Wednesday, May 20, 2015

Nature Chemistry Contents June 2015 Volume 7 Number 6 pp465 -532

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Nature Chemistry

TABLE OF CONTENTS

June 2015 Volume 7, Issue 6

Research Highlights
Blogroll
News and Views
Perspective
Articles
In Your Element
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Research Highlights

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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

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Blogroll: Those who left   p466
Brandon Findlay
doi:10.1038/nchem.2263

News and Views

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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

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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.

Articles

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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

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.

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.

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.

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

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

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.

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

In Your Element

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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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