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Interface Components: Nanoparticles, Colloids, Emulsions, Surfactants, Proteins, Polymers
Structure Dependence of Pyridine and Benzene Derivatives on Interactions with Model Membranes Benjamin J. Peters, Cameron Van Cleave, Allison Haase, John Peter B Hough, Keisha A. Giffen-Kent, Gabriel M. Cardiff, Audra Goach Sostarecz, Dean C. Crick, and Debbie C. Crans Langmuir, Just Accepted Manuscript • DOI: 10.1021/acs.langmuir.8b01661 • Publication Date (Web): 29 Jun 2018 Downloaded from http://pubs.acs.org on July 4, 2018
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Langmuir
Structure Dependence of Pyridine and Benzene Derivatives on Interactions with Model Membranes Benjamin J. Peters1, Cameron Van Cleave1, Allison A. Haase1, John Peter B. Hough1,2, Keisha A. Giffen-Kent1, Gabriel M. Cardiff1,3, Audra G. Sostarecz4, Dean C. Crick5,6, and Debbie C. Crans1, 6* 1Department
of Chemistry of Colorado State University, Fort Collins, Colorado, 80523, United States of Biochemistry Colorado State University, Fort Collins, Colorado, 80523, United States 3Department of Biology Colorado State University, Fort Collins, Colorado, 80523, United States 4Department of Chemistry Monmouth College, Monmouth, Illinois, 61462, United States 5Department of Microbiology, Immunology, and Pathology, Colorado State University, Fort Collins, Colorado, 80523, United States 6Cell and Molecular Biology Program Colorado State University, Fort Collins, Colorado, 80523, United States 2Department
KEYWORDS: Langmuir monolayer, reverse micelle, phospholipid, isoniazid, nicotinamide, pyridine, NMR spectroscopy, membrane ABSTRACT: Pyridine based small molecule drugs, vitamins, and cofactors are vital for many cellular processes, but little is known about their interactions with membrane interfaces. These specific membrane interactions of these small molecules or ions can assist in diffusion across membranes or reach a membrane bound target. This study explores how minor differences in small molecules (isoniazid, benzhydrazide, isonicotinamide, nicotinamide, picolinamide, and benzamide) can affect their interactions with model membranes. Langmuir monolayer studies of dipalmitoylphosphatidylcholine (DPPC) or dipalmitoylphosphatidylethanolamine (DPPE), in the presence of the molecules listed, show that isoniazid and isonicotinamide affect the DPPE monolayer at lower concentrations than the DPPC monolayer, demonstrating a preference for one phospholipid over the other. The Langmuir monolayer studies also suggest that nitrogen content and stereochemistry of the small molecule can affect the phospholipid monolayers differently. To determine the molecular interactions of the simple N-containing aromatic pyridines with a membrane-like interface, 1H 1D NMR and 1H-1H 2D NMR techniques were utilized to obtain information about position and orientation of the molecules of interest within aerosol-OT (AOT) reverse micelles. These studies show that all six of the molecules reside near the AOT sulfonate headgroups and ester linkages in similar positions, but nicotinamide and picolinamide tilt at the water-AOT interface to varying degrees. Combined, these studies demonstrate that small structural changes of small N-containing molecules can affect their specific interactions with membrane-like interfaces, and specificity toward different membrane components.
INTRODUCTION Small molecules (
