WO2004056204A1 - Polymer composition suitable for use in food products - Google Patents

Polymer composition suitable for use in food products Download PDF

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Publication number
WO2004056204A1
WO2004056204A1 PCT/EP2003/012602 EP0312602W WO2004056204A1 WO 2004056204 A1 WO2004056204 A1 WO 2004056204A1 EP 0312602 W EP0312602 W EP 0312602W WO 2004056204 A1 WO2004056204 A1 WO 2004056204A1
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WO
WIPO (PCT)
Prior art keywords
polymer
glyceride
phenolic
covalently linked
polysaccharide
Prior art date
Application number
PCT/EP2003/012602
Other languages
French (fr)
Inventor
Yvonne Evelien Bruggeman
Peter Ravestein
Original Assignee
Unilever N.V.
Unilever Plc
Hindustan Lever Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Unilever N.V., Unilever Plc, Hindustan Lever Limited filed Critical Unilever N.V.
Priority to AU2003289862A priority Critical patent/AU2003289862A1/en
Publication of WO2004056204A1 publication Critical patent/WO2004056204A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12Y—ENZYMES
    • C12Y110/00—Oxidoreductases acting on diphenols and related substances as donors (1.10)
    • C12Y110/03—Oxidoreductases acting on diphenols and related substances as donors (1.10) with an oxygen as acceptor (1.10.3)
    • C12Y110/03002—Laccase (1.10.3.2)
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
    • A23L29/06—Enzymes
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
    • A23L29/10—Foods or foodstuffs containing additives; Preparation or treatment thereof containing emulsifiers
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
    • A23L29/20—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents
    • A23L29/206—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents of vegetable origin
    • A23L29/231—Pectin; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
    • A23L29/30—Foods or foodstuffs containing additives; Preparation or treatment thereof containing carbohydrate syrups; containing sugars; containing sugar alcohols, e.g. xylitol; containing starch hydrolysates, e.g. dextrin
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23P—SHAPING OR WORKING OF FOODSTUFFS, NOT FULLY COVERED BY A SINGLE OTHER SUBCLASS
    • A23P10/00—Shaping or working of foodstuffs characterised by the products
    • A23P10/30—Encapsulation of particles, e.g. foodstuff additives
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P21/00—Preparation of peptides or proteins
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P21/00—Preparation of peptides or proteins
    • C12P21/005—Glycopeptides, glycoproteins
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
    • C12P7/6436—Fatty acid esters
    • C12P7/6445—Glycerides
    • C12P7/6458—Glycerides by transesterification, e.g. interesterification, ester interchange, alcoholysis or acidolysis

Definitions

  • the current invention relates to a polymer composition
  • a polymer composition comprising a glyceride and a building block covalently linked via phenolic residues.
  • Biopolymers are extensively used in food products as emulsifiers, gelling agent, structuring agents, stabilisers, thickeners and the like. Especially biopolymers such as starches, protein and triglycerides are well known and are used for example in sauces, margarine, dressings, soups and many other food compositions.
  • WO-A-96/03440 discloses a method for gelling or increase of viscosity of aqueous media containing gellable polymeric materials having substituents with phenolic hydroxyl groups.
  • This document specifically discloses the gelation of arabinoxylans or pectins by adding an effective amount of a laccase to an aqueous medium containing these substituents.
  • proteins having one or more tyrosine residues in the a ino acid sequence can be gelled by use of a laccase.
  • the resulting compounds are indicated as thickening and/or stabilising agents.
  • the compositions disclosed in WO-A-96/03440 rely on the gelation of single compositions and hence lead to gels with a limited variety in composition and functionality.
  • the invention especially relates to polymers suitable for stabilising oil and water containing emulsions and foams.
  • the invention relates to a polymer composition
  • a polymer composition comprising a glyceride and a molecule (M) selected from the group comprising proteins (P) , glycerides (G) and polysaccharides (S) , wherein the molecule (M) and the glyceride are covalently linked via phenolic residues forming polymer building blocks of P-G, G-G, G-S or combinations thereof.
  • the invention further relates to food products containing these polymers and to a method for preparation of these polymers.
  • the polymers according to the invention are composed of glycerides and molecules (M) which together form building blocks.
  • Building blocks are polymer units which comprise a glyceride and a molecule (M) selected from the group comprising glycerides, proteins and polysaccharides.
  • the glyceride and molecule (M) are covalently linked by 2 connected phenolic residues. This covalent bond is an essential part of the claimed polymers.
  • the individual building blocks may be linked together via further covalent bonds, preferably between 2 phenolic residues.
  • the building blocks of the polymers according to the invention comprise glycerides and at least one of polysaccharides (S) , glycerides (G) and proteins (P) .
  • Glycerides in the context of the invention are glycerol based molecules wherein the glycerol backbone is covalently linked to at least one residue such as a fatty acid, or another hydrophobic acid, aldehyde or ketone e.g. retinoic acid, phenolics, sterols, tocopherols.
  • Well known glycerides are mono, di and tri acyl fatty acid glycerides. Mono- and diglycerides are already known for their emulsifying capacity.
  • Triglycerides are well known texturing agents in products such as margarine, butter, creams.
  • the glycerides may contain any fatty acid, both naturally occurring and synthetic ones.
  • Preferred fatty acids have a chain length of from 10 to 24 carbon atoms, more preferred from 16 to 20 carbon atoms.
  • Suitable fatty acids include oleic acid, stearic acid, palmitic acid linoleic and linolenic acid.
  • the glyceride in the building block is a diglyceride.
  • Molecule (M) optionally is a protein. Proteins are chains of covalently linked amino acids whereby it is possible to use any desired protein. Preferred proteins contain at least one lysine amino acid residue. Food grade proteins are preferred and hence protein is preferably selected from the group of dairy proteins such as casein and whey protein, vegetable proteins, especially soy protein and egg protein or gelatin.
  • the third potential molecule of a building block is polysaccharide.
  • Any polysaccharide can be used in the polymers according to the invention but preferred are those polysaccharides which in their naturally occurring form contain a phenolic residue such as ferulic acid, vannilic acid, coumaric or cinnamic acid esterified to (M) .
  • Sugar beet pectin and arabinoxylanes isolated from cereals are examples of polymers that contain ferulic acid residues in their naturally occurring form. These compositions are described in more detail by Lex Oosterveld , Carbohydrate research 300, 179-181, 1997 and thesis Lex Oosterveld, Landbouwuniversiteit Wageningen Netherlands, 16.12.1997, ISBN 90-5485785-4.
  • the glyceride and molecule (M) in the polymer comprise a link via two phenolic residues.
  • This link is a covalent bond.
  • the phenolic residue that is participating in the covalent bond comprises a radical stabilising group in ortho position in the phenolic ring.
  • the substituent is preferably such that the resulting compound is food grade.
  • An example of a very suitable electron-withdrawing group is the methoxygroup, positioned ortho with respect to the hydroxyl group. Examples of covalent bonds between two phenolic residues are described by Oosterveld (thesis Lex Oosterveld 1997) and in US 5,786,470.
  • the phenolic residue is derived from the group of vanillic acid, ferulic acid, coniferol, caffeic acid, chlorogenic acid.
  • Figure 1 is one example of a specific covalent bond between the two phenolic residues. Other forms of covalent bonding are also encompassed within the invention.
  • the polymer according to the invention comprises a glyceride and at least another molecule selected from protein, glyceride, polysaccharide or a combination thereof. Embodiments wherein n building blocks are linked to obtain a large linear polymer are also encompassed within the invention. Further encompassed in the invention are polymers wherein building blocks are linked via at least 2 phenolic residues or by other (non) covalent linkages.
  • the polymers according to the invention may be both linear and branched polymers.
  • the covalent linkage is between P-G, G-G, G-S, or combinations thereof.
  • the polymer comprises covalently linked proteins and glycerides, preferably diglycerides. These polymers when branched form fat-protein networks which may be applied as structuring agents.
  • the polymer comprises covalently linked polysaccharides and glycerides, preferably diglycerides.
  • glycerides preferably diglycerides.
  • An example of such a composition is shown in figure 1.
  • These compositions were found to be suitable emulsifiers which may be used to stabilise oil and water containing compositions.
  • the polymers are found at the oil/water interface whereby the fatty acid chains are in the oil phase and the polysaccharide part is in the aqueous phase.
  • Preferred glycerides for this purpose are diglycerides containing fatty acids derived from sunflower oil, soybean oil, rapeseed oil, maizgerm oil, olive oil, line oil, peanuts, cottonseed oil, and safflower oil, butter fat.
  • Preferred polysaccharides for this purpose are selected from the group comprising pectins from sugar beet, arabinoxylanes, starches. These polysaccharides may naturally comprise a phenolic group or may have been functionalised with such group.
  • the polymer comprises covalently linked glycerides.
  • the glycerides may be mono or diglycerides with any suitable fatty acid.
  • These polymers preferably contain a multiplicity (n) of glyceride building blocks, with a preference for n between 2 and 1000.
  • Such polymers may be used to structure a fat phase for example in a margarine type food composition.
  • Preferred polymers are those wherein a glyceride is covalently linked to a polysaccharide or protein. Most preferred compositions are those wherein a glyceride is covalently linked to a polysaccharide because these polymers were found to have emulsion stabilising properties.
  • the polymers according to the invention comprise at least 2 phenolic ring systems. Surprisingly these were found to enhance the stability of unsaturated fatty acid residues that may be part of the polymer and of other oxidation sensitive compositions in the same product. Without wishing to be bound by any theory, applicants believe this is due to the mesomeric ring system which can trap radicals which would otherwise cause oxidation of the double carbon-carbon bond.
  • the polymers according to the invention may suitably be applied in food products, whereby depending on their composition the properties of the food product may be influenced. Their use is especially recommended in oil and water containing compositions .
  • the invention relates to food products containing said polymers.
  • compositions which are referred to as acyl-glycerol-phenolic acid hybrids, have superior emulsifying properties especially in oil and water containing compositions of relatively low fat content (i.e. between 10 and 60 wt% fat). Furthermore these compositions may be used as texturising agents, imparting viscosity and/or structure to a composition.
  • compositions especially (G-G)n (n equal to or higher than 1) containing polymers are suitable for encapsulation of ingredients such as flavour compounds or functional ingredients.
  • ingredients such as flavour compounds or functional ingredients.
  • To make such (G-G)n compositions it is preferred to start from monoglycerides functionalised with two phenolic acid groups .
  • the invention relates to an oil and water containing emulsion, preferably an oil in water emulsion, comprising a polymer according to invention.
  • the invention relates to an oil and water emulsion comprising from 20 to 80 wt% fat and from 0.1 to 10 wt% of said polymer.
  • the polymer comprises covalently linked glyceride and polysaccharide.
  • the polymers according to the invention are prepared from glycerides and molecule (M) under suitable circumstances to form a covalent bond.
  • the invention relates to a method for the preparation of said polymer, wherein a composition comprising the elements of the building blocks is treated with an oxidative enzyme.
  • This treatment may suitably be carried out in presence or absence of a solvent.
  • a solvent for most cases, the use of an aqueous medium is preferred.
  • no solvent is needed as long as the oxidation enzyme is functional.
  • the latter can for example be obtained by using well known immobilisation methods for the enzyme.
  • the molecules (building block elements) that form the starting composition in this reaction are preferably functionalised with one or more phenolic residues, preferably containing an ortho ethyxygroup with respect to the hydroxyl group. It will be appreciated that functionalisation is not needed for molecules that naturally contain phenolic residues.
  • Said functionalisation may be obtained through natural occurrence of said phenolic groups in the element of a building block or by synthetic functionalisation of said phenolic groups to the respective molecule. It will be appreciated that naturally occurring polymers with phenolic groups are preferred.
  • the phenolic groups are covalently linked.
  • An example of a possible covalent link is shown in figure 1.
  • the oxidation may be carried out in any way known in the art . Both enzymatic oxidation and chemical oxidation routes may be used. Enzymatic oxidation is preferred. Suitable enzymes that can catalyse the formation of the covalent bond are peroxidase, laccase, polyphenol oxydases. Peroxidase is the preferred enzyme. In case an enzymatic oxidising system is applied, the enzyme is preferably added in the form of a solution or a dispersion in an aqueous buffer system.
  • Some enzymes such as peroxidases, require the presence of a co-oxidant such as hydrogen peroxide for their activity.
  • a co-oxidant such as hydrogen peroxide
  • the co-oxidant is preferably added separately from the enzyme that requires it's presence.
  • the amount of enzyme added is expressed in terms of activity units. Preferably enzyme is present in excess.
  • the temperature during oxidation is preferably from 20 to 60 °C. Most preferred the temperature is around the temperature at which the enzyme shows maximum activity.
  • the oxidant is preferably added in the form of a diluted aqueous solution.
  • Some proteins naturally contain amino acids with phenolic residues.
  • the preparation of a protein containing phenolic residues is straightforward. Any possible covalent link e.g. via esterification is suitable.
  • Di/mono -glycerides containing at least one phenolic residue are preferably prepared by interesterification of a triglyceride oil with the ester form of the phenolic residue.
  • a triglyceride oil with the ester form of the phenolic residue.
  • examples of the latter are ferulic acid ester with para position esterified to an alcohol, vanillic acid ester with para position esterified to an alcohol or caffeic acid ester with para position esterified to an alcohol.
  • Said interesterification reaction can be carried out with chemical or enzymatic catalysts. The use of lipase as catalyst is preferred.
  • the invention relates to a method wherein a polymer comprising covalently linked diacylglyceride and polysaccharide is prepared, comprising the steps of a) preparing a feruloyl diglyceride by transesterification of triacylglycerol with a phenolic compound containing a methoxygroup in ortho position with respect to the hydroxyl group; tj) providing a polysaccharide composition containing a phenolic hydroxygroup containing a methoxygroup in ortho position; c) subjecting the composition according to (a) and (b) to treatment with an oxidative enzyme.
  • reaction conditions in terms of temperature, ratio between the elements of the building blocks and type/amount of catalyst/enzyme, determine the final product composition in terms of polymer length and composition.
  • DG-F was synthesised following the method disclosed by Compton (JAOCS, vol 77, no 5, 2000, pages 513-519) preparing feruloyl diolein starting from triolein.
  • test tubes were filled as given in the table.
  • Tube 1-7 and Tube 10-12 are control experiments, which are not according to the invention.
  • Tubes 8,9 are according to the invention.

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Abstract

Polymer compositions comprising a glyceride and least 1 building block covalently linked via phenolic residues preferably containing an ortho methoxygroup, wherein the building blocks are selected from the group of proteins (P), glycerides (G) and polysaccharides (S) and wherein the covalent linkage is between P-G, G-G, G-S or combinations thereof show good emulsifying, thickening and stabilising properties. The polymers are suitable for use in food products, especially emulsions and foams.

Description

Polymer composition suitable for use in food products
ϊ-Leld of the invention
The current invention relates to a polymer composition comprising a glyceride and a building block covalently linked via phenolic residues.
Background of the invention
Biopolymers are extensively used in food products as emulsifiers, gelling agent, structuring agents, stabilisers, thickeners and the like. Especially biopolymers such as starches, protein and triglycerides are well known and are used for example in sauces, margarine, dressings, soups and many other food compositions.
Many of the polymers are naturally occurring and show good functionality in relation to the above mentioned features.
However there is still a need for alternative compositions with improved functionality and controlled characteristics. This desire is exemplified in WO-A-96/03440, which discloses a method for gelling or increase of viscosity of aqueous media containing gellable polymeric materials having substituents with phenolic hydroxyl groups. This document specifically discloses the gelation of arabinoxylans or pectins by adding an effective amount of a laccase to an aqueous medium containing these substituents. Furthermore it is disclosed that proteins having one or more tyrosine residues in the a ino acid sequence can be gelled by use of a laccase. The resulting compounds are indicated as thickening and/or stabilising agents. The compositions disclosed in WO-A-96/03440 rely on the gelation of single compositions and hence lead to gels with a limited variety in composition and functionality.
It is therefore an object of the current invention to provide polymers which can be used in a variety of food products and which enlarge the group of currently available polymers for use in foods. The invention especially relates to polymers suitable for stabilising oil and water containing emulsions and foams.
Summary of the invention
It has surprisingly been found that specific polymers of a glyceride and a molecule (M) selected from the group of protein, polysaccharides and/or glycerides meet the above objective. Especially those polymers consisting of a polysaccharide and a fatty acid glyceride unit were found to be good emulsifiers and/or stabilisers.
Therefore the invention relates to a polymer composition comprising a glyceride and a molecule (M) selected from the group comprising proteins (P) , glycerides (G) and polysaccharides (S) , wherein the molecule (M) and the glyceride are covalently linked via phenolic residues forming polymer building blocks of P-G, G-G, G-S or combinations thereof.
The invention further relates to food products containing these polymers and to a method for preparation of these polymers.
Detailed description of the invention The polymers according to the invention are composed of glycerides and molecules (M) which together form building blocks. Building blocks are polymer units which comprise a glyceride and a molecule (M) selected from the group comprising glycerides, proteins and polysaccharides. The glyceride and molecule (M) are covalently linked by 2 connected phenolic residues. This covalent bond is an essential part of the claimed polymers. The individual building blocks may be linked together via further covalent bonds, preferably between 2 phenolic residues.
The building blocks of the polymers according to the invention comprise glycerides and at least one of polysaccharides (S) , glycerides (G) and proteins (P) . Glycerides in the context of the invention are glycerol based molecules wherein the glycerol backbone is covalently linked to at least one residue such as a fatty acid, or another hydrophobic acid, aldehyde or ketone e.g. retinoic acid, phenolics, sterols, tocopherols. Well known glycerides are mono, di and tri acyl fatty acid glycerides. Mono- and diglycerides are already known for their emulsifying capacity.
Triglycerides are well known texturing agents in products such as margarine, butter, creams.
The glycerides may contain any fatty acid, both naturally occurring and synthetic ones.
Preferred fatty acids have a chain length of from 10 to 24 carbon atoms, more preferred from 16 to 20 carbon atoms.
Suitable fatty acids include oleic acid, stearic acid, palmitic acid linoleic and linolenic acid. Most preferred, the glyceride in the building block is a diglyceride. Molecule (M) optionally is a protein. Proteins are chains of covalently linked amino acids whereby it is possible to use any desired protein. Preferred proteins contain at least one lysine amino acid residue. Food grade proteins are preferred and hence protein is preferably selected from the group of dairy proteins such as casein and whey protein, vegetable proteins, especially soy protein and egg protein or gelatin.
The third potential molecule of a building block is polysaccharide. Any polysaccharide can be used in the polymers according to the invention but preferred are those polysaccharides which in their naturally occurring form contain a phenolic residue such as ferulic acid, vannilic acid, coumaric or cinnamic acid esterified to (M) . Sugar beet pectin and arabinoxylanes isolated from cereals are examples of polymers that contain ferulic acid residues in their naturally occurring form. These compositions are described in more detail by Lex Oosterveld , Carbohydrate research 300, 179-181, 1997 and thesis Lex Oosterveld, Landbouwuniversiteit Wageningen Netherlands, 16.12.1997, ISBN 90-5485785-4.
The glyceride and molecule (M) in the polymer comprise a link via two phenolic residues. This link is a covalent bond. It is preferred that the phenolic residue that is participating in the covalent bond comprises a radical stabilising group in ortho position in the phenolic ring. The substituent is preferably such that the resulting compound is food grade. An example of a very suitable electron-withdrawing group is the methoxygroup, positioned ortho with respect to the hydroxyl group. Examples of covalent bonds between two phenolic residues are described by Oosterveld (thesis Lex Oosterveld 1997) and in US 5,786,470. Preferably the phenolic residue is derived from the group of vanillic acid, ferulic acid, coniferol, caffeic acid, chlorogenic acid.
Figure 1 is one example of a specific covalent bond between the two phenolic residues. Other forms of covalent bonding are also encompassed within the invention. The polymer according to the invention comprises a glyceride and at least another molecule selected from protein, glyceride, polysaccharide or a combination thereof. Embodiments wherein n building blocks are linked to obtain a large linear polymer are also encompassed within the invention. Further encompassed in the invention are polymers wherein building blocks are linked via at least 2 phenolic residues or by other (non) covalent linkages. The polymers according to the invention may be both linear and branched polymers.
In the polymers the covalent linkage is between P-G, G-G, G-S, or combinations thereof.
These alternative embodiments are described below.
In a first embodiment, the polymer comprises covalently linked proteins and glycerides, preferably diglycerides. These polymers when branched form fat-protein networks which may be applied as structuring agents.
In another embodiment the polymer comprises covalently linked polysaccharides and glycerides, preferably diglycerides. An example of such a composition is shown in figure 1. These compositions were found to be suitable emulsifiers which may be used to stabilise oil and water containing compositions. In such compositions the polymers are found at the oil/water interface whereby the fatty acid chains are in the oil phase and the polysaccharide part is in the aqueous phase. Preferred glycerides for this purpose are diglycerides containing fatty acids derived from sunflower oil, soybean oil, rapeseed oil, maizgerm oil, olive oil, line oil, peanuts, cottonseed oil, and safflower oil, butter fat.
Preferred polysaccharides for this purpose are selected from the group comprising pectins from sugar beet, arabinoxylanes, starches. These polysaccharides may naturally comprise a phenolic group or may have been functionalised with such group.
According to a further embodiment the polymer comprises covalently linked glycerides. The glycerides may be mono or diglycerides with any suitable fatty acid. These polymers preferably contain a multiplicity (n) of glyceride building blocks, with a preference for n between 2 and 1000. Such polymers may be used to structure a fat phase for example in a margarine type food composition.
Preferred polymers are those wherein a glyceride is covalently linked to a polysaccharide or protein. Most preferred compositions are those wherein a glyceride is covalently linked to a polysaccharide because these polymers were found to have emulsion stabilising properties.
The polymers according to the invention comprise at least 2 phenolic ring systems. Surprisingly these were found to enhance the stability of unsaturated fatty acid residues that may be part of the polymer and of other oxidation sensitive compositions in the same product. Without wishing to be bound by any theory, applicants believe this is due to the mesomeric ring system which can trap radicals which would otherwise cause oxidation of the double carbon-carbon bond.
As indicated above, the polymers according to the invention may suitably be applied in food products, whereby depending on their composition the properties of the food product may be influenced. Their use is especially recommended in oil and water containing compositions .
Therefore in a further aspect the invention relates to food products containing said polymers.
The following beneficial characteristics of these compositions have been identified. (G-G)n which are referred to as acyl-glycerol-phenolic acid hybrids, have superior emulsifying properties especially in oil and water containing compositions of relatively low fat content (i.e. between 10 and 60 wt% fat). Furthermore these compositions may be used as texturising agents, imparting viscosity and/or structure to a composition.
Furthermore these compositions, especially (G-G)n (n equal to or higher than 1) containing polymers are suitable for encapsulation of ingredients such as flavour compounds or functional ingredients. To make such (G-G)n compositions, it is preferred to start from monoglycerides functionalised with two phenolic acid groups .
Polymers containing (G-S)n wherein n is preferably 1, were found to stabilise oil and water containing compositions. Furthermore these compositions when included in a two phase system such as water and oil, can fix particles or microorganisms in one of the phases. , _„n J
WO 2004/056204
Therefore in a further aspect, the invention relates to an oil and water containing emulsion, preferably an oil in water emulsion, comprising a polymer according to invention.
In a preferred embodiment, the invention relates to an oil and water emulsion comprising from 20 to 80 wt% fat and from 0.1 to 10 wt% of said polymer. Even more preferred, the polymer comprises covalently linked glyceride and polysaccharide.
The polymers according to the invention are prepared from glycerides and molecule (M) under suitable circumstances to form a covalent bond. In a further aspect the invention relates to a method for the preparation of said polymer, wherein a composition comprising the elements of the building blocks is treated with an oxidative enzyme. This treatment may suitably be carried out in presence or absence of a solvent. For most cases, the use of an aqueous medium is preferred. However for example in case of the preparation of a glyceride-glyceride hybride polymer, no solvent is needed as long as the oxidation enzyme is functional. The latter can for example be obtained by using well known immobilisation methods for the enzyme.
Before oxidation takes place the molecules (building block elements) that form the starting composition in this reaction are preferably functionalised with one or more phenolic residues, preferably containing an ortho ethyxygroup with respect to the hydroxyl group. It will be appreciated that functionalisation is not needed for molecules that naturally contain phenolic residues.
Said functionalisation may be obtained through natural occurrence of said phenolic groups in the element of a building block or by synthetic functionalisation of said phenolic groups to the respective molecule. It will be appreciated that naturally occurring polymers with phenolic groups are preferred.
In the oxidation reaction the phenolic groups are covalently linked. An example of a possible covalent link is shown in figure 1. The oxidation may be carried out in any way known in the art . Both enzymatic oxidation and chemical oxidation routes may be used. Enzymatic oxidation is preferred. Suitable enzymes that can catalyse the formation of the covalent bond are peroxidase, laccase, polyphenol oxydases. Peroxidase is the preferred enzyme. In case an enzymatic oxidising system is applied, the enzyme is preferably added in the form of a solution or a dispersion in an aqueous buffer system.
Some enzymes, such as peroxidases, require the presence of a co-oxidant such as hydrogen peroxide for their activity. The co-oxidant is preferably added separately from the enzyme that requires it's presence.
The amount of enzyme added is expressed in terms of activity units. Preferably enzyme is present in excess.
If the oxidation is carried out enzymatically, the temperature during oxidation is preferably from 20 to 60 °C. Most preferred the temperature is around the temperature at which the enzyme shows maximum activity. In case a chemical oxidant is applied, the oxidant is preferably added in the form of a diluted aqueous solution.
T-he introduction of a phenolic residue is described below for each of the potential elements of building blocks.
Polysaccharides
Well known esterification conditions may be used for introduction of a phenolic group on the polysaccharide chain.
Protein
Some proteins naturally contain amino acids with phenolic residues. The preparation of a protein containing phenolic residues is straightforward. Any possible covalent link e.g. via esterification is suitable.
Glycerides
Di/mono -glycerides containing at least one phenolic residue are preferably prepared by interesterification of a triglyceride oil with the ester form of the phenolic residue. Examples of the latter are ferulic acid ester with para position esterified to an alcohol, vanillic acid ester with para position esterified to an alcohol or caffeic acid ester with para position esterified to an alcohol. Said interesterification reaction can be carried out with chemical or enzymatic catalysts. The use of lipase as catalyst is preferred.
In a preferred embodiment the invention relates to a method wherein a polymer comprising covalently linked diacylglyceride and polysaccharide is prepared, comprising the steps of a) preparing a feruloyl diglyceride by transesterification of triacylglycerol with a phenolic compound containing a methoxygroup in ortho position with respect to the hydroxyl group; tj) providing a polysaccharide composition containing a phenolic hydroxygroup containing a methoxygroup in ortho position; c) subjecting the composition according to (a) and (b) to treatment with an oxidative enzyme.
It will be appreciated that the exact reaction conditions in terms of temperature, ratio between the elements of the building blocks and type/amount of catalyst/enzyme, determine the final product composition in terms of polymer length and composition.
The invention is illustrated by the following examples.
Examples
Example 1
Synthesis of fer loylated diglyceride (DG-F)
DG-F was synthesised following the method disclosed by Compton (JAOCS, vol 77, no 5, 2000, pages 513-519) preparing feruloyl diolein starting from triolein.
The synthesis was performed without the use of solvent. Ethylferulate (3.58 g) was dissloved in 40 g triolein at 60°C. Novozyme 435 (3.55 g) (a lipase) was added and the reaction was allowed to proceed for 7 days at 60 °C under continuous mixing.
Purification 5.3 g of the reaction mixture was brought onto a Silicagel 60 (Merck) column (3.5 cm diam. , 25 cm height). The mixture was s bsequently separated by elution with solvent mixes with increasing polarity in the following order: petroleum ether : diethyl ether = 4:1 (v/v) , petroleum ether : diethyl ether = 7:3 (v/v), petroleum ether : diethyl ether = 3:2 (v/v) and finally by elution with diethyl ether. Fractions of approximately 200ml were collected, solvent was removed by evaporation and analysis was done by means of thin layer chromatography on Kieselgel 60 F254 plates (Merck) using a mixture of toluene: diethyl ether = 4:1 (v/v).
Emulsion tests for controls
11.85 g sunflower oil, 3 ml water and 0.15g of either Admul Woltm, (comparative example) total transesterification mix
(comparative example) or purified DG-F (comparative example) were mixed and emulsified by vigorous stirring for approximately one minute.
No emulsifying properties were observed for purified DG-F or the total transesterification mix. The phases started to separate within two hours standing at room temperature.
Crosslinked polymer according to the invention
In situ preparation of emulsifier: crosslinking of DG-F and • pectin-F with laccase to yield DG-F-F-pectin.
A number of test tubes were filled as given in the table.
The conditions of each experiment are outlined in table 1.
Tube 1-7 and Tube 10-12 are control experiments, which are not according to the invention. Tubes 8,9 are according to the invention.
All tubes were prepared at room temperature. First the tubes were stirred vigorously on a Vortex mixer for 30 seconds.
Next the enzyme was added (or not) and mixing was done for another 30 seconds. Tubes were left at RT and photographed.
Table 1
Figure imgf000015_0001
Pectin = Kelco pectin in water (w/v) Enzyme = Novo Lacase PPL, SP710, PX 5326, 10 μL of a 1:10 dilution in water was added.
Stable emulsions without phase separation of the oil and water phase were only obtained when DG-F and pectin was present and a crosslinking enzyme was used. This confirms that the polymer comprising diglyceride linked to pectin via a ferulic acid- ferulic acid covalent bond is a good emulsifier for oil/water systems.

Claims

Claims
1 : Polymer composition comprising a glyceride and a molecule * (M) selected from the group comprising proteins (P) , glycerides (G) and polysaccharides (S) , characterised in that the molecule (M) and the glyceride are covalently linked via phenolic residues forming polymer building blocks of P-G, G-G, G-S or combinations thereof.
2. Polymer composition according to claim 1 wherein a glyceride is covalently linked to a polysaccharide or a protein.
3. Polymer composition according to claim 1 or 2 wherein the glyceride is a diglyceride.
4. Polymer composition according to any of claims 1-3 wherein the phenolic residue is selected from the group of vanillic acid, ferulic acid, caffeic acid, coniferol, chlorogenic acid.
5. Polymer composition according to any of claims 1-4 wherein the polymer comprises a diglyceride covalently linked to a polysaccharide .
6. Food product comprising a polymer composition according to any of claims 1-5.
7. Oil and water containing emulsion comprising a polymer according to any of claims 1-5.
8. Oil and water emulsion comprising from 20 to 80 wt% fat and from 0.1 to 10 wt% of a polymer according to any of claims 1-5 .
9". Oil in water emulsion according to claim 7 or 8 wherein the • polymer comprises covalently linked glyceride and polysaccharide .
10. Method for the preparation of a polymer according to claim 1, wherein a composition comprising the glyceride and molecule (M) is treated with an oxidative enzyme.
11. Method according to claim 10 wherein a polymer comprising covalently linked diacylglyceride and polysaccharide is prepared, comprising the steps of a) preparing a feruloyl diglyceride by transesterification of triacylglycerol with a phenolic compound containing a methoxygroup in ortho position with respect to the hydroxyl group; b) providing a polysaccharide composition containing a phenolic hydroxygroup containing a methoxygroup in ortho position with respect to the hydroxyl group; c) subjecting the composition according to (a) and (b) to treatment with an oxidative enzyme.
12. Use of a polymer according to claim 1 for the encapsulation of ingredients.
13. Use according to claim 12 wherein the polymer is a polyglyceride (G-G)n.
PCT/EP2003/012602 2002-12-19 2003-11-11 Polymer composition suitable for use in food products WO2004056204A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110498931A (en) * 2019-09-04 2019-11-26 合肥工业大学 Pectin-soybean protein isolate-caffeic acid ternary complex, its preparation method and application

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63246350A (en) * 1987-04-02 1988-10-13 Yamasa Shoyu Co Ltd Omega-o-(ferulyl)-omega-hydroxyacyl-glyceride derivative
WO1996003440A1 (en) * 1994-07-26 1996-02-08 Novo Nordisk A/S Oxidase-promoted gelling of phenolic polymers

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63246350A (en) * 1987-04-02 1988-10-13 Yamasa Shoyu Co Ltd Omega-o-(ferulyl)-omega-hydroxyacyl-glyceride derivative
WO1996003440A1 (en) * 1994-07-26 1996-02-08 Novo Nordisk A/S Oxidase-promoted gelling of phenolic polymers

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DATABASE COMPENDEX [online] ENGINEERING INFORMATION, INC., NEW YORK, NY, US; COMPTON DAVID L ET AL: "Lipase-catalyzed synthesis of ferulate esters", XP002234471, Database accession no. E2000295196342 *
JAOCS J AM OIL CHEM SOC;JAOCS, JOURNAL OF THE AMERICAN OIL CHEMISTS' SOCIETY 2000 AMERICAN OIL CHEMISTS' SOC, CHAMPAIGN, IL, USA, vol. 77, no. 5, 2000, pages 513 - 519 *
PATENT ABSTRACTS OF JAPAN vol. 013, no. 056 (C - 566) 8 February 1989 (1989-02-08) *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110498931A (en) * 2019-09-04 2019-11-26 合肥工业大学 Pectin-soybean protein isolate-caffeic acid ternary complex, its preparation method and application

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