May the force be with you: Xia, Burns, Martinez, and co-workers harnessed the ring strain of ladderenes to enable both their polymerization and mechanochemical unzipping to yield semiconducting polyacetylene-based block copolymers. These materials have promise as functional polymers for applications such as detection of physical stress.
Show your metal: l-Tyrosine is converted into the protective antioxidative polymer melanin in a sequence of reactions. In humans, the catalytic pathway starts with the tyrosinase HsTYR and two tyrosinase-related proteins HsTYRP1 and HsTYRP2. All three enzymes have the same active site but the latter two contain two zinc ions instead of copper ions.
Tail-Me: The N-methylation of backbone amide bonds in peptide natural products was thought to be exclusive to non-ribosomal peptides. A newly discovered methylation mechanism now brings this structural feature into the world of ribosomal peptides, thereby significantly expanding the structural diversity of ribosomally synthesized and post-translationally modified peptides (RiPPs).
Out of bounds: Enantioselective rearrangement reactions are a long-standing challenge in organic synthesis. Recent advances are highlighted that led to the development of the first enantioselective Doyle–Kirmse reaction and enantioselective rearrangement reactions of iodonium ylides.
A hierarchically functionalized hybrid electrode for Zn–air batteries is discussed that requires no carbon. Instead, an oxygen evolution reaction (OER)-active, porous, conductive, and corrosion-resistant nitride Ni3FeN is used as a support for oxygen reduction reaction (ORR)-active ordered intermetallic Fe3Pt NPs. The porosity in the Ni3FeN substrate is an important enabling factor for the high OER activity.
Total syntheses of the tetracyclic terpene waihoensene and the densely functionalized tetracyclic compound ryanodol have recently been reported. Both approaches constitute examples of the efficient and innovative construction of multiple quaternary centers.
Seek, and ye shall find: After years of focusing research on synthetic antibiotics out of fear that all the useful natural ones had already been found, a novel antibacterial compound has been discovered through conventional microbial extract screening. The broad-spectrum nucleoside-analogue inhibitor pseudouridimycin is selective for bacterial RNA polymerase and elicits very low resistance rates.
Caught in the act: Two-domain G-protein-coupled receptors of the class B family mediate peptide hormone signaling and play a pivotal role in diseases such as diabetes and obesity. Drug discovery for these GPCRs has been difficult, especially when agonists are needed. Now, the first structures of full-length active class B GPCRs have been solved, which illuminates the activation mechanism and could accelerate structure-based drug discovery for class B GPCRs.
Wake up! Sleeping sickness and Chagas disease are neglected tropical diseases caused by trypanosome infections. Small molecules that disrupt a crucial protein–protein interaction in the parasites offer a new approach to drug development for these diseases.
A historical challenge: Gas-phase electron diffraction and single-crystal X-ray diffraction are both established techniques, but they were both pushed to their limits by the challenge posed by the highly flexible tetranitromethane molecule. New approaches had to be developed for the structure of the molecule to be elucidated.
A fair exchange: Morandi and co-workers have reported a process that enables the exchange of aryl groups on sulfur or phosphorus. Building on established aryl-transfer reactions, this Pd-catalyzed metathesis can be used to diversify thioanisoles and generate cyclic phosphines.
The right environment: The remarkable properties of a recently reported holmium(III)-based single-ion magnet have been ascribed to the hyperfine interactions with the half-integer nuclear spin in combination with the pentagonal-bipyramidal coordination environment. These results provide insight into the complicated magnetic properties of nanosized magnetic materials.
Observation of Brønsted acid sites: By enhancing the solid-state NMR signals of 17O at natural abundance with dynamic nuclear polarization (DNP), Pruski et al. were able to measure oxygen–proton distances accurately with sub-picometer precision. The results give insight into the Brønsted acidity of a range of solid acid catalysts.
Beyond the crew cut: Highly asymmetric block copolymers self-assemble into microparticles with inverse morphologies far beyond the crew-cut regime. These particles enclose highly ordered channel systems with simple cubic, double diamond, and hexagonally packed hollow-hoop symmetry. The extensive interface and confinement of these particles could enable applications in the storage of cargo, templating, and chemical reactions.
Tighten your belt: The first aromatic nanobelt has been prepared by Itami and co-workers. This synthesis of a truncated Vögtle belt constitutes a milestone in long-standing efforts of numerous chemists. The realization of such a molecule provides not only new opportunities in materials science, but also paves the way to the rational synthesis of carbon nanotubes.
Smooth handoff in the relay: Vinyl boronates enable the direct addition of nucleophilic and electrophilic or nucleophilic and radical-generating carbon reagents across the double bond with retention of the valuable boronate group. The key to the success of this difficult twofold C−C bond-formation strategy is the initial relay of the nucleophilic addition to boron and the rearrangement of a 1,2-metalate rearrangement, shuttling it to the carbon atom.
Bowl me over! A breathtaking bowl-shaped oligoarylene has been created. The structure is analogous to that of corranulene, but instead of twenty sp2-hybridized carbon atoms, the new nanometer-sized molecule has been constructed using twenty 1,3,5-trisubstituted benzene rings.
Donation welcome: Recent developments in visible-light photocatalysis allow the utilization of increasingly negative reduction potentials. Successive energy and electron transfer with polycyclic aromatic hydrocarbons enables the catalytic formation of strongly reducing arene radical anions, classical stoichiometric reagents for one-electron reduction in organic synthesis.
A practical and elegant solution to the long-standing challenge of methylarene partial oxidation has recently been provided by Pappo and co-workers who devised a catalytic aerobic route to benzaldehydes. The solution hinges on the unique hydrogen-bonding capacity of hexafluoroisopropanol, which prevents overoxidation of the aldehyde to the carboxylic acid.
Very highly charged proteins, so-called “supercharged” ions, can lose (excess) protons to background gases like N2. It is remarkable that such extremely acidic species can be generated in electrospray ionization, in the presence of not just N2 but also much higher-basicity solvents. What mechanism(s) can explain such high charging, and what is the ultimate limit?
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