WO2008037578A1 - Composés, qui sont des particules contenant de l'amidon revêtues, intégrées ou encapsulées dans au moins un biopolymère dans un arrangement multicouche - Google Patents

Composés, qui sont des particules contenant de l'amidon revêtues, intégrées ou encapsulées dans au moins un biopolymère dans un arrangement multicouche Download PDF

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Publication number
WO2008037578A1
WO2008037578A1 PCT/EP2007/059329 EP2007059329W WO2008037578A1 WO 2008037578 A1 WO2008037578 A1 WO 2008037578A1 EP 2007059329 W EP2007059329 W EP 2007059329W WO 2008037578 A1 WO2008037578 A1 WO 2008037578A1
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Prior art keywords
biopolymer
solution
starch
compounds
compounds according
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PCT/EP2007/059329
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English (en)
Inventor
Michael Francis Butler
Emmanuel Heinrich
Stive Pregent
Phillippa Rayment
Peter Conrad Schuetz
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Unilever Plc
Unilever N.V.
Hindustan Unilever Limited
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Publication of WO2008037578A1 publication Critical patent/WO2008037578A1/fr

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    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
    • A23L29/20—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents
    • A23L29/206—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents of vegetable origin
    • A23L29/256—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents of vegetable origin from seaweeds, e.g. alginates, agar or carrageenan
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
    • A23L29/20—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents
    • A23L29/206—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents of vegetable origin
    • A23L29/212—Starch; Modified starch; Starch derivatives, e.g. esters or ethers
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23P—SHAPING OR WORKING OF FOODSTUFFS, NOT FULLY COVERED BY A SINGLE OTHER SUBCLASS
    • A23P10/00—Shaping or working of foodstuffs characterised by the products
    • A23P10/30—Encapsulation of particles, e.g. foodstuff additives
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23P—SHAPING OR WORKING OF FOODSTUFFS, NOT FULLY COVERED BY A SINGLE OTHER SUBCLASS
    • A23P20/00—Coating of foodstuffs; Coatings therefor; Making laminated, multi-layered, stuffed or hollow foodstuffs
    • A23P20/10—Coating with edible coatings, e.g. with oils or fats
    • A23P20/15—Apparatus or processes for coating with liquid or semi-liquid products
    • A23P20/17—Apparatus or processes for coating with liquid or semi-liquid products by dipping in a bath
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs

Definitions

  • the present invention relates to compounds, which are starch containing particles coated, embedded or encapsulated by a biopolymer or a mixture of biopolymers in a multilayer arrangement, as well as to its production and, as well as to the use of these compounds in food products.
  • Starches as carbohydrates are the preferred energy source for the body. Starches occur naturally in vegetables and grains During digestion starches are broken down into glucose, which provides essential energy for brain, central nervous system and for muscles during activity. Starches are one prime source of energy. The other source are sugars. Carbohydrates are far easier to break down in the digestive tract (producing less metabolic waste products) than either fat or protein and as a result the body's reserves of carbohydrate energy (stored in the blood, liver and muscles) are utilised first and are rapidly depleted during exercise. If these carbohydrates are not converted to energy, they are mostly converted and stored as fat, with a small amount stored as glycogen in the liver and muscles. When the body calls for more fuel (such as during exercise), the fat or glycogen is converted back to glucose and used accordingly.
  • the digestibility of starch be slowed to provide a controlled and/or steady release of glucose to the body over a period of several hours. Contrarily to the transit time of a meal in the stomach that can vary mainly in function of the type and quantity of food ingested, the transit time in the small intestine where most of carbohydrate digestion occurs is in average of 2 hours roughly before large intestine is reached. Therefore it is desirable that starch hydrolysis happens in a controlled and gradual way in the small intestine so that sustained energy can be delivered to the body. Additionally, the starch digestion should be complete or close to complete after 2 hours transit in the small intestine in order to minimise the quantity of undigested starch entering into the colon.
  • the slow release should work in any kind of food product in which these compounds according to the present invention are incorporated in.
  • the food products can be food for humans (human food product) as well as for animals.
  • the food product, which contains the compounds according to the present invention can have any physical form, which is common for food products.
  • the food product can be solid or liquid, soft or hard, gel-like, frozen, cooked, boiled, pasteurised, unpasteurised, etc.
  • the compounds according to the present invention must be incorporated into the food products without being destroyed.
  • the compounds according to the present invention which are starch containing particles coated, embedded or encapsulated by at least one biopolymer are incorporated into food products, especially in food for humans, then it is desirable that these compounds can not be detected in mouth during the consumption.
  • the mouthfeel of the food product is a very important criteria.
  • the mouthfeel also depends on the softness of the compounds as well as on the format of food product wherein the compounds are to be incorporated in.
  • the term compound means the coated, embedded or encapsulated product.
  • starch containing particle means the particle, which is not (yet) coated, embedded or encapsulated.
  • Compounds according to the present invention are starch containing particles, which are coated, embedded, encapsulated by at least one biopolymer. Starches are not part of the coating, embedding or encapsulating layer. That means that the biopolymer are no starches or do not comprise starches.
  • the compounds as well as the starch containing particle can have any physical form. Usually the starch containing particles are solid or liquid. The starch could also be crystallised.
  • the preferred form of the starch containing particle is the solid and crystallised form.
  • the starch containing particles can have any shape, such as spheres, tubes, fibres, as well as ill- defined forms. The same applies for the compounds.
  • the compounds according to the present invention are usually solid, gel or in a liquid form. Preferably they are solid or gel-like.
  • the compounds can have any shape, such as spheres, tubes, fibres, as well as ill-defined forms.
  • starch containing particles means particles which are made out of starch material, but which can comprise further non-starch material. These materials are not carbohydrates. This means that the term “starch containing particles” covers particles, which are pure starch or mixtures of different starches as well as starch (or mixture of starches) mixed with other non- carbohydrate compounds. The particles do not comprise any sugar compounds.
  • coated, embedded or encapsulated particles are either compounds wherein the starches are concentrated in the core of the particle (coated, encapsulated) or they are starch particles dispersed in a matrix of biopolymeric material (embedded).
  • coated and encapsulated starch containing particles we defined compounds wherein the starch(es) (or starch mixed with other ingredients) is located in the middle (core) of the compound and it is coated or encapsulated by at least one biopolymer. The starch is not part of the coating or the encapsulating material and vice versa the biopolymer is not part of the core.
  • embedded starch containing particles we defined compounds wherein the starch(es) (or starch mixed with other ingredients) are dispersed, so that the starches are always concentrated at certain spots in the matrix. In the sense of the present invention the starches are not part of the matrix and vice versa the biopolymer is not part of the starch.
  • the compounds according to the present invention are starch containing particles coated, embedded or encapsulated by at least one biopolymer, wherein the starch containing particles can optionally comprise at least one non carbohydrate compounds and wherein the biopolymer is no starch or do not contain starch.
  • the compounds according to the present invention can contain starch, which is from natural or synthetic origin. Of course in case that the starch comes from a natural source there are always other compounds present. But it is also possible to mix the starch with other useful compounds, which are not harmful to the animal or human body. Such compounds could be for example proteins, peptides, vitamins, probiotics, etc.
  • starch containing particles falls pure starch as such well as starch mixed with other compounds.
  • the starch can be raw starches, modified starches, and pregelatinized starches. Preferred are raw and modified starches are preferred.
  • the compounds do not coat, embed or capsulate the particles in a permanent way. That means the resulting compounds release the starch during time as already stated above. This release happens inside the human or animal body after the intake of the compounds according to the present invention.
  • the compounds according to the present invention can be described as sponge-like compounds. Therefore the compounds according to the present invention have pores, which are about between 50nm and 100nm.
  • the pores sizes can be measured by Transmission Electron Microscopy (TEM). The following procedure has been used to determine the pore sizes. To enhance fixation, the beads were cut in half and then placed in 0.1 % ruthenium tetroxide for 90 minutes. The beads were then rinsed using distilled water for 20 minutes and this was repeated. The beads were then stained in 1% aq. uranyl acetate overnight. The beads were dehydrated in ethanol and infiltrated with epoxy resin, which was polymerised at 6O 0 C for 48 hours. Sections of approximately 10Onm thickness were prepared and stained in lead citrate. The sections were then examined in Jeol 1200 TEM at 100KV.
  • the size of the starch containing particles can be a few microns as well as a few millimetres.
  • the size of the starch containing particles is less than 1000 microns. Usually their size is between 5 and 1000 microns, preferably between 10 and 800 microns, more preferably between 20 and 500 microns.
  • the size of the compounds according to the present invention can be a few microns as well as a few millimetres.
  • the size of the compounds according to the present invention is less than 1000 microns. Usually it is between 5 and 1000 microns, preferably between 10 and 800 microns, more preferably between 20 and 500 microns.
  • a compound is always larger than the corresponding starch containing particle.
  • the starch containing particles are embedded by at least one biopolymer the compounds is usually much larger than the starch containing particles, which are embedded therein.
  • the compounds as well as the starch containing particles can have any form. They can be a bead, a sphere, a fibre, or any other form. When these coated embedded particles are used it is obvious that mixture of several forms can be used.
  • the biopolymer can be any biopolymer which is able to coat, embed or encapsulate starch containing particles. Additionally, because the compounds according to the present invention are incorporated into food products, the biopolymer should be not harmful to humans and animals.
  • the biopolymer is no starch or does not comprise starch.
  • Preferred biopolymers are physically (such as ionically) and/or covalently crosslinkable polysaccharides.
  • More preferred biopolymers are physically and/or covalently crosslinkable polysaccharides which are ⁇ -linked polysaccharides.
  • Such crosslinkable polysaccharide includes food hydrocolloids such as agarose, chitin, carrageenan, pectins, amidated pectines, xanthan, alginates, gum arabic, galactomannans like locust bean gum, guar and tara gum, and cellulosics like carboxymethylcellulose, methylcellulose, hydroxypropylcellulose and methylhydroxypropylcellulose as well as gellans, ispaghula, ⁇ -glucans, konjacglucomannan, gum tragacanth, detarium and tamarind.
  • food hydrocolloids such as agarose, chitin, carrageenan, pectins, amidated pectines, xanthan, alginates, gum arabic, galactomannans like locust bean gum, guar and tara gum
  • cellulosics like carboxymethylcellulose, methylcellulose, hydroxypropylcellulose and methylhydroxypropylcellulose as well as gellan
  • chitosan is a linear polysaccharide composed of randomly distributed ⁇ -(1-4)-linked D-glucosamine (deacetylated unit) and N-acetyl-D-glucosamine (acetylated unit).
  • Chitosan is produced commercially by deacetylation of chitin (can be produced from chitin also), which is the structural element in the exoskeleton of crustaceans (crabs, shrimp, etc.).
  • the degree of deacetylation (%DA) can be determined by NMR spectroscopy, and the %DA in commercial chitosans is in the range 60-100 %
  • alginates The most preferred physically and/or covalently crosslinkable and ⁇ -linked polysaccharide are alginates.
  • alginate is a linear copolymer with homopolymeric blocks of (1-4)-linked ⁇ -D- mannuronate (M) and its C-5 epimer ⁇ -L-guluronate (G) residues, respectively, covalently linked together in different sequences or blocks.
  • M ⁇ -D- mannuronate
  • G C-5 epimer
  • the ratio of the different blocks can differ widely.
  • the relative amount of each block type varies both with the origin of the alginate.
  • Preferred are alginates with a M:G ratio of 80:20 to 20:80. Alginates are commercially available.
  • the starch containing particle is coated, embedded or encapsulated by a multilayer arrangement, wherein the biopolymers have opposite charges in each layer.
  • the first layer is built up by a biopolymer (or a mixture of biopolymers) which has mainly negative charges and the following layer is built up by a biopolymer (or a mixture of biopolymers) which has mainly positive charges and so on.
  • the first layer has preferably the opposite charge than the starch containing particle.
  • the first layer is a negative charged biopolymer.
  • Negative charged biopolymers are generally understood to mean biopolymers having ionically dissociable groups which may be a component or substituent of the polymer chain.
  • the number of these ionically dissociable groups in the biopolymers is usually large enough to ensure the water- solubility of the polymers in a dissociated form (also referred to as polyions).
  • biopolymer as used herein also refers to ionomers in which the concentration of the ionic groups is not sufficient to make them water soluble but they have sufficient charges for a self-assembly.
  • Negative charged biopolymers which can be inorganic as well as organic polymers can be formed from polyacids when they dissociate with cleavage of protons.
  • Suitable biopolymers include naturally occurring polyanions and as well as synthetic modified polyanions.
  • naturally occurring polyanions are alginate, carboxymethylamylose, carboxymethylcellulose, carboxymethyldextran, carageenan, cellulose sulfate, chrondroitin sulfate, chitosan sulfate, dextran sulfate, gum arabic, guar gum, gellan gum, heparin, hyaluronic acid, pectin, amidated pectines, xanthan and proteins at an appropriate pH.
  • Suitable positive charged biopolymers include naturally occurring polycations and synthetic modified polycations.
  • suitable naturally occurring polycations are chitosan, modified dextrans, e.g. diethylaminoethyl-modified dextrans, hydroxymethylcellulose trimethylamine, lysozyme, polylysine, protamine sulfate, hydroxyethylcellulose trimethylamine and proteins at appropriate pH values.
  • Linear or branched biopolymers can be used.
  • the use of branched biopolymers leads to less compact polyelectrolyte multifilms having a higher degree of wall porosity.
  • the capsule stability can be increased by cross-linking the biopolymers within or/and between the individual layers.
  • the biopolymer is usually present in the form of a gel, where gel comprises 0.5 - 20 wt-% of at least one biopolymer and 80 - 99.5 wt-% of water.
  • the weight percentages are based on the total weight of the biopolymer gel.
  • the gel comprises 0.5 - 15 wt-%, more preferred 0.5 - 10 wt-%, especially preferred 1 - 10 wt-%, very especially preferred 1 - 5 wt-% of at least one biopolymer.
  • the weight percentages are based on the total weight of the biopolymer gel.
  • the water content is preferably 85 - 99.5 wt-%, more preferred 90 - 99.5 wt-%, especially preferred 90 - 99 wt-%, very especially preferred 95 - 99 wt-% of water.
  • the weight percentages are based on the total weight of the biopolymer gel.
  • the content of starch in the compounds, which are starch containing particles coated, embedded or encapsulated by at least one biopolymer is 0.1 - 20 wt-%, based on the total weight of the compounds.
  • the content of starch is 0.5 - 15 wt-%, more preferably, 0.5 - 10 wt-% equally preferred 1 - 15 wt-%, especially preferred 1 - 10 wt-%, based on the total weight of the compounds.
  • a preferred embodiment relates to compounds, which are starch containing particles firstly coated, embedded or encapsulated with alginate and secondly coated, embedded or encapsulated with a positive charged biopolymer.
  • more layers may be added, wherein the third layer is built up by a negative charged biopolymer, the fourth one by a positive charged biopolymer and so on.
  • a more preferred embodiment relates to compounds, which are starch containing particles firstly coated, embedded or encapsulated with alginate and secondly coated, embedded or encapsulated with chitosan, modified dextrans, e.g. diethylaminoethyl-modified dextrans, hydroxymethylcellulose trimethylamine, lysozyme, polylysine, protamine sulfate, hydroxyethylcellulose trimethylamine or proteins at appropriate pH values, as well as a mixture of these biopolymers.
  • modified dextrans e.g. diethylaminoethyl-modified dextrans
  • hydroxymethylcellulose trimethylamine lysozyme
  • polylysine polylysine
  • protamine sulfate hydroxyethylcellulose trimethylamine or proteins at appropriate pH values
  • hydroxyethylcellulose trimethylamine or proteins at appropriate pH values
  • An especially preferred embodiment relates to compounds, which are starch containing particles firstly coated, embedded or encapsulated with alginate and secondly coated, embedded or encapsulated with chitosan.
  • the third layer is built up by a negative charged biopolymer, the fourth one by a positive charged biopolymer and so on.
  • the compounds, which are starch containing particle can be coated, embedded or encapsulated.
  • the first layer can therefore be the coating (or encapsulation) of discrete starch containing particles or starch containing particles which are embedded in the biopolymer of the first layer. In such a matrix the starch particles are randomly distributed.
  • Such embodiments discrete coated or embedded particles are then coated, embedded or encapsulated by the second layer.
  • the process of production of the compounds, which are starch containing particles which are coated, embedded or encapsulated by a biopolymer or a mixture of biopolymers can be done according to well known processes, such as extrusion processes or emulsion processes. It is possible that the different layers are built up by using different processes.
  • a suitable generic process for multilayer compounds according to the present invention is the following:
  • the first layer which may or may not be part of the described process, is the dispersion of starch containing particles (CCP) in a semi-concentrated biopolymer matrix / solution followed by break up into individual entities (extrusion / emulsification).
  • CCP starch containing particles
  • the template material i.e. the untreated CCPs or the entities formed as described in 1.
  • the template material are then immersed in a dilute solution of a charged biopolymer that may or may not contain other electrolytes. This biopolymer solution then interacts with the added template and forms an additional barrier layer.
  • the process described in 2. can be repeated to add consecutive barrier layers that can further change the overall barrier functionality.
  • the process can be summarized as the build-up of multiple barrier layers around CCPs by repeated interactions of a template material with different charged biopolymers from dilute solutions possibly combined with embedding the template or CCPs in a biopolymer matrix that may be modified using further reactants.
  • the present invention relates to a process of production of compounds, which are starch containing particles coated, embedded or encapsulated by a biopolymer or a mixture of biopolymers wherein
  • the starch containing particles are coated, embedded or encapsulated with a first layer of at least one biopolymer and then (ii) coated, embedded or encapsulated with a second layer of at least one biopolymer of the opposite charge than the first layer, (iii) and optionally repeat the steps (i) and (ii).
  • biopolymers When a mixture of biopolymer is used then preferably the biopolymers should have the same charge.
  • a specific method how to produce a multilayer arrangement in one step is the following: Starch is dispersed in a solution of polyanion biopolymer (such as alginate). This solution is extruded drop wise through a syringe into a solution of polycation biopolymer (such as chitosan). Beads with a liquid core of polyanion biopolymer (such as alginate) -starch solution, and coated with a polyanion-polycation (such as chitosan-alginate) complex shell, are formed.
  • polyanion biopolymer such as alginate
  • polycation biopolymer such as chitosan
  • polycation biopolymer such as chitosan
  • polyanion biopolymer such as alginate
  • a further embodiment of the present invention relates to a process for the production of compounds, which are starch containing particles coated, embedded or encapsulated by a biopolymer or a mixture of biopolymers in a two-layer arrangement, wherein (i) the starch containing particle is dispersed in a solution comprising at least one polyanion biopolymer, and (ii) this solution is extruded drop wise into a solution comprising at least one polycation biopolymer.
  • the compounds obtained by that process can be further coated, embedded or encapsulated by biopolymers.
  • a further embodiment of the present invention relates to a process for the production of compounds, which are starch containing particles coated, embedded or encapsulated by a biopolymer or a mixture of biopolymers in a two-layer arrangement, wherein (i) the starch containing particle is dispersed in a solution comprising at least one polycation biopolymer, and (ii) this solution is extruded drop wise into a solution comprising at least one polyanion biopolymer.
  • the compounds obtained by that process can be further coated, embedded or encapsulated by biopolymers.
  • a further embodiment of the present invention relates to a process for the production compounds , which are starch containing particles coated, embedded or encapsulated by a biopolymer or a mixture of biopolymers in a two-layer arrangement, wherein
  • the starch containing particle is dispersed in a solution comprising at least one polyanion biopolymer
  • this solution is extruded drop wise into a solution comprising at least one polycation biopolymer and Ca 2+ cations.
  • the compounds obtained by that process can be further coated, embedded or encapsulated by biopolymers.
  • a further embodiment of the present invention relates to a process for the production of compounds , which are starch containing particles coated, embedded or encapsulated by a biopolymer or a mixture of biopolymers in a two-layer arrangement, wherein
  • the starch containing particle is dispersed in a solution comprising at least one polycation biopolymer
  • this solution is extruded drop wise into a solution comprising at least one polyanion biopolymer and Ca 2+ cations.
  • the compounds obtained by that process can be further coated, embedded or encapsulated by biopolymers.
  • the reaction can also comprise a posthardening step.
  • a posthardening step is carried out in a Ca 2+ solution after the coating, embedding or encapsulating process.
  • the duration of the posthardening step can vary a lot. Such a process can be carried within minutes or it can be carried out during several hours. In some cases the posthardening process can be continued when the end product is stored (or sold) in a Ca 2+ solution.
  • the posthardening reaction solution can also contain in addition to (or as a replacement of) Ca 2+ other alkaline-earth metals.
  • the Ca 2+ can be added in form of any soluble salt.
  • the counterion of the Ca 2+ salt does not affect the posthardening step, therefore the choice of a Ca 2+ salt is not dependent on the counterion.
  • Suitable Ca 2+ salts are for example CaCI 2 , CaSO 4 . It is also possible to use salt which are usually hardly soluble or even insoluble in water, but when using a low pH they become soluble. An example for such a salt is CaCO 3 .
  • the compounds according to the present invention are incorporated into food products.
  • Food products for animals as well as humans can be provided.
  • Preferably food products for humans are provided.
  • the compounds obtained by the inventive process are very stable so they can be used in any food product which needs to have starch in it.
  • the term food products covers any kind of drinks or other liquid food product, snacks, candies and confections, dessert mixes, granola bars, energy bars, various beverages, shelf stable powders, ready to eat foods such as puddings, frozen yogurts, ice creams, frozen novelties; cereals, snacks, meal replacements, baked goods, pasta products, confections, military rations, specially formulated foods for children, and specialized gastric enteral feeding formulations.
  • the food product can be treated with any usually used food technology process like cooking, baking, freezing, pasterizing, etc. without destroying the compounds obtained by the inventive process.
  • the active component is encapsulated by the method of the subject invention, the resulting coated compounds are relatively inert and bland in both aroma and taste. This allows the compounds of the subject invention to be incorporated in the disclosed foods without affecting the characteristic properties and flavours of the food.
  • WO 2005/020717 examples 1 , 2 and 3
  • WO 2005/020718 examples 1 and 2
  • WO 2005/020719 examples 1 , 2 and 3
  • suitable food forms can be found, wherein the particles obtained by the process according to the present invention can be put in.
  • Fig. 1 Confocal scanning light microscopy images of shrunken chitosan-alginate encapsulates containing entrapped rice starch granules (staining with acridine orange for 3 days); initial water phase for making the plain calcium-alginate beads contained 2% alginate and 5% starch.
  • Fig. 2 Starch hydrolysis kinetic curves for rice starch granules entrapped in chitosan- alginate encapsulates, plain Ca-alginate beads and non encapsulated rice starch (in-vitro test data); initial water phase in the emulsion method contained 2% alginate and 5% starch; pretreatment in temperature before hydrolysis assay: 15 min at 75°C.
  • Fig. 3 TEM image of the perimeter of a sliced gel bead. The dense biopolymer multilayer film at the perimeter is clearly visible between the arrows.
  • Fig. 4 Glucose release curve comparing the digestion of multilayer coated and uncoated calcium alginate beads containing rice starch granules.
  • Fig. 5 CLSM image of multilayer coated agar beads.
  • the alginate used for the last layer is labelled with fluorescein.
  • Fig. 6 TEM and CLSM microscopy images of starch granules coated with chitosan / alginate multilayer films (left TEM of rice starch; right CLSM of potato starch, fluorescently labelled alginate was used for the film build-up).
  • Fig. 7 Glucose release as a function of time for digestion of starch, starch encapsulated in beads with a liquid core, starch encapsulated in beads with a gelled core.
  • a 1-2% alginate solution (Sigma-Aldrich no. A-7128: alginic acid sodium salt, high mannuronic acid content) containing 1 to 10% rice starch granules (Remy DR, ex. Remy,
  • a 1 M solution of calcium chloride was then added quickly along the side of the beaker to reach a final calcium ions concentration of 0.1 M in the aqueous phase.
  • the break-up of the water-in-oil emulsion was obtained as the alginate fine droplets start to gel.
  • the oil was removed by repetitive washing of the gel beads on a filter with a 0.1 M CaC ⁇ solution or pure water.
  • the 'plain' calcium-alginate microspheres were finally stored overnight in a 0.1 M CaCb solution at refrigerated temperature (hardening phase).
  • the plain alginate beads were coated with chitosan.
  • the coating was achieved by incubating the alginate beads into a 1.5% solution of chitosan having a degree of deacetylation of 91% (ChitoClear, ex. Primex, Norway).
  • the chitosan solution was prepared by first hydrating the chitosan powder in acidified deionised water using 0.5% glacial acetic acid (Sigma-Aldrich no. 537020). After adjusting the pH to 5.5, the solution was stirred during 5 hours at 60 0 C to achieve maximal swelling of the chitosan. Then the chitosan solution was filtered (0.45 micron pore size filter).
  • the coating of the alginate beads with chitosan was performed by immersing 15g of plain Ca-alginate beads into 100 ml of the chitosan solution. The suspension of encapsulates was gently agitated during
  • the hydrolysis rate of encapsulated starch was evaluated by means of an in-vitro test using alpha-amylase enzyme.
  • Pipes buffer piperazine-1 ,4-bis(2-ethanesulfonic acid), ex. Acros Organics
  • the alginate beads were shrunken from 480 micron down to 200 micron as measured by small angle light scattering.
  • the resulting shape of the chitosan-alginate encapsulates is rather ill-defined and certainly no longer spherical.
  • the starch granules became much more closely packed after the shrinking of the encapsulates.
  • the better compaction of the starch granules and/or the presence of the semi-permeable membrane of chitosan-alginate complex at the outer of the encapsulates did lead to a further delay / control in the hydrolysis of the entrapped starch as can be seen at the Fig. 2 (by comparison to the case of the plain alginate beads).
  • Tablei Encapsulate stability performance in presence of salts and under gentle stirring; performance of chitosan-alginate particles versus plain calcium- alginate beads.
  • Calcium/alginate gel beads are prepared using an emulsion method. 396 g sunflower oil and 4g Admul WoI (non-ionic surfactant, Quest) was mixed well with an overhead stirrer. Then a solution of 4g alginate and 2g rice starch in 150ml of water was added under mixing. A CaCI 2 solution 2Og in 50 ml water was added to the mixture and stirred for another 2h. To separate and clean the beads, the mixture was centrifuged and the supernatant oil was removed. The beads were then twice re- suspended in 11 of an aqueous solution containing 1% Tween 60 and 20 g CaCI 2 using high speed Silverson mixer with a high shear cage.
  • Admul WoI non-ionic surfactant
  • the excess chitosan was removed by three washing steps that consisted of centrifugation of the sample followed by re-dispersion in water (or an appropriate salt solution).
  • the resulting dispersion was agitated for 5 to 15 min to prevent sedimentation and aggregation.
  • the excess alginate was removed by tree washing steps that consisted of centrifugation of the sample followed by re-dispersion in water (or a appropriate salt solution).
  • TEM images revealed a ca. 50 nm thick dense film at the perimeter of the sliced gel beads.
  • the digestibility of the encapsulated starch was determined as maltose release over time using a digestion assay.
  • a defined volume of coated gel beads was put into a suitable mixture of amylase (Sigma No A6255), PBS buffer and Amyloglucosidase (sigma, starch assay reagent SA-20).
  • An electrochemical microdialysis glucose sensor (Sycopel, Jarrow, UK) sensor was used to monitor the release of glucose from the treated beads and from a control of untreated beads.
  • Fig. 4 shows that the release from the coated beads is much lower and doesn't reach a saturation level after 1500 min.
  • Spherical gelled agar beads were made via a water-in-oil emulsion route.
  • Biopolymer solutions were prepared by dissolving agar (Luxara 1253, ArthurBranwell) in deionised water at 98°C at concentrations ranging from 0.5 to 5 wt-%. The solution was then cooled to 85°C.
  • a water-in-oil emulsion was formed by adding the biopolymer solution to oil containing 1 wt % surfactant (Admul WOL, Quest) at 85 0 C. The mixture was then stirred rapidly using a Silverson SLR4 at 85°C for 30 minutes to allow an equilibrium particle size to develop. The stirring speed was varied to control the average particle size obtained.
  • the emulsion was then quenched by placing in an iced water bath to allow the aqueous phase to gel, stirring at a slower speed was continued for a further 2 hours to prevent aggregation and coalescence.
  • the spherical particles produced were then separated from the oil phase by centrifugation, followed by several washes with deionised water to remove residual oil and surfactant. Microgel suspensions were then made by re-dispersing the particles in deionised water.
  • Gelled agar beads with diameters around 50 ⁇ m are obtained and dispersed in water at a concentration of up to 10 weight %.
  • a 10 fold excess of chitosan solution (0.05% wt , 0.2 M sodium chloride, pH 6.0) was added and the resulting dispersion was stirred for 10 minutes. Then the supernatant was removed by filtration through a 5 ⁇ m mesh. Fresh water was added 3 times just before the filter residue was about to get dry to wash off any not interacting material.
  • Alginate solution (0.05% wt , 0.2 M sodium chloride, pH 6.0) was then added in a similar fashion followed by washing as described above. The whole process described above was then repeated until the desired thickness of the multilayer film was obtained.
  • a solution of fluorescently labelled alginate was used. As seen in Fig. 5, confocal scanning laser microscopy revealed, that the surface of the beads was successfully coated.
  • the coated beads were heated to 80 0 C in a water bath alongside a control sample of uncoated beads. As this temperature is above the gellation temperature of agar, the uncoated beads dissolved completely. In contrast to this after re-cooling and thus re-gelling of the core matrix, the coated beads could be recovered unchanged.
  • Starch granules (rice, potato and wheat starch) were coated by alternative adsorption of the biopoymers chitosan (Primex, Chitoclear) (polycationic) and alginate (DMB manugel) (polyanionic).
  • the pH values of the biopolymer solution were both adjusted to pH 6.
  • the protocol for the multilayer coating sequence was the following:
  • Steps 4 and 5 were repeated another 2 times to remove all not adsorbed biopolymer from the system.
  • Steps 4 and 5 were repeated another 2 times to remove all not adsorbed biopolymer from the system.
  • Steps 3 to 10 were repeated until the desired number of layers (typically 8 layers) was reached.
  • calcium chloride (6.82mM) is added to the chitosan solution in order to get a gelled core.
  • the beads prepared were approximately 3.5mm in size for the liquid core ones and 2mm for the gelled one.
  • the digestability of the starch was determining using an enzymatic digestion assay. Stock solutions were used to prepare the reagent mix:
  • Amylase from aspergillus oryzae 150-250 units/mg, Sigma-Aldrich
  • 0.04 mg/mL 8 units/mL, ca. 710 nM assuming a Mw of 56000
  • Amyloglucosidase from aspergillus niger in solution 50 units/mL, Sigma-Aldrich: SA-20
  • Glucose oxidase (GOD, 12.5 units/mL, aspergillus niger) and peroxidase (POD, 2.5 units/mL, horseradish) as glucose oxidase / peroxidase reagent from Sigma-Aldrich (G3660) 2,2'-Azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt 50mg/ml_ solution (ABTS, 9OmM, Fluka).
  • the reagent is prepared by mixing 4 ml. of the GOD/POD solution, 480 ⁇ l_ of ABTS solution, 200 ⁇ l_ of amyloglucosidase solution and 200 ⁇ L of amylase with 4 ml. of deionised water.
  • 0.8 ml. of this reagent is the diluted with 3.2 ml. of water in a vial.
  • One bead is placed in the vials and UV scans in the range of 400 to 600 nm are taken at regular intervals.
  • Vials containing 12.5 ⁇ L of a 5% starch solution are used as control, as 12.5 ⁇ L is the average volume of alginate/starch solution used to make one bead. For each system, the experiment is repeated 3 times. The release of glucose is shown in Figure 7.
  • the chitosan/alginate coating of the beads slows down the digestability of the starch and gelation of the core slows it down further.

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  • Engineering & Computer Science (AREA)
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Abstract

La présente invention concerne des composés, qui sont des particules contenant de l'amidon, revêtues, intégrées ou encapsulées dans un biopolymère ou un mélange de biopolymères dans un arrangement multicouche ; l'invention concerne également la fabrication de ces particules ainsi que leur utilisation dans des produits alimentaires.
PCT/EP2007/059329 2006-09-29 2007-09-06 Composés, qui sont des particules contenant de l'amidon revêtues, intégrées ou encapsulées dans au moins un biopolymère dans un arrangement multicouche WO2008037578A1 (fr)

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WO2010086235A1 (fr) * 2009-01-30 2010-08-05 Unilever Plc Émulsions d'huile dans l'eau
WO2011004375A1 (fr) 2009-07-09 2011-01-13 Rubin, Israel Compositions probiotiques résistant à la chaleur et aliments sains les comprenant
US9808017B2 (en) 2011-02-25 2017-11-07 Kraft Foods R&D, Inc. Food product with a moulded body
CN109180996A (zh) * 2018-07-25 2019-01-11 佛山皖阳生物科技有限公司 一种淀粉基多孔微球的制备方法
US10470488B2 (en) 2011-09-09 2019-11-12 Philip Morris Products S.A. Smoking article comprising a flavour delivery material
US10543175B1 (en) 2013-05-17 2020-01-28 Degama Berrier Ltd. Film composition and methods for producing the same
FR3102913A1 (fr) * 2019-11-07 2021-05-14 Huddle Corp Aliment ou complément alimentaire pour animaux d’élevage
US11039637B2 (en) 2010-12-06 2021-06-22 Degama Berrier Ltd. Composition and method for improving stability and extending shelf life of probiotic bacteria and food products thereof
WO2021126548A1 (fr) * 2019-12-16 2021-06-24 Cooper Tire & Rubber Company Amidon revêtu de silice

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US9961910B2 (en) 2007-11-26 2018-05-08 DeGama Products, Ltd Process for preparing bakeable probiotic food
WO2010086235A1 (fr) * 2009-01-30 2010-08-05 Unilever Plc Émulsions d'huile dans l'eau
US8187583B2 (en) 2009-01-30 2012-05-29 Conopco, Inc. Oil-in-water emulsions
WO2011004375A1 (fr) 2009-07-09 2011-01-13 Rubin, Israel Compositions probiotiques résistant à la chaleur et aliments sains les comprenant
EP2451300A1 (fr) * 2009-07-09 2012-05-16 Rubin, Israel Compositions probiotiques résistant à la chaleur et aliments sains les comprenant
CN102595938A (zh) * 2009-07-09 2012-07-18 德戈玛益生菌有限公司 耐热益生菌组合物及包含该组合物的健康食品
EP2451300A4 (fr) * 2009-07-09 2013-07-31 Degama Probiotics Ltd Compositions probiotiques résistant à la chaleur et aliments sains les comprenant
EP2451300B1 (fr) 2009-07-09 2018-09-05 DeGama Probiotics Ltd. Compositions probiotiques résistant à la chaleur et aliments sains les comprenant
US11039637B2 (en) 2010-12-06 2021-06-22 Degama Berrier Ltd. Composition and method for improving stability and extending shelf life of probiotic bacteria and food products thereof
US9808017B2 (en) 2011-02-25 2017-11-07 Kraft Foods R&D, Inc. Food product with a moulded body
US10470488B2 (en) 2011-09-09 2019-11-12 Philip Morris Products S.A. Smoking article comprising a flavour delivery material
US10543175B1 (en) 2013-05-17 2020-01-28 Degama Berrier Ltd. Film composition and methods for producing the same
CN109180996A (zh) * 2018-07-25 2019-01-11 佛山皖阳生物科技有限公司 一种淀粉基多孔微球的制备方法
CN109180996B (zh) * 2018-07-25 2021-08-06 山东聊城华阳医药辅料有限公司 一种淀粉基多孔微球的制备方法
FR3102913A1 (fr) * 2019-11-07 2021-05-14 Huddle Corp Aliment ou complément alimentaire pour animaux d’élevage
WO2021089969A1 (fr) * 2019-11-07 2021-05-14 Huddle Corp Aliment ou complément alimentaire pour animaux d'élevage
WO2021126548A1 (fr) * 2019-12-16 2021-06-24 Cooper Tire & Rubber Company Amidon revêtu de silice
CN114786739A (zh) * 2019-12-16 2022-07-22 库珀轮胎和橡胶公司 二氧化硅涂覆的淀粉
US11697727B2 (en) 2019-12-16 2023-07-11 The Goodyear Tire & Rubber Company Silica coated starch
CN114786739B (zh) * 2019-12-16 2023-10-31 固特异轮胎和橡胶公司 二氧化硅涂覆的淀粉

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