Angewandte Chemie International Edition

Cover image for Vol. 52 Issue 11

March 11, 2013

Volume 52, Issue 11

Pages 3037–3279

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Author Profile
    6. News
    7. Book Reviews
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    1. You have free access to this content
      Cover Picture: Expression of Fluorescent Cyclotides using Protein Trans-Splicing for Easy Monitoring of Cyclotide–Protein Interactions (Angew. Chem. Int. Ed. 11/2013) (page 3037)

      Dr. Krishnappa Jagadish, Dr. Radhika Borra, Vanessa Lacey, Subhabrata Majumder, Dr. Alexander Shekhtman, Dr. Lei Wang and Dr. Julio A. Camarero

      Article first published online: 21 FEB 2013 | DOI: 10.1002/anie.201301068

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      Cyclotides are natural microproteins found in plants with a head-to-tail circular Cys-knotted topology. In their Communication on page 3126 ff., J. A. Camarero et al. show the recombinant production of a fluorescently labeled cyclotide inside live bacterial cells. Grown in the presence of p-azidophenylalanine and a dibenzocyclooctyne derivative of the fluorescent dye aminomethylcoumarin acetate (AMCA) the peptide is labeled in vivo. Cover art: Isaac Mora.

    2. You have free access to this content
      Inside Cover: A Rare Uranyl(VI)–Alkyl Ate Complex [Li(DME)1.5]2[UO2(CH2SiMe3)4] and Its Comparison with a Homoleptic Uranium(VI)–Hexaalkyl (Angew. Chem. Int. Ed. 11/2013) (page 3038)

      Dr. Lani A. Seaman, Dr. Peter Hrobárik, Michael F. Schettini, Dr. Skye Fortier, Prof. Dr. Martin Kaupp and Prof. Dr. Trevor W. Hayton

      Article first published online: 21 FEB 2013 | DOI: 10.1002/anie.201301041

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      A rare uranyl–alkyl “ate” complex was prepared for comparison with a homoleptic UVI–hexaalkyl. In their Communication on page 3259 ff., P. Hrobárik, T. Hayton, et al. demonstrate that both complexes feature unprecedented high-frequency methylene 13C shifts, consistent with large spin-orbit effects. Relativistic calculations show that the cause is significant f-orbital involvement in σ-bonding.

    3. You have free access to this content
      Inside Back Cover: Ultrafast Damage Following Radiation-Induced Oxidation of Uracil in Aqueous Solution (Angew. Chem. Int. Ed. 11/2013) (page 3281)

      Dr. Pablo López-Tarifa, Prof. Marie-Pierre Gaigeot, Prof. Rodolphe Vuilleumier, Dr. Ivano Tavernelli, Prof. Manuel Alcamí, Prof. Fernando Martín, Dr. Marie-Anne Hervé du Penhoat and Dr. Marie-Françoise Politis

      Article first published online: 4 MAR 2013 | DOI: 10.1002/anie.201301279

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      Of primary cosmic rays, about 99% are nuclei of the most abundant atoms (H, He, Fe). These ions induce multiple ionization events in biomaterials that lead to the Coulombic explosion of biomolecules. In their Communication on page 3160 ff., M.-A. Hervé du Penhoat, M.-F. Politis, et al. use first-principle molecular dynamics to examine the hydroxylation of uracil by an ionized water molecule. The film shows snapshots taken along the picosecond timescale of this reaction.

    4. You have free access to this content
      Back Cover: Supramolecular Velcro for Reversible Underwater Adhesion (Angew. Chem. Int. Ed. 11/2013) (page 3282)

      Youngjoo Ahn, Yoonjung Jang, Dr. Narayanan Selvapalam, Gyeongwon Yun and Prof. Dr. Kimoon Kim

      Article first published online: 21 FEB 2013 | DOI: 10.1002/anie.201301043

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      Underwater supramolecular velcro exhibiting strong and reversible adhesion was achieved using a synthetic ultrahigh-affinity host–guest binding pair of cucurbit[7]uril (CB[7]) and aminomethylferrocene (Fc). In their Communication on page 3140 ff., K. Kim et al. show that the CB[7] loops and Fc hooks anchored on different surfaces adhere robustly under water without the need for curing agents, and the adhesion is mechanically and chemically reversible.

  2. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Author Profile
    6. News
    7. Book Reviews
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    1. Graphical Abstract: Angew. Chem. Int. Ed. 11/2013 (pages 3041–3054)

      Article first published online: 7 MAR 2013 | DOI: 10.1002/anie.201390010

  3. News

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Author Profile
    6. News
    7. Book Reviews
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
  4. Author Profile

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Author Profile
    6. News
    7. Book Reviews
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    1. Zhenyang Lin (page 3062)

      Article first published online: 26 OCT 2012 | DOI: 10.1002/anie.201208007

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      “In a spare hour, I chat with friends. If I could be anyone for a day, I would be a poet …” This and more about Zhenyang Lin can be found on page 3062.

  5. News

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Author Profile
    6. News
    7. Book Reviews
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
  6. Book Reviews

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Author Profile
    6. News
    7. Book Reviews
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    1. Ionic Liquids in Biotransformations and Organocatalysis. Solvents and Beyond. Edited by Pablo Domínguez de María. (pages 3065–3066)

      Fred van Rantwijk

      Article first published online: 10 FEB 2013 | DOI: 10.1002/anie.201208217

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      John Wiley & Sons, Hoboken, 2012. 435 pp., hardcover, € 120.00.—ISBN 978-0470569047

    2. Inventing Chemistry. Herman Boerhaave and the Reform of the Chemical Arts. By John C. Powers. (pages 3066–3067)

      Jan Reedijk

      Article first published online: 5 FEB 2013 | DOI: 10.1002/anie.201209217

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      University of Chicago Press, Chicago, 2012. 272 pp., hardcover, $ 40.00.—ISBN 978-0226677606

  7. Highlights

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Author Profile
    6. News
    7. Book Reviews
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    1. PN Chemistry

      Stabilized Transient R2PN Species (pages 3068–3070)

      Prof. Dr. Axel Schulz and Dr. Alexander Villinger

      Article first published online: 13 FEB 2013 | DOI: 10.1002/anie.201208533

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      Finally isolated: The isolation of a nitridophosphane(V) was described for the first time by the research group of Bertrand. The reactivity and the possibility of stabilizing labile R2PN/R2NP species (see structure) are discussed.

    2. Venoms to Drugs

      Peptides from Mamba Venom as Pain Killers (pages 3071–3073)

      Prof. David J. Craik and Christina I. Schroeder

      Article first published online: 4 FEB 2013 | DOI: 10.1002/anie.201209851

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      The black mamba snake here illustrates the structure of mambaglin-1, a pain-relieving peptide found in its venom. Thick gray lines lines represent the four disulfide bonds linking Cys1–3, 2–4, 5–6, and 7–8. The N-terminus of the 57 amino acid peptide is at the head of the snake and the C-terminus at the tail. The peptide has potential as a pharmacological probe or drug lead. Image design by David Craik and drawing by Peta Harvey, University of Queensland.

  8. Minireview

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Author Profile
    6. News
    7. Book Reviews
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    1. Green Solvents

      Low-Transition-Temperature Mixtures (LTTMs): A New Generation of Designer Solvents (pages 3074–3085)

      Dr. María Francisco, M.Sc. Adriaan van den Bruinhorst and Prof. Dr. Maaike C. Kroon

      Article first published online: 10 FEB 2013 | DOI: 10.1002/anie.201207548

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      Liquefaction: LTTMs are promising “green” media for multiple applications, including separation processes. They can be formed by mixing high-melting-point starting materials, which form a liquid as a result of hydrogen-bond interactions (see picture). Among LTTMs, deep-eutectic solvents (DESs) are presented as renewable, biodegradable, and cost-effective alternatives to conventional ionic liquids (ILs).

  9. Review

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Author Profile
    6. News
    7. Book Reviews
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    1. Polymer Dots

      Highly Fluorescent Semiconducting Polymer Dots for Biology and Medicine (pages 3086–3109)

      Prof. Changfeng Wu and Prof. Daniel T. Chiu

      Article first published online: 10 JAN 2013 | DOI: 10.1002/anie.201205133

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      On the dot: As a new class of fluorescent nanoparticles, semiconducting polymer dots, exhibit excellent characteristics such as extraordinary fluorescence brightness, fast emission rates, excellent photostability, nonblinking, and nontoxicity. This review summarizes recent advances of the polymer dots as nanoparticle labels for biological and medical applications (see figure).

  10. Communications

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Author Profile
    6. News
    7. Book Reviews
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    1. Oxygen Reduction

      Two-Step Boron and Nitrogen Doping in Graphene for Enhanced Synergistic Catalysis (pages 3110–3116)

      Yao Zheng, Dr. Yan Jiao, Lei Ge, Prof. Mietek Jaroniec and Prof. Shi Zhang Qiao

      Article first published online: 22 JAN 2013 | DOI: 10.1002/anie.201209548

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      Don't be a dope: be a double dope! Graphene was doped with both boron and nitrogen at well-defined doping sites to induce a synergistic effect that boosts its catalytic activity for oxygen reduction (see structure). The excellent catalytic performance of the new metal-free catalyst is comparable to that of commercial Pt/C.

    2. Molecular Electronics

      Azaborine Compounds for Organic Field-Effect Transistors: Efficient Synthesis, Remarkable Stability, and BN Dipole Interactions (pages 3117–3120)

      Xiao-Ye Wang, Hao-Ran Lin, Ting Lei, Dong-Chu Yang, Fang-Dong Zhuang, Dr. Jie-Yu Wang, Prof. Si-Chun Yuan and Prof. Jian Pei

      Article first published online: 10 FEB 2013 | DOI: 10.1002/anie.201209706

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      Boron–nitrogen units were incorporated into thiophene-fused polycyclic aromatic compounds. Organic field-effect transistors based on these azaborine compounds were fabricated, demonstrating a novel engineering concept of organic semiconductors and providing opportunities of a broad class of BN-containing compounds for application in future organic electronic devices (see picture; μFET=hole mobility).

    3. Peptide Nanoconjugation

      Orientation-Controlled Conjugation of Haloalkane Dehalogenase Fused Homing Peptides to Multifunctional Nanoparticles for the Specific Recognition of Cancer Cells (pages 3121–3125)

      Dr. Serena Mazzucchelli, Dr. Miriam Colombo, Paolo Verderio, Ewa Rozek, Francesco Andreata, Elisabetta Galbiati, Prof. Paolo Tortora, Prof. Fabio Corsi and Dr. Davide Prosperi

      Article first published online: 5 FEB 2013 | DOI: 10.1002/anie.201209662

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      In control: The ligand positioning and orientation on multifunctional nanoparticles (MNP) are controlled by using a versatile bimodular approach that exploits an 11 amino acid (U11) homing peptide genetically fused with a haloalkane dehalogenase (HALO) enzyme. The resultant nanoparticles have good targeting efficiency and selectivity toward broadly occurring urokinase plasminogen activator receptor positive human cancer cells.

    4. Cyclic Peptides

      Expression of Fluorescent Cyclotides using Protein Trans-Splicing for Easy Monitoring of Cyclotide–Protein Interactions (pages 3126–3131)

      Dr. Krishnappa Jagadish, Dr. Radhika Borra, Vanessa Lacey, Subhabrata Majumder, Dr. Alexander Shekhtman, Dr. Lei Wang and Dr. Julio A. Camarero

      Article first published online: 15 JAN 2013 | DOI: 10.1002/anie.201209219

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      Going in circles: Expression of cyclotides containing non-natural amino acids (see scheme; gray sphere) inside live bacterial cells was accomplished using a highly efficient split intein in combination with nonsense codon suppressor tRNA technology. Cyclotides containing p-azidophenylalanine can be expressed in live bacterial cells and easily labeled using copper-free click chemistry to monitor the cyclotide–protein interactions.

    5. Phosphenium Dications

      A Carbone-Stabilized Two-Coordinate Phosphorus(III)-Centered Dication (pages 3132–3135)

      Madelyn Qin Yi Tay, Dr. Yunpeng Lu, Dr. Rakesh Ganguly and Dr. Dragoslav Vidović

      Article first published online: 31 JAN 2013 | DOI: 10.1002/anie.201209223

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      A coordinatively unsaturated dicationic phosphorus compound has been synthesized and characterized (see structure; P pink, N blue, C gray). DFT calculations revealed that the polycation should show superior Lewis acid and σ-donor properties to the corresponding bis(dimethylamino)phosphenium cations. Preliminary investigations with PMe3 confirmed unusual reactivity patterns for the dication.

    6. Hybrid-Peptide Helices

      Promotion of Folding in Hybrid Peptides through Unconstrained γ Residues: Structural Characterization of Helices in (αγγ)n and (αγα)n Sequences (pages 3136–3139)

      Krishnayan Basuroy, Bhimareddy Dinesh, Prof. Narayanaswamy Shamala and Prof. Padmanabhan Balaram

      Article first published online: 4 FEB 2013 | DOI: 10.1002/anie.201209324

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      The γ-amino acid residue γ4(R)Val promotes helical folding even in short (αγα)n sequences. A mixed C12/C14 helix (in which hydrogen bonds close a ring of 12 or 14 atoms) is established in a 12-residue (αγγ)4 sequence (see picture, right). The 6-residue (αγα)2 sequence (left), devoid of backbone conformational constraints, folds into a C12/C10 helix.

    7. Supramolecular Chemistry

      Supramolecular Velcro for Reversible Underwater Adhesion (pages 3140–3144)

      Youngjoo Ahn, Yoonjung Jang, Dr. Narayanan Selvapalam, Gyeongwon Yun and Prof. Dr. Kimoon Kim

      Article first published online: 4 FEB 2013 | DOI: 10.1002/anie.201209382

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      Sticky job: Excellent underwater adhesion with remarkable mechanical and chemical reversibility has been demonstrated with a supramolecular velcro using host–guest chemistry and multivalent interactions (see scheme). Silicon surfaces (blue) functionalized with cucurbit[7]uril (CB[7]) hosts and aminomethylferrocene (Fc) guests adhere under water because of their extraordinarily high affinity.

    8. Protein NMR Spectroscopy

      You have full text access to this OnlineOpen article
      Probing Arginine Side-Chains and Their Dynamics with Carbon-Detected NMR Spectroscopy: Application to the 42 kDa Human Histone Deacetylase 8 at High pH (pages 3145–3147)

      Dr. Nicolas D. Werbeck, Dr. John Kirkpatrick and Dr. D. Flemming Hansen

      Article first published online: 10 FEB 2013 | DOI: 10.1002/anie.201209385

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      Arginine side-chains play a distinct role because of their high pKa and perpetual positive charge. An NMR method is presented, based on carbon-detected 13Cζ15Nε correlation spectra, which allows probing the arginine side-chains and their dynamics at neutral-to-high pH. The methodology is demonstrated on human histone deacetylase 8.

    9. Medicinal Chemistry

      Chemical Interrogation of Drug/RNA Complexes: From Chemical Reactivity to Drug Design (pages 3148–3151)

      Ester Jiménez-Moreno, Irene Gómez-Pinto, Dr. Francisco Corzana, Dr. Andrés G. Santana, Dr. Julia Revuelta, Dr. Agatha Bastida, Dr. Jesus Jiménez-Barbero, Dr. Carlos González and Dr. Juan Luis Asensio

      Article first published online: 7 FEB 2013 | DOI: 10.1002/anie.201209434

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      When you're in a (RNA) bind: An NMR-based method to explore the reactivity of ligand/RNA complexes can be used as source of valuable information for drug design. By combining NMR spectroscopy and a simple isotopic labeling strategy (see picture), positional chemical reactivity information can be readily extracted from complex aminoglycoside mixtures. C green, N blue, O red, Me purple.

    10. Quantum Interference

      Signatures of Quantum Interference Effects on Charge Transport Through a Single Benzene Ring (pages 3152–3155)

      Dr. Carlos R. Arroyo, Dr. Simge Tarkuc, Riccardo Frisenda, Dr. Johannes S. Seldenthuis, Charlotte H. M. Woerde, Dr. Rienk Eelkema, Dr. Ferdinand C. Grozema and Prof. Dr. Herre S. J. van der Zant

      Article first published online: 5 FEB 2013 | DOI: 10.1002/anie.201207667

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      Molecular electronics: Charge transport through a single benzene ring is studied using the mechanically controlled break-junction technique. The low-bias conductance for a meta-coupled benzene ring is more than an order of magnitude smaller than that of a para-coupled benzene ring. This difference can be explained by a destructive quantum interference effects in the meta-coupled benzene (see picture).

    11. Theoretical Chemistry

      Probing the Synthesis of Two-Dimensional Boron by First-Principles Computations (pages 3156–3159)

      Yuanyue Liu, Dr. Evgeni S. Penev and Prof. Boris I. Yakobson

      Article first published online: 28 JAN 2013 | DOI: 10.1002/anie.201207972

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      Boron synthesis, in theory: Although two-dimensional boron sheets have attracted considerable interest because of their theoretically predicted properties, synthesis of such sheets remains a challenge. The feasibility of different synthetic methods for two-dimensional boron sheets (see picture; red) was assessed using first-principles calculations, possibly paving the way towards its application in nanoelectronics.

    12. Oxidative DNA Damage

      Ultrafast Damage Following Radiation-Induced Oxidation of Uracil in Aqueous Solution (pages 3160–3163)

      Dr. Pablo López-Tarifa, Prof. Marie-Pierre Gaigeot, Prof. Rodolphe Vuilleumier, Dr. Ivano Tavernelli, Prof. Manuel Alcamí, Prof. Fernando Martín, Dr. Marie-Anne Hervé du Penhoat and Dr. Marie-Françoise Politis

      Article first published online: 25 JAN 2013 | DOI: 10.1002/anie.201208038

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      Coulombic explosion of uracil: Ionizing radiation is used in cancer therapy to induce molecular damage in cells. Ab initio molecular dynamics were used to probe the early dissociation processes and ensuing chemical reactions following selective ionization of either uracil or the surrounding water molecules (see scheme; C gray, N blue, O red, H white).

    13. Bionanomaterials

      Stable Aqueous Dispersions of Glycopeptide-Grafted Selectably Functionalized Magnetic Nanoparticles (pages 3164–3167)

      Tushar Borase, Dr. Tsedev Ninjbadgar, Antonios Kapetanakis, Dr. Sandra Roche, Dr. Robert O'Connor, Dr. Christian Kerskens, Dr. Andreas Heise and Dr. Dermot F. Brougham

      Article first published online: 1 FEB 2013 | DOI: 10.1002/anie.201208099

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      Sweet nanomagnets: Suspensions of glycopeptide grafted magnetic nanoparticles can be produced by N-carboxyanhydride ring-opening polymerization with subsequent click glycosylation. The resulting materials have a high sugar density, optimal dispersion and T1-weighted MRI properties, and bio-recognition ability. The approach can be used to attach any type or combination of functional groups, the density of which is not limited by particle surface area.

    14. DNAzyme Biosensor

      A Plasmonic DNAzyme Strategy for Point-of-Care Genetic Detection of Infectious Pathogens (pages 3168–3171)

      Kyryl Zagorovsky and Dr. Warren C. W. Chan

      Article first published online: 10 FEB 2013 | DOI: 10.1002/anie.201208715

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      Always use detection: Signal amplification from DNAzymes (see scheme) was combined with gold nanoparticles (GNPs) to give a simple and sensitive colorimetric assay for various genetic targets. The assay has 50 pM sensitivity without the need for purification steps and can detect multiple targets in parallel. This was applied to rapidly detect gonorrhea, syphilis, malaria, and hepatitis B infections.

    15. Carborane Ligands

      Perhalogenated Carba-closo-dodecaborate Anions as Ligand Substituents: Applications in Gold Catalysis (pages 3172–3176)

      Prof. Dr. Vincent Lavallo, James H. Wright II, Dr. Fook S. Tham and Sean Quinlivan

      Article first published online: 13 FEB 2013 | DOI: 10.1002/anie.201209107

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      Bigger and better! The single-component zwitterionic gold catalyst formed by the coordination of a phosphine ligand bearing an inert and noncoordinating carborane substituent, CB11Cl11, to an AuI ion exhibited the highest reported activity for the hydroamination of alkynes with amines (see scheme). The highest turnover number observed for hydroamination with this catalyst exceeded a stunning 95 000.

    16. Graphene Biofunctionalization

      Preservation of Antibody Selectivity on Graphene by Conjugation to a Tripod Monolayer (pages 3177–3180)

      Jason A. Mann, Dr. Thomas Alava, Prof. Dr. Harold G. Craighead and Prof. Dr. William R. Dichtel

      Article first published online: 5 FEB 2013 | DOI: 10.1002/anie.201209149

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      Three is a magic number: Antibodies adsorbed on bare graphene lose their ability to recognize antigens. However, this obstacle can be overcome by the conjugation of these antibodies to self-assembled monolayers of a tripodal compound (see picture).

    17. Conformational Dynamics

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      Mapping the Population of Protein Conformational Energy Sub-States from NMR Dipolar Couplings (pages 3181–3185)

      Dr. Paul Guerry, Dr. Loïc Salmon, Dr. Luca Mollica, Dr. Jose-Luis Ortega Roldan, Dr. Phineus Markwick, Prof. Nico A. J. van Nuland, Prof. J. Andrew McCammon and Dr. Martin Blackledge

      Article first published online: 1 FEB 2013 | DOI: 10.1002/anie.201209669

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      Molecular dynamics: A general method for the statistical mechanical description of conformational energy landscapes of proteins in solution is proposed. This method combines NMR residual dipolar couplings (RDCs), sampling of conformational space using accelerated molecular dynamics simulation, and ensemble selection using model-free ensemble interpretation of RDCs (see picture).

    18. DNA Photoswitches

      Nucleoside-Based Diarylethene Photoswitches and Their Facile Incorporation into Photoswitchable DNA (pages 3186–3190)

      Dr. Hana Cahová and Prof. Dr. Andres Jäschke

      Article first published online: 12 FEB 2013 | DOI: 10.1002/anie.201209943

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      Come into the light: Pyrimidine nucleosides were found to undergo fast and reversible ring closure upon irradiation with light when covalently attached to 2-[2-methyl-5-phenylthien-3-yl]cyclopent-1-ene (see scheme). Synthesis using an aqueous-phase Suzuki–Miyaura cross-coupling allows for one-step conversion of iodo-modified oligonucleotides into fully reversible DNA photoswitches.

    19. Total Synthesis

      Total Synthesis of Linoxepin through a Palladium-Catalyzed Domino Reaction (pages 3191–3194)

      Prof. Dr. Lutz F. Tietze, Dipl.-Chem. Svenia-C. Duefert, Dr. Jérôme Clerc, Dr. Matthias Bischoff, Dipl.-Chem. Christian Maaß and Prof. Dr. Dietmar Stalke

      Article first published online: 12 FEB 2013 | DOI: 10.1002/anie.201209868

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      Convergent and elegant: Linoxepin (see picture), a new lignan with an unusual oxepin moiety, has been synthesized in only 10 steps. The protecting-group-free total synthesis includes a palladium- catalyzed Sonogashira reaction and a domino carbopalladation/Heck reaction of an allylsilane.

    20. Synthetic Methods

      Protecting-Group-Free Diastereoselective C[BOND]C Coupling of 1,3-Glycols and Allyl Acetate through Site-Selective Primary Alcohol Dehydrogenation (pages 3195–3198)

      Dr. Anne-Marie R. Dechert-Schmitt, Dr. Daniel C. Schmitt and Prof. Michael J. Krische

      Article first published online: 31 JAN 2013 | DOI: 10.1002/anie.201209863

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      Safe from protection! A pronounced kinetic preference for primary alcohol dehydrogenation enables the site-selective iridium catalyzed C[BOND]C coupling of polyols with allyl acetate in the absence of protecting groups, premetallated reagents, chiral auxiliaries, and discrete alcohol-to-aldehyde oxidation.

    21. Analytical Methods

      Quantitative Interpretation of Diffusion-Ordered NMR Spectra: Can We Rationalize Small Molecule Diffusion Coefficients? (pages 3199–3202)

      Dr. Robert Evans, Zhaoxia Deng, Alexandria K. Rogerson, Dr. Andy S. McLachlan, Jeff J. Richards, Dr. Mathias Nilsson and Prof. Gareth A. Morris

      Article first published online: 31 JAN 2013 | DOI: 10.1002/anie.201207403

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      Appealingly simple: A new method is described that allows the diffusion coefficient of a small molecule to be estimated given only the molecular weight and the viscosity of the solvent used. This method makes possible the quantitative interpretation of the diffusion domain of diffusion-ordered NMR spectra (see picture).

    22. Homogeneous Catalysis

      Copper-Catalyzed Hydrodefluorination of Fluoroarenes by Copper Hydride Intermediates (pages 3203–3207)

      Hongbin Lv, Yuan-Bo Cai and Prof. Dr. Jun-Long Zhang

      Article first published online: 10 FEB 2013 | DOI: 10.1002/anie.201208364

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      Breaking bad: Efficient copper-catalyzed C[BOND]F bond activation has been achieved by replacing fluorine with hydrogen. A copper hydride is proposed as the active intermediate, which proceeds through a nucleophilic attack on the fluorocarbon, as determined by experimental and theoretical results (see structure; C gray, H white, Cu light red, F light blue; distances in Å).

    23. Dual Catalysis

      Copper/Palladium-Catalyzed 1,4 Reduction and Asymmetric Allylic Alkylation of α,β-Unsaturated Ketones: Enantioselective Dual Catalysis (pages 3208–3212)

      Fady Nahra, Dr. Yohan Macé, Dr. Dominique Lambin and Prof. Olivier Riant

      Article first published online: 4 FEB 2013 | DOI: 10.1002/anie.201208612

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      Cooperative efforts: The catalytic coupling of the two organometallic intermediates is possible through a Cu/Pd-based dual catalysis (see scheme; LG=leaving group), in which the CuI catalytic cycle generates catalytically the starting material for the Pd0 catalytic cycle. Although reagents are present in stoichiometric amounts in the reaction mixture and are able to trap both active species, the desired reaction proceeds as planned.

    24. Regioselective Catalysis

      Cobalt-Catalyzed C4-Selective Direct Alkylation of Pyridines (pages 3213–3216)

      Dr. Takashi Andou, Yutaka Saga, Hirotomo Komai, Dr. Shigeki Matsunaga and Prof. Dr. Motomu Kanai

      Article first published online: 1 FEB 2013 | DOI: 10.1002/anie.201208666

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      How pyridine got its tail: A new catalyst for the atom-economical C4-selective direct alkylation of pyridines is described. A combination of CoBr2 and LiBEt3H catalyzes the reaction of pyridines with 1-alkenes at 70 °C to give alkylation products with C4/C2 ratios of >20:1. Substrate/catalyst ratios of up to 4000, and a turnover number of 3440 were achieved.

    25. Homogeneous Catalysis

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      Palladium-Catalyzed Oxidative Acyloxylation/Carbocyclization of Allenynes (pages 3217–3221)

      Dr. Youqian Deng and Prof. Dr. Jan-E. Bäckvall

      Article first published online: 5 FEB 2013 | DOI: 10.1002/anie.201208718

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      New bonds: The title reaction provides access to synthetically useful acyloxylated vinylallenes where a new C[BOND]C bond, a new C[BOND]O bond, and a new allene structure are formed. Furthermore, an aerobic version of this transformation was realized using catalytic amounts of p-benzoquinone (BQ) together with catalytic amounts of cobalt salophen.

    26. Metallaboranes

      Boron Beyond the Icosahedral Barrier: A 16-Vertex Metallaborane (pages 3222–3226)

      Dipak Kumar Roy, Dr. Shubhankar Kumar Bose, R. S. Anju, Bijan Mondal, V. Ramkumar and Prof. Sundargopal Ghosh

      Article first published online: 4 FEB 2013 | DOI: 10.1002/anie.201208849

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      A neutral metallaborane comprising a Rh4B12 polyhedron with icosioctahedron geometry with 16 vertices and 28 triangular faces was prepared (see structure; Rh: red, B: green). The cage has the shape of a 12-membered truncated tetrahedron with four capped hexagonal faces.

    27. Metal–Metal Bonding

      Interconversion of Quadruply and Quintuply Bonded Molybdenum Complexes by Reductive Elimination and Oxidative Addition of Dihydrogen (pages 3227–3231)

      Mario Carrasco, Natalia Curado, Dr. Celia Maya, Dr. Riccardo Peloso, Dr. Amor Rodríguez, Prof. Eliseo Ruiz, Prof. Santiago Alvarez and Prof. Ernesto Carmona

      Article first published online: 1 FEB 2013 | DOI: 10.1002/anie.201209064

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      Five plus H2 gives four: UV irradiation of a bis(amidinate) complex with a [(H)Mo[QUAD BOND]Mo(H)] core induces reductive elimination of H2 and formation of a known quintuply bonded Mo[BOND]Mo species (see scheme) that reacts back with H2 to restore [(H)Mo[QUAD BOND]Mo(H)]. UV irradiation of the bis(hydride) species in benzene and toluene gives arene complexes in which the aromatic hydrocarbon bridges the molybdenum atoms. Dipp=2,6-diisopropylphenyl.

    28. Gas Separation

      Stabilization of Low-Temperature Degradation in Mixed Ionic and Electronic Conducting Perovskite Oxygen Permeation Membranes (pages 3232–3236)

      Yan Liu, Dr. Xuefeng Zhu, Dr. Mingrun Li, Huanyin Liu, You Cong and Prof. Dr. Weishen Yang

      Article first published online: 10 FEB 2013 | DOI: 10.1002/anie.201209077

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      An important degradation mechanism of perovskite membranes is related to the operation-induced surface segregation of trace impurities of sulfur that appears to dramatically impact the low-temperature permeation behavior. A simple but remarkably effective method is reported that enables the low-temperature stabilization of the permeation flux in these perovskite membranes (see picture).

    29. Heterocycles

      Rhodium- and Platinum-Catalyzed [4+3] Cycloaddition with Concomitant Indole Annulation: Synthesis of Cyclohepta[b]indoles (pages 3237–3240)

      Dongxu Shu, Wangze Song, Xiaoxun Li and Prof. Dr. Weiping Tang

      Article first published online: 10 FEB 2013 | DOI: 10.1002/anie.201209266

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      Various substituted cyclohepta[b]indoles were prepared from propargylic ethers and dienes by a tandem indole annulation/[4+3] cycloaddition (see scheme; Boc=tert-butoxycarbonyl). Both acyclic and cyclic dienes participated in the [4+3] cycloaddition to afford tri- and tetracyclic products, respectively. Electron-deficient phosphine or phosphite ligands facilitated the tandem reaction.

    30. Photoelectrochemical Water Splitting

      Boron Carbides as Efficient, Metal-Free, Visible-Light-Responsive Photocatalysts (pages 3241–3245)

      Jikai Liu, Dr. Shuhao Wen, Dr. Yang Hou, Dr. Fan Zuo, Prof. Gregory J. O. Beran and Prof. Pingyun Feng

      Article first published online: 28 JAN 2013 | DOI: 10.1002/anie.201209363

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      From armor plating to photocatalysis: Two photocatalysts based on boron carbides, B4.3C and B13C2, are reported. The more stable and efficient B4.3C exhibits H2 evolution rates of about two orders of magnitude higher than graphitic C3N4, and without the need for noble metal cocatalysts. Also, both materials can act as photocathodes for photoelectrochemical water reduction under visible light irradiation.

    31. C[BOND]H Activation

      Palladium- and Copper-Catalyzed Stereocontrolled Direct C[BOND]H Fluoroalkenylation of Heteroarenes using gem-Bromofluoroalkenes (pages 3246–3249)

      Dr. Cédric Schneider, Daniela Masi, Dr. Samuel Couve-Bonnaire, Prof. Xavier Pannecoucke and Prof. Christophe Hoarau

      Article first published online: 30 JAN 2013 | DOI: 10.1002/anie.201209446

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      A gem of a reaction: The palladium- and copper-catalyzed base-assisted direct C[BOND]H fluoroalkenylation of heterocycles 1 with gem-bromofluoroalkenes (E)-2 is reported. This method offers step-economical and stereocontrolled access to valuable trisubstituted heteroarylated monofluoroalkenes (Z)-3.

    32. Indole Chemistry

      Highly Enantioselective Friedel–Crafts Alkylation/N-Hemiacetalization Cascade Reaction with Indoles (pages 3250–3254)

      Hong-Gang Cheng, Dr. Liang-Qiu Lu, Tao Wang, Qing-Qing Yang, Xiao-Peng Liu, Yang Li, Qiao-Hui Deng, Prof. Dr. Jia-Rong Chen and Prof. Dr. Wen-Jing Xiao

      Article first published online: 10 FEB 2013 | DOI: 10.1002/anie.201209998

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      A new ring for your indole: An unprecedented copper-catalyzed enantioselective Friedel–Crafts alkylation/N-hemiacetalization cascade reaction with indoles and β,γ-unsaturated α-ketoesters is reported. This mild strategy provides new access to various synthetically and biologically important 2,3-dihydro-1H-pyrrolo[1,2-a]indoles in a highly enantioselective manner.

    33. NMR Spectroscopy

      Determination of Labile Chiral Supramolecular Ion Pairs by Chromatographic NMR Spectroscopy (pages 3255–3258)

      Manjunatha Reddy G. N., Rafael Ballesteros-Garrido, Prof. Jérôme Lacour and Prof. Stefano Caldarelli

      Article first published online: 30 JAN 2013 | DOI: 10.1002/anie.201209616

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      Chiral recognition: Silica-enhanced NMR diffusometry can distinguish the signals of diastereoisomeric mixtures of supramolecular ion pairs (see picture; DOSY=diffusion-ordered spectroscopy). The experiment has a shorter timescale than liquid chromatography, thus allowing an easier characterization of species that are even configurationally labile on the minutes timescale.

    34. Uranium Chemistry

      A Rare Uranyl(VI)–Alkyl Ate Complex [Li(DME)1.5]2[UO2(CH2SiMe3)4] and Its Comparison with a Homoleptic Uranium(VI)–Hexaalkyl (pages 3259–3263)

      Dr. Lani A. Seaman, Dr. Peter Hrobárik, Michael F. Schettini, Dr. Skye Fortier, Prof. Dr. Martin Kaupp and Prof. Dr. Trevor W. Hayton

      Article first published online: 12 FEB 2013 | DOI: 10.1002/anie.201209611

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      A rare tetraalkyl–uranyl “ate” complex 1 was prepared and characterized for comparison with a UVI–hexaalkyl complex 2. Both 1 and 2 feature unprecedented high-frequency methylene 13C NMR shifts (see picture). That of complex 2 constitutes a new record for diamagnetic mononuclear complexes. Relativistic DFT calculations show that these extreme shifts are due to spin–orbit effects, a consequence of significant f-orbital involvement in the U[BOND]C bond.

    35. Ligand Effects

      Molecular Dynamics and Ligand Exchange in Magnesium Complexes: Evidence for both Dissociative and Associative Ligand Exchange (pages 3264–3266)

      Prof. Malcolm H. Chisholm, Kittisak Choojun, Dr. Albert S. Chow and Prof. Gideon Fraenkel

      Article first published online: 22 FEB 2013 | DOI: 10.1002/anie.201209542

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      Making a swap: The titled studies provide substantial evidence for the kinetically labile Mg2+ ion reacting through both a dissociative (see scheme; thf=tetrahydrofuran) and an associative interchange mechanism. The findings are particularly relevant to the reactions involving [LMgnBu(thf)] and rac-lactide in ring-opening polymerization reactions.

    36. C-H Functionalization

      Direct Selective Oxidative Cross-Coupling of Simple Alkanes with Heteroarenes (pages 3267–3271)

      Dr. Andrey P. Antonchick and Lars Burgmann

      Article first published online: 31 JAN 2013 | DOI: 10.1002/anie.201209584

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      A dream reaction: An efficient and practical method for the oxidative cross-coupling of heteroaromatic compounds and simple alkanes has been developed. The desired products are smoothly and regioselectively formed under mild reaction conditions at ambient temperature in a hypervalent-iodine-mediated transformation. The method allows for preferential transformation of stronger Cinline image[BOND]H bonds in the presence of weaker Cinline image[BOND]H bonds under metal-free conditions.

    37. Natural Product Synthesis

      Palladium-Catalyzed Decarboxylative Vinylation of Potassium Nitrophenyl Acetate: Application to the Total Synthesis of (±)-Goniomitine (pages 3272–3276)

      Dr. Zhengren Xu, Dr. Qian Wang and Prof. Dr. Jieping Zhu

      Article first published online: 7 FEB 2013 | DOI: 10.1002/anie.201209970

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      Merge and divert: The natural product (±)-goniomitine was synthesized by a method featuring two key steps: 1) fragment coupling to a functionalized cyclopentene by a novel palladium-catalyzed decarboxylative vinylation reaction and 2) an unprecedented one-pot integrated oxidation/reduction/cyclization (IORC) process to convert the substituted cyclopentene into the tetracyclic skeleton of goniomitine with high chemo-, regio-, and diastereoselectivity.

    38. Biotransformations

      You have full text access to this OnlineOpen article
      One-Pot Deracemization of sec-Alcohols: Enantioconvergent Enzymatic Hydrolysis of Alkyl Sulfates Using Stereocomplementary Sulfatases (pages 3277–3279)

      Markus Schober, Michael Toesch, Dr. Tanja Knaus, Dr. Gernot A. Strohmeier, Dr. Bert van Loo, Dr. Michael Fuchs, Prof. Florian Hollfelder, Prof. Peter Macheroux and Prof. Kurt Faber

      Article first published online: 10 FEB 2013 | DOI: 10.1002/anie.201209946

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      Hand in hand: The title transformation was achieved using a pair of sulfatases acting through inversion and retention of configuration on opposite substrate enantiomers. Using Pseudomonas aeruginosa arylsulfatase PAS with alkylsulfatase PISA1 in one-pot leads to sec-alcohols (80 to >99 % conversion) with 91 to greater than 99 % ee.

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