Water-soluble chitosan derivatives and pH-responsive hydrogels by selective C-6 oxidation mediated by TEMPO-laccase redox system

Suse Botelho da Silva*, Malgorzata Krolicka, Lambertus A.M. van den Broek, August E. Frissen, Carmen Gabriela Boeriu

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

17 Citations (Scopus)

Abstract

Chitosan is a polysaccharide with recognized antioxidant, antimicrobial and wound healing activities. However, this polymer is soluble only in dilute acidic solutions, which restricts much of its applications. A usual strategy for improving the functionality of polysaccharides is the selective oxidation mediated by 2,2,6,6-tetra-methyl-1-piperidinidyloxy (TEMPO) using laccase as a co-oxidant. In this work, the TEMPO-laccase redox system was used for the first time to selectively oxidize chitosan in order to produce tailored derivatives. The reaction was performed at pH 4.5 under continuous air supply and the oxidized products were characterized structurally and functionally. The TEMPO-laccase oxidation successfully added aldehyde and carboxylate groups to chitosan structure resulting in derivatives with oxidation between 4 and 7%. These derivatives showed increased solubility and decreased viscosity in solution. If chitosan is dissolved in diluted hydrochloric acid prior to TEMPO-laccase oxidation, a crosslinked chitosan derivative was produced, which was able to form a pH-responsive hydrogel.
Original languageEnglish
Pages (from-to)299-309
JournalCarbohydrate Polymers
Volume186
DOIs
Publication statusPublished - 15 Apr 2018

Fingerprint

Laccase
Hydrogels
Chitosan
Derivatives
Oxidation
Water
Polysaccharides
Hydrochloric Acid
Hydrogel
Hydrochloric acid
Antioxidants
Aldehydes
Oxidants
Polymers
Solubility
Oxidation-Reduction
Viscosity
Air

Keywords

  • 2,2,6,6-Tetramethylpiperidinoxyl radical (TEMPO)
  • Chitosan
  • Laccase
  • Oxidation
  • pH-responsive hydrogel
  • Soluble chitosan

Cite this

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title = "Water-soluble chitosan derivatives and pH-responsive hydrogels by selective C-6 oxidation mediated by TEMPO-laccase redox system",
abstract = "Chitosan is a polysaccharide with recognized antioxidant, antimicrobial and wound healing activities. However, this polymer is soluble only in dilute acidic solutions, which restricts much of its applications. A usual strategy for improving the functionality of polysaccharides is the selective oxidation mediated by 2,2,6,6-tetra-methyl-1-piperidinidyloxy (TEMPO) using laccase as a co-oxidant. In this work, the TEMPO-laccase redox system was used for the first time to selectively oxidize chitosan in order to produce tailored derivatives. The reaction was performed at pH 4.5 under continuous air supply and the oxidized products were characterized structurally and functionally. The TEMPO-laccase oxidation successfully added aldehyde and carboxylate groups to chitosan structure resulting in derivatives with oxidation between 4 and 7{\%}. These derivatives showed increased solubility and decreased viscosity in solution. If chitosan is dissolved in diluted hydrochloric acid prior to TEMPO-laccase oxidation, a crosslinked chitosan derivative was produced, which was able to form a pH-responsive hydrogel.",
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author = "{Botelho da Silva}, Suse and Malgorzata Krolicka and {van den Broek}, {Lambertus A.M.} and Frissen, {August E.} and Boeriu, {Carmen Gabriela}",
year = "2018",
month = "4",
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language = "English",
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Water-soluble chitosan derivatives and pH-responsive hydrogels by selective C-6 oxidation mediated by TEMPO-laccase redox system. / Botelho da Silva, Suse; Krolicka, Malgorzata; van den Broek, Lambertus A.M.; Frissen, August E.; Boeriu, Carmen Gabriela.

In: Carbohydrate Polymers, Vol. 186, 15.04.2018, p. 299-309.

Research output: Contribution to journalArticleAcademicpeer-review

TY - JOUR

T1 - Water-soluble chitosan derivatives and pH-responsive hydrogels by selective C-6 oxidation mediated by TEMPO-laccase redox system

AU - Botelho da Silva, Suse

AU - Krolicka, Malgorzata

AU - van den Broek, Lambertus A.M.

AU - Frissen, August E.

AU - Boeriu, Carmen Gabriela

PY - 2018/4/15

Y1 - 2018/4/15

N2 - Chitosan is a polysaccharide with recognized antioxidant, antimicrobial and wound healing activities. However, this polymer is soluble only in dilute acidic solutions, which restricts much of its applications. A usual strategy for improving the functionality of polysaccharides is the selective oxidation mediated by 2,2,6,6-tetra-methyl-1-piperidinidyloxy (TEMPO) using laccase as a co-oxidant. In this work, the TEMPO-laccase redox system was used for the first time to selectively oxidize chitosan in order to produce tailored derivatives. The reaction was performed at pH 4.5 under continuous air supply and the oxidized products were characterized structurally and functionally. The TEMPO-laccase oxidation successfully added aldehyde and carboxylate groups to chitosan structure resulting in derivatives with oxidation between 4 and 7%. These derivatives showed increased solubility and decreased viscosity in solution. If chitosan is dissolved in diluted hydrochloric acid prior to TEMPO-laccase oxidation, a crosslinked chitosan derivative was produced, which was able to form a pH-responsive hydrogel.

AB - Chitosan is a polysaccharide with recognized antioxidant, antimicrobial and wound healing activities. However, this polymer is soluble only in dilute acidic solutions, which restricts much of its applications. A usual strategy for improving the functionality of polysaccharides is the selective oxidation mediated by 2,2,6,6-tetra-methyl-1-piperidinidyloxy (TEMPO) using laccase as a co-oxidant. In this work, the TEMPO-laccase redox system was used for the first time to selectively oxidize chitosan in order to produce tailored derivatives. The reaction was performed at pH 4.5 under continuous air supply and the oxidized products were characterized structurally and functionally. The TEMPO-laccase oxidation successfully added aldehyde and carboxylate groups to chitosan structure resulting in derivatives with oxidation between 4 and 7%. These derivatives showed increased solubility and decreased viscosity in solution. If chitosan is dissolved in diluted hydrochloric acid prior to TEMPO-laccase oxidation, a crosslinked chitosan derivative was produced, which was able to form a pH-responsive hydrogel.

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KW - Laccase

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KW - pH-responsive hydrogel

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DO - 10.1016/j.carbpol.2018.01.050

M3 - Article

VL - 186

SP - 299

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JO - Carbohydrate Polymers

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