Nature Chemistry Contents December 2013 Volume 5 Number 12 pp 979-1066

Advertisement Bio-Rad's new modular NGC™ chromatography system allows users to modify its capabilities when their throughput or application requirements change, obviating the need to purchase a completely new instrument. TABLE OF CONTENTS December 2013 Volume 5, Issue 12 Thesis Books and Arts Research Highlights Blogroll News and Views Perspective Articles In Your Element Advertisement   Frontiers are launching a new collaborative peer review forum We are excited to announce that we will be launching a new collaborative peer-review forum where referees and authors work together to improve the paper until consensus is met. Our new peer-review forum will provide online-tools and increased efficiency to ensure a transparent and fast review process. Follow us for more information! We'll be posting updates about the launch on Twitter and Facebook  Subscribe   Facebook   RSS   Recommend to library   Twitter   Advertisement Subscribe to Nature this Holiday season for only $50, £50 or €50 Enjoy 51 issues in print, online and multimedia content, and access via the nature.com app for iPhone, iPod touch and the new issue-based NatureJournals iPad app with enhanced features.  Subscribe today!    Thesis Top The straight dope on isotopes   pp979 - 981 Brett F. Thornton and Shawn C. Burdette doi:10.1038/nchem.1810 A century ago this month, Frederick Soddy described and named isotopes in the pages of Nature. Brett F. Thornton and Shawn C. Burdette discuss how chemists have viewed and used isotopes since then — either as chemically identical or chemically distinct species as the need required and technology allowed. Books and Arts Top Book and film: Fixing the leak   p983 Jessica Breen doi:10.1038/nchem.1812 Research Highlights Top 2013 Nobel Prize in Chemistry: Model citizens | Spin-crossover transition: Disruption on adsorption | Biochemistry: Gene self-replication | Self-assembly: Laying down the law Blogroll Top Blogroll: Turf wars   p985 Alasdair Taylor doi:10.1038/nchem.1809 News and Views Top Chemical reaction networks: Colour by number   pp986 - 987 Dominic Scalise and Rebecca Schulman doi:10.1038/nchem.1807 Using chemical reactions and diffusion to control pattern formation requires the careful design of reaction networks and a balance of kinetics that is difficult to achieve. Now, it has been shown that DNA-based reaction networks provide a robust method for transforming patterns. See also: Article by Chirieleison et al. Origin of life: Cold-hearted RNA heats up life   pp987 - 989 Niles Lehman doi:10.1038/nchem.1811 An RNA replicase ribozyme has long been sought by chemists interested in the origin of life. Now, a selection strategy employing a low-temperature water-ice mixture as the medium has led to discovery of a ribozyme that can catalyse polymerization of an RNA chain greater than its own length. See also: Article by Attwater et al. Intermolecular forces: A solution to dispersion interactions   pp989 - 990 Ken D. Shimizu doi:10.1038/nchem.1808 London dispersion forces have been cited as an important factor in protein folding, drug-receptor interactions, and catalyst selectivities. However, careful analysis of a model system finds that the dispersion interactions are only minor contributors to the formation of complexes in solution. See also: Article by Yang et al. Polymer chemistry: Macromolecules made to order   pp990 - 992 Bernhard V. K. J. Schmidt and Christopher Barner-Kowollik doi:10.1038/nchem.1806 Mastering how to completely control the exact monomer sequence of synthetic polymers is the ultimate key for establishing true biomimetic macromolecular chemistry. A versatile one-pot approach for the synthesis of well-defined multiblock copolymers with short block lengths offers another approach on the road towards this lofty goal. Chemistry JOBS of the week PhD studentship in Uranium Chemistry Trinity College Dublin PhD scholarships - organic chemistry Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Prague Lecturer in Physical Chemistry University of Glasgow Tenure-Track Position in Materials Chemistry and Physics Université du Québec à Trois-Rivières (UQTR) Full-Time, Tenure-Track Faculty Position: Joint Chemistry-Physics Castleton State College More Science jobs from Chemistry EVENT Modern Synthetic Methods in Organofluorine Chemistry 06.03.14 London, UK More science events from Perspective Top Opportunities and challenges in single-molecule and single-particle fluorescence microscopy for mechanistic studies of chemical reactions   pp993 - 999 Thorben Cordes and Suzanne A. Blum doi:10.1038/nchem.1800 Single-molecule and -particle fluorescence microscopy — traditionally applied to biophysical studies — has recently been used to gain insight into chemical systems. Still at its nascent stage, this approach presents great opportunities for the chemistry community through the observation of chemical reactions and their mechanisms as typically depicted in textbooks: molecule by molecule. Articles Top Pattern transformation with DNA circuits   pp1000 - 1005 Steven M. Chirieleison, Peter B. Allen, Zack B. Simpson, Andrew D. Ellington and Xi Chen doi:10.1038/nchem.1764 The programmable nature of chemical reactions enables the creation of complex networks; however, it can be difficult to redesign the underlying reactions. Here, systematic and quantitative control over the diffusivity and reactivity of DNA molecules yields highly programmable chemical reaction networks that execute macroscale pattern transformation algorithms, such as edge detection. See also: News and Views by Scalise & Schulman How much do van der Waals dispersion forces contribute to molecular recognition in solution?   pp1006 - 1010 Lixu Yang, Catherine Adam, Gary S. Nichol and Scott L. Cockroft doi:10.1038/nchem.1779 Attractive van der Waals dispersion forces have been implicated in mechanisms as diverse as gecko adhesion and anaesthesia. Now, it has been found using synthetic molecular balances that dispersion forces between alkyl chains are an order of magnitude weaker in solution than they are in the gas phase. See also: News and Views by Shimizu In-ice evolution of RNA polymerase ribozyme activity   pp1011 - 1018 James Attwater, Aniela Wochner and Philipp Holliger doi:10.1038/nchem.1781 Molecular self-replication through ribozyme-catalysed RNA synthesis could shed light on the origins of life. Here, a polymerase ribozyme capable of synthesizing an RNA sequence longer than itself is described, based on a cold-adapted ribozyme variant evolved in ice. This process demonstrates the potential for the emergence of novel ribozyme phenotypes in altered reaction environments. See also: News and Views by Lehman Singlet exciton fission in solution   pp1019 - 1024 Brian J. Walker, Andrew J. Musser, David Beljonne and Richard H. Friend doi:10.1038/nchem.1801 Singlet exciton fission produces two triplet excited states from one excited singlet through interchromophoric coupling, which is thought to require local order. Now, a triplet yield of 200% and diffusion-limited triplet formation are reported in solutions of TIPS pentacene. Kinetic studies revealed an excimer intermediate and enabled suggestions of design principles for the promotion of singlet fission. Metal-free binding and coupling of carbon monoxide at a boron–boron triple bond   pp1025 - 1028 Holger Braunschweig, Theresa Dellermann, Rian D. Dewhurst, William C. Ewing, Kai Hammond et al. doi:10.1038/nchem.1778 The coupling of carbon monoxide molecules is an attractive prospect for organic synthesis, but only a few metal complexes are known to do this. A compound containing a boron–boron triple bond has now been shown to induce the coupling of four CO molecules, through an intermediate with a single CO. A boron–boron coupling reaction between two ethyl cation analogues   pp1029 - 1034 Sebastian Litters, Elisabeth Kaifer, Markus Enders and Hans-Jörg Himmel doi:10.1038/nchem.1776 A stable tetranuclear boron dication with a rhomboid B4 skeleton has been formed by B–B coupling between two diborane cations. In the course of this unusual reaction — which is not feasible for the isolobal ethyl cation analogues — two electron-precise B–B bonds are converted into two B–B–B three-centre bonds. Large negative thermal expansion of a polymer driven by a submolecular conformational change   pp1035 - 1041 Xingyuan Shen, Christopher Viney, Erin R. Johnson, Changchun Wang and Jennifer Q. Lu doi:10.1038/nchem.1780 Polymers that exhibit a mechanical response to external stimuli are technologically important. Here, a polymer is described that shows a very large negative thermal expansion on heating or irradiation with near-infrared light. This property is stable over hundreds of cycles and is shown to be driven by a conformational change of an s-dibenzocyclooctadiene unit within the polymer structure. Self-healing chemistry enables the stable operation of silicon microparticle anodes for high-energy lithium-ion batteries   pp1042 - 1048 Chao Wang, Hui Wu, Zheng Chen, Matthew T. McDowell, Yi Cui et al. doi:10.1038/nchem.1802 The ability to self-heal is an important survival feature in nature, with in-built systems working to correct faults and extend the lifetimes of organisms. Now, self-healing chemistry has been applied to overcome the short cycling lifetime of high-capacity rechargeable lithium-ion batteries with silicon-microparticle anodes that suffer from mechanical fractures. Rapid assembly of complex cyclopentanes employing chiral, a,ß-unsaturated acylammonium intermediates   pp1049 - 1057 Gang Liu, Morgan E. Shirley, Khoi N. Van, Rae Lynn McFarlin and Daniel Romo doi:10.1038/nchem.1788 Despite their appearance in a number of bioactive natural products, the synthesis of 5-membered carbocycles has received much less attention than synthesis of their 6-membered counterparts. Here, a Michael-aldol-ß-lactonization cascade is used to forge two C-C bonds, one C-O bond, two rings and up to three contiguous stereocentres and deliver complex cyclopentanes with high levels of relative and absolute stereocontrol. Bacteria clustering by polymers induces the expression of quorum-sensing-controlled phenotypes   pp1058 - 1065 Leong T. Lui, Xuan Xue, Cheng Sui, Alan Brown, David I. Pritchard et al. doi:10.1038/nchem.1793 Bacteria use signalling networks to control population behaviour. Here it is shown that polymers that promote clustering of bacteria can influence bacterial signalling and induce unexpected responses in quorum-sensing-controlled phenotypes. These responses can be better modulated by controlling the affinity of the polymer to both bacteria and signalling molecules. In Your Element Top Mesmerized by mercury   p1066 Joel D. Blum doi:10.1038/nchem.1803 Joel D. Blum considers the two faces of mercury. It has many unique and useful properties in chemistry — yet it comes with a dark and dangerous side. Top Advertisement Featured contents published recently in Polymer Journal:  Peptide Materials Application of Quantum Beams to Polymer Science and Engineering  NMR of Polymers  Self-Assembled Material Ichiro Sakurada Special issue  Polymer Journal promotes research from all aspects of polymer science from anywhere in the world.  Register for your Electronic Table of Contents e-alerts 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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