Ovoselenol, a Selenium-containing Antioxidant Derived from Convergent Evolution.

Selenium is an essential micronutrient, but its presence in biology has been limited to protein and nucleic acid biopolymers. The recent identification of the first biosynthetic pathway for selenium-containing small molecules suggests that there is a larger family of selenometabolites that remains to be discovered. Using a bioinformatic search strategy that relies on mapping of composite active site motifs, we identify a recently evolved branch of abundant and uncharacterized metalloenzymes that we predict are involved in selenometabolite biosynthesis. Biochemical studies confirm this prediction and show that these enzymes form an unusual C-Se bond onto histidine, thus giving rise to a novel selenometabolite and potent antioxidant that we have termed ovoselenol. Aside from providing insights into the evolution of this enzyme class and the structural basis of C-Se bond formation, our work offers a blueprint for charting the microbial selenometabolome in the future.

Highly Selective Transport of Alkali Metal Ions by Nanochannels of Polyelectrolyte Threaded MIL-53 Metal Organic Framework.

Conventional ion-exchange polymeric membranes have limited selectivity due to their nonuniform and unstable structures. The rigid, regular, high porosity of metal organic framework (MOF) generally provides MOF membrane with exclusion/sieving effect but lack of electrostatic screening. Here we report for the first time a nonbiological highly selective MOF membrane with polyelectrolyte threaded in the nanochannel of metal organic framework (polyelectrolyte∼MOF) and its selective transport of alkali metal cations. Poly(sodium vinyl sulfonated-co-acrylic acid)∼MIL-53(Al) is prepared on anodic aluminum oxide substrate via steps of MOF MIL-53(Al) growth followed by in situ polymerization. The poly(VS-co-AA)∼MIL-53(Al) membrane demonstrates highly specific selectivity in transport of alkali metal cations. Rate of ion transport correlates inversely with the hydrated diameter of the ion reaching a low limiting rate near 0.7 nm hydrated diameter. Charge exclusion is demonstrated with blockage of anion transport under a concentration gradient. The highly uniform porous nanostructure of MOF and ionic function of polyelectrolyte offers the MOF membrane with synergistic selectivity based on exclusion forces of the framework and Coulomb forces from fixed charges of polyelectrolytes in nanochannels.

Catalytic Palladium Film Deposited by Scalable Low-Temperature Aqueous Combustion.

This article describes a novel method for depositing a dense, high quality palladium thin film via a one-step aqueous combustion process which can be easily scaled up. Film deposition of Pd from aqueous solutions by conventional chemical or electrochemical methods is inhibited by hydrogen embrittlement, thus resulting in a brittle palladium film. The method outlined in this work allows a direct aqueous solution deposition of a mirror-bright, durable Pd film on substrates including glass and glassy carbon. This simple procedure has many advantages including a very high deposition rate (>10 cm2 min-1) and a relatively low deposition temperature (250 °C), which makes it suitable for large-scale industrial applications. Although preparation of various high-quality oxide films has been successfully accomplished via solution combustion synthesis (SCS) before, this article presents the first report on direct SCS production of a metallic film. The mechanism of Pd film formation is discussed with the identification of a complex formed between palladium nitrate and glycine at low temperature. The catalytic properties and stability of films are successfully tested in alcohol electrooxidation and electrochemical oxygen reduction reaction. It was observed that combustion deposited Pd film on a glassy carbon electrode showed excellent catalytic activity in ethanol oxidation without using any binder or additive. We also report for the first time the concept of a reusable "catalytic flask" as illustrated by the Suzuki-Miyaura cross-coupling reaction. The Pd film uniformly covers the inner walls of the flask and eliminates the catalyst separation step. We believe the innovative concept of a reusable catalytic flask is very promising and has the required features to become a commercial product in the future.

Metal-organic framework threaded with aminated polymer formed in situ for fast and reversible ion exchange.

A porous metal-organic framework composite with flexible anion-exchange polymers threaded within the host cavity demonstrates very fast and reversible ion-exchange activity. Polyvinyl benzyl trimethylammonium hydroxide (PVBTAH) caged in ZIF-8 is synthesized in steps of chloro-monomer impregnation, in situ polymerization, amination, and alkaline ion exchange. The synthesized non-cross-linked PVBTAH∼ZIF-8 material exhibits superior ion-exchange kinetics compared to conventional ion-exchange resins.

A functionalized MIL-101(Cr) metal-organic framework for enhanced hydrogen release from ammonia borane at low temperature.

Hydrogen released from ammonia borane in MIL-101(Cr) can be significantly improved by the attached amino and amide groups. The release with minimum impurities starts at 68 °C, reaching 1.6 equivalent of ammonia borane at 85 °C for the amino modified MOFs (NH2-MIL-101).