EP1124542A1 - Capsules a ecorce minerale poreuse - Google Patents
Capsules a ecorce minerale poreuseInfo
- Publication number
- EP1124542A1 EP1124542A1 EP99950847A EP99950847A EP1124542A1 EP 1124542 A1 EP1124542 A1 EP 1124542A1 EP 99950847 A EP99950847 A EP 99950847A EP 99950847 A EP99950847 A EP 99950847A EP 1124542 A1 EP1124542 A1 EP 1124542A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- mineral
- capsule
- liquid medium
- capsules
- active material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
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- 102000004317 Lyases Human genes 0.000 description 1
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- 102000007474 Multiprotein Complexes Human genes 0.000 description 1
- 108010085220 Multiprotein Complexes Proteins 0.000 description 1
- 102000036675 Myoglobin Human genes 0.000 description 1
- 108010062374 Myoglobin Proteins 0.000 description 1
- 108010024026 Nitrile hydratase Proteins 0.000 description 1
- 101710163270 Nuclease Proteins 0.000 description 1
- 108090000417 Oxygenases Proteins 0.000 description 1
- 102000004020 Oxygenases Human genes 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- 102000035195 Peptidases Human genes 0.000 description 1
- 108091005804 Peptidases Proteins 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004365 Protease Substances 0.000 description 1
- PYMYPHUHKUWMLA-LMVFSUKVSA-N Ribose Natural products OC[C@@H](O)[C@@H](O)[C@@H](O)C=O PYMYPHUHKUWMLA-LMVFSUKVSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 102000019197 Superoxide Dismutase Human genes 0.000 description 1
- 108010012715 Superoxide dismutase Proteins 0.000 description 1
- 108090000992 Transferases Proteins 0.000 description 1
- 102000004357 Transferases Human genes 0.000 description 1
- 102000004338 Transferrin Human genes 0.000 description 1
- 108090000901 Transferrin Proteins 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001323 aldoses Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- HMFHBZSHGGEWLO-UHFFFAOYSA-N alpha-D-Furanose-Ribose Natural products OCC1OC(O)C(O)C1O HMFHBZSHGGEWLO-UHFFFAOYSA-N 0.000 description 1
- SRBFZHDQGSBBOR-STGXQOJASA-N alpha-D-lyxopyranose Chemical compound O[C@@H]1CO[C@H](O)[C@@H](O)[C@H]1O SRBFZHDQGSBBOR-STGXQOJASA-N 0.000 description 1
- 102000005922 amidase Human genes 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- PYMYPHUHKUWMLA-WDCZJNDASA-N arabinose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C=O PYMYPHUHKUWMLA-WDCZJNDASA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- OGBUMNBNEWYMNJ-UHFFFAOYSA-N batilol Chemical class CCCCCCCCCCCCCCCCCCOCC(O)CO OGBUMNBNEWYMNJ-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 235000014121 butter Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 235000013365 dairy product Nutrition 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
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- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000007071 enzymatic hydrolysis Effects 0.000 description 1
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000021323 fish oil Nutrition 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 150000002454 idoses Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002584 ketoses Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- ZBJVLWIYKOAYQH-UHFFFAOYSA-N naphthalen-2-yl 2-hydroxybenzoate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=C(C=CC=C2)C2=C1 ZBJVLWIYKOAYQH-UHFFFAOYSA-N 0.000 description 1
- 229920001206 natural gum Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000000050 nutritive effect Effects 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 150000002482 oligosaccharides Chemical class 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 229940127557 pharmaceutical product Drugs 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000223 polyglycerol Chemical class 0.000 description 1
- 239000003996 polyglycerol polyricinoleate Substances 0.000 description 1
- 235000010958 polyglycerol polyricinoleate Nutrition 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000004621 scanning probe microscopy Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000012064 sodium phosphate buffer Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 239000012581 transferrin Substances 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 238000012800 visualization Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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).
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Zoology (AREA)
- Genetics & Genomics (AREA)
- Biochemistry (AREA)
- Microbiology (AREA)
- Biotechnology (AREA)
- Biomedical Technology (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Medicinal Preparation (AREA)
- Medicines Containing Material From Animals Or Micro-Organisms (AREA)
- Medicines That Contain Protein Lipid Enzymes And Other Medicines (AREA)
- Medicines Containing Plant Substances (AREA)
- Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9813695A FR2785292B1 (fr) | 1998-10-30 | 1998-10-30 | Capsules a ecorce minerale poreuse dans lesquelles sont immobilisees dans un milieu biologique liquide, une ou plusieurs matieres biologiques, leurs procede de preparation et utilisations |
FR9813695 | 1998-10-30 | ||
PCT/FR1999/002614 WO2000025761A1 (fr) | 1998-10-30 | 1999-10-27 | Capsules a ecorce minerale poreuse |
Publications (1)
Publication Number | Publication Date |
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EP1124542A1 true EP1124542A1 (fr) | 2001-08-22 |
Family
ID=9532225
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99950847A Withdrawn EP1124542A1 (fr) | 1998-10-30 | 1999-10-27 | Capsules a ecorce minerale poreuse |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP1124542A1 (ja) |
JP (1) | JP2003515310A (ja) |
AU (1) | AU764016B2 (ja) |
BR (1) | BR9914907A (ja) |
CA (1) | CA2349674A1 (ja) |
FR (1) | FR2785292B1 (ja) |
NZ (1) | NZ511365A (ja) |
WO (1) | WO2000025761A1 (ja) |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1335693A2 (en) * | 2000-04-21 | 2003-08-20 | Sol-Gel Technologies Ltd. | Composition exhibiting enhanced formulation stability and delivery of topical active ingredients |
US7758888B2 (en) | 2000-04-21 | 2010-07-20 | Sol-Gel Technologies Ltd. | Composition exhibiting enhanced formulation stability and delivery of topical active ingredients |
FR2840822B1 (fr) * | 2002-06-18 | 2005-04-08 | Centre Nat Rech Scient | Capsules minerales mesoporeuses par emulsion |
FR2842438B1 (fr) * | 2002-07-22 | 2004-10-15 | Centre Nat Rech Scient | Procede de preparation de billes contenant une matrice minerale reticulee |
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 |
FR2855074A1 (fr) * | 2003-05-22 | 2004-11-26 | Rhodia Chimie Sa | Capsules de phosphate de calcium, procede de preparation et ses utilisations |
EP1656199B1 (en) | 2003-07-31 | 2016-01-06 | Sol-Gel Technologies Ltd. | Microcapsules loaded with active ingredients and a method for their preparation |
CA2612175A1 (en) * | 2005-06-17 | 2006-12-21 | Australian Nuclear Science And Technology Organisation | Particles having hydrophobic material therein |
JP5051490B2 (ja) * | 2005-07-08 | 2012-10-17 | 独立行政法人産業技術総合研究所 | マクロ生体材料を内包する無機マイクロカプセルおよびその製造方法 |
EP2431088A1 (en) | 2005-08-02 | 2012-03-21 | Sol-Gel Technologies Ltd. | Metal oxide coating of water insoluble ingredients |
KR101538295B1 (ko) * | 2006-12-28 | 2015-07-22 | 다우 코닝 코포레이션 | 다핵성 미세캡슐 |
WO2008093346A2 (en) | 2007-02-01 | 2008-08-07 | Sol-Gel Technologies Ltd. | Compositions for topical application comprising a peroxide and retinoid |
JP5344417B2 (ja) * | 2007-04-17 | 2013-11-20 | 国立大学法人群馬大学 | 水油界面を利用した薬物−シリカ封入体の製造法 |
JP5245155B2 (ja) * | 2008-01-31 | 2013-07-24 | 独立行政法人産業技術総合研究所 | 酵素を内包した無機マイクロカプセル、その製造方法及び使用 |
US9687465B2 (en) | 2012-11-27 | 2017-06-27 | Sol-Gel Technologies Ltd. | Compositions for the treatment of rosacea |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4983369A (en) * | 1989-11-22 | 1991-01-08 | Allied-Signal Inc. | Process for forming highly uniform silica spheres |
JPH0775728A (ja) * | 1993-06-18 | 1995-03-20 | Suzuki Yushi Kogyo Kk | 無機質均一微小球体の製造方法 |
US5693513A (en) * | 1995-01-10 | 1997-12-02 | Pope; Edward J. A. | Encapsulation of living tissue cells in an organosilicon |
US5895757A (en) * | 1993-06-30 | 1999-04-20 | Pope; Edward J. A. | Encapsulation of living tissue cells in inorganic microspheres prepared from an organosilicon |
US6416774B1 (en) * | 1996-05-09 | 2002-07-09 | The Trustees Of The University Of Pennsyvania | Hollow bone mineral-like calcium phosphate particles |
-
1998
- 1998-10-30 FR FR9813695A patent/FR2785292B1/fr not_active Expired - Fee Related
-
1999
- 1999-10-27 CA CA002349674A patent/CA2349674A1/fr not_active Abandoned
- 1999-10-27 WO PCT/FR1999/002614 patent/WO2000025761A1/fr not_active Application Discontinuation
- 1999-10-27 BR BR9914907-9A patent/BR9914907A/pt not_active IP Right Cessation
- 1999-10-27 AU AU63469/99A patent/AU764016B2/en not_active Ceased
- 1999-10-27 JP JP2000579202A patent/JP2003515310A/ja active Pending
- 1999-10-27 NZ NZ511365A patent/NZ511365A/en unknown
- 1999-10-27 EP EP99950847A patent/EP1124542A1/fr not_active Withdrawn
Non-Patent Citations (1)
Title |
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See references of WO0025761A1 * |
Also Published As
Publication number | Publication date |
---|---|
CA2349674A1 (fr) | 2000-05-11 |
WO2000025761A1 (fr) | 2000-05-11 |
NZ511365A (en) | 2003-08-29 |
FR2785292B1 (fr) | 2002-06-28 |
FR2785292A1 (fr) | 2000-05-05 |
AU6346999A (en) | 2000-05-22 |
BR9914907A (pt) | 2001-08-07 |
JP2003515310A (ja) | 2003-05-07 |
AU764016B2 (en) | 2003-08-07 |
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