Nature Chemistry Contents October 2013 Volume 5 Number 10 pp 805-894

Advertisement Protein engineering and other bio-synthetic routes for bio-based materials: Current uses and potential applications Topic Editors: Carissa M. Soto and Cherise Bernard ¦ Submission deadline: 17 Feb 2014 In this Research Topic from Frontiers in Chemistry, the topic editors aim to cover current uses and envision future applications of materials generated using protein engineering and biosynthesis techniques. Find out more on how you can contribute to this Research Topic or even host your own TABLE OF CONTENTS October 2013 Volume 5, Issue 10 Thesis Book Review Research Highlights Blogroll News and Views Review Articles In Your Element Advertisement Bio-Rad's new modular NGC™ chromatography system allows users to modify its capabilities when their throughput or application requirements change, obviating the need to purchase a completely new instrument. Subscribe   Facebook   RSS   Recommend to library   Twitter   Thesis Top Bouquets, whiffs and pongs   pp805 - 806 Bruce C. Gibb doi:10.1038/nchem.1759 When it comes to practical chemistry demonstrations designed to provoke the senses, Bruce Gibb suggests that we should follow our noses rather than it all being about bangs and flashes. Book Review Top The missing pieces   p807 Andrew Bissette reviews A Tale of 7 Elements by Eric Scerri doi:10.1038/nchem.1762 Research Highlights Top Stereoselective synthesis: Inverted isonitriles | Solid-state chemistry: Corannulene complexation | Single-atom catalysis: Only a supporting role | Stimuli-responsive materials: A memorable reaction Blogroll Top Blogroll: Sharing your science   p809 Chad Jones doi:10.1038/nchem.1760 News and Views Top Crystal engineering: Covalent crystal growth   pp810 - 811 Michael Mastalerz doi:10.1038/nchem.1763 Millimetre-sized single crystals of covalent organic frameworks have been constructed by taking advantage of a reversible dimerization reaction of nitroso groups. See also: Article by Beaudoin et al. Carbon nanotubes: A bright future for defects   pp812 - 813 Qing Hua Wang and Michael S. Strano doi:10.1038/nchem.1768 Covalently bonding groups to the walls of carbon nanotubes has been previously observed to quench their photoluminescence. Now, it has been shown that, if you get the chemistry just right, their photoluminescence can in fact be significantly brightened by introducing defects through functionalization. See also: Article by Piao et al. Carbene catalysis: An internal affair   pp813 - 815 Jeffrey W. Bode doi:10.1038/nchem.1766 Preparing powerful reactive intermediates such as enolates and homoenolates for C-C bond formation used to require strong bases and stoichiometric reagents. They can now be catalytically generated from α-functionalized aldehydes or even from saturated esters under mild conditions using N-heterocyclic carbene catalysts. See also: Article by Fu et al. Caesium chemistry: Beyond state I   pp815 - 816 Sebastian Riedel and Peter Schwerdtfeger doi:10.1038/nchem.1767 Although caesium is well known in its oxidation state +I, many chemists have speculated about a possible higher state. Such a species has not yet been prepared, but based on quantum-chemical calculations CsFn compounds have now been predicted to be stable. See also: Article by Miao Chemistry JOBS of the week Postdoc Organic Chemistry Qatar Foundation PhD Positions in Theoretical Physics, Quantum Chemistry, Materials Science and Scientific Computing International Max Planck Research School for Dynamical Processes in Atoms, Molecules and Solids Tenure Track Appointment in Inorganic Chemistry University of Pennsylvania Associate Professor in Physical Chemistry University of Fribourg Tenure-track Faculty Position in Environmental Chemistry UC San Diego More Science jobs from Chemistry EVENT The 4th Asia-Oceania Conference on Green and Sustainable Chemistry (AOC-4 GSC) 03.-06.11.13 Taiwan More science events from Review Top Catalysis in service of main group chemistry offers a versatile approach to p-block molecules and materials   pp817 - 829 Erin M. Leitao, Titel Jurca and Ian Manners doi:10.1038/nchem.1749 The application of catalytic methods to main group substrates has recently allowed access to a wide range of catenated structures based on elements across the p-block. These breakthroughs have already impacted areas such as hydrogen storage and transfer, functional inorganic polymers, and ceramic thin films. Articles Top Constructing monocrystalline covalent organic networks by polymerization   pp830 - 834 Daniel Beaudoin, Thierry Maris and James D. Wuest doi:10.1038/nchem.1730 Modular construction using connectable molecular subunits is a powerful strategy for making new carbon-based materials. So far, large crystals have been produced only from subunits linked by weak interactions. Covalently bonded analogues have now been prepared by reversible self-addition polymerization of suitable monomers and structurally characterized by single-crystal X-ray diffraction. See also: News and Views by Mastalerz ß-Carbon activation of saturated carboxylic esters through N-heterocyclic carbene organocatalysis   pp835 - 839 Zhenqian Fu, Jianfeng Xu, Tingshun Zhu, Wendy Wen Yi Leong and Yonggui Robin Chi doi:10.1038/nchem.1710 Direct ß-carbon activation of saturated carbonyl compounds represents a significant fundamental challenge in organic chemistry. Here, the catalytic activation of saturated ester ß-sp3 carbon as nucleophile via N-heterocyclic carbene organocatalysis is reported. The catalytically generated nucleophilic ß-carbon undergoes enantioselective reactions with various electrophiles. Brightening of carbon nanotube photoluminescence through the incorporation of sp3 defects   pp840 - 845 Yanmei Piao, Brendan Meany, Lyndsey R. Powell, Nicholas Valley, Hyejin Kwon et al. doi:10.1038/nchem.1711 The controlled functionalization of single-walled carbon nanotubes has been shown to brighten their photoluminescence up to 28 times, which challenges our current understanding of how chemical defects affect low-dimensional carbon materials. This significantly improved photon conversion efficiency promises to advance a broad range of optoelectronic and imaging applications based on carbon nanotubes. Caesium in high oxidation states and as a p-block element   pp846 - 852 Mao-sheng Miao doi:10.1038/nchem.1754 Caesium has so far not been found in oxidation states higher than +1, but quantum chemical calculations have now shown that, under high pressures, 5p inner shell electrons of caesium can participate in — and become the main components of — bonds. Caesium is predicted to form stable CsFn molecules that resemble isoelectronic XeFn. See also: News and Views by Riedel & Schwerdtfeger End-to-end conformational communication through a synthetic purinergic receptor by ligand-induced helicity switching   pp853 - 860 Robert A. Brown, Vincent Diemer, Simon J. Webb and Jonathan Clayden doi:10.1038/nchem.1747 Biological receptors communicate information through ligand-induced conformational changes. A synthetic receptor with a boron-containing binding site that can selectively and reversibly complex a ligand (such as a purine nucleoside) is shown to function in a similar fashion. The resulting conformational change is relayed through the receptor, communicating structural information about the ligand to a spectroscopic reporter more than 2 nm away. A strategy for the diversity-oriented synthesis of macrocyclic scaffolds using multidimensional coupling   pp861 - 867 Henning S. G. Beckmann, Feilin Nie, Caroline E. Hagerman, Henrik Johansson, Yaw Sing Tan et al. doi:10.1038/nchem.1729 Diversity oriented synthesis (DOS) aims to build structurally diverse compound libraries — potentially useful in drug discovery — from a small number of starting materials. Here, the build/couple/pair algorithm — commonly used in DOS — is extended to incorporate variations in the coupling step as well as in the starting materials. This produces a compound library with exceptionally high diversity in fewer than five steps from a common precursor. Site-specific positioning of dendritic alkyl chains on DNA cages enables their geometry-dependent self-assembly   pp868 - 875 Thomas G. W. Edwardson, Karina M. M. Carneiro, Christopher K. McLaughlin, Christopher J. Serpell and Hanadi F. Sleiman doi:10.1038/nchem.1745 The site-specific incorporation of dendritic DNA amphiphiles into a DNA cage controls whether the resultant structures show intermolecular self-assembly or intramolecular assembly. Intramolecular assembly creates a hydrophobic core within the cage that is capable of encapsulating small molecules. These molecules can be released on addition of specific DNA strands. Equilibrium between a cyclotrisilene and an isolable base adduct of a disilenyl silylene   pp876 - 879 Michael J. Cowley, Volker Huch, Henry S. Rzepa and David Scheschkewitz doi:10.1038/nchem.1751 A base-stabilized silicon analogue of a reactive carbon species (vinyl carbene) is reported that features a silicon–silicon double bond and a silylene functionality, coordinated by an N-heterocyclic carbene. Ultraviolet–visible light and nuclear magnetic resonance spectroscopy in solution confirms that disilenyl silylene exists in equilibrium with the corresponding cyclotrisilene and free N-heterocyclic carbene. A missing link in the transformation from asymmetric to symmetric metallofullerene cages implies a top-down fullerene formation mechanism   pp880 - 885 Jianyuan Zhang, Faye L. Bowles, Daniel W. Bearden, W. Keith Ray, Tim Fuhrer et al. doi:10.1038/nchem.1748 An asymmetric pentalene-containing C1(51383)-C84 fullerene cage is found in two different metal carbide metallofullerenes. This particular cage can, in simple steps, rearrange into many well-known fullerene cages that are more stable and more symmetric, suggesting it is likely that metallofullerenes are generated by a ‘top-down’ formation mechanism. Component-based syntheses of trioxacarcin A, DC-45-A1 and structural analogues   pp886 - 893 Thomas Magauer, Daniel J. Smaltz and Andrew G. Myers doi:10.1038/nchem.1746 The trioxacarcins are polyoxygenated natural products that potently inhibit the growth of cultured human cancer cells. Here, the syntheses of trioxacarcin A, DC-45-A1 and structural analogues are described — the majority of which were found to be active in antiproliferative assays. A convergent, component-based route comprising sequential stereoselective glycosylation reactions allows assembly of these analogues in 11 steps or fewer. In Your Element Top Lead between the lines   p894 Somobrata Acharya doi:10.1038/nchem.1761 Somobrata Acharya explores the history, properties and uses of lead [mdash] an ancient metal that is still very relevant to today's technologies, but should be used with caution. 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