WO2004084627A2 - Cellulose matrix encapsulation and method - Google Patents
Cellulose matrix encapsulation and method Download PDFInfo
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- WO2004084627A2 WO2004084627A2 PCT/US2004/008411 US2004008411W WO2004084627A2 WO 2004084627 A2 WO2004084627 A2 WO 2004084627A2 US 2004008411 W US2004008411 W US 2004008411W WO 2004084627 A2 WO2004084627 A2 WO 2004084627A2
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- 0 *N(CCC1)CC1C1CCCCCCC1 Chemical compound *N(CCC1)CC1C1CCCCCCC1 0.000 description 4
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
- C08B1/003—Preparation of cellulose solutions, i.e. dopes, with different possible solvents, e.g. ionic liquids
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- 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
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
- A01N25/10—Macromolecular compounds
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/26—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
- A01N25/28—Microcapsules or nanocapsules
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/36—Polysaccharides; Derivatives thereof, e.g. gums, starch, alginate, dextrin, hyaluronic acid, chitosan, inulin, agar or pectin
- A61K47/38—Cellulose; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B16/00—Regeneration of cellulose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
- C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
- C08J3/096—Nitrogen containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
- C08L1/06—Cellulose hydrate
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
- C09D101/02—Cellulose; Modified cellulose
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- 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
- C12N11/10—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a carbohydrate
- C12N11/12—Cellulose or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2989—Microcapsule with solid core [includes liposome]
Definitions
- the invention provides new materials and a novel method for their preparation by incorporating molecular, nanoscale, and macroscopic materials within a cellulose matrix.
- the process involves encapsulation or immobilization of the active solid substance in a cellulose framework by regenerating cellulose dissolved in an ionic liquid solvent in a regenerating solution.
- the active substance can be initially present in the ionic liquid, or in the regenerating solvent, either as a solution, or as a dispersion.
- the invention is applicable to molecular encapsulation and to entrapping of larger particles including enzymes, nanoparticles and macroscopic components, and to the formation of bulk materials with a wide range of morphological forms .
- Ionic liquids are now a well-established class of liquids containing solely ionized species, and having melting points largely below 150 °C or most preferably 100 °C.
- ionic liquids are organic salts containing one or more cations that are typically ammonium, imidazolium or pyridinium ions, although many other types are known.
- the range of ionic liquids that are applicable to the dissolution of cellulose are disclosed in US patent application Serial No. 10/256,521, filed on September 27, 2002, entitled “Dissolution and Processing of Cellulose Using Ionic Liquids" , that claimed priority from provisional application Serial no. 60/326,704 that was filed on October 3, 2001, and in Swatloski et a.1 . , J. Am. Chem. Soc. 2002, 124:4974-4975.
- Such solvents include carbon disulfide, N-methylmorpholine-N-oxide (NMMNO) , mixtures of N,N- dimethylacetamide and lithium chloride (DMAC/LiCl) , dimethylimidazolone/LiCl, concentrated aqueous inorganic salt solutions [ZnCl/H 2 0, Ca (SCN) 2 /H 2 0] , concentrated mineral acids (H 2 S0 4 /H 3 P0 4 ) or molten salt hydrates (LiCl0 4 .3H 2 0, NaSCN/KSCN/LiSCN/H 2 0) .
- NMMNO N-methylmorpholine-N-oxide
- PEI polyethyleneimine
- NEPC N-ethylpyridinium chloride
- That research group also reported entrapment of yeast cells in a solution of 1 percent cellulose dissolved in a mixture of NEPC and dimethyl sulfoxide, as well as entrapment using 7.5 to 15 percent cellulose di- or triacetates dissolved in several organic solvents. [ eckstrom et al . , in Food Engineering in Food Processing, Vol. 2, Applied Science Publishers Ltd., pages 148-151 (1979).]
- Entrapped materials have a wide number of uses, from controlled release systems to structural modifiers and sensor or reactive materials.
- the entrapped materials can be formulated as membranes, coatings or capsules. Methods are known for forming encapsulated products including emulsion polymerization, interfacial polymerization, desolution, emulsification, gelation, spray-drying, vacuum coating, and adsorption onto porous particles. Common materials used include polymers, hydrocolloids, sugars, waxes, fats, metals and metal oxides .
- membranes, coatings, and capsules for the controlled release of liquid materials is well known in the art of both agricultural and non-agricultural chemicals, including the preparation of graphic arts materials, pharmaceuticals, food, and pesticide formulations.
- controlled-release techniques have improved the efficiency of herbicides, insecticides, fungicides, bactericides, and fertilizers.
- Non- agricultural uses include encapsulated dyes, inks, pharmaceuticals, flavoring agents, and fragrances.
- controlled-release materials are coated droplets or microcapsules, coated solids, including both porous and non-porous particles, and coated aggregates of solid particles.
- a water-soluble encapsulating film is desired, which releases the encapsulated material when the capsule is placed in contact with water.
- Other coatings are designed to release the entrapped material when the capsule is ruptured or degraded by external force.
- Still further coatings are porous in nature and release the entrapped material to the surrounding medium at a slow rate by diffusion through the pores .
- Materials have been formulated as emulsifiable concentrates by dissolving the materials in an organic solvent mixed with a surface-active agent or as an oily agent.
- the insecticides In solid form, the insecticides have been formulated as a wettable powder in which the insecticide is adsorbed onto finely powdered mineral matter or diatomaceous earth, as a dust or as granules .
- these conventional formulations pose a variety of problems such as the pollution of the environment caused by the organic solvent used in the emulsions or by the dust resulting from the wettable powders.
- an amount much higher than that used in normal application is required, and this increased amount can affect the environment or cause problems of safety.
- Other conventional microcapsules that encapsulate active insecticidal components are obtained through an interfacial polymerization reaction and are not ideal in terms of the production process or as an effective stabilized insecticide.
- Enzyme entrapment on solid supports is a well-established technique for improving stability and separations aspects in enzymatic transformations. Entrapment of enzymes on solid supports can result in improved stability to pH and temperature and aid in separation of the enzyme from the reaction mixture, and also for formation of enzyme electrodes for sensor applications.
- a common method for immobilization is to use polysaccharide activation in which cellulose beads are reacted under alkali conditions with cyanogen bromide. The intermediate produced is then covalently coupled with soluble enzymes. Examples are lactase, penicillin acylase, and aminoacylase enzymes .
- Entrapment of enzymes within gels or fibers is a convenient method for use in processes involving low molecular weight substrates and products. Entrapment is the method of choice for immobilization of microbial, animal and plant cells. Calcium alginate is widely used. Enzymes can be entrapped in cellulose acetate fibers by formulation of an emulsion of the enzyme plus cellulose acetate in dichloromethane, followed by extrusion of fibers.
- Entrapped enzyme methods have wide applicability, but the entrapped enzymes can be technically difficult to prepare and involve moderate to high costs. Hence, new methods of preparing entrapped enzymes are desirable .
- the disclosure hereinafter describes the preparation of encapsulated materials in a cellulose matrix by dispersion and regeneration of IL/cellulose solutions containing an active substance into a regenerating liquid in which the IL is soluble and that is a non-solvent for cellulose and the active agent . It will be clear to those skilled in the art that this invention is applicable to the formulation of beads and fibers in which active agents are entrapped.
- the present invention contemplates a cellulose-encapsulated active substance and an encapsulation method for active substances to form a regenerated cellulose matrix in which the active substance is distributed throughout the matrix.
- the distribution of the active substance is preferably substantially homogeneous within the matrix of regenerated cellulose.
- the regenerated cellulose (i) has about the same molecular weight as the original cellulose from which it is prepared and typically a degree of polymerization (DP) of about 1200, and (ii) is substantially free of substituent groups and entrapped ionic liquid degradation products.
- the material to be encapsulated (active substance) is dispersed, preferably homogeneously, or dissolved in a hydrophilic ionic liquid that is substantially free of water, an organic solvent or nitrogen-containing base containing solubilized cellulose, and the cellulose is subsequently reformed (regenerated) as a solid in which the active substance is dispersed in the cellulose matrix, preferably homogeneously.
- This method has advantages for formation of composites containing many solid substances which are desirable to encapsulate in a cellulose matrix, particularly for the incorporation of active agents that are not soluble in water or other common solvents, for example nanoparticles or macroscopic materials.
- Matrices formed by this process are capable of effecting a slow rate of release of the encapsulated materials by diffusion through the shell to the surrounding medium, swelling in a liquid medium such as water, by slow, controlled degradation of the cellulose matrix structure, or by slow dissolution of the active substance from within the matrix.
- Materials suitable for encapsulation include chemical-biological agents such as herbicides, insecticides, fungicides, bactericides, animal, insect, and bird repellent, plant growth regulators, fertilizers, and flavor and odor compositions, catalysts, photoactive agents, indicators, dyes, and UV adsorbents.
- the final morphological form of the encapsulated composite depends on the regeneration process and on the desired applications of the materials. For example, high surface area beads, cylinders or floes can be manufactured for filtration or separation applications, whereas thin films can be prepared for membrane and sensor uses .
- Entrapment of biomolecules on solid supports is a well-established technique for improving pH and temperature stability particularly for enzymes and whole cells. Entrapment of biomolecules within a cellulose support can result in new materials for sensing and detection application.
- Macroscopic magnetite particles can be incorporated into cellulose to prepare magnetically modified materials. These materials have a number of applications in magnetic fluidized bed extraction processes for protein and metal extraction or detection.
- Fig. 1 is a graph of D w values for 41 Am to CMPO impregnated cellulose (circles) , cellulose only (squares) and regenerated cellulose (diamonds) from aqueous nitric acid solutions as a function of acid concentration;
- Fig. 2 is a graph of D values for 239 Pu to CMPO impregnated cellulose (circles) , cellulose only (squares) and regenerated cellulose (diamonds) from aqueous nitric acid solutions as a function of acid concentration;
- Fig. 3 is a graph of D w values for 233 U0 2 to CMPO impregnated cellulose (circles) , cellulose only (squares) and regenerated cellulose (diamonds) from aqueous nitric acid solutions as a function of acid concentration;
- Fig. 4 is a UV/vis spectrum of a cellulose- cellulose azure film at pH 6.88 (solid line) and pH 2.10 (dotted line);
- Fig. 5 is a UV/vis spectrum of a cellulose film alone (solid line) and a cellulose film containing bovine serum albumin (BSA; dotted line) ;
- Fig. 6 is a UV/vis spectrum of a cellulose film alone (solid line) and cellulose film containing laccase (dotted line) ;
- Fig. 7 is a UV/vis spectrum of a cellulose film alone (solid line) and cellulose film containing ubiquinone (dotted line) .
- the present invention provides an encapsulation method for a wide range of materials referred to herein as active substances that can be effectively carried out to provide active substance substantially homogeneously distributed through out the regenerated cellulose matrix.
- the method uses encapsulation by dispersion or dissolution in a hydrophilic ionic liquid containing solubilized cellulose, that is substantially free of water, an organic solvent or nitrogen-containing base, followed by subsequent reformation of the cellulose as a solid matrix in which the active substance is dispersed in the matrix.
- the resulting material contains the active substance dispersed substantially homogeneously throughout the regenerated cellulose matrix.
- a method for the preparation of new materials incorporating molecular, nanoscale and macroscopic materials within a cellulose matrix is contemplated.
- a contemplated method contemplates encapsulation of the active substance by regenerating a polymer matrix from a hydrophilic ionic liquid (IL) solution containing the active solid substance into a regenerating solution in which both the cellulose and the active substance are insoluble or difficult to dissolve is described; i.e., substantially insoluble.
- IL hydrophilic ionic liquid
- the method contemplates the steps of providing a homogeneous composition that contains cellulose and an active substance dissolved or dispersed in a hydrophilic ionic liquid and in which the ionic liquid solution is substantially free of water, a non-ionic organic solvent or nitrogen- containing base containing solubilized cellulose. That composition is contacted with a liquid non- solvent diluent in which both the cellulose and active substance are substantially insoluble to form a liquid phase and a regenerated solid cellulose phase as a matrix encapsulating the active substance and thereby form composite material that comprises a cellulose-encapsulated active substance. Residual hydrophilic ionic liquid is preferably thereafter removed.
- active substances include the incorporation of water-insoluble metal extractants, water-insoluble dyes, biomolecules, and magnetite particles of about 5 microns in diameter (largest dimension if not approximately spherical) that can be dispersed in the IL solution, either physically to form a suspension or colloid, or by dissolving the components in the IL solvent, and then regenerating the composite material.
- the distribution of the active substance is preferably substantially homogeneous within the matrix of regenerated cellulose.
- the regenerated solid cellulose (i) has about the same molecular weight as the original cellulose from which it is prepared and typically contains a degree of polymerization number (DP) of about 1200 , or more. That regenerated cellulose (ii) is substantially free of an increased amount of substituent groups relative to the starting cellulose and entrapped ionic liquid degradation products.
- the substituent groups of which the regenerated cellulose is substantially free are those that were not present in the cellulose that was dissolved in the IL.
- the dissolution/regeneration process used herein does not cause the formation of more than a few percent more of those groups than were originally present.
- oxidized cellulose that contains a high level of oxo functionality is used as the starting material such as where Regenerated Oxidized Cellulose U.S. P. (ROC), the regenerated cellulose again contains about the same amount of functionality (e.g., about 18 to about 24 percent carboxyl groups for ROC) after dissolution and regeneration as was present prior to those steps being carried out .
- substituents of which the regenerated cellulose is substantially free are those substituents such as xanthate groups, C 2 -C 3 2- hydroxyalkyl (e.g., 2-hydroxyethyl and 2- hydroxypropyl) groups, and carboxyl groups such as acetyl and butyryl that are used in other processes to dissolve cellulose.
- the hydrophilic ionic liquid solution used herein is substantially free of water, a water- or alcohol-miscible organic solvent or nitrogen- containing base and contains solubilized cellulose.
- Contemplated organic solvents of which the solution is free include solvents such as dimethyl sulfoxide, dimethyl formamide, acetamide, hexamethyl phosphoramide, water-soluble alcohols, ketones or aldehydes such as ethanol, methanol, 1- or 2- propanol, tert-butanol, acetone, methyl ethyl ketone, acetaldehyde, propionaldehyde, ethylene glycol, propylene glycol, the C!-C 4 alkyl and alkoxy ethylene glycols and propylene glycols such as 2- methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol , diethyleneglycol, and the like.
- hydrophilic ionic liquid preferably cyclic and correspond in structure to a formula selected from the group consisting of
- R 1 and R 2 are independently a C ⁇ -C alkyl group or a C]_-Cg alkoxyalkyl group, and R 3 , R 4 ,
- R 5 , R 6 , R 7 , R 8 and R 9 when present, are independently a hydrido, a C]_-Cg alkyl, a C ⁇ -Cg alkoxyalkyl group, or a C ⁇ -Cg alkoxy group. More preferably, both R 1 and R 2 groups are C 1 -C alkyl, with one being methyl, and R 3 -R 9 , when present, are preferably hydrido. Exemplary C ⁇ -C alkyl groups and
- C 1 -C 4 alkyl groups include methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, iso-butyl, pentyl, iso- pentyl, hexyl, 2-ethylbutyl, 2-methylpentyl , and the like.
- Corresponding C]_-Cg alkoxy groups contain the above C ⁇ -Cg alkyl group bonded to an oxygen atom that is also bonded to the cation ring.
- An alkoxyalkyl group contains an ether group bonded to an alkyl group, and here contains a total of up to six carbon atoms .
- An anion for a contemplated ionic liquid cation is a halogen ion (fluoride, chloride, bromide, or iodide) , perchlorate, a pseudohalogen ion such as thiocyanate and cyanate or C]_-C carboxylate.
- Pseudohalides are monovalent and have properties similar to those of halides [Schriver et al . , Inorganic Chemistry, W.H. Freeman & Co . , New York (1990) 406-407] .
- Pseudohalides include the cyanide (CN “1 ) , thiocyanate (SCN -1 ) , cyanate (OCN “1 ) , fulminate (CNO “1 ) , and azide (N 3 "1 ) anions .
- Carboxylate anions that contain 1-6 carbon atoms (C ⁇ -Cg carboxylate) and are illustrated by formate, acetate, propionate, butyrate, hexanoate, aleate, fumarate, oxalate, lactate, pyruvate, and the like.
- a contemplated ionic liquid used herein is hydrophilic and therefore differs from the hydrophobic ionic liquids described in Koch et al .
- U.S. Patent No. 5,683,832 that contain one or more fluorine atoms covalently bonded to a carbon atom as in a trifluoromethanesulfonate or trifluoroacetate anion.
- the contemplated solvent can also comprise mixtures of two, or more, of the contemplated ionic liquids. It is preferred that all R groups that are not required for cation formation; i.e., those other than R 1 and R 2 for compounds other than the imidazolium, pyrazolium and triazolium cations shown above, be hydrido.
- the cations shown above preferably have a structure that corresponds to a structure shown below, wherein R 1 and R 2 are as described before.
- a cation that contains a single five- membered ring that is free of fusion to other ring structures is more preferred.
- a cellulose dissolution method is also contemplated using an ionic liquid comprised of those cations. That method comprises admixing cellulose with a hydrophilic ionic liquid comprised of those five-membered ring cations and anions in the substantial absence of water to form an admixture. The admixture is agitated until dissolution is attained. Exemplary cations are illustrated below wherein R ⁇ , R 2 , and R 3 -R5, when present, are as defined before.
- an imidazolium cation that corresponds in structure to Formula A is particularly preferred, wherein R 1 , R 2 , and R 3 -R 5 , are as defined before.
- N,N-l,3-di- (Ci-C alkyl) -substituted- imidazolium ion is a more particularly preferred cation; i.e., an imidazolium cation wherein R 3 -R 5 of
- Formula A are each hydrido, and R 1 and R 2 are independently each a C ⁇ -Cg-alkyl group or a C]_-Cg alkoxyalkyl group.
- R 1 and R 2 are independently each a C ⁇ -Cg-alkyl group or a C]_-Cg alkoxyalkyl group.
- a 1- (Ci-Cg-alkyl) -3- (methyl) - imidazolium [C n -mim, where n 1-6] cation is most preferred, and a halogen is a preferred anion.
- a most preferred cation is illustrated by a compound that corresponds in structure to Formula B, below, wherein R 3 -R 5 of Formula A are each hydrido and R 1 is a C ⁇ -Cg-alkyl group or a C ⁇ -C alkoxyalkyl group.
- a contemplated ionic liquid is liquid at or below a temperature of about 150°C, and preferably below a temperature of about 100°C and above a temperature of about -100°C.
- N-alkylisoquinolinium and N-alkylquinolinium halide salts have melting points of less than about 150°C.
- the melting point of N-methylisoquinolinium chloride is 183 °C
- N-ethylquinolinium iodide has a melting point of 158°C.
- a contemplated ionic liquid is liquid (molten) at or below a temperature of about 120°C and above a temperature of minus 44°C (-44°C) .
- a contemplated ionic liquid is liquid (molten) at a temperature of about -10° to about 100°C.
- Cellulose can be dissolved without derivitization in high concentration in ionic liquids by heating to about 100°C, by heating to about 80°C in an ultrasonic bath, and most effectively by using microwave heating of the samples using a domestic microwave oven.
- a microwave heater it is preferred to heat the admixture of hydrophilic ionic liquid and cellulose to a temperature of about 100° to about 150 °C.
- a contemplated ionic liquid has an extremely low vapor pressure and typically decomposes prior to boiling.
- Exemplary liquification temperatures i.e., melting points (MP) and glass transition temperatures (Tg)
- the ionic liquid is comprised of cations and anions that are preferably those discussed above.
- a more preferred solution is comprised of cellulose dissolved in a hydrophilic liquid whose cations contain a single five-membered ring free of fusion to other ring structures, as discussed previously.
- a contemplated solution can be used as is to carry out further reactions on the cellulose such as acylation to form cellulose acetate or butyrate, or for regeneration.
- Cellulose displays high solubility in the ionic liquids. Viscous, birefringent liquid crystalline solutions are obtained at high concentration, e.g., about 10 to about 25 weight percent .
- a contemplated solution of cellulose in an ionic liquid can contain cellulose in an amount of about 5 to about 35 weight percent of the solution. More preferably, the cellulose is present at about 5 to about 25 weight percent of the solution. More preferably still, the cellulose is present at about 10 to about 25 weight percent of the solution.
- the weight ratio of cellulose to active ⁇ substance in the molten composition can be quite varied. For example, a range of about 1000:1 to about 1:2 by weight of cellulose to active substance is contemplated. More usual weight ratios contemplated are about 100:1 to about 1:1. Those weight ratios are reflected also in the regenerated cellulose product .
- Ionic liquids containing chloride anions appear to be most effective.
- the chloride anion is not required; reasonable solubility was also observed when the ionic liquid contained thiocyanate, perchlorate, and bromide anions. No solubility was observed for ionic liquids containing tetrafluoroborate or hexafluorophosphate anions .
- cellulose is dissolved in an IL, to form a homogeneous, or liquid crystalline anisotropic solution.
- the material for incorporation is then introduced into the IL solution, either dissolved, or dispersed in the medium (for example nanoparticles or macroscopic beads) .
- the cellulose matrix is then formed by regeneration upon contacting the IL solution with a non-solvent diluent, resulting in formation of a regenerated cellulose material (as a floe, film, membrane, fiber, or monolith depending on processing) in which the additives are entrained.
- the order of addition of the components to the IL solvent is not important for the regeneration and encapsulation process, and depends on external consideration such as the stability of the individual components under processing conditions.
- Cellulose can be initially dissolved to form a solution in the IL, followed by dispersion of the active components, and regeneration.
- the active component can be dispersed in the IL, followed by dissolution of cellulose and subsequent regeneration of the composite.
- the regenerating fluid or non-solvent diluent is a non-solvent for the active substance and the cellulose. That is, the regenerating fluid does not dissolve large quantities of either the cellulose or the active agent, so that both ingredients are substantially insoluble in the regenerating fluid.
- the active substance and the cellulose are independently soluble to an extent of less than about 5 percent by weight, and preferably less than about 1 percent in the regenerating fluid.
- the ionic liquid is miscible with the regeneration fluid, and contacting of the IL phase with the regeneration fluid induces regeneration of the solid cellulose polymer that is the matrix in which the active substance is encapsulated.
- extrusion of an ionic liquid solution of cellulose and an additive through a die can be accomplished in a number of manners that are well known.
- a surface of the die containing one or more orifices through which the solution is extruded is below the surface of the regenerating fluid.
- the solution passes from a die orifice through air or another gas such as nitrogen or argon prior to being contacted with the regenerating fluid.
- the liquid non-solvent is preferably miscible with water.
- Exemplary liquid non-solvents include water, an alcohol such as methanol, or ethanol, acetonitrile, an ether such as furan or dioxane, and a ketone such as acetone.
- the advantage of water is that the process avoids the use of a volatile organic compound (VOC) . Regeneration does not require the use of volatile organic solvents.
- VOC volatile organic compound
- the ionic liquid can be dried or otherwise freed of the liquid non-solvent and reused after regeneration.
- This method has advantages for formation of composites containing many solid substances that it can be desirable to encapsulate in a cellulose matrix, but that are not soluble in an ionic liquid, for example nanoparticles or macroscopic materials.
- Engineered cellulose forms containing impregnated additives with enhanced properties and applications can be prepared from ionic liquid solution.
- Useful applications include, but are not limited to membranes/filters, fuel cells, separations devices, electrolysis membranes, flame retardants, biocidal filters, sensors, metal extractants, supports for enzymes, extractant materials for filtration, separations and extractions: metal ions, biomolecules, gas molecules, magnetic particles for membrane/extractant processing, materials modifiers for cellulose coatings, bioactive agents (controlled release, sensing, destruction) , metal complexants (sensing, controlled release, extractants and binding and separations agents for filters) , water insoluble dyes for coloring cellulose, sensing and indicators, photoresists, incorporation of nanoparticles as photonic agents or UV screens, magnetic particles for magneto-responsive beads, filtration and reactive beds, nanoparticle catalysis, dispersions of clays and other fire-retardant materials, enzyme supports, supported polymer electrolytes, cavity-forming pillars/sc
- Example 1 Incorporation of a Hydrophobic Metal Extractant Into a Cellulose Matrix
- actinide complexant complexing agent
- carbamoyl methyl phosphine oxide or CMPO (Strem Chemicals, Newburyport, MA) was incorporated into a reconstituted cellulose matrix to provide a solid supported metal extractant .
- CMPO was encapsulated in a cellulose matrix (referred to as CMPO-cellulose) .
- CMPO (20 weight percent with respect to cellulose) was added to a 10 weight percent solution of cellulose
- CMPO-cellulose was reconstituted by transferring (via pouring) into a 1 L beaker containing 800 mL of deionized water. The contents of the beaker where rapidly stirred, and the water was refreshed 3 times to ensure compete removal of the ionic liquid. The resultant material resembles a floe, and was isolated via suction filtration.
- the dry weight conversion factors for the cellulose, reconstituted cellulose, and CMPO- cellulose materials were determined as follows. A known mass of material was stirred in an excess of water for 24 hours at room temperature. This was followed by 10 min of conditioning (air drying) on a B ⁇ chner f nnel. Once conditioned, samples were transferred to a preweighed crucible and dried in an oven at 110 C until a constant mass was achieved. Each gravimetric analysis was preformed in triplicate. All materials were stored in tightly capped vials and were not exposed to air for any extensive period of time in order to maintain water content .
- a 0 is the activity of the solution prior to contact
- a f is the activity of the solution after contact
- V is the volume (mL) of solution the material is contacted with
- m R is the mass (g) of the cellulose or CMPO-cellulose material
- dwcf is the dry weight conversion factor that relates the mass of the hydrated material to its dry mass.
- the D w studies were carried out as follows.
- the radiotracer was added to 1.3 mL of the solution of interest. This was vortexed for one min, and two 100 ⁇ L aliquots removed for radiometric counting (A 0 ) -
- a 0 100 ⁇ L aliquots removed for radiometric counting
- V 100 ⁇ L aliquots removed for radiometric counting
- m R hydrated CMPO-cellulose material
- the solution was then allowed to stir (ensuring that the cellulose materials are not just suspended in solution) for approximately 60 minutes. The contact time is believed to be sufficient for the systems to reach equilibrium.
- the samples were centrifuged for 2 minutes in order to completely separate the cellulose materials from the aqueous phase.
- CMPO-cellulose successfully extracted the actinide from the nitric acid solution over a wide range of pH values, and the extractions were superior to those obtained using cellulose alone.
- Example 2 Incorporation of Protoporphyrin IX as a Further Hydrophobic Metal Extractant
- Protoporphyrin IX (10 mg, CAS 553-12-8; Aldrich Chemical Co.), was added as a powder to a solution of cellulose (Whatman filter paper, 1 g) in molten [C 4 mim] Cl (10 g) , [prepared by microwave heating of cellulose in the IL with short pulses until a viscous, homogeneous solution was formed] and stirred until dissolved, resulting in a dark red- orange viscous solution containing cellulose (10 weight percent) and dye (0.1 weight percent) .
- the cellulose was regenerated as a film by coating a glass sheet with a thin layer of the ionic liquid solution, followed by immersion into a bath containing deionized water. After immersion for 30 minutes, the orange cellulose film was removed from the regeneration bath and dried in air for 15 minutes to give a soft, pliable film. The wash water was uncolored indicating that none of the protoporphyrin IX had leached from the film.
- the UV/vis spectrum of the film showed the presence of the characteristic broad absorption band with a maximum at 400 nm from the Protoporphyrin IX metal extractant, enclosed within the film.
- Example 3 Formation of Colored Cellulose Products by Trapping of Dye Molecules
- the non-reactive dye Victoria blue B (50 mg, CAS 2185-86-6; J. T. Baker Chemical Company, NJ)
- Victoria blue B 50 mg, CAS 2185-86-6; J. T. Baker Chemical Company, NJ
- cellulose Whatman filter paper, 1.5 g
- molten [C 4 mim] Cl (30 g) [prepared by heating a slurry of the filter paper and [C 4 mim] Cl at 120° C for 5 hours with occasional stirring] .
- the resulting composition was stirred until the dye dissolved, resulting in an intense blue viscous solution containing cellulose (5 weight percent) and dye (0.15 weight percent) .
- the cellulose was regenerated as a film by coating a glass sheet with a thin layer of the ionic liquid solution, followed by immersion into a bath containing deionized water. After immersion for 1 hour, the blue cellulose film was removed from the regeneration bath and dried in air for 15 minutes to give a soft, pliable film. The water was pale blue indicating that a small concentration of dye had leached from the film.
- the UV/vis spectrum of the film showed the presence of the characteristic broad absorption band with a maximum at 597 nm from the Victoria Blue B dye, enclosed within the film.
- Cellulose azure (10 mg, CAS 76296-24-7; Sigma Chemical Co., St. Louis, MO), a pH-sensitive dye molecule (Remazol Brilliant Violet 5R) covalently attached to a cellulose backbone, was added as a powder to a solution of cellulose (microcrystalline cellulose [9004 -34 -6] , 1 g; Sigma) in molten [C 4 mim] Cl (10 g) .
- the initial cellulose in IL solution was formed by pulsed microwave heating of cellulose powder in [C 4 mim]Cl, followed by cooling to about 90° C, at about which temperature the addition took place.
- the resulting composition was stirred until the blue powder dissolved, resulting in an intense blue viscous solution containing cellulose (10 weight percent) and cellulose azure (0.1 weight percent).
- the cellulose was regenerated as a film by coating a glass sheet with a thin layer of the ionic liquid solution, followed by immersion into a bath containing deionized water. After immersion for 20 minutes, the blue cellulose film was removed from the regeneration bath and dried in air for 15 minutes to give a soft, pliable film. The wash water was uncolored indicating that none of the cellulose azure had leached from the film.
- the UV/vis spectrum of the film (transmission) in Fig. 4 shows the pH sensitive cellulose-cellulose azure film with a blue absorption band with a maximum at 570 nm at pH 6.88 and a pink absorption band with a maximum at 550 nm at pH 2.10.
- Example 5 Encapsulation of Bovine Serum Albumin in a Cellulose Film
- Bovine serum albumin (BSA) was added to a solution of cellulose (fibrous, Aldrich; 5 weight percent) dissolved in [Cmim] Cl that was prepared by pulse microwave heating of the cellulose fibers in the IL until a viscous, homogeneous solution was obtained. The mixture was vortexed to disperse the BSA. A thin film was prepared by coating a microscope slide with the IL solution. Immersing the slide in a bath of deionized water regenerated the cellulose.
- BSA Bovine serum albumin
- UV/Visible spectra of a regenerated cellulose matrix from an ionic liquid solution, and a regenerated cellulose matrix from an ionic liquid solution containing the protein, bovine serum albumin (BSA) were taken.
- Example 6 Encapsulation of Laccase and a
- Cellulose pulping sample (0.10 g) , obtained from International Paper (degree of polymerization -1,000), was introduced to 5.0 g [bmim] Cl and microwave-heated in 3-5 second pulses. Complete dissolution of the sample was achieved resulting in a viscous solution. Cellulosic matrix was cooled to room temperature to avoid heat-induced denaturation of the enzyme .
- the colorless film was left in solution overnight (about eighteen hours) and activity of the entrapped enzyme was confirmed by the pink color of the film that is indicative of the laccase-catalyzed oxidization of syringealdizine.
- Example 7 Encapsulation of Ubiquinone in a Cellulose Film Matrix
- Ubiquinone (Coenzyme Q; Sigma Chemical Co.) is a membrane-bound electron carrier employed in the electron transport chain for production of cellular energy and the possibility of its encapsulation can lead to biologically conducting cellulose films regenerated from ionic liquids.
- Microcrystalline cellulose purchased from Sigma Chemical Co. (St. Louis, MO) was dissolved in [C 4 mim] Cl using 3-5 second microwave pulses to create a viscous mixture. The mixture was cooled to room temperature from about 120-130° C, ubiquinone was added with stirring, and the resulting composition was cast into a film. The film was subsequently washed three times with water to rid the film of excess IL.
- the resulting film was permitted to dry for two days and then subjected to UV/vis Scan (500 - 250 nm) on a Varian Cary-3 spectrophotometer.
- a peak corresponding to the encapsulated Coenzyme Q was clearly visible at about 280 nm, which corresponds to aromatic moieties that exist in the bio olecule but not in native, IL-regenerated cellulose films. This spectrum is shown in Fig. 7.
- Cellulose (1 g, Whatman filter paper substantially homogeneously) was dissolved in [C 4 mim] Cl (20 g) by heating at 120 C for 6 hours to form a 5 weight percent solution.
- Magnetite particles (1 g, about 5 micron powder; Aldrich Chemical Co.) were added to the molten solution and homogeneously distributed by vortexing the solution.
- a lozenge of cellulose/magnetite composite was then prepared by coating a plastic sheet (about 6 x 1.5 inch) with a film of the ionic liquid mixture. The sheet was placed in a bath containing deionized water and left to stand for 24 hours permitting all IL to be dissolved and diffuse from the matrix. The lozenge was then washed and maintained in distilled water. The resulting soft, flexible cellulose/magnetite film was air dried to yield a hard, brittle black solid.
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MXPA05010057A MXPA05010057A (en) | 2003-03-21 | 2004-03-19 | Cellulose matrix encapsulation and method. |
CA2519652A CA2519652C (en) | 2003-03-21 | 2004-03-19 | Cellulose matrix encapsulation and method |
AU2004224375A AU2004224375B2 (en) | 2003-03-21 | 2004-03-19 | Cellulose matrix encapsulation and method |
EA200501498A EA009256B1 (en) | 2003-03-21 | 2004-03-19 | Method for encapsulating in cellulose matrix |
BRPI0408606-6A BRPI0408606A (en) | 2003-03-21 | 2004-03-19 | method for forming a regenerated cellulose-encapsulated active substance and regenerated cellulose-encapsulated active substance |
JP2006507356A JP5213329B2 (en) | 2003-03-21 | 2004-03-19 | Cellulose matrix encapsulation and method |
KR1020057017712A KR101064345B1 (en) | 2003-03-21 | 2004-03-19 | Cellulose matrix encapsulation and method |
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Also Published As
Publication number | Publication date |
---|---|
KR20110042243A (en) | 2011-04-25 |
JP5213329B2 (en) | 2013-06-19 |
EA009256B1 (en) | 2007-12-28 |
CN100564019C (en) | 2009-12-02 |
KR20060002839A (en) | 2006-01-09 |
US20040038031A1 (en) | 2004-02-26 |
KR101064345B1 (en) | 2011-09-14 |
JP2006526673A (en) | 2006-11-24 |
CN1867448A (en) | 2006-11-22 |
MXPA05010057A (en) | 2005-11-23 |
ZA200508446B (en) | 2007-04-25 |
CA2519652C (en) | 2012-07-24 |
WO2004084627A3 (en) | 2006-01-05 |
AU2004224375B2 (en) | 2008-07-10 |
AU2004224375A1 (en) | 2004-10-07 |
BRPI0408606A (en) | 2006-03-07 |
US6808557B2 (en) | 2004-10-26 |
EP1648692A4 (en) | 2009-06-10 |
CA2519652A1 (en) | 2004-10-07 |
JP2011125864A (en) | 2011-06-30 |
EA200501498A1 (en) | 2006-06-30 |
EP1648692A2 (en) | 2006-04-26 |
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