WO2012080772A1 - Chitin-chitosan bloc co-polymers - Google Patents

Chitin-chitosan bloc co-polymers Download PDF

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WO2012080772A1
WO2012080772A1 PCT/IB2010/003475 IB2010003475W WO2012080772A1 WO 2012080772 A1 WO2012080772 A1 WO 2012080772A1 IB 2010003475 W IB2010003475 W IB 2010003475W WO 2012080772 A1 WO2012080772 A1 WO 2012080772A1
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chitin
anyone
chitosan
previous
preparation process
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PCT/IB2010/003475
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English (en)
French (fr)
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Laurent David
Keiko Shirai Matsumoto
Stéphane TROMBOTTO
Neith Aracely Pacheco Lopez
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Universite Claude Bernard Lyon I
Universidad Autonoma Metropolitana
Institut National Des Sciences Appliquees De Lyon
Universite Jean Monnet
Centre National De La Recherche Scientifique
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Priority to MX2013006907A priority Critical patent/MX358038B/es
Priority to PCT/IB2010/003475 priority patent/WO2012080772A1/en
Publication of WO2012080772A1 publication Critical patent/WO2012080772A1/en

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    • 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
    • C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
    • C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
    • C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof

Definitions

  • the invention relates to the field of biopolymers, more particularly to alternated 'bloc'-copolymers of chitin and chitosan family.
  • Chitin is the most widespread natural polymer with cellulose. Chitin is a linear co-polysaccharide constituted by D-glucosamine and N-acetyl D- glucosamine repeat units, linked by a ⁇ -(1->4) glycosidic bond.
  • the degree of N-acetylation or DA is the molar fraction of the D-glucosamine residues.
  • the DA in chitin is frequently higher than 80%, resulting in an insoluble polymer in aqueous media.
  • chitin is mainly extracted from the exoskeleton (shell) of arthropods (lobster, crab and shrimp). Chitin can also be extracted from endoskeleton of cephalopods such as squids. Chitin is a fibrillar semicrystalline polymer, organized at several length scales [The crustacean exoesqueleton as an example of a structurally and mechanically graded biological nanocomposite material. Raabe, D., Sachs, C. and Romano, P, 2005, Acta Materialia, 53, pp 4281-4292.]. It is thus composed of crystalline and amorphous phases.
  • Crystalline chitin can be found in two allomorphs, and ⁇ -chitin (specifically found in the endosqueleton of cephalopods), but a- chitin is the main (crystalline) form found in biomass.
  • a crystalline form is well described at atomic level [Structure of Alpha-Chitin Minke R. and Blackwell, J., 1978, Journal of Molecular Biology, 120 (2) pp 167-181 ] with a dense network of hydrogen bonds. This induces a rigidity and low molecular mobility of the chains and a weak accessibility to the deacetylation reactants.
  • a-chitin is not soluble in aqueous acidic media, and swells only weakly in neutral aqueous media.
  • the extraction of chitin from biomass can be operated from a chemical process involving (i) a demineralization process at ambient temperature in HCI 1M or 0.25M for about 30 min and (ii) a deproteinization treatment in aqueous solution of sodium hydroxide NaOH 1M at moderate temperatures (room temperature to 70°C during 24 to 48 hours).
  • a demineralization process at ambient temperature in HCI 1M or 0.25M for about 30 min
  • a deproteinization treatment in aqueous solution of sodium hydroxide NaOH 1M at moderate temperatures (room temperature to 70°C during 24 to 48 hours).
  • Chitosan is a de-acetylated derivative of chitin, and is therefore also a co-polysaccharide with D-glucosamine and N-acetyl D-glucosamine repeat units linked by a ⁇ -(1->4) glycosidic bond.
  • Chitosan usually contains a proportion of N-acetyl-D-glucosamine monomer units lower than 60%.
  • Chitosan is notably obtained by total or partial deacetylation of chitin.
  • Chitosan is, by definition, soluble in acidic media (except sulfuric and phosphoric a ds).
  • chitosans with pure statistical Bernoulli distribution of the residues stay soluble up to a critical DA close to 60%.
  • Such statistical structure is obtained by reacetylation of a low- DA chitosan in solution. After chemical deacetylation of chitin in the solid state, the DA range of soluble chitosan in acidic aqueous solution is typically 0-40%.
  • Chitosan has a higher number of reactive free amine groups than chitin, and also exists in two allomorphs: hydrated (tendon) allomorph and anhydrous allomorph.
  • Chitosan is used or offers potential in a variety of applications from water treatment, cosmetics, nutraceutics, food conservation, agriculture, tissue engineering, biotechnologies...
  • This polymer is biodegradable, bioresorbable, biocompatible and non toxic, it is widely used in pharmacy as an excipient, drug-delivery applications, and also as an active principle (fungistatic, bacteriostatic, wound healing formulation and devices).
  • the interest of chitosan for such applications is a function of the molecular mass and the DA or the amount of reactive amine groups.
  • Such macromolecular features will in turn impact the solubility in acidic media, the reactivity for chemical modification, but also the biological properties such as the biodegradation rate, the immune activity, the processing ability (possibility to form physical hydrogels, high performance fibers, and highly viscous solutions) and the mechanical and rheological properties of the chitosan materials in various physical forms.
  • the patent application WO2007/048974 describes a method for preparing novel D-glucosamine and N-acetyl-D-glucosamine hetero- oligomers, enabling the size, the degree of acetylation and the architecture of the resulting oligomers to be controlled. Nevertheless, this method requires the synthesis of specific monomers, their coupling in order to form dimers and so on ... So, this method is complicated in order to obtain hetero- oligomers of DP (degree of polymerisation) higher than 6 and polymers of higher molecular weight.
  • the invention proposes a new chitosan presenting a degree of N-acetylation (DA) ranging from 5% to 45%, for instance from 10 to 45%, preferably from 10 to 40%, and preferentially from 20 to 40%, wherein its X ray powder diffractogram shows at least one characteristic peak of a crystalline form of chitin.
  • DA N-acetylation
  • the chitosan according to the invention presents a bloc structure defined by the alternation of highly acetylated blocs (with mainly N-acetyl-D- glucosamine rich blocs) and more deacetylated blocs (sequences with mainly D-glucosamine residues) and, as a result, is an amphiphilic polymer. Due to its amphiphilic property, the chitosan according to the invention forms a colloidal solution in an acidic aqueous solution.
  • An other aspect of the invention is related to the different materials and coatings obtained from such a chitosan, namely the nanoparticules the colloidal solutions, the physical hydrogels and the solid forms (films and fibers).
  • the invention also concerns a preparation process of such a chitosan comprising the following steps:
  • Figure 1 displays the diffraction diagram (Cu Ka X-ray radiation at room temperature) of the shrimp shell before and after different treatments at different times.
  • Figure 2 displays the evolution of the diffraction diagrams for initial Biochitin and samples obtained after an FTP deacetylation step in the solid state for various reaction times.
  • Figure 3 studies the second Freeze-Pump-Thaw deacetylation cycle on a sample deacetylated 20 minutes.
  • Figure 4 displays the diffraction diagram of a commercial chitosan sample (from Mahtani Chitosan).
  • Degree of N-acetylation defined above is the mean DA measured by H NMR spectroscopy in liquid media.
  • a specific method for DA determination is that reported by Hirai et al., 1991, (Hirai, A., Odani, H. and Nakajima, A. (1991). Determination of degree of deacetylation of chitosan by 1H NMR spectroscopy. Polymer Bulletin. 26: 87-94).
  • the weight average macromolecular weight ⁇ ! can be determined by the technique described in «Physico-chemical studies of the gelation of chitosan in a hydroalcoholic medium » A. MONTEMBAULT, C. VITON, A. DOMARD Biomaterials, 26(8), 933-943, 2005.
  • a chitin obtained by a lactic fermentation bacteria (LFB) method is named Biochitin.
  • the new alternated 'bloc' chitosans are prepared from the deacetylation of a 'Biochitin' extracted from biomass with a biotechnological process, namely lactic acid fermentation (LAF) process.
  • LAF lactic acid fermentation
  • a biotechnological process namely lactic acid fermentation (LAF) process.
  • LAF lactic acid fermentation
  • MXPA000 722 a biotechnological process
  • such a process includes the treatment of a naturally occurring chitin source, in a medium containing lactic acid bacteria (LAB) and a fermentable carbon source to produce lactic acid for mineral solubilization and the activation of endogenous and produced enzymes for chitin deproteinization.
  • LAB lactic acid bacteria
  • LAB lactic acid bacteria
  • the naturally occurring chitin source is exoskeletons of crustaceans that leads to the a crystalline form of chitin.
  • the treatment of step a) is performed with sucrose (i.e. saccharose), but glucose or lactose could be employed, as well as spray dried cheese whey ["Pilot scale lactic acid fermentation of shrimp wastes for chitin recovery" Luis A. Cira, Sergio Huerta, George M. Hall, Keiko Shirai, Process Biochemistry 37 (2002) 1359-1366].
  • lactic acid bacteria Lactobacillus plantarum Lactobacillus casei, Lactobacillus pentousus, Pediococcus acidolactici ["Effect of initial glucose concentration and inoculation level of lactic acid bacteria in shrimp waste ensilation" Keiko Shirai, Isabel Guerrero, Sergio Huerta, Gerardo Saucedo, Alberto Castillo, R. Obdulia Gonzalez, George M. Hall, Enzyme and Microbial technology 28 (2001): 446-452]
  • L. paracasei ["Lactic acid fermentation of scampi waste in a rotating horizontal bioreactor for chitin recovery" Zainoha Zakaria, George M.
  • the step a) can be followed by a mild acid treatment in order to remove the residual minerals.
  • the necessity of such a treatment is function of the duration of the LAF step.
  • This acid treatment is qualified as mild as it does not destroy the crystals of the chitin obtained by the LAF process, but improves its chitin crystallinity fraction and increases the size and degree of perfection of the chitin crystals as can be deduced of the characteristic diffraction peaks of the chitin (see equation 4.1 and 4.2 below).
  • This mild treatment can be performed with an acid, for instance chosen among HCI, H- COOH, CH3COOH, lactic acid, citric acid, H 3 P0 4 , HN0 3 and H 2 S0 4 , preferably at concentrations from 0.2 to 0.6 N and for instance at a temperature ranging from 10 to 40°C, and preferentially at room temperature (20°C).
  • an acid for instance chosen among HCI, H- COOH, CH3COOH, lactic acid, citric acid, H 3 P0 4 , HN0 3 and H 2 S0 4 , preferably at concentrations from 0.2 to 0.6 N and for instance at a temperature ranging from 10 to 40°C, and preferentially at room temperature (20°C).
  • alkali for instance NaOH or KOH
  • This alkali treatment is optional as the residual proteins can be removed, during the deacetylation step b).
  • the Biochitin extracted by lactic fermentation bacteria (LAB) treatment was found to exhibit a particular well defined crystalline structure.
  • alternated 'bloc' chitosans by deacetylation (for instance, but not preferably according to WO2005/019272) of the 'Biochitin' extracted from biomass with such a biotechnological process.
  • Figure 1 displays the diffraction diagram (Cu Ka X-ray radiation at room temperature) of the shrimp shell before and after different treatments at different times.
  • Figure 1 presents the X-ray diffraction patterns of the samples obtained after different fermentation times (0; 24; 48; 72; 96; 120 and 144h) of a Biochitin (BIO-C) obtained at the end of the fermentation process after 144 h, with an additional mild HCI treatment (0.04M HCI), and of chemical (CH-C) and commercial (CO-C) chitins.
  • BIO-C Biochitin
  • the diffraction diagram exhibits the 6 characteristic reflections, identified as (020), (021), (110), (120), (130) and (013), corresponding to the crystalline structure of a-chitin according to the model proposed by Minke R. and Blackwell, J., 1978, Structure of Alpha-Chitin. Journal of Molecular Biology. 120(2), pp 167-181.).
  • the crystalline microstructure of the obtained Biochitin can be compared with chitin obtained by a full chemical treatments (i.e. according to WO2005/019272 procedure see CH-C in Figure 1) and commercial chitin (alfa-chitin Mahtani P.V.T) see CO-C in Figure 1).
  • the crystalline ratio, crystalline perfection and crystallite size are higher for Biochitin.
  • Biochitin can be defined as a highly crystalline substrate with large nanocrystalline blocs, in comparison with chitins obtained after a full chemical extraction treatment.
  • the inventors show that if such a Biochitin obtained at the end of step a), which includes a highly crystalline chitin in comparison to available commercial chitin or chitin obtainable by chemical route and an amorphous phase, is deacetylated in the solid state, then the N-acetyl D-glucosamine residues located inside the large crystals exhibit low accessibility to deacetylation reagents and are not deacetylated or undergo a limited deacetylation process, while the amorphous phase undergoes a pronounced deacetylation process.
  • the Biochitin which will be deacetylated presents a Crystalline Index (ICR) higher than 80%, preferentially higher than 85%.
  • ICR Crystalline Index
  • the obtained Biochitin corresponding to the Biochitin which will be deacetylated contains preferably crystals of chitin with a largest dimension higher than 6 nm, and preferentially rather than 10 nm.
  • the largest dimension of the crystals corresponds to the large value os D ap deduced from the breadth of the diffraction peaks (see equation 4.2 below) the X-ray diffractogram.
  • Crystallinity index is determined according to the method reported by B. Focher, P.L. Beltrame, A. Naggi and G. Torri , Alkaline N-deacetylation of chitin enhanced by flash treatments. Reaction kinetics and structure modifications. Carbohydrate Polymers 12 (1990), pp. 405-418, as detailed in the examples.
  • the step b) of deacetylation can be performed with any method of deacetylation of chitin known by the man skilled in the art. Most of the time, a concentrated aqueous solution of NaOH (30 to 60 % w/w, preferably 40-55 %w/w) is employed. The temperature usually ranges from 50°C to 110°C and the time of treatment from 1.5 to 5 hours. These parameters are dependent on the desired degree of deacetylation. Even the process described in WO 2005/019272 can be used whereas it could have been unfavourable as it generally leads to the fragmentation of the crystals.
  • This process of heterogeneous deacetylation includes one or several steps of curing a chitin suspension in an aqueous concentrated solution of sodium hydroxide at a temperature lower or equal to 100°C, for instance during 20 to 30 minutes, this curing being performed in a reactor under reduced pressure and without O2.
  • Each step of curing is preceded by a succession of at least 6 cycles of freezing/defreezing as described in WO2005/019272 that can be consulted for more details.
  • this process comprises only one step of curing.
  • the curing can be optionally followed by one or several of these optional steps :- a neutralisation of the hydroxide sodium in the reactive medium until a pH equal to 8.5 ; - a washing step with demineralised water consisting of several washings separated by centrifugation ; - a step of lyophilisation after freezing.
  • a deacetylation process in standard conditions, without steps of freezing/defreezing and lyophilisation, will be performed.
  • the conditions of the deacetylation process will be chosen in order to obtain the required DA, from 5 to 45%, preferably from 10 to 40%, and preferentially from 20 to 40%.
  • the difference of accessibility in the crystalline and in the amorphous phase of the chitin induces a difference in the acetylation degree, whatever the deacetylation process used.
  • the resulting chains are constituted by highly deacetylated segments (preferentially located in the amorphous phase and at the surface of crystals during the deacetylation treatment) and weakly deacetylated segments (preferentially located in the bulk of the nanocrystals during the deacetylation treatment), even if the mean DA is lower than 45%, even lower than 40%.
  • the secondary structure of the chitosan issued from Biochitin is then constituted by:
  • its X ray powder diffractogram shows at least one characteristic peak of the a crystalline form of chitin, and for instance the characteristic peak (020) of the a crystalline form of chitin, that can be expressed as interplanar distance at approximately 9.30 A, and, in particular, 9.30 A. ⁇ 0.40 A.
  • the X ray powder diffractogram of the chitosan of bloc structure according to the invention shows the characteristic peak (110) of the a crystalline form of chitin, that can be expressed as interplanar distance at approximately 4.60 A, and, in particular, 4.60 A. ⁇ 0.40 A.
  • the X ray powder diffractogram of the chitosan of bloc structure according to the invention shows the characteristic peak (013) of the a crystalline form of chitin, that can be expressed as interplanar distance at approximately 3.39 A, and, in particular, 3.39 A. ⁇ 0.40 A.
  • the typical number of re-entrant folds N can be deduced from acid hydrolysis of chitosan in the solid state (see Osorio-Madrazo A, David L, Trombotto S, Lucas JM, Peniche-Covas C, Domard A.
  • the degree of polymerization of the chitin blocs is controlled by crystallite sizes according to a multimodal distribution with modes at 16, 50 and 90; whereas the chitosan blocs result from chain portions from the amorphous phase and are thus following a distribution of sizes with larger breadth.
  • the obtained chitosan corresponds to a block copolymer formed of D-glucosamine (GIcN) homopolymeric units and N- acetyl-D-glucosamine (GIcNAc) homopolymeric units, in which each N-acetyl- D-glucosamine (GIcNAc) homopolymeric unit includes at least 3 monomeric units and preferably from 7 to 25 monomeric units.
  • GcN D-glucosamine
  • GIcNAc N- acetyl-D-glucosamine
  • the obtained chitosan presents a weight average macromolecular weight (/ ,) ranging from 450,000 g/mol to 200,000 g/mol.
  • the chitosan according to the invention with alterned bloc GIcN / GIcNAc structures is an amphiphilic polymer. This property can be qualitatively evaluated by the solubilization speed in a diluted acid solution, since chitin (GIcNAc blocs) is more hydrophobic than chitosan (GIcN blocs): chitin is not soluble in acidic aqueous solutions, whereas chitosan is soluble in acidic aqueous solutions thanks to the protonation of amine groups.
  • Chitosan is a polyamine, and thus the -NH 2 moieties can be used as reactive moieties for the grafting of functional molecules with biological or physico-chemical interest (ex: implied in a specific interaction in order to induce a targeted drug delivery or a specific biological response-adjuvant for vaccines).
  • the use of alternated bloc chitosan/chitin macromolecular structures can also be envisioned in the field of functional surfaces for lab-on chip and in vitro diagnostics applications.
  • the alterned bloc chitosan/chitin structures can also be used for their interaction with colloids (for steric and electrostatic stabilization purposes) and vesicle.
  • amphiphilic structure and resulting self-organization into hydrophilic and hydrophobic domains is to be exploited for bulk materials or coatings such as solid dry materials or gels, hydrogels and in particular physical hydrogels, in particular physical hydrogels with hydrophobic nanodomains, containing active principles and exhibiting a controlled release of active species, in particular hydrophobic active principles.
  • K is a constant; ⁇ ( ⁇ ) is the wave length of the incident radiation; ⁇ (rad) is the width of the crystalline peak at half height and ⁇ (rad) is half the Bragg angle corresponding to the crystalline peak.
  • Biotechnologically prepared chitin (Biochitin) is needed for the preparation of chitosans with block sequence structure with chemical deacetylation process.
  • This Biochitin was obtained by the application of Lactic acid fermentation (LAF), see Mexican patent MXPA00011722 previously cited.
  • LAF Lactic acid fermentation
  • the exoesqueletons of crustacean were minced to a particle size from 0.5 - 6, mixed with sucrose (10 wt wt %) and Lactobacillus plantarum (5 vol/wt%). The mixture was placed into a packed bed column reactor and incubated at operational temperatures between 25 to 40 °C, during 144h.
  • the product obtained after fermentation was treated with HCI (0.5M) ratio 1:15 (w/v) during lh at room temperature (25°C) then treated with NaOH (0.4M) at ratio 1:15 (w/v), during lh at room temperature (25°C), to eliminate the remaining minerals and proteins.
  • Biochitin The chemical deacetylation of the Biochitin was carry out by heterogeneous deacetylation according to the Freeze-Pump-Thaw (FPT) method described by Lamarque et al. (2005), Patent Application WO2005/019272. Biochitins were deacetylated by one cycle of FPT process during different times of reaction at 100°C in a solution of NaOH at 50%. In each case only the water-insoluble fractions (pH 8) of each time were considered for characterization. Samples with values below 50% of deacetylation degree (DD) were re-acetylated according to the method reported by Sorlier et al. (2001).
  • FPT Freeze-Pump-Thaw
  • Samples with DD greater than 50% were purified by solubilization in the presence of the amount of acetic acid necessary to achieve the stoichiometric protonation of the -NH 2 sites.
  • the obtained solution was then filtered through a 0.45 micron filter (Millipore) before addition of aqueous ammonia to fully precipitate the polymer.
  • aqueous ammonia After repeated washings with deionized water followed by centrifugations, until a neutral pH was achieved, the product was dispersed in distilled water and then dried by lyophilization (see Patent Application No. WO2005/19272).
  • Acetylation degree (DA), Crystalline Index (ICR) and apparent crystallite size (Dap) corresponding to the 2 principal reflexions of a-chitin (020 and 110) after a first FTP heterogeneous deacetylation process.
  • ND Not determined.* 1D10B ID first FPT deacetylation, 10, 20, 30, 40, 60, 80 min are reaction times, BC represents biochitin.
  • the diffraction diagrams are characteristic of ⁇ -chitin all through the first deacetylation step, although the value of the DA decreased down to about 40%.
  • the crystals of the obtained semicrystalline materials are made of chitin, and in view of the combined values of the DA and crystalline fraction, the amorphous phase should be completely deacetylated.
  • the copolysaccharide macromolecules thus obtained are thus constituted by the amorphous deacetylated (chitosan) chain portions separated by chitin chain portions inherited from the crystallites.
  • Figure 3 is the X-Ray diffraction patterns after the second heterogeneous FPT deacetylation at several reaction times, 2D two steps, 10, 20, 30 reaction time in min, from Biochitin deacetylated 20 after a first FTP cycle (1D20BC).
  • the deacetylation procedure led to a decrease in the DA (see Table 3) and to the preservation of the crystalline structure of chitine.
  • the crystalline structure is still a- chitin like and the chitosan is still organized in blocs of highly deacetylated chain portions separated with chitin chain portions. This still shows an alterned bloc structure with DA as low as 20%.
  • Figure 4 presents the diffraction diagram of sample CHI in "Kinetics Study of the Solid-State Acid Hydrolysis of Chitosan: Evolution of the Crystallinity and Macromolecular Structure” Anayancy Osorio-Madrazo, Laurent David, Stephane Trombotto, Jean-Michel Lucas, Carlos Peniche-Covas , Alain Domard, Biomacromolecules, 2010, 11 (5), pp 1376-1386 DOI: 10.1021/bml001685.
  • the diffraction pattern was obtained on B2AM beamline at the ESRF (Grenoble France) in transmission mode at an incident photon energy close to 16 keV.
  • the deacetylated sample obtained from Biological chitin is exhibiting the crystalline structure of a-chitin.

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PCT/IB2010/003475 2010-12-17 2010-12-17 Chitin-chitosan bloc co-polymers WO2012080772A1 (en)

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Cited By (1)

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US9527929B2 (en) 2014-01-30 2016-12-27 Sofradim Production Optimized chitosan reacetylation

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MXPA00011722A (es) 2000-11-28 2002-05-31 Univ Autonoma Metropolitana Proceso de aprovechamiento de desperdicios de camaron para obtencion de quitina, proteinas, calcio y pigmentos.
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FR2892419A1 (fr) * 2005-10-24 2007-04-27 Univ Claude Bernard Lyon I Eta Heteroligomeres de d-glucasamine et n-acetyl-d-glucosamine, leur procede de preparation et leur utilisation
WO2007048974A2 (fr) 2005-10-24 2007-05-03 Universite Claude Bernard Lyon I Heterooligomeres de d-glucosamine et n-acetyl-d-glucosamine, leur procede de preparation et leur utilisation

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