Structure-Based Design of Dual Bactericidal and Bacteria-Releasing Nanosurfaces.

Here, we report synergistic nanostructured surfaces combining bactericidal and bacteria-releasing properties. A polystyrene-block-poly(methyl methacrylate) (PS-block-PMMA) diblock copolymer is used to fabricate vertically oriented cylindrical PS structures ("PS nanopillars") on silicon substrates. The results demonstrate that the PS nanopillars (with a height of about 10 nm, size of about 50 nm, and spacing of about 70 nm) exhibit highly effective bactericidal and bacteria-releasing properties ("dual properties") against Escherichia coli for at least 36 h of immersion in an E. coli solution. Interestingly, the PS nanopillars coated with a thin layer (≈3 nm thick) of titanium oxide (TiO2) ("TiO2 nanopillars") show much improved dual properties against E. coli (a Gram-negative bacterium) compared to the PS nanopillars. Moreover, the dual properties emerge against Listeria monocytogenes (a Gram-positive bacterium). To understand the mechanisms underlying the multifaceted property of the nanopillars, coarse-grained molecular dynamics (MD) simulations of a lipid bilayer (as a simplified model for E. coli) in contact with a substrate containing hexagonally packed hydrophilic nanopillars were performed. The MD results demonstrate that when the bacterium-substrate interaction is strong, the lipid heads adsorb onto the nanopillar surfaces, conforming the shape of a lipid bilayer to the structure/curvature of nanopillars and generating high stress concentrations within the membrane (i.e., the driving force for rupture) at the edge of the nanopillars. Membrane rupture begins with the formation of pores between nanopillars (i.e., bactericidal activity) and ultimately leads to the membrane withdrawal from the nanopillar surface (i.e., bacteria-releasing activity). In the case of Gram-positive bacteria, the adhesion area to the pillar surface is limited due to the inherent stiffness of the bacteria, creating higher stress concentrations within a bacterial cell wall. The present study provides insight into the mechanism underlying the "adhesion-mediated" multifaceted property of nanosurfaces, which is crucial for the development of next-generation antibacterial surface coatings for relevant medical applications.

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 .