Patent Application
20100112135
The present invention relates to encapsulated or powdered nutritional compositions, and especially to such compositions containing active ingredients. In particular the invention relates to such products encapsulated in a material that is allergen free or at least free from protein ingredients and especially free from dairy components. Allergen free formulations are particularly important for specific nutritional purposes such as consumer groups with diet limitations due to intolerance to certain allergens.
The need of encapsulation of ingredients which are either unstable or incompatible with the product environment or matrix is a demand for successful product innovations within the food industry. Other important issues for such products are related to the bioavailability and control of release of the active ingredient or to the prevention of undesired perception of the active (taste masking).
Novel functionalities of active ingredients in complex food matrices are of increasing importance for innovative product development. Examples of such active ingredients comprise flavours, vitamins, minerals, fatty acids, probiotics and various classes of bioactive components.
In addition, the present invention is particularly exemplified by the use of long chain poly unsaturated fatty acids (LCPUFAs) in powder form in food products, but other actives which may experience one or more of the sketched problems may also be incorporated in the matrix described in detail hereinbelow.
LCPUFAs have a number of unsaturations in their fatty chains. Such compounds are rather sensitive to oxygen and other chemicals that react with unsaturated bonds. The reacted products loose their favourable effects and may give rise to taste and smell problems. Moreover, the storage stability of LCPUFAs is rather restricted.
It is known that the encapsulation of LCPUFA oils can result in a more easy application of such oils in various food products. For instance the use of LCPUFAs (e.g. arachidonic acid (ARA) docosahexaenoic acid (DHA) gamma linolenic acid (GLA)) in infant formula products or, more in general, in various types of food applications, aimed to improve the nutritional value of such products, is nowadays common.
In, for instance, EP-A-1 586 371, it is proposed to use combinations of proteins with modified starch and in particular with starches modified with n-octenylsuccinyl anhydride (NOSA), to render the obtained encapsulate more stable. However, these encapsulates do not fulfil the demands for an acceptable stability or shelf life and for a dairy free label.
EP 1 237 423 teaches a powder matrix (ex oil) with 40-80% NOSA in combination with 10-30% low molecular weight components, such as mono-, di- and trisaccharides, and 10-30% maltodextrin.
Also WO 04/089113 relates to a coating matrix (ex oil) with 5-95% NOSA or other high molecular weight (HMW) film forming carbohydrate in combination with 5-30% low molecular weight components, such as mono-, di- and trisaccharides, and 0-30% maltodextrin.
Further, EP-A2-1 066 761 describes a formulation, which is dealing with storage stability. More in detail, EP-1 066 761 relates to compositions comprising fat soluble substances in a glassy carbohydrate matrix. The fat soluble substances may e.g. be vitamins, carotenoids and PUFA's. The glassy matrix is composed of maltose or maltose syrup, or a mixture of low molecular weight carbohydrates and high molecular weight carbohydrates. It makes use of emulsifiers, which still results in relatively less stable encapsulates. Another disadvantage of formulations using such emulsifiers is the fact that such emulsifiers as ingredients may not be accepted by local regulations for infant formula or follow-up formulas.
In WO 06/081958, modified starch or polysaccharide based matrices containing an LCPUFA loading which are said to contain less than <0.5% (w oil/w powder) free oil, based on 30% oil LCPUFA loading are described.
In addition, it has been proposed in WO 2006/006856 to use mannitol as predominant coating material for sensitive oils such as LCPUFAs, optionally together with allergen free materials such as soy proteins or modified starches such as nOSA starch or Hi-cap.
Examples of encapsulated LCPUFA ingredients, which are suitably designed for nutritional applications, are known, and specific measures to improve the stability of such encapsulates have been undertaken and are described in the prior art. An example of such an encapsulate with improved stability has been described by Augustin in J. Food Science (71) no 2, (2006), E25-E32 and in WO 01/74175. Another example is EP-A-0 648 076, wherein the use of caseinate is described for the production of well protected oil encapsulates.
To overcome the known difficulties with sensitive components such as oxidation sensitive oils, it has further been proposed in the prior art to encapsulate LCPUFAs, or LCPUFA containing compositions, using as the coating materials proteins and/or other components that may give allergic reactions. For example, milk protein may give rise to allergic reactions.
In an attempt to enhance the antioxidative properties matrices consisting of emulsifying agents such as modified starches in combination with mannitol and reducing carbohydrates, when used in powdered nutritional compositions containing sensitive components, it has now been discovered that in addition to the above components a combination of inorganic or organic metal chelators (or more particular inorganic chelators, or even more particular salts of di- or tri- or poly phosphates) and additional low molecular weight (LMW) emulsifier (or more particularly, mono- and diglycerides of fatty acids, or even more particularly, glycerol mono- and distearates, abbreviated as GMS) has an improved effect on the oxidative stability of powders. Particularly, an enhanced oxidative stability of LCPUFA powdered formulations has been found as will be shown in the working examples hereinbelow.
In accordance with a first aspect, the present invention relates to a spray-dried allergen-free or at least protein or dairy free composition comprising:
In a preferred embodiment, the composition according to the invention further comprises one or more antioxidants. Particularly, the composition may comprise at least one antioxidant in the matrix, preferably an ascorbate such as sodium ascorbate. Alternatively or in addition, the composition according to the invention may comprise at least one antioxidant in the oil, preferably being an antioxidant selected from the group consisting of lecithin, citric acid, tocopherol, rosemary extract, green tea extract, ascorbyl palmitate and mixtures thereof.
The presence of a free flowing aid, such as tricalcium phosphate or silicic acid, is additionally preferred.
In a preferred embodiment, the composition according to the invention is in free flowing form, said powder preferentially having a mean particle size of from 20-800, preferably 100-300 μm.
The most preferred embodiments comprise or contain as sensitve component an oxidation sensitive edible oil LCPUFA.
In a second aspect, the present invention relates to a process for preparing a composition as defined in the present description and appending claims, comprising forming an aqueous emulsion comprising the sensitive components, e.g. the edible oil, glucose syrup, mannitol, reducing sugars and especially the emulsifying starch, the low molecular weight emulsifiers and the metal chelator, and spray-drying said emulsion. In a specifically preferred embodiment, the spray drying is carried out using a Filtermat spray drying installation type spray dryer. Such spray dryers use nozzle atomization in a co-current tower that directs the semi-dried particles downward onto a moving belt. The material is then gently conveyed as a porous layer to zones of post-drying and cooling resulting in a crisp cake-like structure that breaks up at the end of the belt.
In a third aspect, the present invention is directed to the use of the composition according the invention in a food product.
Further advantages and embodiments of the present invention are elaborated herein-below.
The compositions of the invention are suitable for use in a food product. The compositions may be consumed themselves, but they are typically incorporated into a food product or a nutritional supplement before consumption.
The compositions according to the invention are preferably in the form of a free-flowing powder. The term “free-flowing powder”, as used herein, is well known to those skilled in the art and includes particulate materials that can be poured (e.g., from one vessel having an opening of from about 10 cm2 to 50 cm2 to another vessel of similar dimensions) without substantial clumping of the particles. In detail, the term “free-flowing” is used for a powdered material that is not sticky, and thus has no or hardly any tendency to agglomerate or to adhere to contact surfaces. The so-called angle of repose, θr, is sometimes used as a measure for the flow properties of powders. The angle of repose is the angle that a cone of powder forms between a flat surface when it is poured onto that surface. Typically, for a free-flowing powder θr is low, e.g. smaller than 60° or smaller than 45°, such as 40° or less.
Such free-flowing powders are sometimes referred to as “dry powders”, although the word “dry” in this context does not necessarily imply the absence of water from the composition. Typically, the powder has a mean particle size of from about 10 μm to about 1000 μm, preferably from about 50 μm to about 800 μm, more preferably from about 90 to 400 μm and most preferably from 100 μm to about 300 μm. Particle sizes can be determined using techniques known to the skilled man, e.g. by using the well-known Coulter Counter. For example, more than 95% by weight of the particles may have a size of less than 800 μm and/or more than 85% by weight of the particles may have a size of less than 500 μm and/or more than 90% by weight of the particles may have a size of greater than 20 μm and/or 65% by weight of the particles may have a size of greater than 200 μm. The powder form of the composition of the invention preferably has a bulk density of from 200 to 600 g/l, such as from 300 to 500 g/l.
The compositions of the invention preferably comprise the edible oil in an amount of from about 10% to about 80% by weight, more preferably from about 20% to about 60% by weight, even more preferably from about 25% to about 35% by weight. The edible oil comprises at least 10% by weight of one or more carboxylic acids containing at least 18 carbon atoms and at least 2 carbon-carbon double bonds, or an ester thereof. The edible oil may comprise the one or more carboxylic acids or esters thereof either as the sole component or as one component of a mixture. The amount of the one or more carboxylic acids or esters thereof in the edible oil is at least 10% by weight of the edible oil, preferably at least 25% by weight, more preferably at least 28% by weight of the edible oil. Other components of the edible oil may include, for example, saturated carboxylic acids having from 12 to 30 carbon atoms, mono-unsaturated carboxylic acids having from 12 to 30 carbon atoms and mixtures thereof, typically as their esters, such as glyceride esters, e.g. triglycerides.
The edible oil is preferably capable of providing health benefits.
The one or more carboxylic acids comprise at least 18 carbon atoms and at least 2 carbon-carbon double bonds. Preferably, the one or more carboxylic acids comprise from 18 to 30 (for example, 18 to 24) carbon atoms and from 2 to 6 carbon-carbon double bonds. The one or more carboxylic acids may be single carboxylic acids or mixtures of two or more carboxylic acids. Each of the one or more carboxylic acids may be in the form of the free acid, an ester or mixtures of free acid and one or more esters. Typically, the one or more carboxylic acids will be in the form of a complex mixture as present in or derived from a natural source. Examples of suitable carboxylic acids are docosahexaenoic acid (DHA), eicosapentaenoic acid (EPA), conjugated linoleic acid (CLA) (including the cis-9, trans-11 and trans-10, cis-12 isomers and mixtures thereof), stearidonic acid, linoleic acid, alpha-linolenic acid (ALA), gamma-linolenic acid (GLA), arachidonic acid (ARA) and mixtures thereof. Preferably, the one or more carboxylic acids are selected from DHA, EPA and mixtures thereof. In a mixture of DHA and EPA, the components can be present at any ratio, but a weight ratio of DHA/EPA of 0.4 to 8.0 may be preferred for certain applications.
The one or more carboxylic acids may be in the form of free acids (including salts thereof, such as sodium salts), or in the form of esters. Suitable esters include esters of the carboxylic acids with aliphatic alcohols containing from one to six carbon atoms, such as ethyl esters. Other suitable esters include esters with alcohols and polyols that are acceptable in food products. Examples of other esters are mono-, di-, and tri-glycerides and mixtures thereof. Triglyceride esters are particularly preferred, typically as the major component (i.e., greater than 50% by weight) together with mono- and/or di-glycerides, for example up to 35% by weight diglycerides and up to 5% by weight monoglycerides.
The term “edible oil” covers oils that are non-toxic and can be consumed as part of a normal diet. The edible oil is typically a liquid at 25° C. and atmospheric pressure and is preferably liquid within the temperature range of 0° C. to 25° C. at atmospheric pressure. The oil is generally hydrophobic (for example it is substantially immiscible with water at a 1:1 weight ratio at 25° C.). The oil is preferably obtained or obtainable from a natural source, such as a vegetable oil, an animal oil (including fish oil) or animal fat, or a microbial oil, but may also be synthetic. The oil may be a mixture of oils from different sources or a mixture of a synthetic oil with one or more oils from natural sources.
It is particularly preferred that the edible oil is fish oil. The fish oil may be directly or indirectly obtainable from fish and may be, for example, a fish oil concentrate, a fractionated fish oil or a modified fish oil. Fish oils include oils from mackerel, trout, herring, tuna, salmon, cod, menhaden, bonito and sardines. Fish oil typically contains a mixture of omega-3 and omega-6 PUFA as their triglycerides, together with other components. In a particularly preferred embodiment, the oil is a fish oil concentrate comprising at least 30% by weight DHA. Alternatively, also oils obtainable from fungi and algae containing high amounts of LCPUFAs may be used.
The oil component of the composition preferably has a peroxide value of less than 10 meq/kg, preferably less than 9 meq/kg, more preferably less than 8 meq/kg, even more preferably less than 7 meq/kg, such as less than 6 or less than 5 meq/kg after storage in contact with air at 30° C. for 12 weeks up to 16 weeks.
Although in a preferred embodiment LCPUFA's are used as the sensitive component, also other active ingredients, which are sensitive to oxidation and/or are not storage stable, may be used. Examples of other sensitive ingredients comprise flavours, vitamins, minerals, fatty acids and unsaturated fatty acids in general carotenoids, probiotics and various classes of bioactive components.
In addition to the oil and emulsifying agents such as modified starches, the matrix is for the largest part composed of carbohydrates. Carbohydrates with a dextrose equivalent DE in the range of 30-50 are preferred. A typical amount of carbohydrates present in the matrix is in the range of 15-85%, more preferably in the range of 30-60%. The carbohydrates may comprise one or more reducing sugars that may be single reducing sugars or mixtures of two or more reducing sugars. Reducing sugars include mono- and di-saccharides such as glucose, fructose and maltose. Additionally, reducing sugars encompass trisaccharides and higher saccharides. Oligosaccharides having up to 50 (mono) saccharide moieties, more preferably having up to 45 saccharide moieties, such as 10-45 saccharide moieties, may also suitably be used. In preferred embodiments, glucose syrups are used, preferably those having 25-55 dextrose equivalents (DE).
Carbohydrates or more specifically, glucose syrups, can be described as a wide range of hydrolysates from starch, which further can be described in terms of their ‘dextrose equivalent’ (DE) value. DE is a measure of the total reducing power of all sugars present relative to glucose as 100 and expressed on a dry weight basis. A indirect method for determination of the DE of a starch hydrolysate is the determination of the saccharide composition of such a product by methods known in the art such as high performance liquid chromatography (HPLC). The DE value can be obtained by calculation from such a total saccharide composition.
Preferably, the one or more reducing sugars are derived from glucose syrup and, accordingly, are a mixture of reducing sugars. Glucose syrup is a starch hydrolysate containing reducing sugars, dextrin and water and typically contains not less than 20% by weight of reducing sugars calculated as glucose. Very good results are obtained while using glucose syrup having a DE of 30-50.
As is already described in WO-A-06/006856, the ratio mannitol/reducing sugar is critical and should be within the indicated ranges
The composition of the invention is preferably dispersible in water having a temperature of about 15° C.
A specifically suitable surface active ingredient to be included as emulsifying starch, are modified starches, such as Hi cap®. Such modified starches can, e.g., be modified by reaction with n-octenylsuccinyl anhydride (NOSA).
Suitable additional low molecular weight emulsifying agents, include for example, low molecular weight emulsifiers, such as specific esters mono- and diglycerides of fatty acids (such as acetic acid esters, lactic acid esters, citric acid esters, tartaric acid esters, or mixed forms of such esters), sucrose esters of fatty acids, or sorbitan esters of fatty acids and lecithin. Generally, LMW emulsifiers have a molecular weight of less than 1.5 kDa, and preferably less than 1 kDa.
As said, suitable metal chelating agents are salts of di- or tri- or polyphosphates, salts of citric acid, malic acid, calcium dinatrium ethylene diamine tetraacetic acid (EDTA), and allergen-free or hypo-allergenic protein hydrolysates or fractions high in phosphoric ester content (e.g. milk fractions rich in phosphate).
The compositions of the invention optionally comprise, in addition to the above components, and for as far as the required allergen free properties are maintained, one or more of an antioxidant, a flavouring agent, a free flowing agent and a colouring agent, which types of additives are well-known additives for the person skilled in the field of preparing spray-dried food-products and/or storage stable unsaturated oil products.
Suitable antioxidants include ascorbic acid and its salts (e.g., sodium salt), citric acid, rosemary or green tea extracts, tocopherols, ascorbyl palmitate, lecithin, and carotenoids. Free flowing agents, which are also termed anti-caking agents, include e.g. tricalcium phosphate. Other optional components include buffering agents such as salts of citrate and/or ortho phosphate.
The compositions of the invention can be produced by a method which comprises forming an aqueous mixture comprising edible oil, glucose syrup and drying the composition. More particularly, the oil and all other ingredients for the powder are emulsified to a dry matter content of generally 50 to 70% (w/w), all other ingredients being dissolved or dispersed in water prior to addition of/in the oil. The best results are obtained when the emulsification is performed in such a way that an average oil droplet diameter of less than 1 micrometer (which droplet size can be determined using for instance a Malvern Mastersizer®). Typically, pre-emulsification is performed at a temperature of 45-65° C. by means of an Ultra Turrax® at 6000 to 10.000 rpm. Subsequently, a two stage high pressure homogeniser can be used (150-250 bar/30-5-bar). Drying is preferably carried out by spray drying.
Conditions for spray drying are known to, or can be readily determined by, those skilled in the art. Spray drying is preferably carried out under conditions such that the resulting powder has a mean particle size of from 20 μm to 800 μm. Suitable results are obtained when the emulsion prepared is fed in a spray dryer by means of a high-pressure pump operating at a pressure of 50 to 200 bar, using a nozzle system for atomisation known to those skilled in the art. The spray dryer operates typically with an inlet temperature of 150-200° C., and an outlet temperature of 60-90° C.
More preferably, to effectively spray dry formulations according to the invention to obtain free flowable powders in good yield, specific spray dry installations are used. Therefore, most preferably, the use of Deck or Filtermat® spray dry installations are used to render the above formulations into free flowing powders with the described powder morphology. Such installations are in general terms similar and known for its mild and versatile drying capabilities. Such types of spray dryer installation can best be described as dryers composed of a section wherein in a first stage the powder is rendered semi-dry (<15% moisture) and dried to the desired final moisture content (typical <5%) in a second stage after the semi dry powder has been collected on a porous moving belt.
The mixture may be prepared by combining the above components, for example by mixing and optionally stirring to form an emulsion. The emulsion is then preferably spray dried to a water content of less than 5% by weight (preferably less than 4% by weight). The particulate material (i.e., powder) thus formed is then collected.
The composition is preferably packaged in the presence of an inert gas (e.g., nitrogen) and is advantageously stored at a temperature below room temperature, for example from about 5° C. to about 10° C., prior to use.
The food products of the invention comprise from 0.01% to 20% by weight, preferably from 0.01% to 10% by weight, more preferably from 0.01% to 5% by weight, of a composition of the invention. The amount of the composition that is present in the food product will depend on the nature of the food product itself. For example, relatively high amounts of the composition may be tolerated in bakery products while smaller amounts are required in certain beverages. Suitable food products include, for example, bakery products (e.g., bread, biscuits or cookies, snack bars), oil-based products (e.g., spreads, salad dressings), dairy products (e.g., milk, reconstitutable milk products, yoghurt, ice cream), and non-dairy beverages (e.g., fruit juice). Food products of the invention typically comprise up to 99% by weight water and up to 50% by weight of oils or fats other than the edible oil derived from the composition of the invention.
The use of the composition according to the invention has been found to increase the oxidative stability of the edible oil, as determined by off taste and/or odour. Additionally or alternatively, the stability of the edible oil may be determined by peroxide value and/or anisidine value.
The following non-limiting examples illustrate the invention and do not limit its scope in any way. In the examples and throughout this specification, all percentages, parts and ratios are by weight unless indicated otherwise.
All publications, patents and patent applications are incorporated herein by reference. While in the foregoing specification this invention has been described in relation to certain preferred embodiments thereof, and many details have been set forth for purposes of illustration, it will be apparent to those skilled in the art that the invention is susceptible to additional embodiments and that certain of the details described herein may be varied considerably without departing from the basic principles of the invention.
The following formulations (Examples 1 to 5) were prepared (values in the table are parts by weight). Examples 1 to 4 are comparative examples. Example 5 is an example of a composition of the invention.
Examples 1 to 5 were prepared by spray drying a mixture comprising the various components. More specifically, Examples 1 to 5 were prepared by emulsification of the oils together with all ingredients at a dry matter content of 50% w/w. Thereto, the ingredients other than oil were dissolved or dispersed prior to the addition of the oil. Pre-emulsification was performed at a temperature of 45° C. to 65° C. by means of an Ultra Turrax at 6,000 to 10,000 rpm. Subsequently, a two stage high pressure homogeniser was used with 200 bar for the first stage and 50 bar for the second stage of homogenisation. The emulsions thus obtained were then fed in to a spray dryer by means of a high-pressure pump operating at a pressure of 150 bar. The spray dryer was operated at an inlet temperature of 180° C. and an outlet temperature of 75° C. The obtained powders were analysed for moisture content: values ranging from 0.5% to 2.5% were found. The powders were free-flowing.
The compositions of Examples 1 to 5 were stored under air at 40° C. for up to 10 weeks. The stability of the compositions before, during and after storage was assessed. Sensory evaluation was carried out by a team of panellists by tasting the powder when reconstituted in milk and in juice. In the sensory tests, a higher number indicates less smell and taste and therefore a better product.
In sensory evaluations I and II, compositions were scored from 5 (neutral: best) to 1 (off-flavour: worst).
The results show that the composition according to the invention (Example 5) containing, besides mannitol, glucose syrup and emulsifying starch, a metal scavenger (Sodium poly phosphate), Sodium ascorbate and the low molecular weight emulsifier glycerol mono- and diglycerides of fatty acids (GMS), showed superior performance compared to the other compositions missing one of these components.
When the composition according to the invention (Example 5) is compared with the same composition without a metal scavenger (Example 2) the positive influence of a metal scavenger is illustrated.
Comparing Example 1 (without a low molecular weight emulsifier) with Example 2 containing GMS shows that GMS has a beneficial influence on the stability of the powder.
Examples 2, 3 and 4 have different anti-oxidant compositions. The composition with sodium ascorbate performs best.
The following formulations (Examples 6 to 8) were prepared (values in the table are parts by weight). The examples show the influence of the presence of an anti-oxidative agent and the influence of oil load.
Examples 6 to 8 were processed in the same way as Examples 1 to 5.
The powders of Examples 6 to 8 were stored under air at 40° C. for up to 11 weeks. The stability of the compositions before, during and after storage was assessed. Sensory evaluation was carried out by a team of panellists by tasting the powder when reconstituted in milk and in juice. In the sensory tests, a higher number indicates less smell and taste and therefore a better product.
The results show that adding an anti-oxidant (sodium ascorbate) (Example 6 compared to Example 7) improves oxidation stability. The composition containing a lower amount of oil (Example 6) performed better than the composition containing a higher amount of oil (Example 8).
| Number | Date | Country | Kind |
|---|---|---|---|
| 07104057.0 | Mar 2007 | EP | regional |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/NL2008/050143 | 3/12/2008 | WO | 00 | 11/9/2009 |
