Nature Chemistry Contents January 2012 Volume 4 Number 1 pp 1-66

TABLE OF CONTENTS January 2012 Volume 4, Issue 1 Thesis Books and Arts Research Highlights Blogroll News and Views Articles Erratum In Your Element Subscribe   Facebook   RSS   Recommend to library   Twitter   Advertisement NCI Physical Sciences in Oncology Reprint Collection This reprint collection brings together a selection of articles funded by the Physical Sciences–Oncology Centers programme, a network of research centres launched by the National Cancer Institute to explore ways in which physical sciences perspectives could be applied to the study of cancer. Access the collection free online for 6 months Produced with support from Office of Physical Sciences-Oncology/Center for Strategic Scientific Initiatives/Office of the Director/ National Cancer Institute   Thesis Top Judicial chemistry pp1 - 2 Bruce C. Gibb doi:10.1038/nchem.1229 As scientists, are the decisions we make all about weighing up cold hard facts or does the last time we ate come into play? Bruce Gibb offers us some food for thought. Full Text | PDF Books and Arts Top Chemical history in bite-sized pieces p3 Philip Ball reviews The Case of the Poisonous Socks: Tales from Chemistry by William H. Brock doi:10.1038/nchem.1227 Full Text | PDF Research Highlights Top Microfluidics: Bent into shape | Asymmetric catalysis: Access all isomers | Dye-sensitized solar cells: Improving efficiency | Stereochemistry: A photo finish | Hydrogen storage: A liquid solution Blogroll Top Blogroll: A hot topic p5 doi:10.1038/nchem.1240 Full Text | PDF News and Views Top Interlocked molecules: One-pot pentaknot pp7 - 8 Michaele J. Hardie doi:10.1038/nchem.1224 The most complex non-DNA synthetic molecular knot so far has been made in a single step by combining a number of reversible chemical interactions, including metal-directed self-assembly, anion templation and imine bond formation. Full Text | PDF See also: Article by Ayme et al. Exciton dynamics: Electrons take an unexpected turn pp8 - 10 Heather M. Jaeger and Oleg V. Prezhdo doi:10.1038/nchem.1225 Traditional wisdom suggests that excited electrons will move towards positively charged parts of a molecule. Advanced time-domain calculations show that the conventional picture breaks down in the ultrafast regime, providing key insights into photo-activated, attosecond processes. Full Text | PDF Metallo-helical complexes: Resolutely pure helices pp10 - 11 Janice R. Aldrich-Wright doi:10.1038/nchem.1231 Helical coordination compounds that show promising antibiotic activity in aqueous media have been assembled directly in their optically pure form, without the need for a resolution step. Full Text | PDF See also: Article by Howson et al. Biomimetic chemistry: Merging the old with the new pp11 - 13 Marcetta Y. Darensbourg and Ryan D. Bethel doi:10.1038/nchem.1228 The classic organometallic compound ferrocene has been combined with a unique diiron unit in the latest synthetic analogue of an enzyme active site, achieving the three functionalities needed for a working model of diiron hydrogenase, itself of ancient origin. Full Text | PDF See also: Article by Camara & Rauchfuss Drug delivery: Relieving PEGylation pp13 - 14 Matthew C. Parrott and Joseph M. DeSimone doi:10.1038/nchem.1230 A new type of protein-polymer conjugate provides improved stability without detrimentally affecting bioactivity, and thus offers great potential for the development of new peptide-based drugs. Full Text | PDF See also: Article by Keefe & Jiang Chemistry JOBS of the week Biological Chemist Goethe University Frankfurt, Institute of Organic Chemistry and Biological Chemistry Crystallographer Goethe University Frankfurt, Institute of Organic Chemistry and Biological Chemistry Senior Researcher in Metabolomics Technical University of Denmark, the Novo Nordisk Foundation Center for Biosustainability Postdoc position in droplet microfluidics for enzyme and biomarker screening Royal Institute of Technology Physical Chemistry study on polimeric membranes universita' ca' foscari venezia ca' foscari university of venice More Science jobs from Chemistry EVENT European-Winter School on Physical Organic Chemistry 29th January - 3rd February 2012 Bressanone, Italy More science events from Articles Top A synthetic molecular pentafoil knot pp15 - 20 Jean-François Ayme, Jonathon E. Beves, David A. Leigh, Roy T. McBurney, Kari Rissanen and David Schultz doi:10.1038/nchem.1193 The most complex non-DNA molecular knot prepared so far is self-assembled around a chloride anion from five metal cations, five bis-aldehyde and five bis-amine building blocks, in a one-pot reaction. The X-ray crystal structure of the 160-atom-loop pentafoil knot reveals a symmetrical closed-loop double helicate with a chloride anion held at its centre by ten CH···Cl− hydrogen bonds. Abstract | Full Text | PDF | Chemical compounds See also: News and Views by Hardie Scalable enantioselective total synthesis of taxanes pp21 - 25 Abraham Mendoza, Yoshihiro Ishihara and Phil S. Baran doi:10.1038/nchem.1196 The taxane diterpene family is structurally complex and exhibits a wide range of biological activities, best exemplified by the successful drug Taxol. Here, two of the least oxidized taxanes in the family, ‘taxadienone’ and taxadiene, are prepared by total synthesis on a gram scale. The concise synthetic route described herein provides a scalable, enantioselective entry to the taxane family of natural products. Abstract | Full Text | PDF | Chemical compounds Combining acid–base, redox and substrate binding functionalities to give a complete model for the [FeFe]-hydrogenase pp26 - 30 James M. Camara and Thomas B. Rauchfuss doi:10.1038/nchem.1180 The fastest catalysts in nature for producing and oxidizing hydrogen are [FeFe]-hydrogenases, which make use of an extra one-electron redox equivalent from an iron-sulfur cluster that is outside the core. Now, a ferrocene-based ligand that oxidizes at mild potential performs this cluster's role in an excellent synthetic hydrogenase model. Abstract | Full Text | PDF See also: News and Views by Darensbourg & Bethel Optically pure, water-stable metallo-helical ‘flexicate’ assemblies with antibiotic activity pp31 - 36 Suzanne E. Howson, Albert Bolhuis, Viktor Brabec, Guy J. Clarkson, Jaroslav Malina, Alison Rodger and Peter Scott doi:10.1038/nchem.1206 The self-assembly of monometallic moieties with organic ligands has proved to be a highly versatile approach for preparing a range of metal–ligand assemblies that are helical, optically pure and stable in aqueous solutions. One such iron(II) ‘flexicate’ system exhibits significant interactions with DNA, as well as promising antimicrobial activity properties. Abstract | Full Text | PDF | Chemical compounds See also: News and Views by Aldrich-Wright A total-synthesis framework for the construction of high-order colloidal hybrid nanoparticles pp37 - 44 Matthew R. Buck, James F. Bondi and Raymond E. Schaak doi:10.1038/nchem.1195 Colloidal hybrid nanoparticles represent an emerging class of multifunctional artificial molecules. However, unlike actual molecules, their complexity is limited by the lack of a mechanism-driven design framework. Here, nanoparticle analogues of chemoselectivity, regiospecificity, molecular substituent effects, and coupling reactions are used to predictably synthesize hybrid nanoparticle trimers, tetramers, and oligomers. Abstract | Full Text | PDF Three-component reaction discovery enabled by mass spectrometry of self-assembled monolayers pp45 - 51 Timothy J. Montavon, Jing Li, Jaime R. Cabrera-Pardo, Milan Mrksich and Sergey A. Kozmin doi:10.1038/nchem.1212 A general reaction-discovery platform has been used for identification of a new multicomponent transformation. The approach entails rapid analysis of interfacial chemical reactions on arrays of self-assembled monolayers using mass spectrometry. This enabled identification of a simple organic phosphine that catalyses a previously unknown condensation of siloxy alkynes, aldehydes and amines. Abstract | Full Text | PDF | Chemical compounds Redox-induced reversible metal assembly through translocation and reversible ligand coupling in tetranuclear metal sandwich frameworks pp52 - 58 Tetsuro Murahashi, Katsunori Shirato, Azusa Fukushima, Kohei Takase, Tomoyoshi Suenobu, Shunichi Fukuzumi, Sensuke Ogoshi and Hideo Kurosawa doi:10.1038/nchem.1202 Despite their potential roles in catalysis and materials science, the redox-induced dynamic structural changes in (sp2-carbon ligand)–(multiple metals)–(sp2-carbon ligand) systems are not well understood. Now, tetra-palladium sandwich complexes have been described that exhibit redox-switchable assembly of the metal centres or coupling of the ligands. Abstract | Full Text | PDF | Chemical compounds Poly(zwitterionic)protein conjugates offer increased stability without sacrificing binding affinity or bioactivity pp59 - 63 Andrew J. Keefe and Shaoyi Jiang doi:10.1038/nchem.1213 Poly(ethylene glycol) conjugates have been widely used to improve the stability of proteins for use as therapeutics, but this stability comes at the expense of binding affinity. Here, poly(carboxybetaine) — a zwitterionic polymer — is shown to provide increased stability while also enhancing binding due to its super-hydrophilic nature. Abstract | Full Text | PDF See also: News and Views by Parrott & DeSimone Erratum Top Redox-induced reversible metal assembly through translocation and reversible ligand coupling in tetranuclear metal sandwich frameworks p64 Tetsuro Murahashi, Katsunori Shirato, Azusa Fukushima, Kohei Takase, Tomoyoshi Suenobu, Shunichi Fukuzumi, Sensuke Ogoshi and Hideo Kurosawa doi:10.1038/nchem.1232 Full Text | PDF In Your Element Top Oxygen origins p66 Mark H. Thiemens doi:10.1038/nchem.1226 Oxygen has contributed to our understanding of the evolution of life on Earth by providing invaluable clues to geological processes — yet it still holds the key to some unsolved mysteries, as Mark H. Thiemens explains. Full Text | PDF Top Advertisement Nature Insight: Silicon electronics and beyond The trend of scaling down the silicon transistor, which has driven the revolution in computer technology over several decades, is coming to an end. 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