WO1989011783A2 - Composites de cellulose microbienne et leurs procedes de production - Google Patents

Composites de cellulose microbienne et leurs procedes de production Download PDF

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Publication number
WO1989011783A2
WO1989011783A2 PCT/US1989/002356 US8902356W WO8911783A2 WO 1989011783 A2 WO1989011783 A2 WO 1989011783A2 US 8902356 W US8902356 W US 8902356W WO 8911783 A2 WO8911783 A2 WO 8911783A2
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Prior art keywords
cellulose
microbial
microbial cellulose
bacteria
paper
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PCT/US1989/002356
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English (en)
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WO1989011783A3 (fr
Inventor
R. Malcolm Brown
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Brown R Malcolm
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Publication of WO1989011783A2 publication Critical patent/WO1989011783A2/fr
Publication of WO1989011783A3 publication Critical patent/WO1989011783A3/fr

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/52—Cellulose; Derivatives thereof
    • 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
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/04—Macromolecular materials
    • A61L31/041—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
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/08—Materials for coatings
    • A61L31/10—Macromolecular materials
    • 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
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P19/00—Preparation of compounds containing saccharide radicals
    • C12P19/04—Polysaccharides, i.e. compounds containing more than five saccharide radicals attached to each other by glycosidic bonds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • D06M15/05—Cellulose or derivatives thereof
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/34—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising cellulose or derivatives thereof

Definitions

  • the present invention relates to microbial cellulose composites and structures formed therefrom. Additionally, the invention relates to processes for preparing the microbial cellulose structures. More specifically, microbial cellulose (MC) made by certain microorganisms, especially the Acetobacter xylinum bacterium (AB), can be used to produce in situ composites and structures by a variety of predetermined means, such as by filling and covering interstices in porous materials, such as paper, fabrics, filters, membranes, and condoms. The microbial cellulose alters porosity and permeability and supports and protects both porous and nonporous materials. In addition, the microbial cellulose can be used to fabricate entirely novel MC-containing compositions and multicellular articles.
  • MC microbial cellulose
  • AB Acetobacter xylinum bacterium
  • Miicrobial cellulose is the product of a unique class of microorganisms (M) capable of forming microscopic cellulose ribbons as part of their life cycle.
  • Acetobacter xylinum (AB) is a species of this class, well described in the patent literature, such as in U.S. Patent No. 4,378,431 and U.S. Patent No. 4,588,400.
  • the prior art has generally recognized that microbially-produced, cellulose microfibrils are essentially usable directly for end-use and product applications in which the unusual physical properties characteristic of microbially-produced, cellulose microfibrils are useful. Examples of such uses include U.S.
  • Patent 4,588,400 in which microbially-produced, cellulose microfibrils pads are used to retain medical fluids, in a manner similar to a cotton pad or a fabric holding liquids.
  • U.S. Patent No. 4,378,431 utilizes the cellulosic character of microbially-produced, cellulose microfibrils to coat other fibers and fabrics to impart a cellulosic characteristic to the surface thereof. Thereby, articles having such coated fibers have the feel, dyeability, printability, liquid sorbtion and other characteristics of cotton fabrics.
  • U. S. Patent No. 4,742,164 teaches a particular process for producing molded articles using microbial cellulose.
  • the articles are noted for their high dynamic strength and modulus of elasticity.
  • an object of the present invention is to provide improved processes for growing microbial cellulose and using same to produce certain improved structures.
  • Any microbial strain capable of generating cellulose is generally usable for the processes, articles, composites and compositions of the present invention. These will be generically referred to as cellulose producing microbes (M). More specifically, those in the Acetobacter, Rhizobium, Agrobacterium, Alcaligenes, and Pseudomonas genera, as described by the present inventor in his article in J. Applied Science: Appl. Polymer Symp. (1983) 37, 33-78 are preferred.
  • the species Acetobacter xylinum (ACX) is particularly preferred and, unless expressly indicated otherwise, was used as the basis for the inventive concepts described herein. More particularly, those strains of microorganisms within the listed genera, which reverse direction during cellulose production are preferred.
  • the microbes are placed in a culture medium.
  • the major constituent of the culture medium for ACX preferably is a soluble polysaccharide, particularly sugar (sucrose), more particularly a hexose, and especially glucose.
  • Suitable nutrients are well known to the art.
  • One known as Schramm & Hestrin medium is especially preferred. It generally comprises about 20 g/1 glucose, 5 g/1 peptone, 5 g/l yeast extract, 2.7 g/l anhydrous dibasic sodium phosphate, and 1.15 g/l citric acid monohydrate. Corn steep liquor and molasses are practical and inexpensive sources of the hexose component preferred in the nutrients of the invention.
  • Another satisfactory nutrient composition comprises about 8 volume percent vinegar, 5 volume percent ethanol and 4 weight percent malt extract.
  • the pH is preferably adjusted to about 3 to 6, most preferably about 3.5 to 5.5. When it is desired to increase the amount of oxygen-containing components in the nutrient, additional alcohols and mixtures thereof can be included in the nutrient.
  • the ambient temperature for maximum effectiveness of microbial cellulose production is about 15 to 40, preferably about 20 to 30 degrees Centigrade.
  • the total amount of time needed for acceptable cellulose production is generally from about 1 to 25 days. Techniques for improving microbe growth and increased cellulose production from each microbe are contemplated by this invention.
  • the conventional product of cellulose-producing microbes is a mass of intertwined submicron ribbons comprised of cellulosic microfibrils. These ribbons are generated at the oxygen-containing gas (air is operable)/nutrient interface.
  • the nutrient medium contains the cellulose-producing microbes.
  • the mass of intertwined ribbons is translucent and insoluble, but very hydrophilic and wettable. It also has great tensile strength. It appears to be a gel to sight and touch. It has exceptionally high wet and dry tensile strength, as well as excellent dimensional stability.
  • the breakthrough inventive concepts of the present invention are improvements in the method of manufacturing the microbial cellulose.
  • the resulting cellulose evidences unique properties which lead to utility for a number of new applications.
  • certain properties are selected so that microbial cellulose is adapted and tailored to be utilized in processes, products and compositions having no counterpart in the prior art.
  • the microorganisms for growing the microbial cellulose are specifically selected strains from the Acetobacter, Rhizobium, Agrobacterium, Alcaligenes, and Pseudomonas genera.
  • the strains are those which have periodic reversal in cellulose synthesis. These strains include H1A, H1B, H1C, H2A, H2B, H5C, H5D, H6C, H14B, H15A, AND H15B ; particularly preferred is the NQ-5 strain (American Type Culture Collection No. 53582). These strains are described in more detail in United States Serial No. 023,336, filed March 9, 1987, and entitled “Multiribbon Microbial Cellulose", the disclosure of which hereby is incorporated by reference.
  • the size of the initial microorganism seed is important, in that the larger the seed the more dense is the product.
  • CMC carboxymethylcellulose
  • the present invention recognizes that the cultivation of the cellulose-producing microorganism to produce cellulose I or a crystalline polymorph thereof, at the exclusion of cellulose II, produces a preferred product.
  • the cellulose microfibrils produced from microbes according to the present invention have submicron cross-sectional diameter dimensions of from about 1.5 nm (nanometers) [0..0015 micron] to 10 nm (0.01 micron). This results in an enormous fiber surface area per cubic volume of fiber. Moreover, the submicron dimensioned cellulose fibrils produced by microbes have exceptionally high wet and dry tensile strengths. These microfibrils are especially noteworthy with respect to their remarkably high length to diameter ratio which can be in the order of as much as millions to one.
  • One preferred embodiment of the present invention is in situ application to paper documents, especially fragile acid-damaged paper documents or those likely to become so. Another is a modified currency product of improved longevity and anti-counterfeiting aspects. Encapsulation of artifacts and growing MC in situ on bubbles to form multicellular three-dimensional structures (MC3DS) are other features, but the invention is not so limited.
  • the restoration process of the instant invention can be applied to paper substrates to provide enhanced longevity and improved structural integrity.
  • a leading example of the applicability of the present invention involves its advantageous use with the DEZ process described above.
  • the technique of the instant invention can be employed on a given paper substrate after the DEZ treatment or as a substitute therefor. Regardless of whether acidity has been neutralized by a treatment such as by DEZ, the substrate paper requires a transparent, compatible support to maintain or restore its physical integrity. This is accomplished by the M, preferably AB, process technique of the invention. Once integrity has been enhanced by the technique of this invention and some protection from future degradation imparted thereto, further degradation of residual acid may be tolerable. Thus, the necessity for DEZ or comparable treatment will be obviated by the technique of this invention.
  • One embodiment of the instant described process involves forming MC in a relatively wet environment, e.g., a liquid nutrient bath.
  • the invention also contemplates MC formation simply in a damp environment.
  • individual pages or a multiplicity of pages, such as in a book can be sprayed with a solution of M, i.e., AB, and closed.
  • M i.e., AB
  • Sufficient MC will be created in situ in the interstices and surface of a document as will be adequate to reinforce badly degraded paper.
  • This can be an adjustable preliminary step to achieving sufficient stability so that the so-treated pages can be subsequently spread and dipped into a live, preferably AB bath, for further in situ MC deposition.
  • This approach results in a diminished oxygen supply to M. This is compensated for by either carrying out the process in a higher pressure and/or greater concentration oxygen environment to force the molecules into the damp paper.
  • oxygenating agents such as peroxides
  • the bubblebacter technique described elsewhere herein can be utilized to ensure that adequate oxygen is in the bubbles that are contacted with the surface of documents, particularly pages of books.
  • MC provides very strong thin films of excellent optical clarity.
  • the MC also intertwines with the much larger wood cellulose.
  • MC unlike wood cellulose, has excellent wet strength. It also retains its properties at very extreme temperature conditions.
  • the in situ technique of the present invention also can be used to encase small items, such as microchips, and very large objects, such as, electronic components, i.e., circuit boards, and fragile or perishable archeological articles and artifacts.
  • small items such as microchips
  • very large objects such as, electronic components, i.e., circuit boards, and fragile or perishable archeological articles and artifacts.
  • Such encasement provides long term protection from typical ambient conditions which are otherwise harmful to such objects.
  • An excellent example of the utility of the present invention is evidenced by the following situation.
  • the Mary Rose is a recently discovered Elizabethan Era ship found in the River Thames.
  • the wood used in the ship's construction is soaked in water. Upon exposure to air, it is susceptible to rapid degradation.
  • M such as AB to form very thin continuous MC layers around the ship's parts, such degradation can be avoided or restrained.
  • Another important utility for the AB process of the invention is to fill the interstices within articles, such as those made from emulsion polymer castings or deposition processes, such as those made from elastomeric latices.
  • the products made from such processes can be made in a wide variety of shapes and sizes. Often the process results in microscopic voids in the products.
  • the MC generated by AB fills the voids in the article from which the defects stem, increasing the inspection passage factor and lowering the failure rate in use.
  • MC in latex item manufacturing, such as condoms, should reduce rejection rate and increase reliability and safety.
  • the MC can be used as a dispersion or emulsion in the elastomer latex at the time of article formation. Alternatively, it is applied as an after-step analogous to document strengthening as described herein.
  • personalized handcoverings can be made from MC using a suitable mold. These can be carried around as disposables for use in public rest rooms where AIDS virus transmission may be a problem.
  • spreadable emulsions or solutions of MC can be prepared with a wide variety of appropriate thixotropic and other properties using agents such as glycerol, polyethylene glycol and carboxymethyl-cellulose (CMC). These can be then coated and spread on any suitable substrate such as a paper page. By itself or in combination with in situ processes described herein, composites possessing desired new properties can be produced by this non in situ coating process.
  • the MC produced by M or AB is not susceptible to inorganic acidic degradation, it can be fabricated into paper and other cellulosic products that are required to be resistant ab initio from degradation.
  • a typical production run would be as follows: First, Acetobacter is innoculated into a standing culture of growth medium, and the cellulosic pellicle or membrane will form at the gas/liquid interface. The nutrient composition and time of culture will determine the thickness of the membrane. The strain used will determine some of the physical properties such as strength, opacity, etc. Once the cellulose membrane has been generated, it is then thoroughly cleaned. A typical cleaning procedure involves dilute alkali (NaOH) followed by or in combination with a detergent (such as Alconox), heating, and rinsing with distilled water. These processes result in the removal of non-cellulosic substances and cells and cell debris.
  • a detergent such as Alconox
  • the never-dried sheet is now ready for post synthesis processing and drying. It can first be pressed to express most of the water, or it can be air dried. Additives can be in place before drying to modify the final physical properties of the dried product.
  • the never-dried cellulose can be dyed or stained in such a manner to prevent counterfeiting. By doing these procedures before drying, one has additional control over such problems as accessibility of staining or dyeing, addition of binders for printing, etc.
  • the dried microbial cellulose paper for currency printing can then go through conventional processing, much as done with the specialty paper provided to the U.S. Treasury by Crane and Co. in Massachusetts.
  • Another variable would be to add microbial cellulose in very small quantities to the paper stock presently used (cotton rag and linen fibers) for U.S. currency production. By doing so, a sub-microscopic morphology is produced which is very unique and very difficult to counterfeit. This would be analgous to what Crane & Co. does by adding colored fibers to the paper stock for currency, but using microbial cellulose would be much more effective. It is important to note that the chemical composition of the base material for currency would still be exclusively cellulose. Addition of microbial cellulose to the conventional paper stock would also greatly increase the wearability and abrasion resistance of the paper stock, hence increasing the lifetime of the circulating currency.
  • bubblebacter Another important facet of this invention if referred to by its nickname as "bubblebacter.”
  • the microbial cellulose is grown on the surface of a bubble.
  • the bubbles can be comprised of nutrient solution. Alternatively, they can be separately formed and a thin film of nutrient-containing M coated thereon to produce microthin layers of MC.
  • the resulting product is usually a multicelled three dimensional foamed network of MC. In some instances, it can comprise a large single cell.
  • MC is not thermoplastic, and therefore, it cannot be foamed by conventional gaseous foaming agents. Nevertheless, the bubblebacter technique of this invention provides a means of producing a wide variety of multicellular MC structures. These can be designed and engineered to accomplish any structural, support or shape requirements.
  • the foamed bubblebacter version of MC can be made into any shape and used in any application in which non-cellular MC can be employed. It can be fabricated to have both low and high gas and liquid permeability. It will have exceptional applicability for those uses in which electric circuits are desired.
  • the surface structure of this multicellular material is especially well-adapted to thin film vapor deposited and epitaxial grown inorganics, such as superconductors, semiconductors and ordinary conductors, such as laminated metals, i.e., copper. All of this is of special significance because of the strength of thin gauge multicelled and dense MC articles. MC also has a low dielectric constant, adding to its already remarkable utility.
  • MC is produced in a form so dissimilar from cellulose produced from cotton or wood degradation processes, it can be used effectively in process and environments in which conventional cellulose is not well-suited.
  • the multicellular embodiments will have a wide variety of applications not hitherto possible of attainment by existing multicellular polymers.
  • MC in both the dense and multicellular forms, is used as a filler in resins, particularly thermosetting resins. Both forms can be used also in existing porous membranes and filters to modify the capability of passing various materials. When used to fill interstices of porous materials, e.g., filters and membranes, the different components thereof can be selectively leached and dissolved to selectively alter porosity and permeation properties.
  • Example 1 The present invention now will be further illustrated by certain examples and references which are provided for purposes of illustration only and are not intended to limit the present invention.
  • Example 1
  • a 100 mm circle of Whatman #1 filter paper, and cut pieces (about 100 mm in diameter) of old archival paper documents (provided by Dr. Don Etherington of the Humanities Research Center of the University of Texas at Austin), including some old acid papers which were badly degraded and fragile, were added to a tray containing Schramm and Hestrin culture medium which was innoculated with strain NQ-5 of Acetobacter xylinum.
  • the culture medium volume was minimal so that the archival and test paper would be sufficiently close to the gas/liquid interface that microbial cellulose would be generated in the vicinity of the test papers. After 6 days of growth, the microbial cellulose was found to have penetrated the test papers and be incorporated into them.
  • a pellicle of microbial cellulose grown for 3 days in Schramm Hestrin medium was cleaned as described in Example 1 above, then impregnated while still wet with 1% glycerol to decrease brittleness.
  • the wet glycerol impregnated pellicle was placed onto a polyethylene sheet. Then the test document was placed on top of the wet microbial cellulose. Than a 1% aqueous solution of carboxymethylcellulose was hand rubbed into the document after it was pressed to the test document and squeeze dried. The composite was then air dried for 24 hours.
  • the resultant adhesion of the microbial cellulose to the test document was excellent, imparting a much greater mechanical strength to the brittle test document.
  • Acetobacter xylinum strain NQ-5 was grown on Schramm Hestrin liquid medium in an Erlenmeyer flask, and a 5 day culture was vigorously shaken to obtain an active innoculum of cellulose producing cells.
  • 0.5% (wt/vol) albumin which served as the foaming agent.
  • 100 ml of thi ⁇ innoculated medium was placed in the bottom of a 1 liter graduated cylinder and compressed air was sparged into the liquid at the bottom of the cylinder. The numerous small air bubbles caused a dense foam to form. The foam kept its shape and the bubbles did not break.

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  • Health & Medical Sciences (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Epidemiology (AREA)
  • Animal Behavior & Ethology (AREA)
  • Vascular Medicine (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Surgery (AREA)
  • Zoology (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Wood Science & Technology (AREA)
  • Textile Engineering (AREA)
  • Genetics & Genomics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Biotechnology (AREA)
  • Biochemistry (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • General Engineering & Computer Science (AREA)
  • Microbiology (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
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Abstract

On a mis au point un procédé de traitement d'une variété d'objets utilisant de la cellulose microbienne produite in situ ou appliquée sous forme de film, ainsi qu'un procédé de fabrication de papier monnaie à partir de cellulose microbienne.
PCT/US1989/002356 1988-05-28 1989-05-30 Composites de cellulose microbienne et leurs procedes de production WO1989011783A2 (fr)

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US19990688A 1988-05-28 1988-05-28
US199,906 1988-05-28

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WO1989011783A2 true WO1989011783A2 (fr) 1989-12-14
WO1989011783A3 WO1989011783A3 (fr) 1990-02-08

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5079162A (en) * 1986-08-28 1992-01-07 Weyerhaeuser Company Reticulated cellulose and methods and microorganisms for the production thereof
US5144021A (en) * 1985-10-18 1992-09-01 Weyerhaeuser Company Reticulated cellulose and methods and microorganisms for the production thereof
US5207826A (en) * 1990-04-20 1993-05-04 Weyerhaeuser Company Bacterial cellulose binding agent
US5228900A (en) * 1990-04-20 1993-07-20 Weyerhaeuser Company Agglomeration of particulate materials with reticulated cellulose
EP0614773A1 (fr) * 1991-11-06 1994-09-14 The Goodyear Tire & Rubber Company Renforcement à base de cellulose bactérienne réticulée pour élastomères
US5362713A (en) * 1989-12-13 1994-11-08 Weyerhaeuser Company Drilling mud compositions
US5580348A (en) * 1994-05-10 1996-12-03 Kimberly-Clark Corporation Absorbent structure comprising a microbial polysaccharide and a process of making the same
US5821109A (en) * 1985-10-18 1998-10-13 Monsanto Life Sciences Co. Reticulated cellulose and methods and microorganisms for the production thereof
US5871978A (en) * 1985-10-18 1999-02-16 Monsanto Life Sciences Co Method of producing reticulated cellulose having type II crystalline cellulose
US7832857B2 (en) 2008-08-18 2010-11-16 Levinson Dennis J Microbial cellulose contact lens
CN106191165A (zh) * 2016-08-05 2016-12-07 山东纳美德生物科技有限公司 一种细菌纤维素泡沫发酵方法
CN106190819A (zh) * 2016-08-05 2016-12-07 山东纳美德生物科技有限公司 一种细菌纤维素产品泡沫发酵设备及方法

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US4378431A (en) * 1980-09-02 1983-03-29 The University Of N.C. At Chapel Hill Production of a cellulose-synthetic polymer composite fiber
US4788146A (en) * 1982-12-16 1988-11-29 Johnson & Johnson Patient Care, Inc. Liquid loaded pad for medical applications

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US4378431A (en) * 1980-09-02 1983-03-29 The University Of N.C. At Chapel Hill Production of a cellulose-synthetic polymer composite fiber
US4788146A (en) * 1982-12-16 1988-11-29 Johnson & Johnson Patient Care, Inc. Liquid loaded pad for medical applications

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Title
JOURNAL OF CELL BIOLOGY, Vol. 94, 1982, pages 64-69, The Rockefeller University Press, HAIGLER et al.: "Alteration of In Vivo Cellulose Ribbon Assembly by Carboxymethyl-cellulose and Other Derivatives". See entire document. *
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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5821109A (en) * 1985-10-18 1998-10-13 Monsanto Life Sciences Co. Reticulated cellulose and methods and microorganisms for the production thereof
US5144021A (en) * 1985-10-18 1992-09-01 Weyerhaeuser Company Reticulated cellulose and methods and microorganisms for the production thereof
US6429002B1 (en) 1985-10-18 2002-08-06 Cp Kelco U.S., Inc. Reticulated cellulose producing acetobacter strains
US6329192B1 (en) 1985-10-18 2001-12-11 Cp Kelco U.S., Inc. Reticulated cellulose and methods of microorganisms for the production thereof
US5871978A (en) * 1985-10-18 1999-02-16 Monsanto Life Sciences Co Method of producing reticulated cellulose having type II crystalline cellulose
US5079162A (en) * 1986-08-28 1992-01-07 Weyerhaeuser Company Reticulated cellulose and methods and microorganisms for the production thereof
US5362713A (en) * 1989-12-13 1994-11-08 Weyerhaeuser Company Drilling mud compositions
US5228900A (en) * 1990-04-20 1993-07-20 Weyerhaeuser Company Agglomeration of particulate materials with reticulated cellulose
US5207826A (en) * 1990-04-20 1993-05-04 Weyerhaeuser Company Bacterial cellulose binding agent
EP0614773A1 (fr) * 1991-11-06 1994-09-14 The Goodyear Tire & Rubber Company Renforcement à base de cellulose bactérienne réticulée pour élastomères
US5772646A (en) * 1994-05-10 1998-06-30 Kimberly-Clark Worldwide, Inc. Absorbent structure comprising a microbial polysaccharide and a process of making the same
US5580348A (en) * 1994-05-10 1996-12-03 Kimberly-Clark Corporation Absorbent structure comprising a microbial polysaccharide and a process of making the same
US7832857B2 (en) 2008-08-18 2010-11-16 Levinson Dennis J Microbial cellulose contact lens
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