Abstract

An unprecedented approach towards oligosaccharides containing N-acetylglucosamine-N-acetylmuramic (NAG-NAM) units was developed. These novel bacterial cell wall surrogates were obtained from chitosan via a top down approach involving both chemical and enzymatic reactions. The chemical modification of chitosan using a molecular clamp based strategy, allowed obtaining N-acetylglucosamine-N-acetylmuramic (NAG-NAM) containing oligomers. Intercalation of NAM residues was confirmed through the analysis of oligosaccharide fragments from enzymatic digestion and it was found that this route affords NAG-NAM containing oligosaccharides in 33% yield. These oligosaccharides mimic the carbohydrate basic skeleton of most bacterial cell surfaces. The oligosaccharides prepared are biologically relevant and will serve as a platform for further molecular recognition studies with different receptors and enzymes of both bacterial cell wall and innate immune system. This strategy combining both chemical modification and enzymatic digestion provides a novel and simple route for an easy access to bacterial cell wall fragments – biologically important targets.

Original languageEnglish
Article number115133
JournalCarbohydrate Polymers
Volume224
DOIs
Publication statusPublished - 15 Nov 2019

Fingerprint

Oligosaccharides
Acetylglucosamine
Chitosan
Cells
Chemical modification
Molecular recognition
Immune system
Clamping devices
Carbohydrates
Intercalation
Oligomers
Enzymes

Keywords

  • Chemo-enzymatic
  • Chitooligosaccharides
  • Chitosan
  • Regioselective modification

Cite this

@article{379cdc3b139a481cb958185018745625,
title = "A top-down chemo-enzymatic approach towards N-acetylglucosamine-N-acetylmuramic oligosaccharides: Chitosan as a reliable template",
abstract = "An unprecedented approach towards oligosaccharides containing N-acetylglucosamine-N-acetylmuramic (NAG-NAM) units was developed. These novel bacterial cell wall surrogates were obtained from chitosan via a top down approach involving both chemical and enzymatic reactions. The chemical modification of chitosan using a molecular clamp based strategy, allowed obtaining N-acetylglucosamine-N-acetylmuramic (NAG-NAM) containing oligomers. Intercalation of NAM residues was confirmed through the analysis of oligosaccharide fragments from enzymatic digestion and it was found that this route affords NAG-NAM containing oligosaccharides in 33{\%} yield. These oligosaccharides mimic the carbohydrate basic skeleton of most bacterial cell surfaces. The oligosaccharides prepared are biologically relevant and will serve as a platform for further molecular recognition studies with different receptors and enzymes of both bacterial cell wall and innate immune system. This strategy combining both chemical modification and enzymatic digestion provides a novel and simple route for an easy access to bacterial cell wall fragments – biologically important targets.",
keywords = "Chemo-enzymatic, Chitooligosaccharides, Chitosan, Regioselective modification",
author = "Fausto Queda and Gon{\cc}alo Covas and Tom{\'e} Silva and Santos, {C{\'a}tia Almeida} and Bronze, {Maria R.} and Ca{\~n}ada, {Francisco Javier} and Corvo, {Marta C.} and Filipe, {S{\'e}rgio R.} and Marques, {M. Manuel B.}",
note = "info:eu-repo/grantAgreement/FCT/SFRH/SFRH{\%}2FBD{\%}2F89518{\%}2F2012/PT# info:eu-repo/grantAgreement/FCT/3599-PPCDT/127730/PT# info:eu-repo/grantAgreement/FCT/5876/147348/PT# SFRH/BD/52207/2013 (to FQ and GC) Associate Laboratory for Green Chemistry- LAQV which is financed by national funds from FCT/MCTES (UID/QUI/50006/2019) and co-financed by the ERDF under the PT2020 Partnership Agreement (POCI-01-0145-FEDER - 007265). i3N|Cenitmat is financed by national funds from FC&T/MEC (UID/CTM/50025/2019) and co-financed by the ERDF under the PT2020 Partnership Agreement (POCI-01-0145-FEDER-007688). The National NMR Facility is supported by FC&T (ROTEIRO/0031/2013 – PINFRA/22161/2016, co-financed by FEDER through COMPETE 2020, POCI, and PORL and FC&T through PIDDAC). iNOVA4 Health Research Unit (LISBOA-01-0145-FEDER-007344), is co-funded by FC&T/Minist{\'e}rio da Ci{\^e}ncia e do Ensino Superior , and by FEDER under the PT2020 Partnership Agreement. CTQ2012‐32025 and CTQ2015-64597-C2 of Spanish Ministry of Economy and Competitiveness to FJC are acknowledge. The LC–MS/MS equipment is part of The National MS Facility, supported by FC&T (REDE/1518/REM/2005). This work was supported by the Applied Molecular Biosciences Unit-UCIBIO which is financed by national funds from FCT/MCTES (UID/Multi/04378/2019).",
year = "2019",
month = "11",
day = "15",
doi = "10.1016/j.carbpol.2019.115133",
language = "English",
volume = "224",
journal = "Carbohydrate Polymers",
issn = "0144-8617",
publisher = "Elsevier Ltd",

}

TY - JOUR

T1 - A top-down chemo-enzymatic approach towards N-acetylglucosamine-N-acetylmuramic oligosaccharides: Chitosan as a reliable template

AU - Queda, Fausto

AU - Covas, Gonçalo

AU - Silva, Tomé

AU - Santos, Cátia Almeida

AU - Bronze, Maria R.

AU - Cañada, Francisco Javier

AU - Corvo, Marta C.

AU - Filipe, Sérgio R.

AU - Marques, M. Manuel B.

N1 - info:eu-repo/grantAgreement/FCT/SFRH/SFRH%2FBD%2F89518%2F2012/PT# info:eu-repo/grantAgreement/FCT/3599-PPCDT/127730/PT# info:eu-repo/grantAgreement/FCT/5876/147348/PT# SFRH/BD/52207/2013 (to FQ and GC) Associate Laboratory for Green Chemistry- LAQV which is financed by national funds from FCT/MCTES (UID/QUI/50006/2019) and co-financed by the ERDF under the PT2020 Partnership Agreement (POCI-01-0145-FEDER - 007265). i3N|Cenitmat is financed by national funds from FC&T/MEC (UID/CTM/50025/2019) and co-financed by the ERDF under the PT2020 Partnership Agreement (POCI-01-0145-FEDER-007688). The National NMR Facility is supported by FC&T (ROTEIRO/0031/2013 – PINFRA/22161/2016, co-financed by FEDER through COMPETE 2020, POCI, and PORL and FC&T through PIDDAC). iNOVA4 Health Research Unit (LISBOA-01-0145-FEDER-007344), is co-funded by FC&T/Ministério da Ciência e do Ensino Superior , and by FEDER under the PT2020 Partnership Agreement. CTQ2012‐32025 and CTQ2015-64597-C2 of Spanish Ministry of Economy and Competitiveness to FJC are acknowledge. The LC–MS/MS equipment is part of The National MS Facility, supported by FC&T (REDE/1518/REM/2005). This work was supported by the Applied Molecular Biosciences Unit-UCIBIO which is financed by national funds from FCT/MCTES (UID/Multi/04378/2019).

PY - 2019/11/15

Y1 - 2019/11/15

N2 - An unprecedented approach towards oligosaccharides containing N-acetylglucosamine-N-acetylmuramic (NAG-NAM) units was developed. These novel bacterial cell wall surrogates were obtained from chitosan via a top down approach involving both chemical and enzymatic reactions. The chemical modification of chitosan using a molecular clamp based strategy, allowed obtaining N-acetylglucosamine-N-acetylmuramic (NAG-NAM) containing oligomers. Intercalation of NAM residues was confirmed through the analysis of oligosaccharide fragments from enzymatic digestion and it was found that this route affords NAG-NAM containing oligosaccharides in 33% yield. These oligosaccharides mimic the carbohydrate basic skeleton of most bacterial cell surfaces. The oligosaccharides prepared are biologically relevant and will serve as a platform for further molecular recognition studies with different receptors and enzymes of both bacterial cell wall and innate immune system. This strategy combining both chemical modification and enzymatic digestion provides a novel and simple route for an easy access to bacterial cell wall fragments – biologically important targets.

AB - An unprecedented approach towards oligosaccharides containing N-acetylglucosamine-N-acetylmuramic (NAG-NAM) units was developed. These novel bacterial cell wall surrogates were obtained from chitosan via a top down approach involving both chemical and enzymatic reactions. The chemical modification of chitosan using a molecular clamp based strategy, allowed obtaining N-acetylglucosamine-N-acetylmuramic (NAG-NAM) containing oligomers. Intercalation of NAM residues was confirmed through the analysis of oligosaccharide fragments from enzymatic digestion and it was found that this route affords NAG-NAM containing oligosaccharides in 33% yield. These oligosaccharides mimic the carbohydrate basic skeleton of most bacterial cell surfaces. The oligosaccharides prepared are biologically relevant and will serve as a platform for further molecular recognition studies with different receptors and enzymes of both bacterial cell wall and innate immune system. This strategy combining both chemical modification and enzymatic digestion provides a novel and simple route for an easy access to bacterial cell wall fragments – biologically important targets.

KW - Chemo-enzymatic

KW - Chitooligosaccharides

KW - Chitosan

KW - Regioselective modification

UR - http://www.scopus.com/inward/record.url?scp=85070111050&partnerID=8YFLogxK

U2 - 10.1016/j.carbpol.2019.115133

DO - 10.1016/j.carbpol.2019.115133

M3 - Article

VL - 224

JO - Carbohydrate Polymers

JF - Carbohydrate Polymers

SN - 0144-8617

M1 - 115133

ER -