Nature Chemistry Contents December 2012 Volume 4 Number 12 pp 955-1052

Advertisement A*STAR Research - Highlighting the best of research at the Agency for Science, Technology and Research (A*STAR), Singapore's premier research organization Recent Highlights Computational neuroscience: Memory-making is all about the connection | Data storage: How magnetic recording heats up The new print edition of A*STAR Research is now available! TABLE OF CONTENTS December 2012 Volume 4, Issue 12 Editorial Thesis Books and Arts Research Highlights Blogroll Correction News and Views Review Articles Corrigendum In Your Element Subscribe   Facebook   RSS   Recommend to library   Twitter   Advertisement The Ruhr-Universität Bochum (RUB) - Fakultät für Chemie und Biochemie offers job opportunities at all career levels in field of "Solvation Science": www.rub.de/solvation/jobs. The Cluster of Excellence "Ruhr Explores Solvation" (RESOLV) is funded by the German Excellence Initiative. RESOLV: aims at understanding the influence of solvation on reactions, the function of biomolecules, and processes at liquid-solid interface.   Advertisement Nature Arabic Edition allows Arabic speakers throughout the world to access top quality science news and comment from Nature, as well as summaries of all the research papers from the leading multidisciplinary journal. Access Nature Arabic Edition online and apply for your free subscription arabicedition.nature.com. In partnership with: KACST   Editorial Top Take aim   p955 doi:10.1038/nchem.1521 A collection of articles in this issue focuses on the ability to selectively perform a reaction at just one specific site in a complex molecule that contains many other similarly reactive sites. Thesis Top Naming names   pp956 - 957 Michelle Francl doi:10.1038/nchem.1508 Michelle Francl suggests that chemists should keep on name-dropping. Free at last!   p958 Dennis P. Curran doi:10.1038/nchem.1507 Dennis P. Curran invites everyone to join the dawning new era of organic synthesis. Books and Arts Top Tenure bubbles burst   p959 Abigail Klopper doi:10.1038/nchem.1510 Research Highlights Top Living materials: A chemical factory within | 2012 Nobel prize in chemistry: Signalling the way | Organometallic chemistry: An iron-clad analogue | Renewable fuels: Catalytic upgrade Blogroll Top Blogroll: Eye of the beholder   p961 Karl D. Collins doi:10.1038/nchem.1517 Correction Top Materials chemistry: Compliant crystals   p961 doi:10.1038/nchem.1513 News and Views Top Lithium-air batteries: Something from nothing   pp962 - 963 Fangyi Cheng and Jun Chen doi:10.1038/nchem.1516 The reversible reduction and evolution of oxygen are the key processes to be mastered before high-energy rechargeable lithium-air batteries can be successfully created. Now an advance towards this goal has been achieved with the synthesis of a pyrochlore catalyst that benefits from a mesoporous structure and oxygen deficiencies. See also: Article by Oh et al. Site-selective reactions: Remodelling by diversity and design   pp963 - 965 Pamela M. Tadross and Eric N. Jacobsen doi:10.1038/nchem.1509 Bioactive molecules frequently contain several very similarly reactive functional groups and it can thus be difficult to cause one to react selectively. Now, two separate studies present complementary approaches to this desirable goal. See also: Article by Lichtor & Miller | Article by Wilcock et al. Water splitting: Catalyst or spectator?   pp965 - 967 Daniel R. Gamelin doi:10.1038/nchem.1514 The deposition of cobalt-phosphate onto photocatalytic haematite improves its ability to split water and thus create clean hydrogen fuel. The source of this improvement is, however, not yet understood, and now two separate studies suggest different roles for the deposited cobalt-phosphate. Single-molecule magnets: Uranyl steps in the ring   pp967 - 969 Polly L. Arnold doi:10.1038/nchem.1512 Uranium and manganese cations have been combined in a wheel-shaped supramolecular assembly that retains its magnetic spin state after the external field is removed, with a high barrier to its relaxation. This cluster supports recent predictions of the usefulness of the actinides in single-molecule magnetic devices. See also: Article by Mougel et al. Organic photochemistry: Exciting excited-state aromaticity   pp969 - 971 Henrik Ottosson doi:10.1038/nchem.1518 In 1972, Baird published rules describing aromaticity and antiaromaticity in the lowest triplet excited states of annulenes. The fortieth anniversary of Baird's rules — which are the reverse of Huckel's rules for aromaticity and antiaromaticity in the ground state — ought to be celebrated before 2012 comes to an end. Anticancer agents: Unleash the forces within   pp971 - 972 Weiwei Gao and Liangfang Zhang doi:10.1038/nchem.1515 Liposomes are a leading drug-delivery platform in cancer chemotherapy. Now they can be used to destroy cancer cells through a method that converts chemical energy to mechanical force. These localized disruptions can cause cell death while minimizing the collateral damage to neighbouring cells. Chemistry JOBS of the week Postdoctoral Investigator – Environmental Analytical Chemistry Woods Hole Oceanographic Institution - Department of Marine Chemistry and Geochemistry Postdoctoral Associates in Medicinal Chemistry Vanderbilt University Postdoc in Synthetic Carbohydrate Chemistry Xinyu Liu PhD Student Position in Peptide Chemistry / Radiopharmacy Prof. T. Mindt postdoctoral researcher (synthetic chemistry) UC Riverside More Science jobs from Chemistry EVENT 4th International Conference for Young Chemists (ICYC) 30.01.-01.02.13 Penang, Malaysia More science events from Review Top Reaction-based small-molecule fluorescent probes for chemoselective bioimaging   pp973 - 984 Jefferson Chan, Sheel C. Dodani and Christopher J. Chang doi:10.1038/nchem.1500 The complexity of living systems makes attempts to gain a molecular-level understanding of them a unique and inspiring challenge. This Review summarizes progress in the development of bioorthogonal reaction-based fluorescent probes used to follow the spatial and temporal dynamics of biologically important analytes within living systems. Articles Top Inelastic scattering of hydroxyl radicals with helium and argon by velocity-map imaging   pp985 - 989 Gautam Sarma, Sarantos Marinakis, J. J. ter Meulen, David H. Parker and Kenneth G. McKendrick doi:10.1038/nchem.1480 Hydroxyl radicals (OH) are important in many chemical systems, including combustion and atmospheric reactions, however experimentally measuring their velocities in specific internal quantum states has proved difficult. Now differential cross-sections for inelastic scattering of fully state-specified OH with He and Ar have been observed for the first time using velocity-map imaging in a crossed-molecular-beam arrangement. Combinatorial evolution of site- and enantioselective catalysts for polyene epoxidation   pp990 - 995 Phillip A. Lichtor and Scott J. Miller doi:10.1038/nchem.1469 Aspartic acid-based catalysts that are selective for oxidation of either the 2,3 position or the 6,7 position of certain isoprenols have been discovered. The catalysts emerged from a diversity-based approach employing the one-bead-one-compound libraries. The site-selectivity of the catalysis seems to derive from the hydroxyl group in the substrate, although the details of this are not yet known. See also: News and Views by Tadross & Jacobsen Electronic tuning of site-selectivity   pp996 - 1003 Brandon C. Wilcock, Brice E. Uno, Gretchen L. Bromann, Matthew J. Clark, Thomas M. Anderson and Martin D. Burke doi:10.1038/nchem.1495 Site-selective functionalizations of complex small molecules can generate targeted derivatives with exceptional step-efficiency, but general strategies for maximizing selectivity in this context are rare. Investigations with the ion-channel-forming natural product amphotericin B have revealed that site-selectivity can be tuned by simply modifying the electronic nature of the reagents. See also: News and Views by Tadross & Jacobsen Synthesis of a metallic mesoporous pyrochlore as a catalyst for lithium–O2 batteries   pp1004 - 1010 Si Hyoung Oh, Robert Black, Ekaterina Pomerantseva, Jin-Hyon Lee and Linda F. Nazar doi:10.1038/nchem.1499 The lithium–O2 battery can theoretically provide energy densities that greatly exceed that of Li-ion, but it requires more efficient catalysts (or 'promoters') than carbon for oxygen reduction and evolution. Here, we report a tailor-made mesoporous metallic oxide that results in high reversible capacities and operates over many cycles. See also: News and Views by Cheng & Chen Uranium and manganese assembled in a wheel-shaped nanoscale single-molecule magnet with high spin-reversal barrier   pp1011 - 1017 Victor Mougel, Lucile Chatelain, Jacques Pécaut, Roberto Caciuffo, Eric Colineau, Jean-Christophe Griveau and Marinella Mazzanti doi:10.1038/nchem.1494 A {U12Mn6} wheel-shaped cluster that has been assembled through cation–cation interactions exhibits single-molecule-magnet behaviour. Single-molecule magnets are promising for magnetic storage devices at the nanoscale, and the observation of magnetic bistability with an open hysteresis loop and high relaxation barrier in this 5f–3d complex suggests that uranium-based compounds could be useful components. See also: News and Views by Arnold Extreme oxatriquinanes and a record C–O bond length   pp1018 - 1023 Gorkem Gunbas, Nema Hafezi, William L. Sheppard, Marilyn M. Olmstead, Irini V. Stoyanova, Fook S. Tham, Matthew P. Meyer and Mark Mascal doi:10.1038/nchem.1502 Oxatriquinane is a remarkably stable alkyl oxonium ion, despite the fact that its carbon–oxygen bond lengths are 1.54 Å. The robust nature of this fused tricyclic molecule enabled the addition of increasing steric bulk to the system, culminating in a tri-tert-butyloxatriquinane with a record 1.62 Å C–O bond distance. An N-bridged high-valent diiron–oxo species on a porphyrin platform that can oxidize methane    pp1024 - 1029 Evgeny V. Kudrik, Pavel Afanasiev, Leonardo X. Alvarez, Patrick Dubourdeaux, Martin Clémancey, Jean-Marc Latour, Geneviève Blondin, Denis Bouchu, Florian Albrieux, Sergey E. Nefedov and Alexander B. Sorokin doi:10.1038/nchem.1471 A short-lived diiron–oxo species — based on a nitrido-bridged bis-porphyrin platform — capable of efficiently oxidizing the strongest of C–H bonds has been prepared and spectroscopically characterized. The catalytic properties of this high-valent diiron(IV)–oxo complex were elucidated by studying the oxidation kinetics of a range of alkanes. Shape-selective sieving layers on an oxide catalyst surface   pp1030 - 1036 Christian P. Canlas, Junling Lu, Natalie A. Ray, Nicolas A. Grosso-Giordano, Sungsik Lee, Jeffrey W. Elam, Randall E. Winans, Richard P. Van Duyne, Peter C. Stair and Justin M. Notestein doi:10.1038/nchem.1477 Templated atomic layer deposition (ALD) is used to create oxide ‘nanocavities’ on the surface of catalyst particles. Subnanometre films containing nanocavities act as sieves for the underlying catalyst, resulting in high selectivities for the smaller of two reactants in competitive oxidations or reductions. A flow-system array for the discovery and scale up of inorganic clusters   pp1037 - 1043 Craig J. Richmond, Haralampos N. Miras, Andreu Ruiz de la Oliva, Hongying Zang, Victor Sans, Leonid Paramonov, Charalampos Makatsoris, Ross Inglis, Euan K. Brechin, De-Liang Long and Leroy Cronin doi:10.1038/nchem.1489 The discovery and synthesis of inorganic clusters can be both time consuming and limited by a lack of reproducibility. An automated flow process coupled with multiple batch crystallization has now been successfully used to rapidly screen and scale-up the syntheses of inorganic clusters, including polyoxometalates and manganese-based single-molecule magnets. Twin disulfides for orthogonal disulfide pairing and the directed folding of multicyclic peptides   pp1044 - 1049 Chuanliu Wu, Jean-Christophe Leroux and Marc A. Gauthier doi:10.1038/nchem.1487 The precise pairing of cysteine residues in proteins is routinely achieved in nature. However, the comparable pairing within polypeptides is a long-standing challenge for the preparation of multicyclic species. Here, a straightforward approach to direct the inter-/intramolecular pairing of cysteine residues within peptides using a minimal CXC motif is presented. Corrigendum Top Alteration of the oxygen-dependent reactivity of de novo Due Ferri proteins   p1050 Amanda J. Reig, Marcos M. Pires, Rae Ana Snyder, Yibing Wu, Hyunil Jo, Daniel W. Kulp, Susan E. Butch, Jennifer R. Calhoun, Thomas Szyperski, Edward I. Solomon and William F. DeGrado doi:10.1038/nchem.1519 In Your Element Top Plutonium's new horizons   p1052 Jan Hartmann doi:10.1038/nchem.1511 For historical reasons, plutonium brings to mind nuclear weapons. Jan Hartmann brings another side of element 94 to attention, which features an upcoming trip to its eponymous celestial body. Top Advertisement Subscribe to Nature Chemistry Make sure you receive your own personal copy of Nature Chemistry. 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