Nature Chemistry Contents December 2017 Volume 9 Number 12 pp 1151 - 1288

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Ad close deadline: 4 December, 2017    Subscribe   Facebook   RSS   Recommend to library   Twitter   Advertisement npj Clean Water: open for submissions  An open access, online-only journal, dedicated to publishing high-quality papers that describe the significant and cutting-edge research that continues to ensure the supply of clean water to populations. Explore the benefits of submitting your next manuscript.   Advertisement npj Materials Degradation is a new open access journal that is now open for submissions. The journal publishes the finest content describing basic and applied research discoveries in the area of corrosion (degradation) and protection of materials. Sign up for article e-alerts >>>   News and Views Top Superatomic solids: Intercalation without altercation   pp1151 - 1152 Shiv N. Khanna and Arthur C. Reber doi:10.1038/nchem.2895 Building materials with clusters instead of atoms promises unconventional properties, but those 'superatomic solids' are often too fragile to manipulate. Now, intercalating a guest within an ionic layered solid made of fullerenes and metal chalcogenide clusters greatly alters its conductivity and optical properties without disrupting its crystalline structure. See also: Article by O'Brien et al. Molecular organic networks: A step beyond flatland   pp1152 - 1154 Manfred Buck doi:10.1038/nchem.2901 Non-covalent interactions can organize planar molecules into two-dimensional arrays. It has now been shown that such arrays can be combined at the solid-liquid interface into bilayered heterostructures. See also: Article by Korolkov et al. Polymer mechanochemistry: Up another rung   pp1154 - 1155 Stephen L. Craig doi:10.1038/nchem.2902 The use of mechanical force to break and build chemical bonds in polymers can enable transformations that cannot be conducted using stimuli such as light and heat. Now, an insulating polymer has been mechanically unzipped to create a semiconducting polymer with extended regions of conjugation.   Chemistry JOBS of the week Senior Application Scientist Schrodinger, Inc Assistant Director, Member Relations MIT Faculty Positions Thomas Jefferson University (TJU) Transmission Electron Microscopy University of California - Irvine Postdoctoral Associate The Scripps Research Institute - Florida More Science jobs from Chemistry EVENT 6th Annual International Conference on Chemistry 26.07.18 Athens, Greece More science events from Advertisement Do you have a career question? The Naturejobs podcast features one-on-one Q&As, panel discussions and other exclusive content to help scientists with their careers. Hosted on the Naturejobs blog, the podcast is also available on iTunes and Soundcloud. Listen today!   Articles Top De novo design of a hyperstable non-natural protein–ligand complex with sub-Å accuracy   pp1157 - 1164 Nicholas F. Polizzi, Yibing Wu, Thomas Lemmin, Alison M. Maxwell, Shao-Qing Zhang et al. doi:10.1038/nchem.2846 The first demonstration of a protein designed entirely from first principles that binds a small-molecule cofactor in a precisely predetermined orientation has now been described. The design method utilizes a remote protein core that both anchors and predisposes a flexible binding site for the desired cofactor-binding geometry.   Catalyst-controlled oligomerization for the collective synthesis of polypyrroloindoline natural products   pp1165 - 1169 Christopher R. Jamison, Joseph J. Badillo, Jeffrey M. Lipshultz, Robert J. Comito and David W. C. MacMillan doi:10.1038/nchem.2825 The collective synthesis of several oligomeric polypyrroloindoline natural products, including hodgkinsine, hodgkinsine B, idiospermuline, quadrigemine H and isopsychotridines B and C, is accomplished through the iterative action of an asymmetric small molecule copper catalyst. This strategy also enables the synthesis of putatively unnatural quadrigemine H-type isomers. Chemical compounds Single-crystal-to-single-crystal intercalation of a low-bandgap superatomic crystal   pp1170 - 1174 Evan S. O'Brien, M. Tuan Trinh, Rose L. Kann, Jia Chen, Giselle A. Elbaz et al. doi:10.1038/nchem.2844 Intercalation — a cornerstone of materials science with wide-ranging applications — has now been demonstrated in a superatomic crystal. A redox-active tetracyanoethylene guest was inserted into the lattice of a material consisting of alternate layers of {Co6Te8} clusters and C60 fullerenes, leading to a single-crystal-to-single-crystal transformation that significantly modulates the material's optical and electrical transport properties. See also: News and Views by Khanna & Reber Direct mapping of the angle-dependent barrier to reaction for Cl + CHD3 using polarized scattering data   pp1175 - 1180 Huilin Pan, Fengyan Wang, Gábor Czakó and Kopin Liu doi:10.1038/nchem.2858 Two important properties in an activated chemical reaction are the barrier height and its geometrical dependence. Now, a method has been developed to directly map the angle-dependent barrier to reaction from polarized scattering data for the Cl + CHD3 reaction. The method should be applicable to many other direct reactions with a colinear barrier.   Global profiling of lysine reactivity and ligandability in the human proteome   pp1181 - 1190 Stephan M. Hacker, Keriann M. Backus, Michael R. Lazear, Stefano Forli, Bruno E. Correia et al. doi:10.1038/nchem.2826 A chemical proteomic strategy has now been reported for the global profiling of lysine reactivity and ligandability. Using this approach, >9000 lysines in the human proteome were evaluated, leading to the discovery of hyper-reactive lysines, and lysines that can be targeted by electrophilic small molecules to perturb enzyme function and protein–protein interactions.   Supramolecular heterostructures formed by sequential epitaxial deposition of two-dimensional hydrogen-bonded arrays   pp1191 - 1197 Vladimir V. Korolkov, Matteo Baldoni, Kenji Watanabe, Takashi Taniguchi, Elena Besley et al. doi:10.1038/nchem.2824 Supramolecular heterostructures have been formed by the sequential deposition of two molecular layers with different symmetries and lattice constants — one consisting of carboxylic acid, the other of cyanuric acid and melamine — on a hexagonal boron nitride substrate. Characterization by atomic force microscopy and molecular dynamics simulations shows epitaxial arrangements between the layers. See also: News and Views by Buck Enantioselective cyclizations and cyclization cascades of samarium ketyl radicals   pp1198 - 1204 Nicolas Kern, Mateusz P. Plesniak, Joseph J. W. McDouall and David J. Procter doi:10.1038/nchem.2841 Although samarium-mediated cyclizations have the potential to generate significant molecular complexity, historically it has not proven possible to exert enantiocontrol through the use of a chiral ligand in complex product synthesis. Now, an enantioselective SmI2-mediated radical cyclization has been developed using a chiral aminodiol ligand. Desymmetrizing 5-exo ketyl-alkene cyclizations and cyclization cascades of unsaturated ketoesters deliver complex products and typically proceed with high enantioselectivity and diastereoselectivity. Chemical compounds Vibronically coherent ultrafast triplet-pair formation and subsequent thermally activated dissociation control efficient endothermic singlet fission   pp1205 - 1212 Hannah L. Stern, Alexandre Cheminal, Shane R. Yost, Katharina Broch, Sam L. Bayliss et al. doi:10.1038/nchem.2856 Singlet fission — the conversion of one singlet exciton into two triplet excitons, could improve the efficiency of photovoltaic devices — but its mechanism is still to be fully understood. Now, in films of TIPS-tetracene, it has been shown that the formation of the triplet pair state, which has been proposed to mediate singlet fission, is ultrafast and vibronically coherent in this endothermic fission system.   Site-selective oxidation, amination and epimerization reactions of complex polyols enabled by transfer hydrogenation   pp1213 - 1221 Christopher K. Hill and John F. Hartwig doi:10.1038/nchem.2835 Polyoxygenated aliphatic chains with multiple hydroxyl groups are common in a wide array of compounds, often with potent biological activity. Now, a new ruthenium catalyst enables selective dehydrogenation of a single hydroxyl group in a broad scope of complex polyols. This site-selective modification facilitates the rapid incorporation of nitrogen-based functional groups into diverse natural products. Chemical compounds Modular probes for enriching and detecting complex nucleic acid sequences   pp1222 - 1228 Juexiao Sherry Wang, Yan Helen Yan and David Yu Zhang doi:10.1038/nchem.2820 Modular hybridization probes (M-Probes) have been developed that enable sequence-selective binding of complex nucleic acid targets. The M-probes can target sequences that: are hypervariable at prescribed loci, are long continuous sequences of over 500 nucleotides, or contain repetitive sequences. A hybrid-capture assay using the M-probes was developed that was capable of determining the exact triplet repeat expansion number in the Huntington's gene from genomic DNA.   UV-light-driven prebiotic synthesis of iron–sulfur clusters   pp1229 - 1234 Claudia Bonfio, Luca Valer, Simone Scintilla, Sachin Shah, David J. Evans et al. doi:10.1038/nchem.2817 Current mineral-based theories do not fully address how enzymes emerged from prebiotic catalysts. Now, iron–sulfur clusters can be synthesized by UV-light-mediated photolysis of organic thiols and photooxidation of ferrous ions. Iron–sulfur peptides may have formed easily on early Earth, facilitating the emergence of iron–sulfur-cluster-dependent metabolism. Chemical compounds A unifying paradigm for naphthoquinone-based meroterpenoid (bio)synthesis   pp1235 - 1242 Zachary D. Miles, Stefan Diethelm, Henry P. Pepper, David M. Huang, Jonathan H. George et al. doi:10.1038/nchem.2829 Bacterial naphthoquinone meroterpenoid natural products defy biosynthetic logic via classical biochemical paradigms. Now, an enzyme promoted α-hydroxyketone rearrangement catalysed by vanadium-dependent haloperoxidases reveals a conserved biosynthetic reaction in this molecular class that further has inspired a concise biomimetic synthesis of naphthomevalin, a prominent member of the napyradiomycin meroterpenes. Chemical compounds Bicyclic Baird-type aromaticity   pp1243 - 1248 Won-Young Cha, Taeyeon Kim, Arindam Ghosh, Zhan Zhang, Xian-Sheng Ke et al. doi:10.1038/nchem.2834 Realization of the bicyclic aromaticity has attracted much attention because of the potential to modulate the fundamental properties of 3D aromatic organic molecules that are not topologically planar. Now, the synthesis and characterization of dual-aromatic molecules, and their electronically mixed [4n+1]/[4n+1] triplet bi-radical species displaying Baird-type aromaticity, has been realized.   Structure and reactivity of a mononuclear gold(II) complex   pp1249 - 1255 Sebastian Preiß, Christoph Förster, Sven Otto, Matthias Bauer, Patrick Müller et al. doi:10.1038/nchem.2836 Mononuclear gold(II) complexes are very labile (and thus very rare) species. Now, a gold(II) porphyrin complex has been isolated and characterized, and its reactivity towards dioxygen, nitrosobenzene and acids investigated. Owing to a second-order Jahn–Teller distortion, the gold atoms were found to adopt a 2+2 coordination mode in a planar N4 environment. Chemical compounds Structural snapshots of concerted double E–H bond activation at a transition metal centre   pp1256 - 1262 Joseph A. B. Abdalla, Alexa Caise, Christian P. Sindlinger, Rémi Tirfoin, Amber L. Thompson et al. doi:10.1038/nchem.2792 X-ray and neutron diffraction studies, in conjunction with quantum chemical techniques, have been used to define a new oxidative bond activation pathway that involves simultaneous activation of both bonds of a β-diketiminate-stabilized GaH2 unit at a single metal centre. Chemical compounds Infrared spectrum and structure of the homochiral serine octamer–dichloride complex   pp1263 - 1268 Jongcheol Seo, Stephan Warnke, Kevin Pagel, Michael T. Bowers and Gert von Helden doi:10.1038/nchem.2821 Octameric complexes of serine are long known for their special properties, such as their enhanced stability and preference for homochirality. Yet, there is no consensus on their structures. Now, experimental data on the serine octamer–dichloride complex is presented that supports a highly symmetrical, highly stable structure.   Catalytic diastereo- and enantioselective additions of versatile allyl groups to N–H ketimines   pp1269 - 1275 Hwanjong Jang, Filippo Romiti, Sebastian Torker and Amir H. Hoveyda doi:10.1038/nchem.2816 Amines are commonly occurring units in many biologically active molecules. Now, a catalytic method has been developed that merges an unprotected/unactivated ketimine, a monosubstituted allene and a commercially available diboron reagent to afford versatile α-tertiary amines in up to 95% yield, >98% diastereomeric ratio and >99:1 enantiomeric ratio. The utility of this method was demonstrated through its application to the synthesis of the tricyclic core of a class of compounds with anti-Alzheimer activity. Chemical compounds Signal transduction in a covalent post-assembly modification cascade   pp1276 - 1281 Ben S. Pilgrim, Derrick A. Roberts, Thorsten G. Lohr, Tanya K. Ronson and Jonathan R. Nitschke doi:10.1038/nchem.2839 Two coordination cages have been devised that undergo covalent modification during a cascade of two orthogonal Diels–Alder reactions. This results in increased lipophilicity for the second cage, enabling its phase transfer and separation from the first. The trigger, relay and inhibition features of this cascade system mimic key aspects of natural post-translational modification cascades. Chemical compounds Cooperative carbon-atom abstraction from alkenes in the core of a pentanuclear nickel cluster   pp1282 - 1285 Manar M. Shoshani and Samuel A. Johnson doi:10.1038/nchem.2840 Interest in surface-mediated chemistry has led to the design of small molecule models for surfaces, which provide mechanistic insight and have practical applications. Now, the cooperative behaviour of five nickel centres has been shown to provide reactivity reminiscent of highly active metal surface sites, leading to carbon-atom abstraction from alkenes under ambient conditions. Chemical compounds Advertisement Searching for a new career? At Nature Research we frequently recruit talented individuals to join our editorial and publishing teams. If you have a PhD and a passion for science this may be the perfect career for you.  Visit our research editorial and publishing careers website to discover more about what we do.    Retraction Top Retraction: Oligoarginine peptides slow strand annealing and assist non-enzymatic RNA replication   p1286 Tony Z. Jia, Albert C. Fahrenbach, Neha P. Kamat, Katarzyna P. Adamala and Jack W. Szostak doi:10.1038/nchem.2885   In Your Element Top Thoroughly enthralling thulium   p1288 Polly Arnold doi:10.1038/nchem.2897 Named after a mysterious place, thulium — one of the rarest rare earths — has some exotic chemistry in store for us, says Polly Arnold.   Top Advertisement npj Microgravity is a new open access journal specifically dedicated to publishing research which enables space exploration and research that is enabled by spaceflight and ground-based spaceflight analogues. npj Microgravity is published in cooperation the Biodesign Institute at Arizona State University, and is part of the Nature Partner Journals series. 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