title: Mechanically triggered heterolytic unzipping of a low-ceiling-temperature polymer.
abstract: Biological systems rely on recyclable materials resources such as amino acids, carbohydrates and nucleic acids. When biomaterials are damaged as a result of aging or stress, tissues undergo repair by a depolymerization-repolymerization sequence of remodelling. Integration of this concept into synthetic materials systems may lead to devices with extended lifetimes. Here, we show that a metastable polymer, end-capped poly(o-phthalaldehyde), undergoes mechanically initiated depolymerization to revert the material to monomers. Trapping experiments and steered molecular dynamics simulations are consistent with a heterolytic scission mechanism. The obtained monomer was repolymerized by a chemical initiator, effectively completing a depolymerization-repolymerization cycle. By emulating remodelling of biomaterials, this model system suggests the possibility of smart materials where aging or mechanical damage triggers depolymerization, and orthogonal conditions regenerate the polymer when and where necessary.
authors.affiliation: 1] Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA [2] Beckman Institute for Advanced Science and Technology, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA.
authors.forename: Charles E
authors.initials: CE
authors.lastname: Diesendruck
authors.affiliation: Department of Chemistry, University of Washington, Seattle, Washington 98195, USA.
authors.forename: Gregory I
authors.initials: GI
authors.lastname: Peterson
authors.affiliation: 1] Department of Chemistry and the PULSE Institute, Stanford University, Stanford, California 94305, USA [2].
authors.forename: Heather J
authors.initials: HJ
authors.lastname: Kulik
authors.affiliation: Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA.
authors.forename: Joshua A
authors.initials: JA
authors.lastname: Kaitz
authors.affiliation: Department of Chemistry and the PULSE Institute, Stanford University, Stanford, California 94305, USA.
authors.forename: Brendan D
authors.initials: BD
authors.lastname: Mar
authors.affiliation: 1] Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA [2] Beckman Institute for Advanced Science and Technology, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA.
authors.forename: Preston A
authors.initials: PA
authors.lastname: May
authors.affiliation: 1] Beckman Institute for Advanced Science and Technology, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA [2] Department of Aerospace Engineering, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA.
authors.forename: Scott R
authors.initials: SR
authors.lastname: White
authors.affiliation: 1] Department of Chemistry and the PULSE Institute, Stanford University, Stanford, California 94305, USA [2] SLAC National Accelerator Laboratory, Menlo Park, California 94025, USA.
authors.forename: Todd J
authors.initials: TJ
authors.lastname: Martínez
authors.affiliation: Department of Chemistry, University of Washington, Seattle, Washington 98195, USA.
authors.forename: Andrew J
authors.initials: AJ
authors.lastname: Boydston
authors.affiliation: 1] Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA [2] Beckman Institute for Advanced Science and Technology, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA.
authors.forename: Jeffrey S
authors.initials: JS
authors.lastname: Moore
mesh_terms: D056004:Molecular Dynamics Simulation; D058105:Polymerization; D011108:Polymers / Q000737:chemistry*; D013696:Temperature
chemical_list: D011108:Polymers