Over the past several years, the term PFAS (per- and polyfluoroalkyl substances) has grown to be emblematic of environmental contamination, garnering public, scientific, and regulatory concern. PFAS are synthesized by two processes, direct fluorination (e.g., electrochemical fluorination) and oligomerization (e.g., fluorotelomerization). More than a megatonne of PFAS is produced yearly, and thousands of PFAS wind up in end-use products. Atmospheric and aqueous fugitive releases during manufacturing, use, and disposal have resulted in the global distribution of these compounds. Volatile PFAS facilitate long-range transport, commonly followed by complex transformation schemes to recalcitrant terminal PFAS, which do not degrade under environmental conditions and thus migrate through the environment and accumulate in biota through multiple pathways. Efforts to remediate PFAS-contaminated matrices still are in their infancy, with much current research targeting drinking water.

Arginine methylation is important in biological systems. Recent studies link the deregulation of protein arginine methyltransferases with certain cancers. To assess the impact of methylation on interaction with other biomolecules, the pK_a values of methylated arginine variants were determined using NMR data. The pK_a values of monomethylated, symmetrically dimethylated, and asymmetrically dimethylated arginine are similar to the unmodified arginine (14.2 ± 0.4). Although the pK_a value has not been significantly affected by methylation, consequences of methylation include changes in charge distribution and steric effects, suggesting alternative mechanisms for recognition.

Ribonucleotides in DNA can alter the elastic and structural properties of DNA.

The modification of the ribofuranose in nucleic acids is a widespread method of manipulating the activity of nucleic acids. These alterations, however, impact the local conformation and chemical reactivity of the sugar. Changes in the conformation and dynamics of the sugar moiety alter the local and potentially global structure and plasticity of nucleic acids, which in turn contributes to recognition, binding of ligands and enzymatic activity of proteins. This review article introduces the conformational properties of the (deoxy)ribofuranose ring and then explores sugar modifications and how they impact local and global structure and dynamics in nucleic acids.

Per- and polyfluoroalkyl substances (PFAS) migrate into the environment through various means, e.g., soil-amendment impurities and ambient atmospheric deposition, potentially resulting in vegetative uptake and migration to groundwater. Existing approaches for modeling sorption of PFAS commonly treat soil as an undifferentiated homogeneous medium, with distribution constants (e.g., K_d, K_oc) generated empirically using surface soils. Considering the limited mineral variety expected in weathered geologic media, PFAS mobility can be better understood by accounting for predictable mineral assemblages that are ubiquitously distributed in US soils. Here we explore the role of minerals and electrostatic sorption in controlling PFAS mobility in subsurface settings at contaminated agricultural sites by measuring geochemical parameters and PFAS, and calculating pH-dependent mineral surface charges through full soil and aquifer columns. These data suggest subsurface mobility of short-chain PFAS largely is controlled by aluminum-oxide mineral(oid) electrostatic sorption, whereas long-chain PFAS mobility is controlled by organic matter and air-water interfacial area.