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Before the internet, chemists used references books to find necessary information. Michelle Francl takes us on a journey through the weird and wondrous world captured in the most famous reference book of them all, known to some as the ‘Rubber Bible’.
Amines are predominant motifs in pharmaceuticals, but complex amines are challenging to generate. Now, enabled by triple Au–H/Au+/Au–H relay catalysis, the synthesis of complex and structurally diverse amines by a direct reductive hydroamination of alkynes with nitroarenes is reported. Catalytic intermediates were isolated to elucidate the mechanism.
The first steps of charge transfer in molecules after their interaction with light occur on an ultrafast timescale. Now, by combining attosecond pump/few-femtosecond probe spectroscopy with quantum chemistry calculations, it has been shown that a concerted nuclear and electronic motion drives electron transfer in donor–π–acceptor molecules on a sub-10-fs timescale.
Liposomal systems frequently face challenges, such as low encapsulation efficiency and inadequate controlled release capabilities. Innovatively designed multi-compartment liposomes now overcome these limitations by facilitating precise control over cargo loading and release kinetics, and by serving as microreactors for biochemical synthesis.
Although all-solid-state Li batteries offer a safe, energy-dense alternative to commercial Li-ion batteries, their development is impeded by the sluggish Li-ion transport within solid electrolytes. Now, anion configuration regulation has been shown to promote Li-ion migration, offering a new approach for designing highly Li-ion-conductive solid electrolytes.
The translocation of alkenes and remote functional groups is an ingenious strategy to reorganize complex structures, yet it is rarely investigated, owing to the challenges in controlling multiple selectivities. Now, an efficient photo/cobalt dual-catalytic method has been developed to accomplish alkene difunctionalization.
While solid-state lithium-ion batteries offer promising energy densities for safe energy storage, typical solid electrolytes show poor room-temperature ionic conduction. Now the origin of the superionic transition observed in Li3YCl6-type Li-ion conductors is revealed by in-depth crystal structure characterizations and improved ionic conductivities achieved by lowering the transition temperature.
A method called flash-within-flash Joule heating (FWF) has been developed based on a dual reactor design, enabling the gram-scale synthesis of diverse inorganic materials within seconds. Comparison with commercially available materials suggests that FWF products can offer comparable, or superior, electronic characteristics and tribological performance.
Boron dipyrromethenes (BODIPYs) have found widespread applications owing to their spectroscopic and photophysical properties, but strategies for the synthesis of enantioenriched boron-stereogenic BODIPYs are lacking. Now a modular enantioselective assembly of multi-substituted boron-stereogenic BODIPYs via a Pd-catalysed desymmetric Suzuki coupling has been developed, giving access to a range of highly functionalized chiral BODIPYs.
Radical SAM (rSAM) and 2-His-1-carboxylate enzymes are known to co-occur in RiPP biosynthetic pathways. Here we show the fusion of these enzymes in a single protein where the rSAM enzyme catalyzes cyclophane formation. The 2-His-1-carboxylate enzymes—termed αKG-HExxH—are α-ketoglutarate non-haem iron enzymes that harbour a distinct fold and catalyse β-hydroxylation.
Nitrile-containing molecules and their biosynthetic enzymes are uncommon in nature. Now, a nitrile-forming diiron enzyme involved in the biosynthesis of aetokthonotoxin—the ‘eagle-killing’ neurotoxin—has been characterized using biochemical, structural and biophysical methods. High-resolution protein crystal structures together with the identification of catalytically relevant tryptophan-based products provide mechanistic insights into this unusual nitrile-forming reaction.
Biomolecular condensates compartmentalize molecules without membranes. Understanding condensate composition is important given that their function relies on the selective exclusion or enrichment of molecules. Now, investigating small-molecule partitioning reveals variations across compounds, yet correlations indicate physical similarities between disparate condensates. Machine learning accurately predicts partitioning on the basis of physicochemical features, demonstrating the role of a hydrophobic environment in driving enrichment and exclusion.
The synthesis of C-glycosides relies on specially designed glycosyl donors, which are often unstable and require multi-step synthesis. Now a facile method for the synthesis of diverse C-glycosides from readily available and stable 1-deoxyglycosides has been developed. A ligand-controlled site-divergent functionalization of carbohydrates by C–H sampling/nickel-catalysed cross-coupling has also been realized.
Multiple bonds between heavier main-group elements may exhibit different properties and reactivity compared with their second-row counterparts. Now it has been shown that a NHC-stabilized phosphasilyne, a heavier analogue of nitrile, undergoes thermal isomerization to yield a phosphasilenylidene; this represents a rare example of heavier nitrile–isonitrile isomerization.
While Mo carbide catalysts have demonstrated excellent performance for CO2 conversion chemistry, these catalysts require harsh synthetic conditions and have poor reaction stabilities. Here flame-synthesized unsaturated Mo oxides are shown to undergo carburization during the reverse water–gas shift reaction, and reaction-induced Mo oxycarbide active sites provide excellent catalytic performance.
Simultaneous functionalization of reactive and inert remote sites presents a powerful approach to access complex molecules, yet it is hindered by precise remote C(sp3)–H activation. Now, the accurate translocation of functional groups and remote C–H desaturation has been achieved in parallel through combining functional group migration and cobalt-promoted hydrogen atom transfer.
Zinc and manganese are commonly used reductants but their redox potentials in organic solvents have not been studied. Now, these redox potentials have been measured, revealing the impact of solvents and additives. The reductant potential substantially influences the performance of nickel-catalysed cross-electrophile coupling reactions, highlighting the merits of tunable electrochemical reduction.