Nature Chemistry Contents March 2016 Volume 8 Number 3 pp 193 - 282

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TABLE OF CONTENTS March 2016 Volume 8, Issue 3 Commentary News and Views Correction Review Articles Corrigenda In Your Element Subscribe   Facebook   RSS   Recommend to library   Twitter   Commentary Top Wrong but seminal   pp193 - 200 Jeffrey I. Seeman and Stuart Cantrill doi:10.1038/nchem.2455 Publishing the wrong interpretation of experimental data can result in an immediate horde of chemists feeding on the error like vultures. On rare occasions, this phenomenon can open up an entire new field of science — and the structure of ferrocene is a case in point. News and Views Top Antibacterials: A sweet vaccine   pp201 - 202 David Bundle doi:10.1038/nchem.2468 Vaccination with a synthetic glycoconjugate, in combination with the administration of an inhibitor that blocks capsular polysaccharide synthesis in bacteria, could offer an alternative route to combat bacterial infections. See also: Article by Kong et al. Biomimetic catalysis: Taking on the turnover challenge   pp202 - 204 Richard J. Hooley doi:10.1038/nchem.2461 Emulating the efficiency with which enzymes catalyse reactions has often been used as inspiration to develop self-assembled cages. Now two studies present approaches to achieving catalyst turnover — one of the biggest challenges in achieving truly biomimetic catalysis. See also: Article by Cullen et al. | Article by Wang et al. Energy storage: Redox flow batteries go organic   pp204 - 206 Wei Wang and Vince Sprenkle doi:10.1038/nchem.2466 The use of renewable resources as providers to the electrical grid is hampered by the intermittent and irregular nature in which they generate energy. Electrical energy storage technology could provide a solution and now, by using an iterative design process, a promising anolyte for use in redox flow batteries has been developed. Infrared spectroscopy: The acid test for water structure   pp206 - 207 Noam Agmon doi:10.1038/nchem.2465 While there is some qualitative understanding of how excess protons behave in acidic aqueous solutions, there is still much to learn about the structures they form with water molecules. Now, 2D infrared spectroscopy has enabled the definite identification of the 'Zundel cation' in protonated liquid water and an approximate determination of its lifetime. Chemistry JOBS of the week The BP Professorship of Chemistry (1702) University of Cambridge Full Professorship (W3) for Inorganic Chemistry - Cognitive Materials Martin-Luther-University Halle-Wittenberg, Faculty of Natural Sciences II Assistant / Associate / Full Professor in Residence, Computational Chemistry / Biology UCSF - Institute for Neurodegenerative Diseases Dean of the Division of Physical Sciences University of California San Diego More Science jobs from Correction Top Correction   p207 doi:10.1038/nchem.2456 Review Top Remote functionalization through alkene isomerization   pp209 - 219 Alexandre Vasseur, Jeffrey Bruffaerts and Ilan Marek doi:10.1038/nchem.2445 In a remote functionalization, reaction occurs at a site distant from the site of initial activation. This Review discusses attempts to achieve this challenging goal with a particular focus on reactions that exploit alkene isomerizations to effect transit of the catalyst from a reactive alkene to a distant sp3 centre. Articles Top Reversible Bergman cyclization by atomic manipulation   pp220 - 224 Bruno Schuler, Shadi Fatayer, Fabian Mohn, Nikolaj Moll, Niko Pavliček et al. doi:10.1038/nchem.2438 The Bergman cyclization is a fascinating rearrangement reaction with implications beyond organic chemistry. It has now been shown that a reversible Bergman cyclization reaction in a single molecule sitting on an ultrathin NaCl film can be triggered and directly imaged using atomic force microscopy. The interconverted diradical and diyne products are shown to have distinct chemical and physical properties. Chemical compounds Self-assembled nanospheres with multiple endohedral binding sites pre-organize catalysts and substrates for highly efficient reactions   pp225 - 230 Qi-Qiang Wang, Sergio Gonell, Stefan H. A. M. Leenders, Maximilian Dürr, Ivana Ivanović-Burmazović et al. doi:10.1038/nchem.2425 Preorganization of catalysts and substrates can lead to significant rate enhancement—an effect often observed in enzyme catalysis. Now, a self-assembled nanosphere equipped with 24 guanidinium binding sites is demonstrated to strongly bind sulfonate-containing gold catalysts. Base-triggered co-encapsulation of carboxylate containing substrates leads to pronounced gating effects and dramatically enhanced reaction rates. See also: News and Views by Hooley Highly efficient catalysis of the Kemp elimination in the cavity of a cubic coordination cage   pp231 - 236 William Cullen, M. Cristina Misuraca, Christopher A. Hunter, Nicholas H. Williams and Michael D. Ward doi:10.1038/nchem.2452 The Kemp elimination has been catalysed in the cavity of a coordination cage with a rate enhancement (kcat/kuncat) of 200,000 at pD 8.5. The catalysis requires two orthogonal interactions to bring together the components: hydrophobic binding of benzisoxazole, and accumulation of hydroxide ions at the cationic cage surface by ion-pairing. See also: News and Views by Hooley The role of metal ions in X-ray-induced photochemistry   pp237 - 241 V. Stumpf, K. Gokhberg and L. S. Cederbaum doi:10.1038/nchem.2429 Metal centres play an important role in the damage to biomolecules caused by radiation, but the respective microscopic mechanisms are unknown. Now it is shown that the absorption of X-rays by a metal ion leads to an intricate chain of ultrafast relaxation steps that results in the complete degradation of the metal's local environment. An antibacterial vaccination strategy based on a glycoconjugate containing the core lipopolysaccharide tetrasaccharide Hep2Kdo2   pp242 - 249 Lingbing Kong, Balakumar Vijayakrishnan, Michael Kowarik, Jin Park, Alexandra N. Zakharova et al. doi:10.1038/nchem.2432 The presence and linkage of unusual higher sugars in the ‘inner core’ of Gram-negative bacteria makes the core lipopolysacchride tetrasaccharide Hep2Kdo2 a tough target. Now, a 2+2 glycosylation strategy has facilitated the synthesis of this glycoconjugate. Synthesis of Hep2Kdo2 enabled an antibacterial vaccination strategy based on immunization with the glycoconjugate and the subsequent administration of an inhibitor that uncovers the corresponding epitope in pathogenic bacteria. See also: News and Views by Bundle Controlled partial interpenetration in metal–organic frameworks   pp250 - 257 Alan Ferguson, Lujia Liu, Stefanus J. Tapperwijn, David Perl, François-Xavier Coudert et al. doi:10.1038/nchem.2430 Interpenetration of metal–organic frameworks (MOFs) is a common phenomenon, in which a structure consists of two or more identical, entangled sub-lattices. Now, MOFs with variable, fractional degrees of occupancy of one of two sub-lattices have been prepared. The extent of interpenetration can be controlled either during synthesis or by autocatenation, a framework rearrangement process. Chemical compounds Dissociative electron attachment to CO2 produces molecular oxygen   pp258 - 263 Xu-Dong Wang, Xiao-Fei Gao, Chuan-Jin Xuan and Shan Xi Tian doi:10.1038/nchem.2427 Until recently, the three-body recombination reaction was widely regarded as the only reaction pathway to the production of molecular oxygen in Earth's prebiotic primitive atmosphere. Observation of a CO2 photodissociation pathway altered this view, but now, using anion velocity imaging, a further source of molecular oxygen is revealed, formed via the dissociative electron attachment to CO2. Diversification of self-replicating molecules   pp264 - 269 Jan W. Sadownik, Elio Mattia, Piotr Nowak and Sijbren Otto doi:10.1038/nchem.2419 Self-replicating molecules provide a simple molecular level system to study the processes occurring in speciation. Now it is shown that in a pool of interconverting macrocycles, constructed from two building blocks, two distinct sets of self-replicating molecules emerge, and that one is a descendant of the other. Extreme compressibility in LnFe(CN)6 coordination framework materials via molecular gears and torsion springs   pp270 - 275 Samuel G. Duyker, Vanessa K. Peterson, Gordon J. Kearley, Andrew J. Studer and Cameron J. Kepert doi:10.1038/nchem.2431 Highly compressible crystalline materials typically rely on the high compressibility of their chemical bonds. Now, a family of LnFe(CN)6 frameworks (Ln = Ho, Lu or Y) has been shown to exhibit pronounced volumetric and linear compressibilities through a spring-and-gear mechanism instead, in which a torsionally flexible LnN6 unit twists reversibly under pressure. Enantioselective aldol reactions with masked fluoroacetates   pp276 - 280 Jakub Saadi and Helma Wennemers doi:10.1038/nchem.2437 Enantioselective aldol reactions with fluoroacetate would enable access to numerous fluorinated analogues of therapeutically important compounds but have been a long-standing unsolved challenge. Now, bioinspired fluoromalonic acid half thioesters (F-MAHTs) have been devised and allow for highly stereoselective reactions with aldehydes under mild organocatalytic conditions. Chemical compounds Corrigenda Top Corrigendum: Recent advances in the construction of antibody-drug conjugates   p281 Vijay Chudasama, Antoine Maruani and Stephen Caddick doi:10.1038/nchem.2467 Corrigendum: Sustained gastrointestinal activity of dendronized polymer-enzyme conjugates   p281 Gregor Fuhrmann, Andrea Grotzky, Ružica Lukić, Simon Matoori, Paola Luciani et al. doi:10.1038/nchem.2458 Corrigendum: Catalytic enantioselective synthesis of indanes by a cation-directed 5-endo-trig cyclization   p281 Craig P. Johnston, Abhishek Kothari, Tetiana Sergeieva, Sergiy I. Okovytyy, Kelvin E. Jackson et al. doi:10.1038/nchem.2457 Top In Your Element Top Lawrencium's place at the table   p282 Yuichiro Nagame doi:10.1038/nchem.2460 Yuichiro Nagame ponders on the steps it took to make lawrencium, and its location in the periodic table. Natureevents is a fully searchable, multi-disciplinary database designed to maximise exposure for events organisers. 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