Osmolyte depletion viewed in terms of the dividing membrane and its work of expansion against osmotic pressure.pdfVIP

BIOCHE-05962; No of Pages 5 Biophysical Chemistry xxx (2017) xxx–xxx Contents lists available at ScienceDirect Biophysical Chemistry journal homepage: /locate/biophyschem Osmolyte depletion viewed in terms of the dividing membrane and its work of expansion against osmotic pressure Seishi Shimizu a,?, Nobuyuki Matubayasi b,c a York Structural Biology Laboratory, Department of Chemistry, University of York, Heslington, York YO10 5DD, United Kingdom b Division of Chemical Engineering, Graduate School of Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan c Elements Strategy Initiative for Catalysts and Batteries, Kyoto University, Katsura, Kyoto 615-8520, Japan article info Article history: Received 2 January 2017 Received in revised form 26 January 2017 Available online xxxx abstract How osmolytes enhance the folding, binding, and self-assembly of biological macromolecules at a microscopic scale has long been a matter of debate. Ambiguities persist on the key interpretive concepts, such as the “effective membrane” (which marks the boundary of the volume from which osmolytes are excluded) and the “free energy of exclusion” of osmolytes from biomolecular surfaces. In this paper, we formulate these elusive concepts based upon chemical thermodynamics and rigorous statistical thermodynamics (the Kirkwood-Buff theory). Positioning of the membrane at the osmotic dividing surface is crucial in order not to affect the thermodynamics of solvation. The notion of the free energy (work) of excluding osmolytes is re?ned to the expansion work against the osmotic pressure, which indeed describes the change of solvation free energy at dilute osmolyte concentrations. ? 2017 Elsevier B.V. All rights reserved. 1. Introduction Self-assembly is important in a wide range of scienti?c disciplines, from biochemistry (protein assembly and self-aggregation) [1–8] to nanoscience and colloid and interfacial science [9–14]. Self-assembly i