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WO2010128204A1 - Nouveaux matériaux nanocomposites inorgano-bio-organiques, leur préparation et leur utilisation - Google Patents

Nouveaux matériaux nanocomposites inorgano-bio-organiques, leur préparation et leur utilisation Download PDF

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Publication number
WO2010128204A1
WO2010128204A1 PCT/FI2010/050357 FI2010050357W WO2010128204A1 WO 2010128204 A1 WO2010128204 A1 WO 2010128204A1 FI 2010050357 W FI2010050357 W FI 2010050357W WO 2010128204 A1 WO2010128204 A1 WO 2010128204A1
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Prior art keywords
glycan
layered double
double hydroxide
aminoglycan
material according
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Andriy Grafov
Markku Leskelä
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Licentia Oy
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Licentia Oy
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Priority to EP10720643A priority Critical patent/EP2473444A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/40—Compounds of aluminium
    • C09C1/42—Clays
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
    • A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
    • A61K9/51—Nanocapsules; Nanoparticles
    • A61K9/5107—Excipients; Inactive ingredients
    • A61K9/5115—Inorganic compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
    • A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
    • A61K9/51—Nanocapsules; Nanoparticles
    • A61K9/5107—Excipients; Inactive ingredients
    • A61K9/513—Organic macromolecular compounds; Dendrimers
    • A61K9/5161—Polysaccharides, e.g. alginate, chitosan, cellulose derivatives; Cyclodextrin
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3268—Macromolecular compounds
    • B01J20/3272—Polymers obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds
    • B01J20/3274—Proteins, nucleic acids, polysaccharides, antibodies or antigens
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3268—Macromolecular compounds
    • B01J20/328—Polymers on the carrier being further modified
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/007—Mixed salts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/30—Preparation of aluminium oxide or hydroxide by thermal decomposition or by hydrolysis or oxidation of aluminium compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/78—Compounds containing aluminium, with or without oxygen or hydrogen, and containing two or more other elements
    • C01F7/784—Layered double hydroxide, e.g. comprising nitrate, sulfate or carbonate ions as intercalating anions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/78—Compounds containing aluminium, with or without oxygen or hydrogen, and containing two or more other elements
    • C01F7/784—Layered double hydroxide, e.g. comprising nitrate, sulfate or carbonate ions as intercalating anions
    • C01F7/785—Hydrotalcite
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/08—Intercalated structures, i.e. with atoms or molecules intercalated in their structure
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/20—Two-dimensional structures
    • C01P2002/22—Two-dimensional structures layered hydroxide-type, e.g. of the hydrotalcite-type
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer

Definitions

  • the present invention relates to hybrid materials.
  • the present invention concerns novel inorgano-bioorganic hybrid nanocomposite materials that consist of an inorganic component bound to at least one glycan.
  • the invention also concerns methods of producing such nanocomposite materials and various uses of the new materials.
  • Nanocomposite materials encompass a large variety of systems made of distinctly dissimilar components and combined at the nanometer scale.
  • Nanocomposite materials depend not only on the properties of their individual precursors but also on their structure (morphology and interfacial characteristics).
  • Lamellar composites can be divided into two distinct classes, intercalated hybrids and exfoliated nanocomposites.
  • intercalated hybrids In the former, the polymer chains alternate with the inorganic layers in a fixed compositional ratio and have a well defined number of polymer layers in the interlamellar space.
  • the intercalated hybrid materials are more compound-like because of the fixed polymer/layer ratio.
  • exfoliated nano-composites the number of polymer chains between the layers is almost continuously variable, making them more interesting owing to superior functional properties.
  • US Patent Application Publication No. 2005/0244439 concerns intercalation of a wide range of functional organic compounds into anionic clay layered host materials. Based on the application, functional organic compounds are derivatized with carboxylic, sulphonic or sulphate groups in order to facilitate intercalation. The derivatized compounds are then introduced inside the layers of the host material. Polymers are used for forming compositions by mechanical mixing but the polymers have no interaction with the intercalated host materials.
  • the nanocomposite preparation comprises mixing of the natural clay suspensions with biopolymer solutions.
  • the disclosed procedure involves a multi-step process, containing milling, washing and exfoliation. Since the suggested procedure is applied to natural clays (i.e. cationic phyllosilicates), it also includes separation.
  • the known procedure involves laborious reagent and energy- consuming steps. Based on the examples and the supporting drawings of the publication, the materials obtained are micro-scale rather then nano-scaled.
  • inorgano-bioorganic composites and nanocomposites especially those of synthetic anionic clays (LDHs) and polysaccharides (glycans), are typically obtained through mechanical mixing of the components, since they are often incompatible in solutions, owing to intrinsic properties of natural polysaccharides.
  • LDHs synthetic anionic clays
  • glycans polysaccharides
  • compositions known in the art, and methods of their preparation typically involve a step of chemical or biochemical (e.g. enzymatic) glycan derivatization to improve their solubility, or use of special binder agents to ensure suitable contacts between different phases of the material.
  • a further problem is that chemical or biochemical derivatization produces several by-products that must be removed from the modified glycan prior to its further utilisation. Moreover, biochemical enzymatic derivatization or polymer chain scission occur at very strict conditions, including specific buffer solutions, additional reagents being needed to ensure a proper enzyme function. Thus, the final product often contains unavoidable and undesirable contaminants (e.g. ions or groups bonded to the polymer chain), which must be removed by a thorough, multi-step, and resource-consuming purification (e.g. electro- dialysis, membrane ultra-filtration, preparative chromatography, etc.). The above renders the final product highly expensive.
  • contaminants e.g. ions or groups bonded to the polymer chain
  • the present invention is based on the finding that it is possible to combine an inorganic component having an anionic nature not only with anionic glycans but with neutral and cationic ones as well by introducing the inorganic component in dehydrated form into a solution of the bioorganic component and intimately contacting the components.
  • the composites are provided in the form of a homogeneous material in the shape of particles having an average particle size (diameter or smallest dimension) generally smaller than 1 micrometre.
  • the invention also comprises a method of preparing a uniform nanocomposite material of this kind.
  • a dehydrated and preferably decarbonated layered double hydroxide is first dispersed in an aqueous solution of the corresponding glycan to form a suspension.
  • the layered double hydroxide is then reacted with the glycan and the reaction is allowed to proceed under mixing at non-boiling conditions of the medium for a suitable time period to yield particles of a uniform nanocomposite material comprising a layered double hydroxide nano lamellae bound to glycan.
  • the product according to the present invention is mainly characterized by what is stated in the characterising part of claim 1.
  • the method according to the present invention is characterized by what is stated in the characterising part of claim 11.
  • the present invention provides a universal method for obtaining inorgano-bioorganic (layered double hydroxide (LDH) - glycan) nanocomposites.
  • LDH layered double hydroxide
  • the invention allows for a combination of the LDHs with any kind of natural glycans and their derivatives (neutral, cationic or anionic) under controlled conditions and composition.
  • the invention is based on in-situ formation of the composite during the synthesis, and not on mechanical mixing of the components or classical co-precipitation and ion exchange techniques.
  • the invention provides simple and atom-efficient methodology of natural glycan solubilisation in a way suitable for subsequent formation of nanocomposites with the LDHs.
  • the process does not require derivatization although it can be applied to functionalized glycans as well as to unmodified glycans.
  • the present method provides highly functional, stable, nature identical (when applicable) nanodispesions, sols, or gels of the LDH. I.e. direct obtaining of nanoscaled non-modified LDH materials. These objectives have never been achieved in the prior art.
  • the LDH particles were irreversibly modified by chemical treatments, which were performed in order to obtain nanoscale particles. The latter are practically useless, since they are both not stable without a particular reagent applied for the treatment and may not be recovered in their original nature identical form without decomposition (either chemical or physical - reaggregation into bulk).
  • the LDHs and the glycans are used as excipients in drug and cosmetic formulations or as components of a composition.
  • the components are indifferent to each other.
  • the present invention gives rise to composites, wherein the components interact to a certain extent with each other; they are uniformly distributed in the material, providing a synergy of their unique functional properties.
  • the indicated procedures are by-product free, inexpensive and do not involve any biologically incompatible and non-biodegradable reagents.
  • the liquid medium used to perform chemical transformations is water.
  • the invention is of primary interest for pharmaceutical companies and dietary additive producers.
  • individual ingredients hydrotalcite, some polysaccharides
  • hydrotalcite some polysaccharides
  • a combination of those components into the nanocomposite in question would give rise to more mild and prolonged antacide effect owing to synergy of valuable properties of each individual component: enveloping and mitigating effect of polysaccharides, high buffer capacity of both ionic glycans and the LDHs, ion exchange and transport (drug delivery) properties of the LDHs.
  • the nanocomposites under the present invention have controlled composition and structure; they are not a mechanical mixture.
  • the individual components of the nanocomposites in question are known as supplements.
  • the glycans applied are both soluble and non-soluble (in a nutritional meaning of the term, i.e. they may be or may not be fermented and absorbed in the gastrointestinal tract).
  • the nanocomposites in question may be used as dietary supplements, reducing diets, diabetic food components, etc.
  • the invention enables to render the material biodegradable or non-degradable and biocompatible in a controlled way.
  • Figure 1 shows the particle size distribution in the LDH-alginic acid nanocomposite prepared according to Example 1 ;
  • Figure 2 shows an SEM micrograph of the LDH-chitosan (low M w ) nanocomposite prepared according to Example 3.
  • an “acid” (often represented by the generic formula HA or [H + A ]) is considered any chemical compound that is capable of donating a hydrogen ion or proton (H + ) to another compound (called a base, a proton acceptor).
  • Nanoparticle is a three-dimensional particle whose smallest dimension lies in the nanometre range, i.e. each one of its three dimensions is less than about l ⁇ m (10 "6 m or 1000 nm) and at least one of those is less than 200 nm.
  • uniform nanocomposite material is meant a material characterised by structural and compositional uniformity both in bulk, and at the level of individual nanoparticles.
  • Glycan stands for a natural or modified natural polymer or oligomer that consists of several or many (more than 7, preferably more than 10, in particular more than 12) monose (monosaccharide) units bound together solely by O-glycosidic linkages. Glycans may have solely initial monose -OH functional groups, in the present application those are referred to as “neutral” glycans. Based on the above, the term “glycan” is therefore used to cover “glycan and functionalised glycan molecules". Although the term “glycan” is herein frequently used in the singular voice, mixtures of two or more glycans can, naturally, also be employed.
  • glycan or polysaccharide, or polyose is a polymer that consists of different (typically unknown) large number of monosaccharide monomer units.
  • Both natural and modified glycans may also bear different functional groups, typically -COOR; -SO 3 R; -0(PO 2 OR) x R; or -NR 2 (where R may be a proton, a metal ion, a hydrocarbon moiety, a deprotonised alcohol, phenol, carboxylic acid, heterocycle, etc. moieties).
  • those "functionalised glycans” are referred to as "cationic” or "anionic” with respect to their capability to produce exchangeable positively or negatively charged species in aqueous media.
  • “Lamella” is a particle of fine layered structure that is the most typical form of existence of layered double hydroxides. It consists of the hydroxides' layer building blocks of M 2+ and M + octahedra, interstratified by interlayer spaces, which can be occupied by water, charge compensating anions, and adsorbed neutral molecules. Individual layer sheets are stacked into the lamellar particle, hence, its x and y dimensions are more developed than the z-dimension. ' TSf ano lamella” is a nanosized lamella.
  • P.a.c is any chemical compound that can be classified as a Br ⁇ nsted-Lowry acid and is "intended to affect the structure or any function of the body of man or other animals" as well as “for use in the diagnosis, cure, mitigation, treatment, or prevention of disease in man or other animals” .
  • Pharmaceutical activity of the P.a.c.'s is confirmed by including those in the Pharmacopoeia (here the Pharmacopoeia means the USP, European Pharmacopoeia, and National Pharmacopoeias or other similar Acts of National drug regulatory authorities in the countries of the patent's validity).
  • Nutraceutical is any substance that is a food, a part of a food, or dietary supplement and provides medical or health benefits.
  • the present invention provides novel nanocomposite materials. These new uniform materials comprise an inorganic component of a layered double hydroxide nano lamellae bound to at least one glycan.
  • the nanocomposite materials are present essentially in the form of particles having an average size (size of smallest dimension or diameter) of less than 1 ⁇ m.
  • the inorganic component of the particles is formed by a layered double hydroxide having the general formula I
  • M 2+ is selected from Mg 2+ , Ca 2+ , Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ , Cu 2+
  • Zn 2+ M 3+ is selected from Al 3+ , V 3+ , Cr 3+ , Fe 3+ , Co 3+ , Sc 3+ , Ga 3+ , Y 3+ , Rh 3+ , Zr 4+
  • n ⁇ stands for an anion
  • x stands for a value in the range from 0.2 to 0.33
  • n is an integer from 1 to 4
  • z is an integer from 1 to 10.
  • the glycan molecule is bound to the layered double hydroxide nano lamellae at a ratio of approximately 1 monomer-mole of glycan to 0.5 to 1.5 moles of layered double hydroxide.
  • the glycan is immobilised on and/or absorbed to the layered double hydroxide.
  • the glycans i.e. the "glycan” are chemically bonded to the layered double hydroxide nanolamellae.
  • M 2+ is selected from the group consisting of the bivalent ions of earth alkaline metals, such as Mg 2+ and Ca 2+ as well as transition metals, such as Zn 2+ .
  • a suitable trivalent metal ion, M 3+ is represented by Al 3+ . These ions will assist in rendering the material biocompatible and biodegradable.
  • the layered double hydroxide hosts interlayer anions to balance a charge of the hydroxide layers.
  • the former can be selected for example from the group of OH , CO3 2 , CH3COO , CF and fully or partially deprotonated moieties of Br ⁇ nsted-Lowry acids, particularly, nutraceuticals, or pharmaceutically active acids.
  • nutraceuticals and pharmaceutically active acids are, e.g., phosphoric acids, lactic acid, citric acid, derivatives of salicylic and propionic acids, etc.
  • pharmaceutically acceptable acids can be used for the purpose of forming acid addition salts.
  • Such acid include in addition to the foregoing acids also other organic acids, such as acetic acid, propionic acid, gly colic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, benzoic acid, cinnamic acid, methane sulphonic acid, p-toluene sulphonic acid and salicylic acid, and inorganic acids, such as hydrochloric acid, hydrobromic acid and sulphuric acid.
  • the glycan can be selected from, for example, the group consisting of aminoglycans, completely or partially deacetylated aminoglycans, such as chitosan; glycuronans and glycans functionalised with other anionogenic groups, such as alginic acid, carrageenan, chondroitin, gellan or hyaluronan; or a neutral glycan, such as inulin, amylose, or galactomannans .
  • aminoglycans completely or partially deacetylated aminoglycans, such as chitosan
  • glycuronans and glycans functionalised with other anionogenic groups such as alginic acid, carrageenan, chondroitin, gellan or hyaluronan
  • a neutral glycan such as inulin, amylose, or galactomannans .
  • mixtures of two or more glycans can be employed.
  • mixtures of 2 to 10 anionic glycans or 2 to 10 neutral glycans or 2 to 10 cationic glycans can be used.
  • the glycans of the mixtures have properties which with regard to dissolution in water are similar as to provide suitable solutions for the contacting step.
  • the particles have an average particle size (size of smallest dimension or diameter) in the range of 50 to 950 nm, in particular about 100 to 900 nm, preferably about 150 to 850, typically about 200 to 800 nm.
  • a dehydrated and decarbonated layered double hydroxide is dispersed in an aqueous solution or, potentially, dispersion of the corresponding glycan, e.g. native glycan or functionalised glycan, to form a suspension.
  • the aqueous solution can be purified water, deionised water, tap water or a mixture of water and another solution or solvent, typically miscible with water.
  • the glycan is preferably dispersed or dissolved in water that has been chemically purified, e.g. by deionisation.
  • the layered double hydroxide is reacted with the glycan in the aqueous environment and the reaction is allowed to proceed for a prolonged time preferably under mixing.
  • the conditions are preferably "non-boiling", i.e. the temperature is maintained between the melting and boiling points of the aqueous medium.
  • a temperature in the range of about 20 to 80 0 C is suitable.
  • the nanocomposite material can be used in dispersion, but it can also be recovered from the suspension, for example by centrifugation and separation of the aqueous phase.
  • the uniform nanocomposite material produced can be further purified from non-specifically bonded glycans by repeated washing with deionised or otherwise purified water and subsequent centrifugation.
  • the layered double hydroxide Before the reaction, in order to pre-treat the layered double hydroxide (e.g. to remove water and carbonate residues), it is suitably thermally dehydrated and decarbonised before it is contacted with the glycan.
  • the layered double hydroxide is heat treated at a temperature of about 250 to 450 0 C, preferably at 400 to 430 0 C, for 1 to 24 hours to dehydrate and decarbonise the layered double hydroxide.
  • the layered double hydroxide is reacted with the glycan in an aqueous medium, in which the glycan preferably has been dissolved.
  • the pH can be adjusted or additional components added.
  • the pH is typically neutral, although slightly alkaline or acidic conditions (pH about 5 to 9) are equally possible, depending on the specific type of glycan.
  • the glycan containing aqueous medium has a pH which is roughly neutral, in particular about 6 to 8.
  • the glycan is selected from hydro lysed aminoglycan and completely or partially deacetylated aminoglycan, and said aminoglycan or deacetylated glycan is dissolved in an aqueous medium by
  • the dilute aqueous suspension of said aminoglycan or deacetylated aminoglycan has a concentration of about 0.1 to 5 % by weight, in particular about 0.5 to 3 % by weight, in particular about 1 to 1.5 % by weight of the glycan in water.
  • the hydrolysis is performed for 1 to 20 hours, in particular 4 to 16 hours.
  • the temperature is for example about 80 to 100 0 C at atmospheric pressure, or about 100 to 125 0 C at excess pressure (pressure higher than 1 at abs).
  • the dissolved glycan comprises a glycuronan or glycans functionalised with other anionogenic groups, such as alginic acid, carrageenan, hyaluronan, chondroitin, and gellan; the glycan is dissolved in an aqueous medium by adjusting the pH of the aqueous phase to about 6.0 to 7.5.
  • an inorganic or organic base can be employed.
  • the dissolved glycan comprises a neutral glycan, such as inulin, or a galactomannan, which is dissolved in an aqueous medium by adjusting the pH of the aqueous phase to 7.5 to 8.0.
  • pH of the aqueous medium can be adjusted with an aid of a carbonate-free solution of alkali metal or earth alkaline metal hydroxide.
  • the dehydrated and decarbonated layered double hydroxide can be contacted with chloride-anions and fully or partially substituted moieties of Br ⁇ nsted-Lowry acids, particularly, nutraceuticals or pharmaceutically active acids and/or their salts, such as phosphoric acids, lactic and citric acids, during the dispersing of the layered double hydroxide or immediately after, before the layered double hydroxide is being contacted with the glycan or functionalised glycan.
  • Br ⁇ nsted-Lowry acids particularly, nutraceuticals or pharmaceutically active acids and/or their salts, such as phosphoric acids, lactic and citric acids
  • the pH of the aqueous phase of the dispersion is adjusted to 6 to 8 after the addition of the anions.
  • the process for preparing the above compositions comprises the steps of
  • the nanocomposite in the form of paste or gel can be separated by centrifugation for 0.5-3 hours.
  • cationic glycans e.g. chitosan
  • the hydrolysis is performed in an autoclave at 120 0 C for 4 to 16 hours depending on the molecular weight of the starting polymer.
  • anionic glycans e.g.
  • alginic acid, carrageenan, hyaluronan, etc. are dissolved in deionised or otherwise purified water. Several drops of 0.1 M ⁇ 0.01 M carbonate free NaOH or other alkali solution may be added to enable the solubilisation and regulate the pH level between 6.0 and 7.0 values.
  • neutral polysaccharides e.g. inulin, guar
  • the solution pH is regulated to 7.5 ⁇ 8.0 by addition of 0.1 M ⁇ 0.01 M carbonate free NaOH solution.
  • inorgano -organic composites have attracted increasing attention due to their spectacular properties as biodegradable materials, drug release systems, electrochemical sensors, packaging materials, and so on.
  • the new nanocomposite materials developed under present invention reveal a synergic combination of valuable properties of the constituents: synthetic layered double hydroxides (LDH) and natural glycans. Since the latter are relatively complex carbohydrates that are made up of many monosaccharide units joined together by glycosidic bonds, such natural polymers exhibit a wide variety of structures and extraordinary diversity of functional properties.
  • glycans are biologically produced (bio-based) materials that have a unique combination of valuable properties and environmentally friendly features. They are renewable materials, produced from other biological compounds, and generally are non-toxic, and biodegradable.
  • the LDHs are easily obtained, and such synthetic anionic clays have a uniform structure and composition, possess valuable sorption, ion-exchange, and carrier properties.
  • the above properties enable a direct use of Mg-Al and Zn-Al LDHs in humans and animals, harmlessness of these materials has been proven by the FDA several decades ago.
  • Synergic combination of mechanical and functional properties of individual components ensure a myriad of potential applications for novel LDH-glycan nanocomposite materials, making them a natural fit for sustainable development.
  • the potential applications may be more wide and non-limited by the proposed ones.
  • antacid drugs e.g. Mg-Al LDH, hydrotalcite, as Talcid® by Bayer AG and Topalcan® by Pierre Fabre Medicaments
  • excipients in different pharmaceutical formulations, oral and personal hygiene preparations e.g. Mg-Al LDH, hydrotalcite, as Talcid® by Bayer AG and Topalcan® by Pierre Fabre Medicaments
  • the requirements for antacid drugs are: lowering and maintaining of gastric pH levels (pH ⁇ 3; 18/24h); protection of (gastric) mucosae; improvement of gastrointestinal tract (GIT) peristalsis.
  • New nanocomposite materials will have the following advantages over known formulations: synergy of the components' buffering properties; non-resorbability of the LDH, as a consequence of the composite formation (optional and adjustable); prolonged action and higher efficiency (owing to nano-scale and bottom-up assembling; adsorption of ulcerogenic agents, e.g. H. pylori cytotoxin); gel form that enables catheter administration in newborns, infants, and serious patients.
  • the nanocomposites in question are mucosae-friendly and may contain and deliver another pharmaceutically active compounds.
  • the dietary supplements also known as food supplements or nutritional supplements, are preparations intended to supply nutrients, such as vitamins, minerals, fatty or amino acids, dietary substances that are missing or are not consumed in sufficient quantity in a person's diet. They could be further divided as nutraceuticals, designed to promote a healthy lifestyle, and parapharmaceuticals that are non-prescription health care products. The former are intended to supplement a deficiency in essential nutrients, to guide the metabolism correction, to perform an immunomodulatory action, and for nutritional care.
  • Parapharmaceuticals are mainly used for prophylaxis, supplementary care and maintaining of physiological standards, for protection of gastric mucosa, and for improvement of the GIT peristalsis.
  • New nanocomposite materials have the following advantages over known formulations: capability to bind and excrete fats, to improve the cholesterol metabolism, to improve intestinal peristalsis, to provide a sense of fullness, to lower dietary calories, to correct a carbohydrate deficiency. They may also be diabetic dietary products.
  • the nanocomposites in question contain glycans known for their pronounced water-retention effect (e.g. hyaluronan, carrageenan, etc.) that would enable to prevent skin and hair dehumidif ⁇ cation. From the other hand, they also contain the LDHs, known for their pore-constringing effect, drying and healing properties. A synergic combination of the above properties may render the nanocomoposites highly attractive for creams and gels for and after shave, baby care, sun-block, for moisturizing of sensitive and hypersensitive skin, as well as for anti-acne applications.
  • glycans known for their pronounced water-retention effect (e.g. hyaluronan, carrageenan, etc.) that would enable to prevent skin and hair dehumidif ⁇ cation.
  • LDHs known for their pore-constringing effect, drying and healing properties.
  • a synergic combination of the above properties may render the nanocomoposites highly attractive for creams and gel
  • Particular application areas may include creams and gels for purification of skin, cleansing and anti-comedogenic formulations; hydrating and nutrition masks for different types of skin, e.g. both for mixed-oily and tired, fragile, and hypersensitive skin; for exfoliation formulations, UV-protection formulas, baby-care products, etc.
  • Drug delivery (DD) devices are included in particular application areas.
  • the nanocomposites in question may have the following advantages: the materials are made from fully biocompatible components; they are suitable for internal use, topical applications, and for implanted DD devices; the composites possess a synergism of antiseptic, buffer, and sorption properties; the materials are characterised by improved compatibility with mucosa and soft tissues.
  • the devices may be used to maintain normal physiological pH in the case of severe infections (gynaecology, gastroenterology), DD vectors for ulcer therapy (dermatology, gastroenterology), adjuvant therapy means (oncology, embryo implantation).
  • the materials in question must possess high sorption and/or ion exchange capacity, must be stable in media of application, to be easily recyclable and environmentally compatible.
  • the LDHs are known for a while as versatile sorbents for any kind of anions. They have found applications ranging from metallurgy and nuclear power industry to biomedical ones.
  • the glycans are also known both as filters/adsorbents for metal extraction, waste water management, as well as for a variety of medical uses including high-affinity sorbents for therapy and diagnostics.
  • the principal advantage of the proposed materials over existing in the prior art consists in a synergic combination of sorption properties of the individual components (LDH and the glycan) at the nano-level.
  • the materials exhibit improved mechanical properties, more wide pH range of application, improved stability towards aggressive organic and biological media.
  • New materials consist of bio-resorbable glycans and inorganic nano-particles suitable for bone formation. They may be applied as resorbable or non-resorbable gels, pastes, and powders; the resorbability being tailored through ingredient choice (structure) and composition. The materials may be applied for guided bone generation. New nanocomposite materials are supposed to have the following advantages: tailorable bio-resorbablility and mineral content owing to molecular assembly of the material from properly chosen natural structural polysaccharides, lamellar structure of the mineral component is expected to improve a contact of the tissue engineering scaffolds with periosseum and osseointegration. Gels may be used as filers, implants and adhesives with improved compatibility with soft tissue and mucosa.
  • New materials may be advantageous due to: a synergic sorption properties of the components that enable specific immobilisation of electrochemically active probe biomolecules (e.g. enzymes, nucleic acids, probe peptides or proteins, etc.); suitability of the nanocomposites for application in red/ox conditions; high water (and other polar solvent, e.g. methanol) retention properties (particularly important for PEMFC - proton exchange membrane fuel cells); tailorable behaviour of the materials towards non-specific interactions with analyte biomolecules.
  • electrochemically active probe biomolecules e.g. enzymes, nucleic acids, probe peptides or proteins, etc.
  • suitability of the nanocomposites for application in red/ox conditions e.g. high water (and other polar solvent, e.g. methanol) retention properties (particularly important for PEMFC - proton exchange membrane fuel cells); tailorable behaviour of the materials towards non-specific interactions with analyte biomolecules.
  • the materials in question have to possess high sorption and (optionally) ion exchange capacity, high permeability and/or surface resistance, mechanical and environmental stability, and environmental compatibility.
  • Advantages of the proposed materials arise from: synergic sorption properties that enable immobilisation of different catalytic species (inorganic, coordination, and enzymatic); suitability for application in different solvents; bio compatibility, and suitable for tandem catalysis (including the asymmetric one, owing to asymmetric character of natural glycans).
  • Packaging materials that enable immobilisation of different catalytic species (inorganic, coordination, and enzymatic); suitability for application in different solvents; bio compatibility, and suitable for tandem catalysis (including the asymmetric one, owing to asymmetric character of natural glycans).
  • Glycan-based materials are well known packaging materials (chemically modified celluloses, starches, chitosan, alginates). They are non-toxic, easily mouldable and extrudable from solutions.
  • the packaging materials produced are characterised with a good mechanical and weathering stability, they are environmentally compatible.
  • Among the advantages of the proposed materials may be: a possibility of application in direct contact with foodstuffs, tailorable oxygen permeability and germistatic/germicidal properties.
  • Mg-Al layered double hydroxide (Mg-Al LDH) of the formula Mg 0 ,67Alo,33(OH) 2 (C ⁇ 3)o,i65 x 0.4H 2 O was obtained according to classic procedures, known from the prior art (e.g. U. Costantino, F. Marmottini, M. Nocchetti, R. Vivani, Eur. J. Inorg. Chem. 1998, 1439) and calcined at 430 0 C for 12 h to obtain a mixture of metal oxides (further referred to as cLDH), which was cooled in vacuo and stored in an argon filled dry-box.
  • cLDH mixture of metal oxides
  • Residual glycan concentrations in supernatant solutions were determined by polarimetry and spectrophotometry.
  • Particle size measurements were performed by dynamic light scattering on a Zetasizer Nano (Malvern Instruments) using 1% solutions of re-suspended gels in water in a 1 cm polystyrene cuvettes.
  • a specified amount of anionic glycan (see Table 1) was dissolved in 90 ml of water, the pH was adjusted to the values of 7.0 ⁇ 7.5 by addition of carbonate free 0.1M NaOH solution, and the resulting solution was brought to the volume of 100 ml.
  • 0.5 g of cLDH was pre-mixed with a small amount of water (typically 0.5 - 1.5 ml) to form a homogeneous paste that was added to a glycan solution at a specified temperature and vigorous stirring, typically >1000 rpm.
  • the reaction continued for 72 h (120 h for carrageenan). Gel-like nanocomposite was separated from the supernatant liquid by centrifugation and analysed. The reaction conditions and results are shown in the Table 1 and Figure 1.
  • a specified amount of neutral glycan (see Table 1) was dissolved in 90 ml of water, the pH was adjusted to a value of 7.5 ⁇ 8.0 by addition of carbonate free 0.01M NaOH solution, and the resulting solution was brought to the volume of 100 ml.
  • 0.5 g of cLDH was pre-mixed with a small amount of water (typically 0.5 - 1.5 ml) to form a homogeneous paste that was added to a glycan solution at a specified temperature and vigorous stirring, typically >1000 rpm.
  • the reaction continued for 72 h (120 h for guar). Gel-like nanocomposite was separated from the supernatant liquid by centrifugation and analysed. The reaction conditions and results are shown in the Table 1.
  • chitosan (glucosaminoglucan), see Table 2, was dissolved in 30 ml of water, acidified to pH ⁇ 3 by addition of 0.1 M HCl. Resulting viscous solution were transferred into a closed Teflon container placed in a stainless steel autoclave and hydrolysed at 120 0 C for a specified period of time. After cooling of the autoclave, its content was poured into 60 ml of water, the pH was adjusted to the values of 6.5 ⁇ 7.0 by addition of carbonate free 0.05M NaOH solution, and the resulting solution was brought to the volume of 100 ml.
  • Glycan Particle is time, h weight, g ratio uptake, % size, nm

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Abstract

La présente invention a pour objet un matériau nanocomposite uniforme et son procédé de production. Le nouveau matériau comprend un composant inorganique de nanolamelles d'hydroxyde double stratifié liées à au moins une molécule de glycane pour former des particules ayant une taille moyenne inférieure à 1 μm. Le matériau peut être produit par la mise en contact et la réaction en phase aqueuse d'un hydroxyde double stratifié déshydraté et décarboné avec un glycane dissous pour permettre la formation de particules d'un matériau nanocomposite uniforme comprenant des nanolamelles d'hydroxyde double stratifié liées au glycane. Les matériaux peuvent être utilisés, par exemple, dans l'industrie pharmaceutique.
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IT202100003359A1 (it) 2021-02-15 2022-08-15 I L P A S P A Composizione acquosa per imballaggio attivo contenente sostanze naturali antimicrobiche e/o antiossidanti e imballaggio attivo avente uno strato di rivestimento ottenuto da tale composizione acquosa

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Publication number Priority date Publication date Assignee Title
CN103303891A (zh) * 2013-06-14 2013-09-18 北京理工大学 一种聚磷酸铵与层状双羟氢氧化物纳米复合物及其制备方法
CN104928741A (zh) * 2015-05-21 2015-09-23 武汉大学 砖-泥结构的多敏感壳聚糖凝胶及其制备方法和应用
ITUB20159697A1 (it) * 2015-12-14 2017-06-14 Sunyamed S R L Sistema di rilascio di farmaci comprendente un idrossido a doppio strato (ldh) e acido ialuronico
CN108598462B (zh) * 2017-12-29 2020-07-24 北京化工大学 一种钠离子电池负极材料及其制备方法和应用
CN108598462A (zh) * 2017-12-29 2018-09-28 北京化工大学 一种钠离子电池负极材料及其制备方法和应用
EP3848115A4 (fr) * 2018-09-06 2022-05-25 Nikkiso Co., Ltd. Absorbeur d'acide lactique et procédé d'élimination d'acide lactique
EP3653674A1 (fr) * 2018-11-15 2020-05-20 Commissariat à l'Énergie Atomique et aux Énergies Alternatives Procédé de fabrication de pigments cosmétiques omniphobes
US11040000B2 (en) 2018-11-15 2021-06-22 Commissariat À L'Énergie Atomique Et Aux Énergies Alternatives (Cea) Process for manufacturing omniphobic cosmetic pigments
JP7628391B2 (ja) 2018-11-15 2025-02-10 コミサリアット エー エナジー アトミック エト アウクス エナジーズ オルタネイティブス（シーイーエー） オムニフォビック化粧品用顔料の製造方法。
CN110433671A (zh) * 2019-07-23 2019-11-12 江苏大学 一种可见光诱导自清洁碳纤维膜的制备方法及其用途
CN110433671B (zh) * 2019-07-23 2021-09-10 江苏大学 一种可见光诱导自清洁碳纤维膜的制备方法及其用途
CN112979974A (zh) * 2021-02-01 2021-06-18 攀枝花学院 ZnAl二维金属氢氧化物-壳聚糖超分子杂化材料及其制备方法
IT202100003359A1 (it) 2021-02-15 2022-08-15 I L P A S P A Composizione acquosa per imballaggio attivo contenente sostanze naturali antimicrobiche e/o antiossidanti e imballaggio attivo avente uno strato di rivestimento ottenuto da tale composizione acquosa

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