FOOD COMPOSITIONS CONTAINING VEGETABLE OIL AND MIXTURE WITH STABILISING PROPERTIES

Abstract

The present invention relates to food products containing vegetable oils which are sensitive for oxidation, leading to rancidity and unattractive food products for consumers. Objective of the invention is to reduce the oxidation, without using EDTA. The oxidation has been reduced using a mixture of compounds than can be obtained from natural sources. This reduced oxidation of fatty acids has been shown in low-fat mayonnaise, salad dressing, and margarine.

Claims

1. A food composition comprising vegetable oil comprising mono-unsaturated and/or poly-unsaturated fatty acids, wherein the concentration of the vegetable oil ranges from 5% to 85% by weight of the composition, further comprising a mixture comprising or consisting of: a) one or more monocyclic monoterpenes of formula (I) ##STR00007## with R1=hydrogen, hydroxy group or carbonyl group, R2=hydrogen, hydroxy group or carbonyl group, R3=0, hydrogen or hydroxy group and R4=isopropyl group, isopropenyl group or isopropylidene group as well as without or with one, two or three double bonds in the cyclic system, preferably selected from the group consisting of gamma-terpinene, alpha-terpinene, beta-terpinene, beta-phellandrene, limonene, thymol, pulegone, carvacrol and alpha-phellandrene, b) one or more benzoic acid derivatives of formula (II) ##STR00008## with R1, R2 and R3 independently of each other selected from the group consisting of hydrogen, hydroxy group and methoxy group, c) a first 3-phenylpropenoic acid derivative of formula (IV) ##STR00009## with R1=1-carboxy-2-(3,4-dihydroxyphenyl)ethyl, R2=hydrogen and R3=hydrogen, optionally a second 3-phenylpropenoic acid derivative of formula (IV) with R1=5-carboxy-2,3,5-trihydroxycyclohexyl, R2=hydrogen and R3=hydrogen, and optionally a third 3-phenylpropenoic acid derivative of formula (IV) with R1=hydrogen, R2=hydrogen and R3=hydrogen, d) tartaric acid (formula (V)) D-()-form, and/or L-(+)-form, and/or meso-form ##STR00010## e) citric acid (formula (VI)) and/or malic acid (formula (VII)) ##STR00011## f) glucose, fructose and/or sucrose, g) 1,2-propanediol and/or 1,3-propanediol and/or propane-1,2,3-triol, h) water, i) optionally gallocatechin (Formula (III)) (2R,3S)-3,4-dihydro-2-(3,4,5-trihydroxyphenyl)-2H-1-benzopyran-5 3,5,7-triol ##STR00012## j) optionally one or more further flavouring substances, and k) optionally one or more further solvents, preferably selected from the group consisting of triacetin (TRI), isopropanol (iPr), isopropyl myristate (IPM), ethanol, dipropylene glycol (DPG) and triethyl citrate (TEC).

2. A composition according to claim 1, wherein the mixture has an ORAC value of greater than 200 mol TE/g, with respect to the dry weight of the mixture.

3. A composition according to claim 1, wherein the mixture has a polyphenol content according to Folin-Ciocalteu of greater than 5%, with respect to the dry weight of the mixture.

4. A composition according to claim 1, wherein the mixture comprises or consists of, with regard to the total weight of the mixture, respectively, 0.0001 to 80 wt % of component a), 0.0001 to 1.5 wt % of component b), 0.0001 to 3 wt % of component c), 0.005 to 10 wt % of component d), 0.005 to 10 wt % of component e), 0.000005 to 25 wt % of component f), 0.0001 to 98 wt % of component g), 0.0005 to 95 wt % of component h), 0.0001 to 1 wt % of component i), 0.005 to 95 wt % of component j), 0.01 to 95 wt % of component k).

5. A composition according to claim 1, wherein the total amount of mixture in the composition, ranges from 0.05 to 5 wt %.

6. A composition according to claim 1, wherein the composition is in the form of an oil-in-water emulsion.

7. A composition according to claim 6, wherein the composition comprises an oil-in-water emulsifier.

8. A composition according to claim 1, wherein the composition is in the form of a water-in-oil emulsion.

9. A composition according to claim 8, wherein the composition comprises a water-in-oil emulsifier.

10. A composition according to claim 1, wherein the concentration of EDTA is lower than 0.005% by weight of the composition.

11. Use of a mixture comprising or consisting of: a) one or more monocyclic monoterpenes of formula (I) ##STR00013## with R1=hydrogen, hydroxy group or carbonyl group, R2=hydrogen, hydroxy group or carbonyl group, R3=0, hydrogen or hydroxy group and R4=isopropyl group, isopropenyl group or isopropylidene group as well as without or with one, two or three double bonds in the cyclic system, preferably selected from the group consisting of gamma-terpinene, alpha-terpinene, beta-terpinene, beta-phellandrene, limonene, thymol, pulegone, carvacrol and alpha-phellandrene, b) one or more benzoic acid derivatives of formula (II) ##STR00014## with R1, R2 and R3 independently of each other selected from the group consisting of hydrogen, hydroxy group and methoxy group, c) a first 3-phenylpropenoic acid derivative of formula (IV) ##STR00015## with R1=1-carboxy-2-(3,4-dihydroxyphenyl)ethyl, R2=hydrogen and R3=hydrogen, optionally a second 3-phenylpropenoic acid derivative of formula (IV) with R1=5-carboxy-2,3,5-trihydroxycyclohexyl, R2=hydrogen and R3=hydrogen, and optionally a third 3-phenylpropenoic acid derivative of formula (IV) with R1=hydrogen, R2=hydrogen and R3=hydrogen, d) tartaric acid (formula (V)) D-()-form, and/or L-(+)-form, and/or meso-form ##STR00016## e) citric acid (formula (VI)) and/or malic acid (formula (VII)) ##STR00017## f) glucose, fructose and/or sucrose, g) 1,2-propanediol and/or 1,3-propanediol and/or propane-1,2,3-triol, h) water, i) optionally gallocatechin (Formula (III)) (2R,3S)-3,4-dihydro-2-(3,4,5-trihydroxyphenyl)-2H-1-benzopyran-5 3,5,7-triol ##STR00018## j) optionally one or more further flavouring substances, and k) optionally one or more further solvents, preferably selected from the group consisting of triacetin (TRI), isopropanol (iPr), isopropyl myristate (IPM), ethanol, dipropylene glycol (DPG) and triethyl citrate (TEC), in a food composition comprising vegetable oil comprising mono-unsaturated or poly-unsaturated fatty acids, to reduce the oxidation rate of the vegetable oil.

12. A composition according to claim 7, wherein the water emulsifier comprises egg yolk.

13. A composition according to claim 9, wherein the water-in-oil emulsifier comprises a monodiglyceride of fatty acid, or a diglyceride of fatty acids.

Description

DESCRIPTION OF FIGURES

[0110] FIG. 1: Oxygen concentration in the headspace as function of time in light mayonnaises from example 2. Legend: [0111] .circle-solid. sample 204 (with EDTA) [0112] .square-solid. sample 205 (no EDTA) [0113] .box-tangle-solidup. sample 207 (no EDTA, containing mixture with the compounds from mixture M1 in example 1)

[0114] FIG. 2: Hexanal concentration in the headspace in accelerated shelf-life test, samples from example 2.

[0115] Legend: [0116] .circle-solid. sample 204 (with EDTA) [0117] .square-solid. sample 205 (no EDTA) [0118] .box-tangle-solidup. sample 207 (no EDTA, containing mixture with the compounds from mixture M1 in example 1)

[0119] FIG. 3: Oxygen concentration in the headspace as function of time in salad dressings from example 3. Legend: [0120] .circle-solid. sample 267 (with EDTA) [0121] .square-solid. sample 268 (no EDTA) [0122] .box-tangle-solidup. sample 269 (no EDTA, containing mixture with the compounds from mixture M1 in example 1)

[0123] FIG. 4: Oxygen concentration in the headspace as function of time in margarines from example 4. Legend: [0124] .circle-solid. sample 028 (no mixture from example 1) [0125] .box-tangle-solidup. sample 029 (containing 0.15% of a mixture with the compounds from mixture M1 in example 1) [0126] .square-solid. sample 030 (containing 0.2% f a mixture with the compounds from mixture M1 in example 1)

EXAMPLES

[0127] The following non-limiting examples illustrate the present invention.

[0128] Raw Materials [0129] Water: demineralised water is used in all experiments. [0130] Soybean oil ex Cargill (Amsterdam, The Netherlands). [0131] Sunflower oil: ex C Thywissen (Neuss, Germany) [0132] Rapeseed oil: ex Broekelmann [0133] Butter oil: Arla Foods [0134] Palm oil: ex Sime Darby Unimills (Zwijndrecht, Netherlands) [0135] Interesterified oil: ex Sime Darby Unimills (Zwijndrecht, Netherlands) [0136] Sucrose: white sugar W4 ex Suiker Unie (Oud Gastel, Netherlands). [0137] Sorbic acid: ex Univar (Zwijndrecht, Netherlands). [0138] Salt: NaCl suprasel ex Akzo Nobel (Amersfoort, Netherlands). [0139] EDTA: Ethylenediaminetetraacetic acid, calcium disodium complex, dehydrate; Dissolvine E-CA-10 ex Akzo Nobel (Amersfoort, Netherlands). [0140] Liquid egg yolk: 92-8 (8% NaCl), ex Bouwhuis Enthoven (Raalte, Netherlands). [0141] Liquid egg: pasteurised, ex Bouwhuis Enthoven (Raalte, Netherlands). [0142] Spirit vinegar: 12% acetic acid vinegar ex Mizkan (UK). [0143] Lemon juice: concentrate 45 brix ex Dhler (Darmstadt, Germany). [0144] Xanthan gum: ex Jungbunzlauer [0145] Modified corn starch: ex Ingredion [0146] Whey protein concentrate: 80% protein ex Arla Foods [0147] Lecithin: ex Sime Darby Unimills (Zwijndrecht, Netherlands) [0148] Beta-carotene: Natural ex Christian Andersen [0149] Sweet buttermilk powder: ex Lactoland [0150] Potassium sorbate: ex Merck [0151] Thymol: Symrise [0152] Limonene: MCI Miritz [0153] Gamma-Terpinene: Destillerias Munoz Galvez S.A. [0154] Carvacrol: Frutarom [0155] 4-Hydroxy-3,5-dimethoxybenzoic acid: Alfa Aesar [0156] Carvone; Gallic acid; Gallocatechin; 3-(3,4-dihydroxyphenyl)prop-2-enoic acid; 3-(3,4-dihydroxyphenyl)-2-[3-(3,4-dihydroxyphenyl)prop-2-enoyl]oxy-propionic acid; 4-Hydroxy-3,5-dimethoxybenzoic acid; Citric acid; Glucose: Sigma-Aldrich [0157] Tartaric acid; Malic acid: UD Chemie [0158] Propylene glycol: Dow

[0159] Methods

[0160] Accelerated Shelf-Life Test to Follow Lipid Oxidation:

[0161] Vegetable oil is subjected to conditions which promote oxidation, without requiring the typical shelf life of 4 to 9 months which is normal for a mayonnaise.

[0162] Emulsion samples with various compositions are prepared (as described in the examples below) and 1 g of each sample is filled in a capped glass vial (20 mL volume) and kept in a temperature controlled oven at 50 C. Oxidation experiments are carried out during a period up to 42 days and at several time points a sample is picked for headspace-GC-MS measurement of volatile oxidation markers (e.g. hexanal). Usually every data point is measured in triplo. The measurements are performed on a GC-MS combination of Agilent (7890A/5975C). The GC column used is a DB-Wax (20 m-0.18 d-0.3 m) from J&W. The injection volume is 500 L with a split of 40:1 and a column flow of 1 ml/min. Total nine volatiles (mainly aldehydes and alkanesconsidered as marker for lipid oxidation) are analysed, of which hexanal is the most important marker, and reported in here. The hexanal response is given in arbitrary unitsthe higher the response the more hexanal and the more oxidation of triglycerides.

[0163] The oxidation of triglycerides occurs in several steps, in which the first step is the most important. This first step is the lag phase, which is the phase where there is not much oxidation, and after this phase the oxidation starts to accelerate. This means that the amount of oxidation products rapidly starts to increase. The longer the lag phase, the slower the oxidation process, and the better the result.

[0164] Oxygen Concentration in Headspace

[0165] To follow oxidation of fatty acids in emulsions in the experiments, the oxygen concentration is measured in the headspace of closed jars in which emulsions are stored to follow oxidation. The lower this concentration, the more oxygen is consumed for oxidation processes. The oxygen content is determined by taking a sample of gas from the headspace with a needle through the closed lid of the jar. The oxygen concentration in the sample is determined by a gas analyser.

[0166] Equipment [0167] Mixed vessel: temperature controlled mixed vessel (Universal Machine UM-5, ex Stephan Machinery GmbH, Hameln, Germany); [0168] Colloid mill: MZM/VK-7 (Fryma-Maschinen AG, Rheinfelden, Switzerland).

Example 1. Mixture for Use in Food Compositions According to the Invention

[0169] The mixture can be used in food compositions according to the invention.

TABLE-US-00001 TABLE 1 Components in mixture which can be used in food compositions according to the invention M1 Component [wt %] Thymol 0.0011 Limonene 0.0007 gamma-Terpinene 0.0003 Carvone 0.0001 Carvacrol 0.0001 Gallic acid 0.0293 4-Hydroxy-3,5-dimethoxybenzoic acid 0.0046 Gallocatechin 0.0053 3-(3,4-dihydroxyphenyl)prop-2-enoic acid 0.0061 3-(3,4-dihydroxyphenyl)-2-[3-(3,4-dihydroxyphenyl)prop-2- 0.5733 enoyl]oxy-propionic acid Tartaric acid 2.1510 Citric acid 1.4377 Malic acid 1.3670 Glucose 4.9733 Fructose 6.4913 Sucrose 1.1798 Water 50.6485 Propylene glycol 31.1305

[0170] These mixtures are prepared by dissolving the solid compounds in the premixed solvents water and propylene glycol. If necessary, these preparations are slightly heated to maximally 40 C. until all compounds are dissolved. Then the other ingredients are added after cooling to room temperature.

Example 2. Light Mayonnaises

[0171] Various low-fat mayonnaises were prepared containing EDTA, without EDTA, and containing a mixture containing the compounds of and at concentrations of M1 in example 1. The compositions of these water-in-oil emulsions is given in Table 2.

TABLE-US-00002 TABLE 2 Composition of prepared low-fat mayonnaises. 204 205 207 Conc. Conc. Conc. Ingredient [wt %] [wt %] [wt %] Salt 1.5 1.5 1.5 Sucrose 2.5 2.5 2.5 Liquid egg 4 4 4 EDTA 0.0077 Mixture containing the compounds of 0.10 M1 in example 1 Flavour 0.2 0.2 0.2 Soybean oil 23 23 23 Modified corn starch 5 5 5 Lemon juice 0.5 0.5 0.5 Spirit vinegar 2.0 2.0 2.0 Sorbic acid 0.1 0.1 0.1 Water to 100% to 100% to 100% * small differences may occur due to rounding of the numbers; in all tables in this specification

[0172] These mayonnaises were prepared by the following method: [0173] Aqueous phase is prepared by heating the corn starch in water with lemon juice and part of the vinegar for 1 min at 90 C.; [0174] Salt, sucrose, egg and the remaining part of the vinegar are added to the part of the aqueous mixture with starch and mixed in a mixed vessel. [0175] Oil is slowly added and mixed. [0176] Mixture is pumped through a colloid mill to emulsify the oil. [0177] Emulsion is mixed with the rest of starch mixture in a mixed vessel, and samples are filled in jars and closed with a lid.

[0178] In order to assess oxidation of oil, the oxygen concentration in the headspace in the jars containing the emulsions was followed during a period of about 2 months. The emulsions were stored at a temperature of 20 C. The higher the oxygen concentration, the less the oxidation of the oil. This is shown in FIG. 1. The emulsion 204 with EDTA shows least oxidation. The emulsion 207 containing the mixture containing a mixture containing the compounds of and at concentrations of M1 in example 1 shows less oxidation than the emulsion 205 without EDTA. Therefore this mixture of components can be used to decrease oxidation of vegetable oil in an oil-in-water emulsion, and it can at least partly replace EDTA.

[0179] The oxidation of the oil in the emulsions was followed by the accelerated shelf-life test, as described above. Emulsions from Table 2 were stored at 50 C., and samples from the headspace taken as during a time period of about 1.5 months. The hexanal concentration in the headspace is shown in FIG. 2. This figure shows that sample 207 containing the mixture containing a mixture containing the compounds of and at concentrations of M1 in example 1 shows that the length of the lag phase is extended as compared to sample 205 without EDTA. Therefore this mixture of components can be used to decrease oxidation of vegetable oil in an oil-in-water emulsion, and it can at least partly replace EDTA.

Example 3. Salad Dressings

[0180] Various salad dressings were prepared containing EDTA, without EDTA, and containing a mixture containing the compounds of and at concentrations of M1 in example 1. The compositions of these water-in-oil emulsions is given in Table 3.

[0181] These salad dressings were prepared by the following method: [0182] an aqueous mixture containing the corn starch and part of the vinegar is heated for 5 min at 85 C.; [0183] the heated starch mixture is mixed with egg yolk and the other ingredients listed in Table 3, except sunflower oil and mixed in a mixed vessel; [0184] sunflower oil is slowly added to the mixture, and emulsified using a colloid mill, to create an oil-in-water emulsion. The emulsions are filled in jars and closed with a lid/

TABLE-US-00003 TABLE 3 Compositions of prepared salad dressings. 267 268 269 Conc. Conc. Conc. Ingredient [wt %] [wt %] [wt %] Water 58 58 58 Sucrose 2 2 2 Salt 2 2 2 Spirit vinegar 3 3 3 Xanthan gum 0.5 0.5 0.5 Modified corn starch 1 1 1 Whey protein concentrate, 80% protein 0.5 0.5 0.5 Lemon juice 0.5 0.5 0.5 EDTA 0.0070 Mixture containing the compounds of 0.1 M1 in example 1 Liquid egg yolk 2 2 2 Flavour and spices 0.2 0.2 0.2 Sunflower oil 30 30 30

[0185] In order to assess oxidation of oil, the oxygen concentration in the headspace of the emulsions was followed during a period of about 4 months. The emulsions were stored in at a temperature of 20 C. The oxygen concentration is shown in FIG. 3. The salad dressing 267 with EDTA shows least oxidation. The salad dressing 269 containing a mixture containing the compounds of and at concentrations of M1 in example 1 shows considerably less oxidation than salad dressing 268 without EDTA. Therefore this mixture of components can be used to decrease oxidation of vegetable oil in an oil-in-water emulsion, and can at least partly replace EDTA.

Example 4. Margarines

[0186] Various margarines were prepared containing a mixture containing the compounds of and at concentrations of M1 in example 1 at two concentrations, and without such mixture. The compositions of these water-in-oil emulsions is given in Table 4.

TABLE-US-00004 TABLE 4 Compositions of prepared light margarines. 028 029 030 Conc. Conc. Conc. Ingredient [wt %] [wt %] [wt %] Fat phase components Rapeseed oil 32 32 32 Palm oil 6 6 6 Butter oil 18 18 18 Interesterified oil 14 14 14 Lecithin 0.2 0.2 0.2 Beta-carotene 0.0015 0.0015 0.0015 Aqueous phase components Water to 100% to 100% to 100% Sweet buttermilk powder 1 1 1 Salt 1 1 1 Potassium sorbate 0.1 0.1 0.1 Mixture containing the compounds of 0.15 0.20 M1 in example 1

[0187] These margarines were prepared using a mini-votator containing an A-unit and a C-unit. First the aqueous phase and fat phase were prepared, and heated for pasteurisation. The phases were mixed to prepare a pre-emulsion, and then the pre-emulsions were pumped through the mini-votator. Before emulsification, the pH of the aqueous phase was adjusted to 5 by addition of lactic acid 20%.

[0188] In order to assess oxidation of oil, the oxygen concentration in the headspace of the emulsions was followed during a period of more than 4 months. The emulsions were stored in closed packages at a temperature of 5 C. This is shown in FIG. 4.

[0189] The light margarine 028 shows the lowest oxygen concentration in the headspace, thus most oxidation of the fatty acids. The sample 030 containing the highest concentration of the mixture containing the compounds of and at concentrations of M1 in example 1 shows least oxidation.

[0190] Therefore this mixture of components can be used to decrease oxidation of vegetable oil in a water-in-oil emulsions.