Nature Chemistry Contents March 2012 Volume 4 Number 3 pp 141-236

TABLE OF CONTENTS March 2012 Volume 4, Issue 3 Editorial Thesis Research Highlights Blogroll News and Views Perspectives Articles Erratum In Your Element Subscribe   Facebook   RSS   Recommend to library   Twitter   Advertisement Attending the ACS Spring meeting in San Diego? Join us at the Nature Publishing Group Booth #1002 for your chance to: - Browse and take free sample copies of leading journals from NPG, including Nature, Nature Chemistry and Nature Chemical Biology. - Talk to our sales rep Simon Allardice about your advertising plans for 2012 and beyond in print or online. - Subscribe and save 20% - special discount rate for conference attendees on personal subscriptions.   Editorial Top Of polemics and progress p141 doi:10.1038/nchem.1294 Disagreements are common in science and can lead to better understanding, but must be handled carefully. Full Text | PDF Thesis Top Zen and the art of molecules pp142 - 144 Michelle Francl doi:10.1038/nchem.1279 Michelle Francl wonders what it is that makes a molecule elegant. Full Text | PDF Research Highlights Top Chemical sensing: Attoreactor arrays | Natural product synthesis: The halichondrin C campaign | Atmospheric chemistry: Important intermediates | Coordination polymers: Side chains chip in | Main group chemistry: Boron and flat Blogroll Top Blogroll: For safety's sake p147 doi:10.1038/nchem.1292 Full Text | PDF News and Views Top Surface chemistry: Making the right connections pp149 - 150 Neil R. Champness doi:10.1038/nchem.1276 How do you create a molecular circuit board? Covalently coupling different molecules in a sequential manner in surface-based nanostructures opens up new possibilities and hopes for molecular electronics. Full Text | PDF See also: Article by Lafferentz et al. Chirality: Spin and gravity give a helping hand pp150 - 152 Laurence D. Barron doi:10.1038/nchem.1278 The handedness of supramolecular helices formed from achiral monomers has been controlled by applying rotational and gravitational forces, but at the start of the assembly process only. This demonstrates that a falsely chiral influence is able to induce absolute enantioselection. Full Text | PDF See also: Article by Micali et al. Radiochemistry: Flipping fluoride's reactivity pp152 - 154 Veronique Gouverneur doi:10.1038/nchem.1280 A sophisticated palladium(IV)-based species allows nucleophilic fluoride to react as an electrophilic fluorination reagent. This long-awaited reactivity will be especially useful in the preparation of radiochemically labelled molecules for positron emission tomography studies. Full Text | PDF Quantum chemistry: Quadruply bonded carbon pp154 - 155 Jorg Grunenberg doi:10.1038/nchem.1274 Determining molecular bond orders can be a delicate and sophisticated task, especially if the electronic structure of the studied system is complex. Now, two different ab initio methods have revealed that C2 and analogous species have a fourth bond, rather than the previously assumed maximum of three. Full Text | PDF See also: Article by Shaik et al. Nucleic acid hybridization: Robust sequence discrimination pp155 - 157 Gregoire Altan-Bonnet and Fred Russell Kramer doi:10.1038/nchem.1283 Careful consideration of thermodynamics has allowed the design of nucleic acid probes that are highly specific and virtually unaffected by changes in reaction conditions. Full Text | PDF See also: Article by Zhang et al. Ultrafast chemical physics: In search of molecular movies pp157 - 158 Julia A. Weinstein and Neil T. Hunt doi:10.1038/nchem.1282 Ultrafast chemical physics follows in the explosive wake of technological innovation, using light and radiation sources to study phenomena at timescales where the boundaries between physics and chemistry dissolve. UCP 2011, the second meeting in a series, explored the current state of the art in ultrafast time-resolved spectroscopy. Full Text | PDF Metamaterials: Turning a negative into a positive pp159 - 160 Jackie Y. Ying doi:10.1038/nchem.1275 Metamaterials are synthetic materials tailored with unusual properties that are not found in nature. It has now been predicted that they could be engineered with negative refractive index through the use of periodic structures via bottom-up self-assembly synthesis. Full Text | PDF Chemistry JOBS of the week Scientist (Suface Chemistry, Polymer Chemistry) Illumina Group Leader OLED - Chemistry (m / f) 1500 Merck KGaA Chemistry Laboratory Technician Kelly Scientific Resources Chemist - w / HPLC and GC experience Kelly Scientific Resources Analytical Chemist - Permanent Job Yoh More Science jobs from Chemistry EVENT Organometallic chemistry GRC 8th -13th July 2012 RI, US More science events from Perspectives Top Good vibrations in enzyme-catalysed reactions pp161 - 168 Sam Hay and Nigel S. Scrutton doi:10.1038/nchem.1223 This Perspective discusses contemporary ideas for enzymatic reactions that invoke a role for fast 'promoting' (or 'compressive') motions or vibrations that, in principle, can facilitate enzyme-catalysed reactions. With an emphasis on hydrogen-transfer reactions, experimental, theoretical and computational approaches that have lent evidence to this controversial hypothesis are discussed. Abstract | Full Text | PDF Taking Ockham's razor to enzyme dynamics and catalysis pp169 - 176 David R. Glowacki, Jeremy N. Harvey and Adrian J. Mulholland doi:10.1038/nchem.1244 Enzyme-catalysed reactions can involve significant quantum tunnelling and show kinetic isotope effects with complex temperature dependences. In this Perspective, reaction dynamics and enzyme catalysis are linked to transition-state-theory frameworks. It is shown that a multi-state model using standard transition-state theory can account for complex experimental data without invoking a role for enzyme dynamics. Abstract | Full Text | PDF Articles Top The promoting effect of adsorbed carbon monoxide on the oxidation of alcohols on a gold catalyst pp177 - 182 Paramaconi Rodriguez, Youngkook Kwon and Marc T. M. Koper doi:10.1038/nchem.1221 Adsorbed carbon monoxide typically acts to poison the oxidation of alcohols on heterogeneous catalysts and electrocatalysts. Here, it is shown that carbon monoxide that has been adsorbed irreversibly on a Au(111) surface can act as a promoter for this process by enhancing the scission of C–H bonds in the alcohol to yield the corresponding aldehyde. Abstract | Full Text | PDF Darwinian evolution of an alternative genetic system provides support for TNA as an RNA progenitor pp183 - 187 Hanyang Yu, Su Zhang and John C. Chaput doi:10.1038/nchem.1241 The pre-RNA-world hypothesis postulates that RNA was preceded in the evolution of life by a simpler genetic material. Here, Darwinian evolution methods were used to generate a threose nucleic acid (TNA) aptamer. This result provides evidence that TNA could have served as an ancestral genetic system during an early stage of life. Abstract | Full Text | PDF | Chemical compounds Structure and catalytic properties of the most complex intergrown zeolite ITQ-39 determined by electron crystallography pp188 - 194 Tom Willhammar, Junliang Sun, Wei Wan, Peter Oleynikov, Daliang Zhang, Xiaodong Zou, Manuel Moliner, Jorge Gonzalez, Cristina Martínez, Fernando Rey and Avelino Corma doi:10.1038/nchem.1253 Solving the structure of zeolites is often challenging because of their small particle size. Now, electron crystallography reveals the structure of a family of complex intergrown zeolite materials. These zeolites contain unique pair-wise 12-ring channels that intersect with 10-ring channels, and are promising catalysts for converting gasoline into diesel fuel. Abstract | Full Text | PDF Quadruple bonding in C2 and analogous eight-valence electron species pp195 - 200 Sason Shaik, David Danovich, Wei Wu, Peifeng Su, Henry S. Rzepa and Philippe C. Hiberty doi:10.1038/nchem.1263 The bonding order of multiply bonded main-group elements is conventionally thought to be limited to triple bonds. Now, using high-level theoretical methods, it is shown that C2 and its isoelectronic molecules CN+, BN and CB− are quadruply bonded, featuring not only one σ - and two π-bonds, but also one weak ‘inverted’ bond. Abstract | Full Text | PDF See also: News and Views by Grunenberg Selection of supramolecular chirality by application of rotational and magnetic forces pp201 - 207 N. Micali, H. Engelkamp, P. G. van Rhee, P. C. M. Christianen, L. Monsù Scolaro and J. C. Maan doi:10.1038/nchem.1264 It is shown here that the proper combination of physical forces can induce chirality during the self-assembly of achiral molecules. Rotation and effective gravity created by high magnetic fields during the nucleation phase, together with the magnetic alignment of the nanoaggregates initially formed, control the enantioselectivity of porphyrin assemblies. Abstract | Full Text | PDF See also: News and Views by Barron Optimizing the specificity of nucleic acid hybridization pp208 - 214 David Yu Zhang, Sherry Xi Chen and Peng Yin doi:10.1038/nchem.1246 High-fidelity pairing of nucleic acid polymers is important in the development of sensors and for the application of DNA nanotechnology. Here, a set of hybridization probes is described that discriminates single-base changes with high specificity. The probes function robustly across many different temperatures, salinities and nucleic acid concentrations. Abstract | Full Text | PDF See also: News and Views by Altan-Bonnet & Kramer Controlling on-surface polymerization by hierarchical and substrate-directed growth pp215 - 220 L. Lafferentz, V. Eberhardt, C. Dri, C. Africh, G. Comelli, F. Esch, S. Hecht and L. Grill doi:10.1038/nchem.1242 The bottom-up construction of covalently linked molecular architectures on surfaces has recently been demonstrated, but only rather simple structures can be obtained in such one-step connection processes. A sequential approach has now been used to induce the selective connection of molecules with a programmed reactivity, enabling network formation with high selectivity. Abstract | Full Text | PDF | Chemical compounds See also: News and Views by Champness Strongly coupled binuclear uranium–oxo complexes from uranyl oxo rearrangement and reductive silylation pp221 - 227 Polly L. Arnold, Guy M. Jones, Samuel O. Odoh, Georg Schreckenbach, Nicola Magnani and Jason B. Love doi:10.1038/nchem.1270 The oxo groups in the common trans-uranyl ion — present in the majority of known uranium compounds — are linear and inert. Now, a new reduced binuclear uranium–dioxo compound with very strong metal coupling and remarkable air stability has been formed through oxo migration and silylation. Abstract | Full Text | PDF Chemoselective synthesis of ketones and ketimines by addition of organometallic reagents to secondary amides pp228 - 234 William S. Bechara, Guillaume Pelletier and André B. Charette doi:10.1038/nchem.1268 To achieve chemoselective additions of organometallics to carbonyls, it is important to consider the combination of acylating agent and organometallic as a reactive pair rather than either one in isolation. Here, a chemoselective, controlled and general methodology for the conversion of secondary amides to ketones and ketimines is described. Abstract | Full Text | PDF | Chemical compounds Erratum Top Binary fluorous tagging enables the synthesis and separation of a 16-stereoisomer library of macrosphelides p235 Dennis P. Curran, Mantosh K. Sinha, Kai Zhang, Jesse J. Sabatini and Dae-Hyun Cho doi:10.1038/nchem.1271 Full Text | PDF See also: Article by Curran et al. In Your Element Top The deeds to deuterium p236 Dan O'Leary doi:10.1038/nchem.1273 Dan O'Leary examines Harold Urey's decision to name the mass-2 hydrogen isotope 'deuterium'. Full Text | PDF Top Advertisement Frontiers in Electronic Materials: Correlation Effects and Memristive Phenomena June 17-20, 2012 • Aachen, Germany This conference will bring together leaders in the field to discuss breakthroughs and challenges in fundamental research as well as prospects for future applications. To register and for more information, visit: www.nature.com/natureconferences/fem2012   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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