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Hydroxyethyl acrylamide as a functional eROP initiator for the preparation of nanoparticles under "greener" reaction conditions
N -Hydroxyethyl acrylamide was used as a functional initiator for the enzymatic ring-opening polymerisation of -caprolactone and δ-valerolactone. N -Hydroxyethyl acrylamide was found not to undergo self-reaction in the presence of Lipase B from Candida antarctica under the reaction conditions employ...
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Published in: | Polymer chemistry 2022-11, Vol.13 (42), p.632-645 |
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container_title | Polymer chemistry |
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creator | Lentz, Joachim C Cavanagh, Robert Moloney, Cara Falcone Pin, Bruno Kortsen, Kristoffer Fowler, Harriet R Jacob, Philippa L Krumins, Eduards Clark, Charlotte Machado, Fabricio Breitkreuz, Nicholas Cale, Ben Goddard, Amy R Hirst, Jonathan D Taresco, Vincenzo Howdle, Steven M |
description | N
-Hydroxyethyl acrylamide was used as a functional initiator for the enzymatic ring-opening polymerisation of -caprolactone and δ-valerolactone.
N
-Hydroxyethyl acrylamide was found not to undergo self-reaction in the presence of Lipase B from
Candida antarctica
under the reaction conditions employed. By contrast, this is a major problem for 2-hydroxyethyl methacrylate and 2-hydroxyethyl acrylate which both show significant transesterification issues leading to unwanted branching and cross-linking. Surprisingly,
N
-hydroxyethyl acrylamide did not react fully during enzymatic ring-opening polymerisation. Computational docking studies helped us understand that the initiated polymer chains have a higher affinity for the enzyme active site than the initiator alone, leading to polymer propagation proceeding at a faster rate than polymer initiation leading to incomplete initiator consumption. Hydroxyl end group fidelity was confirmed by organocatalytic chain extension with lactide.
N
-Hydroxyethyl acrylamide initiated polycaprolactones were free-radical copolymerised with PEGMA to produce a small set of amphiphilic copolymers. The amphiphilic polymers were shown to self-assemble into nanoparticles, and to display low cytotoxicity in 2D
in vitro
experiments. To increase the green credentials of the synthetic strategies, all reactions were carried out in 2-methyl tetrahydrofuran, a solvent derived from renewable resources and an alternative for the more traditionally used fossil-based solvents tetrahydrofuran, dichloromethane, and toluene.
N
-Hydroxyethyl acrylamide was used as a functional initiator to produce hybrid macromonomers
via
the enzymatic ring-opening polymerisation of -caprolactone and δ-valerolactone. |
doi_str_mv | 10.1039/d2py00849a |
format | article |
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-Hydroxyethyl acrylamide was used as a functional initiator for the enzymatic ring-opening polymerisation of -caprolactone and δ-valerolactone.
N
-Hydroxyethyl acrylamide was found not to undergo self-reaction in the presence of Lipase B from
Candida antarctica
under the reaction conditions employed. By contrast, this is a major problem for 2-hydroxyethyl methacrylate and 2-hydroxyethyl acrylate which both show significant transesterification issues leading to unwanted branching and cross-linking. Surprisingly,
N
-hydroxyethyl acrylamide did not react fully during enzymatic ring-opening polymerisation. Computational docking studies helped us understand that the initiated polymer chains have a higher affinity for the enzyme active site than the initiator alone, leading to polymer propagation proceeding at a faster rate than polymer initiation leading to incomplete initiator consumption. Hydroxyl end group fidelity was confirmed by organocatalytic chain extension with lactide.
N
-Hydroxyethyl acrylamide initiated polycaprolactones were free-radical copolymerised with PEGMA to produce a small set of amphiphilic copolymers. The amphiphilic polymers were shown to self-assemble into nanoparticles, and to display low cytotoxicity in 2D
in vitro
experiments. To increase the green credentials of the synthetic strategies, all reactions were carried out in 2-methyl tetrahydrofuran, a solvent derived from renewable resources and an alternative for the more traditionally used fossil-based solvents tetrahydrofuran, dichloromethane, and toluene.
N
-Hydroxyethyl acrylamide was used as a functional initiator to produce hybrid macromonomers
via
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-Hydroxyethyl acrylamide was used as a functional initiator for the enzymatic ring-opening polymerisation of -caprolactone and δ-valerolactone.
N
-Hydroxyethyl acrylamide was found not to undergo self-reaction in the presence of Lipase B from
Candida antarctica
under the reaction conditions employed. By contrast, this is a major problem for 2-hydroxyethyl methacrylate and 2-hydroxyethyl acrylate which both show significant transesterification issues leading to unwanted branching and cross-linking. Surprisingly,
N
-hydroxyethyl acrylamide did not react fully during enzymatic ring-opening polymerisation. Computational docking studies helped us understand that the initiated polymer chains have a higher affinity for the enzyme active site than the initiator alone, leading to polymer propagation proceeding at a faster rate than polymer initiation leading to incomplete initiator consumption. Hydroxyl end group fidelity was confirmed by organocatalytic chain extension with lactide.
N
-Hydroxyethyl acrylamide initiated polycaprolactones were free-radical copolymerised with PEGMA to produce a small set of amphiphilic copolymers. The amphiphilic polymers were shown to self-assemble into nanoparticles, and to display low cytotoxicity in 2D
in vitro
experiments. To increase the green credentials of the synthetic strategies, all reactions were carried out in 2-methyl tetrahydrofuran, a solvent derived from renewable resources and an alternative for the more traditionally used fossil-based solvents tetrahydrofuran, dichloromethane, and toluene.
N
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via
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-Hydroxyethyl acrylamide was used as a functional initiator for the enzymatic ring-opening polymerisation of -caprolactone and δ-valerolactone.
N
-Hydroxyethyl acrylamide was found not to undergo self-reaction in the presence of Lipase B from
Candida antarctica
under the reaction conditions employed. By contrast, this is a major problem for 2-hydroxyethyl methacrylate and 2-hydroxyethyl acrylate which both show significant transesterification issues leading to unwanted branching and cross-linking. Surprisingly,
N
-hydroxyethyl acrylamide did not react fully during enzymatic ring-opening polymerisation. Computational docking studies helped us understand that the initiated polymer chains have a higher affinity for the enzyme active site than the initiator alone, leading to polymer propagation proceeding at a faster rate than polymer initiation leading to incomplete initiator consumption. Hydroxyl end group fidelity was confirmed by organocatalytic chain extension with lactide.
N
-Hydroxyethyl acrylamide initiated polycaprolactones were free-radical copolymerised with PEGMA to produce a small set of amphiphilic copolymers. The amphiphilic polymers were shown to self-assemble into nanoparticles, and to display low cytotoxicity in 2D
in vitro
experiments. To increase the green credentials of the synthetic strategies, all reactions were carried out in 2-methyl tetrahydrofuran, a solvent derived from renewable resources and an alternative for the more traditionally used fossil-based solvents tetrahydrofuran, dichloromethane, and toluene.
N
-Hydroxyethyl acrylamide was used as a functional initiator to produce hybrid macromonomers
via
the enzymatic ring-opening polymerisation of -caprolactone and δ-valerolactone.</abstract><doi>10.1039/d2py00849a</doi><tpages>14</tpages></addata></record> |
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title | Hydroxyethyl acrylamide as a functional eROP initiator for the preparation of nanoparticles under "greener" reaction conditions |
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