WO2009118282A2

WO2009118282A2 - Encapsulation of oxidation labile compounds

Info

Publication number: WO2009118282A2
Application number: PCT/EP2009/053358
Authority: WO
Inventors: Roar Hauch
Original assignee: Novozymes A/S
Priority date: 2008-03-25
Filing date: 2009-03-23
Publication date: 2009-10-01
Also published as: WO2009118282A3

Abstract

A method for encapsulating oxidation labile compounds by preparing a slurry comprising the oxidation labile compound and a film forming compound followed by spray drying to provide a product with enhanced oxidative stability.

Description

TITLE: ENCAPSULATION OF OXIDATION LABILE COMPOUNDS

FIELD OF INVENTION

The present invention relates to a product and a method for producing a product with enhanced stability towards oxidation of oxidation labile compounds.

BACKGROUND OF THE INVENTION

Consumption of foods rich in omega-3 polyunsaturated fatty acids (PUFAs) has been associated with decreased cardiovascular death by decreasing plasma triglycerides, blood pressure, platelet aggregation, and inflammation. While seafood is the best source of omega- 3 acids, many individuals do not like the taste of seafood, do not have ready access to seafood, or cannot afford seafood. One solution is to supplement the diet with cod liver oil or fish oil capsules, but this solution has low compliance. Another solution is to add omega-3 rich fish oils directly to foods, such as dairy products, cereal products, baked goods, and nutrition bars. A challenge with the latter approach is to provide the benefits of omega-3 fatty acids without imparting any offending fish flavors or fish odors, which are byproducts of lipid oxidation. Similar challenges exist for other oxidation labile compounds.

A need exists, therefore, for a stabilized product comprising oxidation labile compound, in particular PUFAs, such that the oxidation labile compounds protected from oxidation.

SUMMARY OF THE INVENTION

In a first aspect the invention relates to a method for preparing a product comprising an oxidation labile product having high oxidation stability comprising the steps of: a. Providing a slurry comprising i. An oxidation labile compound ii. A film forming protein b. Spray drying the slurry to provide the product.

The method of the invention provides a product comprising an oxidative labile compound, which product has surprisingly high oxidative stability.

In a second aspect the invention related to a product prepared by the inventive method.

In a further aspect the invention relates to a food or nutritional product comprising the product according to the invention. DETAILED DESCRIPTION OF THE DRAWINGS

Figure 1 shows Oxipres data for products of the invention prepared in examples 1-6, demonstrating the high oxidative stability. The relative oxygen pressure over time is shown in the graph. The drop in pressure corresponds to the time when oxidation in the sample accelerated and thus relative oxidative stabilities can be compared.

Figure 2 shows volatile Organic Compounds after 1 , 3, 6 and 15 weeks of storage at 25⁰C of the product prepared in example 1.

Figure 3 shown volatile organic compounds after 1 , 3, 6 and 15 weeks of storage at 25 ⁰C of the product prepared in example 2.

Figure 4 shows volatile organic compounds after 1 , 3, 6 and 15 weeks of storage at 25 ⁰C of the product prepared in example 3.

DETAILED DESCRIPTION OF THE INVENTION

Oxidation labile compounds

An oxidation labile compound having utility in the present invention includes a material comprising a molecule with a carbon backbone having at least one carbon-carbon double bond that is prone to oxidation. Removal of a labile hydrogen atom from a carbon adjacent to the double bond creates a free radical that is susceptible to attack by oxygen to form a free radical peroxide, which may serve as a catalyst for further oxidation.

A variety of oxidation labile compounds are suitable for use in this invention. In general, the oxidation labile compound comprises at least one oxidation labile lipid. Oxidation labile lipids include fatty acids, fatty acid esters, fatty acid methyl esters (FAMEs), tri-, di- and/or mono- glycerides, glycolipids, phospholipids, sphingolipids, sterols, sterol esters, steroid hormones and polyisoprenoids.

The oxidation labile lipids may be neutral or polar and especially include unsaturated fatty acids. In particular the oxidation labile lipid contains polyunsaturated fatty acids. Typical examples of neutral lipids are triacylglycerols, fat-soluble vitamins and waxes. A typical polar lipid class is phospholipids.

According to the present invention a preferred oxidation labile compound may contain long chain polyunsaturated fatty acid, (i.e., fatty acids containing at least 2 unsaturated carbon- carbon bonds, e.g., double bonds and a carbon chain with 18 or more carbon atoms). The long chain polyunsaturated fatty acids are in a particular embodiment omega-3 and/or omega-6 polyunsaturated fatty acids. The polyunsaturated fatty acid may be present within triglycerides.

In still another embodiment, the oxidation labile compound may be a preparation of substantially unsaturated fats or substantially unsaturated oils. In general, fats and oils comprise monoglycerides, diglycerides, triglycerides, and free fatty acids. The glycerides of fats and oils generally comprise fatty acids that are at least 4 carbons in length, and more preferably, unsaturated fatty acids that range in length from 16 to 24 carbons. The unsaturated fatty acid may be monounsaturated or polyunsaturated.

In another embodiment, the oxidation labile compound may be a polyunsaturated fatty acid (PUFA), which has at least two carbon-carbon double bonds generally in the cis- configuration. The PUFA may be a long chain fatty acid having at least 18 carbons atoms. The PUFA may be an omega-3 fatty acid in which the first double bond occurs in the third carbon-carbon bond from the methyl end of the carbon chain (i.e., opposite the carboxyl acid group). Examples of omega-3 fatty acids include alpha-linolenic acid (18:3, ALA), stearidonic acid (18:4), eicosatetraenoic acid (20:4), eicosapentaenoic acid (20:5; EPA), docosatetraenoic acid (22:4), n-3 docosapentaenoic acid (22:5; n-3DPA), and docosahexaenoic acid (22:6; DHA). The PUFA may also be an omega-6 fatty acid, in which the first double bond occurs in the sixth carbon-carbon bond from the methyl end. Examples of omega-6 fatty acids include linoleic acid (18:2), gamma-linolenic acid (18:3), eicosadienoic acid (20:2), dihomo-gamma- linolenic acid (20:3), arachidonic acid (20:4), docosadienoic acid (22:2), adrenic acid (22:4), n-6 docosapentaenoic acid (22:5) and calendic acid (18:3). The fatty acid may also be an omega-9 fatty acid, such as oleic acid (18:1 ), eicosenoic acid (20:1 ), mead acid (20:3), erucic acid (22:1 ), and nervonic acid (24:1 ). In one embodiment, the oxidation labile compound may be derived from a biological source, such that it may be a crude mixture of proteins, lipids, and carbohydrates. In another embodiment, the oxidation labile compound may be a mixture of lipids that is essentially devoid of proteins and/or carbohydrates. In yet another embodiment, the oxidation labile compound may be a purified lipid. In another embodiment, the oxidation labile compound may be a marine animal-derived oil. The marine animal-derived oil may originate from a vertebrate, in-vertebrate or micro- or unicellular-organism fish or a marine organism, e.g. such that the oil may be a fish oil or a marine microorganism oil. The long chain (2OC, 22C) omega-3 and omega-6 fatty acids are found in marine organisms. The ratio of omega-3 to omega-6 fatty acids in marine organisms ranges from about 8:1 to 20:1. Aquatic organisms from which oil rich in omega-3 fatty acids may be derived include, but are not limited to tuna, abalone scallops, albacore tuna, anchovies, catfish, clams, cod, gem fish, herring, lake trout, mackerel, menhaden, orange roughy, salmon, sardines, sea mullet, sea perch, shark, shrimp, squid and trout. In yet another embodiment, the oxidation labile compound may be a plant-derived oil. Plant and vegetable oils are rich in omega-6 fatty acids. Some plant-derived oils, such as flaxseed oil, are especially rich in omega-3 fatty acids. Plant or vegetable oils are generally extracted from the seeds of a plant, but may also be extracted from other parts of the plant. Plant or vegetable oils that are commonly used for cooking or flavoring include, but are not limited to, acai oil, almond oil, amaranth oil, apricot seed oil, argan oil, avocado seed oil, babassu oil, ben oil, blackcurrant seed oil, Borneo tallow nut oil, borage seed oil, buffalo gourd oil, canola oil, carob pod oil, cashew oil, castor oil, coconut oil, coriander seed oil, corn oil, cottonseed oil, evening primrose oil, false flax oil, flax seed oil, grapeseed oil, hazelnut oil, hemp seed oil, kapok seed oil, lallemantia oil, linseed oil, macadamia oil, meadowfoam seed oil, mustard seed oil, okra seed oil, olive oil, palm oil, palm kernel oil, peanut oil, pecan oil, pequi oil, perilla seed oil, pine nut oil, pistachio oil, poppy seed oil, prune kernel oil, pumpkin seed oil, quinoa oil, ramtil oil, rice bran oil, safflower oil, sesame oil, soybean oil, sunflower oil, tea oil, thistle oil, walnut oil, or wheat germ oil. The plant derived oil may also be hydrogenated or partially hydrogenated.

The oxidation labile compound may be derived from microorganisms such as algae, fungi and bacteria. In a particular embodiment the fungi is Mortierella alpine. In still a further embodiment, the oxidation labile compound may be an algae derived oil. Commercially available algae-derived oils include those from and Suitable algae, from which oil is extracted, include Aphanizomenon, Bacilliarophy, Botryococcus, Chlorophyceae, Crypthecodinium, Dunaliella, Euglena, Isochrysis, Nannochloropsis, Nannochloris, Neochloris, Phaeodactylum, Pleurochrysis, Prymnesiumparvum, Scenedesmus, Schizochytrium, Spirulina and Tetraselmis. In one particular embodiment the algae, from which oil is extracted, include Aphanizomenon flos-aquae, Bacilliarophy sp., Botryococcus braunii, Chlorophyceae sp., Crypthecodinium cohnii, Dunaliella tertiolecta, Euglena gracilis, Isochrysis galbana, Nannochloropsis salina, Nannochloris sp., Neochloris oleoabundans, Phaeodactylum tricornutum, Pleurochrysis carterae, Prymnesiumparvum, Scenedesmus dimorphus, Schizochytrium sp., Spirulina sp., and Tetraselmis chui. In one embodiment the core comprising the oxidation labile compound is a lipid enriched biomass produced from a microorganism, in particular from an auxotrophic marine microorganism containing - at least in part - the antioxidants produced by said microorganism. In a particular embodiment auxotrophic marine microorganism according to the invention is an algae, in particular a micro algae or an algae-like microorganism, preferably a member of the Stramenopiles group, more preferably a Hamatores sp, a Proteromonads sp, a Opalines sp, a Developayella sp, a Diplophrys sp, a Labrinthulids sp, a Thraustochytrids sp, a

Biosecids sp, an Oomycetes sp, a Hypochytridiomycetes sp, a Commation sp, a Reticulosphaera sp, a Pelagomonas sp, a Pelagococcus sp, an Ollicola sp, an Aureococcus sp, a Parmales sp, a Diatoms sp, a Xanthophytes sp, a Phaeophytes sp (brown algae), a Eustigmatophytes sp, a Raphidophytes sp, a Synurids sp, an Axodines sp, a Chrysomeridales sp, a Sarcinochrysidales sp, a Hydrurales sp, a Hibberdiales sp, or a Chromulinales sp.

The lipid enriched biomass may be produced as known in the art, e.g., as described in WO 2005/021735.

In another embodiment, the oxidation labile compound may be a spice or fragrance oil. Suitable examples of spice or fragrant oils include angelica oil, anise oil, basil oil, bergamont oil, orange oil, black pepper oil, calamus oil, citronella oil, calendula oil, camphor oil, cardamom oil, celery oil, chamomile oil, cinnamon oil, clove oil, coriander oil, lemon grass oil, cypress oil, cumin seed oil, davana oil, dill seed oil, eucalyptus oil, fennel seed oil, garlic oil, geranium oil, ginger oil, grape seed oil, hyssop oil, jasmine oil, juniper berry oil, lavender oil, lemon oil, lime oil, myrrh oil, neroli oil, neem oil, nutmeg oil, palm Rosa oil, parsley oil, peppermint oil, rose oil, rosemary oil, rose wood oil, sage oil, sesame oil, spearmint oil, tarragon oil, tea tree oil, thyme oil, tangerine oil, turmeric root oil, vetiver oil, wormwood oil, and yara yara oil. In yet another embodiment, the oxidation labile compound may be a pharmaceutical fo rm u l ati o n co m p ri s i n g a n oxi d ati ve ly u n sta bl e p h a rm a ce u ti ca l , s u ch a s arachadonic/arachidonic acid or a prostaglandin. The formulation may also comprise an unstable oil as a carrier. Suitable examples of pharmaceutical grade carrier oils include cod liver oil, corn oil, cottonseed oil, eucalyptus oil, lavender oil, olive oil, peanut oil, peppermint oil, safflower oil, sesame oil, and soybean oil. The oxidation labile compound may also be a formulation comprising a fat-soluble vitamin, such as vitamin A, D, K, or E.

In another embodiment, the oxidation labile compound may be preparation of fish materials or fish meal, which is the solid material that remains after most of the water and oil have been removed from the starting fish material. Non-limiting examples of fish or marine organism that may be used for the preparation of fish meal include anchovy, blue whiting, capelin, crab, herring, mackerel, menhaden, pollack, salmon, shrimp, squid, tuna, and whitefish.

In still another embodiment, the oxidation labile compound may be an animal-derived fat. Non-limiting examples of suitable animal-derived fats include poultry fat, beef tallow, mutton tallow, butter, pork lard, whale blubber, and yellow grease (which may be a mixture of vegetable and animal fats).

In one embodiment the oxidation labile compound is an oil from marine organisms comprising omega-3 and omega-6 fatty acids. In another particular embodiment, the oxidation labile compound is an omega-3 fish oil. In yet another particular embodiment, the oxidation labile compound is an omega-3 fatty acid.

In a particular embodiment of the invention the oxidation labile compound content of the core is in amounts of more thani O % w/w, in particular in amounts of 10-20% w/w. In one embodiment the oxidation labile compound is present in the core in amounts of more than 5%. In another embodiment the oxidation labile compound is present in the core in amounts of more than 10%. In a further embodiment the oxidation labile compound is present in the core in amounts of more than 15%. In a particular embodiment the oxidation labile compound is present in the core in amounts of more than 20%. In a further particular embodiment the oxidation labile compound is present in the core in amounts of more than 25%, more than 30%, more than 35%, more than 40%, more than 50%, more than 60% or even more than 75%.

The expression "a film forming compound" is according to the invention intended to mean a protein capable of forming a film in aquatic environments. Film forming compounds as such are know within the art. Preferably the film forming compound is a water soluble and amphiphilic molecule with film forming properties due to their ability to make molecular interactions. Such molecules are known for the skilled person as molecules capable of stabilizing oil in water emulsions and are generally known as emulsifying compounds, however the present inventors surprisingly have discovered that these film forming proteins can be used for encapsulation of oxidative labile compounds such as PUFA.

Preferably, the film forming protein is an edible or organic compound, more preferred the film forming compound is a protein of plant or animal origin such as a milk protein. The film forming compound may be a partly or fully water soluble protein; it may be an amphiphilic water soluble protein.

As examples can be mentioned wheat gluten, rye gluten, barley gluten, rice proteins, corn protein, zein, soy protein, casein and whey proteins, gelatin and collagen The proteins can be naturally proteins i.e. not modified proteins, or it can be proteins modified by e.g. partly or fully deamidated, hydrolysed or denaturated or any combinations thereof.

In one preferred embodiment the file forming compounds is a partly or fully deamidated cereal proteins, in particular wheat protein, and most preferred a deamidated and amphiphilic water soluble wheat protein. An example of a preferred film forming compound is the deamidated and amphiphilic water soluble wheat protein marketed under the name Meripro brand from Tate & LyIe. In addition to the oxidation labile compound the slurry may also contain other compounds such as antioxidants, vitamins, color etc. Preferably the slurry comprises an antioxidant. These additional compounds are suitably added and mixed together with other ingredients of the slurry.

Antioxidants

Antioxidants may be present in the core together with the oxidation labile compound.

The antioxidant may be natural or synthetic. Suitable antioxidants include, but are not limited to, ascorbic acid and its salts, ascorbyl palmitate, ascorbyl stearate, anoxomer, N- acetylcysteine, benzyl isothiocyanate, o-, m-or p-amino benzoic acid (o is anthranilic acid, p is PABA), butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), caffeic acid, canthaxantin, alpha-carotene, beta-carotene, beta-caraotene, beta-apo-carotenoic acid, camosol, carvacrol, cetyl gallate, chlorogenic acid, citric acid and its salts, clove extract, coffee bean extract, p-coumaric acid, 3,4-dihydroxybenzoic acid, N,N'-diphenyl-p- phenylenediamine (DPPD), dilauryl thiodipropionate, distearyl thiodipropionate, 2,6-di-tert- butylphenol, dodecyl gallate, edetic acid, ellagic acid, erythorbic acid, sodium erythorbate, esculetin, esculin, 6-ethoxy-1 ,2-dihydro-2,2,4-trimethylquinoline, ethyl gallate, ethyl maltol, ethylenediaminetetraacetic acid (EDTA), eucalyptus extract, eugenol, ferulic acid, flavonoids (e.g., catechin, epicatechin, epicatechin gallate, epigallocatechin (EGC), epigallocatechin gallate (EGCG), polyphenol epigallocatechin-3-gallate), flavones (e.g., apigenin, chrysin, luteolin), flavonols (e.g., datiscetin, myricetin, daemfero), flavanones, fraxetin, fumaric acid, gallic acid, gentian extract, gluconic acid, glycine, gum guaiacum, hesperetin, alpha- hydroxybenzyl phosphinic acid, hydroxycinammic acid, hydroxyglutaric acid, hydroquinone, N-hydroxysuccinic acid, hydroxytryrosol, hydroxyurea, lactic acid and its salts, lecithin, lecithin citrate; R-alpha-lipoic acid, lutein, lycopene, malic acid, maltol, 5-methoxy tryptamine, methyl gallate, monoglyceride citrate; monoisopropyl citrate; morin, beta-naphthoflavone, nordihydroguaiaretic acid (NDGA), octyl gallate, oxalic acid, palmityl citrate, phenothiazine, phosphatidylcholine, phosphoric acid, phosphates, phytic acid, phytylubichromel, pimento extract, propyl gallate, polyphosphates, quercetin, trans-resveratrol and/or combinations thereof. Resveratrol is a polyphenol^ phytoalexin. It is a stilbenoid, a derivative of stilbene. It exists as two structural isomers: cis-resveratrol and trans-resveratrol. Resveratrol is produced by plants. It is found in the skins of certain red grapes, in peanuts, blueberries, some pines, the roots and stalks of Japanese knotweed and giant knotweed. Further antioxidants are rice bran extract, rosemary extract, rosmarinic acid, sage extract, sesamol, silymarin, sinapic acid, succinic acid, stearyl citrate, syringic acid, tartaric acid, thymol, tocopherols, or vitamin E, is a fat-soluble vitamin. Natural vitamin E exists in eight different forms or isomers four tocopherols (i.e., alpha-, beta-, gamma-and delta-tocopherol), and four tocotrienols (i.e., alpha-, beta-, gamma-and delta-tocotrienols). Further antioxidants include tyrosol, vanilic acid, 2,6-di-tert-butyl-4-hydroxymethylphenol (i.e., lonox 100), 2,4- (tris-3',5'-bi-tert-butyl-4'-hydroxybenzyl)-mesitylene (i.e., lonox 330), 2,4,5- trihydroxybutyrophenone, ubiquinone, tertiary butyl hydroquinone (TBHQ), thiodipropionic acid, trihydroxy butyrophenone, tryptamine, tyramine, uric acid, vitamin K and derivates, vitamin Q10, wheat germ oil, zeaxanthin, and/or combinations thereof. Preferred antioxidants include tocopherols, ascorbyl palmitate, propyl gallate and rosemary extracts. The concentration of the antioxidant or combination of antioxidants may range from about 0.001% to about 5% by weight. In a particular embodiment the concentration of the antioxidant or combination of antioxidants may range from about 0.01-1 %. In a most particular embodiment the concentration of the antioxidant or combination of antioxidants may range from about 0.03-0.3% by weight. In a further embodiment the antioxidant is selected from the group consisting of tocopherol, resveratrol and/or derivatives thereof, Propyl gallat, rosemary extracts, ascorbic acid, ascorbyl palmitate and combinations thereof. Other preferred examples of suitable antioxidants according to the invention includes: Herbal extracts, e.g. rosemary extract, tocopherols or vitamin E, ascorbyl palmitate, astaxantin, canmthaxantin, ascorbic acid, butylated hydroxyanisole (BHA), butylates hydroxytoluene (BHT), tertiary butyl hydroquinone (TBHQ), alpha-carotene, beta-carotene, ethylele diamine tetraacetic acid (EDTA), dodecyl- & octyl & propylgallate, flavonoids e.g. catechin, epichatechin, epichatechin gallate, epigallocatechin (EGC), epigallocatechin gallate (EGCG) polyphenol epigallochatechin-3-gallate, flavones, apigenin, chrysin, luteolin, flavenols, datiscetin, myricetin, daemfero, flavanones and lecithin.

In the context of the present description and claims the term "slurry" is intended to be understood as a mixture comprising one or more oxidation labile compounds, one or more film forming compounds, water and other optional ingredients to form an oil in water emulsion. The slurry may according to the invention be prepared using any suitable technology as the skilled person will appreciate and will generally be prepared by adding ingredients of the slurry in a suitable container and mixing thoroughly. In some embodiments may be slurry be homogenized using homogenization equipment generally known to the skilled person in order to obtain homogeneous slurry. Preferred are oil droplets <10 μm in diameter, more preferred <5, even more preferred <2.5 μm and most preferred < 1 μm in the o/w emulsion.

The slurry generally comprises film forming agents in an amount of between 10 and 60 % w/w based on the weight of the slurry except water, preferably between 20 and 60% w/w and most preferred around 50% w/w. Water is added in a sufficient amount in order to provide a slurry having satisfactory rheological properties for the preparation of the slurry, optional homogenization and spray drying. Generally water is added in an amount of 10-90% w/w based on the total weight of the slurry, more preferred between 20 and 70% w/w and most preferred around 25-50% w/w.

The prepared slurry is spray dried using methods and equipment known per se in the art. The spray drying should be performed under conditions that on one side provides for an adequate drying of the slurry to provide the desired product and on the other side is not so harsh to damage the product. The desired product being a powder comprising a matrix with the oxidation labile compound is distributed evenly throughout the matrix in multiple compartments. The conditions for the spray drying should be selected to provide a product having a particle size in the range on 10-1000 μm, preferably 20-100 μm. It is within the skills of the average practitioner to select suitable conditions for the spray drying based on general common knowledge with in the field and optionally routine experiments.

Food and feed products A further aspect of the present invention is the provision of a food product comprising an edible material and a product of the invention.

In one embodiment, the food product may be a liquid beverage. Non-limiting examples of liquid beverages include milk, flavored milk drinks, goat milk, liquid yogurt, soy milk, rice milk, fruit drinks, fruit-flavored drinks, vegetable drinks, nutritional drinks, energy drinks, sports drinks, infant formula, teas, and coffee drinks.

In another embodiment, the food product may also be a dairy or an egg product. Examples of dairy products include, but are not limited to, cheese, ice cream, ice cream products, yogurt, whipping cream, sour cream, cottage cheese, buttermilk, egg whites, and egg substitutes. In an alternate embodiment, the food product may be a cereal-based product. Non-limiting examples of food products derived from cereals include breakfast cereals, pasta, breads, baked products (i.e., cakes, pies, rolls, cookies, crackers), tortillas, granola bars, nutrition bars, and energy bars. The food product may be a nutritional supplement. In still another embodiment, the food product may be a vegetable-derived product. Examples of vegetable-derived food products include textured vegetable proteins, tofu, corn chips, potato chips, vegetable chips, popcorn, and chocolate products.

In yet another embodiment, the food product may be a meat product or a meat analog. Examples of meat products include, but are not limited to, processed meats, comminuted meats, and whole muscle meat product. The meat may be animal meat or seafood meat. The meat analog may be a textured vegetable or dairy protein that mimics animal or seafood meat in texture. The meat analog may be part or all of the meat in a food product. The food product may also be a canned food product to which the microcapsule is added to prevent oxidation during the heating process. In yet another embodiment, the food product may be a product for animals. The animal may be a companion animal, an agricultural animal, or an aquatic organism. Non-limiting examples of animal food products include canned pet foods, dried pet foods, agricultural animal feeds, and agricultural animal feed supplements. The feeds may be pelleted, extruded, or formed by other methods. The feeds or feed supplements may be liquid. Examples include a nursery diets for monogastric animals, calf milk replacer, or fish and other oils used to supplement animal feeds.

Another aspect of the invention provides for food products treated with the composition of the invention. The composition may be sprayed on or applied to a food product. Non-limiting examples of suitable food products include food bars, nutrition bars, snacks, nuts, oats, cookies, crackers, dried fish or seafood products, and pet foods or pet snacks. The composition may be added directly to oxidation sensitive foods. Examples include, but are not limited to, cooking oils, frying oils, spray-on oils, salad dressings, margarines, nut oils, herb or spice oils, cream liquors, shelf-stable cream products, fish oils, fish sauce, nutritional supplements containing fat soluble vitamins and oils, and pharmaceutical preparations containing oxidation labile lipids or oils.

In a particular embodiment the PUFA compound is for human consumption with the purpose of supplying additional PUFA to the diet. PU FA's are essential to humans because of inadequate synthesis in the human metabolism and the overall goal of supplying additional PUFA to the diet is to reach the Recommended Daily Intake for PUFA. Several types of delivery routes exist, such as a dietary supplement as capsules, as fortification of diary products, such as infant formula which is fortified products for infants ( 0-12 months of age) and growing up milk also fortified milk for children, or as fortified foods in general, examples being bread, cakes, chocolate, candy, canned food, cereals, spreads and drinks. In another particular embodiment of the present invention the particles of the invention are used in food products, as a nutritional supplement, as a dietary supplement and/or in feed products. The particles of the invention may even be incorporated into pharmaceuticals.

Nonfood Products A further aspect of the invention provides nonfood products comprising lipid-coated stabilized products comprising oxidative labile compounds. The nonfood product may be a cosmetic, a body moisturizer, or an anti-aging cream for humans, or it may be a product to prevent pet coat oil oxidation or prevent pet odor. The nonfood product may be a fragrance product or an air freshener product. The nonfood product may be a paint or varnish. The nonfood product may be a mineral oil, a synthetic oil, or a biodiesel. In a particular embodiment the particles may be used in non food products such as cosmetics, body moisterizers, anti aging creams, fragrances, air freshener, paint and or varnish

EXAMPLES

In the following examples emulsion comprising PUFA were encapsulated according to the invention using following general method.

Method: Slurry production and homogenization were conducted at ~60-65°C at atmospheric conditions. Meripro 711 and maltodextrin were dissolved in (tap) water for 20 minutes using a Silverson Homogenizer L4R for stirring (8300 rpm). The PUFA emulsion (~60-65°C) was added slowly to obtain the primary oil in water emulsion. Final homogenization was achieved via standard operation of a Rannie High Pressure Laboratory Homogeniser, model MINI- LAB, type 8.30H (APV) operated at a homogenizing pressure ensuring average oil droplet size smaller than 1 microns in diameter (Malvern Mastersizer 2000. Cold de-ionized water as diluent). All 5 slurries were spraydried using a MOBIL MINOR^tm spray drier (GEA Niro Inc.) operated with atmospheric air in a standard operation setup: concurrent airstream, inlet/outlet temperatures of 160/70-75⁰C and atomizing nozzle (2 mm orifice). The dry powders were collected in the MOBIL MINOR^tm cyclone and stored at -18⁰C until analysis.

Recovery of PUFA-containing lipid from algal culture broth

PUFA-containing lipid was produced and recovered by the following process:

Cultivation of cells Cells of Schizochytrium sp. were cultivated to obtain a culture broth using the method disclosed in WO 2005/021735 A1. Approx. 50 % (by weight) of the mature cells was lipids. 25-30 % of the lipid content was DHA (22:6(n-3)), and 50-60 % was palmitic acid (16:0). The lipid in the algae was present mainly as lipid vesicles with triglycerides (3 fatty acids pr molecule), and as sterol esters (1 fatty acid) and phospholipids (2 fatty acids) in the cell and organelle membranes.

Pre lysis

A 750 L pressure tank was heated to 75-8O⁰C with steam and flushed with nitrogen.

The pressure was kept at 1 atm + 0.2 bars after flushing. Lysis of cells

The culture broth was run through a bead mill with 0.6 mm SiLi beads (Zirconium

Oxide), Flow was 200 L/h, after which the fluid was heated in a 1 -2 m² heat exchanger to 75⁰C, and transferred to the pressure tank.

The pH in the pressure tank was regulated to pH 10 with 45% KOH, as soon as the fluid level reached the pH sensor in the tank.

P re separation

A Westfalia SB-7 centrifuge was heated to 75⁰C with steam, and jerrycans were prepared for product reception by nitrogen-flushing.

Separation

After 1.5-4.0 hours in the pressure tank, the alkaline liquid still over 7O⁰C was run through the SB-7 oil centrifuge (200 L/h, 4.0-4.4 bars counter pressure), and the lipid emulsion was recovered as the top phase. The lipid emulsion was collected in 25 L jerrycans.

In separate experiments, it was found that very often water should be added in order to get a good separation; 1 to 2 volumes of water to 1 volume alkaline lysed culture broth, especially if the culture broth is rich in biomass.

Example 1 -3

Three slurries for spray drying were formulated according to the table below. The deamidated wheat protein was a commercial product (Meripro 71 1 ) from Tate & LyIe. The maltodextrin "Glucidex IT 21" (powder, DE; 19-23 spec.) was purchased from Roquette. The PUFA emulsion contained 36% (w/w) water, 57% (w/w) lipid (22-24% DHA) and 7% (w/w) non-lipid Nitrogen Free Extract.

Example 4-5

The PUFA source used for spray drying example 4+5 was a pure lipid with a composition equal to the lipid fraction of the PUFA emulsion used for example 1-3. The pure lipid used for these examples were provided by heating the emulsion to above 70⁰C and allowing for a phase separation. The resulting pure lipid top phase was used to further formulation. The deamidated wheat protein and maltodextrin were the same as in example 1-3, and the "RPT40" was an antioxidant blend from Kemin Food Ingredients containing rosemary extract, ascorbyl palmitate and tocopherols.

Example 6 A commercial powder containing polyunsaturated lipids (mostly DHA) was included as a reference for stability analyses. The product was "Martek DHA^tm Powder KSF58" with lot # 7500004068HM was sold by Martek Bioscience Corporation.

Example 1-6 were analyzed in the Oxipres apparatus (www.mikrolab.dk) measuring the pressure over sealed 10 g replica samples of the powders from example 1 -6. This was done under accelerated conditions of pure oxygen at initially 5 bar and 50⁰C. The point in time when the pressure over the samples drastically dropped (Induction Period) was recorded in hours. The IP is seen as a measure of the relative stability of the samples, and corresponds to the time when oxidation in the sample accelerates. Induction Periods for the 6 formulations (ex. 1-6) calculated from the graphs seem in figure 1 were as follows;

For example 1 and 4 with the highest inclusion of deamidated wheat protein a better stability was observed relative to example 2+3 and 5 respectively (not matter the PUFA source or absence/presence of antioxidants). Example 7

The products prepared in examples 1-3 were analyzed for Volatile Organic Compounds after 1 , 3, 6 and 15 weeks of storage (0.2 g powder in a sealed 10 m l vial) at 25⁰C. VOCs were collected and analyzed in a SPME(SoNd Phase Micro Extraction)-GC-Fid setup with the following specifications/settings;

GC: Varian CP3800

GC-column Stabilwax-DA w/integra-guard (crossbond Carbowax-PEG for acidic compounds), 30m, 0.32 mm ID, 0.25 μm df SPME-fiber Carboxen/PDMS, 85 μm, 23-gauge (Supelco 57295-U) Autosample program Incubation of sample: 30 min 80⁰C

Desorb 2 min

Fiber bake out 5 min (300⁰C in bake out station)

GC-program Injector 250⁰C, 50% split during injection (2 min) Column oven 0 min 50°C

2 min 50°C 7 min 70°C 19 min 250⁰C 24 min 250°C Column flow Helium 2 ml/min

Detector FID: 265°C, N₂ makeup flow: 28 ml/min, H₂:

30 ml/min, Air flow: 300ml/min

Figure 2, 3 and 4 show the overlaid chromatograms (week 1 , 3, 6 and 15) for powder/example 1 , 2, 3 respectively.

A development of VOCs is seen over time for all 3 samples. The point in time when the formation of VOCs begins show a good fit to the IP's of the same samples. Powders from example 2 and 3 develop VOCs already between W3-W6 (IP's -37-39 hours) while the example 1 powder only develops VOCs somewhere between W6-W15.

Overall this confirms the high stability of powders with high inclusion of deamidated wheat protein (ex. 1 +4) at both accelerated and ambient conditions.

Claims

1. Method for preparing a product comprising an oxidation labile product having high oxidation stability comprising the steps of: a. Providing a slurry comprising i. An oxidation labile product ii. A film forming protein b. Spray drying the slurry to provide the product.

2. The method of claim 1 , wherein the oxidation labile product comprises a polyunsaturated lipid.

3. The method of claim 1 or 2, wherein the film forming product is a plant protein.

4. The method according to any of the claims 1 -3, wherein the film forming product is deamidated wheat protein.

5. The method according to any of the claims 1-4, wherein the slurry further comprises one or more antioxidants.

6. The method according to any of the claims 1-5, wherein the film forming protein is added in an amount of 10-75% w/w, preferably 20-60% w/w, more preferably 25-50 % w/w based on the total weight of the non-water components of the slurry.

7. A product prepared according to any of the claims 1-4.

8. A food or nutritional product comprising a product of claim 7.