Reviews & Analysis

High-resolution mass spectrometry has unrivalled power to analyse individual components of ensembles, rather than ensembles as a whole. This Perspective describes recent advances in the mass spectrometry of synthetic polymers, as well as the limitations of present methods and possible strategies to overcome them.

Hydrogenotrophic methanogenesis involves enzymatic conversion of carbon dioxide to methane. This Perspective describes the reactions at play, with a particular focus on how [Fe]-hydrogenase cleaves dihydrogen and delivers hydride to an organic substrate.

A hollow multishell structure can feature voids between porous shells that allow it to controllably release multiple guests or play host to cascade reactions. This Perspective describes host–guest chemistry and the temporal–spatial ordering and dynamic responses of multishell structures to their environment.

The rules of biological reproduction and evolution may seem to, at first glance, conflict with simple physico-chemical principles. This Perspective identifies the constraints that must be placed on chemical processes in order for them to mimic natural selection seen in biology.

Silylium ions are highly reactive, strongly Lewis acidic and have historically been tricky to isolate. This Perspective highlights the range of methods available for their preparation and the latest examples of their use as catalysts or reagents in organic synthesis.

In this Perspective, recent advances in measuring rates of elementary reactions at model catalyst surfaces are presented. A recent ion-imaging-based technique — velocity-resolved kinetics — is discussed in the context of a typical surface reaction, CO oxidation on Pt.

Intracellular phase separation is a major regulatory mechanism in several biochemical processes. This Perspective describes the contribution of H₂O and biomolecules to this phenomenon in the framework of two well-known models.

Water oxidation catalysts are key components in water-splitting devices that synthesize fuels by using energy, including that from sunlight. This Perspective presents historical developments in molecular water oxidation catalysis, emphasizing studies of ruthenium complexes that have taught us how to design optimal catalysts.

The selective conjugation of two or more molecules is readily achieved using covalent click chemistry or non-covalent click chemistry. The latter approach makes use of complementary molecular recognition partners, and its speed and reversibility are advantageous for many biological applications.

Automation can help in performing routine tasks quickly and consistently. Algorithms facilitate the searching of current knowledge. Combining the two could lead to a chemically intelligent approach to the discovery of not only new molecules but also novel and unpredictable reactivity.

Lewis’ shared electron-pair model was a stroke of genius, describing the structure and reactivity of molecules purely on the basis of his tremendous knowledge of empirical chemistry without any quantum chemistry. Unprecedented in simplicity, its success unfortunately concealed some misleading interpretations of the physical origin of chemical bonding.

This Perspective introduces energy decomposition analysis as a means of providing a quantum chemically derived bonding model that we can use to rationalize molecular geometries and bonding. The model serves as a bridge between the simple Lewis electron-pair bond and the complicated quantum theoretical nature of the chemical bond.

This Perspective describes the physical molecular driving forces that stabilize native lignocellulosic plant biomass structures and govern thermochemical biomass pretreatments. Understanding these driving forces can help us to design efficient methods for deconstructing biomass into biofuels and other bioproducts.

This Perspective describes how reversible catalysis — a hallmark of enzymes — can be reproduced in synthetic catalysts by rationally designing first and second coordination spheres, as well as amino acid-based outer coordination spheres. We describe this in the context of Ni prototypes for efficient H₂ oxidation and evolution.

The study of [FeFe]-hydrogenases exemplifies how one can manipulate even sophisticated metal clusters to afford insights into structure–function relationships of biological catalysts. This Perspective describes developments in designing artificial proteins and catalytically active nucleic acids towards minimalistic and robust semi-biological catalysts for chemical synthesis.

The discovery of bioactive small molecules is generally driven via iterative design–make–purify–test cycles. Progress has been made towards the automation and integration of adjacent stages within such discovery workflows, which can increase the efficiency and effectiveness of bioactive small-molecule discovery.

Humans have evolved innate and adaptive immune systems to survive infection. Chemical approaches have enabled modulation of the immune system to activate or dampen it, leading to the development of new treatments for cancer and autoimmunity.

Metal–ligand interactions are attracting growing attention for the design of new drugs. Current simulation approaches help us gain deep atomistic understanding of the metal–ligand interactions for the discovery and development of potent metalloenzyme inhibitors and metallodrugs.

Ultrafast X-ray spectroscopies enable the investigation of fast chemical dynamics with time resolutions reaching the order of attoseconds. Processes such as spin crossover, structural deformations in excited states and dissociation reactions can now be studied through the use of short X-ray pulses produced by high-harmonic, free-electron-laser and synchrotron sources.

The development of high-performance olefin polymerization catalysts is a major driving force in polyolefin studies. This Perspective discusses some alternative strategies for catalyst design — strategies in which existing systems are tuned beyond merely modifying the electronic and steric properties.