Nature Chemistry Contents October 2015 Volume 7 Number 10 pp 761 - 854

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TABLE OF CONTENTS October 2015 Volume 7, Issue 10 Thesis Books and Arts News and Views Review Articles In Your Element Advertisement   Ready for a glimpse of tomorrow? Visit KAUST Discovery today KAUST Discovery highlights the cutting-edge research, technologies and innovations emerging from the King Abdullah University of Science and Technology. http://discovery.kaust.edu.sa Subscribe   Facebook   RSS   Recommend to library   Twitter   Advertisement Nature Energy: Call for Papers Launching in January 2016, Nature Energy is now open for submissions and inviting high-quality research from across the natural and social sciences. The journal will be dedicated to exploring all aspects of the on-going discussion of energy provision; from the generation and storage of energy, to its distribution and management, the needs and demands of the different actors, and the impacts that energy technologies and policies have on societies. Submit your next research paper to the journal.     Thesis Top The enlightenment of chemistry   pp761 - 762 Michelle Francl doi:10.1038/nchem.2354 Michelle Francl looks at chemistry in a new light. Books and Arts Top Sex, on steroids   p763 Matthew Salter reviews Testosterone: Sex, Power, and the Will to Win by Joe Herbert doi:10.1038/nchem.2358 News and Views Top Energy transport: Singlet to triplet and back again   pp764 - 765 Sean T. Roberts doi:10.1038/nchem.2356 Spin-triplet excitations commonly migrate through direct electron exchange between neighbouring molecules. Now, experiments show that back-and-forth interconversion between spin-triplet and spin-singlet states can significantly speed up triplet migration in organic crystals. See also: Article by Wan et al. Multicomponent gels: Remote control for self-assembly   pp765 - 767 Haridas Kar and Suhrit Ghosh doi:10.1038/nchem.2351 A patterned, spatially resolved gel has now been devised. The two-component gel is formed by sequential assembly of two independent networks of fibres, and the subsequent selective removal of one network by irradiation. See also: Article by Draper et al. Bioanalytical chemistry: Eavesdropping on interactions   pp767 - 769 Enrique Valera and Ryan C. Bailey doi:10.1038/nchem.2355 A method for directly probing binding interactions in free solution, without the need for chemical tagging, offers exciting opportunities for non-perturbative analyses of biomolecules in their native state. See also: Article by Yates et al. Biomineralization: Nanocrystals by design   pp769 - 770 Li Shang and Gerd Ulrich Nienhaus doi:10.1038/nchem.2357 Nanocrystals with precisely defined structures offer promise as components of advanced materials yet they are challenging to create. Now, a nanocrystal made up of seven cadmium and twelve chloride ions has been synthesized via a biotemplating approach that uses a de novo designed protein. Chemistry JOBS of the week Professor or Associate Professor of Synthetic Chemistry University of California San Diego Chemistry and Integrated Science Curriculum Search Virginia Tech (VT) Tenure Track Group Leader in Environmental (Bio)macromolecular Chemistry Eawag, Swiss Federal Institute of Aquatic Science and Technology Tenure-track Assistant Professor in Synthetic Macromolecular Chemistry Georgetown University Professor of Organic Chemistry ETH / University of Zürich More Science jobs from Chemistry EVENT Trends in Medicinal Chemistry 3rd Dec 2015 London, UK More science events from Review Top Degradable vinyl polymers for biomedical applications   pp771 - 784 Vianney Delplace and Julien Nicolas doi:10.1038/nchem.2343 Vinyl polymers are appealing materials owing to their ease of synthesis and broad diversity. Their carbon-carbon backbones resist degradation, however, which limits the applications for which they can be used. This Review Article considers the most promising approaches to the design of degradable vinyl polymers and discusses the potential of these materials for biomedical applications. Articles Top Cooperative singlet and triplet exciton transport in tetracene crystals visualized by ultrafast microscopy   pp785 - 792 Yan Wan, Zhi Guo, Tong Zhu, Suxia Yan, Justin Johnson et al. doi:10.1038/nchem.2348 Understanding the interplay between singlet fission and exciton transport is important if singlet-fission materials are to be used for solar cell applications. Now, a cooperative singlet–triplet transport mechanism has been revealed through ultrafast transient absorption microscopy. See also: News and Views by Roberts How do metal ions direct ribozyme folding?   pp793 - 801 Natalia A. Denesyuk and D. Thirumalai doi:10.1038/nchem.2330 The question of how divalent metal ions direct the folding of ribozymes is a major unsolved problem. A computational model has now been used to reveal the molecular mechanism by which Mg2+ drives the Azoarcus ribozyme into a catalytically functional state. Simulations also show that although Ca2+ drives folding it leaves the active site unstable. Latent analysis of unmodified biomolecules and their complexes in solution with attomole detection sensitivity   pp802 - 809 Emma V. Yates, Thomas Müller, Luke Rajah, Erwin J. De Genst, Paolo Arosio et al. doi:10.1038/nchem.2344 Labelling biomolecules to improve the sensitivity of analysis can perturb their interactions. Now, microfluidic and chemical tools have been used to allow simple, sensitive detection of a labelled system to reveal the behaviour of the native and physiologically relevant unlabelled system. The system was used to characterize the solution-phase behaviour of a clinically relevant protein–protein interaction. See also: News and Views by Valera & Bailey Iterative exponential growth of stereo- and sequence-controlled polymers   pp810 - 815 Jonathan C. Barnes, Deborah J. C. Ehrlich, Angela X. Gao, Frank A. Leibfarth, Yivan Jiang et al. doi:10.1038/nchem.2346 Regioselective epoxide opening of an enantiopure epoxy–alkyne results in the stereospecific introduction of functional side-chains into growing macromolecules. This process—in combination with 'click' chemistry and orthogonal deprotection of terminal alkynes—underpins an iterative exponential growth methodology that enables the efficient synthesis of >6-kDa stereo- and sequence-controlled polymers. Chemical compounds Formal SiH4 chemistry using stable and easy-to-handle surrogates   pp816 - 822 Antoine Simonneau and Martin Oestreich doi:10.1038/nchem.2329 Cyclohexa-2,5-dien-1-yl groups bound to silicon act as masked Si–H bonds that can be released by the action of tris(pentafluorophenyl)borane (B(C6F5)3). In this way, hazardous SiH4 is unleashed from appropriately substituted precursors and engages in alkene hydrosilylation promoted by the same boron catalyst. The overall process is a transfer hydrosilylation of alkenes with monosilane. Chemical compounds Structure of a PEGylated protein reveals a highly porous double-helical assembly   pp823 - 828 Giada Cattani, Lutz Vogeley and Peter B. Crowley doi:10.1038/nchem.2342 Protein PEGylation is routinely used to produce molecules with improved pharmacokinetic properties. However, despite their importance, the structure of PEGylated proteins has remained elusive. Now, the first crystal structure of a model β-sheet protein modified with a single PEG chain has been reported. NMR spectroscopy data indicates that the protein and PEG behave as independent domains. Diverse sp3 C−H functionalization through alcohol β-sulfonyloxylation   pp829 - 834 Yan Xu, Guobing Yan, Zhi Ren and Guangbin Dong doi:10.1038/nchem.2326 The late-stage functionalization of unactivated C(sp3)−H bonds could be useful for the rapid development of structure–activity relationships, but highly target-specific conditions make it challenging. Now, a strategy for the preparation of a variety of β-functionalized alcohol derivatives through a site-selective C−H sulfonyloxylation and subsequent SN2 reactions is described. Chemical compounds A cascade reaction network mimicking the basic functional steps of adaptive immune response   pp835 - 841 Da Han, Cuichen Wu, Mingxu You, Tao Zhang, Shuo Wan et al. doi:10.1038/nchem.2325 A cascade reaction network has been created that can function in a manner that is superficially similar to the most basic steps of the vertebrate adaptive immune response. This reaction network uses DNA and enzymes as simple artificial analogues of the components of the acquired immune system. Switchable selectivity in an NHC-catalysed dearomatizing annulation reaction   pp842 - 847 Chang Guo, Mirco Fleige, Daniel Janssen-Müller, Constantin G. Daniliuc and Frank Glorius doi:10.1038/nchem.2337 Catalysis with N-heterocyclic carbenes produces diverse outcomes depending on which of the many possible reaction mechanisms dominates. Control of this reactivity within a single reaction type has rarely been demonstrated. Now, starting from identical substrates, a switchable catalytic activation is shown to afford different products with high regio- and stereoselectivity. Chemical compounds Spatially resolved multicomponent gels   pp848 - 852 Emily R. Draper, Edward G. B. Eden, Tom O. McDonald and Dave J. Adams doi:10.1038/nchem.2347 Multicomponent supramolecular hydrogels have been prepared using a self-sorting mixture of two different gelators—one of which is photosensitive. Irradiation of the gels through a mask leads to the photosensitive network being selectively removed by a light-triggered gel-to-sol transition in a process that can be used to produce patterned gels with spatially controlled properties. Chemical compounds See also: News and Views by Kar & Ghosh In Your Element Top Tantalizing tantalum   p854 Giovanni Baccolo doi:10.1038/nchem.2350 Giovanni Baccolo relates tales of tantalum, an element known, and named, for its inertness, yet one that holds some surprises, such as a naturally occurring nuclear isomer. 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