EP1098911A1 - Extraction de matiere hemicellulosique - Google Patents

Extraction de matiere hemicellulosique

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Publication number
EP1098911A1
EP1098911A1 EP99933962A EP99933962A EP1098911A1 EP 1098911 A1 EP1098911 A1 EP 1098911A1 EP 99933962 A EP99933962 A EP 99933962A EP 99933962 A EP99933962 A EP 99933962A EP 1098911 A1 EP1098911 A1 EP 1098911A1
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EP
European Patent Office
Prior art keywords
hemicellulose
alkaline
extraction
gel
extracted
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP99933962A
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German (de)
English (en)
Inventor
Stephen Jonathan Rawling
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Cambridge Biopolymers Ltd
Original Assignee
EI Du Pont de Nemours and Co
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Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP1098911A1 publication Critical patent/EP1098911A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
    • C08B37/0018—Pullulan, i.e. (alpha-1,4)(alpha-1,6)-D-glucan; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0045—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Galacturonans, e.g. methyl ester of (alpha-1,4)-linked D-galacturonic acid units, i.e. pectin, or hydrolysis product of methyl ester of alpha-1,4-linked D-galacturonic acid units, i.e. pectinic acid; Derivatives thereof

Definitions

  • the present invention relates to processes for producing hemicellulose gels which have a wide variety of uses in industry, including the food and medical industries and in agriculture.
  • Plant tissue is made up of several different components, including cellulose, hemicellulose, ⁇ -glucan, starch, protein, phenolic acids, lignin, waxes, cutin and suberin.
  • the present invention is particularly concerned with the extraction and processing of hemicelluloses.
  • hemicellulose is a term of art used to embrace non-cellulosic, non-starch plant polysaccharides. The term therefore embraces inter alia pentosans, pectins and gums. Some hemicelluloses (including arabinoxylan and pectin) are suitable as substrates for oxidative gelation ("gelling hemicelluloses”): such hemicelluloses often have substituents with phenolic groups which are cross-linkable with certain oxidizing agents.
  • Arabinoxylan and pectin constitute two particularly important classes of hemicellulose.
  • Arabinoxylans consist predominantly of the pentoses arabinose and xylose, and are therefore often classified as pentosans. However, in many cases hexoses and hexuronic acid are present as minor constituents, and therefore they may also be referred to descriptively as heteroxylans.
  • the arabinoxylan molecule consists of a linear backbone of (l-4)- ⁇ -xylopyranosyl units, to which substituents are attached through C2 and C3 atoms of the xylosyl residues. The major substituents are single ⁇ -L-arabinofuranosyl residues.
  • Arabinoxylan preparations are usually heterogeneous with respect to the ratio of xylose to arabinose (i.e. the degree of substitution) and in the pattern of substitution of the arabinosyl units along the (l-4)- ⁇ -xylan backbone.
  • Phenolic acid (including ferulic acid) and acetyl substituents occur at intervals along the arabinoxylan chains. These substituents to some extent determine the solubility of the arabinoxylan.
  • Arabinoxylan preparations bearing phenolic (e.g. ferulic acid substituents) are referred to herein as "AXF", while those bearing acetyl substituents are designated “AXA”.
  • preparation bearing both phenolic (e.g. ferulic acid) and acetyl substituents are hereinafter abbreviated to the designation "AXF A”.
  • Arabinoxylan preparations having few phenolic e.g.
  • ferulic acid substituents are designated "AX”: when the degree of substitution falls below that required for oxidative gelation, the arabinoxylan is designated a “non-gelling arabinoxylan” (a term which therefore embraces AX and AXA).
  • Pectins constitute another important class of hemicelluloses. As used herein and unless otherwise indicated, the term “pectin” is used sensu lato to define hemicellulose polymers rich in D-galacturonic acid. Many (but not all) are cell wall components. The term “pectin” is also used herein sensu stricto to define the so-called “true pectins”, which are characterized by the presence of an O-( -D-galacturonopyranosyl)-(l-2)-L-rhamnopyranosyl linkage within the molecule. The pectins may be subcategorized on the basis of their structural complexity. At one extreme are “simple pectins", which are galacturonans.
  • complex pectins exemplified by rhamnogalacturonan II, which contains at least 10 different monosaccharide components in the main chain or as a components of branches.
  • Pectins of intermediate complexity (herein referred to as “mesocomplex pectins” contain alternate rhamnose and galacturonic acid units, while others have branches of glucoronic acid linked to galacturonic acid.
  • Complex and mesocomplex pectins are made up of "smooth" regions (based on linear homogalacturonan) and "hairy" regions corresponding to the rhamnogalacturonan backbone with side-branches of varying length.
  • pectins for example, pectins obtainable from representatives of the plant family Chenopodiaceae, which include beets (e.g. sugar beet), spinach and Hzurzels
  • beets e.g. sugar beet
  • substituents derived from carboxylic acids usually substituted cinnamic acids
  • Such pectins may be oxidatively cross-linked to produce viscous solutions or gels via their phenolic substituents. This can be achieved by powerful oxidants (e.g. persulfate - see J.-F.
  • FR 2 545 101 Al also describes the gelling of beet pectins using an oxidant (e.g. hydrogen peroxide) and an enzyme (peroxidase). Such pectins are referred to herein as "gelling pectins”.
  • Sugar beet pectin is especially rich in arabinan.
  • Arabinan contains ⁇ -l,5-linked arabinose in the backbone with ⁇ -(l->3) or ⁇ -(l->2)-linked arabinose residues
  • arabinogalactan contains ⁇ -1 ,4-linked galactose in the backbone, with ⁇ -(l ->3) or ⁇ -(l->2) linked arabinose residues.
  • Ferulyl substituents are linked to the arabinose and/or the galactose in the arabinan and arabinogalactan side-branches of the rhamnogalacturonan part.
  • the "ferulic acid” content varies according to the extraction method, but is often about 0.6%.
  • Aqueous extracts of several different types of hemicelluloses are known to form gels (or viscous liquids) when treated with certain oxidizing agents.
  • certain flour extracts e.g. wheat and rye flour extracts
  • certain oxidants e.g. upon the addition of hydrogen peroxide
  • oxidative gelation The phenomenon is known in the art as "oxidative gelation", and an extensive literature exists on the subject of oxidative gelation of wheat flour extracts.
  • oxidative gelation is used herein in a broad sense to include the case where viscous solutions are produced rather than true gels, and the term “gel” is therefore to be interpreted loosely to cover viscous liquids. This reflects the fact that oxidative gelation is a progressive phenomenon which may be controlled to vary the degree of gelation to the extent that hard, brittle gels are formed at one extreme and slurries or viscous liquids at the other.
  • the biochemical basis of the gelling process is not completely or consistently described in the prior art.
  • the gels arise as high molecular weight arabinoxylan and protein molecules become inter- and/or intra-linked (via inter alia phenolic substituents, for example ferulic acid-derived diferulate bridges): see e.g. Hoseney and Faubion (1981), Cereal Chem., 58:421.
  • gel formation and/or viscosity increases arise (at least in part) from cross-linking within and/or between macromolecular components of the hemicellulose mediated by ferulic acid residues (for example, involving diferulate generated by oxidative coupling of the aromatic nucleus of ferulic acid).
  • ferulic acid and “ferulate” are used sensu lato encompass ferulyl (often denoted feruloyl) groups (i.e. 4-hydroxy-3-methoxy-cinnamyl groups) and derivatives (particularly oxidized derivatives) thereof.
  • oxidizing agents Only a few oxidizing agents are known to have the ability to induce gelation, and these include hydrogen peroxide (usually in conjunction with a peroxidase), ammonium persulphate and formamidine disulphide.
  • WO 93/10158 describes the preparation of hemicellulosic material from various brans and the oxidative gelation of maize-derived hemicelluloses using an oxidizing system comprising a peroxide (such as hydrogen peroxide) and an oxygenase (such as a peroxidase).
  • a peroxide such as hydrogen peroxide
  • an oxygenase such as a peroxidase
  • the hemicellulosic material for use as a gelling agent is prepared by hot water or mild alkali extraction. Extraction of hemicelluloses
  • gelling hemicelluloses such as arabinoxylan ferulate have been isolated from plants or hemicellulosic starting material by extracting into water or alkaline solutions. Extensive hydrolysis (by e.g. harsh alkaline treatments) is known to strip the ferulic acid residues from the bulk pentosans, and so hemicelluloses for use as starting materials in the production of gels or viscous solutions are usually extracted by water (particularly hot water) or mild alkali extraction.
  • substantially colourless hemicellulose products can be extracted from plant sources using alkaline peroxide extraction (Gould (1984), Biotechnol. Bioeng. 26:46-52; Gould (1985) Biotechnol. Bioeng. 27:893-896; Gould (1985) Biotechnol. Bioeng. 27:225-231; U.S. 4,806,475; Doner and Hicks (1997), Cereal Chem. 74(2):176-181).
  • the present inventors have also found that several important advantages are attendant on the use of alkaline hydrogen extraction, including the bleached/light colour of the end product, high yield and the fact that the entire process can be (but is not necessarily) run at cold temperatures, facilitating enzymic co-processing.
  • the oxidising species which may be used in the method of the invention include the hydrogen peroxide anion, the hydrogen peroxide radical, the hydroxyl radical, the superoxide radical and the oxide radical. Any suitable source of these radicals may therefore be used, including hydrogen peroxide, sodium peroxide, ozone and oxygen.
  • Other oxidising species that have been found useful include the chloronium ion and protonated hypochlorous acid. These latter species may be generated under alkaline conditions by sodium hyperchlorite, chlorine or chlorine dioxide.
  • a process for producing a hemicellulose gel comprising the steps of providing a hemicellulosic material; subjecting the hemicellulosic material to alkaline oxidant extraction; isolating the extracted hemicellulose and oxidatively gelling the isolated hemicellulose to produce a cross-linked hemicellulose gel.
  • the invention provides a process for producing a gelling hemicellulose comprising the steps of providing a hemicellulosic material, subjecting the hemicellulosic material to alkaline oxide extraction, isolating the extracted hemicellulose and supplementing the isolated hemicellulose with an oxidase (e.g. glucose oxidase) supplement and optionally: (i) a peroxidase (e.g. horse radish peroxidase) supplement and/or (ii) an oxidase substrate (e.g. glucose) supplement.
  • an oxidase e.g. glucose oxidase
  • a peroxidase e.g. horse radish peroxidase
  • an oxidase substrate e.g. glucose
  • the term therefore implies the involvement of large scale apparatus (plant) for producing large (commercial) quantities of products over relatively long periods of time (months or years).
  • the hemicellulosic material may be derived from any suitable source, for example from cereal flour, husk or bran (e.g. from maize, wheat, barley, rice, oats or malt) or from legumes or from the other sources described below.
  • the hemicellulose extracted in step (b) may be any gelling hemicellulose.
  • Preferred are pentosans, e.g. a water soluble or alkali soluble pentosans.
  • the pentosan may comprise arabinoxylan, for example arabinoxylan ferulate.
  • the hemicellulose consists (e.g. consists essentially of) arabinoxylan ferulate, so that the gels are cross-linked arabinoxylan ferulate gels.
  • the extraction comprises holding the hemicellulosic material at an alkaline pH in an aqueous solution of H 2 O 2 .
  • the holding time may vary over a wide range, and may for example be anywhere between 0.5-50 hours (for example, up to 1, 2, 4, 5, 6, 7 or 10 hours).
  • the pH is preferably at least 11 (for example, 11-12, e.g. about 11.5), while the aqueous solution of H 2 O 2 may be a 0.1-10.0% (for example, 0.5-5%, e.g. about 1-2%) solution.
  • Any suitable alkalifying agent may be used, but particularly convenient is sodium hydroxide, potassium hydroxide or ammonium hydroxide.
  • the hemicellulosic material may be present at any suitable concentration, but extraction efficiencies may decline if the material is present at very high levels. Preferred are levels of between 0.1-50% w/v (for example, 0.5-10 w/v, e.g. 1-5% w/v).
  • the process is preferably conducted in the absence of heating ("cold" extraction) while for other applications hot alkaline oxidant can be used to advantage, particularly where high yields are critical and/or enzymic modification is to be carried out.
  • cold extractions may be conducted at a temperature of between 10 and 40°C (for example, 20-30°C, e.g. about 25°C), while hot extractions may be conducted at temperatures in excess of 40°C (e.g. in excess of 50, 60, 70, 80, 90 or 100°C).
  • the alkaline oxide extraction preferably at least partially decolourizes the hemicellulosic extract (i.e. has a bleaching effect on the product). This has many important advantages, and extends the range of applications of the end product.
  • the alkaline oxide extraction may be preceded by a preliminary alkaline (e.g. mild alkaline) extraction (e.g. at elevated temperature), and in some circumstances higher yields may be obtained.
  • a preliminary alkaline e.g. mild alkaline
  • Such two stage extraction process preferably further comprise an enzymic modification step.
  • enzymic modification is preferably effected by incorporating one or more enzymes into the aqueous solution of H 2 O 2 .
  • the enzymic treatment may adjust the degree of acetyl ester substitution in the hemicellulose extract (and e.g. comprises treating the hemicellulose with an acetyl esterase).
  • the treatment may comprise acetyl esterase treatment under condensing conditions (e.g. low water activity) to form acetyl hemicellulose esters and/or under hydrolytic conditions (e.g. high water activity) to at least partially de-acetylate the hemicellulose.
  • the enzyme treatment may adjust the degree of phenolic ester substitution in the hemicellulose extract. It may comprise treating the hemicellulose with a ferulic acid esterase, the treatment conveniently being sequential or simultaneous with respect to an acetyl esterase treatment described earlier.
  • the enzyme treatment may also comprise ferulic acid esterase treatment under condensing conditions (e.g. low water activity) to form ferulic acid hemicellulose esters and/or hydrolytic conditions (e.g. high water activity) to at least partially de-feruloylate the hemicellulose.
  • the esterase treatment may modify the solubility of the hemicellulose.
  • the acetyl esterase treatment may be carried out under condensing conditions (e.g. low water activity) to form acetyl hemicellulose esters and/or hydrolytic conditions (e.g. high water activity) to at least partially de-acetylate the hemicellulose.
  • condensing conditions e.g. low water activity
  • hydrolytic conditions e.g. high water activity
  • the modification of the solubility of the hemicellulose has great significance for the fractionation of various kinds of plant material, and in particular facilitates the extraction of gelling hemicelluloses therefrom.
  • the residue remaining forms a particularly useful source of co-products present in a substantially unhydrolysed state, including proteins, starches, ⁇ -glucans, celluloses, lignins, phenolic extracts etc.
  • Adjusting the degree of phenolic ester substitution in the hemicellulose via treatment with a ferulic acid esterase may modify the cross-linking potential of the hemicellulose.
  • the ferulic acid esterase treatment may be carried out under condensing conditions (e.g. low water activity) to form ferulic acid hemicellulose esters and/or hydrolytic conditions (e.g. high water activity) to at least partially de-feruloylate the hemicellulose.
  • condensing conditions e.g. low water activity
  • hydrolytic conditions e.g. high water activity
  • ferulic acid hemicellulose esters may effect an increase in crosslinking potential (and ultimate gel strength), while treatment under hydrolytic conditions (e.g. high water activity) to at least partially de-feruloylate the hemicellulosic starting material may effect a decrease in crosslinking potential (and a decrease in ultimate gel strength).
  • hydrolytic conditions e.g. high water activity
  • Treatment with both acetyl and ferulic acid esterases may be carried out, and here the treatment may be conducted simultaneously or sequentially.
  • the hemicellulose or starting material may be first treated with either the acetyl esterase or the ferulic acid esterase.
  • the invention also contemplates a gel or gelling hemicellulose obtainable by the process of any one of the preceding claims.
  • the gel may be in dehydrated form.
  • Also contemplated are rehydrated dehydrated gels obtainable by the processes of the invention.
  • the invention also contemplates an industrial installation specifically adapted for conducting the process of the invention. DETAILED DESCRIPTION Starting materials for use in the invention
  • Suitable starting materials containing hemicellulose (hemicellulosic materials) for use in the processes of the invention typically include plant material of various kinds and any part or component thereof.
  • Plant materials useful as a starting material in the invention include the leaves and stalks of woody and nonwoody plants (particularly monocotyledonous plants), and grassy species of the family Gramineae. Particularly preferred are gramineous agricultural residues, i.e. the portions of grain-bearing grassy plants which remain after harvesting the seed. Such residues include straws (e.g. wheat, oat, rice, barley, rye, buckwheat and flax straws), corn stalks, corn cobs and corn husks.
  • straws e.g. wheat, oat, rice, barley, rye, buckwheat and flax straws
  • corn stalks corn cobs and corn husks.
  • suitable starting materials include grasses, such as prairie grasses, gamagrass and foxtail.
  • suitable sources include dicotyledonous plants such as woody dicots (e.g. trees and shrubs) as well as leguminous plants.
  • fruits includes the ripened plant ovary (or group thereof) containing the seeds, together with any adjacent parts that may be fused with it at maturity.
  • the term “fruit” also embraces simple dry fruits (follicles, legumes, capsules, achenes, grains, samaras and nuts (including chestnuts, water chestnuts, horsechestnuts etc.)), simple fleshy fruits (berries, drupes, false berries and pomes), aggregate fruits and multiple fruits.
  • fruit is also intended to embrace any residual or modified leaf and flower parts which contain or are attached to the fruit (such as a bract). Encompassed within this meaning of fruit are cereal grains and other seeds.
  • fruit components including bran, seed hulls and culms, including malt culms.
  • Bran is a component of cereals and is defined as a fraction obtained during the processing of cereal grain seeds and comprises the lignocellulosic seed coat as separate from the flour or meal.
  • suitable component parts suitable as starting materials include flours and meals (particularly cereal flours and meals, and including nonwoody seed hulls, such as the bracts
  • root is intended to define the usually underground portion of a plant body that functions as an organ of absorption, aeration and/or food storage or as a means of anchorage or support. It differs from the stem in lacking nodes, buds and leaves.
  • the term “tuber” is defined as a much enlarged portion of subterranean stem (stolon) provided with buds on the sides and tips.
  • Preferred lignocellulosic starting materials include waste stream components from commercial processing of crop materials such as various beets and pulps thereof (including sugar beet pulp), citrus fruit pulp, wood pulp, fruit rinds, nonwoody seed hulls and cereal bran.
  • Suitable cereal sources include maize, barley, wheat, oats, rice, other sources include pulses (e.g. soya), legumes and fruit.
  • Suitable starting materials include pollen, bark, wood shavings, aquatic plants, marine plants (including algae), exudates, cultured tissue, synthetic gums, pectins and mucilages.
  • testaceous plant material for example waste testaceous plant material (preferably containing at least about 20% of arabinoxylan and/or glucoronoarabinoxylan).
  • the starting material may be treated directly in its field-harvested state or (more usually) subject to some form of pre-processing.
  • Typical pre-processing steps include chopping, grinding, cleaning, washing, screening, sieving etc.
  • the starting material is in a substantially ground form having a particle size of not more than about 100 microns. It may be air classified or sieved (for example to reduce the level of starch). Alternatively, or in addition, the starting material may be treated with enzymes to remove starch (e.g. alpha- and/or beta-amylase). The starting material may also be pre-digested with a carbohydrase enzyme to remove ⁇ -glucan.
  • enzymes to remove starch e.g. alpha- and/or beta-amylase
  • the starting material may also be pre-digested with a carbohydrase enzyme to remove ⁇ -glucan.
  • washing treatments include washing with hot water or acid (e.g. at a pH of 3-6, e.g. about 5). This at least partially separates protein.
  • Other pre-treatments include protease treatment.
  • the hemicelluloses extracted in the processes of the invention may be any hemicellulose which is suitable as a substrate for oxidative gelation (i.e. a "gelling hemicellulose"). Such hemicelluloses often have substituents with phenolic groups which are cross-linkable with certain oxidizing agents.
  • the hemicellulose may be an arabinoxylan, heteroxylan or pectin.
  • the hemicellulose may be a synthetic hemicellulose (i.e. a structural analogue of a naturally-occurring hemicellulose synthesised in vitro by any chemical/enzymic synthesis or modification).
  • non-cellulosic, non- starch plant polysaccharides may be extracted in the processes of the invention, including pentosans, pectins and gums.
  • Preferred are arabinoxylans, heteroxylans and pectins.
  • arabinoxylans particularly preferred are AXF A and AXF.
  • pectins including the true pectins, simple pectins, complex pectins, mesocomplex pectins and gelling pectins (e.g. those obtainable from representatives of the plant family Chenopodiaceae, which include beets (e.g. sugar beet), spinach and shaped wurzels). Particularly preferred is sugar beet pectin (for example in the form of sugar beet pulp). Also useful in the invention are treated pectins (as hereinbefore defined). Post-extraction processing/isolation
  • the hemicelluloses may be further processed to concentrate, purify or simply isolate the hemicellulose from the unextracted residue.
  • Other post-extraction treatments include supplementing the extracted hemicellulose with an oxidase (e.g. glucose oxidase) supplement, optionally together with a peroxidase (e.g. horse radish peroxidase) and/or an oxidase substrate (e.g. glucose) supplement.
  • an oxidase e.g. glucose oxidase
  • a peroxidase e.g. horse radish peroxidase
  • an oxidase substrate e.g. glucose
  • This supplementing step is carried out when gelation is to be carried out subsequently by in situ generation of hydrogen oxide by redox enzymes (as described infra).
  • Particularly preferred are post-extraction processes which avoid the use of alcohol precipitation, so avoiding the costs associated with this step.
  • Preferred processing steps include any of centrifugation, filtration (e.g. ultrafiltration or filtration of vega clay), precipitation (e.g. isoelectric precipitation), chromatography (e.g. silica hydrogel and/or ion exchange chromatography). Particularly preferred is ultrafiltration or concentration by spray-, drum- or freeze-drying, vacuum rotary drying or ammonium sulphate precipitation. Other treatments include desalting treatments, for example dialysis or tangential flow ultrafiltration.
  • alcohol e.g. IMS, methanol, ethanol or iso-propanol
  • IMS methanol, ethanol or iso-propanol
  • direct spray or freeze drying followed by drying in the absence of an alcohol precipitation step.
  • the extracted hemicellulose may be dried, either before or after oxidative gelation. Dried preparations may be supplemented with carriers or dispersants, such as glucose.
  • oxidative gelation process Any of a variety of known oxidative gelation process can be used to gel the extracted hemicelluloses of the invention. Only a few oxidizing agents are known to have the ability to induce gelation, and these include hydrogen peroxide (usually in conjunction with a peroxidase), ammonium persulphate and formamidine disulphide.
  • the oxidative gelation may also be accomplished enzymically, for example as described in WO 96/03440 in which an oxidase (preferably a laccase) is used to promote oxidative gelation of inter alia arabinoxylans.
  • an oxidase preferably a laccase
  • enzymic approaches include promoting the generation of hydrogen peroxide in situ by redox enzymes.
  • the redox enzymes preferably comprise an oxidase (e.g. glucose oxidase) and a peroxidase (e.g. horse radish peroxidase), which are preferably present as supplements in the hemicellulosic material.
  • gelation may be achieved as described in WO 93/10158, which describes an oxidizing system comprising a peroxide (such as hydrogen peroxide) and an oxygenase (such as a peroxidase).
  • the hemicellulose products i.e. the gels, dehydrated gels, rehydrated dehydrated gels and viscous liquids of the invention find a variety of applications various therapeutic, surgical, prophylactic, diagnostic and cosmetic (e.g. skin care) applications.
  • the aforementioned materials may be formulated as a pharmaceutical or cosmetic preparation or medical device, for example selected from: a wound plug, wound dressing, wound debriding system, controlled release device, an encapsulated medicament or drug, a lotion, cream (e.g. face cream), suppository, pessary, spray, artificial skin, protective membrane, a nutraceutical, prosthetic, orthopaedic, ocular insert, injectant, lubricant or cell implant matrix.
  • the gelling and gelled hemicelluloses e.g. AXF and gelled AXF
  • AXF and gelled AXF are particularly useful as agents which maintain the integrity of the gut wall lining, and as agents for coating the luminal wall of the gastrointestinal tract. They may therefore find particular application in animal feeds and in the treatment of gastrointestinal disorders.
  • the material, gel or viscous medium of the invention may further comprise an antibiotic, electrolyte, cell, tissue, cell extract, pigment, dye, radioisotope, label, imaging agent, enzyme, co-factor, hormone, cytokine, vaccine, growth factor, protein (e.g. a therapeutic protein), allergen, hapten or antigen (for e.g. sensitivity testing), antibody, oil, analgesic and/or antiinflammatory agent (e.g. NSAID).
  • an antibiotic electrolyte, cell, tissue, cell extract, pigment, dye, radioisotope, label, imaging agent, enzyme, co-factor, hormone, cytokine, vaccine, growth factor, protein (e.g. a therapeutic protein), allergen, hapten or antigen (for e.g. sensitivity testing), antibody, oil, analgesic and/or antiinflammatory agent (e.g. NSAID).
  • the above-listed materials find application in therapy, surgery, prophylaxis or diagnosis, for example in the treatment of surface (e.g. skin or membrane lesions, e.g. burns, abrasions or ulcers).
  • the invention contemplates a wound dressing comprising the above listed materials of the invention, for example in the form of a spray.
  • wound dressings are particularly useful for the treatment of burns, where their great moisture retaining properties help to prevent the wound drying out.
  • compositions comprising gelling hemicellulose supplemented with glucose and peroxidase and/or oxidase enzymes which gels on contact with oxygen in the air.
  • Such compositions can be provided in the form of oxygen-free liquids in airtight containers which can be sprayed onto the skin, whereupon the liquid gels after exposure to the air.
  • Such composition may advantageously be formulated so as to produce a slight excess of hydrogen peroxide on exposure to oxygen, so that a sterilizing, antibacterial, bacteriostatic and/or cleansing effect is obtained which helps promote healing.
  • the invention also contemplates water absorbent nappies, diapers, incontinence pads, sanitary towels, tampons and panty liners comprising the above-listed materials, as well as domestic and industrial cleaning or liquid (e.g. water) recovery operations (e.g. in the oil industry).
  • domestic and industrial cleaning or liquid (e.g. water) recovery operations e.g. in the oil industry.
  • the gels of the invention can be provided in the form of hydrated or dehydrated sheets or pellicles for application to various internal or external surfaces of the body, for example during abdominal surgery to prevent adhesions.
  • the materials listed above also find application as a foodstuff, dietary fibre source, food ingredient, additive, lubricant, supplement or food dressing.
  • Such products are preferably selected from crumb, alginate replacer, cottage cheeses, aerosol toppings, frozen yoghurts, milk shakes, ice cream, low calorie products such as dressings and jellies, batters, cake mixes, frozen chips, binders, gravies, pastas, noodles, doughs, pizza toppings, sauces, mayonnaise, jam, preserve, pickles, relish, fruit drinks, a clouding agent in drinks, syrups, toppings and confectionary (e.g. soft centres), petfood (wherein the gel e.g.
  • a binder acts as a binder
  • a flavour delivery agent acts as a canning gel
  • fat replacer e.g. comprising macerated gel
  • a coating e.g. comprising macerated gel
  • a glaze e.g. comprising macerated gel
  • a bait e.g. a bait
  • a binder in meat and meat analogue products for example vegetarian products
  • an edible adhesive e.g. a yoghurt supplement.
  • the gel of the invention When used as a fat replacer the gel of the invention is preferably macerated to optimize its mouthfeel and fat mimetic properties.
  • EXAMPLE 1 Six extraction vessels containing 400 ml of 0.025 M sodium acetate buffer (pH 5.0) with 1% v/v hydrogen peroxide were agitated (200 ⁇ m) at 25°C. To each vessel, 8 g of maize bran (2% w/v) was added and dispersed over 15 minutes. Potassium hydroxide was then added to raise the pH to 11.5 (approximately 4.2 g per vessel). Extracts were sacrificed at 1, 2.5, 5, 7, 18 and 24 hour intervals.
  • Sacrificed extracts were adjusted to pH 7.0 with acetic acid, filtered to remove the "bran” and chilled overnight at 4°C.
  • the glucan precipitate formed overnight was removed by centrifugation.
  • the pH was then adjusted to pH 5.5 with glacial acetic acid and 1.5 volumes of 99% IMS added.
  • the pH was then re-adjusted to pH 5.0.
  • the precipitate was agitated for 30 minutes and then allowed to stand for 1 hour at RTP. The supernatant was removed and the precipitate washed (triturated) 3 times with IMS and dried rapidly in a rotary evaporator under vacuum at 50°C.
  • Extracts were prepared as described in Example 1 , except that extracts were sacrificed at 2, 3, 4, 5, 6 and 7 hours. The yields increased with extraction time, from about 4% w.r.t the bran (at 2 hours) to about 11% (at 7 hours).
  • the extracts were oxidatively gelled.
  • the extract obtained after 2 hours produced a very brittle gel, while the extract from the 6 and 7 hour extractions thickened (but did not gel).

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Abstract

Cette invention permet l'extraction des hémicelluloses grâce à un traitement avec un peroxyde alcalin sans élimination des résidus tels que les ferulates. Les hémicelluloses préparées de cette façon conservent leur aptitude à la gélification. De telles hémicelluloses gélifiables peuvent s'extraire en employant une brande variété d'espèces d'oxydation telles que l'anion peroxyde d'hydrogène, le radical peroxyde d'hydrogène, le radical hydroxyle, le radical superoxyde, et le radical oxyde. On a ainsi mis au point un traitement permettant la production d'un gel de type hémicellulosique et pouvant être conduit à froid. Ce traitement, qui facilite le cotraitement enzymatique, donne de bons rendements, et permet la production d'un gel qui n'est que faiblement coloré.
EP99933962A 1998-07-14 1999-07-13 Extraction de matiere hemicellulosique Withdrawn EP1098911A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GBGB9815200.2A GB9815200D0 (en) 1998-07-14 1998-07-14 Extraction of hemicellulosic materials
GB9815200 1998-07-14
PCT/US1999/015811 WO2000004053A1 (fr) 1998-07-14 1999-07-13 Extraction de matiere hemicellulosique

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EP1098911A1 true EP1098911A1 (fr) 2001-05-16

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EP (1) EP1098911A1 (fr)
CN (1) CN1309667A (fr)
AU (1) AU4990199A (fr)
CA (1) CA2335642A1 (fr)
GB (1) GB9815200D0 (fr)
WO (1) WO2000004053A1 (fr)
ZA (1) ZA200100094B (fr)

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WO2002079260A1 (fr) * 2001-03-28 2002-10-10 Grain Processing Corporation Hydrolyse enzymatiquement catalysee de fibre de mais et produits obtenus a partir de fibres de mais enzymatiquement hydrolysees
WO2012071004A1 (fr) * 2010-11-23 2012-05-31 Ecohelix Hb Procédé pour augmenter le poids moléculaire de mannanes et de xylanes du bois comprenant des parties aromatiques
CN102746422A (zh) * 2012-06-21 2012-10-24 海南大学 一种从椰壳和椰壳纤维中提取半纤维素的方法
US9434788B2 (en) * 2012-07-11 2016-09-06 The United States Of America, As Represented By The Secretary Of Agriculture Bio-based fiber gums (BFGs) and processes for producing BFGs
WO2016063824A1 (fr) * 2014-10-20 2016-04-28 国立大学法人鹿児島大学 Préparation pour la formation d'emboles, et microcathéter
US9650742B2 (en) * 2014-12-11 2017-05-16 Rayonier Performance Fibers, Llc Process for making hydrogels from hemicaustic byproduct
CN109007860B (zh) * 2018-06-14 2021-09-14 中南林业科技大学 一种提高米糠可溶性膳食纤维抗氧化性的方法
US20220211062A1 (en) * 2019-05-16 2022-07-07 Chr. Hansen A/S Method for producing milk products with modified firmness and/or gelation time and products obtained
CN111040049A (zh) * 2019-12-02 2020-04-21 广西大学 一种分离提纯甘蔗渣中半纤维素的方法

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GB2261671B (en) * 1991-11-16 1996-07-03 Gb Biotech Gel production from plant matter
HU220197B (hu) * 1994-07-26 2001-11-28 Novozymes A/S Eljárás fenolpolimerek viszkozitásának növelésére vagy gélezésére lakkáz enzimmel
WO1998022513A1 (fr) * 1996-11-21 1998-05-28 E.I. Du Pont De Nemours And Company Production de gels vegetaux

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Title
See references of WO0004053A1 *

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GB9815200D0 (en) 1998-09-09
ZA200100094B (en) 2002-01-04
CA2335642A1 (fr) 2000-01-27
CN1309667A (zh) 2001-08-22
WO2000004053A1 (fr) 2000-01-27
AU4990199A (en) 2000-02-07

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