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  • News & Views |

    Polyketide synthases are multi-domain enzymes that catalyse the construction of many bioactive natural products. Now, some of the inefficiencies and limitations of these systems have been solved by designing an artificial pathway for carbon–carbon bond formation via iterative rounds of non-decarboxylative thio-Claisen reactions.

    • Anuran K. Gayen
    • , Lindsay Nichols
    •  & Gavin J. Williams
  • News & Views |

    Macrocyclic peptide natural products are important medicinal compounds. The catalytic properties of an unusual peptide cyclase enzyme have recently been described — providing opportunities for the engineering and synthesis of structurally complex peptides with novel biological activities.

    • Mohamed A. Attia
    •  & Christopher J. Thibodeaux
  • News & Views |

    Catalysts are the heart of CO2 electroreduction technology. Now, a catalyst has been developed that converts CO2 into C2+ products with very high selectivity, stability, and energy efficiency at industrially relevant current densities.

    • Cao-Thang Dinh
  • News & Views |

    A rapid and efficient electrochemical reaction requires active catalytic material, as well as proper electrode and cell design. Now, a gas diffusion electrode based on a stainless steel cloth successfully overcomes gas transport limitations for high-current ammonia electrosynthesis in non-aqueous solvents at ambient conditions.

    • Claudio Ampelli
  • News & Views |

    The chemoenzymatic potential for the construction of complex chiral molecules has not been fully explored. Now, Candida antarctica lipase B has been used to synthesize complex functionalized planar chiral macrocycles, providing a platform for the efficient and sustainable preparation of molecules that are of particular interest in drug discovery.

    • Jose M. Palomo
  • News & Views |

    Understanding the surface structure of a catalyst under a reaction environment is challenging, yet necessary. Now, a combination of in situ methods reveals the reversible formation of a surface alloy as the active phase for core–shell Ni–Au nanoparticles during CO2 hydrogenation, which could not be detected by ex situ methods.

    • Rongming Wang
  • News & Views |

    The introduction of single abiological catalytic groups enables enzymes to catalyse new-to-nature chemical transformations. Now, this concept is extended to two abiological groups in a single protein scaffold to allow synergistic catalysis in a stereoselective Michael addition reaction.

    • Xinkun Ren
    •  & Rudi Fasan
  • News & Views |

    Hydrogen peroxide is a powerful oxidizing agent with many applications. Now, a method is presented to generate it from the oxidation of water on a polytetrafluoroethylene-coated glassy carbon electrode with high efficiency.

    • Carlos Ponce de León
  • News & Views |

    Identifying the rate-determining step (RDS) for oxygen incorporation into mixed ionic and electronic conducting electrodes is very challenging, particularly since the local composition changes during the reaction. Now, a generally applicable method for identifying the RDS is presented, with the example of a Pr0.1Ce0.9O2–x electrode.

    • Ellen Wachtel
    •  & Igor Lubomirsky
  • News & Views |

    The electrochemical synthesis of high-value chemicals is still far from industrial application, mostly due to the lack of stable and efficient catalysts. Now evidence reveals that gaining a fundamental understanding of an electrochemical reaction can lead to faster development of optimal catalytic materials.

    • Marta C. Figueiredo
  • News & Views |

    Intensified interest in the area of nickel catalysis has driven the quest for an air-stable and modular Ni(0) precatalyst. Now, an air-stable Ni(0)-olefin precatalyst allows for the convenient set-up of nickel-catalysed reactions on the benchtop.

    • Timothy B. Boit
    • , Katie A. Spence
    •  & Neil K. Garg
  • News & Views |

    Simple methods to incorporate deuterium into organic compounds are highly sought after as deuteration can enable mechanistic studies or improve the metabolic stability of pharmaceuticals. Now, a catalytic hydrogen–deuterium exchange reaction using deuterated water allows convenient access to deuterated aldehyde building blocks.

    • Sarah M. Anthony
    • , Andrew V. Kelleghan
    • , Milauni M. Mehta
    •  & Neil K. Garg
  • News & Views |

    Because of the high strength of N≡N bonds, N2 is often employed as an inert gas. Now it has been shown that it can partly react to yield surface nitrogen species that facilitate C–O hydrogenolysis reactions on supported Ru catalysts.

    • Thomas J. Schwartz
  • News & Views |

    Enzymes require many, often hundreds, of amino acid residues arranged in a protein fold to promote catalysis. Now, self-assembly of a single amino acid — phenylalanine — in the presence of zinc is shown to form supramolecular structures that promote hydrolysis better than natural enzymes on a weight basis.

    • Olga V. Makhlynets
    •  & Ivan V. Korendovych
  • News & Views |

    Bio-inspired by cellular respiration, the richness of oxygen redox chemistry is a cutting-edge field for building lithium batteries. While the Li–air battery uses external oxygen, a new lithium battery offers a high energy-density and long-term cycling stability just by confining oxygen and lithium between graphene oxides.

    • Yachao Zhu
    •  & Olivier Fontaine
  • News & Views |

    Imine reductases are promising catalysts, facilitating a direct stereoselective route to secondary amines. Now, protein engineering has created stable and efficient variants that allow their application in kilogram-scale synthesis.

    • Matthias Höhne
  • News & Views |

    Given the importance of enantioenriched β2- and β3-amino acids as building blocks, direct and versatile methods for their synthesis are highly coveted by organic chemists. Now, using easily accessible 1,3-oxazinane motifs, a regiodivergent and enantioselective C–H functionalization method permits their synthesis in a straightforward and practical fashion.

    • Oriol Planas
    •  & Josep Cornella
  • News & Views |

    The design of heterogeneous catalysts with tunable activity and selectivity constitutes a remarkable challenge. Now, a synthetic approach towards producing nanocrystals encapsulated within polymer layers has been developed, unravelling the principles to achieve control of transition state and product diffusion using CO oxidation as a case study.

    • Qiang Fu
    •  & Xinhe Bao
  • News & Views |

    Transition metal-catalysed bioorthogonal reactions are severely hindered in biomedical applications, mainly due to a lack of target specificity. Now, research shows that a trojan exosome vesicle can deliver a palladium catalyst specifically to progenitor cells for bioorthogonal catalysis, allowing localized prodrug activation.

    • Zhi Du
    •  & Xiaogang Qu
  • News & Views |

    Fusion systems have been designed that link enzymes to cofactors and immobilization modules through appropriate synthetic spacers. These modular biocatalysts (assembling catalysis, cofactor provision/regeneration and assisted immobilization) are suited to heterogeneous biocatalysis systems and can be efficiently used in continuous flow reactors.

    • Martina Letizia Contente
    •  & Francesco Molinari
  • News & Views |

    Conventional experiments for generating proteins with improved properties by directed evolution are iterative, lengthy and costly. Now, a label-free assay has been developed for ultrahigh-throughput microfluidic screening that can dramatically accelerate the discovery of superior biocatalysts from a single round of genetic randomization.

    • Wolf-Dieter Fessner
  • News & Views |

    A strategy using pressure was devised to structurally identify conformational transitions in protein ensembles, allowing the rational prediction of mutations that induce pressure-driven enzyme activation. These results highlight the power of flexibility–function analyses in protein engineering design and applications.

    • Nicolas Doucet
  • News & Views |

    S-adenosylmethionine (SAM)-dependent methyltransferase enzymes have significant synthetic potential, but their utility as biocatalysts has been limited by the availability of SAM. An elegant and simple method addressing this long-standing problem has now been developed using a halide methyltransferase (HMT) enzyme for SAM regeneration in vitro.

    • Jason Micklefield
  • News & Views |

    Understanding the nature of active sites in carbon electrocatalysis remains a subject of dispute and a great scientific challenge. Convincing new evidence supports the fact that, for oxygen reduction, defects present in carbon materials are more powerful catalytic sites than nitrogenated sites.

    • Magdalena Titirici
  • News & Views |

    Tailoring platinum-based catalysts is of great research interest in the fields of electrochemical energy conversion and storage, as well as other applications. Now, an approach has been developed to boost the activity of platinum catalysts at the atomic scale.

    • Feng Li
    •  & Jong-Beom Baek
  • News & Views |

    Hydrogenases are very powerful biocatalysts for dihydrogen cleavage. Now, X-ray crystallography shows how [Fe]-hydrogenase requires ligand exchanges at the metal centre and significant molecular motions to open and close its active site to effectively transfer a hydride to an electrophilic organic substrate.

    • Yvain Nicolet
  • News & Views |

    The biological functions of glycan motifs such as the Lewis blood antigens are often defined by their precise multivalent presentation on complex glycoconjugates, making synthesis particularly challenging. Access to a number of positionally defined Lewis motifs on natural polysaccharide scaffolds has now been achieved using bacterial glycosyltransferases.

    • Kun Huang
    •  & Sabine L Flitsch
  • News & Views |

    A synthetic DNA enzyme catalyses the formation of a native phosphodiester bond between two RNA fragments, but the molecular details of the mechanism remained elusive. Research using computational and biochemical approaches now suggests that the DNA enzyme recruits two magnesium ions to assist in the catalysis of RNA ligation.

    • Claudia Höbartner
  • News & Views |

    Given the fact that sodium is the most abundant alkali metal on Earth, the direct and indirect use of organosodium compounds in palladium-catalysed carbon–carbon bond forming reactions is an attractive alternative for sustainable organic synthesis.

    • Henry N. C. Wong
  • News & Views |

    Good durability and activity of single Ru atom catalysts is critical for their large-scale utilization in electrochemical water splitting. Now, both of these properties can be better controlled through compressive strain engineering.

    • Boon Siang Yeo
  • News & Views |

    High-yield production of a functionally active mimic of particulate methane monooxygenase in Escherichia coli has been presented. Investigation of its catalytic mode clarifies the role of duroquinol in biomimetic methanol production.

    • Sunney I. Chan
    •  & Steve S.-F Yu
  • News & Views |

    The diversity of engineered amine dehydrogenases for reductive amination remains limited. Now, native amino dehydrogenases offering a different sequence space and catalytic features are discovered — enhancing and broadening the biocatalysis toolbox.

    • Andreas S. Bommarius
  • News & Views |

    The asymmetric synthesis of chiral γ-lactams is difficult and laborious; typically requiring pre-functionalization of starting materials. Now, a highly efficient alternative approach employing direct C−H amidation via chiral hydrogen-bond-donor catalysts has been developed.

    • Tong-De Tan
    •  & Long-Wu Ye
  • News & Views |

    The selective electrochemical conversion of ketones to value-added products still represents a challenge, due to a lack of fundamental understanding. Now, a principle has been revealed that allows the steering of the electroreduction of aliphatic ketones on platinum by carefully controlling the coordination number of the platinum atoms.

    • Ivana Matanović
  • News & Views |

    The synthesis of highly branched low molecular weight products — potential synthetic lubricants — directly from ethylene is challenging when highly efficient early transition metal catalysts are employed. Now, an alkane soluble co-catalyst permits the synthesis of such polyethylenes using a zirconium catalyst in a saturated hydrocarbon solvent, where competitive solvent coordination at the active site of the catalyst is relatively unimportant.

    • Rhett Kempe
  • News & Views |

    Optimization of catalytic stereoselectivity for new substrates often requires a time consuming experimental process, and high-accuracy molecular modelling remains intractable for comprehensive virtual screening. Now, highly enantioselective rhodium hydrogenation catalysts have been identified using a rapid computational transition-state analysis protocol and then experimentally verified.

    • Daniel H. Ess
  • News & Views |

    Nanoscale texture of electrocatalysts, enabled by the tools of nanoscience, is emerging as an important lever for the control of electrochemical reaction pathways.

    • Adam J. Rondinone
    •  & Jingsong Huang
  • News & Views |

    A crucial malonic acid moiety in the antibiotic malonomycin has been shown to be installed by a bacterial vitamin K-dependent (VKD) carboxylase orthologue.

    • Max J. Cryle
  • News & Views |

    The biosynthesis of the pharmacophoric tetrahydropyran of the clinically important antibiotic mupirocin remained enigmatic for a long time. Now, research shows that this ring is formed by a unique epoxidation–epoxide-opening cascade starting from a non-activated alkane.

    • Frank Hahn
  • News & Views |

    Single-atom catalysts recently attracted considerable research interest for heterogeneous electrocatalysis, including the oxygen reduction reaction. Now, an intriguing two-step approach towards a less explored atomic nitrogen-coordinated manganese with a high loading density has been developed.

    • Chenhao Zhang
    •  & James M. Tour
  • News & Views |

    Indirect methods are generally adopted to elucidate complicated mechanisms of transition metal catalysis. Now, a way to directly observe transient manganese species and monitor key reaction steps has been established by using time-resolved multiple-probe spectroscopy.

    • Congyang Wang
  • News & Views |

    Despite being used as a water-oxidation catalyst in alkaline electrolysis for over a century, the details of how Ni–Fe (oxy)hydroxide catalysts function remains unclear. Now, using a nanoparticle model system, the intrinsic activity and underlying catalytic mechanism is probed.

    • Shannon W. Boettcher
  • News & Views |

    The mechanism of methanol coupling to methyl formate over single-crystal gold catalysts has been firmly established but barely reconciled with experiments performed under practical conditions. Now, a method to close this gap has been reported, which enables the prediction of the reaction´s selectivity for a broad range of experimental conditions.

    • Rachel B. Getman
  • News & Views |

    The electroreduction of CO represents a promising approach toward artificial hydrocarbon synthesis, but its rate is limited by the sluggish transport of CO in aqueous electrolytes. Recent work shows how the issue can be circumvented by using gas diffusion electrodes.

    • David Raciti
    •  & Chao Wang
  • News & Views |

    Development of an earth-abundant and inexpensive copper-based catalyst is desirable for CO2 hydrogenation. Now, the combined application of a stable copper hydride and a Lewis pair is shown to effect activation of CO2 as well as heterolysis of H2, achieving significant turnover numbers.

    • Yoshihito Kayaki
    •  & Ryo Watari
  • News & Views |

    Heterogeneous photocatalysts are rarely employed in industry for the synthesis of commodity chemicals due to efficiency problems. Now, a photochromic Bi2WO6–x/amorphous-BiOCl composite is reported, which features a remarkable activity for the photocatalytic oxidation of toluene into benzaldehyde and benzoic acid.

    • Anna Kubacka
    •  & Marcos Fernández-García
  • News & Views |

    Artificial metalloenzymes generally consist of a synthetic (organo)metallic catalyst incorporated into a protein. Asymmetric catalysis by such metalloenzymes could result by virtue of the chiral protein environment. Now, redox-sensitive anchoring enables reversible incorporation of an iridium catalyst for transfer hydrogenation.

    • Jun Okuda
  • News & Views |

    Typically, catalysts are discovered through trial and error coupled with chemical intuition. Now, an automatic machine-learning framework has been developed that can guide itself to find intermetallic surfaces with desired catalytic properties.

    • Zheng Li
    • , Siwen Wang
    •  & Hongliang Xin
  • News & Views |

    The chemical synthesis of natural products, such as sesquiterpenes, is a daunting task due to their complexity and precise functionalization, and multiple synthetic and purification steps that reduce overall yields are usually required. Now, a highly efficient alternative approach using supramolecular chemistry has been proposed by Tiefenbacher and co-workers.

    • Dan Thomas Major
  • News & Views |

    Metalloprotein activity can be tuned by altering first- and second-sphere interactions with the metal ion or ions. Here, a non-canonical haem axial ligand is introduced into a myoglobin variant, modulating both. The resulting enhancement of cyclopropanation activity illustrates the utility of expanding the suite of available amino acids for biocatalyst engineering.

    • Emily H. Edwards
    •  & Kara L. Bren