Nature Chemistry Contents November 2012 Volume 4 Number 11 pp863-954

TABLE OF CONTENTS November 2012 Volume 4, Issue 11 Thesis Research Highlights Blogroll News and Views Review Articles In Your Element Subscribe   Facebook   RSS   Recommend to library   Twitter   Advertisement Submit to Nature Chemistry The online submission system for Nature Chemistry is open, and the editorial team welcome manuscripts describing cutting-edge research from all areas of chemistry. - manuscripts should be submitted through the online submission system - the complete Guide for Authors can be viewed online   Thesis Top 100 years of the hydrogen bond   pp863 - 864 Patrick Goymer doi:10.1038/nchem.1482 For Patrick Goymer, the story behind the scientists who first described the phenomenon known as hydrogen bonding is a familiar one. Research Highlights Top Supramolecular assembly: A protein gets framed | Materials chemistry: Compliant crystals | Atmospheric chemistry: Good vibrations | Metabolomics: Metabolites on the inside Blogroll Top Blogroll: Teaching the teacher   p867 Ashutosh Jogalekar doi:10.1038/nchem.1484 News and Views Top Protein design: Engineering di-iron enzymes   pp868 - 869 Steven M. Berry doi:10.1038/nchem.1483 A dramatic switch of reactivity — from hydroquinone oxidation to N-hydroxylation — can be achieved through the rational engineering of a de novo-designed di-iron protein. Four specific amino-acid mutations spread throughout the first, second and third coordination shells result in a million-fold increase in the relative rate of these two reactions. See also: Article by Reig et al. Heterogeneous catalysis: Teaching an old material new tricks   pp869 - 870 Elio Giamello doi:10.1038/nchem.1486 A classic calcium aluminate has been modified to create an inorganic electride that can be used as a promoter of the catalytic synthesis of ammonia. See also: Article by Kitano et al. Molecular magnetism: A three-headed Janus material   pp871 - 872 Michel Verdaguer doi:10.1038/nchem.1485 Switchable molecular materials generally alternate between two different states that are both stable in identical conditions. A magnetic molecular system is now available that allows switching between three different phases of the same compound. See also: Article by Hoshino et al. Chemistry JOBS of the week Postdoctoral Researcher in Organic Chemistry Ewha Womans University, Department of Chemistry and Nano Science Assistant Professor Of Chemistry Soka University of America Postdoc in Physical Chemistry West Virginia University-department of chemistry Professor of Sustainable Chemistry Monash University Professor of Polymer Chemistry University of Warwick More Science jobs from Chemistry EVENT 4th International Conference for Young Chemists (ICYC) 30.01.-01.02.13 Penang, Malaysia More science events from Review Top Heterogeneities of individual catalyst particles in space and time as monitored by spectroscopy   pp873 - 886 Inge L. C. Buurmans and Bert M. Weckhuysen doi:10.1038/nchem.1478 This Review describes the general trends and implications of heterogeneities within individual catalyst particles as observed by modern spatiotemporal spectroscopy. It discusses how catalytic materials have been found to display heterogeneities in structure, composition and reactivity in space and time. The implications of these findings for future catalyst design are also described. Articles Top Selectivity and direct visualization of carbon dioxide and sulfur dioxide in a decorated porous host   pp887 - 894 Sihai Yang, Junliang Sun, Anibal J. Ramirez-Cuesta, Samantha K. Callear, William I. F. David, Daniel P. Anderson, Ruth Newby, Alexander J. Blake, Julia E. Parker, Chiu C. Tang and Martin Schröder doi:10.1038/nchem.1457 Porous solids are well suited to the capture of environmentally harmful gases, but further understanding of the solid–gas interactions involved is required. Combining dynamic and static characterization with modelling, researchers have now described how a metal–organic framework binds CO2 and SO2 selectively through hydroxyl groups — rather than amine ones as typically featured. Prebiotic synthesis of simple sugars by photoredox systems chemistry   pp895 - 899 Dougal Ritson and John D. Sutherland doi:10.1038/nchem.1467 A demonstration of simple sugar synthesis from single carbon feedstocks would provide significant support for the involvement of RNA in the origin of life. Here, hydrogen cyanide is shown to feed a cyanocuprate photoredox cycle that ultimately provides both the starting material and the reducing power necessary for a Killiani–Fischer-type sugar synthesis. Alteration of the oxygen-dependent reactivity of de novo Due Ferri proteins   pp900 - 906 Amanda J. Reig, Marcos M. Pires, Rae Ana Snyder, Yibing Wu, Hyunil Jo, Daniel W. Kulp, Susan E. Butch, Jennifer R. Calhoun, Thomas G. Szyperski, Edward I. Solomon and William F. DeGrado doi:10.1038/nchem.1454 Representing the first successful rational reprogramming of function in a de novo protein, the reactivity of a designed di-iron carboxylate protein from the Due Ferri family was altered from hydroquinone oxidation to arylamine N-hydroxylation through the introduction of a critical third histidine ligand in the active site. See also: News and Views by Berry Hidden complexity in the isomerization dynamics of Holliday junctions   pp907 - 914 Changbong Hyeon, Jinwoo Lee, Jeseong Yoon, Sungchul Hohng and D. Thirumalai doi:10.1038/nchem.1463 Single-molecule experiments reveal substantial molecule-to-molecule variation in the Mg2+-induced isomerization dynamics of Holliday junctions (HJs). Effective ergodicity breaking of time trajectories results in the partitioning of HJ dynamics into multiple clusters. The observed dynamical heterogeneity is a consequence of various internal multiloop conformations that are frozen by Mg2+ ions. Synthesis of highly strained terpenes by non-stop tail-to-head polycyclization   pp915 - 920 Sergey V. Pronin and Ryan A. Shenvi doi:10.1038/nchem.1458 Sesquiterpenes are biosynthesized from linear isoprenols through the intermediacy of multiple, high-energy carbocations. Here a strategy is demonstrated for mimicking these reactions in bulk solvent to yield strained, acid-labile terpenes. Key to the success of these reactions is the sequestration of the counteranion away from the reactive carbocation, a strategy that should enable further study of challenging polycyclizations. Three-way switching in a cyanide-bridged [CoFe] chain   pp921 - 926 Norihisa Hoshino, Fumichika Iijima, Graham N. Newton, Norifumi Yoshida, Takuya Shiga, Hiroyuki Nojiri, Akiko Nakao, Reiji Kumai, Youichi Murakami and Hiroki Oshio doi:10.1038/nchem.1455 Bistable materials, which exist in either one of two phases under identical conditions, are intriguing both from a fundamental perspective and for their practical applications. A cyanide-bridged [CoFe] coordination chain has now been prepared that shows both magnetic and electric bistabilities in the same temperature range, undergoing thermo- and photo-induced conversions between insulating, semiconducting and single-chain magnet-type phases. See also: News and Views by Verdaguer Amyloid β-sheet mimics that antagonize protein aggregation and reduce amyloid toxicity   pp927 - 933 Pin-Nan Cheng, Cong Liu, Minglei Zhao, David Eisenberg and James S. Nowick doi:10.1038/nchem.1433 A family of robust β-sheet macrocycles that can display a variety of heptapeptide sequences from different amyloid proteins is introduced. These amyloid β-sheet mimics can be tailored to antagonize aggregation of the proteins, thereby reducing the toxicity associated with diseases such as Alzheimer's. Ammonia synthesis using a stable electride as an electron donor and reversible hydrogen store   pp934 - 940 Masaaki Kitano, Yasunori Inoue, Youhei Yamazaki, Fumitaka Hayashi, Shinji Kanbara, Satoru Matsuishi, Toshiharu Yokoyama, Sung-Wng Kim, Michikazu Hara and Hideo Hosono doi:10.1038/nchem.1476 Methods that fix atmospheric nitrogen to ammonia under mild conditions could offer a more environmentally benign alternative to the Haber–Bosch process. Now, a Ru-loaded electride, [Ca24Al28O64]4+(e−)4, is reported that acts as an efficient electron donor and reversible hydrogen store, and is demonstrated to function as an efficient catalyst for ammonia synthesis. See also: News and Views by Giamello RNA catalysis through compartmentalization   pp941 - 946 Christopher A. Strulson, Rosalynn C. Molden, Christine D. Keating and Philip C. Bevilacqua doi:10.1038/nchem.1466 RNA compartmentalization is essential for cellular functions and may have played a pivotal role in the emergence of life. However, the consequences of compartmentalization on RNA catalysis have been largely unexplored. Here, partitioning of catalytic RNA in a two-phase aqueous polymer solution increased local RNA concentration, enhancing ribozyme kinetics. Control of selectivity in heterogeneous catalysis by tuning nanoparticle properties and reactor residence time   pp947 - 952 Elad Gross, Jack Hung-Chang Liu, F. Dean Toste and Gabor A. Somorjai doi:10.1038/nchem.1465 Heterogeneous catalysts are generally more readily recycled than homogeneous catalysts, but the latter are more easily modified to tune reactivity and selectivity. Here, the dendrimer coating of gold nanoparticle catalysts is shown to be a surrogate for the ligands of homogeneous catalysts. Tuning of product distribution and reaction selectivity is possible when these catalysts are employed in a fixed-bed flow reactor. In Your Element Top Osmium weighs in   p954 Gregory Girolami doi:10.1038/nchem.1479 Gregory Girolami recounts how element 76 beat a close competitor to the title of densest known metal and went on to participate in Nobel Prize-winning reactions. Top Advertisement Subscribe to Nature Chemistry Make sure you receive your own personal copy of Nature Chemistry. 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