WO2000025761A1 - Capsules with porous mineral cortex - Google Patents
Capsules with porous mineral cortex Download PDFInfo
- Publication number
- WO2000025761A1 WO2000025761A1 PCT/FR1999/002614 FR9902614W WO0025761A1 WO 2000025761 A1 WO2000025761 A1 WO 2000025761A1 FR 9902614 W FR9902614 W FR 9902614W WO 0025761 A1 WO0025761 A1 WO 0025761A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- mineral
- capsule
- liquid medium
- capsules
- active material
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/14—Enzymes or microbial cells immobilised on or in an inorganic carrier
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/02—Enzymes or microbial cells immobilised on or in an organic carrier
- C12N11/04—Enzymes or microbial cells immobilised on or in an organic carrier entrapped within the carrier, e.g. gel or hollow fibres
Definitions
- the present invention relates to new capsules with a porous mineral shell in which are immobilized, in a liquid medium, one or more biological active materials.
- the techniques for immobilizing active materials aim to limit and more preferably to hinder their free migration into a surrounding medium.
- the first method consists in binding the active material to be immobilized to a surface of support type either by adsorption (interactions of ionic type, Van der Waals bonds), either by covalent bond or via an intermediate compound .
- the second method aims to physically retain the active material inside a solid or porous matrix such as a stabilized gel.
- This second approach is widely used for the immobilization of biological active materials such as cells or enzymes for example.
- a physical encapsulation of the biological active materials considered is carried out inside a polymer matrix.
- the encapsulation material must in fact meet several requirements:
- hydrocolloid gels hydrocolloid gels.
- alginates and carrageenans natural gels
- polyacrylamide polyacrylamide
- This type of encapsulation is generally obtained by adding the active material to be immobilized in the form of a suspension in an aqueous solution of a precursor of the encapsulation material. The precursor solution is then transformed there into droplets generally by dispersion. Finally, these droplets are stabilized in the form of beads in which the active material is trapped, either by polymerization or any other type of crosslinking.
- these inorganic matrices are particularly advantageous. Their mechanical resistance is considerably increased. They generally have a hydrophilic character as well as better stability to solvents and to pH. What is more, they are stable in concentrated saline medium unlike organic matrices based on alginate for example.
- the object of the present invention is precisely to propose a new encapsulation mode, which is particularly advantageous insofar as it precisely allows biological active materials to be preserved in a liquid environment suitable for the conservation of their structure and activity and, where appropriate, their development internal while effectively protecting them against any degradation that may be caused to them by the surrounding environment.
- the present invention therefore has for first object a mineral capsule consisting of a mineral shell and a liquid core in which is immobilized at least one biological active material.
- biological active material any molecule, cell or organism having an industrial interest due to its biological activity.
- cellular organisms such as microorganisms of the bacteria, yeast, fungus and algae type, cells of animal or vegetable origin, enzymes or proteins of the antibody type for example. They are more preferably living cells or organisms.
- enzymes such as hydrolases, nucleases, oxidases, proteases, isomerases and the like.
- oxidoreductases such as alcohol dehydrogenases, oxygenases and glucose dehydrogenases, transferases such as D-glutamyl transferase, lyases such as fumarase and aspartase, hydrolases such as lipases, nitrilehydratases, lactases and acylases as well as isomerases. It can also be proteins or protein complexes of the cytochrome C, hemoglobin, myoglobin, transferrin or superoxide dismutase type or of antibodies.
- the biological active material is in the case of the present invention not adsorbed in a form dispersed within a matrix but concentrated in a liquid medium which is isolated from the surrounding medium with mineral bark.
- liquid medium means a medium capable of ensuring the conservation of the activity and the structure and / or the survival and if necessary the internal development of a biological active material, this medium being under a fluid form of the liquid type. As such, it differs from alginate or carrageenan type media which are similar to media in gel form.
- this liquid biological medium is or is derived from an aqueous medium.
- this liquid medium can be buffered and / or supplemented with trace elements, sugars, salts and any other nutritive agent likely to be necessary for the conservation of the activity and the structure and / or the survival and if necessary internal development of the immobilized biological active material.
- active materials depending on their water-soluble nature, are either dissolved or dispersed in the liquid medium.
- the mineral bark obtained according to the method of the invention has the double advantage of effectively protecting the liquid medium and the active material (s) it contains, and if necessary allowing it to be exchanged with the medium. surrounding capsules. This is in particular achieved by adjusting the degree of porosity of the mineral capsules obtained according to the invention.
- the mineral capsules obtained can be non-porous. This specificity is more particularly advantageous when it is essentially desired to ensure effective protection of the liquid medium, incorporating at least one biological active material, with respect to its surrounding medium.
- the capsules obtained according to the invention are much more resistant mechanically, thermally and chemically due to the mineral character of their bark.
- the aqueous medium and, where appropriate, the active material which it contains are generally released by fractionation of the capsule or by induced degradation of the latter.
- the capsules obtained can be porous and this porosity is controllable.
- the present invention is therefore particularly advantageous insofar as it provides a reliable packaging method, compatible with the internal development of the immobilized active ingredients and adjustable according to the nature and the amount of immobilized active ingredient (s). ).
- the preservation within the capsule of a liquid medium which can be the natural biological medium of the immobilized active material is a guarantee of prolonged functioning of said active material, functioning which can for example result in the production of metabolites or be enzymatic.
- the mineral nature of the bark of the claimed capsules constitutes an effective protective barrier to the biological active material vis-à-vis the surrounding environment while at the same time authorizing its exchanges with it.
- the size of the capsules being controllable, it can be adjusted according to the constraints related to the size of the active ingredients to be encapsulated or even to the number of these biological active ingredients.
- this capsule is prepared in the context of the present invention under operating conditions which are gentle enough not to affect the integrity of said active ingredients.
- the active ingredient to be immobilized is in fact not exposed during its conditioning to temperature and, where appropriate, pH values likely to harm it.
- composition of the mineral shell it consists of at least one oxide and / or hydroxide of aluminum, silicon, zirconium and / or a transition metal.
- transition metal is meant more particularly the metals of the fourth period ranging from scandium to zinc insofar as these are of course compatible in terms of safety with the intended application. More particularly, it is an oxide or hydroxide of titanium, manganese, iron, cobalt, nickel or copper.
- this mineral shell can comprise oxides and / or hydroxides of different natures.
- Particularly suitable for the present invention are the oxides and / or hydroxides of silicon, aluminum, titanium and zirconium.
- the capsules comprise a mineral shell based on at least one silicon oxide.
- the size of the capsules according to the invention can be between 1 and several tens of micrometers.
- the particle size of the mineral material constituting the shell of these capsules can vary for its part between 1 and 200 nm.
- the thickness of the mineral shell it can vary between 1 and 200 nm.
- These capsules can also be characterized by the amount of liquid medium that the mineral shell retains by introducing the retention parameter of the capsule. This corresponds to the ratio of the mass of the liquid medium contained in the capsule to that of the mineral bark. When the bark is too porous, the retention of the capsule is low. One can thus vary the retention of the capsules by fixing the size of the particles of the material constituting the mineral shell as well as the thickness of the latter.
- the present invention also relates to a process useful for preparing mineral capsules in accordance with the present invention, said process comprising 1) the emulsification of a liquid medium containing at least one biological active material within a second immiscible phase with said liquid medium so as to disperse it therein in the form of droplets,
- amphiphilic surfactant system proposed according to the invention has the advantage of blocking the phenomenon of natural diffusion of mineral particles towards the center of the droplets.
- amphiphilic surfactant system is intended to denote either a single compound at the level of which two regions coexist with very different solubilities and sufficiently distant from each other to behave independently, or an association of '' at least two compounds having very different solubilities such as a first compound with hydrophilic character and a second compound with hydrophobic character.
- these two regions or compounds respectively comprise at least one hydrophilic group and one or more long chains of hydrophobic nature.
- the surfactant system used according to the invention can be represented by a single compound and which will then be introduced before carrying out the second stage, that is to say the hydrolysis and polycondensation stage, or further resulting from an in situ interaction of at least two compounds such as for example an organosoluble surfactant initially present in the second generally organosoluble phase and a water-soluble compound present in the generally aqueous liquid medium.
- the two compounds meet at the interface of the droplets formed during the emulsification. Due to their interaction, they help to stabilize the system by decreasing the interfacial tension at the interface of the droplets and probably act as a steric or electrostatic barrier.
- the embodiment using at least two distinct compounds is more particularly preferred capable of interacting to lead to a surfactant system capable of effectively opposing the diffusion of mineral particles in aqueous droplets and of stabilizing said emulsion.
- the surfactant system proposed according to the invention preferably comprises at least one surfactant with an HLB value of less than 7.
- HLB designates the ratio of the hydrophilicity of the polar groups of the surfactant molecule to the hydrophobicity of the lipophilic part of this same molecule.
- the two compounds are preferably respectively present in the liquid medium, generally aqueous and the second phase generally organosoluble and interact with one another during the emulsification of the liquid medium in said second phase.
- This option has the advantage of giving the corresponding emulsion satisfactory stability as soon as it is formed. What is more, it proves possible, if necessary, by appropriately selecting the agents constituting the amphiphilic surfactant system, to adjust the pH to a value compatible with the active ingredient.
- the emulsification it can be carried out by applying a mechanical energy of intense agitation to the two initial phases, and / or a sonication.
- the size of the droplets obtained at the end of the emulsification step can be between approximately 0.1 and ten ⁇ m.
- the compound present in the liquid, generally aqueous medium preferably has a viscosifying action. More particularly, this compound can be a compound chosen from sugars and their derivatives. As such, the oses (or monosaccharides), the osides and the highly depolymerized polyholosides are suitable. Compounds are understood to have a weight mass which is more particularly less than 20,000 g / mole. Among the dares, there may be mentioned aldoses such as glucose, mannose, galactose and ketoses such as fructose.
- Osides are compounds that result from the condensation, with elimination of water, of daring molecules with non-carbohydrate molecules.
- the holosides which are formed by the combination of exclusively carbohydrate units are preferred, and more particularly the oligoholosides (or oligosaccharides) which contain only a limited number of these units, that is to say a number in general. less than or equal to 10.
- oligoholosides mention may be made of sucrose, lactose, cellobiose, maltose.
- the highly depolymerized polyholosides (or polysaccharides) suitable are described for example in the work of P.
- polyholosides are used whose molecular mass in weight is more particularly less than 20,000 g / mole.
- highly depolymerized polyholosides mention may be made of dextran, starch, xanthan gum and galactomannans such as guar or locust bean. These polysaccharides preferably have a melting weight greater than 100 ° C. and a solubility in water of between 10 and 500 g / l.
- gum arabic e.g., kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolinol, sorbitol type, ether carbohydrates such as methyl-, ethyl-, carboxymethyl-, hydroxyethyl- and hydroxypropyl cellulose ethers and glycerols, pentaerythrol, propylene glycol, ethylene glycol, non-viscous diols and / or polyvinyl alcohols.
- fatty acid sucroesters carbohydrate alcohols of the sorbitol, mannitol type
- ether carbohydrates such as methyl-, ethyl-, carb
- hydrocolloid It is preferably a hydrocolloid. Mention may in particular be made, for example of this type of compound, of alginates, polysaccharides of the natural gum type such as carrageenans, xanthan and guar and very particularly cellulose derivatives.
- it is a cellulose derivative and more preferably hydroxyethylcellulose.
- the surfactant (s) generally organosoluble (s) present (s) at the level of the second phase can be chosen from fatty alcohols, triglycerides, fatty acids, sorbitan esters, fatty amines, these compounds being or not in a polyalkoxylated form, liposoluble lecithins, polyalkylenes dipolyhydroxystearates, quaternary ammonium salts, monoglycerides, polyglycerol esters, polyglycerol polyricinoleate and lactic esters.
- Triglycerides can be triglycerides of plant or animal origin (such as lard, tallow, peanut oil, butter oil, cottonseed oil, linseed oil, olive oil, fish oil, coconut oil, coconut oil).
- Fatty acids are fatty acid esters (such as, for example, oleic acid, stearic acid).
- Sorbitan esters are cyclized fatty acid sorbitol esters comprising from 10 to 20 carbon atoms such as lauric acid, stearic acid or oleic acid.
- this surfactant is a sorbitan ester as defined above and more preferably sorbitan sesquioleate.
- the compound present in the generally aqueous liquid medium must interact with the surfactant present in the second generally hydrophobic phase to lead to a surfactant system capable of constituting an effective diffusion barrier with respect to the particles. mineral precipitate. Consequently, their respective choices must be made taking this imperative into account.
- the nature of the active ingredient to be encapsulated, as well as the composition of the mineral crust of the capsules prepared according to the invention are also determining factors in the choice of the surfactant system and the assessment of the respective amounts of the two corresponding compounds. These adjustments are in fact within the competence of a person skilled in the art.
- R 2 represents an alkyl or alkenyl radical comprising 7 to 22 carbon atoms
- Ri represents a hydrogen atom or an alkyl radical comprising 1 to 6 carbon atoms
- A represents a group (CO) or (OCH 2 CH 2 )
- n is 0 or 1
- x is 2 or 3
- y is 0 to 4
- Q represents a radical -R 3 -COOM with R 2 representing an alkyl radical comprising 1 to 6 carbon atoms
- M represents a hydrogen atom, an alkali metal, an alkaline earth metal or also a quaternary ammonium group in which the radicals linked to the nitrogen atom, identical or different, are chosen from hydrogen or an alkyl or hydroalkyl radical having 1 to 6 atoms carbon
- B represents H or Q.
- M represents a hydrogen atom, sodium, potassium and an NH 4 group.
- amphoteric derivatives of alkyl polyamines such as Amphionic XL ®, Mirataine H2C-HA ® marketed by Rhodia Chimie, as well as Ampholac 7T / X ® sold by Berol Nobel.
- a main nonionic surfactant the hydrophilic part of which contains one or more saccharide unit (s).
- Said saccharide units generally contain from 5 to 6 carbon atoms. These can be derived from sugars such as fructose, glucose, mannose, galactose, talose, gulose, allose, altose, idose, arabinose, xylose, lyxose and / or ribose.
- alkylpolyglycosides can be obtained by condensation (for example by acid catalysis) of glucose with primary fatty alcohols (US-A-3,598,865; US-A-4,565,647; EP-A-132,043; EP-A- 132 046; Tenside Surf. Det.
- the concentration of amphiphilic surfactant system can be between approximately 1% and 10% by weight relative to the organosoluble phase.
- the surfactant incorporated at the level of the generally organosoluble second phase is a sorbitan ester and more preferably sorbitan sesquioleate.
- the compound incorporated in the liquid medium it is preferably a cellulose derivative and more particularly hydroxyethyl cellulose.
- the material of the mineral shell derives from the hydrolysis and polycondensation of one or more alkoxides of formula II.
- - M represents an element chosen from titanium, manganese, iron, cobalt, nickel, silicon, aluminum or zirconium, - R is a hydrolysable substituent,
- - n is an integer between 1 and 6,
- - P is a non-hydrolyzable substituent
- - m is an integer between 0 and 6.
- - M is chosen from silica, aluminum, titanium and zirconium
- - R is a group chosen from aikoxy and / or aryloxy groups in Ci to Ci 8 and preferably in C 2 to Ce and n is an integer between 2 and 4 and
- - P is a group chosen from C 1 to C 8 alkyl, aryl or C 2 to C alkenyl groups.
- R is preferably a C1 to Ce aikoxy group and more preferably C 2 to C 4 .
- This aikoxy group may, where appropriate, be substituted by a C 1 to C alkyl or aikoxy group.
- R can represent identical or different aikoxy groups.
- the capsule can be given a more or less hydrophobic character by varying the nature and for example the length of the alkyl and / or alkoxy chains constituting this mineral hydrolyzable and polycondensable compound.
- the hydrolysis and polycondensation of this mineral precursor are carried out either spontaneously by bringing it into contact with the emulsion or are initiated by adjusting the pH and / or the temperature of the emulsion to a suitable value. at their manifestation. This adjustment may in particular arise from the presence in the emulsion of water-soluble ions such as NH OH, NaOH or HCl or organosoluble of the amino type. These adjustments fall within the competence of a person skilled in the art.
- the mineral shell obtained according to the invention is based on silicon oxide. It is derived from the precipitation of at least one silicate.
- silicate suitable for the present invention mention may more particularly be made of tetramethylorthosilicate, TMOS, tetraethylorthosilicate, TEOS, tetrapropylorthosilicate, TPOS, alkylalkoxysilanes and haloalkylsilanes.
- the mineral capsule is obtained by formation of a mineral precipitate in the presence of a hydrolysis and condensation agent of said compound.
- the hydrolysis of these silicon alkoxides can be carried out both in acid catalysis and in basic catalysis provided that the corresponding oxides and / or hydroxides are obtained in powder form.
- a silicon alkoxide such as tetraethylorthosilicate, TEOS, is used in the presence of ammonia, as a hydrolysis and polycondensation agent.
- the second phase is generally an oily phase immiscible with the generally aqueous liquid medium and is preferably composed of an oil chosen from vegetable, animal and mineral oils. It may for example be a parrafinic oil or a silicone oil.
- This second phase comprises at least one generally organosoluble surfactant which is preferably chosen from sorbitan esters and more preferably is represented by sorbitan sesquioleate.
- the generally aqueous liquid medium it comprises at least one hydrocolloid, optionally the hydrolysis and polycondensation agent of the mineral hydrolyzable and polycondensable precursor.
- hydrocolloid it is preferably a cellulose derivative and more preferably hydroxyethylcellulose.
- the mineral capsules according to the invention are particularly advantageous for uses in the fields of biomedical fermentation, food and in the chemical industry. It is thus possible to envisage immobilizing, within the capsules claimed, cells having an activity which is of interest for the production of pharmaceutical products, metabolites and / or reagents such as chemical or pharmaceutical synthesis intermediates or else biodegradable polymers.
- the immobilization according to the invention of microorganisms of the yeast or bacteria type is also particularly advantageous for the food industry and very particularly for the dairy and wine industries.
- Enzymes immobilized according to the invention can represent, for their part, reagents of choice in numerous industrial manufacturing processes for catalytic or analytical methods.
- capsules according to the invention based on living cells or enzymes in the treatment of waste water or waste.
- the examples and the figure which follow are presented by way of illustration and without limitation of the subject of the present invention.
- Aqueous ammonia solution (NH 4 OH) Density at 20 ° C: 0.880
- Methyl silicate Si (OMe) 4 Molar mass: 156 g Density at 20 ° C: 1.032
- Escherichia Coli K12 expressing a ⁇ -galactosidase Escherichia Coli K12 expressing a ⁇ -galactosidase.
- Aqueous phase H 2 0 43.40 g HEC 2.61 g (6% / water)
- the HEC is homogenized in purified water in a water bath at 40 ° C for about 20 minutes. A clear yellow viscous mixture is thus obtained. The cells are then added thereto, followed by the aqueous ammonia solution.
- the Arcacel 83 ® is dissolved in Isopar M ® .
- the organic phase and the aqueous phase are emulsified by means of an Ultraturrax ®, thus obtaining a water / oil emulsion with a stability of several hours.
- the size of the droplets is close to ten microns.
- the size of the silica particles which constitute the shell is close to a few nanometers.
- the capsules have a size of the order of ten ⁇ m
- Example 2 Determination of the enzymatic activity of the biocapsules
- the enzymatic activity of E. coli ⁇ -galactosidase is determined after enzymatic hydrolysis of para-nitrophenyl- ⁇ -D-galactoside (p-NPG) to p-nitrophenol.
- p-NPG para-nitrophenyl- ⁇ -D-galactoside
- the quantitative measurement of p-nitrophenol by spectrophotometry makes it possible to deduce therefrom the enzymatic activity of the biocapsules.
- the enzymatic activity of the biocapsules of Example 1 is expressed in ⁇ mol / h / mg of CS (dry cells), this compared to the bioactivity of the starting cells.
- the enzymatic activity of the starting cells is 0.2 ⁇ mol / h / mg of CS, the activity yield of the biocapsules is approximately 50%. The activity of the cells is therefore well preserved.
- Example 3 Obtaining silica capsules, with a particle size constituting the shell of a few nanometers.
- the HEC is homogenized in purified water in a water bath at 40 ° C for about 20 minutes. A clear yellow viscous mixture is thus obtained. The cells are then added thereto, followed by the aqueous ammonia solution.
- the Arcacel 83 ® is dissolved in Isopar M ® .
- the organic phase and the aqueous phase are emulsified using an ultraturrax, thus obtaining a water / oil dispersion having a stability of several hours.
- the size of the droplets is close to ten microns.
- the size of the capsules is between 1 and ten ⁇ m (SEM).
- the size of the silica particles constituting the shell is a few nanometers. The observations made by MET clearly show the encapsulation of bacteria by the silica capsule.
- Example 4 Obtaining capsules with TMOS and co-alkoxide ([NHj] 0.1 mol / l).
- Aqueous phase H 2 0 43.40 g
- the HEC is homogenized in purified water in a water bath at 40 ° C for about 20 minutes. A clear yellow viscous mixture is thus obtained. The cells are then added thereto and then the aqueous ammonia solution (0.37 g).
- the organic phase 1 and the aqueous phase are emulsified using an ultraturrax, thus obtaining a water / oil dispersion having a stability of several hours.
- the size of the droplets is close to ten microns.
- the mixture of alkoxides (organic phase 2) is added thereto with a flow rate of 0.5 ml / min (the duration of the introduction is 1 hour) at 25 ° C.
- the particles obtained are separated and washed with methanol and then dried at room temperature overnight. The particles thus obtained are hydrophobic.
- the particle size is between 1 and ten ⁇ m (SEM).
- the size of the silica particles constituting the shell is a few nanometers (TEM).
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000579202A JP2003515310A (en) | 1998-10-30 | 1999-10-27 | Capsule with porous inorganic shell |
NZ511365A NZ511365A (en) | 1998-10-30 | 1999-10-27 | Capsules with porous mineral cortex |
AU63469/99A AU764016B2 (en) | 1998-10-30 | 1999-10-27 | Capsules with porous mineral cortex |
BR9914907-9A BR9914907A (en) | 1998-10-30 | 1999-10-27 | Mineral capsule, process for its preparation, and use of the capsules |
CA002349674A CA2349674A1 (en) | 1998-10-30 | 1999-10-27 | Capsules with porous mineral cortex |
EP99950847A EP1124542A1 (en) | 1998-10-30 | 1999-10-27 | Capsules with porous mineral cortex |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR98/13695 | 1998-10-30 | ||
FR9813695A FR2785292B1 (en) | 1998-10-30 | 1998-10-30 | POROUS MINERAL BARK CAPSULES IN WHICH THEY ARE IMMOBILIZED IN A LIQUID BIOLOGICAL MEDIUM, ONE OR MORE BIOLOGICAL MATERIALS, THEIR PREPARATION METHODS AND USES |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2000025761A1 true WO2000025761A1 (en) | 2000-05-11 |
Family
ID=9532225
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR1999/002614 WO2000025761A1 (en) | 1998-10-30 | 1999-10-27 | Capsules with porous mineral cortex |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP1124542A1 (en) |
JP (1) | JP2003515310A (en) |
AU (1) | AU764016B2 (en) |
BR (1) | BR9914907A (en) |
CA (1) | CA2349674A1 (en) |
FR (1) | FR2785292B1 (en) |
NZ (1) | NZ511365A (en) |
WO (1) | WO2000025761A1 (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2855074A1 (en) * | 2003-05-22 | 2004-11-26 | Rhodia Chimie Sa | Calcium phosphate capsules e.g. useful in the food industry comprise an organic core containing an active ingredient and a surfactant and/or amphiphilic polymer |
JP2007015990A (en) * | 2005-07-08 | 2007-01-25 | National Institute Of Advanced Industrial & Technology | Inorganic microcapsule enclosing macro living body material and method for producing the same |
US7758888B2 (en) | 2000-04-21 | 2010-07-20 | Sol-Gel Technologies Ltd. | Composition exhibiting enhanced formulation stability and delivery of topical active ingredients |
US7923030B2 (en) | 2003-03-14 | 2011-04-12 | Sol-Gel Technologies, Inc. | Agent-encapsulating micro- and nanoparticles, methods for preparation of same and products containing same |
US8110284B2 (en) | 2003-07-31 | 2012-02-07 | Sol-Gel Technologies Ltd. | Microcapsules loaded with active ingredients and a method for their preparation |
US9687465B2 (en) | 2012-11-27 | 2017-06-27 | Sol-Gel Technologies Ltd. | Compositions for the treatment of rosacea |
US9868103B2 (en) | 2005-08-02 | 2018-01-16 | Sol-Gel Technologies Ltd. | Metal oxide coating of water insoluble ingredients |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IL152339A0 (en) * | 2000-04-21 | 2003-05-29 | Sol Gel Technologies Ltd | Composition exhibiting enhanced formulation stability and delivery of topical active ingredients |
FR2840822B1 (en) * | 2002-06-18 | 2005-04-08 | Centre Nat Rech Scient | MESOPOREUS EMULSION MINERAL CAPSULES |
FR2842438B1 (en) | 2002-07-22 | 2004-10-15 | Centre Nat Rech Scient | PROCESS FOR THE PREPARATION OF BALLS CONTAINING A CROSSLINKED MINERAL MATRIX |
EP1906915B1 (en) * | 2005-06-17 | 2017-09-27 | Australian Nuclear Science And Technology Organisation | Particles having hydrophobic material therein |
WO2008083092A2 (en) * | 2006-12-28 | 2008-07-10 | Dow Corning Corporation | Polynuclear microcapsules |
AU2008211553B2 (en) | 2007-02-01 | 2013-06-20 | Sol-Gel Technologies Ltd. | Compositions for topical application comprising a peroxide and retinoid |
JP5344417B2 (en) * | 2007-04-17 | 2013-11-20 | 国立大学法人群馬大学 | Method for producing drug-silica inclusion body using water-oil interface |
JP5245155B2 (en) * | 2008-01-31 | 2013-07-24 | 独立行政法人産業技術総合研究所 | Inorganic microcapsule encapsulating enzyme, its production method and use |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1991007349A1 (en) * | 1989-11-22 | 1991-05-30 | Allied-Signal Inc. | Process for forming highly uniform silica spheres |
JPH0775728A (en) * | 1993-06-18 | 1995-03-20 | Suzuki Yushi Kogyo Kk | Production of uniform inorganic microbead |
WO1997041842A1 (en) * | 1996-05-09 | 1997-11-13 | The Trustees Of The University Of Pennsylvania | Hollow bone mineral-like calcium phosphate particles |
US5693513A (en) * | 1995-01-10 | 1997-12-02 | Pope; Edward J. A. | Encapsulation of living tissue cells in an organosilicon |
WO1999009142A1 (en) * | 1997-08-18 | 1999-02-25 | Solgene Therapeutics, Llc | Encapsulation of living tissue cells in a microsphere |
-
1998
- 1998-10-30 FR FR9813695A patent/FR2785292B1/en not_active Expired - Fee Related
-
1999
- 1999-10-27 BR BR9914907-9A patent/BR9914907A/en not_active IP Right Cessation
- 1999-10-27 CA CA002349674A patent/CA2349674A1/en not_active Abandoned
- 1999-10-27 JP JP2000579202A patent/JP2003515310A/en active Pending
- 1999-10-27 NZ NZ511365A patent/NZ511365A/en unknown
- 1999-10-27 EP EP99950847A patent/EP1124542A1/en not_active Withdrawn
- 1999-10-27 WO PCT/FR1999/002614 patent/WO2000025761A1/en not_active Application Discontinuation
- 1999-10-27 AU AU63469/99A patent/AU764016B2/en not_active Ceased
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1991007349A1 (en) * | 1989-11-22 | 1991-05-30 | Allied-Signal Inc. | Process for forming highly uniform silica spheres |
JPH0775728A (en) * | 1993-06-18 | 1995-03-20 | Suzuki Yushi Kogyo Kk | Production of uniform inorganic microbead |
US5693513A (en) * | 1995-01-10 | 1997-12-02 | Pope; Edward J. A. | Encapsulation of living tissue cells in an organosilicon |
WO1997041842A1 (en) * | 1996-05-09 | 1997-11-13 | The Trustees Of The University Of Pennsylvania | Hollow bone mineral-like calcium phosphate particles |
WO1999009142A1 (en) * | 1997-08-18 | 1999-02-25 | Solgene Therapeutics, Llc | Encapsulation of living tissue cells in a microsphere |
Non-Patent Citations (1)
Title |
---|
DATABASE WPI Week 9520, Derwent World Patents Index; AN 95-151536 [18], XP002108961 * |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7758888B2 (en) | 2000-04-21 | 2010-07-20 | Sol-Gel Technologies Ltd. | Composition exhibiting enhanced formulation stability and delivery of topical active ingredients |
US8039020B2 (en) | 2000-04-21 | 2011-10-18 | Sol-Gel Technologies Ltd. | Composition exhibiting enhanced formulation stability and delivery of topical active ingredients |
US8449918B2 (en) | 2000-04-21 | 2013-05-28 | Sol-Gel Technologies Ltd. | Composition exhibiting enhanced formulation stability and delivery of topical active ingredients |
US7923030B2 (en) | 2003-03-14 | 2011-04-12 | Sol-Gel Technologies, Inc. | Agent-encapsulating micro- and nanoparticles, methods for preparation of same and products containing same |
US8425940B2 (en) | 2003-03-14 | 2013-04-23 | Sol-Gel Technologies Ltd. | Agent-encapsulating micro-and nanoparticles, methods for preparation of same and products containing same |
FR2855074A1 (en) * | 2003-05-22 | 2004-11-26 | Rhodia Chimie Sa | Calcium phosphate capsules e.g. useful in the food industry comprise an organic core containing an active ingredient and a surfactant and/or amphiphilic polymer |
WO2004105933A2 (en) * | 2003-05-22 | 2004-12-09 | Rhodia Chimie | Calcium phosphate capsules, method for the production thereof, and uses of the same |
WO2004105933A3 (en) * | 2003-05-22 | 2005-02-17 | Rhodia Chimie Sa | Calcium phosphate capsules, method for the production thereof, and uses of the same |
US8110284B2 (en) | 2003-07-31 | 2012-02-07 | Sol-Gel Technologies Ltd. | Microcapsules loaded with active ingredients and a method for their preparation |
JP2007015990A (en) * | 2005-07-08 | 2007-01-25 | National Institute Of Advanced Industrial & Technology | Inorganic microcapsule enclosing macro living body material and method for producing the same |
US9868103B2 (en) | 2005-08-02 | 2018-01-16 | Sol-Gel Technologies Ltd. | Metal oxide coating of water insoluble ingredients |
US9687465B2 (en) | 2012-11-27 | 2017-06-27 | Sol-Gel Technologies Ltd. | Compositions for the treatment of rosacea |
Also Published As
Publication number | Publication date |
---|---|
BR9914907A (en) | 2001-08-07 |
FR2785292A1 (en) | 2000-05-05 |
AU6346999A (en) | 2000-05-22 |
JP2003515310A (en) | 2003-05-07 |
AU764016B2 (en) | 2003-08-07 |
NZ511365A (en) | 2003-08-29 |
FR2785292B1 (en) | 2002-06-28 |
EP1124542A1 (en) | 2001-08-22 |
CA2349674A1 (en) | 2000-05-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1124542A1 (en) | Capsules with porous mineral cortex | |
CA2349672C (en) | Method for preparing capsules consisting of a liquid active material core enclosed in a mineral coating | |
JP5734106B2 (en) | Protein immobilization carrier, immobilized protein and production method thereof | |
FR2694894A1 (en) | Use of a transacylation reaction between an esterified polysaccharide and a polyamine or polyhydroxylated substance for the manufacture of microparticles, process and composition. | |
Soni et al. | Self-assembled enzyme capsules in ionic liquid [BMIM][BF4] as templating nanoreactors for hollow silica nanocontainers | |
EP2228127A1 (en) | Process for preparing porous silica particles, the silica particles obtained and their use. | |
BE897925A (en) | PROCESS FOR PRODUCING IMMOBILIZED ENZYME PREPARATION, PREPARATION OF IMMOBILIZED ENZYME OBTAINED AND USE THEREOF | |
EP0873180B1 (en) | Water-redispersible granules including a liquid active material | |
WO1999040902A1 (en) | Encapsulation system with organic core and mineral cortex based on aluminium hydroxycarbonate and preparation method | |
US6180378B1 (en) | Immobilization of bioactive protein in phyllosilicates | |
CN113403298B (en) | Immobilization method of free enzyme | |
US5182201A (en) | Lipase immobilization without covalent bonding on an amphiphilic support containing lipophilic alkyl chains | |
JP4799422B2 (en) | Method for preparing crosslinked protein crystals | |
JP3218794B2 (en) | New surfactant-coated enzyme and its manufacturing method. | |
US5834271A (en) | Enzyme-polyelectrolyte coacervate complex and method of use | |
Guisán et al. | Modulation of activity/stability properties of lipase from Pseudomonas fluorescens by multipoint covalent immobilization on glyoxyl-supports | |
US6280983B1 (en) | Enzyme immobilization in a gel containing 30 to 50 percent gelatin | |
CN116814602A (en) | Interface active colloid particle for cascade reaction and preparation method and application thereof | |
WO1999001213A1 (en) | Microbeads prepared from cross-linked polysaccharide hydrogel capable of containing molecules of biological interest or cells | |
JPS5850256B2 (en) | beads | |
WO2017006046A1 (en) | Binding organic molecules to a porous silica matrix | |
JPH0341156B2 (en) |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
ENP | Entry into the national phase |
Ref country code: AU Ref document number: 1999 63469 Kind code of ref document: A Format of ref document f/p: F |
|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AL AM AT AU AZ BA BB BG BR BY CA CH CN CR CU CZ DE DK DM EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GH GM KE LS MW SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
ENP | Entry into the national phase |
Ref document number: 2349674 Country of ref document: CA Ref country code: CA Ref document number: 2349674 Kind code of ref document: A Format of ref document f/p: F |
|
WWE | Wipo information: entry into national phase |
Ref document number: 511365 Country of ref document: NZ |
|
ENP | Entry into the national phase |
Ref country code: JP Ref document number: 2000 579202 Kind code of ref document: A Format of ref document f/p: F |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1999950847 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 63469/99 Country of ref document: AU |
|
WWE | Wipo information: entry into national phase |
Ref document number: 09830737 Country of ref document: US |
|
WWP | Wipo information: published in national office |
Ref document number: 1999950847 Country of ref document: EP |
|
REG | Reference to national code |
Ref country code: DE Ref legal event code: 8642 |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 1999950847 Country of ref document: EP |