Reviews & Analysis

The search for efficient oxygen reduction catalysts made from perovskite oxides rather than expensive precious metals is hindered by the sheer range of these oxides — where should the search begin? Developing design rules that can identify the best candidates is the first step towards a more targeted strategy.

Do unusual geometries always come from the force exerted by a protein, a solid-state lattice or bulky ligands? In a new iron(II) complex, simple ligands stabilize a square-planar high-spin complex through finesse rather than force.

Peptide macrocycles have a number of important applications. Among other things, the reduced conformational freedom of the cyclic structure enables strong binding to the extended contact regions of protein–protein complexes. Here, emerging methods directed towards the synthesis of these valuable molecules are reviewed.

Observing the diffusion of guest molecules in large single crystals of a metal-organic framework reveals surprising insights into the blockage of the channels at the material's surface and the role of defects within its bulk.

A microfluidic device design that allows a nanolitre droplet to be trapped and sequentially diluted without the need for any moving parts opens up new possibilities in high-throughput screening.

Isotopic labelling is widely used to unravel reaction mechanisms, but are conclusions from such studies always robust? Now, studies on the photolysis of CD₃CHO reveal extensive isotopic scrambling before dissociation, which could have implications for our mechanistic understanding of some key aspects of atmospheric photochemistry.

Single-molecule spectroscopy allows fluctuations of conjugated polymer conformation to be monitored during solvent vapour annealing. Dramatic changes in fluorescence behaviour are observed and interpreted in terms of transformations between extended and collapsed polymer geometries.

A diuranium compound featuring an arene bridge shows single-molecule-magnet behaviour, which could arise from a mechanism different from the traditional 'super-exchange' spin coupling.

A highly inventive route for the synthesis of a key substance that stimulates potato cyst nematodes to hatch has been developed. This discovery has potential to impact food supplies, as treatment of crops with this compound could alleviate the devastating effect of these parasites.

The efficient engineering of nanostructures with semiconducting properties is vital to the development of organic electronics. This Perspective discusses a variety of techniques for fabricating such macromolecules, including graphene carving, the stimulus-induced synthesis of conjugated polymers and surface-assisted synthesis, and considers their potential for reproducing chemically and spatially precise molecular arrangements, that is 'molecular blueprints'.

There is a long history of gas-phase studies of bimolecular reactions, but the presence of surrounding molecules complicates analogous studies in solution. Now, advances in ultrafast laser technology have enabled the detailed study of vibrational energy release in a reaction in solution.

Keeping the organic and inorganic precursors in separate, immiscible solutions guides the growth of metal-organic frameworks into uniform thin layers that are shaped just like the liquid-liquid interface.

Enzymes that selectively oxidize unactivated C–H bonds are capable of constructing complex molecules with high efficiency. A new member of this enzyme family is RedG, a Reiske-type oxygenase that catalyses chemically challenging cyclizations in the biosynthesis of prodiginine natural products.

Energetic adsorption of molecules on surfaces is known to either trigger local chemical reactions or initiate the recoil of adsorbates away from the surface. Now, another possible outcome has been observed — the long-range 'cart-wheeling' of energetic molecules across a surface.

Heterogeneous catalyst systems comprising metals supported on oxides are widespread. Evidence now suggests that it is the interfacial regions that are most catalytically active, and this has been exploited to create a tandem nanocatalyst system.

Crystalline networks containing empty cavities can host a variety of molecules but also promote reactions between guests. Through robust crystallinity and a pseudo-solution state (dynamic movements) within their pores, these crystalline molecular flasks enable the direct observation of species — including unstable intermediates — during a reaction by in situ X-ray diffraction.

A model based on the well-known β-cyclodextrin–adamantane receptor–ligand pair has been used to obtain important insight into the kinetics of gradient-driven motion across a surface.

Photosynthesis in plants converts energy from the Sun into chemical fuel in the form of glucose. Now, a strategy to combine carbon dioxide reduction and photochemical water splitting, using a recyclable hydrogen donor, offers the opportunity to develop non-biomimetic photosynthesis.

Photocatalysts such as titanium dioxide that use sunlight to split water and produce hydrogen would be a clean and sustainable solution to many problems, but their efficiency is currently too low to be widely used. Two approaches to engineer the surface properties of titanium dioxide offer hope that its efficiency can be increased.

Controlled energy-transfer on a molecular scale is a goal in many areas of science, from artificial photosynthesis to molecular electronics. Now, DNA origami has been used to direct the transfer of energy from an excited input dye down one of two paths by precisely arranging a mediator dye.