Modified hyaluronic acid as dopant for PEDOT and/or PProDOT polymers
AssigneesCommissariat A L'energie Atomique Et Aux Energies Alternatives, Centre National De La Recherche Scientifique, Universite Grenoble Alpes
InventorsMaxime Leprince, Rachel Auzely, Isabelle Texier-Nogues
Life of this patent
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Abstract
A polymer of hyaluronic acid modified by the grafting thereto of at least one of the functions —SO3− and aromatic rings may be used as dopant for a polymer formed from one or monomers chosen from EDOT, ProDOT, and derivatives thereof. An aqueous suspension, or ink, and materials, in particular hydrogels, based on at least one PEDOT and/or PProDOT polymer may be doped by at least one such modified hyaluronic acid polymer. Such modified hyaluronic acid polymers may be used in bioelectronic or biosensor devices.
Claims24
A method of doping a first polymer, the method comprising:
- doping the first polymer with a modified hyaluronic acid polymer, which is modified by grafting onto a hyaluronic acid polymer at least —SO3− functions and aromatic rings,
- wherein the first polymer comprises, in reacted form, 3,4-ethylenedioxythiophene (EDOT),
- wherein the modified hyaluronic acid polymer has
- an average number of SO3− functions per repeat unit of hyaluronic acid of 4, and
- an average number of aromatic rings per repeat unit of the hyaluronic acid of 0.3, and
- wherein the aromatic ring results from the grafting of aminophenylboronic acid with a carboxylic acid function of the hyaluronic acid.
A method for preparing a hydrogel, the method comprising:
- (a-i) submitting an aqueous suspension, optionally as an ink, to conditions that are favorable for the crosslinking of chains of modified hyaluronic acid to form a hydrogel swollen in an aqueous medium;
- and, optionally,
- (a-ii) submitting the hydrogel swollen in an aqueous medium to a drying, to obtain a dry hydrogel,
- or
- (b-i) polymerizing 3,4-ethylenedioxythiophene (EDOT), 3,4-propylenedioxythiophene (ProDOT), and/or a derivative thereof, in a hydrogel swollen in an aqueous medium;
- and, optionally
- (b-ii) submitting the hydrogel obtained after the polymerizing (b-i) to a drying, to obtain a dry hydrogel,
- or
- (c-i) subjecting an aqueous suspension to conditions that are favorable for polymerizing the EDOT, ProDOT, and/or derivative and for crosslinking of chains of modified hyaluronic acid to form the hydrogel swollen in an aqueous medium;
- and optionally
- (c-ii) submitting the hydrogel obtained after the subjecting (c-i) to a drying to obtain a dry hydrogel,
- wherein the aqueous suspension comprises a first polymer comprising, in polymerized form, EDOT, ProDOT, and/or a derivative thereof, and, as a dopant, a modified hyaluronic acid polymer comprising crosslinkable function and/or a free carboxylic acid function,
- wherein the modified hyaluronic acid polymer is modified by grafting onto a hyaluronic acid polymer at least SO3− functions and aromatic rings, and
- wherein the hydrogel is formed from the first polymer.
A method of doping a first polymer, the method comprising:
- doping the first polymer with a modified hyaluronic acid polymer, which is modified by grafting onto a hyaluronic acid polymer at least —SO3− functions and aromatic rings,
- wherein the first polymer comprises, in reacted form, 3,4-ethylenedioxythiophene (EDOT), 3,4-propylenedioxythiophene (ProDOT) and/or a derivative thereof, and
- wherein the modified hyaluronic acid polymer further comprises a crosslinkable function.
An aqueous suspension, called ink, comprising:
- a polymer comprising, in polymerized form, 3,4-ethylenedioxythiophene (EDOT),
- wherein the polymer is doped with at least one modified hyaluronic acid polymer, which is modified by grafting onto a hyaluronic acid polymer at least —SO3− functions and aromatic rings,
- wherein the modified hyaluronic acid polymer has
- an average number of SO3− functions per repeat unit of hyaluronic acid of 4, and
- an average number of aromatic rings per repeat unit of the hyaluronic acid of 0.3, and
- wherein the aromatic ring results from the grafting of aminophenylboronic acid with a carboxylic acid function of the hyaluronic acid.
A method of doping a first polymer, the method comprising:
- doping the first polymer with a modified hyaluronic acid polymer, which is modified by grafting onto a hyaluronic acid polymer at least —SO3− functions and aromatic rings,
- wherein the first polymer comprises, in reacted form, 3,4-ethylenedioxythiophene (EDOT), 3,4-propylenedioxythiophene (ProDOT) and/or a derivative thereof,
- wherein the modified hyaluronic acid polymer has formula (I):
- wherein
- n is degree of polymerization of the hyaluronic acid polymer,
- R is independently H or a group —SO3−C+, C+ being a counterion of the —SO3−;
- anion,
- R optionally differing from one repeat unit to another, provided that at least some of the groups R are —SO3−C+,
- R′, independently from one repeat unit to another, are:
- O−C+, C+ being a counterion of the O− anion,
- a group bearing an aromatic ring and optionally at least one crosslinkable function, and
- a group bearing at least one crosslinkable function,
- provided that at least some of the R′ are groups bearing an aromatic ring.
Dependencies are inferred from the claim text.