WO2016113933A1 - Nanostructure de cellulose et son procédé de production - Google Patents

Nanostructure de cellulose et son procédé de production Download PDF

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WO2016113933A1
WO2016113933A1 PCT/JP2015/071047 JP2015071047W WO2016113933A1 WO 2016113933 A1 WO2016113933 A1 WO 2016113933A1 JP 2015071047 W JP2015071047 W JP 2015071047W WO 2016113933 A1 WO2016113933 A1 WO 2016113933A1
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cellulose
solvent
glucopyranoside
nanostructure
sponge
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PCT/JP2015/071047
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Japanese (ja)
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芹澤　武
敏樹 澤田
佑輔 家高
秀一 三橋
西澤　剛
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Ｊｘ日鉱日石エネルギー株式会社
国立大学法人東京工業大学
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Priority to JP2016569217A priority Critical patent/JP6604581B2/ja
Publication of WO2016113933A1 publication Critical patent/WO2016113933A1/fr

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B11/00—Preparation of cellulose ethers
    • C08B11/02—Alkyl or cycloalkyl ethers
    • 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

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  • the present invention relates to, for example, an artificially synthesized cellulose nanostructure and a method for producing the same.
  • Cellulose is the most abundant organic polymer on earth. Cellulose is a material material attracting attention because of its high sustainability in addition to its resource. Cellulose obtained from natural products by mechanical treatment or chemical treatment is known to be in a fibrous form, and its use according to its structure and physical properties is being developed. In addition, cellulose nanocrystals (CNC) obtained by acid treatment of natural resources are expected to be used as new cellulose materials. CNC has an I-type crystal structure in which cellulose chains are arranged in parallel, and has attracted attention as a filler for composite materials because of its high aspect ratio, excellent mechanical strength, thermal stability, and the like.
  • crystalline cellulose can also be synthesized artificially (since cellulose obtained by artificial synthesis is generally an oligomer, such cellulose is called cellodextrin. All called cellulose).
  • the following reaction shows the enzymatic synthesis of cellulose using the reverse reaction of cellodextrin phosphorylase (CDP).
  • CDP cellodextrin phosphorylase
  • a cellulose crystal cellulose nanosheet having a nanosheet structure having a length of several ⁇ m, a width of several hundreds of nm, and a thickness of 4.5 nm is obtained by enzymatic synthesis utilizing a reverse reaction of CDP which is a phosphorolytic enzyme.
  • CNS Non-patent Document 1
  • ⁇ -glucose 1-phosphate ( ⁇ G1P) is sequentially polymerized as a monomer with respect to glucose serving as a primer.
  • glucose used for cellulose synthesis is difficult to recognize, but as a result, the polymerization reaction proceeds successfully.
  • CNS has a more stable antiparallel chain type II crystal structure, unlike naturally occurring type I crystals. Therefore, the cellulose chains are arranged in antiparallel to the thickness direction in the CNS, and as a result, the reducing end and non-reducing end of cellulose are regularly exposed on the sheet surface.
  • CNS is stably dispersed in pure water, but has a property of dissolving in an aqueous NaOH solution.
  • a desired functional group can be introduced on the surface of a conventionally synthesized cellulose nanosheet (CNS), it can be widely used as a scaffold material, template, or filler by further chemical modification. Is done.
  • studies on organic nanosheets have few examples compared to inorganic layered compounds such as clay, and the introduction of functional groups has not been studied in CNS either.
  • CDP cellodextrin phosphorylase
  • the present invention uses a glucose derivative having various substituents in the synthesis of cellulose using cellodextrin phosphorylase (CDP) to synthesize a cellulose structure having novel characteristics.
  • CDP cellodextrin phosphorylase
  • cellulose nanostructures having novel characteristics can be obtained by using glucose derivatives having various substituents as primers in the synthesis of cellulose using cellodextrin phosphorylase (CDP).
  • the present inventors have found that the body can be synthesized and have completed the present invention. That is, the present invention includes the following.
  • a cellulose nanostructure containing a compound represented by the formula: (2) A is O-R 1 (R 1 C 2-5 -straight chain alkyl group or branched alkyl group having C 2-5 as a main chain), and the cellulose nanostructure is a solvent
  • the cellulose nanostructure according to (1) which is a three-dimensional structure containing (3)
  • the cellulose nanostructure according to (2), wherein the three-dimensional structure containing the solvent has a three-dimensional network structure containing the solvent.
  • the cellulose nanostructure according to (3), wherein the three-dimensional network structure containing a solvent is a sponge-like structure containing a solvent.
  • a scaffold comprising the cellulose nanostructure according to any one of (1) to (4).
  • a film comprising the cellulose nanostructure according to any one of (1) to (4).
  • a separator comprising the cellulose nanostructure according to any one of (1) to (4) or the film according to (6).
  • This specification includes the disclosure content of Japanese Patent Application Nos. 2015-006062 and 2015-039443 which are the basis of the priority of the present application.
  • FIG. 1 is a photograph of a sample tube overturn test in cellulose synthesis method 1 of Example 1.
  • H (Glc) is a cellulose structure synthesized using D-glucose as a primer.
  • Methodyl is a cellulose structure synthesized using methyl- ⁇ -D-glucopyranoside as a primer.
  • Etyl is a sponge-like cellulose structure synthesized using ethyl- ⁇ -D-glucopyranoside as a primer.
  • butyl is a sponge-like cellulose structure synthesized using butyl- ⁇ -D-glucopyranoside as a primer.
  • FIG. 2 is a scanning electron micrograph of the sponge-like cellulose structure prepared by the cellulose synthesis method 1 of Example 1.
  • “Ethyl” is a sponge-like cellulose structure synthesized using ethyl- ⁇ -D-glucopyranoside as a primer.
  • “Butyl” is a sponge-like cellulose structure synthesized using butyl- ⁇ -D-glucopyranoside as a primer.
  • FIG. 3A shows the infrared absorption spectrum of the sponge-like cellulose structure prepared by the cellulose synthesis method 1 of Example 1 (ATR-IR method, resolution: 2 cm ⁇ 1 , total of 100 times).
  • “Ethyl” is a sponge-like cellulose structure synthesized using ethyl- ⁇ -D-glucopyranoside as a primer.
  • FIG. 3B shows the infrared absorption spectrum of the sponge-like cellulose structure prepared by the cellulose synthesis method 1 of Example 1 (ATR-IR method, resolution: 2 cm ⁇ 1 , total of 100 times).
  • “Pentyl” is a sponge-like cellulose structure synthesized using pentyl- ⁇ -D-glucopyranoside as a primer.
  • FIG. 3C shows an infrared absorption spectrum of the sponge-like cellulose structure prepared by the cellulose synthesis method 1 of Example 1 (ATR-IR method, resolution: 2 cm ⁇ 1 , total of 100 times).
  • T-Butylated is a sponge-like cellulose structure synthesized using tert-butyl- ⁇ -D-glucopyranoside as a primer.
  • FIG. 4A shows a nuclear magnetic resonance spectrum of a sponge-like cellulose structure synthesized using ethyl- ⁇ -D-glucopyranoside as a primer in the cellulose synthesis method 1 of Example 1 (3 in 4% NaOD / D 2 O). % (W / v), 300 MHz, 500 ⁇ L, integrated 32 times).
  • FIG. 4A shows a nuclear magnetic resonance spectrum of a sponge-like cellulose structure synthesized using ethyl- ⁇ -D-glucopyranoside as a primer in the cellulose synthesis method 1 of Example 1 (3 in 4% NaOD / D 2 O). % (W / v), 300 MHz, 500 ⁇ L, integrated 32 times).
  • FIG. 4B shows a nuclear magnetic resonance spectrum of a sponge-like cellulose structure synthesized using butyl- ⁇ -D-glucopyranoside as a primer in the cellulose synthesis method 1 of Example 1 (4 in 4% NaOD / D 2 O). .6% (w / v), 300 MHz, 500 ⁇ L, total 32 times).
  • FIG. 4C shows a nuclear magnetic resonance spectrum of a cellulose structure synthesized using octyl- ⁇ -D-glucopyranoside as a primer in the cellulose synthesis method 1 of Example 1 (3% in 4% NaOD / D 2 O ( w / v), 300 MHz, 500 ⁇ L, integrated 32 times).
  • FIG. 4B shows a nuclear magnetic resonance spectrum of a sponge-like cellulose structure synthesized using butyl- ⁇ -D-glucopyranoside as a primer in the cellulose synthesis method 1 of Example 1 (4 in 4% NaOD / D 2 O). .6% (w / v), 300 MHz,
  • FIG. 5 shows a spongy sample prepared by the cellulose synthesis method 1 of Example 1 ((A) a sponge-like cellulose structure synthesized using ethyl- ⁇ -D-glucopyranoside as a primer; (B) butyl as a primer. (Sponge-like cellulose structure synthesized using - ⁇ -D-glucopyranoside) shows a photograph when the test bar is pushed in until the sponge breaks.
  • FIG. 6 is a photograph showing the enzymatic degradation by cellulase of a sponge-like cellulose structure synthesized using ethyl- ⁇ -D-glucopyranoside as a primer in the cellulose synthesis method 1 of Example 1.
  • FIG. 1 shows a spongy sample prepared by the cellulose synthesis method 1 of Example 1 ((A) a sponge-like cellulose structure synthesized using ethyl- ⁇ -D-glucopyranoside as a primer; (B) butyl as a primer. (Sponge-
  • FIG. 7 is a transmission electron micrograph of a reactive cellulose nanosheet synthesized in Example 2 using 1-azido-1-deoxy- ⁇ -D-glucopyranoside as a primer.
  • FIG. 8 shows a reactive cellulose nanosheet synthesized using 1-azido-1-deoxy- ⁇ -D-glucopyranoside (Azide) as a primer in Example 2, or a cellulose nanosheet synthesized using D-glucose (Glc). The infrared absorption spectrum of is shown. The portion surrounded by a square shows a peak characteristic of type II cellulose.
  • FIG. 8 shows a reactive cellulose nanosheet synthesized using 1-azido-1-deoxy- ⁇ -D-glucopyranoside (Azide) as a primer in Example 2, or a cellulose nanosheet synthesized using D-glucose (Glc). The infrared absorption spectrum of is shown. The portion surrounded by a square shows a peak characteristic of type II cellulose.
  • FIG. 9 shows a nuclear magnetic resonance spectrum of a reactive cellulose nanosheet synthesized in Example 2 using 1-azido-1-deoxy- ⁇ -D-glucopyranoside as a primer.
  • FIG. 10 shows an ultraviolet-visible absorption spectrum in each solvent of cellulose nanosheets into which pyrene was introduced in Example 2 ([cellulose] 0.0034% (w / v)).
  • FIG. 11 shows the fluorescence spectrum in each solvent of the cellulose nanosheet into which pyrene was introduced in Example 2. A portion surrounded by a square indicates an excimer emission region.
  • FIG. 10 shows an ultraviolet-visible absorption spectrum in each solvent of cellulose nanosheets into which pyrene was introduced in Example 2 ([cellulose] 0.0034% (w / v)).
  • FIG. 11 shows the fluorescence spectrum in each solvent of the cellulose nanosheet into which pyrene was introduced in Example 2. A portion surrounded by a square indicates an excimer emission region.
  • FIG. 10 shows an ultraviolet-visible absorption spectrum
  • FIG. 12 is a photograph showing the solvatochromic properties of the cellulose nanosheet dispersion with pyrene introduced in Example 2 ([cellulose] 0.0034% (w / v), ⁇ ex 365 nm).
  • FIG. 13 shows the circular dichroism absorption spectrum characteristics of the cellulose nanosheet dispersion into which pyrene is introduced in Example 2 ([cellulose] 0.034% (w / v), total of 4 times, optical path length 2 mm, 800 ⁇ L). ).
  • the cellulose nanostructure according to the present invention has the following formula (I): [Where: A is a substituent other than hydrogen and a hydroxyl group; n is 4 to 10]
  • the compound (cellulose derivative) shown by these is contained as a structural component.
  • the cellulose nanostructure according to the present invention has a more stable antiparallel chain type II cellulose structure.
  • the degree of polymerization of the compound of the formula (I) is, for example, 6 or more, 7 or more, preferably 8 or more (that is, n is 4 or more, 5 or more, preferably 6 or more in the compound of the formula (I)), and 12 or less, preferably 11 or less (that is, in the compound of formula (I), n is 10 or less, preferably 9 or less).
  • the cellulose nanostructure according to the present invention C 2-5 at cellulose derivative components - by the presence of branched alkyl groups of straight-chain alkyl group or a C 2-5 main chain, including solvent
  • a three-dimensional structure more specifically, a three-dimensional structure having a three-dimensional network structure containing a solvent such as a sponge-like structure containing a solvent.
  • the voids in the network structure are connected to the outer surface (thus, the solvent (moisture) goes out).
  • the three-dimensional structure has a structure in which the solvent (moisture) comes out on the outer surface while being collapsed (applying pressure), accompanied by the collapse of the structure corresponding to the pressure.
  • the C 2-5 -linear alkyl group of the substituent R 1 is an ethyl group, a propyl group, a butyl group, or a pentyl group.
  • the branched alkyl group having C 2-5 as the main chain of the substituent R 1 is a branched alkyl group having 2 to 5 carbon atoms as the main chain, the number or length of branching is particularly For example, isopropyl group, s-butyl group, t-butyl group, isobutyl group, pentan-2-yl group, pentan-3-yl group, isopentyl group, 3-methylbutan-2-yl group, t-pentyl Group, 2-methylbutyl group and the like.
  • the cellulose nanostructure according to the present invention contains a compound of the formula (I) in which the substituent A is an azide group as a constituent component.
  • the cellulose nanostructure according to the present invention has a sheet-like structure (“cellulose nanosheet”).
  • the cellulose chains are arranged antiparallel to the thickness direction, and the reducing end of the cellulose (that is, the substituent A in the compound of the formula (I)) is regularly exposed on the sheet surface. is doing.
  • the functionalization of the sheet can be achieved by using the introduced substituent A (functional group) and chemically modifying the functional molecule on the sheet surface. 3.
  • the cellulose nanostructure according to the present invention described above can be produced according to the reaction shown below. Specifically, ⁇ -glucose 1-phosphate ( ⁇ G1P) and a primer represented by the following formula (II) by enzymatic synthesis utilizing the reverse reaction of cellodextrin phosphorylase (CDP):
  • ⁇ G1P ⁇ -glucose 1-phosphate
  • CDP cellodextrin phosphorylase
  • the cellulose nanostructure which concerns on this invention can be manufactured by making the glucose derivative shown by react with CDP.
  • ⁇ G1P is sequentially polymerized as a monomer.
  • ⁇ G1P and the glucose derivative of formula (II) may be commercially available.
  • glucose derivative of the formula (II) having a specific substituent A is, for example, Z. Shi et al. Agric. Food Chem. , 2014, 62, 3287-3292, and the like.
  • CDP is, for example, M.P. Krishnareddy et al. Appl. Glycosci. , 2002, 49, 1-8.
  • M.M. Krishnareddy et al. Appl. Glycosci. 2002, 49, 1-8 CDP derived from Clostridium thermocellum YM4 can be prepared.
  • the enzyme amount of CDP is determined by, for example, incubating ⁇ -D-glucose 1-phosphate, D-(+)-cellobiose and CDP, quantifying the phosphate produced by CDP, and 1 ⁇ mol of phosphate per minute.
  • the amount of enzyme that liberates can be determined as 1 U.
  • 10-1000 mM preferably 100-300 mM
  • 10-200 mM preferably 10-100 mM, particularly preferably 50-60 mM
  • glucose derivative of formula (II) and 0.01-1.5 U / ML (preferably 0.05 to 0.5 U / mL) of CDP
  • 100 to 1000 mM preferably 250 to 750 mM
  • 4- (2-hydroxyethyl) -1-piperazineethanesulfonic acid (HEPES) buffer solution PH 7.0 to 8.0 (preferably pH 7.5)
  • PES 4- (2-hydroxyethyl) -1-piperazineethanesulfonic acid
  • the cellulose nanostructure according to the present invention can be produced. 4). 4. Use of cellulose nanostructure according to the present invention 4-1. Medical field 4-1-1. Cell culture scaffold
  • the cellulose nanostructure according to the present invention can be used as a scaffold for growing animal cells on its surface, for example.
  • the cells to be grown may be derived from animals, and examples include cells derived from mammals, reptiles, or insects. Further, primary cultured cells isolated from organs and tissues such as heart, liver, spleen and epidermis, subcultured established cells and tumor cells may be used. Furthermore, somatic stem cells such as mesenchymal stem cells (MSC), induced pluripotent stem cells, CHO cells, BHK cells, cell lines such as Vero cells, and the like may be used.
  • MSC mesenchymal stem cells
  • induced pluripotent stem cells CHO cells
  • BHK cells cell lines such as Vero cells, and the like
  • Examples of the medium used for cell culture include a basal medium in which low molecular weight compounds such as amino acids and vitamins are added to a balanced salt solution.
  • the cellulose nanostructure can be formed into a thin film, and cells can be cultured on the surface of the thin film. The culture efficiency can be increased by supplying the nutrient components also from the bottom surface of the thin film. Cells grown in a monolayer on the cellulose nanostructure can be detached and recovered with a cell release agent.
  • a chelating agent for removing divalent cations such as ethylenediaminetetraacetic acid (EDTA), a protease such as trypsin for cell-matrix, cell-cell adhesion protein, or cellulase can be used.
  • the cell can also be detached by decomposing and solubilizing part or all of the cellulose nanostructure. In the latter method using no protease, the cell-cell adhesion does not peel off and does not affect the cells, so that a highly active suspension cell or cell sheet can be obtained.
  • the obtained cell sheet was laminated with the obtained cell sheet in the same manner, or the surface of the cell sheet was coated with an intercellular adhesion protein or the like, and further cultured, the cells were three-dimensionally thick.
  • a cell mass can be obtained.
  • the cellulose nanostructure according to the present invention can be used as a scaffold for growing animal cells therein.
  • the cellulose nanostructure can be formed into a structure having voids of a size that allows cells to enter or larger, and the cells can be cultured in the structure.
  • the cells to be grown may be any cells as long as they are derived from animals, as described in Section 4-1-1 above.
  • the medium used for the culture may be a basal medium, a serum-added medium, or a medium to which other components are added, as described in Section 4-1-1 above.
  • the medium used for the culture may be a basal medium, a serum-added medium, or a medium to which other components are added, as described in Section 4-1-1 above.
  • a new medium is added and cultured again, or a medium containing the target product is continuously collected and a new medium is additionally added.
  • cells that have been cultured at a high concentration can be recovered by subjecting the cellulose nanostructure used as a scaffold to cellulase treatment to release the cells without causing damage to the cells as occurs during protease treatment.
  • Totipotent stem cells such as iPS cells and ES cells can be cultured in a large amount by this technique, and cells necessary for regenerative medicine and drug discovery industry can be supplied.
  • 4-1-3 Three-dimensional structure scaffold
  • the cellulose nanostructure according to the present invention can be used as a scaffold for growing animal cells therein.
  • the cellulose nanostructure can be formed into a structure having voids of a size that allows cells to enter or larger, and the cells can be cultured in the structure.
  • the cells to be grown may be any cells as long as they are derived from animals, as described in Section 4-1-1 above.
  • the medium used for the culture may be a basal medium, a serum-added medium, or a medium supplemented with other components, as described in Section 4-1-1 above.
  • the cellulose nanostructure can be formed into a shape suitable for a target tissue before, during or after cell culture and used for regeneration of a living tissue or organ.
  • the cellulose nanostructure can be reacted in a mold having a desired shape during the polymerization reaction, or can be formed into a desired shape by cutting, laminating, weaving, or the like after molding.
  • the cellulose nanostructure can be decomposed and solubilized by cellulase treatment without affecting cells. Prior to transplantation into the organ, it may be subjected to cellulase treatment, and part or all may be decomposed and solubilized, or may be transplanted together with the scaffold without being subjected to cellulase treatment.
  • the three-dimensional structure in which the cells are grown is used for basic medical research such as elucidation of the mechanism of cancer metastasis, evaluation of the efficacy of anticancer drugs, etc., assuming that the shape and function of the tissue or organ are reproduced ex vivo.
  • it can be used as a material for studying the effects of cosmetics, which have been prohibited from animal tests in recent years, on living tissues such as skin.
  • Transplant Material to Bone Defect Site The cellulose nanostructure according to the present invention can also be used as a transplant material to an animal bone defect site and a regeneration induction material for periodontal tissue.
  • the cellulose nanostructure can be easily molded into a desired shape and can be sterilized by high-pressure steam.
  • the cellulose nanostructure may be engrafted with cells before transplantation, or may be transplanted as it is.
  • the cellulose nanostructure according to the present invention includes a film (for example, a microporous film (application example: separator, adsorbent, biosensor, etc.), a dense film (application example). : Barrier film etc.)) and can be used in the environment / energy field.
  • a film for example, a microporous film (application example: separator, adsorbent, biosensor, etc.), a dense film (application example). : Barrier film etc.)
  • the cellulose nanostructure according to the present invention can also be used as a separator for a secondary battery such as a lithium ion battery. By using it as a separator, it has higher heat resistance than conventional polyolefin separators.
  • the cellulose nanostructure according to the present invention disperses and carries adsorbent fine particles such as silica, alumina, zeolite, Prussian blue, etc. It is possible to adsorb and collect valuable metals. In addition, since the cellulose nanostructure can be easily decomposed using a degrading enzyme, the cellulose nanostructure can also be easily condensed as necessary. 4-2-3. Biosensor The cellulose nanostructure according to the present invention can be used as a biosensor by supporting an enzyme or an antibody.
  • an enzyme such as glucose oxidase
  • it can be used as a glucose sensor.
  • Gas barrier sheet (including structure)
  • a gas barrier sheet that blocks gas such as water vapor
  • the inorganic nanomaterial include nanoparticles such as silica or clay such as montmorillonite. 4-2-5.
  • Heat-dissipating sheet The cellulose nanostructure according to the present invention can be used as a heat-dissipating material by densely supporting a material having high thermal conductivity.
  • the material having high thermal conductivity examples include carbon-based materials such as diamond, graphene, and carbon nanotubes, metal materials such as silver, copper, gold, and aluminum, and inorganic materials such as alumina, magnesia, and hexagonal boron nitride. 4-2-6.
  • Thermal Storage Sheet By dispersing and supporting a material having thermal storage properties on the cellulose nanostructure according to the present invention, it can be used as a thermal storage material.
  • the heat storage material include latent heat storage materials such as erythritol, sodium acetate trihydrate, sodium sulfate decahydrate, paraffin, and Fe-Co alloy, and other sensible heat storage materials and chemical heat storage materials.
  • the latent heat storage material uses the phase transition of the substance, and in the case of the heat storage material using the solid-liquid phase transition, it is necessary to devise so that no leakage occurs when it becomes liquid, such as petroleum resin There is a method of inclusion in the capsule. 4-2-7.
  • Separation and purification substrate column packing, electrophoresis
  • the cellulose three-dimensional structure according to the present invention has a nano-sized space, it can be used as a separation / purification column or a packing for electrophoresis using the space.
  • Pentyl- ⁇ -D-glucopyranoside was purchased from Carbosynch Limited. Tert-butyl- ⁇ -D-glucopyranoside was purchased from Carbosynch Limited. Cellodextrin phosphorylase has been described by M.M. Krishnareddy et al. Appl. Glycosci. , 2002, 49, 1-8. 4- (2-hydroxyethyl) -1-piperazineethanesulfonic acid and 3-morpholinopropanesulfonic acid were purchased from Nacalai Tesque. As the ultrapure water, water purified by a MilliQ system (MilliQ Advantage A-10, Millipore) was used.
  • Cellulase was purchased from Sigma-Aldrich from Trichoderma violet. 1-2. Measurement of enzyme activity The activity of cellodextrin phosphorylase was measured as follows. A 50 mM 3-morpholinopropanesulfonic acid buffer (pH 7.5) containing 10 mM ⁇ -D-glucose 1-phosphate, 10 mM D-(+)-cellobiose, and cellodextrin phosphorylase diluted to a predetermined ratio is added to 37 Incubated at 0 ° C.
  • Phosphoric acid produced by cellodextrin phosphorylase was quantified, and U / mL when the amount of enzyme that liberates 1 ⁇ mol of phosphoric acid per minute was defined as 1 U was determined as enzyme activity.
  • the dilution rate of cellodextrin phosphorylase was determined so that the conversion rate of ⁇ -D-glucose 1-phosphate was 10% or less when the reaction time was 100 minutes. 1-3.
  • Cellulose synthesis method 1 Primer alkyl chain length Monomer ⁇ -D-glucose 1-phosphate is 200 mM, Primer methyl- ⁇ -D-glucopyranoside or ethyl- ⁇ -D-glucopyranoside or butyl- ⁇ -D -Glucopyranoside or pentyl- ⁇ -D-glucopyranoside or hexyl- ⁇ -D-glucopyranoside or octyl- ⁇ -D-glucopyranoside or tert-butyl- ⁇ -D-glucopyranoside at 50 mM or 200 mM, cellodextrin phosphorylase at 0.2 U / mL These were mixed in 500 mM 4- (2-hydroxyethyl) -1-piperazineethanesulfonic acid buffer (pH 7.5) and reacted at 60 ° C.
  • the produced sponge-like cellulose structure was immersed in ultrapure water for 1 week and purified.
  • 1-4. Cellulose Evaluation Method The presence or absence of sponge formation was evaluated by a sample tube overturning test (determined that the sample tube did not flow when the sample tube was placed upside down and was spongy). The yield of the sponge-like cellulose structure was evaluated by weighing the weight after absolute drying or freeze-drying. The structure of the sponge-like cellulose structure was determined by freeze-drying the sponge-like cellulose structure and then using a scanning electron microscope (JSM-7500F, JEOL) and a total reflection infrared spectrophotometer (FT / IR-4100, JASCO). evaluated.
  • JSM-7500F scanning electron microscope
  • JEOL total reflection infrared spectrophotometer
  • the structure and degree of polymerization of cellulose were evaluated by a nuclear magnetic resonance spectrometer (DPX-300, Bruker or JNM-400, JOEL RESONANCE) using a deuterated 4% sodium hydroxide / heavy aqueous solution.
  • a sponge having a diameter of 3 mm was pushed into the sponge-like cellulose at a speed of 1 mm / min by a universal small tester (AGS-X, Shimadzu Corp.) to break the sponge. At this time, the state of cellulose was evaluated from the state after the fracture. 1-5.
  • FIG. 1 shows a photograph of a sample tube tipping test.
  • FIG. 2 shows the result of observation of the spongy sample with a scanning electron microscope. A network-like structure (network) characteristic of the sponge-like cellulose structure was observed.
  • 3A to 3C show the results of analysis of the spongy sample by a total reflection infrared spectrophotometer. Peak derived from a type II cellulose is observed around 3488cm -1 and 3445cm -1, it was found to be sponge-like cellulosic structure including type II cellulose.
  • FIG. 5 shows a photograph when the test rod is pushed into the spongy sample until the sponge breaks. By squeezing the test rod into the sample, the squeezed water was observed, confirming that the sample was sponge-like.
  • FIG. 6 shows a photograph showing cellulase enzymatic degradation of a sponge-like cellulose structure (a sample stored in a refrigerator for 2.5 months) synthesized using ethyl- ⁇ -D-glucopyranoside as a primer. After the cellulase treatment for about 3 hours, most of the sponge-like cellulose structure disappeared by enzymatic degradation. Since the degree of polymerization of cellulose synthesized using ethyl- ⁇ -D-glucopyranoside is higher than that of cellulose synthesized from a primer having a longer alkyl group, butyl- ⁇ -D-glucopyranoside, pentyl- ⁇ -D-glucopyranoside, etc.
  • 1-azido-1-deoxy- ⁇ -D-glucopyranoside was purchased from Sigma-Aldrich.
  • 1-ethynylpyrene was purchased from Tokyo Kasei.
  • 2-Propanol was purchased from Kanto Chemical.
  • As the ultrapure water water purified by a MilliQ system (MilliQ ADVANTAGE A-10, Millipore) was used.
  • Cellodextrin phosphorylase has been described by M.M. Krishnareddy et al. Appl. Glycosci. , 2002, 49, 1-8. 1-2. Measurement of enzyme activity The activity of cellodextrin phosphorylase was measured as follows.
  • a 50 mM 3-morpholinopropanesulfonic acid buffer (pH 7.5) containing 10 mM ⁇ -D-glucose 1-phosphate, 10 mM D-(+)-cellobiose, and cellodextrin phosphorylase diluted to a predetermined ratio is added to 37 Incubated at 0 ° C.
  • Phosphoric acid produced by cellodextrin phosphorylase was quantified, and U / mL when the amount of enzyme that liberates 1 ⁇ mol of phosphoric acid per minute was defined as 1 U was determined as enzyme activity.
  • the dilution rate of cellodextrin phosphorylase was determined so that the conversion rate of ⁇ -D-glucose 1-phosphate was 10% or less when the reaction time was 100 minutes.
  • 1-3 Synthesis and Structural Analysis of Reactive Cellulose Nanosheet Monomer ⁇ -D-glucose 1-phosphate is 200 mM, primer 1-azido-1-deoxy- ⁇ -D-glucopyranoside is 50 mM, cellodextrin phosphorylase is 0.2 U These were mixed in 500 mM 4- (2-hydroxyethyl) -1-piperazineethanesulfonic acid buffer (pH 7.5) and reacted at 60 ° C. for 3 days.
  • the product was purified by repeating the procedure of removing the supernatant by centrifugation and redispersing with ultrapure water.
  • the structure of cellulose was evaluated by a transmission electron microscope (H-7650 Zero. A, Hitachi, Ltd.) and a total reflection infrared spectrophotometer (FT / IR-4100, JASCO).
  • the presence of cellulose was evaluated by a nuclear magnetic resonance spectrometer (DPX-300, Bruker; JSE-ECS 400, JEOL RESONANCE).
  • the average degree of polymerization of the cellulose was determined by a nuclear magnetic resonance spectrometer (DPX-300, Bruker; JSE-ECS 400, JEOL RESONANCE) or elemental analysis (CHN order MT-6, YANACO).
  • DPX-300 nuclear magnetic resonance spectrometer
  • JSE-ECS 400 JEOL RESONANCE
  • CHN order MT-6 YANACO
  • Introduction and functional evaluation of functional groups for reactive cellulose nanosheets 1-azido-1-deoxy- ⁇ -D-glucopyranoside synthesized as a primer is 0.5% (w / v), 1-ethynylpyrene These were mixed in N, N-dimethylformamide and bubbled with dry nitrogen for 30 minutes so that 5 mM of copper sulfide (II) was 0.5 mM.
  • II copper sulfide
  • Cellulose nanosheets with pyrene introduced are dispersed in various solvents (toluene, chloroform, 2-propanol, methanol, N, N-dimethylformamide, N, N-dimethylsulfoxide, ultrapure water), and the optical properties are UV-visible spectrophotometric. Meter (V-550, JASCO) and UV-visible near-infrared spectrophotometer (V670, JASCO) and fluorescence spectrophotometer (FP-6500, JASCO) and circular dichroism spectrophotometer (J-820, Evaluated by JASCO). 2. Result 2-1. Synthesis and Structural Analysis of Reactive Cellulose Nanosheet FIG. 7 shows a transmission electron microscope photograph.
  • FIG. 10 shows the results of measuring the absorption spectrum of cellulose nanosheets into which pyrene has been introduced, dispersed in various solvents so as to be 0.0034% (w / v). In all cases, a peak peculiar to pyrene was observed around the same wavelength (near 343 nm and 360 nm), indicating that pyrene was introduced.
  • FIG. 11 shows the result of measuring the fluorescence spectrum by dispersing cellulose nanosheets with pyrene introduced in various solvents so as to be 0.0034% (w / v).
  • FIG. 12 shows photographs in which cellulose nanosheets into which pyrene has been introduced are dispersed in various solvents at 0.0034% (w / v) and irradiated with ultraviolet rays (365 nm) in a dark place.
  • the solvatochromism characteristic that the color changes with the kind of solvent is shown.
  • FIG. 13 shows the results of measuring a circular dichroism absorption spectrum by dispersing cellulose nanosheets into which pyrene is introduced in each solvent so as to be 0.034% (w / v).
  • a negative cotton effect was observed in the absorption band derived from pyrene, and the introduced pyrene was asymmetrically induced. Further, as shown in the right panel of FIG. 13, the introduced pyrene is considered to be twisted and packed.
  • areas such as a scaffold, and environmental / energy fields, such as a separator for storage batteries, can be provided.
  • areas such as a scaffold
  • environmental / energy fields such as a separator for storage batteries

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Abstract

La présente invention concerne une structure de cellulose ayant de nouvelles propriétés. En particulier, la présente invention concerne la synthèse d'une nanostructure de cellulose ayant de nouvelles propriétés, à l'aide d'un dérivé de glucose ayant divers substituants, utilisé comme amorce dans une synthèse de cellulose qui utilise de la cellodextrine phosphorylase (CDP).
PCT/JP2015/071047 2015-01-15 2015-07-16 Nanostructure de cellulose et son procédé de production WO2016113933A1 (fr)

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WO2020085217A1 (fr) 2018-10-24 2020-04-30 国立大学法人東京工業大学 Véhicule pour une utilisation en immobilisation des enzymes, et enzyme immobilisée
CN114552124A (zh) * 2022-02-28 2022-05-27 华中科技大学 一种富含纳米孔的纤维素膜、制备方法和应用
EP4053141A4 (fr) * 2019-10-31 2023-11-08 DKS Co. Ltd. Additif de milieu pour culture en suspension, composition de milieu et procédé de culture

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JP2011177172A (ja) * 2010-03-03 2011-09-15 Samsung Electronics Co Ltd 高収率のセルロース産生活性がある新規なグルコンアセトバクター属菌株
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WO2019211971A1 (fr) * 2018-05-02 2019-11-07 第一工業製薬株式会社 Procédé de production de cello-oligosaccharides
JP2019193601A (ja) * 2018-05-02 2019-11-07 国立大学法人東京工業大学 セロオリゴ糖の製造方法
CN112074607A (zh) * 2018-05-02 2020-12-11 第一工业制药株式会社 纤维寡糖的制造方法
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WO2020085217A1 (fr) 2018-10-24 2020-04-30 国立大学法人東京工業大学 Véhicule pour une utilisation en immobilisation des enzymes, et enzyme immobilisée
KR20210082158A (ko) 2018-10-24 2021-07-02 고쿠리츠다이가쿠호진 토쿄고교 다이가꾸 효소 고정화용 담체 및 고정화 효소
EP4053141A4 (fr) * 2019-10-31 2023-11-08 DKS Co. Ltd. Additif de milieu pour culture en suspension, composition de milieu et procédé de culture
CN114552124A (zh) * 2022-02-28 2022-05-27 华中科技大学 一种富含纳米孔的纤维素膜、制备方法和应用

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