WO2015101786A1 - Procédé pour la préparation de billes de cellulose par réaction d'un substrat en cellulose avec un agent oxydant - Google Patents

Procédé pour la préparation de billes de cellulose par réaction d'un substrat en cellulose avec un agent oxydant Download PDF

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Publication number
WO2015101786A1
WO2015101786A1 PCT/GB2014/053855 GB2014053855W WO2015101786A1 WO 2015101786 A1 WO2015101786 A1 WO 2015101786A1 GB 2014053855 W GB2014053855 W GB 2014053855W WO 2015101786 A1 WO2015101786 A1 WO 2015101786A1
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Prior art keywords
cellulose
beads
oxidant
substrate
oxidation
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PCT/GB2014/053855
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English (en)
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Jonas Lindh
Albert Mihranyan
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Jonas Lindh
Albert Mihranyan
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Publication of WO2015101786A1 publication Critical patent/WO2015101786A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • C08L1/04—Oxycellulose; Hydrocellulose, e.g. microcrystalline cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/18—Spheres

Definitions

  • the present invention relates to cellulose beads, processes for preparing such beads and their various uses.
  • the present invention relates to 2,3-dialdehyde cellulose (DAC) beads and their preparation via a process comprising the step of oxidizing a cellulose substrate.
  • DAC 2,3-dialdehyde cellulose
  • a suitable solvent e.g. organic solvents or ionic liquids
  • periodate in glycol cleavage reactions to selectively oxidize the vicinal hydroxyl groups in the C-2 and C-3 position of cellulose to the corresponding aldehydes with the concomitant cleavage of the C-2-C-3 bond, is one of the most potent methods for modification of cellulose (Perlin, Advances in Carbohydrate Chemistry and Biochemistry, Vol 60, pp. 183-250 (2006)).
  • the reaction allows for surface oxidation of cellulose to produce 2,3-dialdehyde cellulose (DAC), which has a number of interesting applications (for example in protein immobilization, chromatography, drug delivery and graft co-polymerization).
  • DAC 2,3-dialdehyde cellulose
  • this reaction does not produce cellulose beads; in particular, cellulose beads having high levels of homogenous oxidation.
  • periodate as a stoichiometric oxidizing agent has not been sustainable on an industrial scale due to the consumption of large quantities of periodate.
  • recent investigations have demonstrated the possibility of regenerating the periodate either electrochemically or by using low-cost chemical oxidants; thus making periodate oxidation a viable option even for large-scale applications.
  • cellulose beads may be prepared using a one- step, one-pot method utilizing oxidizing agents in water; thus eliminating the need to use organic solvents or ionic liquids to dissolve the cellulose, atomization equipment or surface-active dispersion aids for droplet formation, and/or coagulation solutions.
  • organic solvents or ionic liquids to dissolve the cellulose, atomization equipment or surface-active dispersion aids for droplet formation, and/or coagulation solutions.
  • a process for the preparation of cellulose beads comprising the step of reacting a cellulose substrate with an oxidant, which process may be referred to herein as the process of the invention.
  • reaction of the cellulose substrate with an oxidant may be performed in a solvent.
  • reaction may be performed in a polar solvent, which solvents are well known to those skilled in the art.
  • Particular polar solvents that may be employed in the reaction of the cellulose substrate with an oxidant include dimethyl sulfoxide (DMSO), acetone, ethyl acetate, acetonitrile, dimethyl formamide (DMF), ionic liquids, methanol, ethanol and water.
  • a process for the preparation of cellulose beads comprising the step of reacting a cellulose substrate with an oxidant in water.
  • reaction of the cellulose substrate with an oxidant in water may refer to oxidation of the cellulose substrate in the form of dispersion in water (i.e. an aqueous dispersion).
  • the process of the invention may be referred to as a process for the preparation of cellulose beads comprising the step of reacting a cellulose substrate with an oxidant, wherein the cellulose substrate is present as a dispersion in water.
  • the process of the invention may be referred to as a process for the preparation of cellulose beads comprising the step of reacting an aqueous dispersion of cellulose with an oxidant.
  • the process of the invention may consist essentially of steps (i) to (iii) as defined in the above-mentioned embodiments.
  • the process of the invention requires reaction of a cellulose substrate with an oxidant in water, which the skilled person will understand as indicating that water is used as a solvent (i.e. the reaction medium) for the reaction (i.e. the oxidation).
  • the process of the invention may be performed using water (e.g. deionized water) as the sole (i.e. only) solvent.
  • water e.g. deionized water
  • the process of the invention may be performed in water comprising one or more additional solvent (i.e. one or more solvent other than water).
  • the process of the invention may be performed in a solvent system (i.e. a mixture of solvents) comprising water and one or more additional solvent.
  • references herein to the solvent system as "water” may refer to a solvent consisting of only water, or to a solvent system comprising water as described herein, as the case may be.
  • Such additional solvents may include solvents that are capable of acting as radical scavengers (i.e. solvents capable of reacting with and thus deactivating radical species, such as oxygen radicals).
  • Particular additional solvents (i.e. radical scavengers) that may be mentioned include alcohols, including but not limited to propan-1-ol.
  • an oxidant i.e. an oxidizing agent
  • an agent capable of oxidizing a vicinal diol moiety i.e. a 1 ,2-dihydroxy moiety
  • aldehyde moieties i.e. through oxidation of the hydroxyl groups and cleavage of the associated carbon-carbon bond.
  • oxidants include:
  • lead (IV) acetate lead (IV) acetate
  • the skilled person will understand that periodic acid and salts thereof may be used as oxidizing agents in the transformation of vicinal diols to dialdehydes.
  • the actual oxidant is not typically the corresponding periodate (ICV). but rather para- or meta-periodate (H Rodl06 (5"n)" ).
  • the general term periodate may refer to all such oxoiodate species of heptavalent iodine, either neutral or deprotonated.
  • the oxidant i.e. the agent used for oxidizing the cellulose substrate
  • the oxidant i.e. the agent used for oxidizing the cellulose substrate
  • the oxidant is sodium metaperiodate.
  • the oxidant in order to achieve high levels of oxidation of the cellulose substrate the oxidant may be employed in a greater than stoichiometric amount in relation to the cellulose substrate. Thus, more than one equivalent of the oxidant may be employed relative to the amount of cellulose substrate.
  • the cellulose substrate is reacted with greater than one equivalent of oxidant (i.e. greater than one equivalent of oxidant relative to the amount of cellulose substrate).
  • the cellulose substrate may be reacted with up to about 5 equivalents of oxidant (such as about 2 to about 5 equivalents).
  • the process of the invention may also comprise regeneration of the oxidant by reaction with an additional oxidant (i.e. a different oxidant to that used for the oxidation of the cellulose substrate), which additional oxidant may be capable of oxidizing the reacted (i.e. reduced) derivative of the oxidant used for the oxidation of the cellulose substrate, which may have the effect of regenerating the oxidant used for the oxidation of the cellulose substrate.
  • an additional oxidant i.e. a different oxidant to that used for the oxidation of the cellulose substrate
  • an additional oxidant i.e. a different oxidant to that used for the oxidation of the cellulose substrate
  • the process of the invention may comprise the further steps of:
  • Particular additional oxidants include those capable of oxidizing the reacted (i.e. reduced) derivative of the oxidant used for the oxidation of the cellulose substrate (i.e. those capable of regenerating the oxidant).
  • the oxidant used in the process of the invention is a salt of periodic acid (such as sodium metaperiodate)
  • the oxidant may be regenerated by reaction with Oxone ® (potassium peroxymonosulfate) under conditions known to those skilled in the art (for example, as described in US patent number US 6,620,928, the contents of which are incorporated herein by reference).
  • the level of crystallinity of the cellulose in the cellulose beads obtained using the process of the invention may be controlled by adjusting the pH of the reaction (i.e. the pH of the solution used in the oxidation of the cellulose substrate). Typically, more acidic conditions will reduce the level of crystallinity obtained in the cellulose beads.
  • the pH of the reaction may be varied from slightly acidic (e.g. a pH of about 6) to strongly acidic (e.g. a pH of about 1), with less acidic conditions having a milder effect on the depression of the degree of cellulose crystallinity.
  • the reaction may be performed at a pH of less than about 6, such as less than about 4 (e.g. less than about 2, such as at a pH of from about 0 to about 2).
  • the step of oxidizing the cellulose substrate i.e. reacting the cellulose substrate with an oxidant
  • a pH of about 4 to about 6 such as a pH of about 4.5 to about 5.5, e.g. at a pH of about 4.5 or about 5.5).
  • the pH of the dispersion may be adjusted and/or maintained through the addition of a buffering agent, which may be added in the form of a buffering solution (e.g. an aqueous solution of a buffering agent).
  • a buffering solution e.g. an aqueous solution of a buffering agent.
  • the process is optionally performed in the presence of a buffering agent (which may be referred to as a buffering solution or simply as a buffer).
  • the solution of the cellulose substrate is buffered at a pH of about 4 to about 6 (such as a pH of about 4.5 to about 5.5, e.g. at a pH of about 4.5 or about 5.5).
  • buffering agents and corresponding buffering solutions
  • Such buffering agents will be known to those skilled in the art and may be selected based on the pH required; for example, a solution buffered at a pH of around 4.5 or around 5.5 may be obtained through addition of a suitable amount of an acetate buffer.
  • the process of the invention requires reacting a cellulose substrate with an oxidant in water.
  • references to a cellulose substrate herein are intended to refer to the cellulose being reacted (with an oxidant).
  • the process of the invention is particularly effective in achieving high levels of oxidation when using a cellulose substrate having a high degree of crystallinity.
  • the process of the invention is also particularly effective when performed using native cellulose.
  • the cellulose substrate is cellulose (e.g. native cellulose) having a high degree of crystallinity (i.e. highly crystalline cellulose, such as highly crystalline native cellulose).
  • the reference to highly crystalline cellulose may be refer to cellulose (e.g. native cellulose) having a degree of crystallinity of at least 60%, such as at least 70% (e.g. at least 80%), which may be measured with X-ray diffraction (XRD).
  • cellulose e.g. native cellulose
  • XRD X-ray diffraction
  • the cellulose substrate is native cellulose having a degree of crystallinity of at least 90%.
  • Examples of highly crystalline (native) cellulose that may be used as the cellulose substrate include:
  • algae cellulose such as cellulose from macroscopic green algae (e.g. those from Cladophorales, including but not limited to Cladophora, Chaetomorpha, Rhizoclonium, Mycrodyction, Siphonocladales, including but not limited to Valonia, Dictyospheria, and Siphonocladus orders), microscopic/planktonic algae (e.g. those from Glaucocystales, including but not limited to Glaucocystis, or Chlorelalles, including but not limited to Oocystis order);
  • macroscopic green algae e.g. those from Cladophorales, including but not limited to Cladophora, Chaetomorpha, Rhizoclonium, Mycrodyction, Siphonocladales, including but not limited to Valonia, Dictyospheria, and Siphonocladus orders
  • microscopic/planktonic algae e.g. those from Glaucocystales
  • bacterial cellulose including but not limited to cellulose from Acetobacter, Agrobacterium, and Sarcina;
  • cellulose derived from aquatic animals e.g. tunnicates, such as Halocynthia.
  • the cellulose substrate is Cladophora cellulose.
  • the cellulose substrate may consist of a mixture of one or more type of cellulose (such as one or more highly crystalline cellulose).
  • the cellulose substrate comprises a single type of cellulose (e.g. a single type of highly crystalline cellulose, such as Cladophora cellulose).
  • the process of the invention (in particular, the process defined in embodiments relating to steps (i) to (iii)) may be performed in a single reaction vessel, which may be referred to as a one pot process.
  • the process of the invention is performed as a one pot process.
  • the process of the invention comprises the step of reacting a cellulose substrate with an oxidant, which may be referred to as the oxidation reaction.
  • the oxidation reaction may be controlled (i.e. to achieve the required level of oxidation) by adjusting the conditions employed (such as the temperature and/or duration of the reaction). Such variation of conditions may be employed in order to achieve levels of oxidation of up to 100%.
  • the step of reacting the cellulose substrate with an oxidant e.g. step (ii) or (iia) as defined in embodiments referred to above
  • references to performing a process i.e. the relevant process step
  • room temperature will refer to performing the process without heating or cooling processes, thus resulting in the reaction being performed at ambient temperature (typically about 18 to about 22 °C, such as at about 20 °C).
  • the period of time for which the reaction between the cellulose substrate and the oxidant is maintained may be varied, for example, in order to achieve the required level of oxidation.
  • the step of reacting the cellulose substrate with an oxidant e.g. step (ii) or (iia) as defined in embodiments referred to above
  • the step of reacting the cellulose substrate with an oxidant e.g.
  • step (ii) or (iia) as defined in embodiments referred to above) may be performed for a period of at least 240 hours (for example, for a period of from about 240 hours to about 500 hours, e.g. for about 240 hours).
  • the step of reacting the cellulose substrate with an oxidant e.g. step (ii) or (iia) as defined in embodiments referred to above
  • reaction of the cellulose substrate may be terminated using techniques known to those skilled in the art, such as by quenching of the oxidant (i.e. as described in step (iib) of the embodiment referred to above).
  • references to quenching of the oxidant will be understood to refer to reaction of any unreacted oxidant (e.g. oxidant that remains unreacted following the step of reacting the cellulose substrate with an oxidant) such that the oxidant is no longer reactive (i.e. is no longer capable of oxidation).
  • the process of the invention comprises the step of quenching the oxidant.
  • the process of the invention may comprise the step of adding a quenching agent to the solution (i.e. following the step of reacting the cellulose substrate with an oxidant).
  • the process of the invention comprises the step of terminating the reaction between the cellulose substrate and the oxidant by quenching of the oxidant.
  • quenching agents examples include compounds having vicinal alcohols, vicinal amines, or a combination thereof (e.g. 1-hydroxy-2-amino compounds, and the like). More particular quenching agents that may be mentioned include ethylene glycol.
  • the process of the invention may comprise the step of quenching the oxidant through the addition of ethylene glycol.
  • the process of the invention results in the production of cellulose beads. Therefore, the process of the invention may comprise (i.e. as a final step) the recovery of those beads. In a particular embodiment, the process of the invention may comprise the step of recovering the cellulose beads (i.e. the cellulose beads formed by the process of the invention).
  • the process of the invention may comprise the step of removing the cellulose beads from the dispersion, and optionally washing the recovered beads (e.g. with water).
  • step (iii) may comprise (or consist of) removing the cellulose beads from the solution, and optionally washing the recovered beads (e.g. with water).
  • the process of the invention is a process for preparing cellulose beads, which process comprises oxidation of a cellulose substrate.
  • the process of the invention comprises oxidation of vicinal diol moieties (i.e. a 1 ,2-dihydroxy moieties) in the cellulose substrate to form corresponding aldehyde moieties (i.e. through oxidation of the hydroxyl groups and cleavage of the associated carbon-carbon bond), which reaction may be referred to herein as oxidation of the cellulose substrate.
  • the vicinal alcohols oxidized in the process of the invention may be those in the C-2 and C-3 positions of the cellulose substrate.
  • the process of the invention may result in the formation of cellulose beads comprising 2,3-dialdehyde cellulose.
  • the process of the invention may be referred to as a process for preparing 2,3-dialdehyde cellulose (DAC) beads.
  • DAC 2,3-dialdehyde cellulose
  • the process of the invention may be referred to as a process for preparing 2,3-dialdehyde cellulose (DAC) beads via oxidation of secondary alcohols in a cellulose substrate. More particularly, the process of the invention may be referred to as a process for preparing 2,3-dialdehyde cellulose (DAC) beads via oxidation of secondary alcohols in the C-2 and C-3 positions in a cellulose substrate with concomitant cleavage of the C-2 to C-3 bond.
  • the cellulose (i.e. DAC) beads obtained using the process of the invention may have a degree of oxidation of at least 60% (i.e. 60-100%).
  • the cellulose (i.e. DAC) beads obtained using the process of the invention may have a degree of oxidation of at least 80% (i.e. 80-100%).
  • the degree of oxidation in the resulting cellulose beads may be controlled by varying the conditions employed in the reaction of the cellulose substrate with the oxidant.
  • the skilled person will understand that the degree of oxidation may be monitored during the reaction using techniques known to those skilled in the art, such as by taking samples (i.e. aliquots) during the reaction and analysis of the aldehyde content of the cellulose contained therein (e.g. by formation of a corresponding Schiff base and elemental analysis thereof).
  • the process of the invention may produce cellulose (i.e. DAC) beads that are homogenously oxidized.
  • the cellulose (i.e. DAC) beads obtained using the process of the invention may possess at least 80% (e.g. 80 to 100%) homogenous oxidation.
  • references to the cellulose beads being homogenously oxidized will be understood to refer to those oxidation of the cellulose (i.e. the formation of dialdehyde moieties) being evenly distributed throughout each resulting cellulose bead (or a majority thereof).
  • the process of the invention may be referred to as a process for preparing homogenously oxidised 2,3-dialdehyde cellulose (DAC) beads via oxidation of secondary alcohols in the C-2 and C-3 positions in a cellulose substrate with concomitant cleavage of the C-2 to C-3 bond.
  • DAC homogenously oxidised 2,3-dialdehyde cellulose
  • the process of the invention may produce cellulose (i.e. DAC) beads that have a homogenously oxidized core, optionally with additional oxidation at the surface (i.e. the surface of the bead).
  • cellulose i.e. DAC
  • the process of the invention may produce cellulose (i.e. DAC) beads that are substantially spherical.
  • the cellulose (i.e. DAC) beads obtained using the process of the invention may be spherical and/or have an average particle size ranging between 0.01 and 100 micron.
  • the process of the invention (in particular, the oxidation reaction, e.g. as described in step (ii) or step (iia) in the embodiments defined above) may comprise stirring of the reaction (for example, stirring using a paddle or a magnetic stirring device).
  • the particle size of the cellulose beads obtained using the process of the invention can be controlled by adjusting the intensity of stirring during (or immediately after) the reaction of the cellulose substrate with an oxidant.
  • the process of the invention may allow for the preparation of cellulose beads having varying degrees of porosity.
  • the process of the invention may be referred to as a process for preparing non-porous 2,3-dialdehyde cellulose (DAC) beads.
  • the process of the invention may be referred to as a process for preparing non-porous, homogenously oxidised 2,3-dialdehyde cellulose (DAC) beads via oxidation of secondary alcohols in the C-2 and C-3 positions in a cellulose substrate with concomitant cleavage of the C-2 to C- 3 bond.
  • porous bead will depend on the accessibility of a given medium to the core of the said material.
  • references to non-porous beads will refer to beads whose core is not accessible to gas molecules, such as inert gas molecules, e.g. air, nitrogen, krypton, argon, or helium, although still accessible to water or other polar molecules.
  • references to porous beads will refer to beads that allow such permeation.
  • Non-porous beads will show no or little difference in the bulk porosity, i.e. mass-to- volume ratio, derived from geometrical dimensions and that by using gas permeametry, i.e. so called true density.
  • such non-porous cellulose beads will also show a specific surface area ⁇ 1 m 2 g _1 measured using nitrogen gas according to the standard Brunauer-Emmett-Teller (BET) method.
  • BET Brunauer-Emmett-Teller
  • porous beads will show bulk density values, which are substantially smaller than the true density values derived from gas permeametry.
  • porous cellulose beads will typically feature a specific surface area > 1 m 2 g _1 measured using nitrogen gas according to the standard Brunauer-Emmett-Teller (BET) method.
  • BET Brunauer-Emmett-Teller
  • cellulose beads obtainable from (or obtained from) the process of the invention (i.e. the process as described in the first aspect of the invention, or any one or more embodiments thereof).
  • 2,3-dialdehyde cellulose (DAC) beads obtainable from (or obtained from) the process of the invention (or any one or more embodiments thereof).
  • 2,3-dialdehyde cellulose (DAC) beads obtainable from (or obtained from) the process of the invention (or any one or more embodiments thereof), wherein the cellulose beads have a degree of oxidation of at least 80% (i.e. 80 to 100%).
  • DAC 2,3-dialdehyde cellulose
  • the 2,3-dialdehyde cellulose (DAC) beads may have a degree of oxidation of at least 80% (i.e. 80-100%). In a more particular embodiment of the third aspect of the invention, the 2,3-dialdehyde cellulose (DAC) beads may have a degree of homogenous oxidation of at least 80% (i.e. 80-100%).
  • the 2,3-dialdehyde cellulose (DAC) beads may be substantially spherical.
  • the 2,3-dialdehyde cellulose (DAC) beads may be substantially spherical and/or have an average particle size ranging between 0.01 and 100 micron.
  • the 2,3-dialdehyde cellulose (DAC) beads may have a degree of homogenous oxidation of at least 80% (i.e. 80-100%) and be substantially spherical having an average particle size ranging between 0.01 and 100 micron
  • the cellulose beads obtained using the process of the invention may derivatized, for example, in order to produce porous cellulose beads.
  • the cellulose beads produced may be described as being porous cellulose beads.
  • the beads used in step (iv) of the process described above are not dried prior to use in step (iv).
  • step (iv) may be referred to as derivatizing never-dried cellulose beads.
  • the process of the fourth aspect of the invention (in particular, comprising steps (a) and (b) as defined above) may be performed as a one pot process.
  • a process for preparing cellulose (e.g. DAC) beads comprising the step of reacting a cellulose bead as defined in the second or third aspect of the invention (including any one or more embodiments thereof) with an agent capable of derivatizing said beads.
  • the cellulose beads produced may be described as being porous cellulose beads.
  • the step of derivatizing the cellulose beads may comprise reacting the cellulose beads with one or more aldehyde protecting agent.
  • aldehyde protecting agents include agents capable of reacting with aldehyde moieties to form a Schiff base (e.g. an imine or a hydroxyimine), such as an agent selected from the group consisting of 1 ,2-diaminoethane, 1 ,3- diaminopropane, 1 ,4-diaminobutane, 1 ,5-diaminopentane, 1 ,6-diaminohexane, 1 ,7- diaminoheptane, aniline, 1 ,10-phenanthrolin-5-amine, 3-(amino methyl)pyridine, tryptophan and hydroxylamine.
  • a Schiff base e.g. an imine or a hydroxyimine
  • the step of derivatizing the cellulose beads may comprise reacting the cellulose beads with one or more amine in a reductive amination reaction.
  • Said reductive amination reactions can be performed using techniques that are well known to those skilled in the art; for example, by reaction of the aldehyde with a suitable (e.g. primary) amine (i.e. to form an imine moiety) followed by reduction using a suitable reducing agent (e.g. sodium borohydride).
  • Particular amines that may be used in reductive amination reactions include 1 ,2- diaminoethane, 1 ,3-diaminopropane, 1 ,4-diaminobutane, 1 ,5-diaminopentane, 1 ,6- diaminohexane, 1 ,7-diaminoheptane, bis-(4-diaminophenyl) ether aniline, o- phenylenediamine, m-phenylenediamine, p-phenylenediamine, 1 ,10-phenanthrolin-5- amine, 3-(amino methyl)pyridine, tryptophan, cysteine and hydroxylamine.
  • cellulose e.g. DAC
  • hydroxylamines e.g. to form a Schiff base
  • AFM atomic force microscopy
  • the step of derivatizing the cellulose beads may comprise reacting the cellulose beads with other agents capable of reacting with the aldehyde moieties in said beads (i.e. DAC beads), such as nucleophiles selected from the group consisting of oxygen nucleophiles (e.g. for hemiacetal and/or acetal formation), nitrogen nucleophiles (e.g. for oxime or hydrazine formation), carbon nucleophiles (e.g. for cyanohydrin formation), bisulfite nucleophiles (e.g. for sulfonate formation) and thiol nucleophiles (e.g. for thioester formation).
  • nucleophiles selected from the group consisting of oxygen nucleophiles (e.g. for hemiacetal and/or acetal formation), nitrogen nucleophiles (e.g. for oxime or hydrazine formation), carbon nucleophiles (e.g. for cyanohydrin
  • Such reactions of the aldehyde groups with nucleophiles may be used to attach functional groups to the cellulose beads (i.e. functional groups bound to the reacting nucleophile).
  • the type of the functional group attached to the said DAC beads will have a direct effect on the utility of the beads. Therefore, moieties having a direct biological and/or chemical function (such as those of amino acids, peptides, glycoproteins, lipoproteins, nucleosides, DNA, RNA, porphirines and/or metal chelating ligands) are particularly useful.
  • the step of derivatizing the cellulose beads may comprise oxidizing the aldehyde groups to the corresponding carboxyl or carboxylate groups.
  • oxidation of such aldehyde groups can be performed using techniques (i.e. reagents and conditions) well known to those skilled in the art.
  • Porous cellulose beads may also be prepared by a process involving exchanging the solvent used in the process of the invention for one or more other solvent, which step may be performed more than once.
  • step (b) or, in particular embodiments, step (iv) is replaced with the step of:
  • the step of polar-to-non-polar solvent exchange may consist of:
  • a water-miscible (polar) solvent such as ethanol, methanol, acetone, acetonitrile or ethylacetate
  • a volatile water-immiscible solvent such as diethyl ether, pentane, hexane, benzene, or chloroform
  • a variety of a polar-to-non-polar solvent exchanges may also include a so-called critical point drying using liquid carbon dioxide.
  • the solvent exchange step may be followed by the step of recovering the porous cellulose beads, as described herein.
  • the step of recovering the porous cellulose beads may be followed by drying of the beads.
  • the (or each) step of exchanging the solvent may be performed without prior drying of the cellulose beads.
  • the step of exchanging the solvent (and the optionally repeated steps) may be performed on never-dried cellulose (e.g. DAC) beads.
  • cellulose beads obtainable from (or obtained from) a process as described in the fourth or fifth aspects of the invention (or any one or more embodiments thereof).
  • cellulose (e.g. DAC) beads obtainable (or obtained) using a process as defined in the first aspect of the invention (including any one or more embodiments thereof), or as defined in the second or third aspect of the invention (including any one or more embodiments thereof) have numerous uses, for example, in chemical processes and therapeutic applications (i.e. in medicine, such as in biomedical, pharmaceutical, and extracorporeal blood treatment applications).
  • cellulose e.g. DAC
  • a seventh aspect of the invention there is provided the use of cellulose (e.g. DAC) beads obtainable (or obtained) using a process as defined in the first, fourth or fifth aspects of the invention (including any one or more embodiments thereof), or as defined in the second, third or sixth aspects of the invention (including any one or more embodiments thereof) in:
  • cellulose e.g. DAC
  • a process as defined in the first aspect of the invention including any one or more embodiments thereof, or as defined in the second or third aspect of the invention (including any one or more embodiments thereof),
  • the beads have an average particle size of less than 1 micron (e.g. ranging between 0.01 and 1 micron,
  • the bead forming ability of these types of cellulose is related both to reduced stiffness of the elementary fibrils and increased surface hydrophobicity due to the augmented aldehyde content.
  • the transition to the characteristic spherical bead shape is achieved at a degree of cellulose oxidation above 60%, and more preferably above 75% (e.g. above 80%), while the corresponding degree of crystallinity can greatly vary dependi. g on the employed pH.
  • the present invention may have the advantage that it allows for a one-step method of dialdehyde cellulose (DAC) beads preparation via oxidation of the vicinal alcohols in water without the use of organic dissolving solvents; atomizing equipment or surface- active additives for droplet formation; or coagulation solutions for solidification.
  • DAC dialdehyde cellulose
  • the disclosed one-pot procedure for DAC bead preparation in water has several benefits compared to the traditional methods of cellulose bead preparation as it does not require organic solvents or ionic liquids to dissolve cellulose; avoids the use of regenerating coagulant solutions and surfactants or other surface active dispersion aids; and does not employ spraying, atomization or any other droplet forming equipment, thereby significantly facilitating large-scale production.
  • the produced beads have a degree of oxidation of 60-100% suggesting a multitude of possibilities for further modifications by utilizing the attractive aldehyde groups to provide the desired functionalized beads with high functional group density.
  • Figure 1 shows SEM micrographs of DAC beads prepared from Cladophora cellulose according to Example 3
  • A DAC beads prepared from bacterial cellulose according to Example 9
  • B Schiff base coupled with hydroxyl amine according to Example 10
  • C Schiff base coupled with 1 ,7-diaminoheptane according to Example 13 (D).
  • Figure 2 shows a solid-state 13 C NMR spectrum of periodate oxidized Cladophora DAC (240 h) which is in agreement with previously reported DAC NMR spectra.
  • Example 1 Preparation of DAC beads under unbuffered conditions
  • Cladophora cellulose 12 g in 900 mL of deionized water was mixed with 79 g sodium metaperiodate (about 5 mol per mol of anhydroglucose units) dissolved in 900 mL deionized water. The periodate-containing reaction mixture was carefully wrapped in aluminum foil to avoid light and 100 mL of 1-propanol was added to the reaction mixture to serve as a radical scavenger. (Painter, Carbohydrate Research, Vol. 179 pp. 259-268 (1988)) The reaction mixture was vigorously stirred at room temperature in the dark for 10 days. Aliquots were withdrawn after 24, 48, 72, 96, 168 and 240 h (300 mL each time).
  • Cladophora cellulose 12 g in 900 mL of acetate buffer pH 4.5 was mixed with 79 g sodium metaperiodate (about 5 mol per mol of anhydroglucose units) dissolved in 900 mL acetate buffer pH 4.5.
  • the periodate-containing reaction mixture was carefully wrapped in aluminum foil to avoid light and 100 mL of 1-propanol was added to the reaction mixture to serve as a radical scavenger.
  • the reaction mixture was vigorously stirred at room temperature in the dark for 10 days. Aliquots were withdrawn after 24, 48, 72, 96, 168 and 240 h (300 mL each time).
  • Example 3 Preparation of DAC beads at pH 5.5
  • Cladophora cellulose 12 g in 900 mL of acetate buffer pH 5.5 was mixed with 79 g sodium metaperiodate (about 5 mol per mol of anhydroglucose units) dissolved in 900 mL acetate buffer pH 5.5.
  • the periodate-containing reaction mixture was carefully wrapped in aluminum foil to avoid light and 100 mL of 1-propanol was added to the reaction mixture to serve as a radical scavenger.
  • the reaction mixture was vigorously stirred at room temperature in the dark for 10 days. Aliquots were withdrawn after 24, 48, 72, 96, 168 and 240 h (300 mL each time).
  • Cladophora cellulose 4 g in 200 mL of acetate buffer (pH 5.5) was mixed with 26.4 g sodium metaperiodate dissolved in 400 mL acetate buffer (pH 5.5). The periodate containing solution was carefully kept wrapped in aluminum foil to avoid light. The mixture was stirred at 20 °C in the dark for 10 days. The reaction mixture was divided in 4 aliquotes (150 mL each). For aliquote 1 : any excess periodate was quenched by addition of 20 mL glycerine (added under stirring and stirred for 3 h at rt). After the excess periodate was decomposed, the product was washed by centrifugation using H2O x 6.
  • Cladophora cellulose 3 g in 300 mL of deionized water was mixed with 20 g sodium metaperiodate (about 5 mol per mol of anhydroglucose units) dissolved in 300 mL deionized water. The periodate-containing reaction mixture was carefully wrapped in aluminum foil to avoid light. The reaction mixture was shaken by an orbital shaker at room temperature in the dark for 10 days. The reaction mixture was quenched via the addition of ethylene glycol and washed repeatedly with water to provide pure bead- shaped DAC material.
  • Cladophora cellulose 2 g in 100 mL of deionized water was mixed with 13.2 g sodium metaperiodate (about 5 mol per mol of anhydroglucose units) dissolved in 100 mL deionized water. The periodate-containing reaction mixture was carefully wrapped in aluminum foil to avoid light. The reaction mixture was vigorously stirred at room temperature in the dark for 10 days. The product of the reaction yielded beads.
  • Example 7 Preparation of DAC beads using bacterial cellulose
  • Example 8 Reductive amination of amines
  • the DAC beads prepared in Example 1 were reacted with each of 1 ,2-diaminoethane, 1 ,3-diaminopropane, 1 ,4-diaminobutane, 1 ,5-diaminopentane, 1 ,6-diaminohexane, 1 ,7- diaminoheptane, bis-(4-diaminophenyl) ether aniline, o-phenylenediamine, m- phenylenediamine, p-phenylenediamine, 1 , 10-phenanthrolin-5-amine, 3-(amino methyl)pyridine, tryptophan, cysteine and hydroxylamine according to the following general procedure: To a stirred 100 mL RB-flask was added never dried DAC (corresponding to a dry weight of 100 mg), 40 mL buffer and amine.
  • Example 9 Preparation of sulfonated DAC beads To a stirred 250 mL RB-flask was added never dried DAC from Example 1 (corresponding to a dry weight of 2 g), and 100 mL 0.5 M sodium bisulfite solution. The reaction mixture was stirred at room temperature for 24 h. The product was washed by centrifugation using EtOH x 6.
  • Example 10 Preparation of thioester DAC beads
  • Example 1 1 - Preparation of porous DAC beads
  • the DAC beads prepared in Example 1 were reacted with 1 ,7-diaminoheptane, according to the following procedure: To a stirred 100 mL RB-flask was added never dried DAC (corresponding to a dry weight of 100 mg), 40 mL buffer and 40 mg 1 ,7- diaminoheptane. The reaction mixture was stirred at room temperature for 24 h. The product was washed by centrifugation using H 2 0 x 6. The resulting imine product was treated with sodium borohydride (1.2 equiv.) and reduction was performed during 2 h.
  • sodium borohydride 1.2 equiv.
  • Figure 1 D shows a SEM micrograph of the 1 ,7-diaminoheptane coupled DAC beads.
  • the diamino coupled DAC beads were stable in alkaline solution (1 M NaOH).
  • Example 12 Preparation of DAC beads at pH 5.5 with regeneration of periodate
  • Cladophora cellulose 20 g in 1000 mL of acetate buffer pH 5.5 was mixed with 132 g sodium metaperiodate (about 5 mol per mol of anhydroglucose units) dissolved in 1000 mL acetate buffer pH 5.5.
  • the periodate-containing reaction mixture was carefully wrapped in aluminum foil to avoid light and 200 mL of 1-propanol was added to the reaction mixture to serve as a radical scavenger.
  • the reaction mixture was vigorously stirred at room temperature in the dark for 10 days.
  • the product was carefully washed with water and the liquid content was collected and reduced to a volume of 1 L via rotary evaporation.
  • To the liquid mixture was added 195 g Oxone in the course of 3 h.
  • the pH was controlled at 6-7 via the addition of sodium hydroxide solution. During the reaction a white precipitate was formed, which was filtered off and identified as periodate.
  • Example 13 Preparation of DAC beads with 1 equiv. of sodium metaperiodate
  • sodium metaperiodate 10.7 g in 100 mL H 2 0 was added Cladophora cellulose, 8.1 g (about 1 mol periodate per mol of anhydroglucose units).
  • the periodate- containing reaction mixture was carefully wrapped in aluminum foil to avoid light.
  • the reaction mixture was vigorously stirred at room temperature in the dark for 10 days.
  • the reaction mixture was quenched via the addition of ethylene glycol and washed repeatedly with water to provide pure bead-shaped DAC material.
  • Example 14 DAC beads functionalized with quaternary ammonium alkylamine
  • the DAC beads prepared in Example 1 were reacted with 1 ,7-diaminoheptane, according to the following procedure: To a stirred 100 mL RB-flask was added never dried DAC (corresponding to a dry weight of 100 mg), 40 mL buffer and 20 mg 1 ,7- diaminoheptane. The reaction mixture was stirred at room temperature for 24 h. The product was washed by centrifugation using H2O x 6. The resulting product was dispersed in 40 mL buffer solution and 100 mg (2-Aminoethyl)trimethylammonium chloride hydrochloride was added. The reaction mixture was stirred at room temperature for 24 h.
  • the DAC beads prepared in Example 1 were reacted with 1 ,7-diaminoheptane, according to the following procedure: To a stirred 100 mL RB-flask was added never dried DAC (corresponding to a dry weight of 100 mg), 40 mL buffer and 20 mg 1 ,7- diaminoheptane. The reaction mixture was stirred at room temperature for 24 h. The product was washed by centrifugation using H 2 0 x 6. The resulting product was dispersed in 40 mL buffer solution and 85 mg 3-Amino-1 -propanesulfonic acid was added. The reaction mixture was stirred at room temperature for 24 h. The product was washed by centrifugation using H 2 0 x 6. The resulting imine product was treated with sodium borohydride (1.2 equiv.) and reduction was performed during 2 h. The crude product was washed by centrifugation using H 2 0 x 6 and EtOH x 2 and dried in air.
  • Example 16 Determination of aldehyde content
  • the DAC samples were transformed to oximes via Schiff base reactions with hydroxylamine according to literature procedure (Kim et al., Biomacromolecules, Vol. 1 pp. 488-492 (2000)) and analyzed for elemental composition (C, H and N) according to the following procedure.
  • To a stirred 100 mL RB-flask was added never dried DAC (corresponding to a dry weight of 100 mg), 40 mL acetate buffer (pH 4.5) and 1.65 mL hydroxylamine solution (ag. 50 wt%) was added.
  • the reaction mixture was stirred at room temperature for 24 h.
  • the product was thoroughly washed with water and dried under reduced pressure prior to elemental analysis.
  • degree of oxidation represents the ratio of 2,3-alcohols in the anhydroglucose units that has been transformed into their corresponding aldehydes.
  • the highest degree of oxidation viz. 100%, corresponds to all anhydroglucose units being converted to the corresponding non-cyclic 2,3-dialdehyde structure, which would correspond to approximately 2.5 mmol of aldehyde groups per gram of cellulose.

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Abstract

L'invention concerne un procédé pour la préparation de billes de cellulose comprenant l'étape consistant à faire réagir un substrat en cellulose avec un agent oxydant.
PCT/GB2014/053855 2013-12-30 2014-12-30 Procédé pour la préparation de billes de cellulose par réaction d'un substrat en cellulose avec un agent oxydant WO2015101786A1 (fr)

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CN105231252A (zh) * 2015-08-30 2016-01-13 陈爱梅 一种天然的食品用干燥剂的制备方法
CN105483179A (zh) * 2015-12-31 2016-04-13 陕西科技大学 一种孔径可控的细菌纤维素多孔微球的制备方法
SE1751540A1 (en) * 2017-12-13 2019-06-14 Stora Enso Oyj A method for manufacturing a film from microfibrillated dialdehyde cellulose and microfibrillated cellulose
CN111393682A (zh) * 2020-04-17 2020-07-10 华南理工大学 一种动态共价交联的纤维素基生物塑料、木塑复合材料及其制备方法与应用
KR20210111831A (ko) * 2019-01-25 2021-09-13 누리온 케미칼즈 인터내셔널 비.브이. 디알코올 셀룰로스계 구형 캡슐

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CN105231252A (zh) * 2015-08-30 2016-01-13 陈爱梅 一种天然的食品用干燥剂的制备方法
CN105231252B (zh) * 2015-08-30 2019-04-26 陈爱梅 一种天然的食品用干燥剂的制备方法
CN105483179A (zh) * 2015-12-31 2016-04-13 陕西科技大学 一种孔径可控的细菌纤维素多孔微球的制备方法
SE1751540A1 (en) * 2017-12-13 2019-06-14 Stora Enso Oyj A method for manufacturing a film from microfibrillated dialdehyde cellulose and microfibrillated cellulose
KR20210111831A (ko) * 2019-01-25 2021-09-13 누리온 케미칼즈 인터내셔널 비.브이. 디알코올 셀룰로스계 구형 캡슐
JP2022518775A (ja) * 2019-01-25 2022-03-16 ヌーリオン ケミカルズ インターナショナル ベスローテン フェノーツハップ ジアルコールセルロース系球状カプセル
KR102659108B1 (ko) * 2019-01-25 2024-04-18 누리온 케미칼즈 인터내셔널 비.브이. 디알코올 셀룰로스계 구형 캡슐
CN111393682A (zh) * 2020-04-17 2020-07-10 华南理工大学 一种动态共价交联的纤维素基生物塑料、木塑复合材料及其制备方法与应用

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