Nature Chemistry Contents February 2015 Volume 7 Number 2 pp 89-180

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TABLE OF CONTENTS February 2015 Volume 7, Issue 2 Correspondence Thesis Research Highlights Blogroll News and Views Review Articles Erratum Corrigendum In Your Element Subscribe   Facebook   RSS   Recommend to library   Twitter   Correspondence Top Entropic factors also contribute to the high melting points of polyhedral alkanes   p89 Andrew D. Bond doi:10.1038/nchem.2146 See also: Correspondence by Shaik & Alvarez Reply to 'Entropic factors also contribute to the high melting points of polyhedral alkanes'   pp89 - 90 Sason Shaik and Santiago Alvarez doi:10.1038/nchem.2147 See also: Correspondence by Bond Thesis Top A chemist's guide to the Solar System   pp91 - 92 Bruce C. Gibb doi:10.1038/nchem.2170 In the first of two essays that offer a chemistry-themed guided tour around the Solar System, Bruce Gibb looks at what sort of organic molecules are out there and just where you can find them. Research Highlights Top Natural product synthesis: Tricycles and tribulations | Xeno-nucleic acids: Unnatural biocatalysts | Self-assembly: Crystal milk | Molecular wheels: Huge hexagons Blogroll Top Blogroll: The bad and the ugly   p95 Mitchell Antalek doi:10.1038/nchem.2169 News and Views Top Metallobiology: Zinc differently   pp96 - 97 Kyle P. Carter and Amy E. Palmer doi:10.1038/nchem.2165 An extracellular ejection of zinc, known as a zinc spark, is triggered by the fertilization of a mammalian egg; however, the origin of this zinc was not clear. Now, a combination of four complementary techniques has revealed the source and provided an unprecedented quantification of the distribution of zinc in a maturing mammalian oocyte. See also: Article by Que et al. Organic cage crystals: Supramolecular joinery   pp97 - 99 Leonard J. Barbour doi:10.1038/nchem.2166 Attempts to create a porous molecular crystal by removing solvent molecules from a solvate usually lead the host to reorganize into a non-porous close-packed structure. The 'virtual porosity' of such an organic cage crystal has now been trapped by introducing a judiciously chosen co-crystal former that prevents rearrangement of the host lattice. See also: Article by Little et al. Synthetic methodology: Catalytic control of chlorination   pp99 - 100 Brian R. Atwood and Christopher D. Vanderwal doi:10.1038/nchem.2163 Previously conspicuous by its absence, a syn-selective dichlorination reaction of alkenes has now been reported, bringing together decades-old stoichiometric chemistry in a useful catalytic process. See also: Article by Cresswell et al. Proton-coupled electron transfer: Metal hydrides find the sweet spot   pp101 - 102 Jillian L. Dempsey doi:10.1038/nchem.2162 The synchronous movement of protons and electrons orchestrated by enzymes gives rise to highly efficient catalytic processes in nature, such as photosynthesis. Now, researchers have choreographed similar reactivity for a metal hydride complex, setting the stage for efficient solar fuel production in artificial systems. See also: Article by Bourrez et al. Chemical biology: Biosynthetic interceptors   pp102 - 104 Niclas Pryk and Frank Schulz doi:10.1038/nchem.2168 Mutated enzymes are useful tools for the investigation of the biosynthetic routes to natural products. Now, they are used in a new approach to carry functionalized substrates through the synthesis and produce simplified or modified unnatural compounds with useful properties. Chemistry JOBS of the week Postdoctoral Position in Medicinal Chemistry University of Michigan Postdoc - Computational Physical Chemistry University of Utah PhD Student in Environmental Chemistry / Exposure Science ETH Zurich Postdoctoral Research Associate in Bio-organic Chemistry Worcester Polytechnic Institute Graduate Student Positions available in Bioanalytical Chemistry University of Texas at El Paso More Science jobs from Chemistry EVENT Cleaner Solvents for Greener Chemistry 15.04.15 Newport Pagnell, UK More science events from Review Top Porphyrins at interfaces   pp105 - 120 Willi Auwarter, David Ecija, Florian Klappenberger and Johannes V. Barth doi:10.1038/nchem.2159 Bringing porphyrins in contact with well-defined interfaces generates a rich playground of chemical behaviour and properties for exploration and exploitation. This Review examines our current understanding of surface-confined tetrapyrroles and their embedding in nanoarchitectures - discussing both the structural and functional attributes, and methods by which to manipulate their intramolecular and organizational features. Articles Top Supramolecular binding and separation of hydrocarbons within a functionalized porous metal–organic framework   pp121 - 129 Sihai Yang, Anibal J. Ramirez-Cuesta, Ruth Newby, Victoria Garcia-Sakai, Pascal Manuel et al. doi:10.1038/nchem.2114 Gas sorption and separation in porous materials is dependent on the host–guest binding within any given system. Now, the molecular details of cooperative binding between small hydrocarbons and a metal–organic framework, NOTT-300, at multiple sites have been elucidated by complementary scattering and diffraction techniques. This material is also capable of separating C1 and C2 hydrocarbons under ambient conditions. Quantitative mapping of zinc fluxes in the mammalian egg reveals the origin of fertilization-induced zinc sparks   pp130 - 139 Emily L. Que, Reiner Bleher, Francesca E. Duncan, Betty Y. Kong, Sophie C. Gleber et al. doi:10.1038/nchem.2133 The mammalian oocyte cell cycle is regulated by massive zinc fluxes which culminate in coordinated ejections of ~1010 zinc ions at fertilization. Four single-cell physiochemical approaches (live-cell fluorescence imaging, scanning transmission electron microscopy with energy dispersive spectroscopy, X-ray fluorescence microscopy and tomography) reveal that these ‘zinc sparks’ originate from thousands of cortical vesicles which each release ~106 zinc ions. See also: News and Views by Carter & Palmer Concerted proton-coupled electron transfer from a metal-hydride complex   pp140 - 145 Marc Bourrez, Romain Steinmetz, Sascha Ott, Frederic Gloaguen and Leif Hammarström doi:10.1038/nchem.2157 Proton-coupled electron transfer (PCET) of metal hydrides, in which electrons and protons go to or from different molecular sites, are key steps in catalytic reactions involving solar fuels. Using [(Cp)W(CO)3H] as a model compound, it is now shown that this PCET reaction can occur in a concerted fashion, suggesting a possible low-barrier pathway to catalysis. See also: News and Views by Dempsey Catalytic, stereospecific syn-dichlorination of alkenes   pp146 - 152 Alexander J. Cresswell, Stanley T.-C. Eey and Scott E. Denmark doi:10.1038/nchem.2141 The synthetic challenge of constructing arrays of contiguous, chlorinated stereogenic centres in natural products, like the chlorosulfolipids, has sparked recent interest in new methods for stereocontrolled chlorination. Now the first catalytic, syn-stereospecific dichlorination of alkenes, employing a redox-active main group element as a group transfer catalyst is described. Chemical compounds See also: News and Views by Atwood & Vanderwal Trapping virtual pores by crystal retro-engineering   pp153 - 159 Marc A. Little, Michael E. Briggs, James T. A. Jones, Marc Schmidtmann, Tom Hasell et al. doi:10.1038/nchem.2156 Organic molecular crystals with guest-occupied cavities are often observed, but the cavities tend to collapse when the guests are removed. Now, the porous domain of a crystalline solvate has been stabilized by formation of a cocrystal with a second molecule whose size and shape matches those of the unstable voids. Chemical compounds See also: News and Views by Barbour Rational design of functional and tunable oscillating enzymatic networks   pp160 - 165 Sergey N. Semenov, Albert S. Y. Wong, R. Martijn van der Made, Sjoerd G. J. Postma, Joost Groen et al. doi:10.1038/nchem.2142 In vitro assembly of out-of-equilibrium enzymatic reaction networks has proved challenging, limiting the development of autonomous synthetic systems. Now, a methodology has been developed to construct an enzymatic reaction network producing oscillations of active trypsin. The modular approach allows amplification or analog-to-digital conversion of the oscillations, and control over a self-assembly process. On the origin of the stability of graphene oxide membranes in water   pp166 - 170 Che-Ning Yeh, Kalyan Raidongia, Jiaojing Shao, Quan-Hong Yang and Jiaxing Huang doi:10.1038/nchem.2145 Porous-alumina filter discs typically used to prepare graphene-oxide films are found to corrode during filtration and release aluminium ions that crosslink the negatively charged sheets and make the films insoluble in water. In contrast, aluminium-free graphene-oxide films are significantly weaker and readily disintegrate in water. Catalytic enantioselective synthesis of indanes by a cation-directed 5-endo-trig cyclization   pp171 - 177 Craig P. Johnston, Abhishek Kothari, Tetiana Sergeieva, Sergiy I. Okovytyy, Kelvin E. Jackson et al. doi:10.1038/nchem.2150 A highly enantio- and diastereoselective route to complex indanes via a 5-endo-trig Michael reaction catalysed by a chiral ammonium salt is described. The preference for this formally disfavoured cyclization over a formally favoured alternative shows that geometric and stereoelectronic constraints may not be decisive in the observed outcome of irreversible ring closing reactions. Chemical compounds Erratum Top Erratum: Copper-catalysed selective hydroamination reactions of alkynes   p178 Shi-Liang Shi and Stephen L. Buchwald doi:10.1038/nchem.2167 Corrigendum Top Corrigendum: Optimized orthogonal translation of unnatural amino acids enables spontaneous protein double-labelling and FRET   p178 Kaihang Wang, Amit Sachdeva, Daniel J. Cox, Nabil M. Wilf, Kathrin Lang et al. doi:10.1038/nchem.2175 In Your Element Top Subtle niobium   p180 Michael Tarselli doi:10.1038/nchem.2164 Michael Tarselli reflects on the intriguing characteristics of a rather underrated element, niobium, in its 'missing' and existing forms. Top 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. For event advertising opportunities across the Nature Publishing Group portfolio please contact natureevents@nature.com More Nature Events

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