Volume 6 Issue 4, April 2014

Research efforts related to the Hofmeister series of salt ions have waxed and waned during its long and storied history. The past few decades have, however, witnessed a renaissance in its study, and the importance of the related solvation science is becoming ever more apparent.

To celebrate Nature Chemistry turning five years old, editors past and present each share the story of a paper that, for one reason or another, stands out from all the others they have shepherded into the journal.

Michelle Francl suggests that self-plagiarism is a misleading term and that repeating yourself in publications isn't always a bad thing.

Amyloid fibrils are formed from polypeptide chains assembled into an organized fibrillar structure. Now, it has been shown that such fibrillar structures can also bind metal ions and catalyse chemical reactions.

Kinetic isotope effects are widely used to elucidate reaction mechanisms and are generally interpreted in terms of simple kinetic models. Measurements of this effect for the Penning ionization reaction between helium and dihydrogen highlight the need for a quantum description of chemical reaction rates when sub-kelvin temperatures are approached.

The development of methods for efficiently using carbon dioxide in synthesis would enable chemists to tap into this abundant resource. Now, an indirect route to the copolymerization of alkenes with carbon dioxide shows how this greenhouse gas may prove useful in the search for new 'green' materials.

Separating carbon monoxide from chemically similar nitrogen gas is particularly challenging. Now, a flexible porous coordination polymer has been developed that recognizes carbon monoxide over nitrogen, with structural changes in the material leading to its accelerated adsorption.

A combination of catalytic asymmetric diboration of terminal alkenes and Suzuki–Miyaura cross-coupling has been exploited in the synthesis of a variety of important medicinal agents. The process overcomes a number of problems in the application of these important catalytic processes.

Ion mobility-mass spectrometry (IM-MS) is enhancing many areas of (bio)chemical analysis because it can separate ions both by their mass-to-charge ratio and differences in their cross-sectional area. IM-MS can be used for structural characterization, enhanced analysis of complex mixtures or to gain insights into conformational dynamics.

Compartmentalization of complex chemical networks is an essential step towards the creation of cell-scale molecular systems. The encapsulation of a synthetic biochemical oscillating reaction system into cell-sized emulsion droplets is now demonstrated; a large variability in its oscillatory dynamics is observed, which is attributed to partitioning effects.

Amyloid fibril formation is often catalysed by mature fibrils or other aggregates on the fibrillization pathway; however, fibrils cannot normally catalyse other chemical reactions. Here, small seven-residue peptides designed from first principles are shown to form amyloid fibrils that can efficiently catalyse ester hydrolysis.

The availability of facile cross-coupling protocols is sometimes blamed for the high occurrence of ‘flat’ aromatic molecules in drug-screening collections. Here, reagents are described that make possible the one-step transformation of aldehydes into medium-ring saturated N-heterocycles. The methodology has exceptional substrate scope and functional group tolerance and provides a route to heterocycles not easily prepared by other methods.

The chemistry of group 13 metals (M) is dominated by +1 and +3 oxidation states, so MX₂ species are typically metal–metal-bonded dimers, M(II)₂X₄ or mixed-valence species M(I)M(III)X₄. Now, monomeric M(II)(boryl)₂ radicals have been prepared for gallium, indium and thallium. The compounds — structurally characterized by X-ray crystallography — are stable up to 130 °C and exhibit dominant metal-centred radical character.

A Ni-Ga catalyst that reduces CO₂ to methanol at ambient pressure has been discovered through a descriptor-based computational analysis, and has been shown experimentally to be particularly active and selective. This represents a first step towards the development of small-scale low-pressure processes for CO₂ reduction to methanol from distributed hydrogen production.

Radical polymerization of a metastable lactone intermediate — formed from carbon dioxide and butadiene using a palladium catalyst — produces a high-CO₂-content (29 wt%) polymer. This approach circumvents the thermodynamic and kinetic barriers typically associated with direct copolymerization of carbon dioxide and olefins, and can also be applied to one-pot co- and terpolymerization of carbon dioxide and 1,3-butadienes.

In cold chemistry, quantum phenomena in reactants' translational motion lead to the temporary trapping of reactants in a collisional complex. It is now shown that this metastable complex is responsible for a dramatic quantum kinetic isotope effect as observed in Penning ionization reactions at low temperatures.

FeFe hydrogenases, the enzymes that oxidize or produce H₂, are inactivated under oxidizing conditions. Here, it is shown that this inactivation results from H₂ binding to coordination positions that are normally blocked by intrinsic CO ligands. This flexibility of the active site prevents irreversible oxidative damage.

A family of dipeptide-based metal–organic frameworks has been shown to respond to the presence of guests in a cooperative manner controlled by one amino acid residue. When the linker features a serine residue, guest removal enables the formation of hydrogen bonds between the residue's side-chains, causing a conformational change that closes the MOF's porous domain.

Restoring a protein's function in response to specific stimuli can enable a signalling pathway to be activated and the effect monitored over time. Here, a chemical rescue strategy for restoring protein function inside live cells is described, in which palladium catalysts are used to deprotect a propargylcarbamate group of a lysine analogue.

The conversion of water to oxygen is an essential process for both natural and artificial photosynthesis. Important intermediates in the stepwise mechanism of water oxidation on the surface of cobalt oxide have now been spectroscopically identified, providing key insights for the development of higher-efficiency catalysts made from Earth-abundant materials.

Claude Piguet reflects on the history of erbium, which is very much intertwined with its rare earth cousins yttrium, ytterbium and terbium.

Nature Chemistry is now five years old! To celebrate, we look at some facts and figures relating to the manuscripts that have passed through our hands — including information about how many submissions we have received and where they came from, our referee pool, the authors and titles of published papers, as well as some citation data. Each editor has also picked out one of their favourite papers and explains why it stood out for them.