Nature Chemistry Contents September 2013 Volume 5 Number 9 pp725-804

TABLE OF CONTENTS September 2013 Volume 5, Issue 9 Thesis Research Highlights Blogroll News and Views Correction Articles In Your Element Subscribe   Facebook   RSS   Recommend to library   Twitter   Advertisement Attending the ACS Fall meeting in Indianapolis? Join us at the Nature Publishing Group Booth #1900-1902 for your chance to: - Take part in Scientific Reports Eye Sci game - have you got what it takes? - Browse and take free sample copies of leading journals from NPG, including Nature, Nature Chemistry and Nature Chemical Biology. - Talk about your advertising plans for 2013 and beyond. - Subscribe and save 20% - special discount rate for conference attendees on personal subscriptions.   Thesis Top Take a number   pp725 - 726 Michelle Francl doi:10.1038/nchem.1733 Back-of-the-envelope calculations are an important part of chemistry argues Michelle Francl. Research Highlights Top Transition metal complexes: 24-carat chemistry | Natural products: Anti-anthrax agents | Reactive intermediates: Non-classical crystals | Copolymer networks: Malleable matter Blogroll Top Blogroll: Everyday chemistry   p729 Andrew Bissette doi:10.1038/nchem.1735 News and Views Top Polycyclic hydrocarbons: Nanographenes do the twist   pp730 - 731 Benjamin T. King doi:10.1038/nchem.1732 A nanographene compound incorporating five- and seven-membered rings is found to have a highly distorted non-planar structure and serves as a model system for studying the effect of defects in graphene sheets. See also: Article by Kawasumi et al. Site-selective reactions: Exploiting intramolecularity   pp731 - 732 André M. Beauchemin doi:10.1038/nchem.1737 Selective reaction of one alcohol among many in complex molecules can be achieved by the use of a catalyst that forms a single covalent bond to a nearby functional group. See also: Article by Sun et al. Self-assembly: Micelles grow more complex   pp733 - 734 Guojun Liu and Ian Wyman doi:10.1038/nchem.1738 A crystalline polymer serves both as the seed and as one component of a diblock copolymer for the growth of unusual multi-armed micelles. Low-temperature reactions: Tunnelling in space   pp734 - 736 Ian R. Sims doi:10.1038/nchem.1736 Chemical reactions with activation barriers generally slow to a halt in the extreme cold of dense interstellar clouds. Low-temperature experiments on the reaction of OH with methanol have now shown that below 200 K there is a major acceleration in the rate that can only be explained by enhanced quantum mechanical tunnelling through the barrier. See also: Article by Shannon et al. C-H bond functionalization: An aminated reaction   pp736 - 738 Tom G. Driver doi:10.1038/nchem.1739 Selective conversion of C-H bonds into C-N bonds to form N-heterocycles would streamline the synthesis of these important structural motifs. Now, an iron(II) catalyst has been developed that can transform alkyl azides into cyclic secondary amines by controlling the iron imido intermediate to react only with the nearby aliphatic C-H bond. Chemistry JOBS of the week Department of Chemistry Faculty Position in Materials Chemistry Simon Fraser University (SFU) Three Professor Positions in Materials Chemistry Eindhoven University of Technology (TU / e) Postdoctoral Research Associate University of Washington Postdoctoral Research Fellow Stanford University A postdoctoral position in chemical proteomics / microbiology Mississippi State University More Science jobs from Chemistry EVENT Discovery Chemistry Congress 17.02.13 Barcelona, Spain More science events from Correction Top Correction   p738 doi:10.1038/nchem.1734 Articles Top A grossly warped nanographene and the consequences of multiple odd-membered-ring defects   pp739 - 744 Katsuaki Kawasumi, Qianyan Zhang, Yasutomo Segawa, Lawrence T. Scott and Kenichiro Itami doi:10.1038/nchem.1704 A grossly warped nanographene, C80H30, that incorporates five 7-membered rings and one 5-membered ring embedded in a hexagonal lattice has been synthesized, isolated and fully characterized. Experiments revealing how the properties of such a large graphene subunit are affected by multiple odd-membered-ring defects are also reported. Chemical compounds See also: News and Views by King Accelerated chemistry in the reaction between the hydroxyl radical and methanol at interstellar temperatures facilitated by tunnelling   pp745 - 749 Robin J. Shannon, Mark A. Blitz, Andrew Goddard and Dwayne E. Heard doi:10.1038/nchem.1692 In interstellar clouds, reactions that have an activation barrier have previously been considered too slow to be significant because of the low temperatures experienced. However, large enhancements in the rate coefficient for the reaction of OH with methanol have now been observed at temperatures below 100 K. A mechanism involving tunnelling has been proposed. See also: News and Views by Sims Photochemical activity of a key donor–acceptor complex can drive stereoselective catalytic α-alkylation of aldehydes   pp750 - 756 Elena Arceo, Igor D. Jurberg, Ana Álvarez-Fernández and Paolo Melchiorre doi:10.1038/nchem.1727 The combination of organocatalytic and photoredox cycles has attracted much attention for its ability to solve long-standing problems in asymmetric catalysis. Here, it is shown that easily available chiral organic catalysts can guide both the stereoselectivity-defining events and, through the transient formation of photon-absorbing chiral electron donor–acceptor complexes, the photoactivation of the substrates. Chemical compounds Mechanochemical strengthening of a synthetic polymer in response to typically destructive shear forces   pp757 - 761 Ashley L. Black Ramirez, Zachary S. Kean, Joshua A. Orlicki, Mangesh Champhekar, Sarah M. Elsakr et al. doi:10.1038/nchem.1720 Materials typically break down in response to the repeated mechanical forces that they experience during use. Now, it has been shown that a mechanochemically active polymer can respond to shear forces by forming more bonds than are broken, leading to improved mechanical properties under conditions that would otherwise be destructive. Sub-ångström-resolution crystallography reveals physical distortions that enhance reactivity of a covalent enzymatic intermediate   pp762 - 767 Stefan Lüdtke, Piotr Neumann, Karl M. Erixon, Finian Leeper, Ronald Kluger et al. doi:10.1038/nchem.1728 Structural analysis of the enzyme transketolase at sub-ångström resolution shows the existence of physically distorted covalent intermediates with elongated scissile substrate bonds. These observations highlight the ability of enzymes to enhance the reactivity of reaction intermediates leading to a more efficient process. Enantioselective silyl protection of alcohols promoted by a combination of chiral and achiral Lewis basic catalysts   pp768 - 774 Nathan Manville, Hekla Alite, Fredrik Haeffner, Amir H. Hoveyda and Marc L. Snapper doi:10.1038/nchem.1708 A counter-intuitive strategy that combines a chiral Lewis base catalyst with an achiral Lewis base co-catalyst results in an exceptionally large increase in the facility of catalytic enantioselective silylation of polyols. The catalytic ensemble drives such reactions to completion within a few hours, rather than the usual two–five days, without loss of enantioselectivity. Exceptional oxidation activity with size-controlled supported gold clusters of low atomicity   pp775 - 781 Avelino Corma, Patricia Concepción, Mercedes Boronat, Maria J. Sabater, Javier Navas et al. doi:10.1038/nchem.1721 The catalytic activity of gold nanoparticles is known to be dependent on size, but less is known about the activity of even smaller gold clusters. It is now shown that clusters with 5 to 10 atoms supported on multiwalled carbon nanotubes are as active as enzymes for the oxidation of thiophenol to disulfide with O2. Conditionally fluorescent molecular probes for detecting single base changes in double-stranded DNA   pp782 - 789 Sherry Xi Chen, David Yu Zhang and Georg Seelig doi:10.1038/nchem.1713 A molecular probe has been designed that distinguishes double-stranded DNA with single base-pair specificity. In this approach, two destabilizing bubbles, in which the base pairs are mismatched, are generated for each point mutation in the target DNA. Catalyst recognition of cis-1,2-diols enables site-selective functionalization of complex molecules   pp790 - 795 Xixi Sun, Hyelee Lee, Sunggi Lee and Kian L. Tan doi:10.1038/nchem.1726 The manipulation of complex molecules offers an avenue for developing new therapeutics and biological probes. Here, a catalyst is described that forms a covalent bond to the substrate before selectively functionalizing a proximal functional group. Cis-1,2-diols are targeted allowing for the derivatization of the axial hydroxyls of monosaccharides in the presence of unprotected equatorial hydroxyls. Chemical compounds See also: News and Views by Beauchemin On the cooperative formation of non-hydrogen-bonded water at molecular hydrophobic interfaces   pp796 - 802 Joel G. Davis, Blake M. Rankin, Kamil P. Gierszal and Dor Ben-Amotz doi:10.1038/nchem.1716 Hydrophobe/water interfaces are crucial for many chemical processes, but to be fully understood, a better appreciation of the behaviour of non-hydrogen-bonded OH groups of water is required. It is now shown that such ‘dangling’ OH structures are entropically stabilized and form cooperatively, that is, the probability of their formation depends nonlinearly on hydrophobic surface area. In Your Element Top Recalling radon's recognition   p804 Brett F. Thornton and Shawn C. Burdette doi:10.1038/nchem.1731 Brett F. Thornton and Shawn C. Burdette look back at the discovery—and the many different names—of element 86. 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