Angewandte Chemie International Edition

Cover image for Vol. 53 Issue 24

June 10, 2014

Volume 53, Issue 24

Pages 6009–6275

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Correspondence
    11. Review
    12. Communications
    1. You have free access to this content
      Cover Picture: Cytoskeletal Actin Dynamics are Involved in Pitch-Dependent Neurite Outgrowth on Bead Monolayers (Angew. Chem. Int. Ed. 24/2014) (page 6009)

      Dr. Kyungtae Kang, Seo Young Yoon, Sung-Eun Choi, Mi-Hee Kim, Matthew Park, Prof. Dr. Yoonkey Nam, Prof. Dr. Jin Seok Lee and Prof. Dr. Insung S. Choi

      Article first published online: 15 APR 2014 | DOI: 10.1002/anie.201401146

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      Pitch-dependent neurite outgrowth was demonstrated in primary hippocampal neurons on monolayers of silica beads. In their Communication on page 6075 ff., Y. Nam, J. S. Lee, I. S. Choi, and co-workers report that neurite outgrowth is accelerated on larger beads (white) compared to smaller beads (black) up to a bead diameter of approximately 1 μm. Biochemical analysis indicated that cytoskeletal actin dynamics are primarily responsible for the recognition of surface topography.

    2. You have free access to this content
      Inside Cover: Oxidation Monitoring by Fluorescence Spectroscopy Reveals the Age of Fingermarks (Angew. Chem. Int. Ed. 24/2014) (page 6010)

      Annemieke van Dam, Janina C. V. Schwarz, Judith de Vos, Dr. Maria Siebes, Dr. Titia Sijen, Prof. Ton G. van Leeuwen, Prof. Maurice C. G. Aalders and Dr. Saskia A. G. Lambrechts

      Article first published online: 20 MAY 2014 | DOI: 10.1002/anie.201404827

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      Forensic fingerprint-age estimation is currently impossible. Knowledge on time passed since fingerprint deposition is desired as it can distinguish between crime-related and unrelated fingerprints and support or refute statements made by fingerprint donors. In their Communication on page 6272 ff., S. A. G. Lambrechts and co-workers describe a successful fluorescence-based method to estimate fingerprint age that relies on the protein–lipid oxidation rate and the subsequent generation of fluorescent oxidation products.

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      Inside Back Cover: Direct Umpolung of Glycals and Related 2,3-Unsaturated N-Acetylneuraminic Acid Derivatives Using Samarium Diiodide (Angew. Chem. Int. Ed. 24/2014) (page 6277)

      Tien Xuan Le, Caroline Papin, Gilles Doisneau and Jean-Marie Beau

      Article first published online: 28 APR 2014 | DOI: 10.1002/anie.201404338

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      One hundred years ago while exploring the reductive metalation of “Acetobromglucose” with zinc, Emil Fischer discovered the glycals. Since that time, these very useful unsaturated carbohydrates have been extensively used for the preparation of important complex carbohydrates and natural products following the natural electrophilic route. In their Communication on page 6184 ff., G. Doisneau, J.-M. Beau et al. reveal a new nucleophilic route by direct and selective umpolung using samarium diiodide.

    4. You have free access to this content
      Back Cover: Sequential Intra-Intercellular Nanoparticle Delivery System for Deep Tumor Penetration (Angew. Chem. Int. Ed. 24/2014) (page 6278)

      Dr. Caoyun Ju, Dr. Ran Mo, Jingwei Xue, Lei Zhang, Zekai Zhao, Dr. Lingjing Xue, Prof. Qineng Ping and Dr. Can Zhang

      Article first published online: 23 APR 2014 | DOI: 10.1002/anie.201401142

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      A nanoparticle delivery system enables deep tumor penetration. As R. Mo, C. Zhang et al. show in their Communication on page 6253 ff., pH-sensitive nanogels (small yellow spheres) accumulate at the tumor tissues (red cells). After internalization, the nanogels swell (large spheres) releasing the encapsulated chemotherapeutics (blue). The nanogel contracts (small yellow spheres), is liberated from the dead cells (grape-like cells), infects neighboring cancer cells nearer the center of the tumor, and the process is repeated.

  2. Frontispiece

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Correspondence
    11. Review
    12. Communications
    1. You have free access to this content
      Frontispiece: NMR Fingerprints of the Drug-like Natural-Product Space Identify Iotrochotazine A: A Chemical Probe to Study Parkinson’s Disease

      Dr. Tanja Grkovic, Dr. Rebecca H. Pouwer, Marie-Laure Vial, Luca Gambini, Alba Noël, Dr. John N. A. Hooper, Dr. Stephen A. Wood, Dr. George D. Mellick and Prof. Dr. Ronald J. Quinn

      Article first published online: 5 JUN 2014 | DOI: 10.1002/anie.201482471

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      1H NMR fingerprints are used to identify novel compounds including iotrochotazine A. This natural product has activity on a human Parkinson's disease cell model, as reported by R. J. Quinn and co-workers in their Communication on page 6070 ff.

  3. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Correspondence
    11. Review
    12. Communications
  4. Corrigenda

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Correspondence
    11. Review
    12. Communications
    1. You have free access to this content
    2. You have free access to this content
  5. News

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Correspondence
    11. Review
    12. Communications
  6. Author Profile

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Correspondence
    11. Review
    12. Communications
    1. Vivian Wing-Wah Yam (pages 6034–6035)

      Article first published online: 19 FEB 2014 | DOI: 10.1002/anie.201400644

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      “I can never resist good food, good wine, and research funding. My favorite foods are hot pot and soup …” This and more about Vivian Wing-Wah Yam can be found on page 6034.

  7. News

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Correspondence
    11. Review
    12. Communications
  8. Book Review

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Correspondence
    11. Review
    12. Communications
    1. Stereoselective Synthesis of Drugs and Natural Products. Edited by Vasyl Andrushko and Natalia Andrushko. (page 6037)

      Evgeny V. Prusov

      Article first published online: 5 JUN 2014 | DOI: 10.1002/anie.201403819

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      John Wiley & Sons, Hoboken, 2013. Two-volume set, 1836 pp., hardcover, € 396.00.—ISBN 978-1118032176

  9. Correspondence

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Correspondence
    11. Review
    12. Communications
    1. Chemical Bonding

      Dative Bonds in Main-Group Compounds: A Case for More Arrows! (pages 6040–6046)

      Prof. Dr. Gernot Frenking

      Article first published online: 21 MAY 2014 | DOI: 10.1002/anie.201311022

      Semantics, definitions? The description of the electronic structure of main-group compounds with dative bonds significantly enriched the chemistry of sp block elements. The new viewpoint has proved to be a useful guideline for the synthesis of unusual donor–acceptor complexes and for explaining novel molecular structures. New compound classes such as carbones CL2 and borylene complexes (BH)L2 have been found.

    2. Dative or Not Dative? (pages 6047–6048)

      Dr. Daniel Himmel, Prof. Dr. Ingo Krossing and Prof. Dr. Andreas Schnepf

      Article first published online: 28 MAY 2014 | DOI: 10.1002/anie.201403078

      Is a meatball an animal praline? The authors of the Essay Dative Bonds in Main-Group Compounds: A Case for Fewer Arrows! respond to the criticism of Gernot Frenking and correct one point in their original Essay.

  10. Review

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Correspondence
    11. Review
    12. Communications
    1. Main-Group Chemistry

      Interpnictogen Cations: Exploring New Vistas in Coordination Chemistry (pages 6050–6069)

      Dr. Alasdair P. M. Robertson, B.Sc. Paul A. Gray and Prof. Neil Burford

      Article first published online: 26 MAY 2014 | DOI: 10.1002/anie.201307658

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      Coordinate or donor–acceptor bonding defines much of transition-metal chemistry, but is also prevalent between the nonmetals. This Review demonstrates the application of coordinate interactions between the pnictogen elements, revealing structural diversity and novelty. Compounds containing Pn[BOND]Pn or Pn′[BOND]Pn bonds involving cationic acceptors based on each of the pnictogen elements are discussed sequentially.

  11. Communications

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Correspondence
    11. Review
    12. Communications
    1. Natural Products

      You have full text access to this OnlineOpen article
      NMR Fingerprints of the Drug-like Natural-Product Space Identify Iotrochotazine A: A Chemical Probe to Study Parkinson’s Disease (pages 6070–6074)

      Dr. Tanja Grkovic, Dr. Rebecca H. Pouwer, Marie-Laure Vial, Luca Gambini, Alba Noël, Dr. John N. A. Hooper, Dr. Stephen A. Wood, Dr. George D. Mellick and Prof. Dr. Ronald J. Quinn

      Article first published online: 15 APR 2014 | DOI: 10.1002/anie.201402239

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      Seeing the invisible: A novel natural product, iotrochotazine A was isolated using an NMR-based strategy focused on the analysis of 1H NMR fingerprints of a prefractionated natural-product library. In a phenotypic assay panel based on hONS cells derived from idiopathic Parkinson's disease (PD) patients, it affected the morphology and cellular distribution of lysosomes and early endosomes.

    2. Neurochemistry

      Cytoskeletal Actin Dynamics are Involved in Pitch-Dependent Neurite Outgrowth on Bead Monolayers (pages 6075–6079)

      Dr. Kyungtae Kang, Seo Young Yoon, Sung-Eun Choi, Mi-Hee Kim, Matthew Park, Prof. Dr. Yoonkey Nam, Prof. Dr. Jin Seok Lee and Prof. Dr. Insung S. Choi

      Article first published online: 5 MAR 2014 | DOI: 10.1002/anie.201400653

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      What a nerve: The initial neurite development of hippocampal neurons was studied on assembled silica beads with diameters ranging from 700 to 1800 nm. Neurite outgrowth accelerated with increasing bead size up to a bead diameter of approximately 1000 nm, above which saturation was observed. Biochemical analysis indicated that cytoskeletal actin dynamics were primarily responsible for the recognition of surface topography.

    3. Protein Electrostatics

      Ester Carbonyl Vibration as a Sensitive Probe of Protein Local Electric Field (pages 6080–6084)

      Ileana M. Pazos, Dr. Ayanjeet Ghosh, Prof. Dr. Matthew J. Tucker and Prof. Dr. Feng Gai

      Article first published online: 30 APR 2014 | DOI: 10.1002/anie.201402011

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      A telling relationship: Electrostatic interactions between proteins and other molecules often play a key role in mediating biological processes. However, quantification of the underlying electrostatic forces requires knowledge of the local electrostatic environment. The C[DOUBLE BOND]O stretching frequency of an ester moiety on two non-natural amino acids was found to be a good probe of the local electrostatic field and dielectric constant (see graph).

    4. Vesicular Imaging

      Acidic-pH-Activatable Fluorescence Probes for Visualizing Exocytosis Dynamics (pages 6085–6089)

      Daisuke Asanuma, Yousuke Takaoka, Shigeyuki Namiki, Kenji Takikawa, Mako Kamiya, Prof. Tetsuo Nagano, Prof. Yasuteru Urano and Prof. Kenzo Hirose

      Article first published online: 6 MAY 2014 | DOI: 10.1002/anie.201402030

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      Going live: Live imaging of the dynamics of exocytosis is crucial for a precise spatiotemporal understanding of secretion phenomena. Small-molecular fluorescent probes designed to be activated under acidic intravesicular conditions enabled the sensitive and reliable visualization of vesicular dynamics with high spatiotemporal precision (see picture).

    5. Molecular Recognition

      Responsive Supramolecular Polymers Based on the Bis[alkynylplatinum(II)] Terpyridine Molecular Tweezer/Arene Recognition Motif (pages 6090–6094)

      Yu-Kui Tian, Yong-Gang Shi, Zhi-Shuai Yang and Dr. Feng Wang

      Article first published online: 8 MAY 2014 | DOI: 10.1002/anie.201402192

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      Trigger happy: Supramolecular polymers are constructed based on the novel bis[alkynylplatinum(II)] terpyridine molecular tweezer/pyrene recognition motif. Successive addition of anthracene as the diene and a cyano-functionalized dienophile triggers the reversible supramolecular polymerization process, thus advancing the concept of utilizing Diels–Alder chemistry to access stimuli-responsive materials in compartmentalized systems.

    6. Gene Delivery

      Significance of Branching for Transfection: Synthesis of Highly Branched Degradable Functional Poly(dimethylaminoethyl methacrylate) by Vinyl Oligomer Combination (pages 6095–6100)

      Tianyu Zhao, Hong Zhang, Dr. Ben Newland, Ahmed Aied, Dr. Dezhong Zhou and Dr. Wenxin Wang

      Article first published online: 30 APR 2014 | DOI: 10.1002/anie.201402341

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      Branching out into new territory: Highly branched poly(dimethylaminoethyl methacrylate) (PDMAEMA) copolymers (see structure) with a controlled degree of branching and the ability to undergo efficient degradation were investigated as gene-delivery vectors. Their transfection profile in terms of both transfection capability and the preservation of cell viability was superior to that of linear PDMAEMA.

    7. Protein Engineering | Hot Paper

      SpyTag/SpyCatcher Cyclization Confers Resilience to Boiling on a Mesophilic Enzyme (pages 6101–6104)

      Christopher Schoene, Jacob O. Fierer, Dr. S. Paul Bennett and Prof. Mark Howarth

      Article first published online: 9 MAY 2014 | DOI: 10.1002/anie.201402519

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      Spy ring: The enzymes β-lactamase and dihydrofolate reductase were cyclized through an N-terminal SpyTag peptide and a C-terminal SpyCatcher protein, which spontaneously react to form an amide bond. The cyclized enzymes display substantially increased resilience, remaining soluble and active following boiling at 100 °C. This strategy is an easy way to cyclize proteins and can lead to major enhancement of the robustness of biological catalysts.

    8. Trifluoromethylthiolation

      Silver-Catalyzed Decarboxylative Trifluoromethylthiolation of Aliphatic Carboxylic Acids in Aqueous Emulsion (pages 6105–6109)

      Dr. Feng Hu, Xinxin Shao, Dianhu Zhu, Prof. Dr. Long Lu and Prof. Dr. Qilong Shen

      Article first published online: 24 APR 2014 | DOI: 10.1002/anie.201402573

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      Oil-in-water: Secondary and tertiary carboxylic acids were successfully transformed to their trifluoromethylthiolated derivatives using the title reaction, which tolerates a wide range of functional groups. The reaction was dramatically accelerated by the use of an aqueous emulsion as the reaction medium, which was formed by the addition of sodium dodecyl sulfate (SDS) in water.

    9. Dye-Sensitized Solar Cells | Hot Paper

      Wearable Solar Cells by Stacking Textile Electrodes (pages 6110–6114)

      Shaowu Pan, Zhibin Yang, Peining Chen, Jue Deng, Houpu Li and Prof. Huisheng Peng

      Article first published online: 30 APR 2014 | DOI: 10.1002/anie.201402561

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      Wearable and efficient dye-sensitized solar cells (DSC) that are based on textile electrodes were synthesized according to a new and general method. These DSC textiles are flexible and stable and can be easily integrated to tune the output voltage or current. The use of these wearable DSC textiles to drive a light-emitting diode was successfully demonstrated.

    10. Site-Specific Bioconjugation

      Enzyme-Mediated Site-Specific Bioconjugation of Metal Complexes to Proteins: Sortase-Mediated Coupling of Copper-64 to a Single-Chain Antibody (pages 6115–6119)

      Dr. Brett M. Paterson, Dr. Karen Alt, Charmaine M. Jeffery, Prof. Roger I. Price, Shweta Jagdale, Dr. Sheena Rigby, Dr. Charlotte C. Williams, Prof. Karlheinz Peter, Prof. Christoph E. Hagemeyer and Assoc. Prof. Paul S. Donnelly

      Article first published online: 28 APR 2014 | DOI: 10.1002/anie.201402613

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      Enzyme-mediated bioconjugation with sortase A resulted in the site-specific and controlled attachment of a macrocyclic metal-binding amine ligand to a single-chain antibody against the platelet integrin GPIIb/IIIa in its active ligand-bound form. The new conjugate was radiolabeled with copper-64 and proved to be a promising imaging agent for positron emission tomography.

    11. Protein Modification

      Nonenzymatic Rubylation and Ubiquitination of Proteins for Structural and Functional Studies (pages 6120–6125)

      Dr. Rajesh K. Singh, Adithya Sundar and Prof. David Fushman

      Article first published online: 24 APR 2014 | DOI: 10.1002/anie.201402642

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      Aye, there's the Rub: Studying the structure and function of diverse polymeric chains of ubiquitin (Ub) or Ub-like proteins such as Rub1 is a significant challenge owing to a lack of conjugating E2 enzymes. A method was developed for the rubylation of Ub and Rub1 and the ubiquitination of Rub1 with no need for E2 and E3 enzymes. This made it possible to investigate the structure, recognition, and processing of these chains.

    12. Ligand Discovery

      You have full text access to this OnlineOpen article
      A Series of Potent CREBBP Bromodomain Ligands Reveals an Induced-Fit Pocket Stabilized by a Cation–π Interaction (pages 6126–6130)

      Timothy P. C. Rooney, Dr. Panagis Filippakopoulos, Dr. Oleg Fedorov, Dr. Sarah Picaud, Wilian A. Cortopassi, Duncan A. Hay, Dr. Sarah Martin, Dr. Anthony Tumber, Dr. Catherine M. Rogers, Dr. Martin Philpott, Dr. Minghua Wang, Dr. Amber L. Thompson, Dr. Tom D. Heightman, Dr. David C. Pryde, Dr. Andrew Cook, Prof. Dr. Robert S. Paton, Dr. Susanne Müller, Prof. Dr. Stefan Knapp, Dr. Paul E. Brennan and Prof. Dr. Stuart J. Conway

      Article first published online: 12 MAY 2014 | DOI: 10.1002/anie.201402750

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      Ligands made to fit: A series of dihydroquinoxalinone fragments were employed as acetyl lysine mimics in the development of CREBBP bromodomain ligands. The side chain of these ligands binds in an induced-fit pocket and forms a cation–π interaction with R1173 of CREBBP. The most potent compound inhibits binding of CREBBP to chromatin in U2OS cells.

    13. Asymmetric Catalysis

      Catalytic Enantioselective Inverse Electron Demand Hetero-Diels–Alder Reaction with Allylsilanes (pages 6131–6134)

      Yuki Matsumura, Takahiro Suzuki, Prof. Dr. Akira Sakakura and Prof. Dr. Kazuaki Ishihara

      Article first published online: 29 APR 2014 | DOI: 10.1002/anie.201402934

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      New on the block: The first diastereo- and enantioselective title reaction of β,γ-unsaturated α-ketoesters with allylsilanes is described. Chiral copper(II) catalysts successfully activate the β,γ-unsaturated α-ketoesters and promote the reaction with allylsilanes with excellent enantioselectivities. This process represents a new entry to chiral oxanes, which are useful building blocks. Tf=trifluoromethanesulfonyl.

    14. Spin Switching

      A Trinuclear Defect-Grid Iron(II) Spin Crossover Complex with a Large Hysteresis Loop that is Readily Silenced by Solvent Vapor (pages 6135–6139)

      Dipl.-Chem. Markus Steinert, Dr. Benjamin Schneider, Dr. Sebastian Dechert, Dr. Serhiy Demeshko and Prof. Dr. Franc Meyer

      Article first published online: 22 MAY 2014 | DOI: 10.1002/anie.201403068

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      The effect of a defect: A new type of [2×2] matrix-like complexes with one vertex devoid of a metal ion, namely a “defect-grid” triiron(II) complex, exhibits a sharp and complete spin-crossover (SCO) with wide hysteresis near room temperature. The H-bonded vertex results in the stabilization of spin states but also mediates a dramatic, yet reversible, response to the uptake of exogenous solvent molecules leading to silencing of the SCO.

    15. Synthetic Methods

      [CpRu]-Catalyzed Carbene Insertions into Epoxides: 1,4-Dioxene Synthesis through SN1-Like Chemistry with Retention of Configuration (pages 6140–6144)

      Dr. Thierry Achard, Cecilia Tortoreto, Dr. Amalia I. Poblador-Bahamonde, Dr. Laure Guénée, Prof. Thomas Bürgi and Prof. Jérôme Lacour

      Article first published online: 6 MAY 2014 | DOI: 10.1002/anie.201402994

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      Oxygen sticks around: Rather than lead to the usual deoxygenation pathway, metal carbenes derived from α-diazo-β-ketoesters undergo three-atom insertions into epoxides using a combination of 1,10-phenanthroline and [CpRu(CH3CN)3][BArF]. 1,4-Dioxene motifs are obtained as single regio- and stereoisomers with perfect syn stereochemistry. BArF=tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, Cp=cyclopentadienyl.

    16. Allylboration

      Highly Selective Allylborations of Aldehydes Using α,α-Disubstituted Allylic Pinacol Boronic Esters (pages 6145–6149)

      Dr. Matthew J. Hesse, Dr. Stéphanie Essafi, Charlotte G. Watson, Prof. Dr. Jeremy N. Harvey, Dr. David Hirst, Prof. Dr. Christine L. Willis and Prof. Dr. Varinder K. Aggarwal

      Article first published online: 5 MAY 2014 | DOI: 10.1002/anie.201402995

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      Asymmetric C[BOND]C coupling: α,α-Disubstituted allylic pinacol boronic esters undergo highly selective allylborations of aldehydes to give tetrasubstituted homoallylic alcohols with exceptional levels of anti-Z-selectivity (see scheme). The scope of the reaction includes both acyclic and cyclic allylic boronic esters. β-Borylated allylic boronic esters gave fully substituted vinyl boronates suitable for further cross-coupling.

    17. Asymmetric Catalysis

      A Designed Amide as an Aldol Donor in the Direct Catalytic Asymmetric Aldol Reaction (pages 6150–6154)

      Dr. Karin Weidner, Dr. Naoya Kumagai and Prof. Dr. Masakatsu Shibasaki

      Article first published online: 30 APR 2014 | DOI: 10.1002/anie.201403118

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      In play: Direct catalytic asymmetric aldol reactions offer efficient access to β-hydroxy carbonyl entities. Described is the robust title reaction of α-sulfanyl 7-azaindolinylamide, which affords both aromatic and aliphatic β-hydroxy amides with high ee values. The transformation features the cooperative interplay of a soft and a hard Lewis acid.

    18. Bioassays

      Pullulan Encapsulation of Labile Biomolecules to Give Stable Bioassay Tablets (pages 6155–6158)

      Sana Jahanshahi-Anbuhi, Kevin Pennings, Vincent Leung, Dr. Meng Liu, Carmen Carrasquilla, Dr. Balamurali Kannan, Prof. Dr. Yingfu Li, Prof. Dr. Robert Pelton, Prof. Dr. John D. Brennan and Prof. Dr. Carlos D. M. Filipe

      Article first published online: 24 APR 2014 | DOI: 10.1002/anie.201403222

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      Locked and loaded: Pullulan encapsulation enables the room-temperature shipping and long-term storage of unstable biomolecules (such as enzymes and their substrates). The pullulan tablets dissolve quickly in aqueous solution to release defined premeasured amounts of the reagent. The reagent stabilization and ease of use afforded by this method would be particularly advantageous for bioassays intended for use in resource-limited settings.

    19. Polycyclic Aromatic Hydrocarbons

      Synthesis and Properties of a New Class of Fully Conjugated Azahexacene Analogues (pages 6159–6162)

      Dr. Wan Yue, Dr. Sabin-Lucian Suraru, David Bialas, Matthias Müller and Prof. Dr. Frank Würthner

      Article first published online: 5 MAY 2014 | DOI: 10.1002/anie.201403227

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      Making acene: A family of novel, persistent 6-5-5-5-5-6 fused ring systems, which in their fully conjugated state closely resemble azahexacene aromatic systems, were synthesized starting from their respective diketopyrrolopyrroles (see structure; C black, N blue, F green). The optical and electronic properties of these new molecular scaffolds suggest that they have potential as alternatives to the traditionally utilized acenes for materials application.

    20. Smart Materials

      Controlled Directional Water-Droplet Spreading on a High-Adhesion Surface (pages 6163–6167)

      Shile Feng, Sijie Wang, Prof. Longcheng Gao, Dr. Guangjun Li, Dr. Yongping Hou and Prof. Yongmei Zheng

      Article first published online: 12 MAY 2014 | DOI: 10.1002/anie.201403246

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      No two ways about it: Directional spreading was made possible on a high-adhesion surface by simply controlling anodic oxidation. When a droplet came into contact with the substrate, it immediately spread along the direction of the wettability gradient, even when the surface was turned upside down (see picture). V- and inverse-V-shaped wettability gradients, on which two droplets spread either toward or away from one another, were also formed.

    21. Cancer MicroRNAs

      Magnetobiosensors Based on Viral Protein p19 for MicroRNA Determination in Cancer Cells and Tissues (pages 6168–6171)

      Dr. Susana Campuzano, Rebeca M. Torrente-Rodríguez, Dr. Eva López-Hernández, Felipe Conzuelo, Dr. Rosario Granados, Dr. José M. Sánchez-Puelles and Prof. José M. Pingarrón

      Article first published online: 30 APR 2014 | DOI: 10.1002/anie.201403270

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      A throw-away idea: An amperometric magnetosensor based on a specific RNA probe (red strands) and protein p19 as biorecognition elements was developed as a disposable diagnostic tool for the determination of miR-21 (green strands) in cancer cells and tissues. Labeling of the biotinylated RNA hybrid with streptavidin conjugated to horseradish peroxidase (Strep–HRP) enabled electrochemical detection on a screen-printed carbon electrode (SPCE).

    22. Metal–Protein Interactions

      Unusual Structural Features in the Lysozyme Derivative of the Tetrakis(acetato)chloridodiruthenium(II,III) Complex (pages 6172–6175)

      Prof. Luigi Messori, Tiziano Marzo, Rute Nazaré Fernandes Sanches, Hanif-Ur-Rehman, Prof. Denise de Oliveira Silva and Dr. Antonello Merlino

      Article first published online: 5 MAY 2014 | DOI: 10.1002/anie.201403337

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      Paddling through: The adduct formed between the paddle-wheel tetrakis(acetato)chloridodiruthenium(II,III) complex and hen egg-white lysozyme (turquoise ribbon structure) was characterized through ESI mass spectrometry and X-ray crystallography. Unusual and interesting features were revealed in the binding mode of the diruthenium centers (circled) to the protein side chains.

    23. Shape Shifting

      Stereoselective Fluorination Alters the Geometry of a Cyclic Peptide: Exploration of Backbone-Fluorinated Analogues of Unguisin A (pages 6176–6179)

      Dr. Xiang-Guo Hu, Dr. Donald S. Thomas, Prof. Renate Griffith and Dr. Luke Hunter

      Article first published online: 21 MAY 2014 | DOI: 10.1002/anie.201403071

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      What an impact! Stereoselective fluorination is developed as a new strategy for fine-tuning the shapes of cyclic peptides. Four vicinal difluorinated analogues of a natural cyclic heptapeptide were efficiently synthesized. The analogues (one is shown on the right) adopt dramatically different geometries compared to the natural product.

    24. Vicinal Quaternary Stereocenters | Very Important Paper

      Catalytic Enantioselective Nazarov Cyclization: Construction of Vicinal All-Carbon-Atom Quaternary Stereocenters (pages 6180–6183)

      Anais Jolit, Dr. Patrick M. Walleser, Dr. Glenn P. A. Yap and Prof. Dr. Marcus A. Tius

      Article first published online: 18 MAY 2014 | DOI: 10.1002/anie.201403587

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      Nazarov cyclization: The diastereoselective asymmetric synthesis of vicinal all-carbon-atom quaternary stereocenters is a challenging problem in organic synthesis. A catalytic asymmetric Nazarov cyclization of fully substituted dienones now provides cyclopentenone derivatives with vicinal quaternary stereocenters in high optical purity and as single diastereoisomers.

    25. Umpolung

      Direct Umpolung of Glycals and Related 2,3-Unsaturated N-Acetylneuraminic Acid Derivatives Using Samarium Diiodide (pages 6184–6187)

      Tien Xuan Le, Caroline Papin, Gilles Doisneau and Jean-Marie Beau

      Article first published online: 24 APR 2014 | DOI: 10.1002/anie.201402891

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      Samarium can do it alone: Without the help of transition metals, samarium(II) iodide induces a chemoselective reductive coupling of carbonyl compounds with glycals. The high regioselectivity and stereoselectivity of the transformation are controlled by the structure of the substrates.

    26. Electron Transfer in Proteins

      Control of the Electronic Ground State on an Electron-Transfer Copper Site by Second-Sphere Perturbations (pages 6188–6192)

      Marcos N. Morgada, Dr. Luciano A. Abriata, Ulises Zitare, Dr. Damian Alvarez-Paggi, Prof. Daniel H. Murgida and Prof. Alejandro J. Vila

      Article first published online: 28 APR 2014 | DOI: 10.1002/anie.201402083

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      The electronic structure of the CuA center can be tuned by second-shell perturbations. An equilibrium between two alternative ground states of σu* and πu symmetry can be perturbed without altering the identity of the metal ligands, so that the redox potential of the metal site is preserved while alternative electron-transfer pathways become possible.

    27. Mechanisms of Mechanochemistry

      Laboratory Real-Time and In Situ Monitoring of Mechanochemical Milling Reactions by Raman Spectroscopy (pages 6193–6197)

      Dr. Davor Gracin, Dr. Vjekoslav Štrukil, Prof. Tomislav Friščić, Dr. Ivan Halasz and Dr. Krunoslav Užarević

      Article first published online: 24 APR 2014 | DOI: 10.1002/anie.201402334

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      Out of the dark: Mechanochemical reaction mechanisms were studied by a laboratory Raman spectroscopy technique developed for in situ and real-time monitoring of milling reactions (see picture). The technique enabled the course of mechanochemical transformations of coordination polymers and organic materials to be followed as well as the study of liquid additives.

    28. Photochemistry

      anti-Markovnikov Hydroamination of Alkenes Catalyzed by a Two-Component Organic Photoredox System: Direct Access to Phenethylamine Derivatives (pages 6198–6201)

      Tien M. Nguyen, Namita Manohar and Prof. David A. Nicewicz

      Article first published online: 24 APR 2014 | DOI: 10.1002/anie.201402443

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      On the (anti )mark: Disclosed is a general catalytic system for the intermolecular anti-Markovnikov hydroamination of alkenes. An organocatalytic photoredox system tolerates α- and β-substituted styrenes, as well as aliphatic alkenes. Heterocyclic amines were also successfully employed as nitrogen nucleophiles, thus providing a direct route to heterocyclic motifs common in medicinal agents.

    29. Natural Product Synthesis

      Total Synthesis of (+)-Madangamine D (pages 6202–6205)

      Roberto Ballette, Dr. Maria Pérez, Dr. Stefano Proto, Prof. Dr. Mercedes Amat and Prof. Dr. Joan Bosch

      Article first published online: 2 MAY 2014 | DOI: 10.1002/anie.201402263

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      Mad about madangamines: The first total synthesis of an alkaloid of the madangamine group has been accomplished. Using a phenylglycinol-derived lactam as the starting enantiomeric scaffold, the synthesis of (+)-madangamine D involves the successive construction of the six-membered carbocyclic C and heterocyclic A rings to generate the functionalized diazatricyclic ABC intermediates and the subsequent assembly of the peripheral macrocyclic D and E rings. Ts=4-toluenesulfonyl.

    30. Natural Products

      Enantioselective Total Synthesis of (−)-Lansai B and (+)-Nocardioazines A and B (pages 6206–6210)

      Haoxuan Wang and Prof. Sarah E. Reisman

      Article first published online: 28 APR 2014 | DOI: 10.1002/anie.201402571

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      No-cardio required: The concise total syntheses of the bis(pyrroloindolines) (−)-lansai B and (+)-nocardioazines A and B are reported. The key pyrroloindoline building blocks are rapidly prepared by enantioselective formal (3+2) cycloaddition reactions. The macrocycle of (+)-nocardioazine A is constructed by an unusual intramolecular diketopiperazine formation.

    31. Gold-Catalyzed Cross-Coupling

      Gold-Catalyzed Allylation of Aryl Boronic Acids: Accessing Cross-Coupling Reactivity with Gold (pages 6211–6215)

      Mark D. Levin and Prof. Dr. F. Dean Toste

      Article first published online: 5 MAY 2014 | DOI: 10.1002/anie.201402924

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      Teaching Au new tricks: A novel manifold for reactivity in gold catalysis has been realized, allowing the cross-coupling of arylboronic acids and allylic bromides without a sacrificial oxidant. A bimetallic catalyst is employed, providing allylbenzene products with unique scope and chemoselectivity. A mechanistic proposal is put forward based on stoichiometric experiments, including the isolation of an AuIII allyl complex.

    32. Heterocycle Synthesis | Hot Paper

      Intramolecular Metal-Free Oxidative Aryl–Aryl Coupling: An Unusual Hypervalent-Iodine-Mediated Rearrangement of 2-Substituted N-Phenylbenzamides (pages 6216–6219)

      Siyun Shang, Dr. Daisy Zhang-Negrerie, Prof. Dr. Yunfei Du and Prof. Dr. Kang Zhao

      Article first published online: 24 APR 2014 | DOI: 10.1002/anie.201402925

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      Making (re)arrangements: Hypervalent-iodine-mediated oxidative coupling of the two aryl groups in either 2-acylamino-N-phenyl-benzamides or 2-hydroxy-N-phenylbenzamides with concomitant insertion of the ortho-substituted N or O atom into the tether is described. This unusual metal-free rearrangement reaction involves an oxidative C(sp2)[BOND]C(sp2) aryl–aryl bond formation, cleavage of a C(sp2)[BOND]C(O) bond, and a lactamization/lactonization.

    33. Asymmetric Catalysis

      Catalytic Asymmetric Synthesis of 3,3′-Diaryloxindoles as Triarylmethanes with a Chiral All-Carbon Quaternary Center: Phase-Transfer-Catalyzed SNAr Reaction (pages 6220–6223)

      Dr. Seiji Shirakawa, Kenta Koga, Takashi Tokuda, Kenichiro Yamamoto and Prof. Dr. Keiji Maruoka

      Article first published online: 6 MAY 2014 | DOI: 10.1002/anie.201403046

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      Going through a phase: Catalytic asymmetric synthesis of unsymmetrical triarylmethanes, with a chiral all-carbon quaternary center, was achieved by using a chiral bifunctional quaternary phosphonium bromide catalyst in the SNAr reaction of 3-aryloxindoles. The reactions proceeded under phase-transfer conditions. Boc=tert-butoxycarbonyl.

    34. σ-Bond Metathesis

      Accessing the Single-Electron Manifold: Magnesium-mediated Hydrogen Release from Silanes (pages 6224–6227)

      David J. Liptrot, Professor Michael S. Hill and Dr. Mary F. Mahon

      Article first published online: 29 APR 2014 | DOI: 10.1002/anie.201403208

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      Upping the tempo: Reactions of TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy) with magnesium hydride species initiate catalytic hydrogen release through sequential TEMPO-mediated redox and Mg[BOND]O/Si[BOND]H metathesis processes (see scheme). This is the first example of catalytic single-electron transfer reactivity involving an s-block metal.

    35. Synthetic Methods | Hot Paper

      Single-Electron/Pericyclic Cascade for the Synthesis of Dienes (pages 6228–6231)

      Natalie E. Campbell and Prof. Glenn M. Sammis

      Article first published online: 29 APR 2014 | DOI: 10.1002/anie.201403234

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      Make it to break it: The highly efficient and diastereoselective synthesis of E dienes has been accomplished through radical cyclization of bromoallyl hydrazones. This methodology proceeds through a one-pot condensation/radical cyclization/cycloreversion cascade from simple aldehyde starting materials in high yields and diastereoselectivities (see scheme; AIBN=azobis(isobutyronitrile), Ts=4-toluenesulfonyl).

    36. Polycyclic Aromatics

      A Metal-Bridged Tricyclic Aromatic System: Synthesis of Osmium Polycyclic Aromatic Complexes (pages 6232–6236)

      Congqing Zhu, Qin Zhu, Jinglan Fan, Dr. Jun Zhu, Prof. Dr. Xumin He, Dr. Xiao-Yu Cao and Prof. Dr. Haiping Xia

      Article first published online: 29 APR 2014 | DOI: 10.1002/anie.201403245

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      Poly put the metal on: A general route is developed to synthesize metal-bridged polycyclic aromatic complexes, in which the metal center is shared by three aromatic fused five-membered rings. This synthetic method opens a new way to prepare large, metal-bridged polycyclic aromatic complexes.

    37. Borane Reduction

      Redox Chemistry of a Hydroxyphenyl-Substituted Borane (pages 6237–6240)

      Po-Yeng Feng, Yi-Hung Liu, Prof. Tien-Sung Lin, Prof. Shie-Ming Peng and Prof. Ching-Wen Chiu

      Article first published online: 29 APR 2014 | DOI: 10.1002/anie.201403247

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      A radical approach: Chemical reduction of a hydroxyphenyl-substituted borane triggers a sequential electron- and hydrogen-atom-transfer process to afford a hydridoborate phenoxide dianion. Hydrogen-atom abstraction of the borane allows isolation of a neutral borylated phenoxyl radical, which can be transformed to a benzoquinone borataalkene by reduction with cobaltocene.

    38. Cyclopentadienyl Modification

      Alkyne Cycloaddition to a Titanocene Oxide as a Route to Cyclopentadienyl Modification (pages 6241–6244)

      Iraklis Pappas and Prof. Paul J. Chirik

      Article first published online: 5 MAY 2014 | DOI: 10.1002/anie.201403584

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      A scenic route: Cycloaddition of terminal and internal alkynes with a base-free titanocene oxide generates kinetically unstable oxatitanacyclobutene complexes that undergo C[BOND]C reductive elimination with the cyclopentadienyl ring. Subsequent ejection of a SiMe3 group results in a unique sequence for cyclopentadienyl modification.

    39. Organocatalysis

      Asymmetric [5+3] Formal Cycloadditions with Cyclic Enones through Cascade Dienamine–Dienamine Catalysis (pages 6245–6248)

      Xiang Yin, Dr. Yi Zheng, Xin Feng, Dr. Kun Jiang, Xue-Zhen Wei, Prof. Dr. Ning Gao and Prof. Dr. Ying-Chun Chen

      Article first published online: 29 APR 2014 | DOI: 10.1002/anie.201403753

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      A fusion work: The title reaction is described for β-substituted 2-cyclopentenones or 2-cyclohexenone and bis(electrophilic) 3-vinyl-1,2-benzoisothiazole-1,1-dioxides. The α′-regioselective Michael addition and subsequent γ-regioselective Mannich reaction leads to fused or bridged frameworks with excellent stereoselectivity. Some of the chiral products exhibited promising anticancer activity.

    40. Total Synthesis

      Synthesis, Discovery, and Quantitation of Dihomo-Isofurans: Biomarkers for In Vivo Adrenic Acid Peroxidation (pages 6249–6252)

      Aurélien de La Torre, Yiu Yiu Lee, Dr. Camille Oger, Per Torp Sangild, Dr. Thierry Durand, Dr. Jetty Chung-Yung Lee and Dr. Jean-Marie Galano

      Article first published online: 18 MAY 2014 | DOI: 10.1002/anie.201402440

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      White matter matters: The enantioselective synthesis of dihomo-Isofurans (dihomo-IsoFs), metabolites from in vivo peroxidation of adrenic acid (found in white matter of the brain), is described and employs a C2-symmetric precursor in a divergent strategy. Mass-spectrometry analysis accurately validated its presence in pig brain, and quantitation analysis showed, for the first time, the importance of such a novel biomarker in assessing lipid peroxidation.

    41. Drug Delivery | Very Important Paper

      Sequential Intra-Intercellular Nanoparticle Delivery System for Deep Tumor Penetration (pages 6253–6258)

      Dr. Caoyun Ju, Dr. Ran Mo, Jingwei Xue, Lei Zhang, Zekai Zhao, Dr. Lingjing Xue, Prof. Qineng Ping and Dr. Can Zhang

      Article first published online: 16 APR 2014 | DOI: 10.1002/anie.201311227

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      Special delivery: A nanoparticle delivery system consisting of a reversible swelling–shrinking nanogel allows deep tumor penetration of chemotherapeutics. It shows efficient drug release and intracellular trafficking to kill cancer cells, and after being released from the dead cells, can continue infecting neighboring cancer cells closer to the center of the tumor.

    42. Super Bases

      Assessing the Brønsted Basicity of Diaminoboryl Anions: Reactivity toward Methylated Benzenes and Dihydrogen (pages 6259–6262)

      Nicole Dettenrieder, Dr. Yoshitaka Aramaki, Benjamin M. Wolf, Dr. Cäcilia Maichle-Mössmer, Dr. Xiaoxi Zhao, Prof. Dr. Makoto Yamashita, Prof. Dr. Kyoko Nozaki and Prof. Dr. Reiner Anwander

      Article first published online: 6 MAY 2014 | DOI: 10.1002/anie.201402175

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      Back to basics: The deprotonation reactions of methylated benzenes and H2 by superbasic boryl anions were studied. In the reaction of methylated benzenes, subsequent nucleophilic substitution on the boron center of intermediate B–H produces benzylborane species (structure of the B unit shown in the scheme; Dip=2,6-iPr2C6H3). A general mechanism for these reactions is elaborated and the reactivity of B-Li(THF)2 toward H2 investigated by DFT calculations.

    43. Borirene Ligands

      Trihapto Ligation of a Borirene to a Single Metal Atom: A Heterocyclic Analogue of the η3-Cyclopropenyl Ligand (pages 6263–6266)

      Prof. Dr. Holger Braunschweig, Dr. Rian D. Dewhurst, Dr. Krzysztof Radacki, Dr. Christopher W. Tate and Dr. Alfredo Vargas

      Article first published online: 6 MAY 2014 | DOI: 10.1002/anie.201402815

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      A borirene provides the­ ansa: The photolytic transfer of an arylborylene fragment from a bulky arylborylene complex to diphenylacetylene and loss of three CO ligands from the precursor resulted in the first complex containing an η3-coordinated borirene ligand bound to a single metal atom (see scheme). Like its more electron-rich and π-stabilized amino/organometallic counterparts, an aryl-substituted borylene ligand can be transferred from a transition-metal borylene.

    44. RNA Repair

      Improving Site-Directed RNA Editing In Vitro and in Cell Culture by Chemical Modification of the GuideRNA (pages 6267–6271)

      Paul Vogel, Marius F. Schneider, Jacqueline Wettengel and Dr. Thorsten Stafforst

      Article first published online: 28 MAY 2014 | DOI: 10.1002/anie.201402634

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      Adenosine-to-inosine editing can be re-addressed to arbitrary mRNAs by applying antagomir-like guideRNAs. Extensive chemical modification of the guideRNA clearly improves performance of the covalent conjugates between guideRNA and SNAP-ADAR inside the cell. Furthermore, modification allows control over editing selectivity and is exploited for the challenging repair of the Factor 5 Leiden missense mutation.

    45. Forensic Science

      Oxidation Monitoring by Fluorescence Spectroscopy Reveals the Age of Fingermarks (pages 6272–6275)

      Annemieke van Dam, Janina C. V. Schwarz, Judith de Vos, Dr. Maria Siebes, Dr. Titia Sijen, Prof. Ton G. van Leeuwen, Prof. Maurice C. G. Aalders and Dr. Saskia A. G. Lambrechts

      Article first published online: 21 MAY 2014 | DOI: 10.1002/anie.201402740

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      Marking time: Currently no method exists that can estimate the age of a fingermark. Information on the time passed since fingermark deposition is of forensic value as it may link the fingermark donor not only to the crime scene but also to the assumed time of crime. Based on the oxidation of proteins present in fingermarks and the corresponding change in fluorescence, the age of a subset of fingermarks could be estimated up to three weeks after deposition with an uncertainty of 1.9 days.

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