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23.05.2013

Current issue



Top

Thesis




How to counteract chemophobia pp439 - 440


Michelle Francl


doi:10.1038/nchem.1661


Michelle Francl ponders ways in which we can talk about chemistry without triggering chemophobia.








Top

Books and Arts




Detective work p441


Paul Bonvallet reviews The Scientific Sherlock Holmes by James O'Brien


doi:10.1038/nchem.1665









Top

Blogroll




Blogroll: Welcome to the club p443


Doctor Galactic


doi:10.1038/nchem.1659








Top

News and Views




Biophysical chemistry: Unravelling capsid transformations pp444 - 445


Masaki Uchida & Trevor Douglas


doi:10.1038/nchem.1666


The interactions between a virus capsid and its cargo are essential for viral infection as well as in the design of synthetic virus-like particles. Now a combination of analytical techniques has unravelled key steps in the transformation of a model virus and the release of its RNA cargo.



See also: Article by Snijder et al.








Li–O2 batteries: An agent for change pp445 - 447


Yonggang Wang & Yongyao Xia


doi:10.1038/nchem.1658


The rechargeable Li–O2 battery has low energy efficiency, which is mainly due to kinetic difficulties in the electrochemical oxidation of the insulating discharge product, Li2O2. Now a redox mediator, acting as an electron–hole transfer agent, has been used to promote this oxidation reaction.



See also: Article by Chen et al.








Reactive intermediates: Radicals with multiple personalities pp447 - 449


Malcolm D. E. Forbes


doi:10.1038/nchem.1663


A combined theoretical and experimental approach has revealed that radicals can be significantly stabilized by the presence of a remote anionic site in the same molecule. This finding has implications for understanding and potentially controlling the reactivity of these important reactive intermediates.



See also: Article by Gryn'ova et al.








Inorganic protocells: Gated access to microreactors pp449 - 451


Christine D. Keating


doi:10.1038/nchem.1657


A pH-responsive inorganic membrane has been devised that acts as a gatekeeper for the transport of charged solutes into and out of its interior volume. This behaviour was further used to regulate an enzymatic reaction.



See also: Article by Li et al.








Uranium chemistry: An actinide milestone pp451 - 452


Trevor W. Hayton


doi:10.1038/nchem.1643


A complex featuring a uranium(VI) terminal nitride functional group has been isolated through mild oxidation, and shown to be highly reactive. Under photolysis, it converts into a compound that is capable of C–H bond activation.



Subject terms: Inorganic chemistry | Organometallic chemistry | Synthesis


See also: Article by King et al.







Top

Review




Rationally synthesized two-dimensional polymers pp453 - 465


John W. Colson & William R. Dichtel


doi:10.1038/nchem.1628


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Two-dimensional polymers, which exhibit periodic bonding in two orthogonal directions, offer mechanical, electronic and structural properties distinct from their linear or irregularly crosslinked polymer counterparts. Their potential is largely unexplored because versatile and controlled synthetic strategies are only now emerging. This Review describes recent developments in two-dimensional polymerization methods.



Subject terms: Materials chemistry | Synthesis







Top

Articles




Competition of shape and interaction patchiness for self-assembling nanoplates pp466 - 473


Xingchen Ye, Jun Chen, Michael Engel, Jaime A. Millan, Wenbin Li, Liang Qi, Guozhong Xing, Joshua E. Collins, Cherie R. Kagan, Ju Li, Sharon C. Glotzer & Christopher B. Murray


doi:10.1038/nchem.1651


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Thin lanthanide fluoride nanoplates are shown to self-organize at the liquid/air interface into long-range-ordered two-dimensional planar tilings. In this joint experimental–computational, multiscale investigation, the assembly behaviour is shown to be dictated by entropic forces arising from particle shape and enthalpic forces arising from interaction anisotropy.



Subject terms: Nanotechnology | Physical chemistry | Theoretical chemistry








Switching radical stability by pH-induced orbital conversion pp474 - 481


Ganna Gryn'ova, David L. Marshall, Stephen J. Blanksby & Michelle L. Coote


doi:10.1038/nchem.1625


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In most radicals the unpaired electron occupies the highest-energy molecular orbital. Here, it is shown that for certain stabilized radicals the presence of a remote negatively charged group not only inverts this ordering, but also leads to a dramatic increase in radical stability that is easily manipulated by pH.



Subject terms: Organic chemistry | Theoretical chemistry


See also: News and Views by Forbes








Isolation and characterization of a uranium(VI)–nitride triple bond pp482 - 488


David M. King, Floriana Tuna, Eric J. L. McInnes, Jonathan McMaster, William Lewis, Alexander J. Blake & Stephen T. Liddle


doi:10.1038/nchem.1642


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A terminal uranium(VI)–nitride has been shown to be accessible and isolable by a redox strategy whereas a photochemical approach resulted in decomposition. Computational analyses suggest that the U≡N triple bonds are surprisingly comparable to analogous group 6 transition metal nitrides, with a covalent character dominated by 5f rather than 6d contributions.



Subject terms: Inorganic chemistry | Organometallic chemistry | Synthesis


See also: News and Views by Hayton








Charging a Li–O2 battery using a redox mediator pp489 - 494


Yuhui Chen, Stefan A. Freunberger, Zhangquan Peng, Olivier Fontaine & Peter G. Bruce


doi:10.1038/nchem.1646


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Recharging Li–O2 batteries requires oxidation of the discharge product solid Li2O2. Now a redox-mediating molecule is shown to assist this process by transferring electron–holes between solid Li2O2 and the positive electrode in a non-aqueous Li–O2 cell. This allows the cell to be charged at rates that are otherwise impossible.



Subject terms: Electrochemistry | Materials chemistry | Physical chemistry


See also: News and Views by Wang & Xia








Competition between model protocells driven by an encapsulated catalyst pp495 - 501


Katarzyna Adamala & Jack W. Szostak


doi:10.1038/nchem.1650


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Darwinian evolution involves competition between members of a population. Here, the synthesis of a hydrophobic dipeptide catalysed by a second dipeptide in a model protocell — a vesicle — is described. The reaction product partitions to the vesicle membrane, which grows by accumulating fatty acids derived from neighbouring vesicles. Thus, an encapsulated catalyst drives competition between the model protocells.



Subject terms: Chemical biology | Organic chemistry








Probing the biophysical interplay between a viral genome and its capsid pp502 - 509


J. Snijder, C. Uetrecht, R. J. Rose, R. Sanchez-Eugenia, G. A. Marti, J. Agirre, D. M. A. Guérin, G. J. L. Wuite, A. J. R. Heck & W. H. Roos


doi:10.1038/nchem.1627


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The stability of the capsid of a virus is strongly affected by its genome. Here the interplay between capsid and genome is explored using native mass spectrometry and atomic force microscopy. A mechanism is proposed to explain how the genome of the Triatoma virus stabilizes the capsid at neutral pH, but triggers disassembly under alkaline conditions.



Subject term: Chemical biology


See also: News and Views by Uchida & Douglas








Simultaneous structure–activity studies and arming of natural products by C–H amination reveal cellular targets of eupalmerin acetate pp510 - 517


Jing Li, Justin S. Cisar, Cong-Ying Zhou, Brunilda Vera, Howard Williams, Abimael D. Rodríguez, Benjamin F. Cravatt & Daniel Romo


doi:10.1038/nchem.1653


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Natural products are enduring leads for exploring cell biology, yet structure–activity relationship studies and 'arming' of these small molecules for subsequent cellular probe synthesis remains a challenge. Here, a strategy for derivatization of natural products by C–H amination, aziridination and unusual N-aminations is described. Selective derivatization of eupalmarin acetate led to identification of this natural product's target.



Subject terms: Organometallic chemistry | Medicinal chemistry | Synthesis








The use of elemental sulfur as an alternative feedstock for polymeric materials pp518 - 524


Woo Jin Chung, Jared J. Griebel, Eui Tae Kim, Hyunsik Yoon, Adam G. Simmonds, Hyun Jun Ji, Philip T. Dirlam, Richard S. Glass, Jeong Jae Wie, Ngoc A. Nguyen, Brett W. Guralnick, Jungjin Park, Árpád Somogyi, Patrick Theato, Michael E. Mackay, Yung-Eun Sung, Kookheon Char & Jeffrey Pyun


doi:10.1038/nchem.1624


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A polymerization method for converting elemental sulfur into a chemically stable, processable and electrochemically active copolymer has been described. This methodology — termed inverse vulcanization — is conducted by a one-step process using liquid sulfur, as both reaction medium and reactant, and vinylic comonomers to form polymeric materials with a high content of sulfur (50–90 wt%).



Subject terms: Polymer chemistry | Materials chemistry | Electrochemistry








RNA with iron(II) as a cofactor catalyses electron transfer pp525 - 528


Chiaolong Hsiao, I-Chun Chou, C. Denise Okafor, Jessica C. Bowman, Eric B. O'Neill, Shreyas S. Athavale, Anton S. Petrov, Nicholas V. Hud, Roger M. Wartell, Stephen C. Harvey & Loren Dean Williams


doi:10.1038/nchem.1649


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Removing Mg2+ from RNA and replacing it with Fe2+ confers on some RNAs the ability to catalyse single-electron transfer. Here, it is hypothesized that Fe2+ was an RNA cofactor on the early Earth, when iron was benign and abundant, and was replaced by Mg2+ during a period known as the great oxidation, brought on by photosynthesis.



Subject terms: Biochemistry | Catalysis








Electrostatically gated membrane permeability in inorganic protocells pp529 - 536


Mei Li, Rachel L. Harbron, Jonathan V. M. Weaver, Bernard P. Binks & Stephen Mann


doi:10.1038/nchem.1644


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Colloidosomes based on silica nanoparticles self-assembled at water droplet/oil interfaces are promising inorganic protocells, but they often leak small molecules on transfer into bulk water. Through silane crosslinking and copolymer grafting, colloidosomes have now been endowed with membranes that exhibit pH-responsive permeability to small molecules. The resulting water-dispersible colloidosomes further serve to host and control enzyme reactions.



Subject term: Materials chemistry


See also: News and Views by Keating








Heterogenized cobalt oxide catalysts for nitroarene reduction by pyrolysis of molecularly defined complexes pp537 - 543


Felix A. Westerhaus, Rajenahally V. Jagadeesh, Gerrit Wienhöfer, Marga-Martina Pohl, Jörg Radnik, Annette-Enrica Surkus, Jabor Rabeah, Kathrin Junge, Henrik Junge, Martin Nielsen, Angelika Brückner & Matthias Beller


doi:10.1038/nchem.1645


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Pyrolysis of defined nitrogen-ligated cobalt acetate complexes onto a commercial carbon support transforms the complexes into heterogeneous Co3O4 materials. These reusable non-noble-metal catalysts are highly selective for the industrially important hydrogenation of structurally diverse and functionalized nitroarenes to anilines.



Subject terms: Catalysis | Organic chemistry







Top

Corrigenda




The hydrodeoxygenation of bioderived furans into alkanes p544


Andrew D. Sutton, Fraser D. Waldie, Ruilian Wu, Marcel Schlaf, Louis A. 'Pete' Silks, III & John C. Gordon


doi:10.1038/nchem.1664









The hydrodeoxygenation of bioderived furans into alkanes p544


Andrew D. Sutton, Fraser D. Waldie, Ruilian Wu, Marcel Schlaf, Louis A. 'Pete' Silks, III & John C. Gordon


doi:10.1038/nchem.1670








Top

In Your Element




Titanium tales p546


Michael A. Tarselli


doi:10.1038/nchem.1656


From toothpaste to Tebbe reagents, Michael Tarselli takes a look at the many different faces of titanium.






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