PNNL

Abstract

Understanding the basis of templated molecular assembly on a solid surface requires a fundamental comprehension of both short- and long-range aqueous response to the surface under a variety of solution conditions. Herein we provide a detailed picture of how the molecular-scale response to different mica surfaces yields distinct solvent orientations that produce quasi-static directional 2 potentials onto which macromolecules can adsorb. We connect this directionality to observed (a)symmetric epitaxial alignment of designed proteins onto these surfaces, corroborate our findings with 3D Fast Force Mapping experiments, and identify slight differences in surface structure as the origin of this effect. Our work provides a detailed picture of the intrinsic electrolyte response in the vicinity of mineral interfaces, with clear predictions for experiment, and highlights the role of solvent on the predictive assembly of hierarchical materials on mineral surfaces. Acknowledgements: We thank Rohit Subramanian, Jiarun Zhou, and Hendrik Heinz for helpful discussions. This work was supported by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences (BES), as part of the Energy Frontier Research Centers program: CSSAS–The Center for the Science of Synthesis Across Scales–under Award Number DE-SC0019288. All simulations were conducted at the University of California, San Diego (UCSD). Initial development of simulation methodologies and codes were supported by the DOE-BES (Division 19 of Materials Sciences, Biomolecular Materials, Award DE-SC0003844 to F.A.T). R.G.A. was partially supported by a UCSD Distinguished Graduate Student Fellowship. Atomic Force Microscopy experiments were performed at Pacific Northwest National Laboratory (PNNL). Fast Force Mapping investigations of water structure were supported by a US DOE Office of Science Distinguished Scientist Fellows award at PNNL. PNNL is a multi-program national laboratory operated for DOE by Battelle under Contract No. DE-AC05-76RL01830.