Nature Chemistry Contents February 2013 Volume 5 Number 2 pp77-146

TABLE OF CONTENTS February 2013 Volume 5, Issue 2 Books and Arts Research Highlights Blogroll News and Views Articles Corrigendum In Your Element Subscribe   Facebook   RSS   Recommend to library   Twitter   Advertisement Polymer Journal is proud to present a special issue on the Application of Quantum Beams to Polymer Science and Engineering, which brings together a series of articles with specially solicited topical reviews. The accompanying web focus presents additional links to related articles in this subject area from across Nature Publishing Group.  Take advantage of FREE access to select articles today!    Books and Arts Top Try this at home?   p77 Declan Fleming reviews Itch by Simon Mayo doi:10.1038/nchem.1558 Research Highlights Top Protein chemistry: A new Western front | Arsenic complexes: Mellow yellow | Synthetic methodology: Better borylation | Semiconducting polymers: Drop by drop Blogroll Top Blogroll: Numerous nitrogens   p79 Fredrik von Kieseritzky doi:10.1038/nchem.1553 News and Views Top Fluorescent imaging: Shining a light into live cells   pp81 - 82 Kathrin Lang and Jason W. Chin doi:10.1038/nchem.1555 A new biocompatible near-infrared fluorescent probe enables super-resolution imaging of cellular proteins in live cells using a range of different labelling techniques. See also: Article by Lukinavicius et al. Air/water interface: Two sides of the acid-base story   pp82 - 84 Richard J. Saykally doi:10.1038/nchem.1556 The ability of the water surface to donate or accept protons critically influences vital processes in chemistry and biology, but intense disagreement persists regarding this property. Researchers show new evidence that the air side of the air/water interface is more basic than the aqueous one. Mechanochemistry: Demonstrated leverage   pp84 - 86 Roman Boulatov doi:10.1038/nchem.1541 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. See also: Article by Klukovich et al. Bürgenstock 2012: Reflections on stereochemistry   pp86 - 88 Stuart J. Conway doi:10.1038/nchem.1552 No longer held in Bürgenstock or the preserve of stereochemists, the Bürgenstock conference on stereochemistry is much more than its name suggests. The diverse range of subjects discussed at the meeting highlights the fundamental importance of chemistry in other scientific disciplines ranging from molecular biology to materials science. Main group chemistry: Metal-reinforced bonding   pp88 - 89 Hans-Jörg Himmel doi:10.1038/nchem.1554 It is well known that donation of electron density from a metal atom back into an empty orbital on a coordinating ligand, such as an alkene, weakens the π bond. Now, it has been shown that in a metal-diborene complex, π-backdonation involves bonding π-orbitals on the ligand and leads to B-B bond strengthening. See also: Article by Braunschweig et al. Gas separation: Trapdoors in zeolites   pp89 - 90 Trees De Baerdemaeker and Dirk De Vos doi:10.1038/nchem.1560 Selective gas uptake in zeolites often relies on size — hosts accommodate guests that are small enough to fit into their pores. Now, a zeolite containing cations that function as molecular trapdoors allows guest-selective, size-inverse separations that could help with carbon capture and hydrogen purification. Methane activation: Oxidation goes soft   pp91 - 92 Frerich J. Keil doi:10.1038/nchem.1557 Creating useful feedstocks from methane is impeded by over-oxidation when O2 is used as the oxidant. Now, gaseous sulfur has been shown to be a promising 'soft' oxidant for the selective conversion of methane to ethylene. See also: Article by Zhu et al. Chemistry JOBS of the week Postdoc in Synthetic Organic Chemistry Baylor College of Medicine Postdoctoral Fellow in Organic Chemistry University of Texas at Austin (UT-Austin) PhD positions in Materials Chemistry University of Liverpool Early Stage Researcher in Marie Curie Initial Training Network AccliPhot University of Aberdeen Postdoctoral position Masaryk University, Faculty of Science More Science jobs from Chemistry EVENT Drug Discovery Chemistry 04.06.13 San Diego, US More science events from Articles Top Synthetic cascades are enabled by combining biocatalysts with artificial metalloenzymes   pp93 - 99 V. Köhler, Y. M. Wilson, M. Dürrenberger, D. Ghislieri, E. Churakova, T. Quinto, L. Knörr, D. Häussinger, F. Hollmann, N. J. Turner and T. R. Ward doi:10.1038/nchem.1498 An artificial transfer hydrogenase, based on the incorporation of a biotinylated iridium-piano-stool complex in streptavidin, is shown to be fully compatible with a range of biocatalysts. The location of the active metal centre inside the protein scaffold efficiently prevents mutual inactivation processes and enables the concurrent interplay with oxidative enzymes. A supramolecular approach to combining enzymatic and transition metal catalysis   pp100 - 103 Z. Jane Wang, Kristen N. Clary, Robert G. Bergman, Kenneth N. Raymond and F. Dean Toste doi:10.1038/nchem.1531 Combinations of enzymatic and chemo-catalysis can result in powerful synthetic transformations. Here, encapsulation of Au(I) or Ru(II) within a supramolecular assembly prevents diffusion of the organometallic complexes into solution where they can compromise the activity of an enzyme. This strategy has been applied to tandem reactions employing supramolecular host–guest complexes and enzymes in the catalysis of organic transformations. Sulfur as a selective ‘soft’ oxidant for catalytic methane conversion probed by experiment and theory   pp104 - 109 Qingjun Zhu, Staci L. Wegener, Chao Xie, Obioma Uche, Matthew Neurock and Tobin J. Marks doi:10.1038/nchem.1527 The oxidation of methane to create useful feedstocks is hampered by over-oxidation when using O2. Now a process using gaseous sulfur as a ‘soft’ oxidant for selective conversion to ethylene over metal sulfide catalysts has been developed. Simulations show that both methane activation and ethylene selectivity is linearly correlated with catalyst metal-sulfur bond strength. See also: News and Views by Keil A backbone lever-arm effect enhances polymer mechanochemistry   pp110 - 114 Hope M. Klukovich, Tatiana B. Kouznetsova, Zachary S. Kean, Jeremy M. Lenhardt and Stephen L. Craig doi:10.1038/nchem.1540 Polymer mechanochemistry can trigger a wide range of often unanticipated reactivity, but the focus of these systems typically falls on the structure of the mechanophore rather than the intervening polymer backbone. Now, it has been shown that a poly(norbornene) backbone has a substantial impact on a mechanochemical ring-opening reaction, despite having only a minor effect on the force-free reaction. See also: News and Views by Boulatov Bond-strengthening π backdonation in a transition-metal π-diborene complex   pp115 - 121 Holger Braunschweig, Alexander Damme, Rian D. Dewhurst and Alfredo Vargas doi:10.1038/nchem.1520 A form of π backbonding is observed in a π-diborene complex of platinum, and confirmed by calculations. This interaction partially fills a bonding π orbital on the diborene ligand, strengthening the B–B bond. That π backbonding can strengthen bonds overturns ingrained notions that π backbonding is exclusively a bond-weakening phenomenon. See also: News and Views by Himmel Catalytic transformation of alcohols to carboxylic acid salts and H2 using water as the oxygen atom source   pp122 - 125 Ekambaram Balaraman, Eugene Khaskin, Gregory Leitus and David Milstein doi:10.1038/nchem.1536 The development of a catalytic, mild and atom-economical transformation of alcohols to carboxylic acid salts and hydrogen gas is described. The reaction uses water as a source of oxygen, with a homogenous Ru catalyst at low (0.2 mol%) catalyst loadings in basic aqueous solution. A divergent approach to the synthesis of the yohimbinoid alkaloids venenatine and alstovenine    pp126 - 131 Terry P. Lebold, Jessica L. Wood, Josh Deitch, Michael W. Lodewyk, Dean J. Tantillo and Richmond Sarpong doi:10.1038/nchem.1528 A hydrindanone-based approach to yohimbinoid natural products has been developed. A judicious choice of reaction conditions — inspired by prior work by the Stork group — allows effective control of the stereochemistry at C3 of the yohimbinoid skeleton. This approach has resulted in the first total syntheses of the C3 epimeric natural products venenatine and alstovenine. A near-infrared fluorophore for live-cell super-resolution microscopy of cellular proteins   pp132 - 139 Gražvydas Lukinavičius, Keitaro Umezawa, Nicolas Olivier, Alf Honigmann, Guoying Yang, Tilman Plass, Veronika Mueller, Luc Reymond, Ivan R. Corrêa Jr, Zhen-Ge Luo, Carsten Schultz, Edward A. Lemke, Paul Heppenstall, Christian Eggeling, Suliana Manley and Kai Johnsson doi:10.1038/nchem.1546 Fluorescent probes for bioimaging need to exhibit bright fluorescence, be biocompatible and offer several alternatives for attachment to biomolecules of interest. Here, a near-infrared silicon–rhodamine fluorophore is introduced that can be coupled to intracellular proteins in live cells and tissues and can be exploited for super-resolution microscopy. See also: News and Views by Lang & Chin A sustainable catalytic pyrrole synthesis   pp140 - 144 Stefan Michlik and Rhett Kempe doi:10.1038/nchem.1547 Pyrroles are a highly important class of compounds with a wide variety of applications in biochemistry, pharmacy and materials science. Here, an iridium-catalysed synthesis of pyrroles is described, starting from renewable resources, alcohols that may be derived from lignocellulosic feedstocks and amino alcohols. The reaction proceeds by a condensation reaction that liberates two equivalents of hydrogen gas. Corrigendum Top Real-time and in situ monitoring of mechanochemical milling reactions   p145 Tomislav Friščić, Ivan Halasz, Patrick J. Beldon, Ana M. Belenguer, Frank Adams, Simon A.J. Kimber, Veijo Honkimaki and Robert E. Dinnebier doi:10.1038/nchem.1566 In Your Element Top Barium bright and heavy   p146 Katharina M. Fromm doi:10.1038/nchem.1551 Katharina M. Fromm relates how barium and its ores went from a magical, glowing species that attracted witches and alchemists to components in a variety of compounds that are key parts of modern life. Top Advertisement Subscribe to Nature Chemistry Make sure you receive your own personal copy of Nature Chemistry. Your personal subscription gives you either 12 or 24 monthly print issues plus online access to the journal for 12 or 24 months. - subscribe online here today   Natureevents is a fully searchable, multi-disciplinary database designed to maximise exposure for events organisers. The contents of the Natureevents Directory are now live. The digital version is available here. Find the latest scientific conferences, courses, meetings and symposia on natureevents.com. For event advertising opportunities across the Nature Publishing Group portfolio please contact natureevents@nature.com More Nature Events

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