Organocatalysis by hydrogen-bonding: a new approach to controlled/living polymerization of α-amino acid N-carboxyanhydrides

Handle URI:
http://hdl.handle.net/10754/594074
Title:
Organocatalysis by hydrogen-bonding: a new approach to controlled/living polymerization of α-amino acid N-carboxyanhydrides
Authors:
Zhao, Wei ( 0000-0001-7177-3180 ) ; Gnanou, Yves ( 0000-0001-6253-7856 ) ; Hadjichristidis, Nikolaos ( 0000-0003-1442-1714 )
Abstract:
A new method, based on hydrogen-bonding organocatalysis, was developed to achieve living ring-opening polymerization of N-carboxyanhydride of α-amino acids using aminoalcohols as initiators in the presence of N,N′-bis[3,5-bis(trifluoromethyl)phenyl]thiourea (TU-S). The thiourea provides, through hydrogen bonding, simultaneous activation of NCA monomers/reversible deactivation of polymer chain-ends/silencing of the tertiary amine and thus allows the polymerization to proceed in a highly controllable mode. For example, by using N,N-dimethyl ethanolamine (DMEA), as an initiator in the presence of TU-S, a series of well-defined linear polypeptides with differently designed Mns (3.01 × 104-18.10 × 104) and low PDI values (1.02-1.05) were successfully synthesized. This general strategy was also extended to the synthesis of well-defined di- and multi-armed polypeptides by using di-, tri-, or tetra-aminoalcohol initiators (methyldiethanolamine (MDEA), triethanolamine (TEA) or N,N,N′,N′-tetrakis(2-hydroxyethyl)ethylenediamine (THEED)) in the presence of TU-S. © The Royal Society of Chemistry 2015.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division; Polymer Synthesis Laboratory
Citation:
Zhao W, Gnanou Y, Hadjichristidis N (2015) Organocatalysis by hydrogen-bonding: a new approach to controlled/living polymerization of α-amino acid N-carboxyanhydrides. Polym Chem 6: 6193–6201. Available: http://dx.doi.org/10.1039/c5py00874c.
Publisher:
Royal Society of Chemistry (RSC)
Journal:
Polym. Chem.
Issue Date:
2015
DOI:
10.1039/c5py00874c
Type:
Article
ISSN:
1759-9954; 1759-9962
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorZhao, Weien
dc.contributor.authorGnanou, Yvesen
dc.contributor.authorHadjichristidis, Nikolaosen
dc.date.accessioned2016-01-19T13:20:57Zen
dc.date.available2016-01-19T13:20:57Zen
dc.date.issued2015en
dc.identifier.citationZhao W, Gnanou Y, Hadjichristidis N (2015) Organocatalysis by hydrogen-bonding: a new approach to controlled/living polymerization of α-amino acid N-carboxyanhydrides. Polym Chem 6: 6193–6201. Available: http://dx.doi.org/10.1039/c5py00874c.en
dc.identifier.issn1759-9954en
dc.identifier.issn1759-9962en
dc.identifier.doi10.1039/c5py00874cen
dc.identifier.urihttp://hdl.handle.net/10754/594074en
dc.description.abstractA new method, based on hydrogen-bonding organocatalysis, was developed to achieve living ring-opening polymerization of N-carboxyanhydride of α-amino acids using aminoalcohols as initiators in the presence of N,N′-bis[3,5-bis(trifluoromethyl)phenyl]thiourea (TU-S). The thiourea provides, through hydrogen bonding, simultaneous activation of NCA monomers/reversible deactivation of polymer chain-ends/silencing of the tertiary amine and thus allows the polymerization to proceed in a highly controllable mode. For example, by using N,N-dimethyl ethanolamine (DMEA), as an initiator in the presence of TU-S, a series of well-defined linear polypeptides with differently designed Mns (3.01 × 104-18.10 × 104) and low PDI values (1.02-1.05) were successfully synthesized. This general strategy was also extended to the synthesis of well-defined di- and multi-armed polypeptides by using di-, tri-, or tetra-aminoalcohol initiators (methyldiethanolamine (MDEA), triethanolamine (TEA) or N,N,N′,N′-tetrakis(2-hydroxyethyl)ethylenediamine (THEED)) in the presence of TU-S. © The Royal Society of Chemistry 2015.en
dc.publisherRoyal Society of Chemistry (RSC)en
dc.titleOrganocatalysis by hydrogen-bonding: a new approach to controlled/living polymerization of α-amino acid N-carboxyanhydridesen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentPolymer Synthesis Laboratoryen
dc.identifier.journalPolym. Chem.en
kaust.authorZhao, Weien
kaust.authorGnanou, Yvesen
kaust.authorHadjichristidis, Nikolaosen
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