RT info:eu-repo/semantics/article
T1 Molecular dynamics simulations on self-healing behavior of ionene polymer-based nanostructured hydrogels
A1 Bertran, Oscar
A1 Saldías, César
A1 Díaz Díaz, David
A1 Alem´an, Carlos
K1 DABCO
K1 Molecular dynamics
K1 Polyelectrolyte hydrogels
K1 Econstituted hydrogels
K1 Self-healing mechanism
K1 dinámicas moleculares
K1 hidrogel de polielectrolitos
K1 mecanismo de autocuración
AB The microscopic mechanism accounting for the self-healing attribute of aromatic ionene-forming hydrogelsderived from 1,4-diazabicyclo [2.2.2]octane (DABCO) and N,N’-(x-phenylene)dibenzamide (x = ortho-/meta-/para-) is unknown. Interestingly, the self-healing property of such DABCO-containing hydrogels is largelydependent on the polymer topology, the ortho ionene being the only self-healable without adding oppositelycharged species. In this work, Molecular Dynamics (MD) simulations have been conducted to evaluate the influenceof the topology on ionene⋅⋅⋅ionene and ionene⋅⋅water interactions, as well as their effect on the selfhealingbehavior. For this purpose, destabilized and structurally damaged models were produced for ionenehydrogels with ortho, meta and para topologies and used as starting geometries for simulations. These modelswere allowed to evolve without any restriction during MD production runs and, subsequently, the temporalevolution of ionene⋅⋅⋅ionene and water⋅⋅⋅ionene interactions was examined. Analysis of the results indicated thatthe ortho-isomer rapidly forms unique interactions that are not detected for other two isomers. Thus, in additionto the interactions also identified for the meta-and para-ionenes, the ortho-isomer exhibits the formation of strongintermolecular three-centered (N–)H⋯O (=C)⋯H (–N) hydrogen bonds, intramolecular planar sandwich π-πstacking interactions and Cl- ⋅⋅⋅N+ electrostatic interactions. Furthermore, the amount of intermolecular π-πstacking interactions and the strength of water⋅⋅⋅polymer interaction are also influenced by the topology, favoringthe stabilization of the ortho-ionene reconstituted hydrogels. Overall, the arrangement of the functionalgroups in the ortho topology favors the formation of more types of ionene⋅⋅⋅ionene interactions, as well asstronger interactions, than in the meta and para topologies.
PB Elsevier
YR 2020
FD 2020
LK http://riull.ull.es/xmlui/handle/915/22007
UL http://riull.ull.es/xmlui/handle/915/22007
LA en
NO MINECO/FEDER
DS Repositorio institucional de la Universidad de La Laguna
RD 19-dic-2024