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A molecular 'walker' can be made to move up and down a molecular 'track' by alternately locking and unlocking the two different types of covalent bonds that join the two components together. By changing the conditions under which one of the bond-forming/bond-breaking processes occurs, a directional bias for walking can be achieved.
The use of conventional computers to calculate molecular properties is hindered by the exponential increase in computational cost on increasing the size of the molecules studied. Using quantum computers could be the solution and the initial steps are now being taken.
Quantum tunnelling can at times be the cause of kinetic isotope effects, and in these cases conventional wisdom has been that molecules with isotopes of larger mass will react more slowly. New calculations, however, predict that sometimes the reverse should be true.
An enzyme that is unusually tolerant of a truly broad range of substrates can catalyse aldol-type chemistry on sugars in which the various hydroxyl groups are protected. The new methodology combines some of the most important advantages of enzyme and small-molecule catalysis.
In the search for superheavy elements, element 112 was a stepping stone towards the 'islands of stability'. Sigurd Hofmann now relates the steps that led to its 'creation' and detection.
Chlorine-activation reactions on polar stratospheric cloud (PSC) particles are crucial to ozone depletion in the winter/spring polar stratosphere and their rates depend on the phase state of the PSC particle surface. Now experiments show that, on particle formation, a phase separation into pure ice with a residual solution coating takes place.
The ability to rapidly functionalize polymers is vital for application development. Here, a method for the introduction of masked ketenes into monomers for both ring-opening metathesis and radical-type polymerizations is described. These ketenes — a group previously underexploited in polymer chemistry — allow both crosslinking and post-polymerization functionalization of the polymers.
The selective construction of multiple adjacent stereocentres is an important challenge for synthetic organic methodology, and only a handful of catalytic methods exist that can forge adjacent quaternary and tertiary stereocentres. Here, a palladium-catalysed multiple-bond-forming cascade leads to the construction of such systems in high yield, diastereomeric ratio and enantiomeric excess.
A method for observing the photodynamics of single molecules, without having to immobilize them to a surface or confine them within vesicles, has been used to study the important photosynthetic antenna protein, allophycocyanin. Light-induced conformational changes and a complex relationship between fluorescence intensity and lifetime have been observed.
Insertion of tungsten into a carbon–carbon bond of a heterocyclic ligand is a rare example of C–C bond activation and could provide new opportunities for the functionalization of aromatic molecules.
Details of how an ion's reactivity is affected by the size and shape of the water network surrounding it have been elucidated using infrared spectroscopy.
A combined theoretical and experimental approach has been used to investigate the structure and bonding of an all-boron cluster (B19−). Calculations suggest that the minimum energy structure is a near-planar one — in which a pentagonal B6 unit is encircled by a larger B13 ring — possessing two concentric aromatic π systems.
A perforated framework material of gallium antimony sulfide is able to selectively extract caesium ions from solution. After this capture, the holes close and prevent the ions leaching back out. This dynamic response could be used to remove caesium from nuclear waste.
The formation of single-layer-thick molecular networks at metal surfaces is governed by the interplay between intermolecular and interfacial interactions. This Review highlights how, with films built by vacuum deposition, these interactions can be modulated to form substrates that may be useful as catalysts or templates for further deposition steps.
Silicon, like carbon, favours a four-coordinate geometry and this underpins the frameworks of the wide range of inorganic and organosilicon compounds, from silicate minerals to polysilanes. Although some pentavalent silicon compounds have already been reported, this work presents the first example where two five-coordinate silicon atoms are bonded to each other.
Ready access to sugars in which the various hydroxyl groups are differentially protected will be of benefit in the production of vaccines, antibiotics and drugs. Here, a chemoenzymatic method that provides a direct route to such protected sugars is described.
Highly diastereoselective Negishi cross-coupling reactions between 2-, 3- and 4-substituted cycloalkylzinc reagents and aryl iodides are described. In all cases, the thermodynamically most stable diastereomers of the cross-coupling products were obtained. NMR spectroscopy and density functional theory calculations were performed in order to rationalize the observed stereoselectivities.