Nature Chemistry Contents August 2012 Volume 4 Number 8 pp587-686

Advertisement Looking to keep pace with global news and research in chemical science? Join RSC e-membership today to receive a digital subscription to Chemistry World, the unrivalled monthly magazine with an international readership of 49,000 scientists. Access the latest developments in research and government policy, business news, features and opinion columns, jobs board, and networking opportunities. TABLE OF CONTENTS August 2012 Volume 4, Issue 8 Editorial Thesis Books and Arts Interview Research Highlights Blogroll News and Views Review Articles In Your Element Subscribe   Facebook   RSS   Recommend to library   Twitter   Advertisement 21st IUPAC International Conference on Physical Organic Chemistry 9 - 13 September 2012, Durham University ICPOC21 is a key event to celebrate and discuss the current status, the development and the future of physical organic chemistry. This symposium will bring together a broad range of scientists who share a quantitative perspective on chemistry. Submit and register now   Advertisement Nature Chemistry - New Impact Factor The 2011 ISI impact factor for Nature Chemistry is 20.524*, according to the ISI Journal Citation Reports®. This places Nature Chemistry first among all primary research journals in chemistry. *2011 Journal Citation Reports® (Thomson Reuters, 2012)   Editorial Top Double-helix disruption   p587 doi:10.1038/nchem.1423 Structure by structure, more information is steadily being gathered on how small molecules bind to DNA. A better understanding of the interactions involved in such processes will be crucial for the successful design of compounds for specific diagnostic and therapeutic purposes. Thesis Top Slow science   pp588 - 589 Jean-François Lutz doi:10.1038/nchem.1415 Jean-François Lutz wonders whether chemists should slow down. Books and Arts Top Reactions at your fingertips   p590 Jon T. Njardarson reviews SANROS (Strategic Applications of Named Reactions in Organic Synthesis) by László Kürti & Barbara Czakó doi:10.1038/nchem.1416 Interview Top Binding manners   p591 Interview with Claudia Turro doi:10.1038/nchem.1420 Claudia Turro from The Ohio State University talks Nature Chemistry through the different binding modes small metal complexes can adopt when interacting with DNA — and why elucidating them in detail matters. Research Highlights Top Interlocked molecules: Protecting polyynes | Natural products: Sensitive synthesis | DNA replication: High fidelity | DNA binding: Visible changes Blogroll Top Blogroll: Toxicity and death   p593 Paul Bracher doi:10.1038/nchem.1414 News and Views Top Interactions with DNA: Into the minor groove   pp594 - 595 Stephen Neidle doi:10.1038/nchem.1413 The interactions between ruthenium complexes and DNA duplexes, elucidated in detail in three different crystal structures, have been found to occur through the minor groove — an unexpected binding mode, but perhaps not such a strange one. See also: Article by Song et al. | Article by Niyazi et al. Electrochemical sensors: Taking charge of detection   pp595 - 597 Anthony M. Burke and Alon A. Gorodetsky doi:10.1038/nchem.1418 An electrochemical sensor that relies on displacement of a 'neutralizer' from a surface-bound, charged probe molecule by the analyte enables the use of a single platform for the detection of multiple analytes irrespective of their charge. See also: See also: Article by Das et al. Catalyst-support interactions: Electronic perturbations   pp597 - 598 Charles T. Campbell doi:10.1038/nchem.1412 Oxide materials typically used as supports for the active metal nanoparticles of heterogeneous catalysts are known to influence catalytic activity through strong metal-support interactions. Researchers have now revealed electronic interactions between platinum and ceria that go well beyond known effects and lead to excellent catalytic activity. Supramolecular dye aggregates: Nanotube knockout   pp598 - 600 Jurgen Köhler doi:10.1038/nchem.1410 Organic molecular building blocks can self-assemble into structures with interesting optoelectronic properties. A combination of selective chemistry, spectroscopy and thorough theoretical analysis of a double-wall supramolecular nanotube has now led to a detailed model of its structure and internal excitonic coupling. See also:Article by Eisele et al. Protein folding: Turbo-charged crosslinking   pp600 - 602 David J. Craik doi:10.1038/nchem.1417 The efficient production of stable bioactive proteins often requires the selective formation of several disulfide crosslinks. Two recent studies have now shown that replacing cysteine with selenocysteine in the unfolded protein can autocatalyse the formation of the desired crosslinks. Chemistry JOBS of the week Postdoc in Experimental Laser Chemistry Aarhus University - Denmark Full Professor Theoretical Chemistry (1,0 fte) University of Groningen Tenure-track Assistant Professor in Chemistry Skidmore College Assistant Professor - Forensic Science or Forensic Chemistry JOhn Jay College of Criminal Justice Professor in Organic Chemistry The University of the South Pacific [USP] More Science jobs from Chemistry EVENT 40th International Conference on Coordination Chemistry 09.-13.09.12 Valencia, Spain More science events from Review Top The progression of chiral anions from concepts to applications in asymmetric catalysis   pp603 - 614 Robert J. Phipps, Gregory L. Hamilton and F. Dean Toste doi:10.1038/nchem.1405 Novel concepts in asymmetric catalysis have the potential to open up previously inaccessible reaction space. This Review reflects on the origins of an area that has undergone dramatic recent advancement: the use of chiral anions in asymmetric catalysis. Details of a selection of the latest examples are also given. Articles Top Crystal structure of Δ-[Ru(bpy)2dppz]2+ bound to mismatched DNA reveals side-by-side metalloinsertion and intercalation   pp615 - 620 Hang Song, Jens T. Kaiser and Jacqueline K. Barton doi:10.1038/nchem.1375 A ‘light switch’ ruthenium complex is known to show enhanced luminescence in the presence of DNA mismatches — emerging targets for cancer diagnostics and therapeutics — but the way it interacts with DNA has remained unclear. Now, metalloinsertion into and metallointercalation at the minor groove of the double helix have been unambiguously observed in a high-resolution crystal structure. See also: News and Views by Neidle Crystal structures of Λ-[Ru(phen)2dppz]2+ with oligonucleotides containing TA/TA and AT/AT steps show two intercalation modes   pp621 - 628 Hakan Niyazi, James P. Hall, Kyra O'Sullivan, Graeme Winter, Thomas Sorensen, John M. Kelly and Christine J. Cardin doi:10.1038/nchem.1397 Elucidating how small molecules bind to DNA is crucial to bio-sensing and therapy applications. Two crystal structures now show the binding modes of a ‘light switch’ ruthenium complex — whose luminescence in solution increases in the presence of DNA — with oligonucleotide duplexes containing either TA/TA or AT/AT central steps, revealing a specific intercalation mode with the TA/TA species. See also: News and Views by Neidle Guided desaturation of unactivated aliphatics   pp629 - 635 Ana-Florina Voica, Abraham Mendoza, Will R. Gutekunst, Jorge Otero Fraga and Phil S. Baran doi:10.1038/nchem.1385 A bench-stable, aryl sulfonyl triazene is described that can be appended to alcohols or amines and used as a directing group to effect remote desaturation of unactivated aliphatics to produce olefins. The reaction is mild, operationally simple, requires no added metals and produces unsaturated tosylates or tosylamides available for further functionalization. Revealing the stereospecific chemistry of the reaction of Cl with aligned CHD3(v1 = 1)pp636 - 641 Fengyan Wang, Kopin Liu and T. Peter Rakitzis doi:10.1038/nchem.1383 Steric effects are a key concept for understanding chemical reactivity. Now, by aligning reactants through control of the polarization of the infrared laser in a crossed-beam experiment, a three-dimensional view of how a reaction proceeds is reported. The results show striking dependences on the direction from which the laser-aligned reagents approach. An ultrasensitive universal detector based on neutralizer displacement   pp642 - 648 Jagotamoy Das, Kristin B. Cederquist, Alexandre A. Zaragoza, Paul E. Lee, Edward H. Sargent and Shana O. Kelley doi:10.1038/nchem.1367 A universal detector of small molecules, proteins and nucleic acids is described that relies on the displacement of a neutralizer molecule from a sensor surface. When the neutralizer is displaced by an analyte, an electrochemical signal is generated. Ultrasensitive limits of detection are achieved, and a new record for the electrochemical detection of bacteria (0.15 colony-forming units per microlitre) is reported. See also: News and Views by Burke & Gorodetsky Catalytic asymmetric carbon–carbon bond formation using alkenes as alkylmetal equivalents   pp649 - 654 Rebecca M. Maksymowicz, Philippe M. C. Roth and Stephen P. Fletcher doi:10.1038/nchem.1394 Organometallic reagents are widely used as nucleophiles in asymmetric catalysis. Here, alkylmetal species generated in situ by hydrometallation of alkenes are used in enantioselective copper-catalysed C–C bond formation. The process is formally an asymmetric reductive coupling of an alkene to an enone, and tolerates many functional groups. Utilizing redox-chemistry to elucidate the nature of exciton transitions in supramolecular dye nanotubes   pp655 - 662 D. M. Eisele, C. W. Cone, E. A. Bloemsma, S. M. Vlaming, C. G. F. van der Kwaak, R. J. Silbey, M. G. Bawendi, J. Knoester, J. P. Rabe and D. A. Vanden Bout doi:10.1038/nchem.1380 The collective excited states (excitons) in supramolecular light-harvesting systems depend intimately on their structure and it is crucial to understand how these states interact. Now it is shown that simple redox chemistry can be used to address this fundamental question by simplifying the complex excitonic interactions in such multichromophoric systems. See also: News and Views by Köhler Dissecting the mechanisms of a class of chemical glycosylation using primary 13C kinetic isotope effects   pp663 - 667 Min Huang, Graham E. Garrett, Nicolas Birlirakis, Luis Bohé, Derek A. Pratt and David Crich doi:10.1038/nchem.1404 Chemical glycosylations are perhaps the most important reactions in glycoscience, but the mechanisms are not well understood. Here, quantum chemical calculations combined with natural-abundance NMR measurements of 13C kinetic isotope effects reveal both associative and dissociative mechanisms at the extremes of a continuum that depends on the relative stereochemistry of the substrate and the anomeric configuration of the product. Spontaneous reduction and C–H borylation of arenes mediated by uranium(III) disproportionation   pp668 - 674 Polly L. Arnold, Stephen M. Mansell, Laurent Maron and David McKay doi:10.1038/nchem.1392 Simple uranium complexes, UX3, are shown to disproportionate in the presence of a reducing agent under mild conditions, cooperatively binding and reducing arenes. This enables arene C–H bond activation and borylation, and the trapping of reactive substituted arenes in inverse sandwich complexes. Optically switchable transistor via energy-level phototuning in a bicomponent organic semiconductor   pp675 - 679 Emanuele Orgiu, Núria Crivillers, Martin Herder, Lutz Grubert, Michael Pätzel, Johannes Frisch, Egon Pavlica, Duc T. Duong, Gvido Bratina, Alberto Salleo, Norbert Koch, Stefan Hecht and Paolo Samorì doi:10.1038/nchem.1384 One of the goals for devices using organic semiconductors is to make the materials themselves multifunctional or tunable, reducing the complexity of the device. Now, a film created by blending two components is shown to be phototunable with bistable energy levels and has been used in an organic thin-film transistor. Total synthesis of marinomycin A using salicylate as a molecular switch to mediate dimerization   pp680 - 684 P. Andrew Evans, Mu-Hua Huang, Michael J. Lawler and Sergio Maroto doi:10.1038/nchem.1330 Marinomycin A is a member of a new class of bis-salicylate-containing polyene macrodiolide, with potent antibiotic activity against methicillin-resistant Staphylococcus aureus (MRSA) and vancomycin-resistant Enterococcus faecium (VREF). Here, a triply convergent synthesis of this agent is described that uses the salicylate moiety as a novel molecular switch for the chemoselective construction of the macrodiolide. In Your Element Top Life and death with nitrogen   p686 Michael A. Tarselli doi:10.1038/nchem.1419 Although first known among chemists for its noxious or lifeless character, nitrogen was later revealed to be involved in many life, and death, processes. Michael Tarselli ponders on this unforeseen characteristic. Top Advertisement Feel like your paper is lost in a sea of submissions? Scientific Reports publishes your research quickly and efficiently, and makes it freely available to the global scientific community. Learn more with our one minute illustrative video.   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. 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