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Comparing how cyclopropanated polymers with different backbones behave when stretched with an atomic force microscope reveals that it is not only the strained rings that influence the mechanochemical response, but that the structure of the polymer backbone itself is far from innocent in this regard.
The metal cofactors responsible for the activity of CDK2 — a representative member of the kinase superfamily of enzymes — have now been shown to also have inhibitory effects during the catalytic cycle.
Quantum mechanics rears its head in many places and one of them is inorganic chemistry, where the electronic spin associated with unpaired electrons has a profound influence. This was the topic of the 2012 CECAM workshop.
Natural products contain a range of chemical structures optimized for biological interactions. Fragmenting these compounds could help to combine this diversity with the broad coverage of chemical space offered by fragment-based drug discovery, and help to improve the efficiency with which screening hits can become successful drugs.
An experimental set-up has been devised to monitor mechanochemical processes in situ, yielding direct insights into mechanistic and kinetic aspects of solid-state reactions that are promoted by grinding, such as the synthesis of metal–organic frameworks.
The biosynthesis of peptidoglycan is an important step in bacterial cell division and cell-wall maturation. Now it has been shown that fluorescent D-amino acids can be used to label the peptidoglycan cell wall of living bacteria, providing a new tool to study this important process.
Uranium and manganese cations have been combined in a wheel-shaped supramolecular assembly that retains its magnetic spin state after the external field is removed, with a high barrier to its relaxation. This cluster supports recent predictions of the usefulness of the actinides in single-molecule magnetic devices.
The deposition of cobalt-phosphate onto photocatalytic haematite improves its ability to split water and thus create clean hydrogen fuel. The source of this improvement is, however, not yet understood, and now two separate studies suggest different roles for the deposited cobalt-phosphate.
The reversible reduction and evolution of oxygen are the key processes to be mastered before high-energy rechargeable lithium–air batteries can be successfully created. Now an advance towards this goal has been achieved with the synthesis of a pyrochlore catalyst that benefits from a mesoporous structure and oxygen deficiencies.
In 1972, Baird published rules describing aromaticity and antiaromaticity in the lowest triplet excited states of annulenes. The fortieth anniversary of Baird's rules — which are the reverse of Hückel's rules for aromaticity and antiaromaticity in the ground state — ought to be celebrated before 2012 comes to an end.
Bioactive molecules frequently contain several very similarly reactive functional groups and it can thus be difficult to cause one to react selectively. Now, two separate studies present complementary approaches to this desirable goal.
Liposomes are a leading drug-delivery platform in cancer chemotherapy. Now they can be used to destroy cancer cells through a method that converts chemical energy to mechanical force. These localized disruptions can cause cell death while minimizing the collateral damage to neighbouring cells.
The complexity of living systems makes attempts to gain a molecular-level understanding of them a unique and inspiring challenge. This Review summarizes progress in the development of bioorthogonal reaction-based fluorescent probes used to follow the spatial and temporal dynamics of biologically important analytes within living systems.
A dramatic switch of reactivity — from hydroquinone oxidation to N-hydroxylation — can be achieved through the rational engineering of a de novo-designed di-iron protein. Four specific amino-acid mutations spread throughout the first, second and third coordination shells result in a million-fold increase in the relative rate of these two reactions.
Switchable molecular materials generally alternate between two different states that are both stable in identical conditions. A magnetic molecular system is now available that allows switching between three different phases of the same compound.
This Review describes the general trends and implications of heterogeneities within individual catalyst particles as observed by modern spatiotemporal spectroscopy. It discusses how catalytic materials have been found to display heterogeneities in structure, composition and reactivity in space and time. The implications of these findings for future catalyst design are also described.
The combination of addressable synthetic macromolecules with proteins of precise structure and function often leads to materials with unique properties, as is now shown by the efficient multi-site initiation of polymer growth inside the cavity of a virus capsid.
Limitation controls reactivity — structural constraint of phosphorus has now enabled the development of a phosphine-catalysed transfer hydrogenation process akin to transition metals.
Nucleic acid aptamers have been employed to shield small molecules so that one among many similar reactive functional groups can be modified. This provides access to new chemical entities with potentially interesting properties while avoiding the use of covalent protecting groups.
