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Enzymatic synthesis and polymerisation of β-mannosyl acrylates produced from renewable hemicellulosic glycans

Rosengren, Anna LU ; Butler, Samuel LU ; Arcos Hernandez, Monica LU ; Bergquist, Karl-Erik LU ; Jannasch, Patric LU and Stålbrand, Henrik LU (2019) In Green Chemistry 21(8). p.2104-2118
Abstract
We show that glycoside hydrolases can catalyse the synthesis of glycosyl acrylate monomers using renewable hemicellulose as glycosyl donor, and we also demonstrate the preparation of novel glycopolymers by radical polymerisation of these monomers. For this, two family 5 β-mannanases (TrMan5A from Trichoderma reesei and AnMan5B from Aspergillus niger) were evaluated for transglycosylation capacity using 2-hydroxyethyl methacrylate (HEMA) as glycosyl acceptor. Both enzymes catalysed conjugation between manno-oligosaccharides and HEMA, as analysed with MALDI-ToF mass spectrometry (MS) as initial product screening method. The two enzymes gave different product profiles (glycosyl donor length) with HEMA, as well as with allyl alcohol as... (More)
We show that glycoside hydrolases can catalyse the synthesis of glycosyl acrylate monomers using renewable hemicellulose as glycosyl donor, and we also demonstrate the preparation of novel glycopolymers by radical polymerisation of these monomers. For this, two family 5 β-mannanases (TrMan5A from Trichoderma reesei and AnMan5B from Aspergillus niger) were evaluated for transglycosylation capacity using 2-hydroxyethyl methacrylate (HEMA) as glycosyl acceptor. Both enzymes catalysed conjugation between manno-oligosaccharides and HEMA, as analysed with MALDI-ToF mass spectrometry (MS) as initial product screening method. The two enzymes gave different product profiles (glycosyl donor length) with HEMA, as well as with allyl alcohol as acceptor molecules. AnMan5A appeared to prefer saccharide acceptors with lower intensity MS peaks detected for the desired allyl and HEMA conjugations. Contrary to AnMan5A, TrMan5A gave pronounced MS peaks for HEMA-saccharide conjugation products.TrMan5A was shown to catalyse the synthesis of β-mannosyl acrylates using locust bean gum galactomannan or softwood hemicellulose (acetyl-galactoglucomannan) as donor substrate. Evaluation of reaction conditions using galactomannan as donor, HEMA as acceptor and TrMan5A as enzyme catalyst was followed by the enzymatic production and preparative liquid chromatography purification of 2-(β-manno(oligo)syloxy) ethyl methacrylates (Mannosyl-EMA and Mannobiosyl-EMA). The chemical structures and radical polymerisations of these novel monomers were concluded using 1H and 13C NMR spectroscopy and size-exclusion chromatography. The two new water soluble polymers have a polyacrylate backbone with one or two pendant mannosyl groups per monomeric EMA unit, respectively. These novel glycopolymers may show properties suitable for various technical and biomedical applications responding to the current demand for functional greener materials to replace fossil based ones. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Green Chemistry
volume
21
issue
8
pages
2104 - 2118
publisher
Royal Society of Chemistry
external identifiers
  • scopus:85064552599
ISSN
1463-9270
DOI
10.1039/c8gc03947j
language
English
LU publication?
yes
id
4afee950-34c7-4dac-ba2d-c418082839bc
date added to LUP
2019-03-18 09:27:37
date last changed
2019-05-12 04:58:33
@article{4afee950-34c7-4dac-ba2d-c418082839bc,
  abstract     = {We show that glycoside hydrolases can catalyse the synthesis of glycosyl acrylate monomers using renewable hemicellulose as glycosyl donor, and we also demonstrate the preparation of novel glycopolymers by radical polymerisation of these monomers. For this, two family 5 β-mannanases (TrMan5A from Trichoderma reesei and AnMan5B from Aspergillus niger) were evaluated for transglycosylation capacity using 2-hydroxyethyl methacrylate (HEMA) as glycosyl acceptor. Both enzymes catalysed conjugation between manno-oligosaccharides and HEMA, as analysed with MALDI-ToF mass spectrometry (MS) as initial product screening method. The two enzymes gave different product profiles (glycosyl donor length) with HEMA, as well as with allyl alcohol as acceptor molecules. AnMan5A appeared to prefer saccharide acceptors with lower intensity MS peaks detected for the desired allyl and HEMA conjugations. Contrary to AnMan5A, TrMan5A gave pronounced MS peaks for HEMA-saccharide conjugation products.TrMan5A was shown to catalyse the synthesis of β-mannosyl acrylates using locust bean gum galactomannan or softwood hemicellulose (acetyl-galactoglucomannan) as donor substrate. Evaluation of reaction conditions using galactomannan as donor, HEMA as acceptor and TrMan5A as enzyme catalyst was followed by the enzymatic production and preparative liquid chromatography purification of 2-(β-manno(oligo)syloxy) ethyl methacrylates (Mannosyl-EMA and Mannobiosyl-EMA). The chemical structures and radical polymerisations of these novel monomers were concluded using <sup>1</sup>H and <sup>13</sup>C NMR spectroscopy and size-exclusion chromatography. The two new water soluble polymers have a polyacrylate backbone with one or two pendant mannosyl groups per monomeric EMA unit, respectively. These novel glycopolymers may show properties suitable for various technical and biomedical applications responding to the current demand for functional greener materials to replace fossil based ones.},
  author       = {Rosengren, Anna and Butler, Samuel and Arcos Hernandez, Monica and Bergquist, Karl-Erik and Jannasch, Patric and Stålbrand, Henrik},
  issn         = {1463-9270},
  language     = {eng},
  number       = {8},
  pages        = {2104--2118},
  publisher    = {Royal Society of Chemistry},
  series       = {Green Chemistry},
  title        = {Enzymatic synthesis and polymerisation of β-mannosyl acrylates produced from renewable hemicellulosic glycans},
  url          = {http://dx.doi.org/10.1039/c8gc03947j},
  volume       = {21},
  year         = {2019},
}