TABLE OF CONTENTS
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June 2015 Volume 7, Issue 6 |
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Research Highlights | Top |
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Stimuli-responsive materials: Falling to pieces faster | Oxygen-evolving complex: The state of manganese | Proteomics: Profiling lipidated proteins | Molecular sensors: Spoiler alert |
Blogroll | Top |
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Blogroll: Those who left p466 Brandon Findlay doi:10.1038/nchem.2263 |
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News and Views | Top |
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 Organofluorine chemistry: A Janus cyclohexane ring pp467 - 468 Nico Santschi and Ryan Gilmour doi:10.1038/nchem.2240 The first synthesis of the all-cis isomer of 1,2,3,4,5,6-hexafluorocyclohexane, a molecule with one hydrocarbon face and one fluorocarbon face, is a tour de force of organofluorine chemistry and opens up new possibilities for molecular design.
See also: Article by Keddie et al. |  |  |  | Main group chemistry: Small silicon oxides isolated pp468 - 470 Yitzhak Apeloig doi:10.1038/nchem.2271 Bulk SiO2 is widespread in nature, and silicon oxide clusters are important to a variety of applications, yet molecular silicon oxides have remained elusive. Two molecular compounds featuring silicon oxide moieties, Si2O3 and Si2O4, have now been isolated by oxidation of a carbene-stabilized disilicon precursor.
See also: Article by Wang et al. |  |  |  | Metal-organic frameworks: Shuttling in the solid state pp470 - 471 Mark A. Olson doi:10.1038/nchem.2268 Incorporating mechanically interlocked molecular shuttles within a metal-organic framework that has enough free space in the crystal lattice to permit volume-conserving translational motion sets the stage for defect-free molecular-electronic device fabrication and more.
See also: Article by Zhu et al. |  |  |  | Supramolecular polymers: Chain growth in control pp472 - 473 Renren Deng and Xiaogang Liu doi:10.1038/nchem.2265 Supramolecular polymerizations typically proceed through stepwise intermolecular mechanisms, concomitant with many side reactions to yield aggregates of unpredictable size, shape and mass. Now, a chain-growth strategy is shown to allow assembly of molecules into supramolecular chain structures endowed with precisely controlled characteristics. |  |  |  | Computational chemistry: Making a bad calculation pp473 - 475 Arthur Winter doi:10.1038/nchem.2267 Computations of the energetics and mechanism of the Morita-Baylis-Hillman reaction are “not even wrong” when compared with experiments. While computational abstinence may be the purest way to calculate challenging reaction mechanisms, taking prophylactic measures to avoid regrettable outcomes may be more realistic. |  | |  | |
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Perspective | Top |
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Orthogonal tandem catalysis pp477 - 482 Tracy L. Lohr and Tobin J. Marks doi:10.1038/nchem.2262

One-pot tandem reactions are attractive for both waste and time reduction, but can also enable transformations otherwise unobtainable in single-step processes. This Perspective covers recent advances in orthogonal tandem catalysis, while introducing the concept of thermodynamically leveraging multiple catalytic systems together to perform challenging transformations. |
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Articles | Top |
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All-cis 1,2,3,4,5,6-hexafluorocyclohexane is a facially polarized cyclohexane pp483 - 488 Neil S. Keddie, Alexandra M. Z. Slawin, Tomas Lebl, Douglas Philp and David O'Hagan doi:10.1038/nchem.2232

The highest-energy stereoisomer of 1,2,3,4,5,6-hexafluorocyclohexane, with all the fluorines ‘up’, has been prepared in a 12-step protocol. The molecule adopts a chair conformation with three triaxial C–F bonds on one face generating a polarized ring. In the solid state the molecules pack in an orientation consistent with electrostatic ordering. Chemical compounds See also: News and Views by Santschi & Gilmour |
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Applying green chemistry to the photochemical route to artemisinin pp489 - 495 Zacharias Amara, Jessica F. B. Bellamy, Raphael Horvath, Samuel J. Miller, Andrew Beeby et al. doi:10.1038/nchem.2261

Two semi-synthetic processes for the production of the antimalarial natural product artemisinin have been developed by applying the principles of green chemistry. Solvent manipulation allows catalyst recycling and reduction of waste, ultimately leading to a purification-free process with lower environmental and economic costs; a potential contribution to the world-wide fight against malaria. |
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The critical role of phase-transfer catalysis in aprotic sodium oxygen batteries pp496 - 501 Chun Xia, Robert Black, Russel Fernandes, Brian Adams and Linda F. Nazar doi:10.1038/nchem.2260

Better understanding of the chemistry of rechargeable metal–oxygen batteries is needed to fulfil their potential. It is now shown that proton phase-transfer catalysts drive Na–O2 batteries, transporting superoxide between the electrode surface and the electrolyte as HO2. The chemistry uncovered gives rise to the system's high reversible capacity. |
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Freeze–thaw cycles as drivers of complex ribozyme assembly pp502 - 508 Hannes Mutschler, Aniela Wochner and Philipp Holliger doi:10.1038/nchem.2251

During the early stages of life on Earth sophisticated RNA catalysts must have formed from simple precursors. Here it is shown that freeze–thaw cycles can drive the assembly of complex RNA polymerase ribozymes from networks of short RNA oligonucleotides through an unanticipated RNA chaperone effect. |
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Stabilization of elusive silicon oxides pp509 - 513 Yuzhong Wang, Mingwei Chen, Yaoming Xie, Pingrong Wei, Henry F. Schaefer III et al. doi:10.1038/nchem.2234

Molecular SiO2 and other simple silicon oxides have remained elusive despite the importance of silicon dioxide materials in advanced electronic devices. Clusters Si2O3 and Si2O4 have now been experimentally realized by direct oxidation of a carbene-stabilized disilicon using N2O and O2, respectively. Chemical compounds See also: News and Views by Apeloig |
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A molecular shuttle that operates inside a metal–organic framework pp514 - 519 Kelong Zhu, Christopher A. O'Keefe, V. Nicholas Vukotic, Robert W. Schurko and Stephen J. Loeb doi:10.1038/nchem.2258

The piston-like, translational motion of a molecular shuttle — a process that is fundamental to many mechanically interlocked molecular switches and machines — has now been demonstrated to occur inside the highly organized and dense structure (containing approximately 1021 shuttles per cm3) of a metal–organic framework material. Chemical compounds See also: News and Views by Olson |
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Adsorption-induced auto-amplification of enantiomeric excess on an achiral surface pp520 - 525 Yongju Yun and Andrew J. Gellman doi:10.1038/nchem.2250

Equilibrium adsorption of non-racemic mixtures of enantiomers onto an achiral surface is shown to lead to enantioenrichment by formation of homochiral clusters. Such auto-amplification must influence enantioselective processes such as heterogeneous catalysis, adsorption-based separations, and perhaps the processes that lead to the homochirality of life on Earth. |
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An infinite chainmail of M6L6 metallacycles featuring multiple Borromean links pp526 - 531 Flora L. Thorp-Greenwood, Alexander N. Kulak and Michaele J. Hardie doi:10.1038/nchem.2259

Metallacycles made up of six copper ions and six cyclotriguaiacylene-based ligands form a unique topological entanglement in the solid state. Individual metallacycles are interwoven into an infinite 2D chainmail network where each one forms multiple Borromean-ring-like associations with its neighbours. Crystals of the complex grow in an unusual tubular morphology. Chemical compounds |
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In Your Element | Top |
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Homely holmium p532 Brett F. Thornton and Shawn C. Burdette doi:10.1038/nchem.2264 Brett F. Thornton and Shawn C. Burdette consider holmium's hotly contested discovery and later obscurity. |
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