Formation of the Metastable MnIII Water Oxidation Intermediate in Birnessite is Controlled by a Dissolution-Deposition Process Involving Labile MnII.

Birnessite, the closest naturally occurring analog of the Mn4 CaO5 cluster of photosystem II, is an important model compound in the development of bio-inspired electrocatalysts for the water oxidation reaction. The present work reports the formation mechanism of the key MnIII intermediate realized through the study of the effects of several electrolyte anions and cations on the catalytic efficiency of birnessite. In situ spectroelectrochemical measurements show that the activity is controlled by a dynamic dissolution-oxidation process, wherein MnIII is formed through the oxidation of labile uncomplexed MnII that reversibly shuttles between the birnessite and the electrolyte in a manner similar to the photoactivation in photosystem II. The role of electrolyte cations of different ionic radii and hydration strengths is to control the interlayer spacing, whereas electrolyte anions control the extent of deprotonation of complexed MnII in the lattice. Both in turn govern the shuttling efficiency of uncomplexed MnII and its subsequent electro-oxidation to MnIII .

High-Conductivity and High-Capacitance Electrospun Fibers for Supercapacitor Applications.

Electrospinning is a simple method for producing nanoscale or microscale fibers from a wide variety of materials. Intrinsically conductive polymers (ICPs), such as polyaniline (PANI), show higher conductivities with the use of secondary dopants like m-cresol. However, due to the low volatility of most secondary dopants, it has not been possible to electrospin secondary doped ICP fibers. In this work, the concept of secondary doping has been applied for the first time to electrospun fibers. Using a novel design for rotating drum electrospinning, fibers were efficiently and reliably produced from a mixture of low- and high-volatility solvents. The conductivity of electrospun PANI-poly(ethylene oxide) (PEO) fibers prepared was 1.73 S/cm, two orders of magnitude higher than the average value reported in the literature. These conductive fibers were tested as electrodes for supercapacitors and were shown to have a specific capacitance as high as 3121 F/g at 0.1 A/g, the highest value reported, thus far, for PANI-PEO electrospun fibers.

Beyond electrostatics: Antimicrobial peptide selectivity and the influence of cholesterol-mediated fluidity and lipid chain length on protegrin-1 activity.

Antimicrobial peptides (AMPs) are a promising class of innate host defense molecules for next-generation antibiotics, as they uniquely target and permeabilize membranes of pathogens. This selectivity has been explained by the electrostatic attraction between these predominantly cationic peptides and the bacterial membrane, which is heavily populated with anionic lipids. However, AMP-resistant bacteria have non-electrostatic countermeasures that modulate membrane rigidity and thickness. We explore how variations in physical properties affect the membrane affinity and disruption process of protegrin-1 (PG-1) in phosphatidylcholine (PC) membranes with altered lipid packing densities and thicknesses. From isothermal titration calorimetry and atomic force microscopy, our results showed that PG-1 could no longer insert into membranes of increasing cholesterol amounts nor into monounsaturated PC membranes of increasing thicknesses with similar fluidities. Prevention of PG-1's incorporation consequently made the membranes more resistant to peptide-induced structural transformations like pore formation. Our study provides evidence that AMP affinity and activity are strongly correlated with the fluidity and thickness of the membrane. A basic understanding of how physical mechanisms can regulate cell selectivity and resistance towards AMPs will aid in the development of new antimicrobial agents.