WO1994002029A1 - Matrices spongieuses au glucomannane - Google Patents

Matrices spongieuses au glucomannane Download PDF

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Publication number
WO1994002029A1
WO1994002029A1 PCT/US1993/006500 US9306500W WO9402029A1 WO 1994002029 A1 WO1994002029 A1 WO 1994002029A1 US 9306500 W US9306500 W US 9306500W WO 9402029 A1 WO9402029 A1 WO 9402029A1
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WO
WIPO (PCT)
Prior art keywords
spongeous
article
manufacture
matrix
konjac
Prior art date
Application number
PCT/US1993/006500
Other languages
English (en)
Inventor
William Curtis Snow
Donald Walter Renn
Original Assignee
Fmc Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fmc Corporation filed Critical Fmc Corporation
Priority to EP93917085A priority Critical patent/EP0650348A4/fr
Priority to AU46720/93A priority patent/AU673848B2/en
Priority to JP6504511A priority patent/JPH07505922A/ja
Priority to KR1019950700266A priority patent/KR950702400A/ko
Publication of WO1994002029A1 publication Critical patent/WO1994002029A1/fr

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Classifications

    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G24/00—Growth substrates; Culture media; Apparatus or methods therefor
    • A01G24/30—Growth substrates; Culture media; Apparatus or methods therefor based on or containing synthetic organic compounds
    • A01G24/35—Growth substrates; Culture media; Apparatus or methods therefor based on or containing synthetic organic compounds containing water-absorbing polymers
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G24/00—Growth substrates; Culture media; Apparatus or methods therefor
    • A01G24/40—Growth substrates; Culture media; Apparatus or methods therefor characterised by their structure
    • A01G24/48—Growth substrates; Culture media; Apparatus or methods therefor characterised by their structure containing foam or presenting a foam structure
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/36—Surgical swabs, e.g. for absorbency or packing body cavities during surgery
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/225—Mixtures of macromolecular compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/28—Polysaccharides or their derivatives
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/425—Porous materials, e.g. foams or sponges
    • 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
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
    • C08J2201/052—Inducing phase separation by thermal treatment, e.g. cooling a solution
    • C08J2201/0524—Inducing phase separation by thermal treatment, e.g. cooling a solution the liquid phase being aqueous
    • 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
    • C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
    • C08J2305/14—Hemicellulose; Derivatives thereof

Definitions

  • This invention relates to articles of manufacture comprising spongeous matrices formed from coprocessed mixtures of a glucomannan, especially konjac derived glucomannan, and at least one other hydrocolloid; processes for fabrication of the spongeous matrices; and uses for the spongeous matrices.
  • Gels prepared from aqueous sols of konjac glucomannan are known in the art.
  • Japanese published patent application 59-146560 discloses a spongy, porous konjac glucomannan as a food additive.
  • Japanese published patent application 60-83564 discloses a water- resistant food wrap containing konjac which "becomes a water-resistant gel upon freezing.” The thawed gel is then dried to produce the food wrap.
  • Japanese published patent application 60-141250 discloses the production of konjac which is water insoluble and which does not absorb water, by drying or freezing an alkaline sol or paste of konjac.
  • Japanese published patent application 59-227267 relates to a method of freezing konjac to produce a product stable at a pH of 10.0 to 12.2. See also Japanese published patent application 59-227267 which discloses a method of freezing, drying or dehydrating konjac to produce a water insoluble or non-plastic product.
  • Gels containing agar or agarose are also known to the art.
  • U.S. patent 4,755,377 discloses aerated agar gels formed by mixing gaseous components into the sol before gelation.
  • Gels containing agarose are commercial products and are the subject of various patents.
  • multi-component gels containing konjac and one or more other components such as starch (Japanese published patent application 62- 259550) , alginic acid or starch with xanthan or galactomannan (Japanese published patent application 01-
  • Japanese patent application 63-79572 Japanese patent application 63-79572
  • a milk-type material Japanese patent application 62-107751
  • alginic acid and propylene glycol alginic acid and propylene glycol
  • starch and sodium glycolate alginic acid and propylene glycol
  • starch and sodium glycolate alginic acid and propylene glycol
  • starch and a sodium stearate ester Japanese patent applications 62-272952 and 62-195264
  • this invention comprises an article of manufacture which is a spongeous matrix, whose pores may be controlled as to size and/or distribution, when desired.
  • the article of manufacture is formed from a coprocessed mixture of (a) konjac glucomannan and (b) at least one other aqueous gel- forming polysaccharide.
  • Component (a) can be any glucomannan, of which glucomannan derived from konjac is particularly preferred.
  • the konjac glucomannan is not limited as to source and may be obtained from crude konjac flour, or from purified or clarified konjac flour, or from konjac glucomannan which has been chemically or physically derivatized or modified.
  • Component (b) comprises a polysaccharide other than a glucomannan which is capable of forming an aqueous gel.
  • Component (b) preferably comprises: agar, agaroids, agarose, algin, alginates, carrageenan, curdlan, gellan, a gel-forming chemical or physical derivative of any of the foregoing, or a mixture thereof.
  • Component (b) more preferably comprises agar, agarose, kappa-carrageenan, a gel-formimg chemical derivative or physical modification of any of the foregoing, or a mixture thereof.
  • component (b) is agar, agarose, kappa-carrageenan, or a mixture thereof.
  • Components (a) and (b) are present in a ratio [a:b] based on their respective dry weights, of 1:0.125-8.0, preferably 1:0.25-4.0, more preferably 1:0.5-2.
  • the article of manufacture of this invention may be formed including an additional component (c) which comprises one or more water soluble polysaccharides other than (a) or (b) , and which need not form an aqueous gel.
  • Component (c) preferably comprises: guar gum, gum arabic, karaya gum, locust bean gum, starch, tragacanth, or a mixture thereof; more preferably: guar gum, locust bean gum, starch, or a mixture thereof; and most preferably, starch.
  • Component (c) may be present in up to 200.0 % by dry weight, preferably 0.5 to 200.0 % by dry weight compared to the combined dry weight of (a) and (b) .
  • component (c) is starch, it preferably is present in 5.0 to 100.0 %, more preferably 20.0 to 75.0 % all by dry weight compared to the combined dry weight of (a) and
  • the spongeous matrix may have a coating.
  • the coating may be comprised of one or more of the materials suitable for forming the spongeous matrix itself, in which instance the coating is in a non-spongeous form.
  • the coating may comprise a material other than that used for forming the spongeous matrix.
  • the coating may be a dried water- soluble substance that otherwise would be added to the matrix during use, for example a nutrient medium, buffer salt, catalyst, reagent, or the like; to which water would be added to activate or reactivate.
  • the coating may be water insoluble or soluble and independently may be water permeable or impermeable, all depending upon the use for which the inventive article is intended and the environment in which the inventive article is placed.
  • the inventive spongeous matrix can be at least partially saturated with a carrier medium.
  • the preferred carrier is water, although other liquids that do not adversely affect the spongeous matrix for its intended purpose also may be used.
  • the substance carried may be medium soluble or dispersible or may be medium borne particulate matter.
  • the carrier medium may remain therein, or may be partially or completely removed.
  • carried substances include, but are not limited to: cell growth or sustenance nutrient mediums, reagents, pharmaceuticals, flavorings, colors, scents, cosmetics, air fresheners, deodorants, adjuvants to any of the foregoing, affinity or ion-exchange particulate, living or dead cells or cellular matter, activated charcoal, or mixtures thereof.
  • This invention includes all combinations of the inventive spongeous matrices with these carried substances, although the substances are themselves known.
  • the inventive article comprises the spongeous matrix of the above embodiments in substantially dry form.
  • substantially dry is defined as having no readily expressible water, or as generally 20 % or less by weight of water based on the total weight of the spongeous matrix. The percentage weight of water will vary depending upon the ambient atmospheric humidity.
  • Another group of embodiments of this invention are processes for fabricating the above articles of manufacture.
  • 6.0 for example it can be 6.66 using a phosphate buffer] ;
  • step A the respective concentrations in water of (a) and (b) , are independently of each other 0.25 to 2.0 wt %, preferably 0.5 to 2.0 wt %, more preferably 0.5 to 1.0 wt %, all based upon the total weight of the sol.
  • the formation of the sol in step A preferably may be accompanied by heating, although this is not required. It is important that during freezing the cooling gradient of the gel is relatively uniform and in particular that local areas of greater cooling intensity are avoided. A local "cold spot" during freezing may prevent the production of a satisfactory spongeous matrix by producing a local zone of extremely small pores whose appearance is similar to a gel.
  • the second fabrication embodiment according to this invention comprises including in step A of the first embodiment the water soluble polysaccharide identified above as component (c) , present in the above dry weight percentages relative to (a) and (b) combined.
  • the third fabrication embodiment according to this invention comprises including in any of the other embodiments an optional step E of the process, in which at least a portion, preferably substantially all, of the water content of the spongeous matrix is removed.
  • the fourth fabrication embodiment according to this invention comprises sterilizing the spongeous matrix of any of the foregoing processes, by any known method such as gamma radiation, microwave exposure, or preferably heating.
  • the fifth fabrication embodiment according to this invention comprises using potassium carbonate as the base used to form the gel in step B.
  • the sixth fabrication embodiment according to this invention comprises adding sufficient base in step B to result in a sol pH of 9.0 to 12.0.
  • the seventh fabrication embodiment according to this invention comprises coating the inventive spongeous matrix to form the product described in the third article embodiment, by applying a coating comprising a substance other than that of the spongeous matrix itself.
  • the coating application can be in any known manner, including dipping, spraying, and painting.
  • the eighth fabrication embodiment according to this invention comprises coating the inventive spongeous matrix to form the product described in the third article embodiment, by applying a coating comprising a substance disclosed above as comprising the spongeous matrix itself, either in sol or in thin gel form, but without forming a spongeous matrix of the coating by the inventive steps of freezing and thawing.
  • the coating application can be in any known manner, including dipping, spraying, and painting.
  • the first use embodiment for the inventive articles of manufacture comprises employing the above-described spongeous matrices for the growth or storage of a living plant material, optionally at least partially saturated with a suitable growth or storage medium.
  • the living plant material may be a seed, embryo, graft, cutting, young plant, callus, or any viable grouping of cells.
  • the third use embodiment comprises the continuous or intermittent replenishment or addition of plant nutrient medium when employing the second use embodiment.
  • the fourth method of use embodiment comprises employing the spongeous matrix of this invention as a support for tissue or cell culture in a manner similar to its use for plant material.
  • the fifth use embodiment comprises employing the spongeous matrices as surgical sponges, [optionally utilizing an above-described carried substance therein] .
  • This use takes advantage of the inventive matrices slow dissolution in aqueous fluids including body fluids and/or its biodegradability.
  • the spongeous matrices used for this purpose are first sterilized by known means.
  • the sixth use embodiment comprises forming the spongeous matrices into suitable spacer shapes and employing them in substantially dry form as a packing or packaging material, [taking advantage of their inherent biodegradability for eventual disposal] .
  • the seventh use embodiment comprises employing the spongeous matrices of this invention as filters for gases and/or fluids.
  • the components comprising the inventive article of manufacture are complex organic polymers of natural origin and therefore cannot be defined by exact chemical formulae.
  • Most of the hydrocolloids and/or polysaccharides useful as components in the inventive articles of manufacture are genera rather than species, and where a genus is referred to all known species thereof are probably useful and are included unless otherwise indicated.
  • the Webster's New World Dictionary of the American Language, second edition (World Pub. Co., New York, 1972) defines gum arabic as being obtained from several African acacias and tracracanth as coming from any of various, especially Asiatic, plants (genus A. stragalus) of the legume family.
  • Components (a) and (b) , and optional Component (c) refer to not only purified materials, but also crude or native materials in which the pure materials are present in an operative amount for the purposes of this invention.
  • the terms "chemical derivative” or “chemically modified” used in referring to a component of the inventive spongeous matrix refer to that component having a substituent moiety, examples of which moieties include, but are not limited to, acetyl, C ⁇ - 4 alkyl, C - ⁇ alkoxyl, C 2 _ 4 hydroxyl, carboxy C 1 -_ i alkyl, or an alkali metal or alkaline earth metal salt thereof where appropriate.
  • the removal of a pre-existing moiety such as by deacetylation is also a possible chemical modification.
  • the terms "physical derivative” or “physically modified” used in referring to a component of the inventive spongeous matrix refer to that component having properties which have been modified by a physical manipulation which may or may not result in a change of the complex organic polymers.
  • the product of depolymerization (degradation) in varying degrees is also considered a physical derivative.
  • glucomannan useful in this invention theoretically is not limited and includes glucomannans derived from trees. Because of commercial availability, and because of its known favorable properties, konjac-origin glucomannan is preferred, and references to "konjac” or “glucomannan” in this application should be understood as to konjac-derived glucomannan unless otherwise indicated.
  • Konjac glucomannan is a hydrocolloidal poly ⁇ saccharide obtained from the tubers of various species of Amorphophallus. It is a high molecular weight, non- ionic glucomannan primarily consisting of mannose and glucose at a respective molar ratio of approximately 1.6:1.0. This slightly branched polysaccharide is connected by -1,4 linkages and has an average molecular weight of 200,000 to 2,000,000 daltons. Acetyl moieties along the glucomannan backbone contribute to water solubility properties and are located, on average, every 9 to 19 sugar units.
  • Konjac flour is obtained by slicing, drying and then wet- or dry-milling the Amorphophallus tuber. This material is then pulverized, sifted and air-classified. This crude konjac flour contains numerous impurities including starches, cellulose and nitrogen-containing materials including proteins. Konjac flour is dispersible in hot or cold water and forms a highly viscous sol with a pH between 4.0 and 7.0. Solubility is increased by heat and mechanical agitation.
  • this crude konjac flour is suitable for producing the spongeous matrices of the invention, it may optionally be further refined by such methods as alcohol washing or by dissolution followed by filtration.
  • Konjac flour is available as a commercial product from a number of sources.
  • One source, and method for preparing konjac flour, is disclosed in Marine Colloids Bulletin K-l, "Nutricol ® Konjac Flour” (1989) (product and bulletin of FMC Corporation, Food Ingredient (formerly Marine Colloids) Division, Philadelphia, PA, 19103 U.S.A.) .
  • konjac tubers and raw or semirefined konjac can also be employed to form the inventive spongeous matrices, since the glucomannan is contained within tiny sacs or granules in the tubers which rupture upon hydration.
  • a higher molecular weight konjac glucomannan is preferable, such as that afforded by a native or crude konjac flour.
  • a more purified or a clarified konjac glucomannan is preferable for certain particular uses of the spongeous matrix (for example in medical, pharmaceutical or biotechnical utilization) .
  • Clarified (purified) konjac is an experimental product of FMC Corporation, Food Ingredient Division, Philadelphia, Pennsylvania, U.S.A. It forms a clear sol, as compared to the cloudy sol formed from more crude konjac glucomannan.
  • Such konjac glucomannan usually has a lower molecular weight as a result of the purification or clarification process. In such instance, a higher concentration aqueous gel can be obtained, and is preferably used to provide better structural integrity of the spongeous matrix.
  • Cold-melt konjac which is distinguished by its unexpected property of liquifying at lower (cold) temperatures and solidifying at higher temperatures also may be used as the konjac glucomannan component (a) .
  • Cold-melt konjac and clarified konjac and their manufacture are disclosed in pending Unites States patent application 07/742,136 and/or 07/742,260 and their corresponding Patent Cooperation Treaty publications, the contents of which are incorporated herein by reference.
  • agar a phycocolloid derived from red algae, such as Gelidium and Gracilaria, and is primarily a polysaccharide mixture of a variety of galactan molecules containing varying amounts of ester sulfate and/or pyruvate and/or methoxyl groups, the least ionic being termed "agarose”.
  • Carrageenan for use in the spongeous matrices of the invention can be a mixture of the known carrageenan fractions, but is preferably predominantly, (and most preferably entirely) the kappa fraction.
  • chitosan is unsuitable because it requires acid conditions to be water soluble and the spongeous matrix forming processes require alkaline conditions. Exposing a chitosan aqueous sol to the alkaline conditions used in forming the inventive spongeous matrices results in the chitosan coming out of the sol. Gum arabic, karaya gum, and tragacanth are each useful as component (c) when present at 5.0 % dry weight, but work poorly or not at all at 50.0 % dry weight. These polysaccharides therefore are less desirable as component (c) , but still form compositions at lower concentrations of up to approximately 25.0 % dry weight, or when combined with starch, and are useful in forming inventive articles of manufacture that have utility for certain applications.
  • Starches that can be employed herein can be obtained from any source, e.g. from corn, potatoes, tapioca, rice, and wheat, and can be high or low in amylose.
  • the term "spongeous matrix" used to characterize the articles of manufacture of this invention refers to matrices having a predominantly sponge-like character upon formation. For most (but not all) utilities, it is preferred that they possess excellent structural stability and mechanical strength, and in addition have a porous, mostly interconnecting pocket-like structure*, from which liquid present can be readily expressed.
  • mostly interconnecting is meant that at least 60% and generally at least 75% of the pockets interconnect.
  • spongeous matrices when compressed exhibit rapid return to their precompressed size and shape, with rapid uptake of aqueous solutions, for example where the pores of the spongeous matrix are substantially filled with the aqueous solution when compressed, immersed in the aqueous solution, and then pressure released.
  • most of the spongeous matrices of the invention exhibit at least some stability to short immersion in boiling water. While spongeous matrices can sometimes be formed from the individual components of the present spongeous matrices, for example from konjac glucomannan alone or agar or agarose alone, such spongeous matrices do not possess all of the favorable characteristics of the spongeous matrices of the invention.
  • these single component spongeous matrices tend to be weaker than those of the present invention, possessing little structural integrity and contain cavities more like channels or tunnels rather than the mostly interconnecting pockets characteristic of the inventive articles of manufacture.
  • Single component spongeous matrices specifically are excluded from this invention.
  • the spongeous matrices of the invention have many uses.
  • One important use is in agriculture.
  • Solid aqueous nutrient gel media have been used previously as supports in the growth and storage of seeds, plant cells, tissues, explants, embryos, grafts, young plants, and callus cultures.
  • lack of air space in such solid supports inhibits growth and provides a barrier to root development and growth for the plant cultures.
  • it is often desirable to change the nutrient media at different stages of growth by adding ox deleting specific nutrients or plant hormones. Such desired change in nutrient media is not feasible in solid media supports, but is with the inventive spongeous matrices.
  • inventive spongeous matrices can be hydrated in aqueous nutrient media to provide a beneficial combination of aqueous nutrient media and air space, which also permits rapid continuous or intermittent nutrient media replacement and/or exchange.
  • plant root systems readily penetrate the spongeous matrix supports, which need not be removed prior to transplanting since the spongeous matrices are completely biodegradable.
  • spongeous matrices in strip form can be used as biodegradable seed tapes.
  • spongeous matrices in sterile form are as surgical sponges and in the external treatment or packing of surface wounds or conditions, for example as ear packings or for wound cleaning in which medicaments can also be present in or on the matrices.
  • surgical spongeous matrices of this invention purposely or accidentally are left in a wound, they may present little problem where they can be absorbed by body fluids, depending upon their component materials.
  • a particularly important use for the spongeous matrices of the invention is as packing or packaging filler and protective materials which after use can be reused, discarded or buried in landfills without concern since the spongeous matrices are biodegradable.
  • the spongeous matrices can be formed in any shape including those conventionally used for packaging filler.
  • inventive spongeous matrices can also be used in many other fields such as for reagent delivery substrates, adsorbents, controlled release devices, chromatography packing, perfusion/dialysis equipment, diagnostic reagent carriers, immobilized enzyme reactors, collagen substitutes, cosmetic and air freshener substrates, scent and flavoring carriers such as lobster or fish baits, filters, electrophoresis wicks, microbial growth supports and sampling devices, filtration media, controlled release of reactants, substrates for the release of insect repellants, and the like.
  • bases for forming the gels are well known and those that can be used include (but are not limited to) ammonia, alkali metal hydroxides,
  • alkali metal carbonates especially sodium and potassium
  • potassium carbonate being most preferred.
  • Sufficient base is added to the sol to create an alkaline pH, preferably one having a pH of 9.0 to 12.0, and the resulting sol is then heated until it forms a uniform gel.
  • the thawed spongeous matrix in an optional step E, may be compressed to remove most of the liquid content of the spongeous matrix.
  • the spongeous matrix can be dried completely in known manner such as by drying at ambient or at an elevated temperature, by freeze-drying, and by drying under a vacuum.
  • the spongeous matrix is rinsed by squeeze/swell cycles in water, and then in a C* ] __ 6 alkanol or alkanol-water mixture, for example 65% 2-propanol.
  • the dry spongeous matrices of the invention can be sterilized as desired by using heat (e.g., by autoclaving while being protected from direct contact with steam) .
  • the resulting sponge has a tough surface layer or skin, which may be advantageous for some applications.
  • the skin can be removed prior to use.
  • Alternative methods of forming a skin include: immersion of the formed spongeous matrix in a dessicating medium such as isopropyl alcohol or acetone, or coating the matrix with other (preferably water- insoluble) known agents.
  • a dessicating medium such as isopropyl alcohol or acetone
  • a 1% w/v clarified konjac sol was divided into a number of 50 ml aliquots.
  • Various amounts of agarose powders were added to the aliquots and dissolved by heating and stirring.
  • the agarose samples were; Seakem ® LE low electroendoos osis agarose (0.5% w/v, 1%, and 2%) , and Seakem Gold agarose (1% and 2%) .
  • Seakem® agarose products are manufactured by FMC BioProducts, Rockland, Maine 04841 U.S.A.].
  • Each sample was mixed with 2 ml 5M NH4OH, heated for 20 minutes in a boiling water bath and then frozen. The samples were slowly thawed at room temperature.
  • the samples containing Seakem LE and Seakem Gold agaroses formed spongeous matrices with large cavities, which easily shed their liquid when squeezed. As agarose concentration increased, cavity size decreased. When squeezed flat and released, the matrices rebounded to full size indicating a vast increase in structural integrity over sponges formed from the individual components. When placed in water, the spongeous matrices completely filled by capillary action. All but the 0.5% agarose- containing spongeous matrix were soaked in 83% 2- propanol, drained and then dried for an hour at 80°C. When placed back in water, they quickly rehydrated and filled with water.
  • Kon ⁇ ac/Agar Composite Spongeous Matrices Crude konjac flour was used to prepare two 100 ml samples of a 1% aqueous sol.
  • One gram of Gracilaria- derived agar was added to one sample and dissolved by heating to boiling in a microwave oven. The sample was then stirred in a hot water bath until fully dissolved. Two aliquots were removed; one of 25 g and one of 50 g. The smaller aliquot was diluted with water 1:1 thus giving a concentration of 0.5% w/v konjac and 0.5% agar.
  • the second 100 ml konjac sol was mixed with 2 g of agar and treated in the same manner.
  • the four 50 g samples were all mixed with 0.375 ml of a 1M K 2 CO 3 solution and heated for 25 minutes in a boiling water bath. The resulting gels were covered and frozen overnight. The resulting spongeous matrix samples were thawed and examined. The spongeous matrices appeared very similar to the konjac/agarose matrices of Example 1 with minor exceptions. Whereas the agarose-containing matrices were covered with a strong skin and had to be forcibly squeezed to remove liquid, the konjac/agar matrices had a thin skin which allowed most of the internal liquid to drain away by gravity. The spongeous matrices were processed and dried as previously described. The dried samples all rehydrated and filled with water. The 0.5% konjac/1% agar matrix was the fastest to swell while the 0.5%/0.5% matrix was the slowest.
  • a sol of 1% konjac from crude konjac flour containing 1% Seakem ® LE agarose was prepared. A portion of this (150 ml) was cast into a crystallizing dish and gelled by adding 1.125 ml of 1M K2CO 3 in a boiling water bath. The gel was placed in a freezer at -15°C for 1.5 hours and then transferred to a freezer at -80°C for 1 hour. The sample was placed in a lyophilizer on a glass plate and dried under vacuum ( ⁇ 0.1 Torr) with a shelf temperature of 100°F (about 38°C) . After 3 days the sample was removed and weighed (3.59 g) . The resulting spongeous matrix readily hydrated and filled when placed in water. It had numerous small uniform cavities.
  • the composite spongeous matrices of Examples 1-3 were formed by gelling the konjac component (a) through the use of a base and heat.
  • a 100 ml solution of 1% konjac/1% LE agarose was prepared and split into two equal aliquots.
  • One sample was gelled as described in Example 2 by heating the alkaline solution and cooling.
  • the second sample was mixed with the same amount of
  • a sol of 1% konjac from crude flour and 1% low electroendoosmosis agarose was prepared as in example 1 and divided into seven 50 ml aliquots. Different amounts of 5M NH4OH ranging from 0.1 to 4 ml was stirred into five of these aliquots. The pH of each was quickly measured and the aliquots were gelled for 20 minutes in a boiling water bath. The last 2 aliquots were mixed with 0.1 and 0.2 ml volumes of 5M NaOH and gelled in the same manner. Their pH was also measured with a pH meter (model 155 pH/ion meter; Corning Science Products; Halstead, Essex; England) . The volumes and type of alkali used, as well as the corresponding pH's, are shown in the following table: Alkali Concentration Volume (mL) pH
  • the most desirable spongeous matrices were full sized, durable and fully rebounded after a squeeze/release cycle resulted from the following konjac / agar concentrations: 0.75%/l%, 0.5%/l% and l%/0.75%. Intermediate samples were 1%/1% and 0.75%/0.75%. The remaining matrices were generally soft and shrunken, remaining flat after squeezing, but swelling when placed in water.
  • the dried spongeous matrices were placed in water and observed. Although the spongeous matrices did fill with water, they lacked their initial structural integrity and were partially collapsed.
  • Two 1% konjac (from crude konjac flour) / 1% agar spongeous matrices were formed and dried as described above. The dried matrices were accurately weighed.
  • a 50 ml volume of a 1% crude konjac solution was diluted to 200 ml or 0.25%.
  • To this 1.5 ml of IMK2CO3 was added and the sample gelled in a boiling water bath for 35 minutes. The gel was placed in an ice bath where it cold melted, forming a cold- melt konjac. This cold-melt sol was filtered through a cloth filter to remove debris such as the sacs which are found in konjac flour.
  • One of the dry spongeous matrices was placed in this filtered cold-melt sol coating material and allowed to hydrate.
  • the matrix was massaged to remove air bubbles and to allow thorough coating.
  • the spongeous matrix was removed, squeezed to remove excess liquid and hardened briefly in 99% 2-propanol.
  • the matrix was transferred to a 92°C oven for 30 minutes to partially dry, removed, and recoated as before.
  • Excess cold-melt liquid was removed by squeezing and the spongeous matrix redried at 75°C overnight (no alcohol used) .
  • the matrix was reweighed. Each matrix was placed in 300 ml of boiling water for 60 minutes. Excess liquid was squeezed from each spongeous matrix and both were then dried overnight at 75°C. The dried matrices were reweighed to calculate the % weight loss due to leaching.
  • Example 8 Three Component Spongeous Matrices Two 50 ml samples of 1% konjac sol (from crude konjac flour) were taken from a larger volume. To the first sample, 0.25 g of agar and 0.25 g of kappa carrageenan were mixed in and dissolved. The final composition was 1% konjac, 0.5% agar and 0.5% carrageenan. The first sample was gelled by heating in a boiling water bath for 20 minutes after the addition of 0.5 g KCl and 0.375 ml IM K 2 C0 3 .
  • the gels were frozen and thawed as described in Example 1, to form spongeous matrices.
  • the matrix containing agar and carrageenan was very firm and thus hard to squeeze. When placed in water, it swelled slowly.
  • the starch/agar containing matrix was softer and easier to squeeze. It was also quicker to swell in water than the first matrix.
  • the starch containing spongeous matrix was covered with a thin but leathery skin.
  • Example 9 Konjac/Kappa Carrageenan Composite Spongeous Matrices A.
  • An aqueous sol of 1% (w/v) konjac (from crude konjac flour) containing 3% kappa carrageenan was prepared and divided into three 200 ml aliquots.
  • 2 g (1%) KCl was added -under heating to initiate gelation of the carrageenan.
  • the hot aliquot was allowed to cool and then frozen.
  • the second aliquot was mixed with 1.5 ml IM K 2 C0 3 (for konjac gelation) and 0.89% KCl (for carrageenan gelation) .
  • the aliquot was heated in a boiling water bath for a period of 30 minutes.
  • the gel was allowed to cool and then frozen.
  • the third aliquot was mixed with 0.5 ml of 1.0 M NaOH, heat-set for 30 minutes and frozen overnight.
  • the first sample (KCl only) was transparent, with a rubbery, thick-walled corrugated skin.
  • the sample was firm, containing numerous large irregular cavities, and would rebound to full size after squeezing and releasing. It did not absorb much water through capillary action and would only fill if squeezed and released under water.
  • the sample was found to be hot-water soluble.
  • the second sample (KCl and K 2 C0 3 ) was white, rubbery, contained few cavities and had a thin skin. The sponge would rebound after a squeeze/release cycle. The sample did break up somewhat when placed in boiling water but did not dissolve. There was evidence that at least a portion of the carrageenan did leach out into the water.
  • the third sample was very rubbery and tough with very few cavities and looked and felt more like a slightly fractured gel.
  • the spongeous matrix containing 1% konjac and 1% kappa carrageenan was dried and weighed. The matrix was then placed into 500 ml of hot water for 20 minutes and then boiled for an additional 60 minutes. The sponge turned white in color and became slimy. The sponge was redried and reweighed to determine weight loss. The result was: initial weight - 3.564 g final weight - 2.754 g percentage loss - 22.7%. The dried matrix was then placed in water and observed. The matrix was slimy with a thick rubber feel and possessed no sponge-like characteristics.
  • Example 10 Konjac/Gellan Gum Composite Spongeous Matrix On hundred ml of a 2% (w/v) hot solution of gellan gum was admixed with 100 ml of a 2% (w/v) hot solution of konjac, to prepare 200 ml of l%konjac / 1% gellan. The mixture was cooled to 60°C and 1.5 ml of IM K2CO 3 and MgS ⁇ 4 -7 ⁇ 0 were admixed therein. A 150 mg portion of the sample was introduced into a 6.5 x 6.5 x 10 cm plastic container. The sample was heated in an 85°C water bath for 60 minutes.
  • Konjac/Sodium Alginate Composite Matrices Two hundred ml of 1% konjac / 1 % sodium alginate (w/v) mixture was prepared by admixing 100 ml of a 2 % (w/v) hot solution of sodium alginate with 100 ml of a 2% (w/v) hot solution of konjac. The sol was cooled to 60°C and 1.5 ml of IM K 2 CO 3 and 0.4 g CaCl 2 were admixed. The alginate component began precipitating immediately and its gel structure was disrupted by subsequent mixing. Despite this, a 150 g portion of the sol was placed in a 6.5 x 6.5 x 10 cm plastic container and covered.
  • the sample was heat-set for 60 minutes in an 85°C water bath. The gel was removed and cooled overnight at room temperature and then frozen for 24 hours at -15°C. The sample was thawed at room temperature and examined. The sample was completely porous while the matrix was soft and filled with many small, fine pores. When squeezed and released, the sample did not rebound significantly. Additionally, the matrix crumbled quite easily, especially along its edges.
  • a duplicate 200 ml sample of 1% konjac / 1% sodium alginate was prepared in the above manner. When cooled to 60°C, only the K2CO 3 was added. The sol was gelled by heating in the above manner.
  • the gel was then removed from the container and placed in 750 ml of 2% CaCl 2 for 48 hours to set the alginate component.
  • the gel which shrank during this, was frozen and thawed in the above manner.
  • the matrix was fully porous, yet was filled by much larger cavities. It was also much firmer and quickly rebounded after being compressed and released.
  • Example 12 Use of Inventive Spongeous Matrices for plant culture A.
  • a 150 ml volume of an aqueous sol containing 1% crude, alcohol-washed konjac (from crude konjac flour) and 1% agar was prepared as described in Example 2.
  • the sample was mixed with 1.125 ml of IM K2CO 3 and cast into a 6.5 x 6.5 x 10 cm plastic plant embryo culture container (type GA 7, Magenta Corp.; Chicago, IL.).
  • the sol was then gelled by heating in an 85°C hot water bath for 35 minutes.
  • the sample was frozen at -15°C overnight and thawed slowly at room temperature.
  • the resulting matrix was squeezed flat, placed in clean tap water and allowed to reswell.
  • the spongeous matrix was hydrated with 25 ml of Murashige and Skoog salt base buffer (Hazelton Research Products; Denver, PA) . Two small slits were cut into the surface of the sponge and a Kentucky Wonder ® pole bean seed was inserted into each. The seeds began germinating after 2 days. After 10 days, a complex root system had developed and leaves had appeared. In some places where the thin skin covering the sponge was ripped or torn, roots had penetrated through to the exterior. Throughout this period, the sponge was kept moist by additional buffer. Two weeks after planting the seeds, the seedlings were transplanted outside by placing the entire sponge into the ground and slightly covering it with soil. After nine days, the plants were carefully excavated to examine the root system and sponge.
  • Murashige and Skoog salt base buffer Hazelton Research Products; Denver, PA
  • Roots which had already penetrated the skin had begun to develop smaller tap roots whereas those still within the sponge had not yet exited the matrix which was beginning to show signs of deterioration. After 7 weeks the plant was again excavated. There was very little left of the spongeous matrix. What little remained was a soft gel-like material which readily fell away from the extensive root system which had developed.
  • Two 1% konjac (from crude konjac flour) /1% agar spongeous matrices were prepared by freeze/thawing gel which were prepared in 50 ml disposable centrifuge tubes. The samples were processed and dried as described above. The dried matrices ( ⁇ 5 cm long) were hydrated in water and holes were cut through them along their long axis. Cuttings from a Coleus sp. house plant ( ⁇ 13 cm in length) were inserted 4 cm into the matrices. The matrices/cuttings were placed back into centrifuge tubes containing water. Within 2 weeks numerous roots had sprouted from the stem and had grown throughout the sponge matrix.
  • Example 13 Spongeous Matrices prepared varying Component (c) A solution of 1% glucomannan as crude konjac [Component (a)] containing 0.75% agar [Component (b) ] was prepared by dissolving 15 g konjac and 12 g agar in 1.5 1 distilled water over 60 minutes in a hot water bath. The sample was split into 100 g aliquots.
  • Various Component (c) gums were incorporated as dry powders either by adding 0.088 g (5% w/w based on konjac and agar) or 0.875 g (50% w/w). Each aliquot was stirred and heated to effect dissolution. Samples were cooled slightly and 0.75 ml of IM K 2 C0 3 was admixed. Each sample was heat-set in a boiling water bath for 30 minutes. Gels were removed, cooled to room temperature and then frozen overnight. The frozen materials were thawed at room temperature and examined. The results are summarized below.
  • Chitosan is only soluble under acidic conditions, and was dissolved in aliquots of the konjac/agar by adding acetic acid. However, when alkali was added to adjust the pH for heat-setting, the chitosan precipitated. An attempt was then made to gel the sample by cooling the sol and allowing the agar component to gel. At this point, the gel was soaked in alkali to raise the pH. While this was in process, much of the chitosan leached out of the gel and precipitated in the alkaline buffer. Further efforts to incorporate chitosan into a konjac/agar sponge were then abandoned.
  • the syneresate from two of the samples produced a slight coag when dropped in 99% 2-propanol.
  • the syneresate from the acidified sample produced no such coag.
  • All three samples formed fibrous, spongy matrices which had little structural integrity and which were quite similar in texture and appearance.
  • One exception was that the matrix formed from acidified cold-melt sol reswelled in liquid more rapidly than the others after squeezing.
  • the samples were thawed and examined. All samples were full sized although the 1% sample's sides were slightly constricted. The 1% sample had a corrugated surface, a few large irregular cavities, had no structural integrity, was soft and easily broke up. The sample did swell when placed in water. The 2% and 3% samples resembled fractured gels with no visible cavities. The samples were not compressible (3%) or released very little water. Both were soft, yet somewhat brittle and thus broke up very easily.
  • Comparison Example F Attempt At Matrix Formation Using Only Agar
  • Three agar gels were prepared at 1%, 2% and 3% concentrations.
  • the starting material was a Gracilaria-derived agar (Algas Marinas; Santiago, Chile).
  • the three gels were cooled and then covered,, frozen overnight and then thawed at room temperature.
  • the 1% sample was much like the 1% agarose sample in Comparison Example E. It was however softer and weaker. After squeezing, the sample did not rebound and remained compressed but did swell when placed in water.
  • the matrix which contained some large and randomly distributed cavities, was weak and easily broke apart if force was used.
  • the 2% sample was fully compressible and when released, partially rebounded. This sample also swelled in water.
  • the matrix was still rather weak and contained some cavities which were smaller, more numerous and evenly distributed.
  • the 3% sample was much like the 2% agar matrix although it fully rebounded after being squeezed. Although it
  • concentrations of konjac/xanthan were 1%/1% and 0.5%/ 0.5%.
  • a duplicate of the 1%/1% was prepared and allowed to gel without added alkali and heat.
  • the first 2 samples were gelled as previously described. All gels were frozen and thawed. None of the thawed samples displayed any sponge-like characteristics and were either mush or gel-like.
  • a sample of CMA was used to prepare 2 gels.
  • the first sample 1%/1%) was observed to be mushy, was not squeezable, and there were no visible cavities.
  • the sample began breaking up after a very small amount of fluid was expressed.
  • the second sample had more structural integrity and did contain some visible cavities. It could be squeezed flat but would remain that way until placed in water where it would swell.
  • a solution containing 0.5% konjac/5% PAA (36:1 acrylamide:bis-acrylamide) was prepared by dissolving 0.25 g konjac, 2.432 g acrylamide (Sigma Chemical Co.; St. Louis, MO.) and 0.068 g of bis-acrylamide (American International Chemical; Natick, MA) in 50 ml water at room temperature. Once dissolved, 0.375 ml of IM K 2 C0 3 , 12.5 ]Jl N,N,N' ,N'-tetramethylethylenediamine (TEMED) and 250 ⁇ 1 of 10% ammonium persulfate (both from FMC Corporation, Philadelphia, PA) were added and the sample gelled for 20 minutes in a hot water bath ( ⁇ 80°C) . This sample was frozen and thawed as previously described. The thawed sample was gel-like and very rubbery. There were no cavities visible and no liquid could be squeezed from the sample.
  • a 1% konjac/1% Seakem LE agarose sol (200 ml) was prepared as described in Example 1. To this, 20 g (10% w/v) NaCl was added. The sample was gelled by adding 1.5 ml IM K 2 CO 3 and heating for 30 minutes in a boiling water bath. A control was also prepared without the added salt. Both gels were covered, frozen overnight and thawed at room temperature. The control had formed a typical sponge as described in Example 1. The sample which contained 10% NaCl was a firm strong gel with no evidence of cavities or fracturing. The sample was frozen again at -80°C overnight and thawed. There was some very slight fracturing but no sponge-like properties.
  • a 200 ml solution of 1% konjac/1% agar was prepared to which 10 g (5% w/v) of glycerol (EM Science; Cherry Hill, N.J.) was added.
  • the sample was gelled by adding 1.5 ml of IM K 2 C0 3 and heating in a boiling water bath for 30 minutes. The gel was covered, frozen overnight and thawed. The sample was largely intact, showing only minimal fracturing. The sample was not compressible and there was no release of liquid.

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Abstract

Cette invention concerne des articles manufacturés comprenant des matrices pouvant présenter une grosseur et/ou une distribution de pores contrôlées, qui sont constituées: d'un composant (a) qui est du glucomannane; et d'un composant (b) qui est au moins un autre polysaccharide aqueux formant un gel; et facultativement d'un composant (c) qui est au moins un hydrocolloïde soluble dans l'eau différent du composant (b). Cette invention concerne également des procédés de fabrication de matrices spongieuses et leur utilisation comme milieux de culture pour des plantes, éponges chirurgicales et matériau d'emballage.
PCT/US1993/006500 1992-07-23 1993-07-09 Matrices spongieuses au glucomannane WO1994002029A1 (fr)

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EP93917085A EP0650348A4 (fr) 1992-07-23 1993-07-09 Matrices spongieuses au glucomannane.
AU46720/93A AU673848B2 (en) 1992-07-23 1993-07-09 Glucomannan spongeous matrices
JP6504511A JPH07505922A (ja) 1992-07-23 1993-07-09 グルコマンナンスポンジ状マトリックス
KR1019950700266A KR950702400A (ko) 1992-07-23 1993-07-09 글루코만난 스폰지성 매트릭스(glucomannan spongeous matrices)

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US918,992 1992-07-23

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JPH08290051A (ja) * 1995-04-21 1996-11-05 Kobayashi Pharmaceut Co Ltd 含水性ゲル基剤
EP0745392A1 (fr) * 1994-02-18 1996-12-04 Kanebo Ltd. Matiere de couverture de lesions
EP0792653A2 (fr) * 1996-02-28 1997-09-03 JOHNSON & JOHNSON MEDICAL, INC. Matériau polysaccharide solide et son utilisation comme pansement pour blessure
EP0838491A2 (fr) * 1996-10-28 1998-04-29 Johnson & Johnson Medical Ltd. Eponges de polysaccharide séchée au moyen d'un solvant
US6309661B1 (en) 1996-02-28 2001-10-30 Carla A. Haynes Solid polysaccharide materials for use as wound dressings
US6586590B1 (en) 2000-07-03 2003-07-01 Marine Bioproducts International Clarified hydrocolloids of undiminished properties and method of producing same
DE10358250A1 (de) * 2003-12-11 2005-07-07 Zeiss, Karl Reinhard, Dipl.-Ing. Verfahren zur Herstellung und Ausbringung von Saatgut und Saatgut
WO2021086862A1 (fr) * 2019-10-29 2021-05-06 Anemorix, LLC Échafaudages poreux de glucomannane et procédé de production des échafaudages
CN113261492A (zh) * 2021-03-22 2021-08-17 苏州市生科新材料科技有限公司 一种用于植物栽培的凝胶基质及其制备和使用方法
CN114699382A (zh) * 2022-04-24 2022-07-05 江苏瀚仁生物科技有限公司 一种ph敏感的葡甘聚糖胃减重材料及其制备方法

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JP2005015482A (ja) * 2004-06-07 2005-01-20 Koki Bussan Kk 有害物質の吸着除去剤
ATE547004T1 (de) * 2005-09-26 2012-03-15 Rogosin Inst Inc Sekretionszellenhaltige macrobeads, die seakem- gold-agarose enthalten, und ihre verwendungen
WO2023105878A1 (fr) * 2021-12-09 2023-06-15 日東電工株式会社 Matériau poreux et son procédé de fabrication

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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0745392A4 (fr) * 1994-02-18 2000-04-05 Kanebo Ltd Matiere de couverture de lesions
EP0745392A1 (fr) * 1994-02-18 1996-12-04 Kanebo Ltd. Matiere de couverture de lesions
JP4279361B2 (ja) * 1995-04-21 2009-06-17 小林製薬株式会社 皮膚貼付用含水ゲル基剤
JPH08290051A (ja) * 1995-04-21 1996-11-05 Kobayashi Pharmaceut Co Ltd 含水性ゲル基剤
SG84503A1 (en) * 1996-02-28 2001-11-20 Johnson & Johnson Medical Solid polysaccharide materials for use as wound dressings
EP0792653A3 (fr) * 1996-02-28 1999-03-10 JOHNSON & JOHNSON MEDICAL, INC. Matériau polysaccharide solide et son utilisation comme pansement pour blessure
US6309661B1 (en) 1996-02-28 2001-10-30 Carla A. Haynes Solid polysaccharide materials for use as wound dressings
EP0792653A2 (fr) * 1996-02-28 1997-09-03 JOHNSON & JOHNSON MEDICAL, INC. Matériau polysaccharide solide et son utilisation comme pansement pour blessure
EP0838491A3 (fr) * 1996-10-28 1999-01-13 Johnson & Johnson Medical Ltd. Eponges de polysaccharide séchée au moyen d'un solvant
EP0838491A2 (fr) * 1996-10-28 1998-04-29 Johnson & Johnson Medical Ltd. Eponges de polysaccharide séchée au moyen d'un solvant
US6586590B1 (en) 2000-07-03 2003-07-01 Marine Bioproducts International Clarified hydrocolloids of undiminished properties and method of producing same
DE10358250A1 (de) * 2003-12-11 2005-07-07 Zeiss, Karl Reinhard, Dipl.-Ing. Verfahren zur Herstellung und Ausbringung von Saatgut und Saatgut
DE10358250B4 (de) * 2003-12-11 2005-11-24 Zeiss, Karl Reinhard, Dipl.-Ing. Verfahren zur Herstellung und Ausbringung von Saatgut
WO2021086862A1 (fr) * 2019-10-29 2021-05-06 Anemorix, LLC Échafaudages poreux de glucomannane et procédé de production des échafaudages
CN114599314A (zh) * 2019-10-29 2022-06-07 安纳摩利斯有限责任公司 多孔葡甘露聚糖支架和生产该支架的方法
CN113261492A (zh) * 2021-03-22 2021-08-17 苏州市生科新材料科技有限公司 一种用于植物栽培的凝胶基质及其制备和使用方法
CN114699382A (zh) * 2022-04-24 2022-07-05 江苏瀚仁生物科技有限公司 一种ph敏感的葡甘聚糖胃减重材料及其制备方法

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AU673848B2 (en) 1996-11-28
JPH07505922A (ja) 1995-06-29
EP0650348A4 (fr) 1995-06-14
AU4672093A (en) 1994-02-14
EP0650348A1 (fr) 1995-05-03
CA2140864A1 (fr) 1994-02-03

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