WO2013092024A1

WO2013092024A1 - Compositions comprising structured fat phase

Info

Publication number: WO2013092024A1
Application number: PCT/EP2012/072703
Authority: WO
Inventors: Kees Frederik Van Malssen; Edward George Pelan; Simeon Dobrev Stoyanov; Lin Wang; Weizheng Zhou
Original assignee: Unilever N.V.; Unilever Plc; Hindustan Unilever Limited; Conopco, Inc., D/B/A Unilever
Priority date: 2011-12-21
Filing date: 2012-11-15
Publication date: 2013-06-27

Abstract

The present invention relates to edible composition comprising a fat phase, wherein the fat phase comprises less than 55% by weight of fat phase of saturated fatty acids, wherein the fat phase is structured by a lipophilic fibrous material comprising a polymer. The invention further relates to dough compositions comprising flour, fat and a lipophilic fibrous material comprising a polymer as well as bakery products comprising such products.

Description

COMPOSITIONS COMPRISING STRUCTURED FAT PHASE

The present invention relates to a composition comprising a fat phase, which is structured by fibres that are produced by a spinning method.

BACKGROUND OF THE INVENTION

The structure and morphology of a consumer product is essential for the properties and the appreciation of the product. For example, a food product like a margarine should not be too soft and not be too hard, and should be spreadable under all normal household conditions and should melt at in body temperature when consumed. This can be achieved by using a correct ratio of saturated and unsaturated fats and oils in the formulation of the product. These required properties may lead to contradictory requirements in product development. Fat continuous food products are well known in the art and include for example shortenings comprising a fat phase and water-in-oil spreads like margarine comprising a fat phase and an aqueous phase.

The fat phase of margarine and similar edible fat continuous spreads is often a mixture of liquid oil (i.e. fat that is liquid at ambient temperature) and fat which is solid at ambient temperatures. The solid fat, also called structuring fat or hardstock fat, serves to structure the fat phase (being the case in for example a shortening as well as in a water in oil emulsion) and helps to stabilize the aqueous phase, if present, by forming a fat crystal network. For a margarine or spread, ideally the structuring fat has such properties that it melts or dissolves at mouth temperature. Otherwise the product may have a heavy and/or waxy mouthfeel.

Bakery products like e.g. cookies and cakes generally require a certain amount of fat to achieve product properties like moistness and crispness. Also, the dough that is used to prepare such bakery products may benefit from the presence of fat as this e.g. may influence handling properties like firmness and kneadability. Most bakery products require a certain amount of saturated fat (i.e. fat having a certain amount of saturated fatty acids) to get the desired product properties.

It is known that thickeners and fibres can be used to create useful structures in foods. Numerous fibrous materials have been described, and several methods have been disclosed to produce fibrous materials. The production of fibres out of vegetable or dairy proteins has been described in order to use these fibres as meat replacers.

WO 2007/068344 A1 discloses fibres like microcrystalline cellulose, that have been 5 modified to give them surface-active properties, and that are used as stabiliser for aerated food products and emulsions.

WO 89/10068 discloses microfragmented ionic polysaccharide/protein complex aqueous dispersions that are used for nutritious bulking, viscosity or texture control agents (also fat 10 replacer) in food products. These materials may be formed in the form of fibres, and the method may involve a fragmentation step by homogenisation.

WO 2006/136817 A1 discloses various polymers which may be used as source to create fibres by electrospinning.

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US 4,287,219 discloses fibres made from proteins, with fat containing phase in the core of the fibrous materials. These are used as meat replacers.

Kriegel C.-A. et al. (Critical Reviews in Food Science and Nutrition, vol. 48, 2008, 775- 20 779) disclose the use of electrospun fibres in food products as ingredients.

Wongsasulak S. et al. (Journal of Food Engineering, vol. 98, 2010, p. 370-376) discloses electrospinning of food-grade nanofibres from cellulose acetate and egg albumen blends. These can be used for controlled delivery of nutraceuticals or pharmaceuticals to the 25 gastro-intestinal tract.

Schiffman J.D. et al. (Polymer Reviews, vol. 48, 2008, p. 317-352) disclose various combinations of cellulose materials and other polymers to create fibres by electrospinning. They also describe that proteins can be used to create fibres by means of electrospinning.

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SUMMARY OF THE INVENTION

In spite of these disclosures, there still is a need to produce new compositions containing a fat phase that is structured by lipophilic fibrous materials. This is required to develop food products like for example bakery products, which are healthy, or have beneficial 35 sensory benefits. These fat phases may be incorporated as ingredients of products such as water-in-oil emulsions, dough compositions and bakery products. We have now determined that this objective can be met by edible fat phases which are structured by a lipophilic fibrous material comprising a polymer, wherein the fibrous material comprises one or more compounds chosen from the group of prolamins and lipophilic cellulose derivatives, and wherein the fibrous material has been prepared by a method involving spinning. These fibres are very efficient structurants of edible fat phases.

Using these edible fat phases structured by lipophilic fibres has the advantage that in case of structuring food products, less saturated fats are required to structure the food product. Nevertheless similar product properties, sensory and in-use physical properties can be achieved, like moistness, crispness, rheology, spreadability, firmness, kneadability and storage stability. Reducing the amounts of saturated fat in a product makes a food product healthier. Accordingly the invention relates to an edible composition comprising a fat phase wherein the fat phase is structured by a lipophilic fibrous material comprising a polymer.

The invention further relates to a dough composition comprising flour, fat and a lipophilic fibrous material comprising a polymer, wherein the fibrous material comprises one or more compounds chosen from the group of prolamins and lipophilic cellulose derivatives, and wherein the fibrous material has been prepared by a method involving spinning.

The invention also relates to a bakery product comprising a dough composition according to the invention.

The invention also relates to a method for production of a bakery product comprising flour, fat and a lipophilic fibrous material comprising the steps:

a. providing a lipophilic fibrous material comprising a polymer, wherein the fibrous material comprises one or more compounds chosen from the group of prolamins and lipophilic cellulose derivatives, and wherein the fibrous material has been prepared by a method involving spinning; and

b. dispersing the fibrous material obtained from step a) in a fat phase; and

c. homogenising the mixture from step b), to fragment the fibrous material to an average length from 1 micrometer to 10 millimeter; and

d. bringing the mixture obtained from step c) into contact with one or more other ingredients of the bakery product. The invention also relates to the use of a composition according to the invention to prepare a bakery product. DETAILED DESCRIPTION

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art.

All percentages, unless otherwise stated, refer to the percentage by weight. The abbreviation 'wt%' refers to percentage by weight.

In the context of the present invention, an average particle diameter is generally expressed as the d_{3 2} value, which is the Sauter mean diameter, unless stated otherwise. The Sauter mean diameter is the diameter of a sphere that has the same volume/surface area ratio as a particle of interest. In case of fibrous material of which the cross-section may not be completely circular, the diameter of the fibre as expressed herein, is the diameter of a circle having the same surface area as the cross-section of the fibre. Also the d_{4 3} value, which is the volume weighted mean diameter, may be used herein. The volume based particle size equals the diameter of the sphere that has same the same volume as a given particle.

In case a range is given, the given range includes the mentioned endpoints.

By the term 'fibre' or 'fibrous material', we mean any water-insoluble structure wherein the ratio between the length and the diameter ranges from about 10 to infinite. Here, the diameter means the largest distance of the cross-section. The materials of the "fibre" substance can be organic, inorganic, polymeric and macromolecular. The cross-sectional area of the fibre may be not completely circular, and may be in the form of an oval or the like.

The terms 'fat' and 'oil' are used interchangeably. Where applicable the prefix 'liquid' or 'solid' is added to indicate if the fat or oil is liquid or solid at ambient temperature as understood by the person skilled in the art. The term 'structuring fat' refers to a fat that is solid at ambient temperature. Ambient temperature is a temperature of about 20 degrees Celsius. Edible composition comprising a fat phase

The edible composition of the invention is a composition comprising a fat phase, wherein the fat phase comprises less than 55% by weight of fat phase of saturated fatty acids, wherein the liquid phase is structured by a lipophilic fibrous material comprising a polymer, wherein the fibrous material comprises one or more compounds chosen from the group of prolamins and lipophilic cellulose derivatives, and wherein the fibrous material has been prepared by a method involving spinning.

Spinning is a process that can be used to create fibres of polymeric materials. A preferred way of performing a spinning process, is by pressing a polymer in a liquid form through for example one or more nozzles or other orifices, to form continuous filaments. Usually the pressing through the nozzle may be done using an extruder, and there may be multiple nozzles to create parallel filaments, like in a spinneret to form multiple continuous filaments. The polymer may be brought in liquid form by melting, or by dissolving in a suitable solvent. By pressing the molten polymer through the nozzle it may solidify by cooling (melt spinning). If the polymer is dissolved in a solvent, it may solidify by precipitation in a liquid bath (wet spinning), or may solidify by evaporation of the solvent (dry spinning). Examples of the spinning process are shear-driven spinning, centrifugation spinning, jet spinning, and electrospinning.

In the context of the present invention, a lipophilic fibrous material is considered to be a fibre which preferably has a three-phase contact angle between a drop of liquid edible oil, and a film of the fibrous material, and air of less than 70° at 20°C. Preferably the liquid edible oil comprises sunflower oil. Preferably the contact angle is less than 50°, more preferred less than 40°.

In the present context, the contact angle is measured as the angle in the droplet, as schematically depicted in Figure 1 . Preferably the fat phase is selected from the group consisting of oil of vegetable origin, oil of dairy origin, oil of marine origin, oil of algae origin and mixtures thereof. The fat phase may also contain other animal oils like lard and tallow, but preferably this is less than 15 wt%, preferably less than 10 wt%, more preferably less than 5 wt%, even more preferably less than 1 wt% and still even more preferably essentially absent. Preferably at least 50 wt% of the fat phase (based on total amount of fat phase) is of vegetable origin, more preferably at least 60 wt%, even more preferably at least 70 wt%, still more preferably at least 80 wt%, even still more preferably at least 90 wt% and even still more further preferably at least 95 wt%. Most preferably the fat phase essentially consists of fat of vegetable origin.

Preferably the fat phase comprises less than 50 wt% of saturated fatty acids, more preferably less than 40 wt%, even more preferably less than 30 wt%, still more preferably less than 20 wt% and still even more preferably less than 10 wt%. For example the fat phase may comprise 0 to 55 wt%, 5 to 45 wt%, 8 to 35 wt% or 10 to 25 wt% of saturated fatty acids.

Preferred oils of vegetable origin include soybean oil, sunflower oil, linseed oil, low erucic rapeseed oil (Canola), corn oil (maize oil), olive oil, palm oil, palm kernel oil, allanblackia fat.

Preferred oils of dairy origin include milk fat such as butter or butter oil. Preferably from cow milk. Lipophilic cellulose derivatives

In order to achieve good structuring capacity, a fibre should have a good compatibility or adhesion to a fat phase. A poor compatibility causes agglomeration of the fibres and weak interaction with the fat phase, which may induce a reduction of mechanical properties. The preferential route is to use fibres that are compatible with the fat phase, which are either made from appropriate materials or modified chemically of physically during the process of their production.

The compatibility between fibre and fat phase can be estimated by measuring the fibre wetting by the fat phase. Measure for this is the three phase contact angle of fat phase or water droplet in air placed on the substrate made from the same material the fibres are made from. Alternatively the contact angle of fat phase in water (or other way around) on the substrate can be measured as well. Here the implicit assumption is that both fibre and substrate have the comparable surface roughness and that line tension effects can be neglected. A better fat phase wetting (or poorer water wetting) are indicative of better compatibility between the fibre and the fat phase. Therefore one can convert the problem of compatibility between the fibre and fat phase to a problem of preparing fibres with optimal lipophilicity measured via the contact angle.

The fibrous material comprises one or more compounds chosen from the group of prolamins and lipophilic cellulose derivatives. The lipophilic cellulose derivative is defined as a cellulose derivative wherein preferably the three-phase contact angle between sunflower oil, and a film of the lipophilic cellulose derivative, and air is less than 70° at 20°C. Preferably the angle is less than 50°, most preferred less than 40°. The contact angle can be measured using standard equipment like the Drop shape analysis DSA100 (Kruss GmbH, Neunkirchen am Brand, Germany). This technique is common in the art.

Preferably the lipophilic cellulose derivative comprises an alkylated cellulose. Examples of such alkylated celluloses are methyl-ethylcellulose, ethylcellulose, propylcellulose or butylcellulose. Another preferred lipophilic cellulose derivative is cellulose diacetate. Also combinations of these compounds are within the scope of the present invention. Most preferred lipophilic cellulose derivative comprises ethylcellulose. The general structural formula of ethylcellulose is:

The degree of substitution of the ethylcellulose preferably used in the present invention is preferably from 2 to 3, more preferably about 2.5. The average number of hydroxyl groups substituted per anhydroglucose unit (the 'monomer') is known as the 'degree of substitution' (DS). If all three hydroxyls are replaced, the maximum theoretical DS of 3 results.

Suitable sources and types of the ethylcellulose preferably used in the present invention are supplied by for example Ashland (formerly Hercules), Aldrich, and Dow Chemicals. Suitable ethylcellulose preferably has a viscosity ranging from 5 to 300 cP at a concentration of 5 % in toluene/ethanol 80:20, more preferably from 100 to 300 cP at these conditions.

The viscosity is expressed in centipoise (cP). It will be appreciated that the viscosity can 5 also be expressed in the SI physical unit of viscosity, which is the millipascal-second (mPa.s). The viscosity expressed in cP can be converted to the viscosity expressed in mPa.s. For example 1 cP equals 1 mPa.s.

Prolamins

10 Prolamins are a group of plant storage proteins having a high proline content and are found in the seeds of cereal grains. Examples of these grains are wheat (protein gliadin), barley (protein hordein), rye (protein secalin), corn (protein zein) and as a minor protein, avenin in oats. The prolamins are characterised by a high glutamine and proline content and are generally soluble only in strong alcohol solutions.

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Preferably the prolamin is chosen from the group of zein, gliadin, hordein, secalin, and avenin. Also combinations of these compounds are within the scope of the present invention.

20 Zein is the alcohol-soluble protein of corn and is classified as a prolamin. Biologically, zein is a mixture of proteins varying in molecular size and solubility. These proteins can be separated by differential solubilities and their related structures into four distinct types: alpha, beta, gamma, and delta. Alpha-zein is by far the most abundant, accounting for about 70% of the total. The next most abundant zein is gamma-zein, contributing to about

25 20% of the total.

Gluten is a storage protein from wheat and comprises two major protein groups, namely the gliadins (molecular weight 30,000-80,000) and glutenin polymers (molecular weight higher than 100,000). It is classified as prolamins due to the presence of aqueous alcohol 30 soluble gliadin groups.

Gliadin is a glycoprotein present in wheat and several other cereals within the grass genus Triticum. Gliadins are prolamins and are separated on the basis of electrophoretic mobility and isoelectric focusing. Together with glutenin it forms an important component 35 of wheat gluten. Hordein is a major storage protein from barley. It is a glycoprotein also classified as prolamin based on its solubility characteristics. Secalin, a storage protein found in rye, with high glutamine and proline content and low lysine content is also classified as prolamin.

Lipids

Preferably the fibrous material comprises one or more lipid compounds. Lipid compounds in the context of the present invention are lipophilic materials which often are from natural origin, but may also be a synthetic compound. Preferably the lipid compound comprises lecithin, fatty acid, monoglyceride, diglyceride, triglyceride, phytosterol, phytostanol, phytosteryl-fatty acid ester, phytostanyl-fatty acid ester, wax, fatty alcohol, carotenoid, oil- soluble colourant, oil-soluble vitamin, oil soluble flavour, or oil soluble fragrance. Also combinations of these compounds are within the scope of the present invention.

Oils and fats such as dairy fats, or vegetable oils are a common source for

monoglycerides, diglycerides, and triglycerides. Examples of fat-soluble vitamins are vitamin A, vitamin D2, vitamin D3, vitamin E, and vitamin K. These vitamins include all compounds which function as the respective vitamin. The carotenoids include alpha- carotene, beta-carotene, lycopene, lutein, zeaxanthin.

Lecithin: is a general term for a mixture which may originate from plant origin (e.g. soy bean) or animal origin (e.g. egg yolk), and is used as emulsifier. The most important compounds in lecithin are phosphatidylcholine, phosphatidylethanolamine, and phosphatidylinositol. In commercially available lecithins also free fatty acids, triglycerides and mono- and diglycerides can be present. The nature of the phosphoric group and said fatty acids determine the emulsification properties of lecithin.

Fatty acid: fatty acids suitable in the present invention are C3 fatty acids and longer chains, preferably at least C12, up to preferably C26. The aliphatic tail may be saturated or unsaturated. The chain can be unbranched or have branches like a hydroxy, methyl- or ethyl group. The fatty acid suitable in the present invention consists of minimum 3 carbon atoms and a maximum of 26.

Monoglyceride: an ester of glycerol and one fatty acid, wherein the fatty acid may be as described above.

Diglyceride: an ester of glycerol and two fatty acids, wherein the fatty acids may be as described above.

Triglyceride: a glycerol which is esterified with three fatty acids, as described above. The fatty acids may be saturated, or monounsaturated or polyunsaturated. Edible oils and fats are made up mainly of triglycerides. They can also contain diglycerides, monoglycerides and free fatty acids. Fats include: plant oils (for example: allanblackia oil, apricot kernel oil, arachis oil, arnica oil, argan oil, avocado oil, babassu oil, baobab oil, black seed oil, blackberry seed oil, blackcurrant seed oil, blueberry seed oil, borage oil, calendula oil, camelina oil, camellia seed oil, castor oil, cherry kernel oil, cocoa butter, coconut oil, corn oil, cottonseed oil, evening primrose oil, grapefruit oil, grape seed oil, hazelnut oil, hempseed oil, illipe butter, jojoba oil, lemon seed oil, lime seed oil, linseed oil, kukui nut oil, macadamia oil, maize oil, mango butter, meadowfoam oil, melon seed oil, moringa oil, mowrah butter, mustard seed oil, olive oil, orange seed oil, palm oil, palm kernel oil, papaya seed oil, passion seed oil, peach kernel oil, plum oil, pomegranate seed oil, poppy seed oil, pumpkins seed oil, rapeseed (or canola) oil, red raspberry seed oil, rice bran oil, rosehip oil, safflower oil, seabuckthorn oil, sesame oil, shea butter, soy bean oil, strawberry seed oil, sunflower oil, sweet almond oil, walnut oil, wheat germ oil); fish or marine oils (for example: sardine oil, mackerel oil, herring oil, cod-liver oil, oyster oil); animal oils (for example: butter or conjugated linoleic acid, lard or tallow); or any mixture or fraction thereof. The oils and fats may also have been modified by hardening, fractionation, chemical or enzymatical interesterificiation or by a combination of these steps.

Phytosterol: a group of steroid alcohols, phytochemicals naturally occurring in plants. At room temperature they are white powders with mild, characteristic odor, insoluble in water and soluble in alcohols. They can be used to decrease the LDL-cholesterol level in plasma in humans.

Phytostanol: similar to the phytosterol, a group of steroid alcohols, phytochemicals naturally occurring in plants. They may also be obtained by hardening a phytosterol.

Phytosteryl-fatty acid ester: a phytosterol which has been modified by esterifying it with a fatty acid.

Phytostanyl-fatty acid ester: a phytostanol which has been modified by esterifying it with a fatty acid.

Waxes: a wax is a non-glyceride lipid substance having the following characteristic properties: plastic (malleable) at normal ambient temperatures; a melting point above approximately 45°C; a relatively low viscosity when melted (unlike many plastics);

insoluble in water but soluble in some organic solvents; hydrophobic. Waxes may be natural or artificial, but natural waxes, are preferred. Beeswax, carnauba (a vegetable wax) and paraffin (a mineral wax) are commonly encountered waxes which occur naturally. Some artificial materials that exhibit similar properties are also described as wax or waxy. Chemically speaking, a wax may be an ester of ethylene glycol (ethane-1 ,2-diol) and two fatty acids, as opposed to fats which are esters of glycerol (propane-1 ,2,3-triol) and three fatty acids. It may also be a combination of fatty alcohols with fatty acids, alkanes, ethers or esters. Preferred waxes are one or more waxes chosen from carnauba wax, shellac wax or beeswax or their synthetic equivalents. Also paraffin-based synthetic waxes are within the scope of the present invention.

Fibres used in the compositions of the invention

Fibres which are used in the composition according to the invention are fibres which comprise a lipophilic cellulose derivative, or a prolamin, or a combination of a lipophilic cellulose derivative and a prolamin. These classes of compound have been defined herein before. The fibres additionally may contain a lipid compound as defined herein before. Preferably the fibre comprises a prolamin and a lipid compound; or a lipophilic cellulose derivative and a lipid compound; or a prolamin, a lipophilic cellulose, and a lipid compound. Preferably the fibre used in the composition according to the invention has a length from 1 micrometer to 10 millimeter, wherein the fibre has a diameter from 30 nanometer to 50 micrometer, and wherein the aspect ratio of the fibre is larger than 10. Preferably the fibre has a length from 1 micrometer to 1 ,000 micrometer, preferably from 2 micrometer to 500 micrometer. Preferably the fibre has a length from 5 micrometer to 300 micrometer.

Preferably the fibre used in the composition according to the invention has a diameter from 50 nanometer to 40 micrometer, preferably from from 100 nanometer to

25 micrometer, preferably from 200 nanometer to 25 micrometer, preferably from 300 nanometer to 10 micrometer, more preferably from 500 nanometer to 5 micrometer.

Preferably the fibre used in the composition according to the invention has an aspect ratio of larger than 50, preferably larger than 100, or preferably even larger than 200 or 500. The aspect ratio is defined as the ratio between the length and the diameter of an individual fibre.

The cross-sectional area of the fibres used in the composition according to the invention may be not completely circular, and may be in the form of an oval or the like. This may mean that for instance the cross-section of a fibre according to the invention may have a longest dimension of 2 to 5 microns, while the shortest dimension may be less than 1 micrometer. In that case the diameter of the fibre as expressed herein, is the diameter of a circle having the same surface area as the cross-section of the fibre. In one preferred embodiment the fibrous material used in the composition according to the invention comprises a lipophilic cellulose derivative, and a prolamin. In that case preferably the fibre comprises from 1 % by weight to 99% by weight of a lipophilic cellulose derivative and from 1 % by weight to 99% by weight of a prolamin. Preferably the fibre comprises from 10% by weight to 90% by weight of a lipophilic cellulose derivative and from 10% by weight to 90% by weight of a prolamin. Preferably the fibre comprises from 20% by weight to 80% by weight of a lipophilic cellulose derivative and from 20% by weight to 80% by weight of a prolamin.

In another preferred embodiment the fibrous material used in the composition according to the invention comprises a lipophilic cellulose derivative, and a lipid material. In that case preferably the fibre comprises from 10% by weight to 99.9% by weight of lipophilic cellulose derivative and from 0.7% by weight to 90% by weight of a lipid compound.

Preferably the fibre comprises from 70% by weight to 99% by weight of lipophilic cellulose derivative and from 1 % by weight to 30% by weight of a lipid compound. Preferably the fibre comprises from 90% by weight to 98% by weight of lipophilic cellulose derivative and from 2% by weight to 10% by weight of a lipid compound. In another preferred embodiment the fibrous material used in the composition according to the invention comprises a prolamin, and a lipid material. In that case preferably the fibre comprises from 10% by weight to 99.9% by weight of a prolamin and from 0.7% by weight to 90% by weight of a lipid compound. Preferably the fibre comprises from 70% by weight to 99% by weight of a prolamin and from 1 % by weight to 30% by weight of a lipid compound. Preferably the fibre comprises from 90% by weight to 98% by weight of a prolamin and from 2% by weight to 10% by weight of a lipid compound.

Preferably the fibrous material prepared used in the composition according to the invention comprises the three mentioned classes of compounds. In that case preferably the fibre comprises 1 % by weight to 98.9% by weight of a lipophilic cellulose derivative and from 1 % by weight to 98.9% by weight of a prolamin, and from 0.1 % by weight to 90% by weight of a lipid compound. Preferably the fibre comprises from 10% by weight to 89% by weight of a lipophilic cellulose derivative and from 10% by weight to 89% by weight of a prolamin, and from 1 % by weight to 30% by weight of a lipid compound. Preferably the fibre comprises from 10% by weight to 88% by weight of a lipophilic cellulose derivative and from 10% by weight to 88% by weight of a prolamin, and from 2% by weight to 10% by weight of a lipid compound.

Examples of such composite fibres are the following: ethylcellulose-zein composite;

ethylcellulose-lecithin composite; ethylcellulose-triglyceride composite; zein- triglyceride composite; ethylcellulose-phytosterol composite; zein-phytosterol composite;

ethylcellulose-phytosterol ester composite; and zein-phytosterol ester composite.

The functions of lipid or other lipophilic materials in the fibres can be used to tune the lipophilicity of fibres for oil structuring; and/or to tune the meltdown property of fibre structured oil; and/or to tune the mechanical strength of fibres; and/or to tune the mechanical strength of the fibre network. This behaviour makes it possible to modify the properties of a product containing such structured fat phase, for example to create a nice melting emulsion.

In principle long fibre lengths lead to good structuring properties when used to structure a fat phase. On the other hand long hairy structures are often not desired in food products. By using fibres having a relatively short length for structuring as compared to longer fibres, the lengths as defined in this specification lead to shear alignment. This means that under shear forces the fibres can align, and therewith give the impression to the consumer that a solid-liquid transition is obtained. This can be perceived to be analogous to a melting curve of a solid fat which melts upon chewing in the mouth.

Electrospinning

Preferably the fibrous material has been prepared by a method involving electrospinning. In an electrospinning process (as described by Schiffman J.D. et al., Polymer Reviews, vol. 48, 2008, p. 317-352) a molten or dissolved polymer is pressed through for example a capillary, to be collected on a collector. An electric field is applied between the capillary and the collector. Alternatively a system may be used that does not utilise nozzles or capillaries to create cones or jets of polymeric material. An example of such a system is the Nanospider™ technology from Elmarco (Liberec, Czech Republic). A cylinder is partly submerged in a bath of liquid polymer (solution). When the cylinder rotates, a thin layer of polymer is carried on the cylinder surface and exposed to a high voltage electric field. If the voltage exceeds a critical value, a number of electrospinning jets are generated from the polymer bath towards a collector. The jets are distributed over the electrode surface with periodicity. Both the spinning and electrospinning methods are known in the art. Preferably the electrospinning process which uses a capillary uses the following settings and parameters. The nozzle from which the solution of the compounds is pressed preferably has an internal diameter of at least 0.1 millimeter. The upper diameter is 5 preferably less than 2 millimeter. During the electrospinning process cone is formed at the bottom and fibers are formed from the tip of this cone. The cone diameter usually is much smaller than the nozzle diameter. The nozzle play an indirect role as it is used as electrode as well that it influences electric filed gradients. The flow rate from the nozzle preferably is from 0.1 to 1 ,000 milliliter per hour, preferably from 1 to 100 milliliter per

10 hour. These flow rates are per nozzle; multiple nozzles can be applied to create parallel flows. Preferably the metal collector is placed from 1 to 100 centimeter from the tip of the nozzle, preferably from 10 to 18 centimeter. The collector preferably is a copper mesh covering on a stainless steel mandrel, for example having about 12 cm internal diameter and a length of about 30 cm. The positive lead from a high DC voltage supply is attached

15 to the nozzle metal portion, and the collector is grounded. The voltage between the nozzle and the collector preferably is from 1 kV to 100 kV, preferably from 12 kV to 25 kV. The mandrel may rotate to create an evenly distributed mat during the spinning process, preferably at a rotational speed from 10 to 200 rpm, preferably from 70 to 130 rpm. The temperature and pressure that are applied during the process preferably is from 5°C to

20 60°C, preferably from 20°C to 40°, preferably from 20°C to 25°C. The pressure may be at atmospheric pressure, but may also be reduced to facilitate the evaporation of the solvent. A mat of electrospun fibres is formed on the grounded copper mesh during the process.

Method for production of a bakery product

25 The invention also concerns a method for production of a bakery product comprising flour, fat and a lipophilic fibrous material comprising the steps:

a) providing a lipophilic fibrous material comprising a polymer, wherein the fibrous material comprises one or more compounds chosen from the group of prolamins and lipophilic cellulose derivatives, and wherein the fibrous material has been prepared by a

30 method involving spinning; and

b) dispersing the fibrous material obtained from step a) in a fat phase; and

c) homogenising the mixture from step b), to fragment the fibrous material to an average length from 1 micrometer to 10 millimeter; and

d) bringing the mixture obtained from step c) into contact with one or more other 35 ingredients of the bakery product. Step a) of the method comprises the spinning of the fibrous material from a polymer, wherein the polymer is in liquid form during the spinning. The general principles of a spinning process have been described herein before. Especially preferred in step a) the spinning process is an electrospinning process. Also electrospinning has been described herein before.

The polymer being in liquid form should be understood to mean the following. The polymer from which the lipophilic fibre is spun may be used in a molten state when being spun. Alternatively the polymer is preferably dissolved in a suitable solvent when being spun. When the polymer is pressed through a nozzle, the polymer may solidify, e.g. by cooling, or alternatively the polymer may form a solid fibrous material by evaporation of the solvent.

In case of producing composite fibres, the compounds used for making the fibres may be dissolved in a suitable solvent separately, and after dissolving the separate solutions may be combined, before being pressed through the nozzle to be collected on the collector. Alternatively the various compounds may be dissolved in the solvent simultaneously in order to make a mixture of compounds to be pressed through the nozzle. This way fibres are made with a fixed composition.

Alternatively multiple parallel solutions can be made, which are mixed in a micro chamber or junction formed between different channels in line, just before its being pressed through a nozzle. Each solution may have its own pump and consequently its own flow rate. For example one solution contains the lipophilic cellulose derivative, while another solution contains a prolamin. Both solutions are pumped to a three way valve where they mix, and subsequently they are pressed through the nozzle, and a fibrous material is collected on the collector. This has the advantage that the composition of the fibre can be varied during the preparation process, by adjusting the flow rate of one of the pumps relative to the other. Additionally one of the solutions may contain a second compound (e.g. a lipid compound), or a third solution may be coupled in line, parallel to the other two solutions.

The solvent in the method according to the invention is a solvent in which the polymer can be dissolved. Preferred polymers to be used in the method according to the invention are chosen from lipophilic cellulose derivatives and prolamins, or combinations of these. These materials have been described herein before. A lipid compound as herein described before, may be mixed with the one or more polymers to be spun together with the polymers. Examples of these solvents are alcohols, preferably ethanol, ethyl acetate, acetic acid, acetone, /V,/V-dimethylformamide (DMF), or any suitable combination of these solvents. The concentration of the compounds in the solvent is preferably from 5% by weight to 50% by weight, preferably between 10% by weight to 30% by weight. When the 5 solution is released from the nozzle, the solvent evaporates. It will be appreciated that preferably the solvent is a food grade solvent.

In a preferred embodiment the fibrous material used in the composition according to the invention comprises a lipophilic cellulose derivative and a prolamin. In that case the

10 solution in the spinning step preferably comprises in addition to the solvent from 1 % by weight to 99% by weight of a lipophilic cellulose derivative and from 1 % by weight to 99% by weight of a prolamin. Preferably the solution comprises from 10% by weight to 90% by weight of a lipophilic cellulose derivative and from 10% by weight to 90% by weight of a prolamin. Preferably the solution comprises from 20% by weight to 80% by weight of a

15 lipophilic cellulose derivative and from 20% by weight to 80% by weight of a prolamin.

Here this is all based on the weight of the compounds in the solvent.

In another preferred embodiment the fibrous material used in the composition according to the invention comprises a prolamin and a lipid material. In that case the solution in the

20 spinning step preferably comprises in addition to the solvent from 10% by weight to 99.9% by weight of prolamin and from 0.7% by weight to 90% by weight of a lipid compound. Preferably the solution comprises from 70% by weight to 99% by weight of prolamin and from 1 % by weight to 30% by weight of a lipid compound. Preferably the solution comprises from 90% by weight to 98% by weight of prolamin and from 2% by weight to

25 10% by weight of a lipid compound.

In another preferred embodiment the fibrous material used in the composition according to the invention comprises a lipophilic cellulose derivative and a lipid material. In that case the solution in the spinning step preferably comprises in addition to the solvent from 10%

30 by weight to 99.9% by weight of lipophilic cellulose derivative and from 0.7% by weight to 90% by weight of a lipid compound. Preferably the solution comprises from 70% by weight to 99% by weight of lipophilic cellulose derivative and from 1 % by weight to 30% by weight of a lipid compound. Preferably the solution comprises from 90% by weight to 98% by weight of lipophilic cellulose derivative and from 2% by weight to 10% by weight of a lipid

35 compound. Preferably the fibrous material used in the composition according to the invention comprises the three mentioned classes of compounds. In that case the solution in the spinning step preferably comprises in addition to the solvent from 1 % by weight to 98.9% by weight of a lipophilic cellulose derivative and from 1 % by weight to 98.9% by weight of 5 a prolamin, and from 0.1 % by weight to 90% by weight of a lipid compound. Preferably the solution comprises from 10% by weight to 89% by weight of a lipophilic cellulose derivative and from 10% by weight to 89% by weight of a prolamin, and from 1 % by weight to 30% by weight of a lipid compound. Preferably the solution comprises from 10% by weight to 88% by weight of a lipophilic cellulose derivative and from 10% by weight to 10 88% by weight of a prolamin, and from 2% by weight to 10% by weight of a lipid

compound.

The method according to the invention further comprises the steps:

b) dispersing the fibrous material obtained from step a) in a fat phase; and

15 c) homogenising the mixture from step b), to fragment the fibrous material to an

average length from 1 micrometer to 10 millimeter.

This way the correct length of fibrous material is obtained. Preferably the length of the fibre that is obtained is from 1 micrometer to 1 ,000 micrometer, preferably from

20 2 micrometer to 500 micrometer. Preferably the fibre has a length from 5 micrometer to 300 micrometer.

In step b) the fat phase, may be chosen from for example sunflower oil, palm oil, olive oil, rapeseed oil, or any other suitable oil or combinations of oils. The fat phase may be liquid 25 at room temperature, or alternatively may be solid at room temperature, in which case the fat phase should be melted first by increasing the temperature.

In step c) the homogenisation preferably is carried out by subjecting the mixture of fibrous material and non-aqueous liquid to high shear. This high shear can be created by

30 methods common in the art. These methods include rotor-stator systems, e.g. the Ultra- Turrax^® (IKA Werke GmbH & Co. KG, Staufen, Germany), or a Silverson mixer (Silverson Machines Ltd., Chesham, Bucks, UK). Another method is high pressure homogenisation. An example of such a high pressure homogeniser is the Microfluidizer^® (Microfluidics International Corporation, MA-Newton, USA). Also sonication, a colloid mill, and a ball mill

35 may be used to homogenise the mixture. In case of a rotor-stator system, e.g. the Ultra-Turrax^®, the rotational speed preferably ranges from 1 ,000 to 30,000 rpm. The system is preferably homogenised during a period from 15 seconds to 60 minutes. This way a homogeneous mixture of cut fibres in oil can be achieved.

The amount of fibre to be added to the non-aqueous liquid in step b) of the method ranges from 0.01 % by weight to 50% by weight, preferably from 0.1 % by weight to 40% by weight, more preferred from 0.2% by weight to 25% by weight, more preferred from 0.5% by weight to 10% by weight. The mixture of homogenised fat phase and fibrous material may be used as an ingredient of a food product as applicable. In that case it may be brought into contact with other ingredients of such product.

After the homogenisation step the material obtained in step c) may need to be cooled, as the temperature may have risen due to the homogenisation operation.

By the homogenisation step two possible fragmenting operations take place. First, if the fibrous material has been obtained from a spinning process and a mat of fibrous material has been formed, then the homogenisation first leads to break up of the mat. Individual fibres are obtained. Second the long fibres which are formed are broken into smaller pieces, leading to reduction of the length of the fibre. These two steps may take place simultaneously, such that while the fibrous mat is broken into pieces, also long individual fibres are broken into shorter fibres.

In step d) of the method according to the invention, the mixture obtained from step c) is brought into contact with one or more other ingredients of the bakery product. This way bakery products can be made which comprise the structured fat phase. The structured fat phase can be used in the manufacturing of the composition according to the invention in any method which is commonly used for preparing such product. Compositions containing the structured fat phase

Preferred products that may be structured by the composition in the form of fibre according to the invention are food products. Food products may be fat continuous products like shortening or liquid oil (i.e. containing less than 5 wt% of water, preferably essentially no water). Preferably the products further comprises up to 95% by weight an aqueous phase. Such products may be bi-continuous or oil-in-water emulsions, but preferably are water-in-oil emulsions like for example margarine. The compositions of the invention may also be double emulsions and multiple emulsions (like oil-in-water-in-oil and water-in-oil-in-water emulsions), of which the fat phase can be structured by the fibrous material. Hence preferably the composition is a water-in-oil emulsion, containing between 1 % by weight and 99% by weight of fat phase, preferably 5 to 95%, more preferably 8 to 90%, even more preferably 10 to 85%, still even more preferably 15 to 80% and even still more preferably 20 to 70%. For example a shortening may contain 99% by weight of fat phase. Margarine usually contains about 80% edible oils and fats. A water-in-oil spread may contain from 20 to 70% by weight of edible oils and fats.

Preferably the concentration of fibrous material is between 0.01 % and 50% by weight, preferably between 0.1 % and 40% by weight, more preferably between 0.2% and 25% by weight, still more preferably between 0.5% and 10% by weight based on the amount of fat phase.

The fibrous material leads to structuring of the non-aqueous liquid phase. By rheology measurements it can be shown that the physical behaviour of the structured lipids is such that it resembles lipid phases that are structured by solid triglycerides (for example like in butter and margarine), for example in meltdown behaviour upon increase of temperature. Also extended temperature stability can be obtained.

By rheology measurements is meant that storage modulus G' (in Pa) and loss modulus G" (in Pa) are determined. The elasticity of the system is determined by these rheology measurements. G' and G" can be determined as function of the strain γ (gamma, in %) at a fixed temperature, and as function of temperature at a fixed strain. When measured as function of temperature, the meltdown behaviour is determined. This determines how structured non-aqueous liquid behaves under the influence of temperature. In general, the storage modulus (G') describes how a material behaves like solid, and the loss modulus (G") describes how a material behaves like liquid. If G' is larger than G", it means that the oil behaves like a solid or semi-solid, and otherwise, like a liquid. The point where G' equals G" is a characteristic one: beyond this point the material starts to flow. Temperature-dependent behaviour can characterize the meltdown process of sample. Meltdown is an important property for margarine, but also for other products an appropriate temperature dependency is important. 5°C is to mimic temperature in a refrigerator, and higher value indicates good stability of margarine in the fridge. 25°C is to mimic temperature when margarine is taken out of fridge and in use. A value at 25°C should be slightly lower than that at 5°C, but not too much. 37°C is to mimic mouth temperature. A lower value indicates more thorough meltdown in the mouth. An ideal temperature curve should be high enough from 5° C to 25° C, then decrease gradually with temperature increasing, finally reach a very low level.

The meltdown index is introduced to determine how much structured fat phase looses its structure upon temperature increase. The meltdown index is calculated by:

meltdown index = logi₀ (G'₅°c / G'₃7°c)

A meltdown index of more than 1 is considered to be good, and the higher the meltdown index, the better the structuring behaviour connected with acceptable properties of the structured fat phase for the consumer. For example a food emulsion structured by the fibrous network shows similar behaviour as a standard margarine wherein the oil is structured by solid fat crystals. These crystals melt upon consumption and/or use, leading to favourable properties. Also the viscosity (in Pa.s) of a structured fat phase can be determined as function of the shear rate (in 1/s) in order to compare for example a margarine (structured by solid (saturated) fat crystals) and structured fat phase according to the invention.

Here the temperature influences the interaction within the fibrous network, by increase of temperature the interactions between fibres becomes less, generally leading to softer fat phases at increased temperature. The relatively short fibres that structure the fat phase may align, to soften the structured fat phase. This way the meltdown behaviour of vegetable edible oils that are structured by saturated fat crystals can be mimicked, while not using the saturated fats. For dough this means that the relatively short fibres that structure the edible fat phase may align during kneading of the dough making the mixing easy whilst holding the fat in the dough at the same time. This way the dough quality of butter based doughs that are structured by saturated fat crystals can be mimicked while not using saturated fats or at least less saturated fats. The advantage of using the fibrous materials according to the invention is that the amount of saturated triglycerides that is required to structure triglycerides can be reduced, which leads to a healthier triglyceride profile of foods containing such structured lipid phase. It has also been found that using the fibrous materials according to the invention in bakery products the amount of saturated fat may be reduced while maintaining at least part of bakery product required product properties like moisture (of e.g. cakes) and crispness / crunch (of e.g. cookies). Further, it has been found that using the fibrous materials according to the invention in dough compositions, like e.g. cookie dough or cake batter, results in improved product properties like kneadability, shape retention and oil leaking from the dough.

Dough making and properties thereof

The quality of dough can be classified by looking at the dough properties.

For example a cookie made from a traditional recipe with flour, eggs, sugar and fibre structured edible oil will maintain shape during baking as good or better than from a dough made with butter. Such cookies will form much better than one where the butter is replaced by liquid edible oil.

The dough quality can be characterised by means of rheology. Cakes made with oil rather than butter will be soggy and fluffy, where edible oil structured by the fibrous network will have a firmness comparable or better than butter, despite having a much lower saturated fat content.

Making of the bakery dough with butter can be hard work in order to get the butter sufficiently liquefied. Replacing the butter by plain edible oil will result in a dough from which oil will leak. Fibrous structured edible oil will have the ease of working with oil, whilst the dough will have the quality of the butter dough.

Therefore, the invention further relates to dough composition comprising flour, fat and a lipophilic fibrous material comprising a polymer, wherein the fibrous material comprises one or more compounds chosen from the group of prolamins and lipophilic cellulose derivatives, and wherein the fibrous material has been prepared by a method involving spinning. The lipophilic fibrous material concerns fibrous material as described herein including any one of the preferred materials and methods of making them. Preferably the dough composition of the invention comprises 5 to 70% by weight of flour, 5 to 60% by weight of fat and 0.01 to 30% by weight of lipophilic fibrous material.

Preferably the composition further comprises 1 to 40% by weight of water.

5

It will be appreciated that the applicable amounts will depend on the type of bakery product the dough composition is used for. Such recipes are known to the skilled person. For example, a cookie dough will typically contain 30 to 60 wt% flour, 20 to 50 wt% fat and less than 10 wt% water. A sponge cake batter typically contains 10 to 40 wt% flour, 10 to 10 40 wt% fat and 10 to 30 wt% water.

Preferred bakery products are cookie, sponge cake, cup cake, biscuit, brownie, pastry and short bread type bakery products.

15 The bakery product may comprise further ingredients like sugar, salt and emulsifiers.

Typically the amount of sugar is from 0 to 50 wt%, like for example 5 to 40wt% or 10 to 30 wt%. Typical amounts of salt are between 0 and 10 wt%, like for example between 1 and 8 wt%, 2 and 6 wt% and 3 and 5 wt%. It will be appreciated that e.g. a savoury bakery product like e.g. a savoury biscuit will contain no or at least a low amount of sugar like e.g.

20 between 0.01 and 2 wt%. On the other hand, salt is often used in sweet bakery products to enhance the overall taste impression and typically an amount of between 0.05 and 1 wt% of salt is used in addition to sugar.

The invention also relates to the use of compositions according the invention to prepare a 25 bakery product, preferably a bakery product comprising less than 25% by weight of

saturated fatty acid, preferably less than 20% by weight and more preferably less than 15% by weight on total product. Typically the amount of saturated fatty acid is between 1 and 25 wt%, like for example between 5 and 20 wt% or 10 and 15 wt%.

30 DESCRIPTION OF FIGURES

Figure 1 : Schematic representation of the contact angle as defined herein. Droplet is dark, on the surface of a film. The contact angle as indicated is the angle in the droplet between the surface and the tangential line hitting the droplet.

Figure 2: Three scanning electron microscope pictures of fibrous mat produced by 35 electrospinning ethylcellulose, as described in example 2. From top to bottom: A magnification 80χ (scale width 500 micrometer); B magnification 1 ,000x (scale width 50 micrometer); C magnification "Ι Ο,ΟΟΟχ (scale width 5 micrometer).

Figure 3: Optical microscopy image of ethylcellulose fibre after homogenising. Bar width is 100 micrometer.

Figure 4: Image of the dispersion of ethylcellulose fibre in oil by means of phase contrast microscopy, bar width 100 micrometer; from example 2.

Figure 5: Rheology profile (G' (closed squares and triangles) and G" (open squares and triangles) (in Pa) as function of temperature (in °C), at fixed strain of 0.1 % and frequency of 1 Hz) of ethylcellulose fibre structured oil (squares) and margarine (triangles); from example 2.

Figure 6: Viscosity η (eta, in Pa.s) as function of shear rate γ (gamma, in 1/s) of various compositions at 25°C, from example 2:

Curve A: Margarine; B: sunflower oil; C: sunflower oil structured with 0.625%

ethylcellulose fibre; D: sunflower oil structured with 2% ethylcellulose fibre; E: sunflower oil structured with 5% ethylcellulose fibre.

Figure 7 Two scanning electron microscope pictures of fibrous mat produced by electrospinning zein, as described in example 3. A magnification 2,000x (scale width 20 micrometer); B magnification 5,000x (scale width 10 micrometer).

Figure 8: Image of the dispersion of zein fibre in oil by means of phase contrast microscopy; bar width 100 micrometer; from example 3.

Figure 9: Rheology profile (G' (closed triangles) and G" (open triangles) (in Pa) as function of temperature (in °C), at fixed strain of 0.1 % and frequency of 1 Hz) of zein fibre structured oil, from example 3.

Figure 10: Viscosity η (eta, in Pa.s) as function of shear rate γ (gamma, in 1/s) of various compositions at 25°C, from example 3:

Curve A: Margarine; B: sunflower oil; C: sunflower oil structured with 2% zein fibre; D: sunflower oil structured with 5% zein fibre; E: sunflower oil structured with 10% zein fibre.

Figure 11 : Two scanning electron microscope pictures of fibrous mat produced by electrospinning zein-inES48, as described in example 4. A: magnification 100x (scale width 20 micrometer); B: magnification 10,000x (scale width 10 micrometer).

Figure 12: Image of the dispersion of zein-inES48 fibre in oil by means of phase contrast microscopy; bar width 100 micrometer; from example 4.

Figure 13: Rheology profile (G' (closed squares and triangles) and G" (triangles) (in Pa) as function of temperature (in °C), at fixed strain of 0.1 % and frequency of 1 Hz) of zein- inES48 fibre structured oil (triangles) and zein-fibre structured oil (squares), from example 4. Figure 14: Scanning electron microscope picture of fibres obtained by electrospinning ethylcellulose-zein mixture, as described in example 5; scale width 10 micrometer.

Figure 15: Rheology profile of oil structured with ethylcellulose-zein fibre (G' (closed squares and triangles) and G" (open squares and triangles) (in Pa) as function of strain γ (gamma, in %), at 25°C; from example 5. Squares: margarine; triangle: ethylcellulose-zein structured oil.

EXAMPLES

The following non-limiting examples illustrate the present invention.

Raw materials:

Ethylcellulose: Aqualon^® Ethylcellulose (type N 100) was purchased from Hercules (Widnes, UK). Ethoxyl content was 48.0-49.5%, and degree of substitution was 2.46-2.57. Viscosity was 80-105 mPa.s (at 5% and 25°C in 80/20 toluene/ethanol).

Ethanol (95%) supplied by Shanghai Dongfeng regent (China)

Sunflower oil, (100%), brand: Duoli, supplied by Shanghai Jia Ge Food Co., Ltd (China). Dimethicone: Polydimethylsiloxanem, trademark & product name: PMX-200 Fluid, 50 cPs, molecular weight: 3,200; refractive index: 1 .402, specific gravity: 0.960, manufacturer: Dow Corning (Midland Ml, USA).

Demineralised water was obtained from a Millipore filter system.

Zein from corn was obtained from Sigma-Aldrich (Schnelldorf, Germany).

inES48 triglyceride: inES48 is an interesterified mixture of 65% dry fractionated palm oil stearin with an iodine value of 14 and 35% palm kernel oil. inES48 contains about 86.2% saturated fatty acids, about 1 1.5% mono-unsaturated fatty acids, and about 2.3% poly- unsaturated fatty acids, and is free from trans fatty acids. Obtained from Unimills

(Zwijndrecht, Netherlands).

PGPR (polyglycerol polyricinoleate, water-in-oil emulsifier) was obtained from Danisco Shanghai (China). Rheology analysis

Rheological analysis was performed in a controlled stress rheometer (Anton Paar, Physica MCR501 , Austria) with a parallel-plate (PP 25) measuring system. This configuration has been chosen because of some particles contained in some samples. Prior to each experiment, samples were left to equilibrate for the same time after loading PP25. Also viscosity experiments were performed using this device. Hardness

Hardness was measured at 20°C using TA XT Plus texture analyzer (Stable

Microsystems, Surrey, UK) equipped with a knife edge probe (length 30 mm, width 20 mm, basement thickness 5 mm) using the following procedure:

- test mode: compression;

- test speed: 0.5 mm/s;

- post-test speed 10 mm/s;

- penetration distance: 5 mm. Rheology measurement of dough compositions

Rheological measurements were performed using an AR2000 rheometer (TA instruments, Newcastle, Delaware, US) with controlled temperature (20°C) and with a 20 mm diameter plate. (Geometry parallel-plate, oscillation procedure). The gap between the plates is maintained at 1000 μηη.

To differentiate the strength of the dough samples, strain sweep measurments are performed from 0.002 to 100 strain %. The frequency is set to 1 Hz. Storage (elastic) G' modulus has been recorded.

Example 1 - Measurement of Contact Angle

The contact angle of ethylcellulose and zein was determined using a Drop shape analysis DSA100 (Krijss GmbH, Neunkirchen am Brand, Germany). In the present context, the contact angle is measured as the angle in the droplet, as schematically depicted in Figure 1 . The method applied was the following:

dissolve ethylcellulose or zein in a solvent to make homogenous solution;

- case a few drops of a solution onto a whole glass slide, under slowly spinning the glass slide to evenly spread the drops on the glass slide;

dry, smooth and even film formed after solvent has evaporated;

5 microliter drop of demineralised sunflower oil or dimethicone is brought onto the surface, at ambient pressure, humidity and temperature;

Measured contact angles:

Sunflower oil - ethylcellulose film: 37°.

Sunflower oil - zein film: 29°.

Dimethicone - ethylcellulose film 24°.

Dimethicone - zein film: 31 °. Example 2 - Standard Procedure for making Fibres and Structuring

Preparation of electrospun ethylcellulose fibre

This example shows the basic procedure for making fibres by electrospinning. 1 gram ethylcellulose was dissolved in 9 gram aqueous ethanol solution (90 wt%). The solution 5 was loaded onto a 10 mL syringe plunger. A blunt end stainless steel adapter with outer diameter of 0.9 mm was then placed on the syringe to act as the electrospinning nozzle and charging point for the contained ethylcellulose solution. The filled syringe was placed in a cole-parmer syringe pump with flowing rate of 1 .25 ml/hr. The positive lead from the high DC voltage supply was attached to the adapter metal portion. The voltage was set at

10 19 kV. The grounded collector was a copper mesh covering on a stainless steel mandrel (12 cm internal diameter and 30 cm length) placed 10 cm from the tip of the adapter. The mandrel was rotated at 100 rpm during the spinning process. In the experiment, 10 ml of the ethylcellulose solution was electrospun to form a nice, white mat on the grounded copper mesh. After electrospinning, the ethylcellulose mat was removed from the copper

15 mesh and processed for scanning electron microscopy evaluation. The results of fibrous mat can be seen in Figure 2 (magnification 80^χ, 1 ,000^χ, and 10,000^χ, respectively). The average diameter of ethylcellulose fibre varied from 100 nanometer to 500 nanometer. The thickness of ethylcellulose mat was approximately 500 micrometer.

20 Preparation of ethylcellulose fibre structured oil

2 gram inES48 (triglyceride hardstock) was melted in 17.6 g sunflower oil used as lipid phase. 0.6 gram of ethylcellulose mat was torn into small pieces first, and then dispersed into oil phase under homogenization at the rate of 10,000 min^"1 for 5 min using an Ultra Turrax® IKA T-25 digital (IKA Werke GmbH & Co. KG, Staufen, Germany). The

25 concentration of fibre in the lipid phase was 3 % by weight. After totally dispersing the oil phase containing ethylcellulose fibre continued homogenizing at the rate of 14,000 min^"1 for another 5 min. The resultant oil was put in the ethanol/water bath where temperature is -20 °C, then fast stirred using spatula to transfer heat as quick as possible. The cooling rate can vary from -15 °C/min to -20 °C/min. When temperature decreased to 5 °C, the

30 structured oil was stored at 5°C for 48 hr. Through this process ethylcellulose mat was broken down into single and short ethylcellulose fibre dispersing evenly in oil (see Figure 3), and the fibre structured oil showed good rheological behavior and temperature response. Figure 4 shows the dispersion of ethylcellulose fibre in oil by means of phase contrast microscopy. Figure 5 shows rheological response (G' and G" as function of

35 temperature, at fixed strain of 0.1 % and frequency of 1 Hz) profile of fibre structured oil and of commercial margarine (as a comparison for proof of principle). The margarine was a commercially available Flora margarine (ex Unilever, bought in a local shop in

Shanghai, China), containing 70% fat, of which 25% is saturated fats.

G' and G" of the fibre structured oil (squares in Figure 5) both show a plateau first upon increase of temperature from 5°C to about 20°C, and upon reaching higher temperatures the structured oil starts to loose its structure (G' and G" decrease). The meltdown index of ethylcellulose structured oil was 2.9.

The curve of margarine (triangles in Figure 5 ) as comparison for proof of principle also shows a plateau until a temperature of 25°C, and then drop of G' and G" upon higher temperatures. The meltdown index in the present case is larger than 2.9.

The similarities between the curves of the structured oil and of the margarine is remarkable, both in absolute values of G' and G", as well in decrease of G' and G" upon increase of temperature, leading to softening of the structured oil or margarine.

This experiment shows that the rheology profile of margarine can be mimicked by the oil structured by the lipophilic fibres. And the amount of saturated fat is reduced from 25% to 17%, which makes the product healthier for consumption.

Viscosity profile of structured sunflower oil

Sunflower oil was structured as described above, at three concentrations of ethylcellulose fibre: 0.625%, 2% and 5% by weight. The viscosity η (eta, in Pa.s) as function of shear rate γ (gamma, in 1/s) of these compositions was determined at 25°C, and compared to pure sunflower oil and with margarine. The margarine was a commercially available Flora margarine (ex Unilever, bought in a local shop in Shanghai, China), containing 70% fat, of which 25% is saturated fats. Figure 6 shows the result; curve A: Margarine; B: sunflower oil; C: sunflower oil structured with 0.625% ethylcellulose fibre; D: sunflower oil structured with 2% ethylcellulose fibre; E: sunflower oil structured with 5% ethylcellulose fibre. This shows that the sunflower oil structured with 5% ethylcellulose fibre has the same viscosity profile as function of shear stress at 25°C as the commercially available margarine. This shows that by using the lipophilic fibres the amount of saturated fats in a margarine can be reduced, while keeping the same viscosity profile.

Example 3 - Preparation of electrospun zein fibre

The method for this example is the same as the example 2 except for the electrospun solution. In this case, the spinning solution consisted of 2 gram zein dissolved in 8 gram aqueous ethanol solution (80 wt%). In this experiment, 10 ml of yellow, clear solution was spun to form off-white mat. The results are shown by SEM pictures in Figure 7 (magnification 2,000^χ and 5,000^χ, respectively). The fibres showed a flattened, ribbon-like structure. The average diameter of zein fibre varied from 500 nanometer to 2 micrometer, the thickness of the fibres was less than 1 micrometer. The thickness of the zein mat was approximately 800 micrometer.

5

Preparation of zein fibre structured oil

The process for this example is the same as the example 2 except for the electrospun fibre. In this case the electrospun fibre was zein as described above. The microscopy and rheology results are shown in Figure 8, Figure 9. The meltdown index of zein fibre

10 structured oil was 2.2.

G' and G" show a kind of plateau when the temperature is raised from 5 to about 20°C; and subsequently loses structure rapidly when the temperature is raised further. Slow melting as shown here is a positive property, as such melting behaviour is similar to liquid oils stabilised by solid fat, as in margarine.

15

Determination of average length of the fibres after fragmentation

1 g Zein fibre mat was dispersed in 9g sunflower oil under homogenisation (using an Ultra Turrax IKA T-25 digital) at the rate of 10,000 min^"1 for 5 min, then continue homogenising at 22,000 min^"1 for another 5 min. The average length of the fibres after fragmentation was 20 also determined using the method described herein before. The number average length of the fibres was 47.6 micrometer. Distribution: 53.8% of the fibres was in the range of 20-50 micrometer.

Viscosity profile of structured sunflower oil

25 Sunflower oil was structured as described above, at three concentrations of zein fibre: 2%, 5%, and 10% by weight. The viscosity η (eta, in Pa.s) as function of shear rate γ (gamma, in 1/s) of these compositions was determined at 25°C, and compared to pure sunflower oil and compared to margarine. The margarine was a commercially available Flora margarine (ex Unilever, bought in a local shop in Shanghai, China), containing 70% fat, of which

30 25% is saturated fats. Figure 10 shows the result; Curve A: Margarine; B: sunflower oil; C: sunflower oil structured with 2% zein fibre; D: sunflower oil structured with 5% zein fibre; E: sunflower oil structured with 10% zein fibre.

This shows that the viscosity of sunflower oil structured with zein fibre can be modified by 35 modifying the concentration of zein fibre. When also the results from example 2 are taken into account, it shows that by choosing the type and concentration of fibre the rheology behaviour can be tuned.

Example 4 - Preparation of electrospun zein-triglyceride composite fibre

The method for this example is the same as the examples 2 and 3 except for the electrospun solution. In this case, the spinning solution consisted of 1 gram zein, 0.05 gram inES48 dissolved in 9 gram aqueous ethanol solution (90 wt%) at 53°C. In this experiment, 10 ml of solution was spun to form off-white mat. The results are shown by means of SEM pictures in Figure 1 1 (magnification 100^χ, 10,000x). The diameter of zein- inES48 composite fibre varied from 500 nanometer to 2 micrometer. The thickness of Zein-inES48 composite fibre mat was approximately 500 micrometer.

Preparation ofzein-inES48 composite fibre structured oil

The process for this example is similar as in example 2 except for the composition of oil. In this case the structured oil consisted of sunflower oil, containing 5% inES48 triglyceride, and either 5% zein-inES48 fibre as structurant, or 5% zein fibre as structurant. The microscopy, rheology results (G' and G" as function of temperature) of structured oil are shown in Figure 12, and Figure 13. Example 5 - Preparation of ethylcellulose-zein composite fibre

Preparation of ethylcellulose-zein composite fibres with two syringes:

1 . Ethylcellulose was dissolved in 90 wt% ethanol/water to prepare 10%

ethylcellulose solution.

2. Zein was dissolved in 80 wt% ethanol/water to prepare 23% zein solution.

3. Ethylcellulose and zein solution were loaded into two 10 ml syringes, respectively.

4. The syringes were fixed onto one pump and the two solutions were mixed in a three valve connector at a volume ratio of 1 to 1 , then the mixture was spun from one spinneret.

5. The electrospinning parameters were: 1 ) voltage: 18-20 kV; 2) distance from the tip of needle to collector: 10 cm; 3) flowing rate: 1 .25 ml/hr.

6. Ethylcellulose/zein composite fibres were collected on the rotary copper mesh.

7. The fibres were separated from the copper mesh and torn into small pieces.

A SEM image of the composite fibre is shown in Figure 14. The diameter of ethylcellulose- zein composite fibre varied from 500 nanometer to 3 micrometer. Preparation of ethylcellulose-zein composite fibre structured oil

The procedure applied for this example is the same as in example 3. The concentration of ethylcellulose-zein composite fibre was 5% by weight, and the composition also contained 5% by weight of inES48 triglyceride, in addition to the fibre and the sunflower oil.

Figure 15 shows the rheology profile of oil structured with the ethylcellulose-zein fibre (G' and G" (in Pa) versus strain γ (gamma in %), at temperature 25°C. The rheology profile was compared to the rheology profile of margarine. The margarine was a commercially available Flora margarine (ex Unilever, bought in a local shop in Shanghai, China), containing 70% fat, of which 25% is saturated fats. This graph shows that the rheology profile of oil structured with ethylcellulose-zein composite fibres is comparable with margarine. An oil phase structured by lipophilic fibres can be designed such that the viscosity profile of margarine is effectively mimicked. Example 6 - Preparation of cookies based on fibre structured oils

Dough was prepared as follows: 50 g of crystal sugar (Van Gilse) was hand-mixed with 150 g of all-purpose wheat flour (Albert Heijn) and 100 g of (structured) sunflower oil or butterfat. Resulting dough was shaped in a roll using a sheet of baking paper, cut into pieces, which were then put on flat trays covered with another sheet of baking paper. Cookies were baked for 20 min at 160^°C in a Palux GXB Injection Hot-Air Steamer. After that the trays with baked cookies were left at ambient conditions, cookies were removed from trays upon cooling to ambient and used for subsequent rheological and hardness measurements. Butterfat was used as a benchmark fat phase (example I).

Unstructured sunflower oil was used as fat phase in a negative benchmark (example II). In examples III and IV the fat phase consisted of sunflower oil with 2% respectively 4% ethylcellulose powder. In examples V and VI the fat phase consisted of sunflower oil with 2% zein powder. Examples lll-VI are used as negative control.

In examples VII, VIII and IX sunflower oil was structured with 2% or 4% ethylcellulose fibre (from example 2) as fat phase. In examples X, XI and XII the fat phase consisted of sunflower oil structured with 2% or 4% of zein fibre (from example 3). In examples XIII and XIV the fat phase consisted of sunflower oil structured with 2% or 4% ethylcellulose zein composite fibre (from example 5). The fibre structured sunflower oil in examples VII, IX, X, XII, XIII and XIV was prepared according to the method in example 2, without adding additional inES48 prior to further use in the recipe.

The fibre structured sunflower oil in examples VIII and XI was prepared by adding pieces of torn apart fibre mat into the oil and homogenising by using a hand-held kitchen blender Bamix Gastro G200 (200W; ESGE AG, Mettlen, Switzerland) for 2 minutes.

Fat phases in examples III, IV and V were prepared by adding the powder to the oil and homogenising by means of an Ultra-Turrax for 5 minutes at 10,000 rpm.

Fat phase in example VI was prepared by adding the powder to the oil and homogenising for 2.5 minutes by means of the before mentioned hand-held kitchen blender.

It was noticed that it took considerably more effort to get a homogeneous dough from the butter recipe than from the other recipes. From the dough based on pure sunflower oil or sunflower oil with EC or zein particles oil exudation could be observed.

Hardness was measured and a minimum of 4 measurements was taken for the negative controls and a minimum of 8 measurements was taken for all other samples.

It was observed that the dough from examples II to VI did not maintain shape during the baking process. The dough prepared with EC fibres, either at 2% or at 4% level, maintained shape at a level equivalent to the butter benchmark. Dough made with 2% or 4% ethylcellulose-zein composite fibre or made with 2% or 4% zein fibre maintained shape even more than the butter benchmark. The firmness of the dough was established with the herein mentioned method for rheology measurement of dough compositions. It was observed that dough from examples II, III and IV were lacking all firmness and that the firmness of the dough from example V is only slightly better. It was also observed that the dough from example I had less firmness than all the fibre based examples, except for the very high strains. This shows that the fibre structured doughs maintain shape better than butter based dough.

This shows that it is possible to replace butter in the cookie recipe only by oil structured by any of the used fibres and achieve at least the strength of the butter benchmark, whilst at the same time get a significant reduction in the saturated fat level, as is exemplified in the tables below. Table 1

Table 2

Sample VII VIII IX X XI XII XIII XIV

Sugar 16.7% 16.7% 16.7% 16.7% 16.7% 16.7% 16.7% 16.7%

Flour 50% 50% 50% 50% 50% 50% 50% 50%

Oil 32.6% 32.6% 31.9% 32.6% 32.6% 31.9% 32.6% 31.9%

EC fibre 0.7% 0.7% 1 .4% - - - -

Zein Fibre - - - 0.7% 0.7% 1 .4% - -

EC/Zein composite Fibre - - - - - - 0.7% 1 .4%

Saturated fat 3.1 % 3.1 % 3.0% 3.1 % 3.1 % 3.0% 3.1 % 3.0%

Hardness 3.9 4.8 6.4 10.1 8.8 12.0 8.8 9.6

Claims

1 . Edible composition comprising a fat phase, wherein the fat phase comprises less than 55% by weight of fat phase of saturated fatty acids, wherein the fat phase is structured by a lipophilic fibrous material comprising a polymer, wherein the fibrous material comprises one or more compounds chosen from the group of prolamins and lipophilic cellulose derivatives, and wherein the fibrous material has been prepared by a method involving spinning.

2. Composition according to claim 1 , wherein the fat phase is selected from the group consisting of oil of vegetable origin, oil of dairy origin, oil of marine origin, oil of algae origin and mixtures thereof.

3. Composition according to claim 1 or 2, further comprising up to 95% by weight of an aqueous phase and preferably is an oil-in-water emulsion comprising 1 to 99% by weight of fat phase.

4. Composition according to any of claims 1 to 3, wherein the concentration of fibrous material is between 0.01 % and 50% by weight, preferably between 0.1 % and 40% and more preferably between 0.5% and 10% by weight, based on the amount of fat phase.

5. Dough composition comprising flour, fat and a lipophilic fibrous material comprising a polymer, wherein the fibrous material comprises one or more compounds chosen from the group of prolamins and lipophilic cellulose derivatives, and wherein the fibrous material has been prepared by a method involving spinning.

6. Dough composition according to claim 5 comprising 5 to 70% by weight of flour, 5 to 60% by weight of fat and 0.01 to 30% by weight of lipophilic fibrous material, preferably further comprising 1 to 40% by weight of water.

7. Bakery product comprising a dough composition according to claims 5 or 6, preferably the bakery product is a cookie, sponge cake, cup cake, biscuit, brownie, pastry or short bread type bakery product.

8. Composition according to any of claims 1 to 7, wherein the lipophilic cellulose derivative comprises ethylcellulose.

9. Composition according to any of claims 1 to 7, wherein the prolamin is chosen from the group of zein, gliadin, hordein, secalin, and avenin.

10. Composition according to any of claims 1 to 9, wherein the fibrous material comprises one or more lipid compounds and preferably wherein the lipid compound comprises lecithin, fatty acid, monoglyceride, diglyceride, triglyceride, phytosterol, phytostanol, phytosteryl-fatty acid ester, phytostanyl-fatty acid ester, wax, fatty alcohol, carotenoid, oil-soluble colourant, oil-soluble vitamin, oil soluble flavour, or oil soluble fragrance.

1 1 . Composition according to any of claims 1 to 10, wherein the fibre has a length from 1 micrometer to 10 millimeter, wherein the fibre has a diameter from 30 nanometer to

50 micrometer and wherein the aspect ratio of the fibre is larger than 10.

12. Composition according to any of claims 1 to 1 1 , wherein the fibrous material has been prepared by a method involving electrospinning.

13. Method for production of a bakery product comprising flour, fat and a lipophilic fibrous material comprising the steps:

a) providing a lipophilic fibrous material comprising a polymer, wherein the fibrous material comprises one or more compounds chosen from the group of prolamins and lipophilic cellulose derivatives, and wherein the fibrous material has been prepared by a method involving spinning; and

b) dispersing the fibrous material obtained from step a) in a fat phase; and c) homogenising the mixture from step b), to fragment the fibrous material to an average length from 1 micrometer to 10 millimeter; and

d) bringing the mixture obtained from step c) into contact with one or more other ingredients of the bakery product.

14. Method according to claim 13, wherein step a) the spinning process is an electrospinning process.

15. Use of a composition according to any one of claims 1 to 7 to prepare a bakery product, preferably a bakery product comprising less than 25% by weight of saturated fatty acid.