is used in food and especially in beverages is sulfuric acid, while in meat products, e.g. sausages, meat and meat preserves, stabilizers are often added that reduce water activity, such as potassium and/or sodium nitrites and -nitrates. Smoke is also commonly used to preserve meat products, with the undesirable side effect of forming polycyclic aromatic hydrocarbons, which have carcinogenic properties.

In summary, many preservatives and preservation methods with antimicrobial activity have undesirable side effects such as toxicity, allergenicity, carcinogenicity, occasional resistance development and/or are often recognized by consumers at a time when natural preservation is replacing preservation with synthetic or other products with a negative health image should not be accepted.

Accordingly, there is still a great need for effective

preservatives.

Glycolipids are known from WO-A 2012/167920, which can be used as preservatives in beverages, cosmetics, foods, pharmaceuticals, medical devices or packaging materials.

Furthermore, the effect of dialkyl dicarbonates, in particular of dimethyl dicarbonate (Velcorin®) for preserving beverages, is known, for example from EP-A 2161999.

Surprisingly, it has now been found that the glycolipids of this application, in combination with at least one dialkyl dicarbonate, have a particularly high preservative effect in beverages and have a synergistic effect.

The subject matter of the invention is therefore a process for the sterilization and preservation of beverages, in which at least one compound of the formula (I) with m = 3 to 5, preferably 3 or 5; n = 2 to 5, preferably 3; o = 0 or 1 and R ¹ = H or OH

R ² = is -H, alkali metal or an equivalent of an alkaline earth metal cation or -Ci-C ₆ -alkyl; preferably -H or alkali metal- or an equivalent of an alkaline earth metal cation and p = 3 to 17, preferably 5 to 15 wherein the sum of m + n + o + p is not less than 14 and R represents a carbohydrate residue which has a carbon atom attached to the Oxygen atom is bonded and at least one dialkyl dicarbonate is added to the beverage and a concentration of the dialkyl dicarbonate of 10 to 300 ppm is set in the beverage and the weight ratio of the compounds of the formula (I) and the dialkyl dicarbonate is from 1:10 to 1:70 in the drink. .

The carbohydrate residue R is preferably a trisaccharide. This trisaccharide particularly preferably contains at least one xylopyranose unit and/or at least one glucopyranose unit. The carbohydrate radical R is preferably a radical of the formula (II). wherein rings A, B and C are independently monosaccharide residues containing at least one hydroxyl group which may optionally be acylated. Preferably rings A and B are xylopyranose residues and ring C is a glucopyranose residue.

The compounds of formula (I) may be in the form of an ester and contain one or more -(C=O)-O- functional groups. Preferably the compounds of formula (I) contain more than one ester group. The compounds of the formula (I) very particularly preferably contain two ester groups.

The esters can also be present intramolecularly, in the form of a lactone. In this case, an ester bond is formed between the carboxyl function of the linear fatty acid residue and a terminal hydroxyl group of the carbohydrate residue R.

Alternatively or additionally, each of the hydroxyl groups of the carbohydrate residue R and/or the linear fatty acid residue can be esterified by a carboxylic acid. It is preferably an aliphatic, branched, straight-chain or cyclic carboxylic acid with a Ci-Ci2-alkyl radical. It is particularly preferably an aliphatic carboxylic acid with a Ci-C ₆ -alkyl radical. The carboxylic acids by which the hydroxyl groups of the carbohydrate residue R and/or of the linear fatty acid residue are esterified are very particularly preferably acetic acid and isovaleric acid.

In a further embodiment of the invention, 1, 2 or 3 hydroxyl groups of the carbohydrate residue R of the formula (I) and/or of the linear fatty acid residue are esterified by a carboxylic acid. It is preferably an aliphatic, branched, straight-chain or cyclic carboxylic acid with a Ci-Ci2-alkyl radical. It is particularly preferably an aliphatic, straight-chain carboxylic acid with a Ci-C ₆ -alkyl radical. Even more preferably, one or two hydroxyl groups of the carbohydrate residue R of formula (I) are esterified by acetic acid and/or one hydroxyl group by isovaleric acid. The aliphatic, straight-chain carboxylic acid is very particularly preferably isovaleric acid.

In a further embodiment of the invention, at least one of the hydroxyl groups of the carbohydrate residue R of the formula (I) is esterified with a carboxylic acid having at least three carbon atoms. At least one of the hydroxyl groups of the carbohydrate residue R of the formula (I) is preferably esterified with an isovaleryl group.

The carbohydrate radical R is particularly preferably a compound of the formula (III) Bonding to an oxygen atom of the lipid group of the formula (I) (|||) where Ft ³ , Ft ⁴ , Ft ⁵ , Ft ⁶ and Ft ⁷ are independently Fl or -C(=O)Ci-Ci ₂ -alkyl and Ft ⁸ = Fl or -C(=O)Ci-Ci ₂ -alkyl; where Ft ³ , Ft ⁴ , Ft ⁵ , Ft ⁶ Ft ⁷ and Ft ⁸ are preferably independently Fl or -C(=0)Ci-C ₆ -alkyl, where Ft ³ , Ft ⁴ , Ft ⁵ , Ft ⁶ and Ft ⁷ are particularly preferably independently Fl or -C(=O)C ₃ -C ₆ -alkyl and Ft ⁸ are preferably Fl or -C(=O)Ci-C ₆ -alkyl, even more preferably Ft ⁴ = -C (=0)isobutyi and Ft ³ , Ft ⁵ , Ft ⁶ , Ft ⁷ and Ft ⁸ independently = Fl or/and -C(=0)CFi ₃ .

In another embodiment of the invention, at least one compound of formula (I) is a compound of formula (IV) where, m = 3 or 5, n = 3, o = 1 p = 11 or 13

R ¹ is -H or -OH, preferably R ¹ = OH,

R ² is -H, alkali metal or an equivalent of an alkaline earth metal cation, or -Ci-C ₆ -alkyl; preferably -H or alkali metal or an equivalent of an alkaline earth metal cation; and

R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently H or -C(=0)Ci-Ci ₂ -alkyl and R ⁸ = H or -C(=0)Ci-Ci ₂ -alkyl .

In a preferred embodiment of the invention, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are independently H or -C(=O)Ci-C ₆ -alkyl, more preferably H or -C{=O )C ₃ -Ce-alkyl and R ⁸ = H or -C(=0)Ci-C ₆ -alkyl, more preferably R ⁴ = -C(=0)isobutyl and R ³ , R ⁵ , R ⁶ , R ⁷ , R ⁸ = H or/and -C(=O)CH ₃ .

In another preferred embodiment, R ² , R ⁶ and R ⁷ = H.

In a further preferred embodiment, the compound of the formula (I) is at least one compound of the formulas (VA) to (VD) or mixtures of these compounds

(VA) (VD) and salts of these compounds.

In a further preferred embodiment, salts within the meaning of the invention are alkali metal and/or alkaline earth metal salts, particularly preferably alkali metal salts.

The compounds of formula (V) are specific glycolipids.

The compounds of the formulas (I) to (V) are obtained from fungi by fermentation. The preparation of these compounds is known, for example, from WO-A 2012/167920. Preferably, for the preparation of the compounds of the formulas (I) to (V), fungi of the families Dacrymycetaceae, preferably of the genera Dacryopinax, Ditiola, Guepiniopsis and/or Femsjonia, particularly preferably of the species Dacryopinax spathularia, Dacrymyces sp., Dacrymyces stillatus, Dacrymyces chrysocomus, Guepinopsis buccina and/or Femsjonia luteo-alba (= Ditiola pezizaeformis) are used. The compounds of the formulas (I) to (V) from fungi of the species Dacryopinax spathularia of the strain MUCL 53181, Dacryopinax spathularia of the strain MUCL 53182, Ditiola radicata of the strain MUCL 53180, Ditiola nuda of the strain MUCL 53179, Dacrymyces chrysocomus of the strain are particularly preferred CBS280.84 and Femsjonia luteo-alba (= Ditiola pezizaeformis) of strain MUCL 53500. The compounds of the formula (I) are preferably obtained from the fungi as mixtures in the form of an extract. These can then be further purified, for example by column chromatography, such as in particular by high-pressure column chromatography, or by filtration and precipitation. The purification processes are known to those skilled in the art, for example from WO-A 2012/167920.

In a further embodiment of the invention, the fungus Dacryopinax sphatularia of the strain MUCL 53181 is used to prepare the compounds of the formulas (I) to (V).

In a further embodiment of the invention, the compounds of the formula (I) are used as mixtures.

In a further embodiment of the invention, mixtures of the compounds of the formula (V-A), formula (V-B), formula (V-C) and the compounds of the formula (V-D) are used. Preference is given to mixtures of the compounds of the formula (V-A) and compounds of the formula (V-B) and compounds of the formula (V-C) and compounds of the formula (V-D) in an amount of 30% by weight to 96% by weight, based on the total dry mass of the compounds used Compounds of formula (I) used.

Mixtures of the compounds of the formula (VA) and compounds of the formula (VB) and compounds of the formula (VC) and compounds of the formula (VD) in an amount of 75% by weight to 96% by weight, based on the total dry mass of the used compounds of formula (I). The remaining compounds in the mixtures can be inorganic salts or other compounds of the formula (I). Dialkyl dicarbonates are preferably compounds of the formula (VI) wherein

R ⁹ and R ¹⁰ independently represent straight-chain or branched C 1 -C 5 alkyl, cycloalkyl, C 2 -C 5 alkenyl or C 2 -C 5 alkynyl, each of which is optionally substituted one or more times, identically or differently, by halogen; nitro; cyano; Ci-C ₆ alkoxy; dialkylamino; or phenyl which is optionally substituted one or more times, identically or differently, by halogen; nitro; cyano; alkyl; haloalkyl; alkoxy; haloalkoxy; acyl; acyloxy; alkoxycarbonyl; carboxyl, preferred

R ⁹ and R ¹⁰ independently represent straight-chain or branched Ci-Cs-alkyl or C2-Cs-alkenyl, particularly preferred

R ⁹ and R ¹⁰ are, independently of one another, straight-chain or branched Ci-C ₅ -alkyl or C3-alkenyl, and are very particularly preferred

R ⁹ and R ¹⁰ are independently methyl, ethyl, isopropyl, tert-butyl, tert-amyl, allyl or benzyl.

Dialkyl dicarbonate is particularly preferably diethyl dicarbonate or dimethyl dicarbonate, in particular dimethyl dicarbonate.

Dimethyl dicarbonate is preferably used in a mixture with 100 ppm to 500 ppm phosphates. The preparation of this mixture and the possibility for Stabilization of dimethyl dicarbonate with phosphorus compounds is known, for example, from US Pat. No. 8,207,368.

The compounds of the formula (I) are used in the beverages preferably in a concentration of 1 to 30 ppm, particularly preferably of 1 to 20 ppm and even more preferably in a concentration of 1 to 15 ppm.

Dialkyl dicarbonates are preferably used in the beverages in a concentration of 20 ppm to 150 ppm, particularly preferably 30 to 100 ppm.

The weight ratio of the compounds of formula (I) and the dialkyl dicarbonates is preferably from 1:30 to 1:60.

More preferably, the weight ratio of the compounds of formula (I) and the dialkyl dicarbonates is 1:30 to 1:60 and the concentration of the dialkyl dicarbonates is 10 to 300 ppm in the beverages.

In a further embodiment of the invention, 1 ppm to 30 ppm of the compounds of the formula (I) and 50 to 300 ppm of dialkyl dicarbonates, in particular dimethyl dicarbonate, are used in a weight ratio of 1:10 to 1:70, the amount of the compounds of the formula ( I) must be chosen so that the amount of dialkyl dicarbonates in the beverage is less than or equal to 300 ppm.

Beverages within the meaning of the invention are aqueous products for drinking, typically including water, consumed for thirst quenching, nourishment, savoring or enjoyment and/or for other functional purposes, for example for the delivery of drugs or other functional materials be able.

In the sense of the invention, beverages are preferably aqueous products for drinking which contain at least 60% by weight of water. In addition, these products may also contain flavorings, sugars, emulsifiers, artificial and natural flavor enhancers, buffering agents, acids or other consumable beverage additives.

Beverages particularly preferably contain 80 to 90% by weight water, 2 to 8% by weight artificial and/or natural flavorings, 4 to 8% by weight sucrose and 4 to 14% by weight acidulants, such as preferably citric acid and sugar other than sucrose. Very particularly preferably, beverages contain 80 to 90% by weight water, 0.1 to 10% by weight artificial and/or natural flavorings, 4 to 8% by weight sucrose and 0.1 to 4% by weight acidifiers, such as preferably citric acid and Sugar unlike sucrose. Other beverage additives can preferably be included. In another In a preferred embodiment of the invention, the sum of water, artificial and/or natural flavorings, sucrose, acidifier and sugar other than sucrose in the beverages is _> 90% by weight. In addition, further compounds such as, for example and preferably, emulsifiers, artificial and natural flavor enhancers and buffer substances can be included.

Beverages are preferably water, flavored water, fortified water, flavored beverages, carbonated water, flavored seltzer or soda water, juices, cola, lemon-lime, ginger beer, and root beer beverages that are carbonated in the manner of soft drinks, and beverages that are Health or wellness benefits may be provided by the presence of metabolically active substances such as vitamins, amino acids, proteins, carbohydrates, lipids or polymers thereof, such products may also be formulated to contain milk, coffee or tea (e.g. green tea) or other vegetable solids , syrup, diet drinks, carbonated soft drinks, fruit juices e.g. B. Orange Juice, Grapefruit Juice, Apple Juice, Red Grape Juice, White Grape Juice, Pear Juice, Concord Grape Juice, Pineapple Juice, Pomegranate Juice, Cranberry Juice, Passion Fruit Juice, Lime Juice, Lemon Juice, Mango Juice, Guava Juice, Banana Juice, Redcurrant Juice, Blackcurrant Juice, Cashew Juice, Cantaloupe Juice , Apricot Juice, Blackberry Juice, Cranberry Juice, Pigeon Juice, Gooseberry Juice, Crab Juice, Prune Juice, Prune Juice, Kiwi Juice, Strawberry Juice, Blueberry Juice, Red Raspberry Juice, Black Raspberry Juice, Cherry Juice, Watermelon Juice, Peach Juice, Nectarine Juice, Loganberry Juice, Honeydew Melon Juice, Papaya Juice, Boysenberry Juice, Young Berry Juice, Rhubarb Juice., Guanabana Juice , Agai juice, goji juice, fig juice, elderberry juice, date juice, carambola juice, acerola juice, quince juice, blueberry juice, tangerine juice, fruit-based drinks, preferably fruit drinks that have the taste of e.g. B. impart one of the aforementioned fruit juices and contain more than 0% fruit juice but less than 100% fruit juice, fruit-flavored beverages, vegetable juices, preferably tomato juice, beet juice, carrot juice, celery juice, vegetable-containing beverages that impart the flavor of one of the aforementioned vegetable juices and containing more than 0% vegetable juice but less than 100% vegetable juice, isotonic beverages, non-isotonic beverages, soft drinks containing a fruit juice, coffee, tea, tea beverages made from tea concentrate. Extracts or powders, drinkable milk products, eg drinkable yoghurts (drinking yoghurt), kefir or buttermilk, hot chocolate, chocolate powder/mixtures, drinkable soy products, non-diet milk, preferably. Coconut milk, alcoholic beverages, preferably malt beverages, wine, beer, distilled liqueurs, spirits, sparkling wine, champagne or liqueurs, fruit smoothies, horchata (vegetable and/or rice components that go into a drink processed), sports drinks, energy drinks, health drinks, shakes, protein drinks (e.g. milk, soy, rice or other), drinkable soy yoghurts, low-acid drinks as defined in US 21 CFR Part 113. Acidified drinks as defined in US 21 CFR Part 114, nectars, tonics, frozen carbonated beverages, frozen non-carbonated beverages, liquid meal substitutes, infant formulas, and combinations or blends thereof.

A "juice" is the aqueous liquid expressed or extracted from one or more fruits or vegetables, purees of the edible parts of one or more fruits or vegetables, or concentrates of that liquid or puree.

Carbonated drinks are also referred to as carbonated drinks within the scope of the patent application. Beverages to which no carbon dioxide is added are also referred to as non-carbonated beverages within the scope of the patent application.

Preferably, at least one compound of the formula (I) is first added to the beverage in step a.) and then at least one dialkyl dicarbonate is added to the beverage in step b.). The addition can take place at any temperatures and pressures. The compounds of the formula (I) and the dialkyl dicarbonates are preferably added at from 15 to 30.degree.

The compounds of the formula (I) are added either as a solid, preferably in powder form, or as a stock solution in water, which is preferably introduced with stirring. The addition to the drink or the corresponding aqueous precursors, which are preferably placed in a tank, can be done at any time manually or mechanically via a corresponding dosing device. However, the compounds of the formula (I) and the dialkyl dicarbonates can also be initially taken and the beverages or the precursors of the beverages can be added thereto. A point in time before the finished beverage is filled is preferably selected. The dosing into the beverage preferably takes place at least 2 hours before the beverage is filled. In order to ensure better mixing, a stock solution is preferably used, preferably in a concentration of 0.1 to 10% by weight, particularly preferably in a concentration of 1-5% by weight. To prepare the stock solution, the compounds of the formula (I) are preferably dissolved in water (for example 10 g in one liter of water) at room temperature while stirring for 2-3 minutes using a hand mixer (eg KitchenAid 5KHB1231). The dialkyl dicarbonates can be added as a liquid manually or mechanically via a metering device. The addition preferably takes place with the aid of a dosing pump, preferably before the finished beverage is filled.

The amount of the compounds of formula (I) and/or the dialkyl dicarbonates in the beverages after addition is preferably not measured but calculated.

In the beverages, the compounds of the formula (I) used and the dialkyl dicarbonates act against infestation and/or decomposition by microorganisms, such as, for example and preferably, bacteria, fungi or yeasts.

The compounds of the formula (I) used and the dialkyl dicarbonates have a controlling effect on a number of microorganisms such as fermentative yeasts, molds or fermentative bacteria. The mixtures of compounds of the formula (I) and the dialkyl dicarbonates preferably act against Aspergillus brasiliensis, Aspergillus niger Byssochlamys fulva, Dekkera bruxellensis, Saccharomyces cerevisiae, Mycoderma, Brettanomyces spp, Lactobacillus brevis, Lactobacillus buchneri, Lactobacillus plantarum, Zygosaccharomyces bailii and Candida intermedia. The mixtures of compounds of the formula (I) and the dialkyl dicarbonates act particularly preferably against Saccharomyces cerevisiae, Zygosaccharomyces bailii and Candida intermedia.

The beverages produced according to the method according to the invention are also encompassed by the invention. The compounds of the formula (I) used in the beverages and the dialkyl dicarbonates surprisingly have a synergistic effect in the range according to the invention and are highly effective against microorganisms. Outside the scope of the invention, their effect is rather poor or even antagonistic.

examples

The following mixture of compounds of the formula (I) was used in Examples 1 to 4:

Table 1

^* Percentages by weight of the compounds of formula (I) used in the mixture.

The total amount of the compounds of the formula (I) used was 95% by weight, based on the dry matter.

dimethyl dicarbonate (DMDC) was used as a liquid (99.9% purity) (Velcorin®, Lanxess)

The non-carbonated apple juice from Rewe “Beste Wahl Apfelsaft” from PET bottles was used as the test matrix, diluted 1:1 with sterilized tap water with a pH of 3.56.

The following fungal spoilage organism was used to assess antifungal activity as described in Table 2.

The specification in mg/l represents a concentration specification. 1 mg/l is 1 ppm.

The compounds of the formula (I) are referred to below as glycolipids. Table 2

The beverage samples for determining the minimum inhibitory concentration (MIC) were created by directly pipetting DMDC or a 5% stock solution of the natural glycolipids into the test matrix and then shaking for an adequate distribution.

The following parameters were selected as microbial test conditions:

Temperature: 28°C Growth time: 3 days

Readout: Live cell count using the pour plate / streak plate method [1 ml/plate] Inoculation concentration (inoculum): 100 cfu/ml as the concentration of spoilage organisms in the test matrix.

Example 1 (not according to the invention)

MIC of glycolipids or DMDC

The MIC was determined by using only the glycolipids or DMDC in the test matrix in accordance with DIN 58940-8. The initial test solution was serially diluted with the test matrix so that each subsequent solution contained 50% of the previous drug concentration, while maintaining the nutrient concentration (test matrix). The MIC is defined as the minimum concentration of drug that inhibits cell growth, determined by counting viable cells after 72 hours of incubation on agar plates.

Results for DMDC:

Table 3 The MIC value is therefore 90 mg/l.

Results for glycolipids: Table 4

The MIC value is therefore 3.1 mg/l. Example 2 (according to the invention)

MIC of combined use with glycolipids and DMDC and calculation of the synergistic effect.

The MIC was determined according to DIN 58940-8 using combinations of glycolipids and DMDC in the test matrix. The initial test solution was serially diluted with the test matrix as described in Example 1.

Various combinations were used to determine MICs as described in Tables 5 and 6 below.

Table 5

S. cerevisiae (inoculum: 100 cfu/ml)

MICs have been observed for the following combinations where the concentrations are below the MICs of the individual components:

A mixture of 8 mg/L DMDC and 1 mg/L glycolipids is inactive. Table 6

[l] The synergistic effect was calculated using the Fractional Inhibitory Concentration (FIC) Index (FICI) as described in US Patent No. 7,074,447. Of the

FIC Index is calculated according to the formula:

FICI = FIC (Component 1) + FIC (Component 2),

The Fractional Inhibitory Concentration is calculated according to the formula: FIC = MIC of the combination of both components / MIC of the individual component.

If the FICI is calculated as <1, the two components 1 and 2 behave synergistically; the lower the FICI (<1), the stronger the synergistic effect of the two components together. If the FICI is <0.5 then the synergy is considered very strong.

According to the MIC values from the tables above, the following FIC and FICI values are calculated as laid out in Table 7:

Table 7

Ό/N = DMDC/glycolipids ratio As can be seen from the table above, DMDC and the glycolipids act synergistically in combination on the MIC value. For example, the combination of DMDC and glycolipids in a ratio of 30:1 is more than twice as effective as the individual components against S. cerevisiae. At a ratio of 80:1, however, an antagonistic effect can be seen. At 8:1 ratios of DMDC and glycolipids and a concentration of DMDC <=15 ppm and glycolipids <= 2 ppm, no effect is seen. These mixtures are inactive.

Example 3

Long-lasting growth inhibition of yeast spoilage organisms by DMDC, glycolipids and combined application of both components

The test matrix (apple juice with water, 1:1) was contaminated with 100 cfu/ml of a mixture of three yeasts (Candida intermedia, Saccharomyces cerevisiae, Zygosaccharomyces bailii; all independently isolated from beverage samples and stored in our own strain collection). As described in Example 1, the MIC values were determined after incubation at 28° C. for two weeks for the individual components and for combinations of both components.

According to the MIC values, the following FIC and FICI values are calculated as laid out in Table 8.

Table 8

example 4

Long-term preservation of carbonated and non-carbonated beverages using DMDC combined with glycolipids

An apple juice drink was prepared using the example recipe as in described in Table 9:

Table 9

The amount of compounds of formula (I) in the beverages (carbonated and non-carbonated beverage) is 5 ppm.

Carbonated Beverage: The ingredients were combined in a tank at 25°C in the order named in the table and mixed into a syrup. In this step, 10.34% of the above amount of water was used. After each addition, the ingredients were homogenized using a centrifugal pump via a tank-in-tank mixing system. The aqueous glycolipid stock solution was then added with gentle stirring. The syrup was then mixed with carbonated water in proportion to volume using an Ortmann + Herbst intermix (consisting of vacuum degassing, carbonation and buffer tank). The product was transferred from the buffer tank to the Kosme filling machine using a frequency-controlled centrifugal pump. The VDT dosing pump was integrated in the product line Touch (Serial No. 90332615) injected dimethyl dicarbonate at a rate of 90mg/L. The carbonated apple juice drink was then filled into 0.5L PET bottles. A total of 505 bottles were filled. These were stored at room temperature for 35 days. The filled product was then inspected for visual changes caused by microbiological factors. For this purpose, each bottle was individually positioned in front of a light source and checked for sediment formation, turbidity, flocculation, mycelium formation or similar deviations. After the end of the incubation period, none of the bottles showed any changes that indicated microbiological contamination. In addition, 5 samples from the beginning, middle and end of production were each plated in duplicate on MRS (De Man, Rogosa and Sharpe) and OSA (Orange Serum Agar) and aerobically at 30°C for 3 days (MRS) and 5 days ( OSA) incubated. The germ count displayed was < 1 CFU/ml.

Non-carbonated drink:

The ingredients were added at 25°C in a tank in the order named in the table. After each addition, the ingredients were homogenized using a centrifugal pump via a tank-in-tank mixing system. The aqueous glycolipid stock solution was then added with gentle stirring. The finished product was then transferred directly from the batch tank to the Kosme filling machine using a frequency-controlled centrifugal pump. 90mg/l of dimethyl dicarbonate were injected into the product line using a VDT Touch dosing pump (serial no. 90332615). The apple juice drink was then filled into 0.5L PET bottles.

A total of 404 bottles were filled. These were stored at room temperature for 35 days. The filled product was then inspected for visual changes caused by microbiological factors. For this purpose, each bottle was individually positioned in front of a light source and checked for sediment formation, turbidity, flocculation, mycelium formation or similar deviations. After the end of the incubation period, none of the bottles showed any changes that indicated microbiological contamination. In addition, 5 samples from the beginning, middle and end of production were each plated in duplicate on MRS (De Man, Rogosa and Sharpe) and OSA (Orange Serum Agar) and aerobically at 30°C for 3 days (MRS) and 5 days ( OSA) incubated. The germ count displayed was < 1 CFU/ml.

Claims

patent claims

1. A method for sterilizing and preserving beverages, characterized in that at least one compound of formula (I) with m = 3 to 5, preferably 3 or 5; n = 2 to 5, preferably 3; o = 0 or 1 and

^R1 = H or OH

R ² = is H, alkali metal or an equivalent of an alkaline earth metal cation, or -Cr C ₆ alkyl; preferably H or alkali metal or an equivalent of an alkaline earth metal cation and p = 3 to 17, preferably 5 to 15 wherein the sum of m + n + o + p is not less than 14 and

R represents a carbohydrate residue which is bonded to the oxygen atom via a carbon atom and at least one dialkyl dicarbonate, is added to the beverage and a concentration of the dialkyl dicarbonates of 10 to 300 ppm is adjusted in the beverage and the weight ratio of the compounds of formula (I) and the dialkyl dicarbonate is from 1:10 to 1:70 in the beverage.

2. The method according to claim 1, characterized in that the carbohydrate radical R is a compound of formula (III).

Bonding to an oxygen atom of the lipid group of the formula (I) (|||) where R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently H or -C(=0)Ci-Ci ₂ -alkyl and R ⁸ = H, -C(=O)-CH ₂ -C((CH ₃ )(OH))-CH ₂ -COOH or -C(=O)Ci-Ci ₂ -alkyl; where R ³ , R ⁴ , R ⁵ , R ⁶ R ⁷ and R ⁸ are preferably independently -H or - C(=O)Ci-C ₆ -alkyl, where R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are particularly preferably independently H or -C(=0)C ₃ -C ₆ -alkyl and R ⁸ are preferably H or -C(=0)Ci-C ₆ -alkyl, even more preferably R ⁴ = - C(=O)isobutyl and R ³ , R ⁵ , R ⁶ , R ⁷ and R ⁸ independently of one another = H or/and -C(=O)CH ₃ .

3. The method according to claim 1 or 2, characterized in that the compound of formula (I) corresponds to a compound of formula (IV). whereby, m = 3 or 5, n = 3, o = 1 p = 11 or 13

R ¹ is H or -OH, preferably R ¹ = OH,

R ² is H, alkali metal or alkaline earth metal cation or -Ci-C ₆ -alkyl; preferably - H or alkali metal or alkaline earth metal cation; and

R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently H or -C(=0)Ci-Ci ₂ -alkyl and R ⁸ = H, -C(=0)-CH ₂ -C(( CH ₃ )(0H))-CH ₂ -C00H or -C(=O)Ci-Ci ₂ -alkyl.

4. The method according to at least one of claims 1 to 3, characterized in that the compound of formula (I) corresponds to at least one compound of formula (VA) to (VD).

(VA)

5. The method according to at least one of claims 1 to 4, characterized in that mixtures of the compounds of the formula (VA) and compounds of the formula (VB) and compounds of the formula (VC) and compounds of the formula (VD) in an amount of 30 wt% to 96 wt% based on the total dry matter of the compounds of the formula (I) used.

6. The method according to at least one of claims 1 to 5, characterized in that the dialkyl dicarbonate is preferably a compound of the formula (VI) wherein

R ⁹ and R ¹⁰ are independently straight-chain or branched Ci-Cs-alkyl, cycloalkyl, C2-Cs-alkenyl or C2-Cs-alkynyl, each of which is optionally substituted one or more times, identically or differently, by halogen; nitro; cyano; Ci-C ₆ alkoxy; dialkylamino; or phenyl which is optionally substituted one or more times, identically or differently, by halogen; nitro; cyano; alkyl; haloalkyl; alkoxy; haloalkoxy; acyl; acyloxy; alkoxycarbonyl; are carboxyl.

7. The method according to at least one of claims 1 to 6, characterized in that dialkyl dicarbonates selected from the group of diethyl dicarbonate and dimethyl dicarbonate.

8. The method according to at least one of claims 1 to 7, characterized in that the dialkyl dicarbonate to the compound of formula (I) is used in a weight ratio of 60:1 to 30:1 in the beverage.

9. The method according to at least one of claims 1 to 8, characterized in that the dialkyl dicarbonate is used in a concentration of 30 to 100 ppm in the beverage.

10. The method according to at least one of claims 1 to 9, characterized in that the compounds of formula (I) are used in a concentration of 1 to 30 ppm in the beverage and the concentration of the dikydicarbonate in the beverage is then selected such that a Concentration range of 10 ppm to 300 ppm is maintained and the weight ratio of the compounds of formula (I) and the dialkyl dicarbonates when added is 1:10 to 1:70.

11. The method according to at least one of claims 1 to 10, characterized in that the beverages are sterilized and preserved against the microorganisms Saccharomyces cerevisiae, Zygosaccharomyces bailii and Candida intermedia.

12. The method according to at least one of claims 1 to 11, characterized in that the drinks contain 80 to 90% by weight water, 2 to 8% by weight artificial and/or natural flavorings, 4 to 8% by weight sucrose and 4 to 14 % by weight of acidulant, such as preferably citric acid and sugar other than sucrose.

13. The method according to at least one of claims 1 to 12, characterized in that in a first step a.) at least one dialkyl dicarbonate is added to the beverage and after this addition in a step b.) at least one compound of the formula (I) in be given the drink.

14. Beverage produced according to any one of claims 1 to 13.

15. Use of at least one compound of the formula (I) and at least one dialkyl dicarbonate in a weight ratio of the compounds of the formula (I) and the dialkyl dicarbonates of 1:10 to 1:70 and a concentration of the dialkyl dicarbonates of 10 to 300 ppm for sterilization and preservation of beverages.