Nature chemistry最新文献

The photophysical processes of singlet fission and triplet fusion have numerous emerging applications. They involve the separation of a photo-generated singlet exciton into two dark triplet excitons and the fusion of two dark triplet excitons into an emissive singlet exciton, respectively. The role of the excimer state and the nature of the triplet-pair state in these processes have been a matter of contention. Here we analyse the room temperature time-resolved emission of a neat liquid singlet fission chromophore and show that it exhibits three spectral components: two that correspond to the bright singlet and excimer states and a third component that becomes more prominent during triplet fusion. This spectrum is enhanced by magnetic fields, confirming its origins in the recombination of weakly coupled triplet pairs. It is thus attributed to a strongly coupled triplet pair state. These observations unite the view that there is an emissive intermediate in singlet fission and triplet fusion, distinct from the broad, unstructured excimer emission.

Lys ubiquitination is catalysed by E3 ubiquitin ligases and is central to the regulation of protein stability and cell signalling in normal and disease states. There are gaps in our understanding of E3 mechanisms, and here we use protein semisynthesis, chemical rescue, microscale thermophoresis and other biochemical approaches to dissect the role of catalytic base/acid function and conformational interconversion in HECT-domain E3 catalysis. We demonstrate that there is plasticity in the use of the terminal side chain or backbone carboxylate for proton transfer in HECT E3 ubiquitin ligase reactions, with yeast Rsp5 orthologues appearing to be possible evolutionary intermediates. We also show that the HECT-domain ubiquitin covalent intermediate appears to eject the E2 conjugating enzyme, promoting catalytic turnover. These findings provide key mechanistic insights into how protein ubiquitination occurs and provide a framework for understanding E3 functions and regulation.

While natural terpenoid cyclases generate complex terpenoid structures via cationic mechanisms, alternative radical cyclization pathways are underexplored. The metal-catalysed H-atom transfer reaction (M-HAT) offers an attractive means for hydrofunctionalizing olefins, providing access to terpenoid-like structures. Artificial metalloenzymes offer a promising strategy for introducing M-HAT reactivity into a protein scaffold. Here we report our efforts towards engineering an artificial radical cyclase (ARCase), resulting from anchoring a biotinylated [Co(Schiff-base)] cofactor within an engineered chimeric streptavidin. After two rounds of directed evolution, a double mutant catalyses a radical cyclization to afford bicyclic products with a cis-5-6-fused ring structure and up to 97% enantiomeric excess. The involvement of a histidine ligation to the Co cofactor is confirmed by crystallography. A time course experiment reveals a cascade reaction catalysed by the ARCase, combining a radical cyclization with a conjugate reduction. The ARCase exhibits tolerance towards variations in the dienone substrate, highlighting its potential to access terpenoid scaffolds.

The relationship between the shape of a molecule and its chemical reactivity is a central tenet in chemistry. However, the influence of the molecular geometry on reactivity can be subtle and result from several opposing effects. Here, using a crossed-molecular-beam experiment in which individual rotational quantum states of specific conformers of a molecule are separated, we study the chemi-ionization reaction of hydroquinone with metastable neon atoms. We show that collision-induced alignment of the reaction partners caused by geometry-dependent long-range forces influences reaction pathways, which is, however, countered by molecular rotation. The present work provides insights into the conformation-specific stereodynamics of complex polyatomic systems and illustrates the capability of advanced molecule-control techniques to unravel these effects.