WO2010139987A2 - Matériaux mésoporeux - Google Patents

Matériaux mésoporeux Download PDF

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Publication number
WO2010139987A2
WO2010139987A2 PCT/GB2010/050914 GB2010050914W WO2010139987A2 WO 2010139987 A2 WO2010139987 A2 WO 2010139987A2 GB 2010050914 W GB2010050914 W GB 2010050914W WO 2010139987 A2 WO2010139987 A2 WO 2010139987A2
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mesoporous
silicon
use according
ingredient
previous
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PCT/GB2010/050914
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WO2010139987A3 (fr
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Leigh Trevor Canham
Joe Raguso
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Intrinsiq Materials Global Limited
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
    • 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
    • A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
    • A23L27/70—Fixation, conservation, or encapsulation of flavouring agents
    • 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
    • A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
    • A23L27/70—Fixation, conservation, or encapsulation of flavouring agents
    • A23L27/77—Use of inorganic solid carriers, e.g. silica
    • 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
    • A23L29/015—Inorganic compounds
    • 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
    • A23L29/294—Inorganic additives, e.g. silica
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/20—Halogens; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/24—Phosphorous; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/25—Silicon; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34—Alcohols
    • A61K8/345—Alcohols containing more than one hydroxy group
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/60—Sugars; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73—Polysaccharides
    • A61K8/731—Cellulose; Quaternized cellulose derivatives
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/92—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
    • A61K8/922—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof of vegetable origin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41—Particular ingredients further characterized by their size
    • A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/56—Compounds, absorbed onto or entrapped into a solid carrier, e.g. encapsulated perfumes, inclusion compounds, sustained release forms

Definitions

  • This invention relates to mesoporous materials and their use for modifying food and oral hygiene compositions, including their taste and/or texture.
  • the flavour of foods is a combination of taste and smell and in many cases is closely associated with mouthfeel.
  • the five main classes of taste are sweet, salt, sour, bitter and umami.
  • the main classes of taste are detected on the tongue, the pharynx and soft palate of the human mouth.
  • Other flavours are associated with odours. Odours are detected in the nose when volatile compounds in minute quantities come into contact with the olfactory nerve endings.
  • a sweet taste is typical of the low molecular weight carbohydrates such as fructose, glucose and sucrose. These have little “after-taste” but promote tooth decay and obesity when consumed in excess.
  • Sugar substitutes range from potent sweeteners such as saccharin (up to 500 times the sweetness of sucrose) to low calorie polyols such as xylitol and sorbitol.
  • Some combinations of amino acids are also very sweet, such as aspartame which is made from phenylalanine and aspartic acid.
  • the salt taste is a property of low molecular weight salts, particularly those comprising a halide such as sodium chloride.
  • the order of decreasing saltiness is chlorides, bromides, iodides, sulphates and nitrates.
  • Sodium salts are more salty than potassium salts which can be quite bitter.
  • a number of organic and inorganic compounds provide a bitter taste.
  • examples include the alkaloids such as quinone and caffeine, and some compounds comprising magnesium, calcium or ammonium ions.
  • the umami taste is due to the carboxylate anion of glutamic acid, a naturally occurring amino acid present in meats, cheese and other protein-rich foods.
  • Food flavours are usually complex mixtures of hydrocarbons, alcohols, acids, aldehydes, ketones and esters.
  • volatile food flavours from fruit and vegetables are essential oils. Examples include oil of almond, clove, garlic, ginger, lemon, lime, mace, orange and thyme.
  • Oleoresins are a class of less volatile flavour substances extracted from herbs and spices using solvents. Terpenoids are a very large group of odour compounds present in foods.
  • mouthfeel is often used to indicate the texture of food during consumption, but it can also cover sensations such as "tingling", “hot” and “watery”.
  • the physical texture of food can influence its flavour.
  • Flavour modifiers are agents used to enhance or reduce the level of a flavour.
  • An official definition currently in use is "any substance which is capable of enhancing, reducing or otherwise modifying the taste or odour, or both, of a food but does not include water or enzymes or any substance primarily used to impart taste, or odour, or both, to a food.”
  • Factors which influence taste perception include flavour molecule concentration, its rate and duration at receptor sites, the temperature, viscosity and area of application, the chemical state of the saliva and the presence of other flavours in the mouth.
  • the present invention is based on the surprising finding that mesoporous materials, preferably in microparticulate form, are suitable as flavour modifiers for use in foodstuff compositions and oral hygiene compositions.
  • a mesoporous material for modifying the flavour and/or texture of a foodstuff composition or an oral hygiene composition wherein at least some of the pores of the mesoporous material are loaded with at least one ingredient.
  • a method for modifying the flavour of a foodstuff composition or an oral hygiene composition comprising blending a mesoporous material wherein at least some of the pores of the mesoporous material are loaded with at least one ingredient with other components of the foodstuff or oral hygiene composition.
  • a method of increasing the potency of a food ingredient, such as a flavouring agent comprising blending a mesoporous material wherein at least some of the pores of the mesoporous material are loaded with at least one flavouring agent with other components of the foodstuff or oral hygiene composition.
  • a method of masking the taste of a food ingredient comprising blending a mesoporous material wherein at least some of the pores of the mesoporous material are loaded with at least one flavouring agent with other components of the foodstuff or oral hygiene composition.
  • An increase in the potency of a food ingredient may be measured relative to the potency of that food ingredient in the absence of the mesoporous material.
  • the ability of the mesoporous material to mask the taste of a food ingredient may be measured relative to when the mesoporous material is not present.
  • said ingredient may be retained in an amorphous state by the mesoporous material.
  • the present invention extends to a method for retaining an ingredient in an amorphous state and/or converting an ingredient suitable for use in a foodstuff or oral hygiene composition to a different physical form.
  • the present invention also extends to the use of a mesoporous material wherein at least some of the pores of the mesoporous material are loaded with at least one ingredient for delivering said at least one ingredient to the human or animal tongue, the pharynx or soft palate.
  • the at least one loaded ingredient is released on contact or shortly after contact with the human or animal tongue, the pharynx or soft palate.
  • a foodstuff composition or an oral hygiene composition suitable for delivering flavour to the human and/or animal tongue comprising a mesoporous material wherein at least some of the pores of the mesoporous material are loaded with at least one ingredient.
  • the loaded ingredient may be chosen from a range of flavour ingredients.
  • the at least one ingredient may be selected from sugar and/or salt.
  • suitable ingredients include water, polyol, an antiseptic agent, an antimicrobial agent, an essential oil.
  • the mesoporous materials may be selected from a preferred range of diameters.
  • the present inventors have found that mesoporous materials possessing a particle size diameter of about 5 to 15 ⁇ m are particularly effective at delivering flavour ingredients to the tongue, thus allowing appropriate reductions of the amounts of flavour agents such as salt and/or sugar in food.
  • the mesoporous microparticulate material may be encapsulated by a capping layer.
  • the mesoporous material may be a mesoporous microparticulate material.
  • the use of the mesoporous materials according to the present invention provides for a range of benefits, including avoidance of mouth cooling during food hydrolysis, increase in mouth warming during food ingestion ("melt in the mouth"), salt reduction in foods, sugar reduction in foods, calorie reduction in foods, improved targeting in the mouth, taste masking for bitter actives.
  • the present inventors have found that the potency of hydrophilic core flavourings such as salt and sugar can be increased by increasing their surface area and utilizing particle sizes tuned to taste bud morphology on the human or animal tongue.
  • the present inventors have found that by carefully selecting the mesoporous particulate materials to lie within a certain size range, e.g.
  • flavourings such as salt and sugar may be delivered to the human or animal mouth much more effectively such that the amount of sugar and/or salt may be reduced but without compromising the intensity of flavour. More specifically, such highly targeted delivery with rapid dissolution lowers the fraction of salt or sugar that is swallowed before it contributes to taste allowing either salt or sugar reduction in the corresponding foodstuff composition.
  • the present inventors have also found that through careful selection of the degree of mesoporosity in combination with pore diameter then mouthfeel may be controlled.
  • starch possessing a mesoporosity above about 70% in combination with all of or substantially all of the pores being less than 75nm in diameter and loaded with sweetener such as xylitol is beneficial in providing a so called melt in the mouth sensation in food compositions such as ice cream.
  • the flavour and mouthfeel of loaded mesoporous materials may be assessed using analysis techniques such as the flavour profile method and the texture profile method. These methods are described in Chapter 10 of Sensory Evaluation Techniques, 4 th edition (CRC Press 2007), edited by M. C. Meilgaard et al.
  • Suitable mesoporous materials include organic and inorganic materials. More specifically, suitable mesoporous materials include mesoporous silicon, oxidised mesoporous silicon, mesoporous silica, mesoporous calcium phosphates (e.g. hydroxyapatite), mesoporous metal carbonates, mesoporous alumina, mesoporous carbon, mesoporous vegetable materials (e.g. cellulose), mesoporous starch, mesoporous titania, mesoporous silicates (e.g. calcium silicate), mesoporous polymers.
  • mesoporous silicon oxidised mesoporous silicon
  • mesoporous silica mesoporous calcium phosphates (e.g. hydroxyapatite)
  • mesoporous metal carbonates e.g. hydroxyapatite
  • Mesoporous materials contain pores having a diameter in the range of 2 to 50nm.
  • the mesoporous materials have a pore diameter of 5 to 50nm.
  • the present inventors have found that pore diameters in the ranges specified can maintain high wt% of entrapped ingredients in an amorphous state that radically changes their behaviour when released in the human or animal mouth.
  • the present inventors have also found that when sufficiently nanoentrapped many ingredients can be kept in an amorphous state that alters their heat of solution when dissolving in the mouth. This can make the dissolution process more exothermic or change an endothermic process to an exothermic one.
  • the average pore diameter is measured using a known technique.
  • Mesopore diameters are measured by very high resolution electron microscopy. This technique and other suitable techniques which include gas-adsorption-desorption analysis, small angle x-ray scattering, NMR spectroscopy or thermoporometry, are described by R. Herino in "Properties of Porous Silicon", chapter 2.2, 1997.
  • the mesoporous material may have a BET surface area of 10m 2 /g to 700m 2 /g for example 100m 2 /g to 400m 2 /g.
  • the BET surface area is determined by a BET nitrogen adsorption method as described in Brunauer et at., J. Am. Chem. Soc, 60, p309, 1938.
  • the BET measurement is performed using an Accelerated Surface Area and Porosimetry Analyser (ASAP 2400) available from Micromeritics Instrument Corporation, Norcross, Georgia 30093.
  • ASAP 2400 Accelerated Surface Area and Porosimetry Analyser
  • the sample is outgassed under vacuum at 350 0 C for a minimum of 2 hours before measurement.
  • Microparticles are particles of about 1 to 1000 ⁇ m in diameter. Methods for making microparticles are well known in the art. These include chemical or gas phase synthesis methods or electrochemical etching or comminution (e.g. milling as described in Kerkar et al. J. Am. Ceram. So ⁇ , vol. 73, pages 2879-2885, 1990).
  • the present inventors have found that advantageously the d 50 of the mesoporous material may be about 1 to 10 ⁇ m, for example 1 to 5 ⁇ m, for example about 2 ⁇ m. In particular, these values of d 50 provide increased levels of salty taste without increasing the amount of salt ingested.
  • silicon refers to solid elemental silicon. For the avoidance of doubt, and unless otherwise stated, it does not include silicon-containing chemical compounds such as silica, silicates or silicones, although it may be used in combination with these materials.
  • the silicon may be about 95 to 99.99999% pure, for example about 96 to 99.9% pure.
  • So-called metallurgical silicon which is suitable for use in foodstuffs according to the present invention, has a purity of about 98 to 99.5%.
  • the physical forms of silicon which are suitable for use according to the present invention may be chosen from or comprise one or more of amorphous silicon, single crystal silicon and polycrystalline silicon (including nanocrystalline silicon, the grain size of which is typically taken to be 1 to 100nm) and including combinations thereof. Any of the above-mentioned types of silicon may be porosified to form mesoporous silicon.
  • Methods for making silicon powders such as silicon microparticles are well known in the art. Methods for making silicon powders are often referred to as "bottom-up" methods, which include, for example, chemical synthesis or gas phase synthesis.
  • top-down methods refer to such known methods as electrochemical etching or comminution (e.g. milling as described in Kerkar et al. J.
  • PCT/GB02/03493 and PCT/GB01/03633 the contents of which are incorporated herein by reference in their entirety, describe methods for making particles of silicon, said methods being suitable for making silicon for use in the present invention. Such methods include subjecting silicon to centrifuge methods, or grinding methods.
  • the method involves anodising, for example, a heavily boron doped CZ silicon wafer in an electrochemical cell which contains an electrolyte comprising a 20% solution of hydrofluoric acid in an alcohol such as ethanol, methanol or isopropylalcohol (IPA).
  • IPA isopropylalcohol
  • porous silicon Following the passing of an anodisation current with a density of about 50mAcm "2 , a porous silicon layer is produced which may be separated from the wafer by increasing the current density for a short period of time. The effect of this is to dissolve the silicon at the interface between the porous and bulk crystalline regions. Porous silicon may also be made using the so-called stain-etching technique which is another conventional method for making porous silicon. This method involves the immersion of a silicon sample in a hydrofluoric acid solution containing a strong oxidising agent. No electrical contact is made with the silicon, and no potential is applied. The hydrofluoric acid etches the surface of the silicon to create pores.
  • the mesoporous silicon may be generated from a variety of non-porous silicon powders by so-called “electroless electrochemical etching techniques", as reviewed by K. Kolasinski in Current Opinions in Solid State & Materials Science 9, 73 (2005). These techniques include “stain-etching”, “galvanic etching”, “hydrothermal etching” and “chemical vapour etching” techniques. Stain etching results from a solution containing fluoride and an oxidant. In galvanic or metal-assisted etching, metal particles such as platinum are also involved. In hydrothermal etching, the temperature and pressure of the etching solution are raised in closed vessels.
  • Mesoporous silicon can be made by techniques that do not involve etching with hydrofluoric acid.
  • An example of such a technique is chemical reduction of various forms of porous silica as described by Z. Bao et al in Nature vol. 446 8th March 2007 p172-175 and by E. Richman et a!, in Nano Letters vol. 8(9) p3075-3079 (2008). If this reduction process does not proceed to completion then the mesoporous silicon contains varying residual amounts of silica.
  • the mesoporous silicon may be dried. For example, it may be supercritically dried as described by Canham in Nature, vol. 368, (1994), pp133-135. Alternatively, the mesoporous silicon may be freeze dried or air dried using liquids of lower surface tension than water, such as ethanol or pentane, as described by Bellet and Canham in Adv. Mater, 10, pp487-490, 1998.
  • Silicon hydride surfaces may, for example, be generated by stain etch or anodisation methods using hydrofluoric acid based solutions.
  • the surface of the mesoporous silicon may or may not be suitably modified in order, for example, to improve the stability of the mesoporous silicon in the composition.
  • the surface of the mesoporous silicon may be modified to render the silicon more stable in alkaline conditions.
  • the surface of the mesoporous silicon may include the external and/or internal surfaces formed by the pores of the mesoporous silicon.
  • the stain etching technique may result in partial oxidation of the mesoporous silicon surface.
  • the surfaces of the mesoporous silicon may therefore be modified to provide: silicon hydride surfaces; silicon oxide surfaces wherein the mesoporous silicon may typically be described as being partially oxidised; or derivatised surfaces which may possess Si-O-C bonds and/or Si-C bonds.
  • Silicon hydride surfaces may be produced by exposing the mesoporous silicon to HF.
  • Silicon oxide surfaces may be produced by subjecting the silicon to chemical oxidation, photochemical oxidation or thermal oxidation, as described for example in Chapter 5.3 of Properties of Porous Silicon (edited by LT. Canham, IEE 1997).
  • PCT/GB02/03731 the entire contents of which are incorporated herein by reference, describes how mesoporous silicon may be partially oxidised in such a manner that the sample of mesoporous silicon retains some elemental silicon.
  • PCT/GB02/03731 describes how, following anodisation in 20% ethanoic HF, the anodised sample was partially oxidised by thermal treatment in air at 500 0 C to yield a partially oxidised mesoporous silicon sample.
  • the surface of the elemental mesoporous silicon may comprise one or more silicon compounds.
  • the mesoporous silicon surface may comprise silicon bonded to oxygen to form an oxide layer.
  • the silicon particles may possess an oxide content corresponding to between about one monolayer of oxygen and a total oxide thickness of less than or equal to about 4.5nrm covering the entire silicon skeleton.
  • the mesoporous silicon may have an oxygen to silicon atomic ratio between about 0.04 and 2.0, and preferably between 0.60 and 1.5. Oxidation may occur in the pores and/or on the external surface of the silicon.
  • the mesoporous silicon for use in the present invention may be derivatised.
  • Derivatised porous silicon is porous silicon possessing a covalently bound monolayer on at least part of its surface.
  • the monolayer typically comprises one or more organic groups that are bonded by hydrosilylation to at least part of the surface of the porous silicon.
  • Derivatised porous silicon is described in PCT/GBOO/01450, the contents of which are incorporated herein by reference in their entirety.
  • PCT/GBOO/01450 describes derivatisation of the surface of silicon using methods such as hydrosilyation in the presence of a Lewis acid. In that case, the derivatisation is effected in order to block oxidation of the silicon atoms at the surface and so stabilise the silicon.
  • the mesoporous silicon may be derivatised during its formation in HF-based electrolytes, using the techniques described by G. Mattei and V. Valentin! in Journal American Chemical Society vol 125, p9608 (2003) and Valentini et al., Physica Status Solidi (c) 4 (6) p2044-2048 (2007).
  • mesoporous silica may be made according to the methods described in US 5951962 and US 20070003492, the contents of which are hereby incorporated by reference in their entirety.
  • the mesoporous silica may be made by converting a silica precursor in a water containing reaction medium containing a polymer dispersion.
  • Mesoporous calcium phosphates e.g. mesoporous hydroxyapatites
  • Mesoporous metal carbonates may be made as described in US 6749825, the entire contents of which are hereby incorporated by reference in their entirety.
  • Mesoporous alumina may be made as described in Chem. Commun., 1986-1987 (2005).
  • Mesoporous vegetable materials, for example, cellulose may be made according to the methods described in US 5011701 the contents of which are hereby incorporated by reference in their entirety.
  • Mesoporous starch may be made according to the methods described in US 5919486 and US 4985082 the contents of which are hereby incorporated by reference in their entirety.
  • Mesoporous silicates (or bioactive glasses) such as calcium silicate may be made as described in J. Controlled Release 110, 522(2006).
  • Mesoporous titania may be made as described in Mater. Lett 59, 3308 (2005). Mesoporous carbon materials may be made with reference to Angewandte Chemie 7, (20) 3696 (2008). The contents of all of these references are incorporated herein in their entirety by reference.
  • particle size distribution measurements including the mean particle size (d 50 / ⁇ m) of the particles are measured using a Malvern Particle Size
  • a helium-neon gas laser beam is projected through a transparent cell which contains the particles suspended in an aqueous solution.
  • Light rays which strike the particles are scattered through angles which are inversely proportional to the particle size.
  • the photodetector array measures the quantity of light at several predetermined angles. Electrical signals proportional to the measured light flux values are then processed by a microcomputer system, against a scatter pattern predicted from theoretical particles as defined by the refractive indices of the sample and aqueous dispersant to determine the particle size distribution of the particles.
  • the mesoporous material is loaded such that one or more ingredients are present in the pores of the material.
  • the loaded ingredient or ingredients may be referred to as being entrapped.
  • the loaded one or more ingredients may be selected from one or more of food ingredients or oral hygiene ingredients which modify the flavour and/or texture of the foodstuff composition and oral hygiene composition.
  • the loaded ingredient may be water or ice.
  • the loaded ingredient may be selected from one or more of a sweetener including aspartame, acesulfame K, sucralose, fructose, xylitol, sorbitol, mannitol, lactitol, isomalt, mannitol, trehalose.
  • the loaded ingredient may be a salt selected from sodium chloride, potassium chloride.
  • the loaded ingredient may be selected from one or more oral hygiene agents including sweeteners, flavours, breath freshening agents, anti-plaque agents, anti-gingivitis agents, anti-calculus agents, tooth whitening agents, herbal extracts, pain-relief agents, sensates, cooling agents, warming agents, colouring agents, stimulants, essential oils.
  • the ingredient to be loaded with the mesoporous material may be dissolved or suspended in a suitable solvent, and mesoporous particles may be incubated in the resulting solution for a suitable period of time.
  • aqueous and non-aqueous slips have been produced from ground silicon powder and the processing and properties of silicon suspensions have been studied and reported by Sacks in Ceram. Eng. Sci. Proc, 6, 1985, pp1109-1 123 and Kerkar in J. Am. Chem. Soc. 73, 1990, pp2879-85.
  • the removal of solvent will result in the ingredient penetrating into the pores of the mesoporous material by capillary action, and, following solvent removal, the ingredient will be present in the pores.
  • Preferred solvents, at least for use in connection with mesoporous silicon are water, ethanol, and isopropyl alcohol, GRAS solvents and volatile liquids amenable to freeze drying.
  • the one or more ingredients are present in the range, in relation to the loaded mesoporous particulate material, of 0.01 to 90wt%, for example 1 to 40wt%, for example 20 to 55wt%, for example 20 to 50wt% (optionally, in combination with about 70% porosity) and for example 2 to 10wt%.
  • Higher levels of loading for example, at least about 15wt% of the loaded ingredient based on the loaded weight of the mesoporous material may be achieved by performing the impregnation at an elevated temperature.
  • loading may be carried out at a temperature which is at or above the melting point of the ingredient to be loaded.
  • Quantification of gross loading may conveniently be achieved by a number of known analytical methods, including gravimetric, EDX (energy-dispersive analysis by x-rays), Fourier transform infra-red (FTIR), Raman spectroscopy, UV spectrophotometry, titrimetric analysis, HPLC or mass spectrometry. If required, quantification of the uniformity of loading may be achieved by techniques that are capable of spatial resolution such as cross-sectional EDX, Auger depth profiling, micro- Raman and micro-FTIR.
  • the loading levels can be determined by dividing the volume of the ingredient taken up during loading (equivalent to the mass of the ingredient taken up divided by its density) by the void volume of the mesoporous material prior to loading, multiplied by one hundred.
  • the optional capping layer serves to encapsulate the mesoporous particulate material.
  • the openings to the pores are sealed.
  • the whole of the particle, or substantially the entire particle is coated with the capping layer and the capping layer may be referred to herein as a bead.
  • the capping layer at least seals the openings to the pores at the surface of the mesoporous material, thus ensuring that the at least one loaded ingredient is retained.
  • the capping layer, or bead may encapsulate more than a single mesoporous microparticulate material.
  • the thickness of the capping layer may be about 0.1 to 50 ⁇ m in thickness, for example about 0.5 to 45 ⁇ m for example about 1 to 10 ⁇ m, for example about 1 to 5 ⁇ m.
  • the capping layer may provide retention of an ingredient over a period of a few months to many months, for example up to about 5 years, followed by triggered release through site specific degradation which occurs in the human or animal mouth.
  • the capping layer may be an organic or an inorganic capping layer.
  • the encapsulated particles may consist essentially of inorganic particles capped with an organic material or an organic particle capped with an inorganic material. Alternatively, the encapsulated particles may consist essentially of organic particles capped with an organic material or inorganic particles capped with an inorganic material.
  • the use of a capping layer is particularly advantageous when used with wet products and when used with dry products where the loaded ingredient is volatile.
  • the thickness of the capping layer is measured by mechanically fracturing a number of the capped particles and examining their cross-sectional images in a high resolution scanning electron microscope, equipped with energy dispersive x-ray analysis (EDX analysis) of chemical composition.
  • EDX analysis energy dispersive x-ray analysis
  • the average thickness of micron thick layer caps can be estimated.
  • the density of the capping layer is known accurately, then accurate gravimetric measurements of weight increase that accompanies capping can also yield an average cap thickness.
  • the capping layer may comprise, consist of, or consist essentially of, a material which is present in the loaded ingredient.
  • the capping layer may include one or more of: titanium dioxide, carageenan, xanthum gum, cellulose gum, tocopherol.
  • the capping layer may include one or more of: cocoa butter, vegetable fat, milk fat, lecithin. The functions of capping layer and loaded ingredient may be provided by the same material.
  • the capping layer may comprise one or more than one distinct layer.
  • the capping layer may comprise a hydrophilic layer and a hydrophobic layer. Where there are distinct layers present of different materials then one of the layers may overlie the other.
  • the capping layer or layers may be selected from one or more of the following: carbohydrates, gums, lipids, proteins, celluloses, polymers, elastomers, inorganic materials.
  • Suitable examples of carbohydrates include starch, dextran, sucrose, corn, syrup.
  • Suitable examples of gums include carrageenan, alginate, e.g. sodium alginate, gum Arabic, agar.
  • Suitable examples of lipids include fats, hardened oils, paraffin, stearic acid, wax, diglycerides, monoglycerides.
  • Suitable examples of proteins include albumin, casein, gluten, gelatine.
  • Suitable examples of celluloses include carbomethylcellulose, acetylcellulose, methylcellulose.
  • Suitable examples of polymers include synthetic polymers such as polyacrylate, polyethylene, polystyrene, polyvinyl alcohol, polyurea.
  • Suitable examples of elastomers include acrylonitrile, polybutadience.
  • Suitable examples of inorganic materials include calcium sulphate, silicates, clays, silicon, silicon dioxide, calcium phosphate.
  • the capping layer may comprise, consist of, or consist essentially of elemental silicon, for example, in the form of an amorphous silicon coating or a discontinuous layer of silicon nanoparticles.
  • Suitable methods for capping the mesoporous material include: spray drying, fluidised bed coating, pan coating, modified microemulsion techniques, melt extrusion, spray chilling, complex coacervation, vapour deposition, solution precipitation, emulsification, supercritical fluid techniques, physical sputtering, laser ablation, very low temperature sintering and thermal evaporation.
  • Spray drying techniques are usually carried out from aqueous feed formulations, in which case the capping layer should be soluble in water at an acceptable level.
  • Typical materials include gum acacia, maltodextrins, hydrophobically modified starch and mixtures thereof.
  • Other polysaccharides such as alginate, carboxymethylcellulose, guar gum and proteins such as whey proteins, soy proteins, sodium caseinate are also suitable.
  • Aqueous two phase systems (ATPs) which may result from the phase separation of a mixture of soluble polymers in a common solvent due to the low entropy of mixing of polymer mixtures can be used to design double encapsulated ingredients in a single spray drying step.
  • Spray chilling or cooling is generally considered one of the least expensive encapsulation technologies.
  • This technique may also be referred to as matrix encapsulation, it is particularly suitable for encapsulating organic and inorganic materials as well as textural ingredients, enzymes, flavours and other ingredients to improve heat stability. Matrix encapsulation may lead to some of the loaded ingredient being incorporated in the capping layer.
  • Extrusion is suitable for the encapsulation of volatile and unstable flavours. This process is suitable for imparting long shelf life to normally oxidation prone flavour compounds such as citrus oils.
  • Coacervation is particularly useful in connection with the use of high levels of loaded ingredient and is typically used for encapsulating flavour oils, fish oils, nutrients, vitamins, preservatives, enzymes.
  • Coacervation requires the phase separation of one or many hydrocolloids from solution and the subsequent deposition of the newly formed coacervate phase around the mesoporous material which is suspended or emulsified in the same reaction media.
  • the hydrocolloid shell may then be crosslinked using an appropriate chemical or enzymatic crosslinker if required.
  • the amorphous silicon coating may be deposited by physical sputtering and may have a thickness of 500nm to 5 ⁇ m.
  • the silicon nanoparticles are preferably bound to the microparticles (e.g. silicon microparticles) by solution based techniques.
  • the silicon nanoparticles typically possess a particle size distribution comparable to that of the mesopore particle size distribution of the microparticles.
  • the capping layer may be degraded by enzymes or bacteria present at the intended site of use (active release).
  • active release An example is starch degraded by salivary amylase for oral hygiene products.
  • the capping layer and, optionally, the microparticle may be degraded by mechanical forces at the intended site of use, such as forces exerted when brushing teeth or biting and chewing food.
  • the capping layer may be degraded by a sudden increase of temperature such as exposure to body temperature (37°C) or boiling water (100 0 C).
  • the capping layer may be degraded by a change in the chemical environment, such as a pH change or immersion in a liquid such as milk.
  • the loaded mesoporous materials are suitable for use in foodstuff compositions and oral hygiene compositions.
  • the loaded ingredients may be selected from one or more of: oxygen sensitive edible oils; minerals; oxygen sensitive fats including dairy fats; oil soluble ingredients; vitamins; fragrances or aromas; flavours including salt and sugar (including one or more of glucose, sucrose, fructose); enzymes; probiotic bacteria; prebiotics; nutraceuticals; amino acids; herbal extracts; herbs; plant extracts; edible acids; antioxidants; therapeutic agents.
  • the one or more ingredients are present in the range, in relation to the loaded material, of 0.01 to 90wt%, for example 1 to 40wt%, for example 20 to 55wt%, for example 20 to 50wt% (optionally in combination with about 70% porosity) and for example 2 to 10wt%.
  • the food may be in the form of a beverage or non-beverage.
  • the food may be a dry food or a non-dry food.
  • the dry food may be a food that does or does not normally come into contact with a liquid prior to ingesting.
  • a breakfast cereal is typically a dry food which normally comes into contact with a liquid prior to ingestion.
  • Suitable foods for use in the present invention may comprise one or more of the following: meat; poultry; fish; vegetables; fruit; chocolate and confectionary including chewing gum; cereals and baked products including bread, cakes, biscuits, nutrition or cereal bars; pastry; pasta; dairy products such as milk, cream, butter, margarine, eggs, ice cream, cheese.
  • the food may be in the form of any of the following: convenience meals; frozen food; chilled food; dried food; freeze dried food; rehydrated food; pickles; soups; dips; sauces.
  • Suitable beverages include alcoholic and non-alcoholic beverages.
  • suitable drinks include: water, for example bottled water; tea; coffee; cocoa; drinking chocolate; fruit juices and smoothies; wine; beer; ales; lager; spirits.
  • the beverages may, for example, be in the form of granules, including those which have been freeze dried, which are suitable for making instant coffee and tea and the like.
  • the present invention extends to products suitable for making beverages, such as instant beverage powders and granules. These include coffee granules, coffee powder, coffee tablets, tea, cocoa powder, chocolate powder.
  • Other suitable products include coffee oil and concentrates, for example, fruit juice concentrates.
  • the pH of the food is preferably such that the mesoporous material does not dissolve in the food over a significant period of time and will thus afford an acceptable shelf-life.
  • the pH of the food is typically 2 to 6.
  • Suitable fragrances, aromas and flavours are non-toxic and suitable for inclusion in foodstuffs.
  • Bauer et al, “Common Fragrances & Flavours”, Wiley, 1997, pp278 describes a range of suitable fragrances, aromas and flavours.
  • Preferred fragrances, aromas and flavours are "Generally Recognised As Safe” (GRAS) by the FDA.
  • Alcohols, aldehydes, ketones, esters and lactones are classes of compounds most frequently used in natural and artificial fragrances.
  • suitable flavours include: one or more of spice oleoresins derived from allspice, basil, capsicum, cinnamon, cloves, cumin, dill, garlic, marjoram, nutmeg, paprika, black pepper, rosemary and tumeric; essential oils such as anise oil, caraway oil, clove oil, eucalyptus oil, fennel oil, garlic oil, ginger oil, peppermint oil, onion oil, pepper oil, rosemary oil, spearmint oil; citrus oils including orange oil, lemon oil, bitter orange oil and tangerine oil; alliaceous flavours which include garlic, leek, chive, and onion; botanical extracts such as arnica flower extract, chamomile flower extract, hops extract, and marigold extract; botanical flavour extracts such as blackberry, chicory root, cocoa, coffee, kola, liquorice root, rose hips, sarsaparilla root, sassafras bark, tamarind and vanilla
  • flavour compounds are, for example: benzaldehyde, diacetyl (2,3- butanedione), vanillin, ethyl vanillin and citral (3,7-dimethyl-2,6-octadienal).
  • the flavouring agent may be in the form of an oil, aqueous solution, non-aqueous solution or an emulsion.
  • Flavour essences i.e. the water soluble fraction derived from fruit or citrus can be utilized, and typically at lower levels than the ingredients mentioned above.
  • sustained release may be carried out using mesoporous silicon possessing a pore diameter in the range of about 2-1 Onm. The small pore size suppresses the release of the fragrant volatiles.
  • Particularly suitable food aromas include food aromas for liquid food products, particularly instant soups and beverages such as coffee.
  • Other suitable food aromas include those used in desserts such as instant puddings, and frozen food products such as frozen pizza.
  • the food aromas may also be those suitable for use in food which needs to be reconstituted with hot water or milk or heated by the consumer prior to consumption.
  • Suitable food aromas include the following: cheese aroma; aromas for hot soluble coffee-based beverages such as coffee, hazelnut, amaretto, chocolate, cream and vanilla; aromas for hot soluble tea-based beverages such as raspberry, cream and vanilla; aromas for hot cocoa-based beverages such as raspberry, amaretto, cream, chocolate and vanilla; aromas for hot soups such as mushroom, tomato, beef and chicken; aromas for beverages such as coffee, tea, cherry, grape, and strawberry; aromas for dessert products such as raspberry, chocolate, butterscotch, cherry, grape, strawberry, banana, and vanilla; aromas for other products such as cream, seafood, meat, garlic and onion.
  • the aroma flavour may be part of an aromatizing composition which may optionally also include one or more other constituents such as a non-volatile edible fat or oil, a surfactant, a wetting agent, a foaming agent, an extremely volatile solvent, a propellant, dissolved edible solids, an antioxidant, or an aroma precursor.
  • a non-volatile edible fat or oil such as coffee oil or triglyceride oils used as a source of flavour or as a flavour solvent.
  • a surfactant may also be present which acts as a spreading agent or ernulsifier to control the droplet size of the aromatizing composition and its degree of spreading on the surface of a food product.
  • Suitable highly volatile solvents such as acetone and acetaldehyde may be used as a co-solvent for the volatile food aroma and modify the rate of evaporation of the aroma delivery system.
  • a dissolved or entrapped propellant gas such as air, nitrogen, carbon dioxide, nitrous oxide, or a gas generator such as a chemical carbonation reagent, may be included to increase buoyancy or to accelerate aroma release and evaporation.
  • Dissolved edible solids increase the viscosity of the composition.
  • Antioxidant additives such as butylated hydroxyanisole, butylated hydroxyl toluene, tertiary butylhydroquinone, vitamins A, C and E and derivatives, and various plant extracts such as those containing carotenoids, tocopherols or flavonoids having antioxidant properties, may be included to increase the shelf-life of the aromatized carrier.
  • Aroma precursors that would not react during storage but would react to generate aroma during food preparation may also be included in the aromatizing composition.
  • dehydrated food compositions often involves processing conditions such as elevated temperature, which often causes loss of desirable food aroma.
  • One known technique of overcoming such loss is to add additional aroma and flavour to dehydrated foodstuffs and beverages.
  • Such aromas and flavours are usually complex, comprising many organoleptically active compounds, which combine to create the characterizing aroma of the product. Since aromas and flavours are often extremely powerful and unstable in their undiluted state, they are combined with a carrier to render them more stable and easier to handle.
  • the carriers are preferably neutral or complementary in organoleptic impact and do not contribute to the characterizing aroma of the product. Desirable characteristics of carriers for liquid systems include blandness and miscibility with other liquid carriers and with liquid aromas.
  • Traditional carriers include ethanol, propylene glycol, glycerol, vegetable oil, benzyl alcohol, triacetin, thpropionin, triethyl citrate, and tributyrin.
  • Oxygen sensitive edible oils include polyunsaturated fatty acids which themselves include canola oil, borage oil, evening primrose oil, safflower oil, sunflower oil, pumpkinseed oil, rosemary oil, rice bran oil, flaxseed oil, wheatgerm oil, grapeseed oil, linseed oil. Some of these oils contribute linoleic acid, alpha-linoleic acid, oleic acid, palmitic acid, stearic acid. Also included are marine oils, for example, those derived from fish such as tuna, herring, mackerel, sardine, cod liver and shark.
  • Suitable minerals include: macrominerals comprising Ca, P, Mg, Na, K; microminerals comprising Fe, Zn, Cu, Se, Cr, I, Mn, Mo, F.
  • Suitable trace elements include Ni, V, B, Co. Vitamins
  • Suitable vitamins include Ascorbic Acid, Beta-carotene, Biotin, Choline, Folic Acid, Niacin, Pantothenic Acid (Vitamin B5), Phylloquinone (Vitamin K), Pyridoxine (Vitamin B6), Riboflavin (Vitamin B2), Thiamin (Vitamin B1 ), Vitamin A, Vitamin B12, Vitamin D, Vitamin E and mixtures thereof.
  • the vitamin and mesoporous material may be combined by allowing the vitamin to impregnate the mesoporous material, optionally in the presence of gentle heat, typically in the range of 4O 0 C and 200 0 C.
  • Suitable enzymes are selected from the classes of carbohyd rases, pectic enzymes, celluloses, proteases, oxidases, and lipases. Examples include amylase, bromelain, catalase, ficin, glucoamylase, glucose isomerase, glucose oxidase, invertase, lactase, lipase, papain, pepsin, pullulanase and rennet.
  • a prebiotic is a natural or synthetic substance that supports the growth of and/or nurtures probiotics. More specifically the prebiotic is a nondigestible food ingredient that beneficially affects the host by selectively stimulating the growth and/or activity of one or a limited number of bacteria in the colon. They are typically carbohydrates of relatively short length. Examples are the inulin-type fructans such as lactulose and inulin.
  • a nutraceutical ingredient provides medical or health benefits, including the prevention and treatment of disease.
  • a nutraceutical is specifically adapted to confer a particular health benefit on the consumer.
  • Suitable nutraceuticals for use in the present invention may be selected from Aloe Vera (Aloe ferox, A.
  • Suitable amino acids may be selected from Alanine, Arginine, Aspartic Acid,
  • Glycine Histidine, Isoleucine, Leucine, Lysine, Methionine, Ornithine, Phenylalanine, Proline, Serine, Taurine, Threonine, Tryptophan, Tyrosine, Valine and mixtures thereof.
  • Suitable plant extracts include one or more plant sterols, these include beta-sitosterol, campesterol, stigmasterol.
  • Suitable plant stands include sitostanol, octacosanol, policosanol.
  • Suitable herbs include black walnut, burdock, chamomile, comfrey, Echinacea, eucalyptus, hawthorn, hyssop, ginkgo, hyssop, lemon balm, milk thistle, mullein, peppermint, psyllium, sage, saw palmetto, sheep sorrel, slippery elm, St John's Wort, thyme, turkey rhubarb, valerian, vitex.
  • Herbs suitable for use for medicinal purposes are described in The Natural Pharmacy by M. Polunin & C. Robbins (Dorling Kindersley 1999), 144pp. In particular, pages 30 -131 list suitable herbs. Suitable culinary herbs are described in Food Commodities, 2nd Edition pp158-163 by B. Davis (Butterworth Heinemann 1994). Edible acids
  • Suitable edible acids for use in the present invention may be selected from citric acid, ascorbic acid, malonic acid, acetic acid, tartaric acid, sorbic acid, fumaric acid, malic acid, phosphoric acid, succinic acid and nicotinic acid.
  • Suitable antioxidants for use in the present invention may be selected from sodium carbonate, calcium carbonate, butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), lecithins, sodium lactate, calcium lactate, calcium malate and ammonium citrate.
  • Methods for incorporating the mesoporous material into food are numerous.
  • the mesoporous material is loaded with the at least one ingredient prior to incorporating the mesoporous material into the food.
  • Suitable mixing equipment for use in the present invention is diverse and includes, for example, screw mixers, ribbon mixers and pan mixers. Other examples include high speed propeller or paddle mixers for liquid food or beverages; tumble mixers for dry powders; Z-blade mixers for doughs and pastes.
  • Suitable grinding machines include hammer, disc, pin and ball millers.
  • Extrusion is an important very high throughput (about 300-9000kg/hr) technique for mixing and providing shape to foodstuffs and is suitable for use in the present invention. Cold and hot extruders may be used. These can be single or twin screw.
  • Extruded foods include cereals, pasta, sausages, sugar or protein based products.
  • the loading levels can be determined by dividing the volume of the ingredient taken up during loading (equivalent to the mass of the ingredient taken up divided by its density) by the void volume of the mesoporous material prior to loading multiplied by one hundred.
  • the total quantity of mesoporous material present in the food may be about 0.01 to 50wt%, for example about 0.01 to 20wt% and for example about 0.1 to 5wt%.
  • the loaded mesoporous material may be used in an oral hygiene composition such as a mouthwash or a dentifrice composition such as a toothpaste, tooth powder, lozenge, or oral gel. It may be present as an abrasive in addition to delivering one or more ingredients.
  • the dentifrice composition will comprise constituents well known to one of ordinary skill; these may broadly be characterised as active and inactive agents. Active agents include anticahes agents such as fluoride, antibacterial agents, desensitising agents, antitartar agents (or anticalculus agents) and whitening agents.
  • Inactive ingredients are generally taken to include water (to enable the formation of a water phase), detergents, surfactants or foaming agents, thickening or gelling agents, binding agents, efficacy enhancing agents, humectants to retain moisture, flavouring, sweetening and colouring agents, preservatives and, optionally further abrasives for cleaning and polishing.
  • the oral gel may be of the type suitable for use in multi-stage whitening systems.
  • Suitable mesoporous particulate materials for use in toothpaste include silicon and silica.
  • the dentifrice composition typically comprises a water-phase which comprises an humectant.
  • Water may be present in an amount of from about 1 to about 90wt%, preferably from about 10 to about 60wt%.
  • the water is deionised and free of organic impurities.
  • Any of the known humectants for use in dentifrice compositions may be used. Suitable examples include sorbitol, glycerin, xylitol, propylene glycol.
  • the humectant is typically present in an amount of about 5 to 85wt% of the dentifrice composition.
  • the dentifrice composition according to the present invention may comprise an anticaries agent, such as a source of fluoride ions.
  • the source of fluoride ions should be sufficient to supply about 25ppm to 5000ppm of fluoride ions, for example about 525 to 1450ppm.
  • Suitable examples of anticaries agents include one or more inorganic salts such as soluble alkali metal salts including sodium fluoride, potassium fluoride, ammonium fluorosilicate, sodium fiuorosilicate, sodium monofluorophosphate, and tin fluorides such as stannous fluoride.
  • antitartar agents may be used in the dentifrice compositions according to the present invention.
  • Suitable examples of antitartar agents include pyrophosphate salts, such as dialkali or tetraalkali metal pyrophosphate salts, long chain polyphosphates such as sodium hexametaphosphate and cyclic phosphates such as sodium trimetaphosphate. These antitartar agents are included in the dentifrice composition at a concentration of about 1 to about 5wt%.
  • any of the known antibacterial agents may be used in the compositions of the present invention.
  • these include non-cationic antibacterial agents such as halogenated diphenyl ethers, a preferred example being triclosan (2,4,4'-trichloro-2'- hydroxydiphenyi ether).
  • the antibacterial agent(s) may be present in an amount of about 0.01 to 1.0wt% of the dentifrice composition, for example about 0.3wt%.
  • the mesoporous material can be used as the sole abrasive in preparing the dentifrice composition according to the present invention or in combination with other known dentifrice abrasives or polishing agents.
  • Commercially available abrasives may be used in combination with the mesoporous material and include silica, aluminium silicate, calcined alumina, sodium metaphosphate, potassium metaphosphate, calcium carbonate, calcium phosphates such as tricalcium phosphate and dehydrated dicalcium phosphate, aluminium silicate, bentonite or other siliceous materials, or combinations thereof.
  • the dentifrice composition of the present invention may also contain a flavouring agent.
  • Suitable examples include essential oils such as spearmint, peppermint, wintergreen, sassafras, clove, sage, eucalyptus, majoram, cinnamon, lemon, lime, grapefruit, and orange.
  • Other examples include flavouring aldehydes, esters and alcohols.
  • Further examples include menthol, carvone, and anethole.
  • the flavour may be delivered over a prolonged period of time.
  • the thickening agent may be present in the dentifrice composition in amounts of about 0.1 to about 10% by weight, preferably about 0.5 to about 4% by weight.
  • Thickeners used in the compositions of the present invention include natural and synthetic gums and colloids, examples of which include xanthan gum, carrageenan, sodium carboxymethyl cellulose, starch, polyvinylpyrrolidone, hydroxyethylpropyl cellulose, hydroxybutyl methyl cellulose, hydroxypropylmethyl cellulose, and hydroxyethyl cellulose.
  • Suitable thickeners also include inorganic thickeners such as amorphous silica compounds including colloidal silica compounds.
  • Surfactants may be used in the compositions of the present invention to achieve increased prophylactic action and render the dentifrice compositions more cosmetically acceptable.
  • the surfactant is typically present in the dentifrice compositions according to the present invention in an amount of about 0.1 to about 5wt%, preferably about 0.5 to about 2wt%.
  • the dentifrice compositions according to the present invention may comprise one or more surfactants, which may be selected from anionic, non-ionic, amphoteric and zwitterionic surfactants.
  • the surfactant is preferably a detersive material, which imparts to the composition detersive and foaming properties.
  • Suitable examples of surfactants are well known to an ordinary skilled person and include water-soluble salts of higher fatty acid monoglycehde monosulfates, such as the sodium salt of the monosulfated monoglyceride of hydgrogenated coconut oil fatty acids, higher alkyl sulfates such as sodium lauryl sulfate, alkyl aryl sulfonates such as sodium dodecyl benzene sulfonate, higher alkyl sulfoacetates, sodium lauryl sulfoacetate, higher fatty acid esters of 1 ,2-dihydroxy propane sulfonate, and the substantially saturated higher aliphatic acyl amides of lower aliphatic amino carboxylic acid compounds, such as those having 12 to 16 carbons in the fatty acid, alkyl or acyl radicals.
  • water-soluble salts of higher fatty acid monoglycehde monosulfates such as the sodium salt of the monos
  • N-lauroyl sarcosine and the sodium, potassium, and ethanolamine salts of N-lauroyl, N-myristoyl, or N-palmitoyl sarcosine.
  • Efficacy enhancing agents include N-lauroyl sarcosine, and the sodium, potassium, and ethanolamine salts of N-lauroyl, N-myristoyl, or N-palmitoyl sarcosine.
  • efficacy enhancing agents for any antibacterial, antitartar or other active agent within the dentifrice composition may also be included in the dentifrice composition.
  • Suitable examples of efficacy enhancing agents include synthetic anionic polycarboxylates. Such anionic polycarboxylates may be employed in the form of their free acids or partially, or more preferably, fully neutralized water soluble alkali metal
  • M.W. molecular weight
  • the efficacy enhancing agent for example the anionic polycarboxylate
  • the anionic polycarboxylate(s) are present within the dentifrice composition from about 0.05wt% to about 4wt%, preferably from about 0.5wt% to about 2.5wt%.
  • dentifrice compositions of this invention including: preservatives; silicones; desensitizers, such as potassium nitrate; whitening agents, such as hydrogen peroxide, calcium peroxide and urea peroxide; and chlorophyll compounds.
  • Some toothpastes include bicarbonate in order to reduce the acidity of dental plaque.
  • Suitable methods for making the dentifrice compositions according to the present invention include the use of high shear mixing systems under vacuum.
  • the preparation of dentifrices is well known in the art.
  • an humectant may be dispersed in water in a conventional mixer under agitation.
  • Organic thickeners are combined with the dispersion of humectant along with: any efficacy enhancing agents; any salts, including anticaries agents such as sodium fluoride; and any sweeteners.
  • the resultant mixture is agitated until a homogeneous gel phase is formed.
  • One or more pigments such as titanium dioxide may be combined with the gel phase along with any acid or base required to adjust the pH. These ingredients are mixed until an homogenous phase is obtained.
  • the mixture is then transferred to a high speed/vacuum mixer, wherein further thickener and surfactant ingredients may be combined with the mixture. Any abrasives may be combined with the mixture to be used in the composition.
  • Any water insoluble antibacterial agents such as triclosan, may be solubilized in the flavour oils to be included in the dentifrice composition and the resulting solution is combined along with the surfactants with the mixture, which is then mixed at high speed for about 5 to 30 minutes, under vacuum of from about 20 to 50mm of Hg.
  • the resultant product is typically an homogeneous, semi-solid, extrudable paste or gel product.
  • the pH of the dentifrice composition is typically such that the mesoporous material will not dissolve in the composition over a significant period of time and will thus afford an acceptable shelf-life.
  • the pH of the dentifrice composition is typically less than or equal to about 9 and preferably, particularly for compositions other than powders such as toothpastes, less than or equal to about 7.
  • the lower limit of pH may typically be about 3.5 or about 4.
  • the pH may be about 3.5 or about 4 when the dentifrice composition is a gel, such as those used in multi-stage whitening systems.
  • the abrasivity of the dentifrice compositions of the present invention can be determined by means of Radioactive Dentine Abrasion (RDA) values as determined according to the method recommended by the American Dental Association, as described by Hefferren, J. Dental Research, vol. 55 (4), pp 563-573, (1976) and described in US 4340583, US 4420312 and US 4421527, the contents of which are contained herein by reference in their entirety.
  • RDA Radioactive Dentine Abrasion
  • a reference slurry containing 10g of calcium pyrophosphate in 15 ml of a 0.5% aqueous solution of sodium carboxymethyl cellulose is also measured and the RDA of this mixture is arbitrarily taken as 100.
  • the dentifrice composition to be tested is prepared as a suspension at the same concentration as the pyrophosphate and submitted to the same brushing regime.
  • the RDA of the dentifrice compositions according to the present invention may lie in the range of about 10 to 150, for example less than about 100, for example, less than about 70.
  • the pellicle cleaning ratio (PCR) of the dentifrice compositions of the present invention is a measurement of the cleaning characteristics of dentifrices and generally may range from about 20 to 150 and is preferably greater than about 50.
  • the PCR cleaning values can be determined by a test described by Stookey et al., J. Dental Research, vol. 61 (11 ), pp 1236-9, (1982). Cleaning is assessed in vitro by staining 10mm 2 bovine enamel specimens embedded in resin, which are acid etched to expedite stain accumulation and adherence. The staining is achieved with a broth prepared from tea, coffee and finely ground gastric mucin dissolved into a sterilized trypticase soy broth containing a 24-hour Sarcina lutea turtox culture. After staining, the specimens are mounted on a V-8 cross-brushing machine equipped with soft nylon toothbrushes adjusted to 15Og tension on the enamel surface.
  • the specimens are then brushed with the dentifrice composition to be tested and a calcium pyrophosphate standard which comprises 10g of calcium pyrophosphate in 50 ml of 0.5% aqueous solution of sodium carboxymethyl cellulose.
  • the specimens are brushed with dentifrice slurries consisting of 25g of toothpaste in 4Og of deionized water, for 400 strokes.
  • the specimens are cleaned with Pennwalt pumice flour until the stain is removed. Reflectance measurements are taken using a Minolta Colorimeter using the standard Commission Internationale de I'Eclairage (CIE) L * a * b * scale in order to measure the colour of the specimens before and after brushing.
  • CIE Commission Internationale de I'Eclairage
  • the cleaning efficiency of the dentifrice compositions according to the present invention which is a measure of the ratio of PCR/RDA, may lie in the range from about 0.5 to about 2.0, and may be greater than about 1.0 for example greater than about 1.5.
  • mesoporous microparticulate material in an oral hygiene composition provides increased efficacy (e.g. through increased antimicrobial activity).
  • Mesoporous calcium phosphate powder is loaded with a mixture of lemon and lime flavour oils by the "mop up" technique.
  • the calcium phosphate surfaces have known hydroxyapatite binding activity and remineralizing activity.
  • the oil is gradually mixed into the powder with continuous stirring at room temperature and pressure in ambient air. Further oil addition is terminated before the "wet point" is reached where the mesopores are filled and residual oil adheres to the exterior surfaces of the microparticles.
  • the flavoured particles are added to toothpaste formulations at the 1-10wt% level. During brushing a fraction of these particles adhere to the tooth enamel surfaces and all particles contribute to a burst release of flavour. During mouth rinsing the majority of the particles are removed but retained particles provide sustained release of flavour in the mouth.
  • Mesoporous starch particles are packed into glass columns through which aqueous solutions of xy ⁇ tol are flowed.
  • the starch has a mesoporosity above 70% and all of the pores are less than 75nm in diameter.
  • Solution transport is continued until excess xylitol is detectable at the exit point of the stacked column.
  • the sweetened starch composition is then added to ice cream formulations at 5-25wt% and co-frozen.
  • the xylitol remains in an amorphous form within the frozen ice cream. Upon ingestion and contact with saliva, the exothermic heat of solvation contributes to a melt in the mouth sensation.
  • Mesoporous silica is loaded with salt by heating appropriate mixtures to above the melting point (801 "C) in high temperature ovens.
  • the mesoporous silica particles have diameters, e.g. d 50 diameters, in the range 5-15 ⁇ m, more preferably d 50 diameters in the range 1-1 O ⁇ m and may have hydrophillic surfaces.
  • the salt loaded microparticles are applied to the surfaces of dry snack products, such as DoritosTM, at the 0.001 -0.1 wt% level. Upon ingestion and direct contact with the tongue, there is burst and sustained release of salt in the immediate vicinity of salt taste receptors.
  • Mesoporous silicon is loaded with a nutritional essential oil with a bitter taste by the mop up technique.
  • the mesoporous silicon is prepared by partial reduction of porous silica using magnesium vapour, has a pale brown colour, and takes up more than 30wt% oil.
  • the oil loaded microparticles are then capped with a hydrophobic pigment such as turmeric by, for example, spray drying.
  • the capped microparticles have an orange hue and disperse readily in orange juice.
  • the nutritional oil is partly released in the stomach but the majority is released in the intestine as a result of the biodegradation of the carrier material.
  • Mesoporous oxidized silicon powders with a porosity of 70%, a d 50 of 6 ⁇ m and a d 90 of 19 ⁇ m were prepared from anodized membranes by rotary-milling and then sedimentation filtration. The powders were oxidized for 3hrs at 800 0 C in air to render them hydrophilic and manipulate their colour to off-white.
  • Stain etched oxidized mesoporous silicon powders were prepared by an etching process.
  • the powders had a d 50 of 2 ⁇ m and a d 90 of 9 ⁇ m.
  • the porosified surface area was 381.3 m 2 /g and the pore volume was 0.496 ml/gm.
  • the powders were oxidized for 0.5 hrs at 700 0 C and were dark brown in colour.
  • a "mop-up" technique was used to load salt into the oxidized porous silicon powders.
  • the mop-up technique used repeated adsorption of volumes of liquid below the "wet point" where mesopores become full and microparticle "dumping" starts to occur.
  • 900mg batches of oxidized mesoporous silicon powder were spread evenly over glass Petri plates. 0.5ml of salt solution (0.3g/ml) at a time was pipetted onto the powder and was mixed thoroughly at ambient temperature. The Petri dish was then transferred to a hot plate at 90 0 C to remove water. Salt solution addition and drying was repeated until the targeted wt% loading was achieved (the increasing weight of the powder was monitored). Both the anodized oxidized and stain etched oxidized silicon powders were loaded (54.5wt%) with salt.
  • a snack mix was manually coated with first a thin layer of oil and then either the salted mesoporous powders or micronized salt powder, using a simple spray bottle (oil), sprinkler (salt) and mixing bowl.
  • the coated samples were stored at room temperature in plastic bags until use. After coating the snacks, the level of salt present on each snack was 0.4wt%.
  • Mesoporous silicon model structures (membranes) and mesoporous silicon powders were prepared with various porosities and pore volumes.
  • the powders were prepared from the membranes by hand-milling with a mortar and pestle.
  • the membranes and powders were oxidized (0.5hr at 600°C, in air) to render them hydrophilic, such that the aqueous salt solution rapidly and easily permeated the porous network.
  • the oxidation process reduced the available porosity/pore volume and this was taken into account when calculating loading levels.
  • PVDF membrane with powder, mounting these in 1 ml polypropylene Eppendorf tubes and filling with 0.5ml salt solution. After 30min, the samples were centrifuged at
  • the release kinetics of salt into deionised water was evaluated for two model (membrane) oxidized porous silicon structures of different porosities. After loading, the membranes were immersed in the water for a set time, removed and dried as described previously. The weight loss, attributed to leaching of the salt, was monitored for different immersion times, to determine the release profiles (percentage loading versus time).
  • Tabie 1 Variation in NaCI payload with porosity of oxidised mesoporous silicon membranes (solution loading)
  • the release profiles for NaCI-loaded oxidised (60% porosity) mesoporous silicon into de-ionised water indicated that the porous silicon retained NaCI up to about 4 minutes after immersion. This was higher than when compared to the 43% porosity mesoporous silicon.
  • This release profile indicates the suitability of the material for use in foods which are exposed to liquids before they are ingested such as cereals to which a liquid such as milk may be added.
  • mesoporous silicon samples were prepared by preparing a 36 ⁇ m thick mesoporous silicon film of 79% porosity which was oxidized for 1 hour at 500 0 C. The wafers were cleaved to yield a number of 1 cm x 1 cm squares. A control non-porous silicon wafer was cleaved to yield a number of 1 cm x 1cm squares. Salt solutions were prepared in deionized water and pipetted onto the silicon surfaces. The liquid was evaporated (few minutes on a hotplate at 60 0 C, followed by gentle heating).
  • Two 1 g batches of glucose were simultaneously heated to 200°C +/- 10°C for 10 minutes in air, one as a free flowing dry powder, prepared by mixing molten glucose with 1g Syloid 74FP mesoporous silica (WR Grace Davison GmbH) at 185 0 C, the other as molten glucose mass. Much more intense caramel aromas were evident from the dry powder during heating. After the heating period, the molten glucose mass was mixed with a similar 1g batch of Syloid. Both Syloid/glucose batches were then hand ground by a pestle and mortar.
  • Starch microparticles containing mesopores were prepared by a modification of the techniques described in "Carbonized starch microcellular foam-cellulose fiber composite structures" by Rutlidge et al in BioResources 3(4), 1063-1080, (2008).
  • the process involved the thermal treatment of an aqueous starch solution followed by dehydration with ethanol.
  • the ethanol dehydration is carried out in successive water baths containing different v/v percentages of ethanol.
  • the final dehydration step involved immersion of starch in absolute ethanol followed by vacuum drying at ambient temperature. This results in porous starch particles with an open-cell matrix with pore sizes in the sub-micrometer range.
  • 5Og of cornstarch was mixed into one litre of deionized water and then heated to 12O 0 C for 45 minutes.
  • the viscous solution was poured into moulds and then stored at 4°C for 12 hours.
  • the aquagels were then bathed for 2 hours in 10% ethanol solution, 2 hours in 20% ethanol solution and 2 hours in 30% ethanol solution, followed by a final 10 hour soak in 100% ethanol.
  • Incorporation of flavour oil into a solid matrix is regarded as a means of formulating liquid compounds in a solid dosage form such as bouillon cubes. This can have an application in soup based products with extended aroma release.
  • a model flavour compound, ginger oil was incorporated at the 50wt% level using the mop up technique described in Example 1. At 8O 0 C, sufficient oil was retained within the mesopores of the starch for the aroma to persist for longer than 1 hour in the headspace above the powder.

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Abstract

La présente invention concerne l'utilisation d'un matériau mésoporeux pour modifier la saveur et/ou la texture d'une composition d'aliment ou d'une composition d'hygiène buccale, au moins certains des pores du matériau mésoporeux étant chargés d'au moins un ingrédient.
PCT/GB2010/050914 2009-06-02 2010-05-28 Matériaux mésoporeux WO2010139987A2 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011073666A1 (fr) * 2009-12-17 2011-06-23 Intrinsiq Materials Global Limited Silicium poreux
WO2012114126A1 (fr) * 2011-02-25 2012-08-30 Psimedica Limited Silicium mésoporeux
WO2012171090A1 (fr) * 2011-06-16 2012-12-20 Universidade Federal Do Rio Grande Do Sul-Ufrgs Zéolite et matériaux mésoporeux organisés utilisés comme charge pour la formulation de composés de caoutchouc, de caoutchouc thermoplastique et de plastique, ainsi que pour la fabrication de produits
EP2584913A1 (fr) * 2010-06-24 2013-05-01 Prayon S.A. Composé actif stabilisé
WO2013085859A1 (fr) 2011-12-08 2013-06-13 Dow Global Technologies Llc Composition de sel
WO2013085858A2 (fr) 2011-12-08 2013-06-13 Dow Global Technologies Llc Composition de sel
WO2013128201A2 (fr) 2012-02-28 2013-09-06 Nexeon Limited Particules de silicium structurées
US9548489B2 (en) 2012-01-30 2017-01-17 Nexeon Ltd. Composition of SI/C electro active material
EP3228594A3 (fr) * 2016-03-15 2017-12-27 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Utilisation de microparticules de sio2 mésoporeuses, modifiées de manière hydrophile, à structures ouvertes destinées à lutter contre la grêle et/ou à déclencher l'aspersion d'un nuage d'orage et procédé de fabrication desdites particules
US10008716B2 (en) 2012-11-02 2018-06-26 Nexeon Limited Device and method of forming a device
US10077506B2 (en) 2011-06-24 2018-09-18 Nexeon Limited Structured particles
US10090513B2 (en) 2012-06-01 2018-10-02 Nexeon Limited Method of forming silicon
US10396355B2 (en) 2014-04-09 2019-08-27 Nexeon Ltd. Negative electrode active material for secondary battery and method for manufacturing same
US10476072B2 (en) 2014-12-12 2019-11-12 Nexeon Limited Electrodes for metal-ion batteries
US10522824B2 (en) 2014-07-23 2019-12-31 Nexeon Ltd Method for preparing silicon-based active material particles for secondary battery and silicon-based active material particles
US10586976B2 (en) 2014-04-22 2020-03-10 Nexeon Ltd Negative electrode active material and lithium secondary battery comprising same
WO2021116866A1 (fr) * 2019-12-09 2021-06-17 Nicoventures Trading Limited Produits en sachet à stabilité de saveur améliorée
BE1028282B1 (fr) * 2019-10-10 2022-02-04 Silinnov Scrl Composition de silice mésoporeuse soluble, méthode de solubilisation de silice mésoporeuse et utilisation de celle-ci
US20220347095A1 (en) * 2009-10-30 2022-11-03 Ix Biopharma Ltd Solid Dosage Form
WO2023187223A1 (fr) * 2022-04-01 2023-10-05 Amplicon Ab Formulations de nicotine
US11793230B2 (en) 2019-12-09 2023-10-24 Nicoventures Trading Limited Oral products with improved binding of active ingredients
US11826462B2 (en) 2019-12-09 2023-11-28 Nicoventures Trading Limited Oral product with sustained flavor release
US11872231B2 (en) 2019-12-09 2024-01-16 Nicoventures Trading Limited Moist oral product comprising an active ingredient
US11969502B2 (en) 2019-12-09 2024-04-30 Nicoventures Trading Limited Oral products
US12064424B2 (en) 2019-12-09 2024-08-20 Nicoventures Trading Limited Moist oral compositions

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3980767A (en) 1968-07-23 1976-09-14 Beecham Group Limited Gel toothpastes
US3996863A (en) 1976-03-15 1976-12-14 The United States Of America As Represented By The United States Energy Research And Development Administration Rapid ignition of fluidized bed boiler
US4328205A (en) 1978-07-12 1982-05-04 Beecham Group Limited Inhibition of corrosion of aluminium tubes by toothpastes
US4340583A (en) 1979-05-23 1982-07-20 J. M. Huber Corporation High fluoride compatibility dentifrice abrasives and compositions
US4358437A (en) 1978-11-29 1982-11-09 Beecham Group Limited Compositions
US4420312A (en) 1979-05-23 1983-12-13 J. M. Huber Corporation Method for production of high fluoride compatibility dentifrice abrasives and compositions
US4421527A (en) 1977-12-20 1983-12-20 J. M. Huber Corporation High fluoride compatibility dentifrice abrasives and compositions
US4985082A (en) 1987-11-20 1991-01-15 Lafayette Applied Chemistry, Inc. Microporous granular starch matrix compositions
US5011701A (en) 1988-12-30 1991-04-30 Kraft General Foods, Inc. Low calorie food products having smooth, creamy, organoleptic characteristics
US5919486A (en) 1993-12-27 1999-07-06 San-Ei Sucrochemical Co., Ltd. Powder preparation and a process for preparing the same
US5951962A (en) 1996-09-23 1999-09-14 Basf Aktiengesellschaft Mesoporous silica, its preparation and its use
US6558703B1 (en) 1997-11-28 2003-05-06 Astrazeneca Ab Porous hydroxyapatite particles as carriers for drug substances
US6749825B2 (en) 2002-05-02 2004-06-15 Battelle Memorial Institute Mesoporous carbonates and method of making
US20070003492A1 (en) 2003-09-11 2007-01-04 Kabushiki Kaisha Toyota Chuo Kenkyusho Porous silica having substance carried thereon

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0118689D0 (en) * 2001-08-01 2001-09-19 Psimedica Ltd Pharmaceutical formulation
GB0508174D0 (en) * 2005-04-22 2005-06-01 Psimedica Ltd Oral hygiene compositions
CN101166426B (zh) * 2005-05-04 2011-12-21 弗门尼舍有限公司 包含胶囊化香料的脂肪、蜡或油基食品成分的制备方法
GB0526332D0 (en) * 2005-12-23 2006-02-01 Psimedica Ltd Pharmaceutical product

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3980767A (en) 1968-07-23 1976-09-14 Beecham Group Limited Gel toothpastes
US3996863A (en) 1976-03-15 1976-12-14 The United States Of America As Represented By The United States Energy Research And Development Administration Rapid ignition of fluidized bed boiler
US4421527A (en) 1977-12-20 1983-12-20 J. M. Huber Corporation High fluoride compatibility dentifrice abrasives and compositions
US4328205A (en) 1978-07-12 1982-05-04 Beecham Group Limited Inhibition of corrosion of aluminium tubes by toothpastes
US4358437A (en) 1978-11-29 1982-11-09 Beecham Group Limited Compositions
US4340583A (en) 1979-05-23 1982-07-20 J. M. Huber Corporation High fluoride compatibility dentifrice abrasives and compositions
US4420312A (en) 1979-05-23 1983-12-13 J. M. Huber Corporation Method for production of high fluoride compatibility dentifrice abrasives and compositions
US4985082A (en) 1987-11-20 1991-01-15 Lafayette Applied Chemistry, Inc. Microporous granular starch matrix compositions
US5011701A (en) 1988-12-30 1991-04-30 Kraft General Foods, Inc. Low calorie food products having smooth, creamy, organoleptic characteristics
US5919486A (en) 1993-12-27 1999-07-06 San-Ei Sucrochemical Co., Ltd. Powder preparation and a process for preparing the same
US5951962A (en) 1996-09-23 1999-09-14 Basf Aktiengesellschaft Mesoporous silica, its preparation and its use
US6558703B1 (en) 1997-11-28 2003-05-06 Astrazeneca Ab Porous hydroxyapatite particles as carriers for drug substances
US6749825B2 (en) 2002-05-02 2004-06-15 Battelle Memorial Institute Mesoporous carbonates and method of making
US20070003492A1 (en) 2003-09-11 2007-01-04 Kabushiki Kaisha Toyota Chuo Kenkyusho Porous silica having substance carried thereon

Non-Patent Citations (20)

* Cited by examiner, † Cited by third party
Title
ANGEWANDTE CHEMIE, vol. 7, no. 20, 2008, pages 3696
BELLET; CANHAM, ADV. MATER, vol. 10, 1998, pages 487 - 490
BRUNAUER ET AL., J. AM. CHEM. SOC., vol. 60, 1938, pages 309
CANHAM, NATURE, vol. 368, 1994, pages 133 - 135
CHEM. COMMUN., 2005, pages 1986 - 1987
E. RICHMAN ET AL., NANO LETTERS, vol. 8, no. 9, 2008, pages 3075 - 3079
G. MATTEI; V. VALENTINI, JOURNAL AMERICAN CHEMICAL SOCIETY, vol. 125, 2003, pages 9608
HEFFERREN, J., DENTAL RESEARCH, vol. 55, no. 4, 1976, pages 563 - 573
J. CONTROLLED RELEASE, vol. 110, 2006, pages 522
J. SALONEN ET AL.: "Studies of thermally carbonized porous silicon surfaces", PHYS STAT. SOLIDI (A), vol. 182, 2000, pages 123 - 126
J.H. SONG; M.J. SAILOR: "Chemical Modification of Crystalline Porous Silicon Surfaces", INORG. CHEM., vol. 21, no. 1-3, 1999, pages 69 - 84
KERKAR ET AL., J. AM. CERAM. SOC., vol. 73, 1990, pages 2879 - 2885
KERKAR, J. AM. CHEM. SOC., vol. 73, 1990, pages 2879 - 85
MATER. LETT, vol. 59, 2005, pages 3308
RUTLIDGE ET AL.: "Carbonized starch microcellular foam-cellulose fiber composite structures", BIORESOURCES, vol. 3, no. 4, 2008, pages 1063 - 1080
S.T. LAKSHMIKUMAR ET AL.: "Stabilisation of porous silicon surface by low temperature photoassisted reaction with acetylene", CURR. APPL. PHYS., vol. 3, 2003, pages 185 - 189
SACKS, CERAM. ENG. SCI. PROC., vol. 6, 1985, pages 1109 - 1123
STOOKEY ET AL., J. DENTAL RESEARCH, vol. 61, no. 11, 1982, pages 1236 - 9
VALENTINI ET AL., PHYSICA STATUS SOLIDI (C), vol. 4, no. 6, 2007, pages 2044 - 2048
Z. BAO ET AL., NATURE, vol. 446, 8 March 2007 (2007-03-08), pages 172 - 175

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US9540246B2 (en) 2009-12-17 2017-01-10 Psimedica Limited Porous silicon
EP2584913A1 (fr) * 2010-06-24 2013-05-01 Prayon S.A. Composé actif stabilisé
EP2584913B1 (fr) * 2010-06-24 2019-03-20 Prayon S.A. Composé actif stabilisé
US9745199B2 (en) 2011-02-25 2017-08-29 Psimedica Limited Mesoporous silicon
WO2012114126A1 (fr) * 2011-02-25 2012-08-30 Psimedica Limited Silicium mésoporeux
CN103687808A (zh) * 2011-02-25 2014-03-26 Psi医疗有限公司 介孔硅
JP2014511331A (ja) * 2011-02-25 2014-05-15 サイメディカ リミテッド メソポーラスシリコン
WO2012171090A1 (fr) * 2011-06-16 2012-12-20 Universidade Federal Do Rio Grande Do Sul-Ufrgs Zéolite et matériaux mésoporeux organisés utilisés comme charge pour la formulation de composés de caoutchouc, de caoutchouc thermoplastique et de plastique, ainsi que pour la fabrication de produits
US10822713B2 (en) 2011-06-24 2020-11-03 Nexeon Limited Structured particles
US10077506B2 (en) 2011-06-24 2018-09-18 Nexeon Limited Structured particles
WO2013085859A1 (fr) 2011-12-08 2013-06-13 Dow Global Technologies Llc Composition de sel
WO2013085858A2 (fr) 2011-12-08 2013-06-13 Dow Global Technologies Llc Composition de sel
US9548489B2 (en) 2012-01-30 2017-01-17 Nexeon Ltd. Composition of SI/C electro active material
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WO2013128201A2 (fr) 2012-02-28 2013-09-06 Nexeon Limited Particules de silicium structurées
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US10586976B2 (en) 2014-04-22 2020-03-10 Nexeon Ltd Negative electrode active material and lithium secondary battery comprising same
US10522824B2 (en) 2014-07-23 2019-12-31 Nexeon Ltd Method for preparing silicon-based active material particles for secondary battery and silicon-based active material particles
US11196042B2 (en) 2014-07-23 2021-12-07 Nexeon Ltd Method for preparing silicon-based active material particles for secondary battery and silicon-based active material particles
US10476072B2 (en) 2014-12-12 2019-11-12 Nexeon Limited Electrodes for metal-ion batteries
EP3228594A3 (fr) * 2016-03-15 2017-12-27 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Utilisation de microparticules de sio2 mésoporeuses, modifiées de manière hydrophile, à structures ouvertes destinées à lutter contre la grêle et/ou à déclencher l'aspersion d'un nuage d'orage et procédé de fabrication desdites particules
BE1028282B1 (fr) * 2019-10-10 2022-02-04 Silinnov Scrl Composition de silice mésoporeuse soluble, méthode de solubilisation de silice mésoporeuse et utilisation de celle-ci
WO2021116866A1 (fr) * 2019-12-09 2021-06-17 Nicoventures Trading Limited Produits en sachet à stabilité de saveur améliorée
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US11872231B2 (en) 2019-12-09 2024-01-16 Nicoventures Trading Limited Moist oral product comprising an active ingredient
US11969502B2 (en) 2019-12-09 2024-04-30 Nicoventures Trading Limited Oral products
US12064424B2 (en) 2019-12-09 2024-08-20 Nicoventures Trading Limited Moist oral compositions
WO2023187223A1 (fr) * 2022-04-01 2023-10-05 Amplicon Ab Formulations de nicotine

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