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Chiral iminium ions generated from an amine catalyst and enals are key organocatalytic intermediates in thermal asymmetric processes. Now, visible-light excitation of these iminium ions can turn these compounds into strong oxidants to enable enantioselective photochemical β-alkylations of enals with silanes, which are unachievable via conventional ground state pathways.
Although DNA nanotechnology has found many applications in developing functional structures, there has never been an independent device contained within a 3D crystal. Now, a self-assembled three-state device that can change the colour of its crystal by diffusion of DNA-ligated dyes has been reported, representing the potential to develop programmable nanomechanical devices.
Main-chain polymetallocenes are typically static in nature due to strong metal–ligand bonding. Now, it has been shown that such polymers based on nickelocene are dynamic due to weaker nickel–cyclopentadienyl interactions, and at low concentration or at elevated temperature, depolymerization to the moderately strained monomer occurs.
Breathing metal–organic frameworks (MOFs) are functional materials whose molecular-scale pores can reversibly open and close. In contrast to typical defined structural transitions, continuous breathing has now been observed for a diamondoid MOF. Removal of two different solvents leads to two desolvated MOF polymorphs with dramatically different porosities and gas uptake properties, including CO2/CH4 selectivities. Partial desolvation introduces pressure-gated CO2 adsorption.
Chlorodifluoromethane (ClCF2H), an inexpensive and abundant industrial raw material, represents an ideal and straightforward reagent for introducing the difluoromethyl group. However, efficient approaches for activation of the typically inert ClCF2H are limited. Now, ClCF2H is employed via a difluorocarbene pathway for palladium-catalysed difluoromethylation of arylboronic acids with broad substrate scope.
Ligand development underlies many advances in Pd-catalysed cross coupling but has seen limited application in the growing field of Ni catalysis. Now, a phosphine framework is shown to enable Ni-catalysed Suzuki coupling of acetals. Parameterization studies provide structural insight into ligand success and a quantitative model to facilitate further ligand design.
Lysine-rich peptides from the ribosomal core and derived homolysine decapeptides of either L-, D- or mixed chirality have now been shown to enhance RNA polymerase ribozyme activity at low magnesium concentrations, accelerate ribozyme evolution and enable templated RNA synthesis within membranous protocells.
A dynamic foldamer scaffold has now been ligated to a water-compatible, metal-centred binding site and a conformationally responsive fluorophore to form a receptor mimic that inserts into the membrane of artificial vesicles. Binding of specific carboxylate ligands induces a global conformational change that depends on the structure of the ligand, and can be detected via fluorescence.
Converting oxygen-rich biomass into fuels requires the removal of oxygen groups through hydrodeoxygenation. MoS2 monolayer sheets decorated with isolated Co atoms bound to sulfur vacancies in the basal plane have now been synthesized that exhibit superior catalytic activity, selectivity and stability for the hydrodeoxygenation of 4-methylphenol to toluene when compared to conventionally prepared materials.
The biomimetic syntheses of bipleiophylline, one of the most complex monoterpene indole alkaloids, and voacalgine A, its biosynthetic precursor, have been achieved from pleiocarpamine starting material. The development of a divergent oxidative coupling for the formation of the benzofuro[2,3-b]indolenine and isochromano[3,4-b]indolenine moieties was key to this accomplishment.
Di- and tripeptide building blocks in which the C-terminus has been converted into an aldehyde are shown to form dynamic chemical networks through imine condensation followed by the formation of cyclic N,N-acetals. The networks exhibit multi-phase growth of prion-like assemblies that template the formation of chain-length-specific peptide-like oligomers.
The development of methods for the site-selective modification of natural products is a topic of contemporary investigation and importance. Now, it has been shown that benzynes produced by the hexadehydro-Diels–Alder (HDDA) reaction react with many secondary metabolites, with a substantial preference for one of several potential pathways.
Simple peptides are shown to assemble into well-defined amyloid phases with paracrystalline surfaces that can catalyse reactions in an enantioselective manner. Modifying individual amino acids in the building blocks enables the structure of the assembled aggregates, and the reactions that they can catalyse, to be controlled predictably.
Made under a cloak of wartime secrecy, yet announced in the most public of ways — a radioactive element that governments insist we take into our homes. Ben Still explains how element 95 is one of real contradiction.
Free radicals are notorious for unselective coupling reactions; however, the coupling of free radicals generated from acyl tellurides has now been shown to form C–C bonds with remarkable fidelity, which enables easy one-step assembly of densely oxygenated natural product motifs.
The process of electronic energy transfer between molecules has long fascinated chemists. Femtosecond spectroscopy measurements of a series of molecular dimers now reveal signals that arise from non-Born–Oppenheimer coupling, suggesting a new mechanism to enhance energy transfer.
Synthetic heterodimers provide a platform to demonstrate molecular design principles of vibronic coupling. Now, it has been shown that quantum beating caused by vibronic coupling can be controlled by packing a structurally flexible heterodimer on single-walled carbon nanotubes. This quantum beating requires a vibration to be resonant with the energy gap between excited states and structural rigidity.
Many properties of polymers are dictated by topology. However, the topology of a macromolecule is typically a static feature after synthesis. Now, an approach to dynamic and transformable macromolecular architecture has been developed. When triggered by an external stimulus, macromolecular topology can be triggered to transform via thermodynamic control.
Electron-transfer-mediated decay (ETMD) is a recently discovered type of electronic relaxation that involves the refilling of a core hole by an electron from a neighbouring species. It has now been observed in LiCl solution, when previously it had only been seen in rare-gas clusters. Spectra generated during ETMD are observed to be sensitive to the immediate environment of the initially ionized ion.
