Angewandte Chemie International Edition

Cover image for Vol. 51 Issue 20

May 14, 2012

Volume 51, Issue 20

Pages 4755–5012

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Inside Back Cover
    5. Back Cover
    6. Graphical Abstract
    7. News
    8. Author Profile
    9. News
    10. Obituary
    11. Book Review
    12. Highlights
    13. Minireview
    14. Review
    15. Communications
    16. Preview
    1. Cover Picture: Circular Dichroism in the Photoelectron Angular Distributions of Camphor and Fenchone from Multiphoton Ionization with Femtosecond Laser Pulses (Angew. Chem. Int. Ed. 20/2012) (page 4755)

      Christian Lux, Prof. Dr. Matthias Wollenhaupt, Tom Bolze, Dr. Qingqing Liang, Jens Köhler, Cristian Sarpe and Prof. Dr. Thomas Baumert

      Article first published online: 2 MAR 2012 | DOI: 10.1002/anie.201201229

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      Mirror, mirror The ionization of chiral molecules with circularly polarized light creates an enhancement of the photoelectron angular distribution in the forward direction relative to the laser beam. The mirror-image distribution is obtained with the mirror-image enantiomer. The effect allows enantiomers to be distinguished in the gas phase. To date a synchrotron source was required, now as T. Baumert and co-workers show in their Communication on page 5001 ff., only a laser set-up is necessary.

  2. Inside Cover

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Inside Back Cover
    5. Back Cover
    6. Graphical Abstract
    7. News
    8. Author Profile
    9. News
    10. Obituary
    11. Book Review
    12. Highlights
    13. Minireview
    14. Review
    15. Communications
    16. Preview
    1. Inside Cover: Infrared Spectrum and Structure of the Adamantane Cation: Direct Evidence for Jahn–Teller Distortion (Angew. Chem. Int. Ed. 20/2012) (page 4756)

      Dipl.-Phys. Alexander Patzer, B. Sc. Markus Schütz, Prof. Dr. Thomas Möller and Prof. Dr. Otto Dopfer

      Article first published online: 2 MAR 2012 | DOI: 10.1002/anie.201201228

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      The gas-phase infrared spectrum of the adamantane radical cation, C10H16+, provides the first spectroscopic characterization of the geometric and electronic structure of this cycloalkane carbocation and direct evidence for the Jahn–Teller distortion in the 2A1 ground electronic state. In their Communication on page 4925 ff., O. Dopfer et al. show that the characteristic IR fingerprint may be used for the identification of C10H16+ in hydrocarbon plasmas, including the interstellar medium.

  3. Inside Back Cover

    1. Top of page
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    3. Inside Cover
    4. Inside Back Cover
    5. Back Cover
    6. Graphical Abstract
    7. News
    8. Author Profile
    9. News
    10. Obituary
    11. Book Review
    12. Highlights
    13. Minireview
    14. Review
    15. Communications
    16. Preview
    1. Inside Back Cover: Air-Stable, Highly Fluorescent Primary Phosphanes (Angew. Chem. Int. Ed. 20/2012) (page 5013)

      Laura H. Davies, Dr. Beverly Stewart, Dr. Ross W. Harrington, Prof. William Clegg and Dr. Lee J. Higham

      Article first published online: 4 APR 2012 | DOI: 10.1002/anie.201202206

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      Air-stable primary phosphanes that are highly fluorescent are presented by L. J. Higham and co-workers in their communication on page 4921 ff. These primary phosphanes (RPH2) can be used to prepare tripodal phosphanes which form rhenium complexes that retain a desirable photophysical profile and have potential applications as mimics of technetium imaging agents.

  4. Back Cover

    1. Top of page
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    3. Inside Cover
    4. Inside Back Cover
    5. Back Cover
    6. Graphical Abstract
    7. News
    8. Author Profile
    9. News
    10. Obituary
    11. Book Review
    12. Highlights
    13. Minireview
    14. Review
    15. Communications
    16. Preview
    1. Back Cover: Material Transfer and Polarity Reversal in Contact Charging (Angew. Chem. Int. Ed. 20/2012) (page 5014)

      Dr. H. Tarik Baytekin, Dr. Bilge Baytekin, Jared T. Incorvati and Prof. Dr. Bartosz A. Grzybowski

      Article first published online: 4 APR 2012 | DOI: 10.1002/anie.201202246

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      Alessandro Volta (portrait by N. Cianfanelli) was the first modern scientist who aimed to rank dielectric materials. No such rankings have proven accurate because of the effects of material transfer, as described by B. A. Grzybowski and co-workers in their Communication on page 4843 ff. In the picture, the upper half of the circle illustrates a typical ranking of contact charging (red=positive polarity, blue=negative polarity). The lower half shows atomic force microscopy images of contact-charged surfaces.

  5. Graphical Abstract

    1. Top of page
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    5. Back Cover
    6. Graphical Abstract
    7. News
    8. Author Profile
    9. News
    10. Obituary
    11. Book Review
    12. Highlights
    13. Minireview
    14. Review
    15. Communications
    16. Preview
  6. News

    1. Top of page
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    5. Back Cover
    6. Graphical Abstract
    7. News
    8. Author Profile
    9. News
    10. Obituary
    11. Book Review
    12. Highlights
    13. Minireview
    14. Review
    15. Communications
    16. Preview
  7. Author Profile

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Inside Back Cover
    5. Back Cover
    6. Graphical Abstract
    7. News
    8. Author Profile
    9. News
    10. Obituary
    11. Book Review
    12. Highlights
    13. Minireview
    14. Review
    15. Communications
    16. Preview
    1. Kiyotomi Kaneda (page 4778)

      Article first published online: 14 MAR 2012 | DOI: 10.1002/anie.201200634

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      “My favorite piece of music is “The Four Seasons” (Antonio Vivaldi). My biggest motivation is the joy of doing research with my colleagues and students …” This and more about Kiyotomi Kaneda can be found on page 4778.

  8. News

    1. Top of page
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    5. Back Cover
    6. Graphical Abstract
    7. News
    8. Author Profile
    9. News
    10. Obituary
    11. Book Review
    12. Highlights
    13. Minireview
    14. Review
    15. Communications
    16. Preview
  9. Obituary

    1. Top of page
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    5. Back Cover
    6. Graphical Abstract
    7. News
    8. Author Profile
    9. News
    10. Obituary
    11. Book Review
    12. Highlights
    13. Minireview
    14. Review
    15. Communications
    16. Preview
  10. Book Review

    1. Top of page
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    5. Back Cover
    6. Graphical Abstract
    7. News
    8. Author Profile
    9. News
    10. Obituary
    11. Book Review
    12. Highlights
    13. Minireview
    14. Review
    15. Communications
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    1. Metal-Organic Frameworks. Applications from Catalysis to Gas Storage. Edited by David Farrusseng. (pages 4782–4783)

      Jiří Čejka

      Article first published online: 18 APR 2012 | DOI: 10.1002/anie.201200812

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      Wiley-VCH, Weinheim, 2011. 392 pp., hardcover, € 119.00.—ISBN 978-3527328703

  11. Highlights

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    6. Graphical Abstract
    7. News
    8. Author Profile
    9. News
    10. Obituary
    11. Book Review
    12. Highlights
    13. Minireview
    14. Review
    15. Communications
    16. Preview
    1. Atom Tunneling

      Atom Tunneling in Organic Transformations (pages 4784–4786)

      Prof. Dr. Frederic W. Patureau

      Article first published online: 21 MAR 2012 | DOI: 10.1002/anie.201200991

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      There and gone: Atoms, such as hydrogen or deuterium, commonly disappear and reappear at different locations in molecular structures. For example, carboxylic acids and hydroxycarbenes isomerize through atom tunneling events. It could happen in your reaction!

    2. Switching in Vivo

      Azobenzenes in a New Light—Switching In Vivo (pages 4787–4788)

      Dr. Hermann A. Wegner

      Article first published online: 29 MAR 2012 | DOI: 10.1002/anie.201201336

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      Two bands make light work: Since the isomerization of azobenzenes is usually induced by UV light, its application is limited in living systems. A new azobenzene switch now operates entirely in the visible range. The new design is based on the introduction of OMe groups in the ortho positions, which splits the n–π* transition into two absorption bands. The two isomeric forms can be obtained with more than 80 % enrichment from the respective photostationary state.

    3. Reaction Monitoring

      In Situ XPS Monitoring of Bulk Ionic Liquid Reactions: Shedding Light on Organic Reaction Mechanisms (pages 4789–4791)

      Prof. Dr. Peter Licence

      Article first published online: 19 APR 2012 | DOI: 10.1002/anie.201201070

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      In the swim: Until now, X-ray photoelectron spectroscopy (XPS) has been predominantly applied to the investigation of near-surface regions. Recent work has now brought XPS into a new domain with the direct monitoring of bulk reactions in the liquid phase. In the monitored reaction, the cation of an ionic liquid (IL) reacts with the anion of another IL (see scheme).

  12. Minireview

    1. Top of page
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    11. Book Review
    12. Highlights
    13. Minireview
    14. Review
    15. Communications
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    1. Nanomagnetism

      Exploring the No-Man’s Land between Molecular Nanomagnets and Magnetic Nanoparticles (pages 4792–4800)

      Prof. Dante Gatteschi, Dr. Maria Fittipaldi, Dr. Claudio Sangregorio and Dr. Lorenzo Sorace

      Article first published online: 4 APR 2012 | DOI: 10.1002/anie.201105428

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      That's about the size of it: A comparison of structural and magnetic properties of iron oxo based molecular nanomagnets (see picture, right) and magnetic nanoparticles (left) gives a deeper understanding of the magnetic behavior at the intermediate scale between molecular and bulk objects.

  13. Review

    1. Top of page
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    7. News
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    11. Book Review
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    13. Minireview
    14. Review
    15. Communications
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    1. Natural Enantiomers

      Enantiomeric Natural Products: Occurrence and Biogenesis (pages 4802–4836)

      Jennifer M. Finefield, Prof. Dr. David H. Sherman, Prof. Dr. Martin Kreitman and Prof. Dr. Robert M. Williams

      Article first published online: 3 MAY 2012 | DOI: 10.1002/anie.201107204

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      Two sides to the story: The formation of enantiomerically opposite natural products by nature is known, although rare (see examples). To date, many puzzles and stereochemical anomalies remain regarding the biogenesis of these unique natural products, despite the substantial body of research that has been carried out over the years in an attempt to understand the biogenesis of enantiomeric metabolites.

  14. Communications

    1. Top of page
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    6. Graphical Abstract
    7. News
    8. Author Profile
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    10. Obituary
    11. Book Review
    12. Highlights
    13. Minireview
    14. Review
    15. Communications
    16. Preview
    1. Imaging Agents

      Genetically Encoded pH Sensor for Tracking Surface Proteins through Endocytosis (pages 4838–4842)

      Anmol Grover, Dr. Brigitte F. Schmidt, Dr. Russell D. Salter, Dr. Simon C. Watkins, Dr. Alan S. Waggoner and Dr. Marcel P. Bruchez

      Article first published online: 29 MAR 2012 | DOI: 10.1002/anie.201108107

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      Traffic cam: A tandem dye prepared from a FRET acceptor and a fluorogenic donor functions as a cell surface ratiometric pH indicator, which upon internalization serves to follow protein trafficking during endocytosis. This sensor was used to analyze agonist-dependent internalization of β2-adrenergic receptors (see scheme). It was also used as a surrogate antigen to reveal direct surface-to-endosome antigen transfer between dendritic cells (not shown).

    2. Contact Electrification

      Material Transfer and Polarity Reversal in Contact Charging (pages 4843–4847)

      Dr. H. Tarik Baytekin, Dr. Bilge Baytekin, Jared T. Incorvati and Prof. Dr. Bartosz A. Grzybowski

      Article first published online: 15 MAR 2012 | DOI: 10.1002/anie.201200057

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      In touch: The outcome of contact electrification between dielectrics depends not only on the transfer of charge but also on the transfer of material (see picture). Although only minute quantities of materials are being exchanged during contact, they can reverse the polarity of dielectrics. The reported results corroborate the mosaic model and suggest that the observations are because of the mechanical softness/hardness of the materials.

    3. High-Pressure Chemistry

      Immobilization of Large, Aliovalent Cations in the Small-Pore Zeolite K-Natrolite by Means of Pressure (pages 4848–4851)

      Prof. Yongjae Lee, Yongmoon Lee, Donghoon Seoung, Jun-Hyuk Im, Hee-Jung Hwang, Tae-Hyun Kim, Dr. Dan Liu, Dr. Zhenxian Liu, Dr. Seung Yeop Lee, Dr. Chi-Chang Kao and Prof. Dr. Thomas Vogt

      Article first published online: 4 APR 2012 | DOI: 10.1002/anie.201201045

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      High-pressure ion exchange of small-pore zeolite K-natrolite allows immobilization of nominally non-exchangeable aliovalent cations such as trivalent europium. A sample exchanged at 3.0(1) GPa and 250 °C contains about 4.7 EuIII ions per unit cell, which is equivalent to over 90 % of the K+ cations being exchanged (see picture).

    4. Arresting Particle Growth

      Structural and Mechanistic Revelations on an Iron Conversion Reaction from Pair Distribution Function Analysis (pages 4852–4855)

      Dr. Badri Shyam, Dr. Karena W. Chapman, Dr. Mahalingam Balasubramanian, Dr. Robert J. Klingler, Dr. George Srajer and Dr. Peter J. Chupas

      Article first published online: 11 APR 2012 | DOI: 10.1002/anie.201200244

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      Not simply small particles: Pair distribution function analysis (see picture) yields comprehensive insights into the electrochemical reaction of α-Fe2O3 with lithium. The metallic Fe formed in this reaction was found to be defect-rich nanoparticles that restructure continuously without growing—an unusual characteristic likely linked to its highly reversible capacity.

    5. Graphene

      Visualizing Chemical Reactions Confined under Graphene (pages 4856–4859)

      Rentao Mu, Prof. Qiang Fu, Li Jin, Liang Yu, Guangzong Fang, Dali Tan and Prof. Xinhe Bao

      Article first published online: 11 APR 2012 | DOI: 10.1002/anie.201200413

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      An undercover agent: Graphene has been used as an imaging agent to visualize interfacial reactions under its cover, and exhibits a strong confinement effect on the chemistry of molecules underneath (see picture). In a CO atmosphere, CO penetrates into the graphene/Pt(111) interface and reacts with O2 therein, whereas intercalated CO desorbs from the Pt surface.

    6. Glycan Microarrays

      Recognition of Sialylated Poly-N-acetyllactosamine Chains on N- and O-Linked Glycans by Human and Avian Influenza A Virus Hemagglutinins (pages 4860–4863)

      Dr. Corwin M. Nycholat, Ryan McBride, Dr. Damian C. Ekiert, Dr. Rui Xu, Janani Rangarajan, Dr. Wenjie Peng, Dr. Nahid Razi, Dr. Michel Gilbert, Dr. Warren Wakarchuk, Prof. Ian A. Wilson and Prof. James C. Paulson

      Article first published online: 13 APR 2012 | DOI: 10.1002/anie.201200596

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      Human influenza viruses are proposed to recognize sialic acids (pink diamonds) on glycans extended with poly-LacNAc chains (LacNAc=(yellow circle+blue square)). N- and O-linked glycans were extended with different poly-LacNAc chains with α2-3- and α2-6-linked sialic acids recognized by human and avian influenza viruses, respectively. The specificity of recombinant hemagglutinins (receptors in green) was investigated by using glycan microarray technology.

    7. Nanopore-Based Sensors

      DNA Origami Gatekeepers for Solid-State Nanopores (pages 4864–4867)

      Ruoshan Wei, Thomas G. Martin, Ulrich Rant and Hendrik Dietz

      Article first published online: 4 APR 2012 | DOI: 10.1002/anie.201200688

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      DNA has it covered: DNA origami gatekeeper nanoplates convert nanopores in solid-state membranes into versatile devices for label-free macromolecular sensing applications. The custom apertures in the nanoplates can be chemically addressed for sequence-specific detection of DNA.

    8. Fluorescence

      Triple-Color Super-Resolution Imaging of Live Cells: Resolving Submicroscopic Receptor Organization in the Plasma Membrane (pages 4868–4871)

      Stephan Wilmes, Markus Staufenbiel, Domenik Liße, Christian P. Richter, Oliver Beutel, Prof. Dr. Karin B. Busch, Prof. Dr. Samuel T. Hess and Prof. Dr. Jacob Piehler

      Article first published online: 5 APR 2012 | DOI: 10.1002/anie.201200853

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      In living color: Efficient intracellular covalent labeling of proteins with a photoswitchable dye using the HaloTag for dSTORM super-resolution imaging in live cells is described. The dynamics of cellular nanostructures at the plasma membrane were monitored with a time resolution of a few seconds. In combination with dual-color FPALM imaging, submicroscopic receptor organization within the context of the membrane skeleton was resolved (see figure).

    9. Palladium Catalysts

      Porous Single-Crystalline Palladium Nanoparticles with High Catalytic Activities (pages 4872–4876)

      Feng Wang, Chuanhao Li, Prof. Ling-Dong Sun, Chun-Hu Xu, Prof. Jianfang Wang, Prof. Jimmy C. Yu and Prof. Chun-Hua Yan

      Article first published online: 4 APR 2012 | DOI: 10.1002/anie.201107376

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      Palladium's pore cousin: A facile approach is described for the size-controlled preparation of porous single-crystalline Pd nanoparticles. These porous Pd nanoparticles exhibit size-independent catalytic activities for the Suzuki coupling and are more active than commercial Pd/C catalysts.

    10. Electron Transfer

      Pyrrole Aminoimidazole Alkaloid Metabiosynthesis with Marine Sponges Agelas conifera and Stylissa caribica (pages 4877–4881)

      Dr. E. Paige Stout, Dr. Yong-Gang Wang, Prof. Dr. Daniel Romo and Prof. Dr. Tadeusz F. Molinski

      Article first published online: 4 APR 2012 | DOI: 10.1002/anie.201108119

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      Game-SET-match: Pyrrole aminoimidazole alkaloids (PAIs) are metabiosynthesized from chlorinated analogues of oroidin by cell-free enzyme preparations from PAI-producing sponges. Evidence and implications for the biosynthesis of PAIs include putative single-electron transfers (SETs) that promote C[BOND]C bond-forming reactions of precursors.

    11. Supramolecular Polymers

      Organogold(III) Supramolecular Polymers for Anticancer Treatment (pages 4882–4886)

      Jing-Jing Zhang, Dr. Wei Lu , Dr. Raymond Wai-Yin Sun and Prof. Dr. Chi-Ming Che

      Article first published online: 4 APR 2012 | DOI: 10.1002/anie.201108466

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      Gold cures: The depicted gold(III) complex self-assembles into supramolecular polymers which form nanofibrillar networks that display sustained cytotoxicity and can also act as carriers for other cytotoxic agents.

    12. Metal–Organic Frameworks

      Electronic Effects of Linker Substitution on Lewis Acid Catalysis with Metal–Organic Frameworks (pages 4887–4890)

      Frederik Vermoortele, Matthias Vandichel, Ben Van de Voorde, Dr. Rob Ameloot, Prof. Michel Waroquier, Prof. Veronique Van Speybroeck and Prof. Dirk E. De Vos

      Article first published online: 5 APR 2012 | DOI: 10.1002/anie.201108565

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      Functionalized linkers can greatly increase the activity of metal–organic framework (MOF) catalysts with coordinatively unsaturated sites. A clear linear free-energy relationship (LFER) was found between Hammett σm values of the linker substituents X and the rate kX of a carbonyl-ene reaction. This is the first LFER ever observed for MOF catalysts. A 56-fold increase in rate was found when the substituent is a nitro group (see picture).

    13. Stem Cell Differentiation

      Directing Stem Cell Fate by Controlling the Affinity and Density of Ligand–Receptor Interactions at the Biomaterials Interface (pages 4891–4895)

      Prof. Kristopher A. Kilian and Prof. Milan Mrksich

      Article first published online: 13 APR 2012 | DOI: 10.1002/anie.201108746

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      Sticky situation: The differentiation of mesenchymal stem cells can be influenced by the affinity and density of an immobilized ligand for the integrin receptors. Cells adherent to monolayers that present the high-affinity, cyclic-RGD peptide (left) show increased expression of osteogenic markers, while cells on monolayers presenting the lower-affinity, linear-RGD peptide (right) express early markers of myogenesis at a high density and neurogenesis at a low density of the ligand.

    14. Point-of-Care Diagnostics

      Rapid, Sensitive, and Quantitative Detection of Pathogenic DNA at the Point of Care through Microfluidic Electrochemical Quantitative Loop-Mediated Isothermal Amplification (pages 4896–4900)

      Kuangwen Hsieh, Adriana S. Patterson, Dr. B. Scott Ferguson, Prof. Kevin W. Plaxco and Prof. H. Tom Soh

      Article first published online: 4 APR 2012 | DOI: 10.1002/anie.201109115

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      Single-step DNA detection: A microfluidic electrochemical loop mediated isothermal amplification platform is reported for rapid, sensitive, and quantitative detection of pathogen genomic DNA at the point of care (see picture). DNA amplification was electrochemically monitored in real time within a monolithic microfluidic device, thus enabling the detection of as few as 16 copies of Salmonella genomic DNA through a single-step process in less than an hour.

    15. Graphene

      Reversible Grafting of α-Naphthylmethyl Radicals to Epitaxial Graphene (pages 4901–4904)

      Santanu Sarkar, Dr. Elena Bekyarova and Prof. Robert C. Haddon

      Article first published online: 5 APR 2012 | DOI: 10.1002/anie.201201320

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      The Kolbe electrochemical oxidation strategy has been utilized to achieve an efficient quasireversible electrochemical grafting of the α-naphthylmethyl functional group to graphene. The method facilitates reversible bandgap engineering in graphene and preparation of electrochemically erasable organic dielectric films. The picture shows Raman D-band maps of both systems.

    16. Nanotemplates

      Oligopyrenotides: Chiral Nanoscale Templates for Chromophore Assembly (pages 4905–4908)

      Vladimir L. Malinovskii, Alina L. Nussbaumer and Prof. Robert Häner

      Article first published online: 11 APR 2012 | DOI: 10.1002/anie.201201352

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      Getting organized: DNA-like supramolecular polymers formed of short oligopyrenotides serve as a helical scaffold for the molecular assembly of ligands (see picture). The cationic porphyrin meso-tetrakis(1-methylpyridin-4-yl)porphyrin interacts with the helical polymers in a similar way as with poly(dA:dT).

    17. Natural Products

      Biomimetic Total Synthesis of (+)-Gelsemine (pages 4909–4912)

      Xuan Zhou, Tao Xiao, Yusuke Iwama and Prof. Dr. Yong Qin

      Article first published online: 4 APR 2012 | DOI: 10.1002/anie.201201736

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      Challenging: (+)-gelsemine was synthesized from (R,R)-aziridine 1 in 25 steps with approximately 1 % overall yield. A multistep, one-pot enol–oxonium cyclization cascade was used to construct, simultaneously, the E ring, F ring, C3 stereocenter, and C7 quaternary stereocenter. This synthesis using the enol–oxonium cyclization reaction as a key step to make the cage structure has demonstrated the proposed biosynthetic pathway of the gelsemine family.

    18. Flexible Pores

      In Situ X-ray Structural Studies of a Flexible Host Responding to Incremental Gas Loading (pages 4913–4916)

      Dr. Tia Jacobs, Dr. Gareth O. Lloyd, Dr. Jan-André Gertenbach, Prof. Kristian K. Müller-Nedebock, Prof. Catharine Esterhuysen and Prof. Leonard J. Barbour

      Article first published online: 5 APR 2012 | DOI: 10.1002/anie.201201281

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      Crystallographic pressure-lapse snapshots of a porous material responding to gas loading were used to investigate the stepwise uptake of carbon dioxide and acetylene molecules into discrete confined spaces. Based on the data, a qualitative statistical mechanical model was devised that reproduces even subtle features in the experimental gas sorption isotherms.

    19. Transmetalation

      Strong Metallophilic Interactions in the Palladium Arylation by Gold Aryls (pages 4917–4920)

      Dr. Mónica H. Pérez-Temprano, Dr. Juan A. Casares, Prof. Ángel R. de Lera, Prof. Rosana Álvarez and Prof. Pablo Espinet

      Article first published online: 4 APR 2012 | DOI: 10.1002/anie.201108043

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      It's the second step that counts: Arylation of Pd by Au takes place through transition states and intermediates featuring strong Au⋅⋅⋅Pd metallophilic interactions (see picture). However, the aryl transfer from [AuArL] to [PdArClL2] is thermodynamically disfavored and will not occur unless an irreversible Ar[BOND]Ar coupling from [PdAr2L2] follows.

    20. Phosphaorganic Chemistry

      You have full text access to this OnlineOpen article
      Air-Stable, Highly Fluorescent Primary Phosphanes (pages 4921–4924)

      Laura H. Davies, Dr. Beverly Stewart, Dr. Ross W. Harrington, Prof. William Clegg and Dr. Lee J. Higham

      Article first published online: 19 MAR 2012 | DOI: 10.1002/anie.201108416

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      Light without fright: A synthetic route to fluorescent primary phosphanes (RPH2) that are resistant to air oxidation both in the solid state and in chloroform solution is described. These versatile precursors undergo hydrophosphination to give tripodal ligands and subsequently fluorescent transition-metal complexes.

    21. Infrared Spectroscopy

      Infrared Spectrum and Structure of the Adamantane Cation: Direct Evidence for Jahn–Teller Distortion (pages 4925–4929)

      Dipl.-Phys. Alexander Patzer, B. Sc. Markus Schütz, Prof. Dr. Thomas Möller and Prof. Dr. Otto Dopfer

      Article first published online: 27 JAN 2012 | DOI: 10.1002/anie.201108937

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      The fundamentals: The IR spectrum of the adamantane cation, C10H16+, has been derived by resonant IR photodissociation of weakly bound C10H16+⋅Ln clusters (see picture). The analysis of the IR spectrum provides the first spectroscopic characterization of this fundamental cycloalkane carbocation in the gas phase and direct evidence for the Jahn–Teller distortion in the 2A1 ground electronic state.

    22. Natural Products

      Scalable Total Synthesis of (−)-Berkelic Acid by Using a Protecting-Group-Free Strategy (pages 4930–4933)

      Prof. Dr. Francisco J. Fañanás, Dr. Abraham Mendoza, Tamara Arto, Dr. Baris Temelli and Prof. Félix Rodríguez

      Article first published online: 4 APR 2012 | DOI: 10.1002/anie.201109076

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      Supply chain: The polycyclic core of (−)-berkelic acid (1) was constructed in just one step from very simple starting materials. The total synthesis of 1 involves a seven-step linear sequence. Protection/deprotection steps were avoided and all but the last step were performed on a gram scale. This synthesis could solve the supply problem associated with the exhaustion of the natural source.

    23. Self-Powered Nanosystems

      Paper-Based Supercapacitors for Self-Powered Nanosystems (pages 4934–4938)

      Dr. Longyan Yuan, Xu Xiao, Tianpeng Ding, Junwen Zhong, Xianghui Zhang, Dr. Yue Shen, Dr. Bin Hu, Prof. Yunhui Huang, Prof. Jun Zhou and Prof. Zhong Lin Wang

      Article first published online: 4 APR 2012 | DOI: 10.1002/anie.201109142

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      Energy storage on paper: Paper-based, all-solid-state, and flexible supercapacitors were fabricated, which can be charged by a piezoelectric generator or solar cells and then discharged to power a strain sensor or a blue-light-emitting diode, demonstrating its efficient energy management in self-powered nanosystems (see picture).

    24. Corannulenes

      A Buckybowl with a Lot of Potential: C5-C20H5(CF3)5 (pages 4939–4942)

      Dr. Igor V. Kuvychko, Sarah N. Spisak, Dr. Yu-Sheng Chen, Dr. Alexey A. Popov, Prof. Marina A. Petrukhina, Prof. Steven H. Strauss and Dr. Olga V. Boltalina

      Article first published online: 11 APR 2012 | DOI: 10.1002/anie.201200178

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      Lots of potential: A trifluoromethylated corannulene, C5-C20H5(CF3)5, has been prepared and characterized spectroscopically and by X-ray crystallography. The structure exhibits a highly ordered bowl stacking that is unusual for corannulenes with acyclic substituents. The first reduction of C5-C20H5(CF3)5 is anodically shifted by 0.95 V, making it the strongest corannulene-based electron acceptor to date.

    25. Synthetic Methods

      When Bigger Is Better: Intermolecular Hydrofunctionalizations of Activated Alkenes Catalyzed by Heteroleptic Alkaline Earth Complexes (pages 4943–4946)

      Dr. Bo Liu, Dr. Thierry Roisnel, Prof. Dr. Jean-François Carpentier and Dr. Yann Sarazin

      Article first published online: 11 APR 2012 | DOI: 10.1002/anie.201200364

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      New alkaline-earth amido complexes catalyze the regioselective intermolecular hydroamination (see scheme; Ae=alkaline earth) and hydrophosphination of styrene and isoprene with unprecedented activities. The catalytic performances increased linearly with the size of the metal.

    26. Aromatic Cations

      Benzylium versus Tropylium Ion Dichotomy: Vibrational Spectroscopy of Gaseous C8H9+ Ions (pages 4947–4949)

      Dr. Barbara Chiavarino, Prof. Maria Elisa Crestoni, Prof. Dr. Otto Dopfer, Dr. Philippe Maitre and Prof. Simonetta Fornarini

      Article first published online: 4 APR 2012 | DOI: 10.1002/anie.201200558

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      Definitely different: The path towards sorting out a long-standing dichotomy in carbocation chemistry is disclosed by infrared multiple photon dissociation spectroscopy of tropylium and benzylium isomers of C8H9+ ions (see picture).

    27. C[BOND]H Activation

      Palladium-Catalyzed Alkylation of 1,4-Dienes by C[BOND]H Activation (pages 4950–4953)

      Prof. Barry M. Trost, Max M. Hansmann and David A. Thaisrivongs

      Article first published online: 4 APR 2012 | DOI: 10.1002/anie.201200601

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      Activated: The title reaction proceeds with a broad range of nucleophiles and variously substituted 1,4-dienes under mild conditions, and provides direct access to the corresponding 1,3-diene-containing products with high regio- and stereocontrol (see scheme; 2,6-DMBQ=2,6-dimethylbenzoquinone, EWG=electron-withdrawing group). This is the first catalytic allylic C[BOND]H alkylation that proceeds in the absence of sulfoxide ligands.

    28. Surface Chemistry

      Multiquantum Vibrational Excitation of NO Scattered from Au(111): Quantitative Comparison of Benchmark Data to Ab Initio Theories of Nonadiabatic Molecule–Surface Interactions (pages 4954–4958)

      Dr. Russell Cooper, Dr. Christof Bartels, Dr. Alexander Kandratsenka, Prof. Igor Rahinov, Dr. Neil Shenvi, Kai Golibrzuch, Zhisheng Li, Prof. Daniel J. Auerbach, Prof. John C. Tully and Prof. Alec M. Wodtke

      Article first published online: 4 APR 2012 | DOI: 10.1002/anie.201201168

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      Surface phenomena: Measurements of absolute probabilities are reported for the vibrational excitation of NO(v=0[RIGHTWARDS ARROW]1,2) molecules scattered from a Au(111) surface. These measurements were quantitatively compared to calculations based on ab initio theoretical approaches to electronically nonadiabatic molecule–surface interactions. Good agreement was found between theory and experiment (see picture; Ts=surface temperature, P=excitation probability, and E=incidence energy of translation).

    29. Organocatalysis

      Organocatalytic Asymmetric Synthesis of Trifluoromethyl-substituted Diarylpyrrolines: Enantioselective Conjugate Cyanation of β-Aryl-β-trifluoromethyl-disubstituted Enones (pages 4959–4962)

      Hiroyuki Kawai, Satoshi Okusu, Etsuko Tokunaga, Hiroyasu Sato, Dr. Motoo Shiro and Prof. Norio Shibata

      Article first published online: 4 APR 2012 | DOI: 10.1002/anie.201201278

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      Ether way: The cinchona-alkaloid-catalyzed title reaction was achieved in high yields with high to excellent ee values for the first time, and affords key intermediates for the biologically important 2 having a trifluoromethylated all-carbon quaternary chiral center. Ether-type catalysts (1) are more efficient in this transformation than the conventional hydroxy analogues.

    30. Asymmetric Catalysis

      An N-Heterocyclic Carbene/Lewis Acid Strategy for the Stereoselective Synthesis of Spirooxindole Lactones (pages 4963–4967)

      Dr. Julien Dugal-Tessier, Dr. Elizabeth A. O'Bryan, Thomas B. H. Schroeder, Daniel T. Cohen and Prof. Karl A. Scheidt

      Article first published online: 4 APR 2012 | DOI: 10.1002/anie.201201643

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      A cooperative catalysis approach for the enantioselective formal [3+2] addition of α,β-unsaturated aldehydes to isatins has been developed. Homoenolate annulations of β-aryl enals catalyzed by an N-heterocyclic carbene (NHC) require the addition of lithium chloride for high levels of enantioselectivity. This NHC-catalyzed annulation has been used for the total synthesis of maremycin B.

    31. Natural Product Synthesis

      Three Rings in One Step: A Quick Approach to IKD-8344 (pages 4968–4971)

      Dr. Yang Zou and Prof. Dr. Yikang Wu

      Article first published online: 11 APR 2012 | DOI: 10.1002/anie.201201395

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      A highly efficient enantioselective total synthesis of the natural antibiotic IKD-8344 is achieved through a convergent route. This route features an otherwise impossible concurrent formation of the THF rings from a linear polyketide precursor through intramolecular O alkylations of mesylates in competition with normally rather facile β elimination and/or α racemization reactions (see scheme, Ms=methanesulfonyl).

    32. Total Synthesis of (−)-13-Oxyingenol and its Natural Derivative (pages 4972–4975)

      Dr. Takayuki Ohyoshi, Shota Funakubo, Yamato Miyazawa, Keisuke Niida, Dr. Ichiro Hayakawa and Prof. Dr. Hideo Kigoshi

      Article first published online: 5 APR 2012 | DOI: 10.1002/anie.201201383

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      Ring functionalization: The total synthesis of a natural derivative of (−)-13-oxyingenol, a potent anti-HIV diterpenoid, is reported. The key steps in this synthesis include a ring-closing olefin metathesis and a Mislow–Evans-type [2,3]-sigmatropic rearrangement. This synthesis provides access to (−)-13-oxyingenol and its natural derivative in 21 steps from a synthetic intermediate previously prepared by Kigoshi and co-workers.

    33. Reductive Amination

      Knölker’s Iron Complex: An Efficient In Situ Generated Catalyst for Reductive Amination of Alkyl Aldehydes and Amines (pages 4976–4980)

      Anastassiya Pagnoux-Ozherelyeva, Dr. Nicolas Pannetier, Dr. Mbaye Diagne Mbaye, Dr. Sylvain Gaillard and Prof. Jean-Luc Renaud

      Article first published online: 4 APR 2012 | DOI: 10.1002/anie.201201360

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      An aminated series: A well-defined iron-catalyzed reductive amination reaction of aldehydes and ketones with aliphatic amines using molecular hydrogen is presented. Under mild conditions, good yields for a broad range of alkyl ketones as well as aldehydes were achieved.

    34. Synthetic Methods

      Absolute Asymmetric Synthesis of Tertiary α-Amino Acids (pages 4981–4984)

      Thi Thoa Mai, Dr. Mathieu Branca, Didier Gori, Dr. Régis Guillot, Prof. Cyrille Kouklovsky and Dr. Valérie Alezra

      Article first published online: 5 APR 2012 | DOI: 10.1002/anie.201200950

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      Frozen: The spontaneous crystallization of an achiral compound in a chiral conformation is used as the unique source of chirality in an absolute asymmetric synthesis of tertiary amino acids. The dynamic axial chirality of tertiary aromatic amides is frozen in a crystal (see picture) and is responsible for the stereoselectivity of the deprotonation/alkylation (see scheme). α-Amino acid derivatives are synthesized in up to 96 % ee.

    35. Coordination Chemistry

      σ-Accepting Properties of a Chlorobismuthine Ligand (pages 4985–4988)

      Tzu-Pin Lin, Iou-Sheng Ke and Prof. Dr. François P. Gabbaï

      Article first published online: 27 MAR 2012 | DOI: 10.1002/anie.201200854

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      BiZness as usual? Not exactly! The bismuth atom of the tridentate diphosphinobismuthine (o-(Ph2P)C6H4)2BiCl behaves as a Z rather than L ligand when in the coordination sphere of late transition metals such as gold. The σ-acceptor behavior of Bi is supported by its disphenoid coordination geometry and theoretical studies, which show a Au[RIGHTWARDS ARROW]Bi interaction.

    36. Metallophilic Interactions

      Gold– and Platinum–Bismuth Donor–Acceptor Interactions Supported by an Ambiphilic PBiP Pincer Ligand (pages 4989–4992)

      Dipl.-Chem. Carolin Tschersich, Prof. Dr. Christian Limberg, Dr. Stefan Roggan, Dr. Christian Herwig, Prof. Dr. Nikolaus Ernsting, Dr. Sergey Kovalenko and Dr. Stefan Mebs

      Article first published online: 4 APR 2012 | DOI: 10.1002/anie.201200848

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      Noble metals meet a heavyweight: A pincer ligand brings together bismuth with gold and platinum, so that metallophilic interactions are established. According to DFT calculations, these interactions contain dominant metal[RIGHTWARDS ARROW]bismuth contributions.

    37. Crystallization Processes

      First Seconds in a Building’s Life—In Situ Synchrotron X-Ray Diffraction Study of Cement Hydration on the Millisecond Timescale (pages 4993–4996)

      Moritz-Caspar Schlegel, Adnan Sarfraz, Urs Müller, Ulrich Panne and Dr. Franziska Emmerling

      Article first published online: 11 APR 2012 | DOI: 10.1002/anie.201200993

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      Setting cement: Highly dynamic hydration processes that occur during the first seconds of cement hydration were studied by time-resolved synchrotron X-ray diffraction. Polycarboxylate ether additives were found to influence the formation of the initial crystalline hydration products on a molecular level.

    38. Polysulfates

      The Elusive Tetrasulfate Anion [S4O13]2− (pages 4997–5000)

      Dipl.-Chem. Christian Logemann, Prof. Dr. Thorsten Klüner and Prof. Dr. Mathias S. Wickleder

      Article first published online: 4 APR 2012 | DOI: 10.1002/anie.201108206

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      Sulfates united: The unique tetrasulfate S4O132− anion was observed in the structure of (NO2)2[S4O13] that forms in the reaction of N2O5 with SO3. Theoretical investigations show that the anion is a stable member of the polysulfate series [SnO3n+1]2−, which was investigated up to n=11.

    39. Chirality

      Circular Dichroism in the Photoelectron Angular Distributions of Camphor and Fenchone from Multiphoton Ionization with Femtosecond Laser Pulses (pages 5001–5005)

      Christian Lux, Prof. Dr. Matthias Wollenhaupt, Tom Bolze, Dr. Qingqing Liang, Jens Köhler, Cristian Sarpe and Prof. Dr. Thomas Baumert

      Article first published online: 20 FEB 2012 | DOI: 10.1002/anie.201109035

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      Shine a light: A circular dichroism effect in the ±10 % regime on randomly oriented chiral molecules in the gas phase is demonstrated. The signal is derived from images of photoelectron angular distributions (see picture) produced by resonance-enhanced multiphoton ionization and allows the enantiomers to be distinguished. To date, this effect could only be generated with a synchrotron source. The new tabletop laser-based approach will make this approach far more accessible.

    40. Reversible SO2 Coordination

      Catching Gaseous SO2 in Cone-Type Lanthanide Complexes: An Unexpected Coordination Mode for SO2 in f-Element Chemistry (pages 5006–5010)

      Dr. Paul Benndorf, Sophia Schmitt, Dr. Ralf Köppe, Dr. Pascual Oña-Burgos, Dr. Andreas Scheurer, Prof. Dr. Karsten Meyer and Prof. Dr. Peter W. Roesky

      Article first published online: 4 APR 2012 | DOI: 10.1002/anie.201109109

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      Easy come, easy go: The first molecular SO2 complexes of the lanthanides (Ln=Sm, Eu) have been prepared. The compounds can reversibly coordinate gaseous SO2. Concomitant with the addition and removal of SO2, the color of the complexes changes reversibly (see scheme). The structures of the SO2 compounds could be confirmed in solution and in the solid state.

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