Nature Chemistry Contents June 2013 Volume 5 Number 6 pp439-546

TABLE OF CONTENTS June 2013 Volume 5, Issue 6 Thesis Books and Arts Research Highlights Blogroll News and Views Review Articles Corrigenda In Your Element Subscribe   Facebook   RSS   Recommend to library   Twitter   Advertisement SciBX Collections Macrocycles and constrained peptides This special collection explores the factors behind the growing interest in macrocycles and constrained peptides over the last five years and their effect on drug discovery. Click here to access the collection for free! Produced with support from: Aileron Therapeutics, Inc., Polypeptide Group, Polyphor LTD., Lanthiopharma B.V.   Thesis Top How to counteract chemophobia   pp439 - 440 Michelle Francl doi:10.1038/nchem.1661 Michelle Francl ponders ways in which we can talk about chemistry without triggering chemophobia. Books and Arts Top Detective work   p441 Paul Bonvallet reviews The Scientific Sherlock Holmes by James O'Brien doi:10.1038/nchem.1665 Research Highlights Top Interlocked molecules: Tangled tetrahedra | Periodic patterns: Snub square tiling | Self-assembly: A SAGE design | Alkene synthesis: Activating iodoniums Blogroll Top Blogroll: Welcome to the club   p443 Doctor Galactic doi:10.1038/nchem.1659 News and Views Top Biophysical chemistry: Unravelling capsid transformations   pp444 - 445 Masaki Uchida and Trevor Douglas doi:10.1038/nchem.1666 The interactions between a virus capsid and its cargo are essential for viral infection as well as in the design of synthetic virus-like particles. Now a combination of analytical techniques has unravelled key steps in the transformation of a model virus and the release of its RNA cargo. See also: Article by Snijder et al. Li-O2 batteries: An agent for change   pp445 - 447 Yonggang Wang and Yongyao Xia doi:10.1038/nchem.1658 The rechargeable Li-O2 battery has low energy efficiency, which is mainly due to kinetic difficulties in the electrochemical oxidation of the insulating discharge product, Li2O2. Now a redox mediator, acting as an electron–hole transfer agent, has been used to promote this oxidation reaction. See also: Article by Chen et al. Reactive intermediates: Radicals with multiple personalities   pp447 - 449 Malcolm D. E. Forbes doi:10.1038/nchem.1663 A combined theoretical and experimental approach has revealed that radicals can be significantly stabilized by the presence of a remote anionic site in the same molecule. This finding has implications for understanding and potentially controlling the reactivity of these important reactive intermediates. See also: Article by Gryn'ova et al. Inorganic protocells: Gated access to microreactors   pp449 - 451 Christine D. Keating doi:10.1038/nchem.1657 A pH-responsive inorganic membrane has been devised that acts as a gatekeeper for the transport of charged solutes into and out of its interior volume. This behaviour was further used to regulate an enzymatic reaction. See also: Article by Li et al. Uranium chemistry: An actinide milestone   pp451 - 452 Trevor W. Hayton doi:10.1038/nchem.1643 A complex featuring a uranium(VI) terminal nitride functional group has been isolated through mild oxidation, and shown to be highly reactive. Under photolysis, it converts into a compound that is capable of C-H bond activation. See also: Article by King et al. Chemistry JOBS of the week PostDoc in Chemistry Institute of Chemistry - Unicamp Goldhaber Fellowship Brookhaven National Laboratory Metabolomics platform technical manager Gustave Roussy Cancer Institute PhD position in organic chemistry Masaryk University Brno, Faculty of Science More Science jobs from Review Top Rationally synthesized two-dimensional polymers   pp453 - 465 John W. Colson and William R. Dichtel doi:10.1038/nchem.1628 Two-dimensional polymers, which exhibit periodic bonding in two orthogonal directions, offer mechanical, electronic and structural properties distinct from their linear or irregularly crosslinked polymer counterparts. Their potential is largely unexplored because versatile and controlled synthetic strategies are only now emerging. This Review describes recent developments in two-dimensional polymerization methods. Articles Top Competition of shape and interaction patchiness for self-assembling nanoplates   pp466 - 473 Xingchen Ye, Jun Chen, Michael Engel, Jaime A. Millan, Wenbin Li, Liang Qi, Guozhong Xing, Joshua E. Collins, Cherie R. Kagan, Ju Li, Sharon C. Glotzer and Christopher B. Murray doi:10.1038/nchem.1651 Thin lanthanide fluoride nanoplates are shown to self-organize at the liquid/air interface into long-range-ordered two-dimensional planar tilings. In this joint experimental–computational, multiscale investigation, the assembly behaviour is shown to be dictated by entropic forces arising from particle shape and enthalpic forces arising from interaction anisotropy. Switching radical stability by pH-induced orbital conversion   pp474 - 481 Ganna Gryn'ova, David L. Marshall, Stephen J. Blanksby and Michelle L. Coote doi:10.1038/nchem.1625 In most radicals the unpaired electron occupies the highest-energy molecular orbital. Here, it is shown that for certain stabilized radicals the presence of a remote negatively charged group not only inverts this ordering, but also leads to a dramatic increase in radical stability that is easily manipulated by pH. See also: News and Views by Forbes Isolation and characterization of a uranium(VI)–nitride triple bond   pp482 - 488 David M. King, Floriana Tuna, Eric J. L. McInnes, Jonathan McMaster, William Lewis, Alexander J. Blake and Stephen T. Liddle doi:10.1038/nchem.1642 A terminal uranium(VI)–nitride has been shown to be accessible and isolable by a redox strategy whereas a photochemical approach resulted in decomposition. Computational analyses suggest that the U≡N triple bonds are surprisingly comparable to analogous group 6 transition metal nitrides, with a covalent character dominated by 5f rather than 6d contributions. See also: News and Views by Hayton Charging a Li–O2 battery using a redox mediator   pp489 - 494 Yuhui Chen, Stefan A. Freunberger, Zhangquan Peng, Olivier Fontaine and Peter G. Bruce doi:10.1038/nchem.1646 Recharging Li–O2 batteries requires oxidation of the discharge product solid Li2O2. Now a redox-mediating molecule is shown to assist this process by transferring electron–holes between solid Li2O2 and the positive electrode in a non-aqueous Li–O2 cell. This allows the cell to be charged at rates that are otherwise impossible. See also: News and Views by Wang & Xia Competition between model protocells driven by an encapsulated catalyst   pp495 - 501 Katarzyna Adamala and Jack W. Szostak doi:10.1038/nchem.1650 Darwinian evolution involves competition between members of a population. Here, the synthesis of a hydrophobic dipeptide catalysed by a second dipeptide in a model protocell — a vesicle — is described. The reaction product partitions to the vesicle membrane, which grows by accumulating fatty acids derived from neighbouring vesicles. Thus, an encapsulated catalyst drives competition between the model protocells. Probing the biophysical interplay between a viral genome and its capsid   pp502 - 509 J. Snijder, C. Uetrecht, R. J. Rose, R. Sanchez-Eugenia, G. A. Marti, J. Agirre, D. M. A. Guérin, G. J. L. Wuite, A. J. R. Heck and W. H. Roos doi:10.1038/nchem.1627 The stability of the capsid of a virus is strongly affected by its genome. Here the interplay between capsid and genome is explored using native mass spectrometry and atomic force microscopy. A mechanism is proposed to explain how the genome of the Triatoma virus stabilizes the capsid at neutral pH, but triggers disassembly under alkaline conditions. See also: News and Views by Uchida & Douglas Simultaneous structure–activity studies and arming of natural products by C–H amination reveal cellular targets of eupalmerin acetate    pp510 - 517 Jing Li, Justin S. Cisar, Cong-Ying Zhou, Brunilda Vera, Howard Williams, Abimael D. Rodríguez, Benjamin F. Cravatt and Daniel Romo doi:10.1038/nchem.1653 Natural products are enduring leads for exploring cell biology, yet structure–activity relationship studies and 'arming' of these small molecules for subsequent cellular probe synthesis remains a challenge. Here, a strategy for derivatization of natural products by C–H amination, aziridination and unusual N-aminations is described. Selective derivatization of eupalmarin acetate led to identification of this natural product's target. The use of elemental sulfur as an alternative feedstock for polymeric materials   pp518 - 524 Woo Jin Chung, Jared J. Griebel, Eui Tae Kim, Hyunsik Yoon, Adam G. Simmonds, Hyun Jun Ji, Philip T. Dirlam, Richard S. Glass, Jeong Jae Wie, Ngoc A. Nguyen, Brett W. Guralnick, Jungjin Park, Árpád Somogyi, Patrick Theato, Michael E. Mackay, Yung-Eun Sung, Kookheon Char & Jeffrey Pyun doi:10.1038/nchem.1624 A polymerization method for converting elemental sulfur into a chemically stable, processable and electrochemically active copolymer has been described. This methodology — termed inverse vulcanization — is conducted by a one-step process using liquid sulfur, as both reaction medium and reactant, and vinylic comonomers to form polymeric materials with a high content of sulfur (50–90 wt%). RNA with iron(II) as a cofactor catalyses electron transfer   pp525 - 528 Chiaolong Hsiao, I-Chun Chou, C. Denise Okafor, Jessica C. Bowman, Eric B. O'Neill, Shreyas S. Athavale, Anton S. Petrov, Nicholas V. Hud, Roger M. Wartell, Stephen C. Harvey and Loren Dean Williams doi:10.1038/nchem.1649 Removing Mg2+ from RNA and replacing it with Fe2+ confers on some RNAs the ability to catalyse single-electron transfer. Here, it is hypothesized that Fe2+ was an RNA cofactor on the early Earth, when iron was benign and abundant, and was replaced by Mg2+ during a period known as the great oxidation, brought on by photosynthesis. Electrostatically gated membrane permeability in inorganic protocells   pp529 - 536 Mei Li, Rachel L. Harbron, Jonathan V. M. Weaver, Bernard P. Binks and Stephen Mann doi:10.1038/nchem.1644 Colloidosomes based on silica nanoparticles self-assembled at water droplet/oil interfaces are promising inorganic protocells, but they often leak small molecules on transfer into bulk water. Through silane crosslinking and copolymer grafting, colloidosomes have now been endowed with membranes that exhibit pH-responsive permeability to small molecules. The resulting water-dispersible colloidosomes further serve to host and control enzyme reactions. See also: News and Views by Keating Heterogenized cobalt oxide catalysts for nitroarene reduction by pyrolysis of molecularly defined complexes   pp537 - 543 Felix A. Westerhaus, Rajenahally V. Jagadeesh, Gerrit Wienhöfer, Marga-Martina Pohl, Jörg Radnik, Annette-Enrica Surkus, Jabor Rabeah, Kathrin Junge, Henrik Junge, Martin Nielsen, Angelika Brückner & Matthias Beller doi:10.1038/nchem.1645 Pyrolysis of defined nitrogen-ligated cobalt acetate complexes onto a commercial carbon support transforms the complexes into heterogeneous Co3O4 materials. These reusable non-noble-metal catalysts are highly selective for the industrially important hydrogenation of structurally diverse and functionalized nitroarenes to anilines. Corrigenda Top The hydrodeoxygenation of bioderived furans into alkanes   p544 Andrew D. Sutton, Fraser D. Waldie, Ruilian Wu, Marcel Schlaf, Louis A. 'Pete' Silks, III and John C. Gordon doi:10.1038/nchem.1664 The hydrodeoxygenation of bioderived furans into alkanes   p544 Andrew D. Sutton, Fraser D. Waldie, Ruilian Wu, Marcel Schlaf, Louis A. 'Pete' Silks, III and John C. Gordon doi:10.1038/nchem.1670 In Your Element Top Titanium tales   p546 Michael A. Tarselli doi:10.1038/nchem.1656 From toothpaste to Tebbe reagents, Michael Tarselli takes a look at the many different faces of titanium. 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