Nature Chemistry Contents April 2013 Volume 5 Number 4 pp247-348

TABLE OF CONTENTS April 2013 Volume 5, Issue 4 Editorial Thesis Research Highlights Blogroll News and Views Review Articles In Your Element Subscribe   Facebook   RSS   Recommend to library   Twitter   Advertisement Submit to Nature Chemistry The online submission system for Nature Chemistry is open, and the editorial team welcome manuscripts describing cutting-edge research from all areas of chemistry. - manuscripts should be submitted through the online submission system - the complete Guide for Authors can be viewed online   Editorial Top All you can tweet   p247 doi:10.1038/nchem.1608 Nature Chemistry signed up for a Twitter account in March 2009. More than 5,000 tweets later, what have we learned and how do we use it? Thesis Top Big (chemistry) data   pp248 - 249 Bruce C. Gibb doi:10.1038/nchem.1604 Bruce Gibb ponders what the future of chemistry research might look like if we take a more data-driven approach. Research Highlights Top Catalyst design: Supra selectivity | Hydrogen bonding: Unconventional connections | DNA-protein interactions: Appreciating allostery | Amyloid fibrils: Peptides do the twist Blogroll Top Blogroll: Fighting fear   p251 DrRubidium  doi:10.1038/nchem.1605 News and Views Top Polymer chemistry: Not lost in translation   pp252 - 253 Rachel K. O'Reilly doi:10.1038/nchem.1603 Strategies for making sequence-controlled polymers in the laboratory are really quite primitive in comparison with those used in nature. By combining concepts from natural systems and synthetic polymer chemistry, it has now been shown that DNA codes can be translated into non-nucleic-acid polymers with defined sequences. See also: Article by Niu et al. Reaction dynamics: OH electron, where art thou?   pp253 - 255 Millard H. Alexander doi:10.1038/nchem.1598 The study of the reaction of a ground-state O atom with H2 has previously proved difficult because of its high activation barrier. Now, new experiments have revealed unexpected OH product states; but perhaps there is a simple explanation? See also: Article by Lahankar et al. Hydrogen electrocatalysis: A basic solution   pp255 - 256 Marc T. M. Koper doi:10.1038/nchem.1600 Hydrogen-oxygen alkaline fuel cells are promising devices for the 'hydrogen economy' but their oxidation of hydrogen fuel is slow compared with that of acidic fuel cells. More efficient electrocatalysts have now been prepared in which the adsorption of hydroxyl groups onto the electrode surface is controlled through suitable promoters. See also: Article by Strmcnik et al. Peptide deactivation: Spectroscopy meets theory   pp257 - 258 Wolfgang Domcke and Andrzej L. Sobolewski doi:10.1038/nchem.1601 Combined spectroscopic measurements and theoretical calculations bring to light an ultrafast excited-state deactivation process in peptides that may contribute to the ultraviolet photostability of proteins. Inorganic chemistry: Deconstructing water oxidation   pp259 - 260 Sarah A. Cook and A. S. Borovik doi:10.1038/nchem.1606 During photosynthesis, the oxygen-evolving complex oxidizes water to produce molecular oxygen. Now, a possible role for the calcium ion in this complex has been proposed based on the electrochemical properties of a series of synthetic heterometallic clusters. See also: Article by Tsui et al. Interlocked molecules: A molecular production line   pp260 - 262 Paul R. McGonigal and J. Fraser Stoddart doi:10.1038/nchem.1599 A small molecule that mimics the sequence-specific peptide synthesis of nature's ribosomes paves the way for more elaborate artificial molecular synthesizers. Chemistry JOBS of the week University Professor of Materials- and Nano-Chemistry University of Innsbruck, Austria M.Sc. / Ph.D. Opportunities in Hydrothermal Physical Chemistry University of Guelph Postdoctoral Position -- Organic and Medicinal Chemistry University of Hawaii at Hilo College of Pharmacy Associate Professorship W2 for Organic Chemistry University of Bonn, Kekulé Institut for Organic Chemistry and Biochemistry Head of Medicinal Chemistry UCB More Science jobs from Chemistry EVENT Flow Chemistry Congress 05.14.13 Boston, US More science events from Review Top The chemistry of two-dimensional layered transition metal dichalcogenide nanosheets   pp263 - 275 Manish Chhowalla, Hyeon Suk Shin, Goki Eda, Lain-Jong Li, Kian Ping Loh and Hua Zhang doi:10.1038/nchem.1589 Two-dimensional materials have recently garnered much interest in the scientific and technology communities. This Review describes how ultrathin transition metal dichalcogenides combine tunable structure and electronic properties, achieved through altering their composition, with versatile chemistry. This makes them attractive in various fields, for example as lithium-ion battery electrodes and electrocatalysts for the hydrogen evolution reaction. Articles Top Molecular shape sorting using molecular organic cages   pp276 - 281 Tamoghna Mitra, Kim E. Jelfs, Marc Schmidtmann, Adham Ahmed, Samantha Y. Chong, Dave J. Adams and Andrew I. Cooper doi:10.1038/nchem.1550 A crystalline porous organic cage molecule is shown to have exceptional specificity for separating different structural isomers of C9 aromatics. Uniquely, this solid-state specificity is preconfigured in the discrete molecular building block, which shows an analogous specificity in solution. Both solution and solid-state behaviours can be understood by molecular dynamics simulations. Enzyme-free translation of DNA into sequence-defined synthetic polymers structurally unrelated to nucleic acids   pp282 - 292 Jia Niu, Ryan Hili and David R. Liu doi:10.1038/nchem.1577 An enzyme-free system that translates DNA into sequence-defined non-nucleic acid polymers including polyethylene glycol, α-(D)-peptides and β-peptides is described. Sequence-defined polymers with molecular weights of 26 kDa containing 16 consecutively coupled building blocks and 90 densely functionalized β-amino acids were translated from DNA templates using this strategy. See also: News and Views by O'Reilly Redox-inactive metals modulate the reduction potential in heterometallic manganese–oxido clusters   pp293 - 299 Emily Y. Tsui, Rosalie Tran, Junko Yano and Theodor Agapie doi:10.1038/nchem.1578 The presence of Ca2+ is essential for the activity of the oxygen-evolving complex (OEC) of Photosystem II, although its exact role is still unclear. Now, electrochemical measurements of structural mimics of the OEC — based on mixed-metal trimanganese dioxido complexes — reveal a correlation between the Lewis acidity of the redox-inactive metal and the reduction potential of the complex. See also: News and Views by Cook & Borovik Improving the hydrogen oxidation reaction rate by promotion of hydroxyl adsorption   pp300 - 306 Dusan Strmcnik, Masanobu Uchimura, Chao Wang, Ram Subbaraman, Nemanja Danilovic, Dennis van der Vliet, Arvydas P. Paulikas, Vojislav R. Stamenkovic and Nenad M. Markovic doi:10.1038/nchem.1574 Hydrogen is an attractive alternative to fossil fuels, but the slow rate of the hydrogen oxidation reaction in alkaline fuel cells hinders their development. It is now proposed that bifunctional materials can be devised to offer the optimal balance between hydrogen and hydroxyl adsorption, thus significantly reducing the amount of precious metal on the anode. See also: News and Views by Koper Synthesis of 19-substituted geldanamycins with altered conformations and their binding to heat shock protein Hsp90   pp307 - 314 Russell R. A. Kitson, Chuan-Hsin Chang, Rui Xiong, Huw E. L. Williams, Adrienne L. Davis, William Lewis, Donna L. Dehn, David Siegel, S. Mark Roe, Chrisostomos Prodromou, David Ross and Christopher J. Moody doi:10.1038/nchem.1596 The heat shock protein Hsp90 is a potential target for cancer and neurodegeneration drugs. Here, the introduction of a substituent into the 19-position of the naturally occurring inhibitor geldanamycin by chemical synthesis is shown to ameliorate toxicity, and also cause a favourable conformational switch that is required for protein binding. Product-state-resolved dynamics of the elementary reaction of atomic oxygen with molecular hydrogen O(3P) + D2 → OD(X2Π) + Dpp315 - 319 Sridhar A. Lahankar, Jianming Zhang, Kenneth G. McKendrick and Timothy K. Minton doi:10.1038/nchem.1588 The reaction O(3P) + H2 → OH(X2Π) + H has, until now, eluded detailed experimental investigation. Now, a laser-induced fluorescence study of the deuterated analogue has revealed product-state distributions that defy the current descriptions of non-Born–Oppenheimer mixing on coupled potential energy surfaces, issuing new challenges to theory. See also: News and Views by Alexander Ammonia formation by a thiolate-bridged diiron amide complex as a nitrogenase mimic   pp320 - 326 Yang Li, Ying Li, Baomin Wang, Yi Luo, Dawei Yang, Peng Tong, Jinfeng Zhao, Lun Luo, Yuhan Zhou, Si Chen, Fang Cheng and Jingping Qu doi:10.1038/nchem.1594 Although it is achieved routinely by nitrogenases, the conversion of molecular dinitrogen into ammonia under ambient conditions is proving difficult with synthetic systems. A thiolate-bridged diiron complex has now been developed that produces ammonia from coordinated N2H2 through a sequence of reduction and protonation reactions that may well mimic biological nitrogen fixation. A multistep single-crystal-to-single-crystal bromodiacetylene dimerization   pp327 - 334 Tobias N. Hoheisel, Stephen Schrettl, Roman Marty, Tanya K. Todorova, Clémence Corminboeuf, Andrzej Sienkiewicz, Rosario Scopelliti, W. Bernd Schweizer & Holger Frauenrath doi:10.1038/nchem.1575 The photochemical-induced dimerization of bromine-terminated oligo(ethynylene)s in the solid state is shown to give 1,2-dibromoeneynes on a preparative scale. This single-crystal-to-single-crystal transformation proceeds through a multistep reaction that involves the making and breaking of several bonds in addition to large atom displacements. The reaction represents an atom-efficient and catalyst-free pathway towards functional carbon-rich molecular scaffolds. Highly ordered alignment of a vinyl polymer by host–guest cross-polymerization   pp335 - 341 Gaetano Distefano, Hirohito Suzuki, Masahiko Tsujimoto, Seiji Isoda, Silvia Bracco, Angiolina Comotti, Piero Sozzani, Takashi Uemura and Susumu Kitagawa doi:10.1038/nchem.1576 A strategy to endow vinyl polymers with pseudo-crystalline order has been devised that relies on host–guest cross-polymerization, through functionalization of the channels of a porous coordination polymer with divinyl moieties. Polymerization of vinyl monomers within the channels is accompanied with lateral crosslinking, which ensures the polymer chains remain highly ordered after removal of the host. A homogeneous transition metal complex for clean hydrogen production from methanol–water mixtures   pp342 - 347 Rafael E. Rodríguez-Lugo, Mónica Trincado, Matthias Vogt, Friederike Tewes, Gustavo Santiso-Quinones & Hansjörg Grützmacher doi:10.1038/nchem.1595 A ruthenium complex bearing a chemically and redox-non-innocent tetradentate diolefin diazadiene ligand is shown to be an efficient homogeneous catalyst for the conversion of a 1:1 mixture of methanol and water to hydrogen and carbon dioxide. Development of this process is an important step in the production of hydrogen for use as a fuel from biomass. In Your Element Top Cerium under the lens   p348 Eric J. Schelter doi:10.1038/nchem.1602 Eric J. Schelter ponders on cerium's rather puzzling redox reactivity, and the varied practical applications that have emerged from it. Top Advertisement Subscribe to Nature Chemistry Make sure you receive your own personal copy of Nature Chemistry. 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