{"database":"biostudies-literature","file_versions":[],"scores":null,"additional":{"submitter":["Bannin TJ"],"funding":["National Institute of General Medical Sciences","NIGMS NIH HHS"],"pagination":["5481-5486"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC4863702"],"repository":["biostudies-literature"],"omics_type":["Unknown"],"volume":["48(16)"],"pubmed_abstract":["Organocatalysts typically used for the ring-opening polymerization (ROP) of cyclic ester monomers are applied to a thiolactone, <i>ε</i>-thiocaprolactone (tCL). In the absence of an H-bond donor, a nucleophilic polymerization mechanism is proposed. Despite the decreased ability of thioesters and thiols (versus esters and alcohols) to H-bond, H-bonding organocatalysts-a thiourea in combination with an H-bond accepting base-are also effective for the ROP of tCL. The increased nucleophilicity of thiols (versus alcohols) is implicated in the increased <i>M</i><sub>w</sub>/<i>M</i><sub>n</sub> of the poly(thiocaprolactone) versus poly(caprolactone), but deleterious transesterification is suppressed in the presence of a thiourea. The thioester monomer, tCL, is shown to be thermodynamically similar to <i>ε</i>-caprolactam but kinetically similar to <i>ε</i>-caprolactone."],"journal":["Macromolecules"],"pubmed_title":["Poly(thioester) by Organocatalytic Ring-Opening Polymerization."],"pmcid":["PMC4863702"],"funding_grant_id":["8 P20 GM103430-12","P20 GM103430"],"pubmed_authors":["Bannin TJ","Kiesewetter MK"],"additional_accession":[]},"is_claimable":false,"name":"Poly(thioester) by Organocatalytic Ring-Opening Polymerization.","description":"Organocatalysts typically used for the ring-opening polymerization (ROP) of cyclic ester monomers are applied to a thiolactone, <i>ε</i>-thiocaprolactone (tCL). In the absence of an H-bond donor, a nucleophilic polymerization mechanism is proposed. Despite the decreased ability of thioesters and thiols (versus esters and alcohols) to H-bond, H-bonding organocatalysts-a thiourea in combination with an H-bond accepting base-are also effective for the ROP of tCL. The increased nucleophilicity of thiols (versus alcohols) is implicated in the increased <i>M</i><sub>w</sub>/<i>M</i><sub>n</sub> of the poly(thiocaprolactone) versus poly(caprolactone), but deleterious transesterification is suppressed in the presence of a thiourea. The thioester monomer, tCL, is shown to be thermodynamically similar to <i>ε</i>-caprolactam but kinetically similar to <i>ε</i>-caprolactone.","dates":{"release":"2015-01-01T00:00:00Z","publication":"2015 Aug","modification":"2025-04-22T06:22:27.556Z","creation":"2019-03-27T02:13:29Z"},"accession":"S-EPMC4863702","cross_references":{"pubmed":["27182085"],"doi":["10.1021/acs.macromol.5b01463"]}}