title: Hydration Effects Turn a Highly Stretched Polymer from an Entropic into an Energetic Spring.
abstract: Polyethylene glycol (PEG) is a structurally simple and nontoxic water-soluble polymer that is widely used in medical and pharmaceutical applications as molecular linker and spacer. In such applications, PEG's elastic response against conformational deformations is key to its function. According to text-book knowledge, a polymer reacts to the stretching of its end-to-end separation by a decrease in entropy that is due to the reduction of available conformations, which is why polymers are commonly called entropic springs. By a combination of single-molecule force spectroscopy experiments with molecular dynamics simulations in explicit water, we show that entropic hydration effects almost exactly compensate the chain conformational entropy loss at high stretching. Our simulations reveal that this entropic compensation is due to the stretching-induced release of water molecules that in the relaxed state form double hydrogen bonds with PEG. As a consequence, the stretching response of PEG is predominantly of energetic, not of entropic, origin at high forces and caused by hydration effects, while PEG backbone deformations only play a minor role. These findings demonstrate the importance of hydration for the mechanics of macromolecules and constitute a case example that sheds light on the antagonistic interplay of conformational and hydration degrees of freedom.
authors.forename: Susanne
authors.identifier: 0000-0001-7420-5488
authors.initials: S
authors.lastname: Liese
authors.affiliation: Department of Physics and IRIS Adlershof, Humboldt-Universität zu Berlin , Berlin 12489, Germany.
authors.forename: Manuel
authors.initials: M
authors.lastname: Gensler
authors.affiliation: Physik Department and IMETUM, Technische Universität München , Garching 85748, Germany.
authors.forename: Stefanie
authors.initials: S
authors.lastname: Krysiak
authors.forename: Richard
authors.initials: R
authors.lastname: Schwarzl
authors.forename: Andreas
authors.initials: A
authors.lastname: Achazi
authors.forename: Beate
authors.initials: B
authors.lastname: Paulus
authors.affiliation: Institute of Physical Chemistry, University of Freiburg , Freiburg 79104, Germany.
authors.forename: Thorsten
authors.initials: T
authors.lastname: Hugel
authors.affiliation: Department of Physics and IRIS Adlershof, Humboldt-Universität zu Berlin , Berlin 12489, Germany.
authors.forename: Jürgen P
authors.initials: JP
authors.lastname: Rabe
authors.forename: Roland R
authors.initials: RR
authors.lastname: Netz
keywords: hydration; macromolecule elastic response; molecular dynamics simulation; polyethylene glycol; single-molecule force spectroscopy