Search

Enzyme immobilisation is of great importance for the fabrication of heterogeneous biocatalysts, as it allows the stabilisation of proteins using a solid support. Moreover, it permits their reuse in continuous and discontinuous reactors. The behaviour of enzymes at the interface with the materials where they are supported is not well understood during operational conditions. Here, we use X-ray fluorescence (XRF) imaging to study the changes in the overall structure of a heterogeneous biocatalyst formed by two unmodified metalloenzymes (a copper-dependent laccase and a zinc-dependent dehydrogenase) upon incubation, either under drastic (high temperature) or operational conditions. Those two enzymes were co-immobilised reversibly (by electrostatic interactions and His-tag metal coordination) to form a cascade reaction that catalyses the NAD + -dependent oxidation of diols coupled to a laccase-mediator for the in situ regeneration of the redox cofactor. Both the protein scaffolds and the metal cofactors undergo rearrangements during operational use or thermal incubation, but they seem to move as a whole unit within the support. Migration inside the support apparently causes only small alterations to the structure of the protein, yet it leads to the exhaustion of the heterogeneous biocatalyst. As such, we show that the use of advanced X-ray spectroscopy with spatial resolution can help obtain a better understanding of the molecular phenomena that occur during the operation of heterogeneous biocatalysts. Overall, this is fundamental to guide the optimisation for more productive and robust bioprocesses based on immobilised enzyme systems., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Recently, planar and neutral tricoordinated oxygen embedded in graphene has been imaged experimentally ( Nat. Commun. , 2019, 10 , 4570-4577). In this work, this unusual chemical species is studied utilizing a variety of state-of-the-art methods and combining periodic calculations with a fragmental approach. Several factors influencing the stability of trivalent oxygen are identified. A σ-donation and a π-backdonation mechanism between graphite and oxygen is established. π-Local aromaticity, with a delocalized 4c-2e bond involving the oxygen atom and the three nearest carbon atoms aids in the stabilization of this system. In addition, the framework in which the oxygen is embedded is crucial too to the stabilization, helping to delocalize the "extra" electron pair in the virtual orbitals. Based on the understanding gathered in this work, a set of organic molecules containing planar and neutral trivalent oxygen is theoretically proposed for the first time., Competing Interests: The authors declare no conflict of interest., (This journal is © The Royal Society of Chemistry.)

A catalytic system based on earth-abundant elements that efficiently hydrogenates aryl olefins using visible light as the driving-force and H 2 O as the sole hydrogen atom source is reported. The catalytic system involves a robust and well-defined aminopyridine cobalt complex and a heteroleptic Cu photoredox catalyst. The system shows the reduction of styrene in aqueous media with a remarkable selectivity (>20 000) versus water reduction (WR). Reactivity and mechanistic studies support the formation of a [Co-H] intermediate, which reacts with the olefin via a hydrogen atom transfer (HAT). Synthetically useful deuterium-labelled compounds can be straightforwardly obtained by replacing H 2 O with D 2 O. Moreover, the dual photocatalytic system and the photocatalytic conditions can be rationally designed to tune the selectivity for aryl olefin vs. aryl ketone reduction; not only by changing the structural and electronic properties of the cobalt catalysts, but also by modifying the reduction properties of the photoredox catalyst., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Catalysis-based approaches for the activation of anticancer agents hold considerable promise. These principally rely on the use of metal catalysts capable of deprotecting inactive precursors of organic drugs or transforming key biomolecules available in the cellular environment. Nevertheless, the efficiency of most of the schemes described so far is rather low, limiting the benefits of catalytic amplification as strategy for controlling the therapeutic effects of anticancer compounds. In the work presented here, we show that flavin reactivity within a hydrogel matrix provides a viable solution for the efficient catalytic activation and delivery of cisplatin, a worldwide clinically-approved inorganic chemotherapy agent. This is achieved by ionically adsorbing a flavin catalyst and a Pt(iv) prodrug as substrate into porous amino-functionalized agarose beads. The hydrogel chassis supplies high local concentrations of electron donating groups/molecules in the surrounding of the catalyst, ultimately boosting substrate conversion rates (TOF >200 min -1 ) and enabling controlled liberation of the drug by light or chemical stimuli. Overall, this approach can afford platforms for the efficient delivery of platinum drugs as demonstrated herein by using a transdermal diffusion model simulating the human skin., Competing Interests: The authors declare that 1-FMN@AGM is protected under the patent application EP20383067.4., (This journal is © The Royal Society of Chemistry.)