Angewandte Chemie International Edition

Cover image for Vol. 53 Issue 29

July 14, 2014

Volume 53, Issue 29

Pages 7371–7673

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlight
    11. Minireview
    12. Review
    13. Communications
    1. You have free access to this content
      Cover Picture: Double C[BOND]F Bond Activation through β-Fluorine Elimination: Nickel-Mediated [3+2] Cycloaddition of 2-Trifluoromethyl-1-alkenes with Alkynes (Angew. Chem. Int. Ed. 29/2014) (page 7371)

      Tomohiro Ichitsuka, Dr. Takeshi Fujita, Tomohiro Arita and Prof. Dr. Junji Ichikawa

      Article first published online: 18 MAY 2014 | DOI: 10.1002/anie.201405100

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      The carbon–fluorine bond is known as one of the strongest chemical bonds. It is typically difficult to cleave, however, this cleavage can be achieved by a metal-mediated approach involving oxidative addition. In their Communication on page 7564 ff., J. Ichikawa and co-workers demonstrate a new method for C[BOND]F bond cleavage that utilizes β-fluorine elimination for a nickel-mediated [3+2] cycloaddition. The cover image illustrates two different tools for processing wood—a metal saw (oxidative addition) and a chisel (β-elimination)—as an analogy to the methods for metal-mediated C[BOND]F bond cleavage.

    2. You have free access to this content
      Inside Cover: Organic Photovoltaics: Elucidating the Ultra-Fast Exciton Dissociation Mechanism in Disordered Materials (Angew. Chem. Int. Ed. 29/2014) (page 7372)

      Henry M. Heitzer, Brett M. Savoie, Prof. Tobin J. Marks and Prof. Mark A. Ratner

      Article first published online: 30 MAY 2014 | DOI: 10.1002/anie.201405393

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      It has proven difficult to obtain a mechanistic understanding of exciton dissociation in bulk-heterojunction organic solar cells because of confounding factors, such as phase impurity, domain size, and the extent of exciton delocalization. In their Communication on page 7456 ff., T J. Marks, M. A. Ratner et al. present a new exciton dissociation model, which reproduces experimentally verified ultrafast and diffusion-limited behavior by combining initial exciton delocalization with traditional Förster energy transfer.

    3. You have free access to this content
      Inside Back Cover: Supramolecular Inhibition of Amyloid Fibrillation by Cucurbit[7]uril (Angew. Chem. Int. Ed. 29/2014) (page 7675)

      Hong Hee Lee, Tae Su Choi, Shin Jung C. Lee, Jong Wha Lee, Junghong Park, Dr. Young Ho Ko, Prof. Dr. Won Jong Kim, Prof. Dr. Kimoon Kim and Prof. Dr. Hugh I. Kim

      Article first published online: 18 MAY 2014 | DOI: 10.1002/anie.201405096

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      Amyloid fibrillation of the amyloidogenic proteins insulin and β-amyloid is inhibited by cucurbit[7]uril (CB[7]) through host–guest interactions. In their Communication on page 7461 ff., K. Kim, H. I. Kim, and co-workers demonstrate that CB[7] exhibits high binding affinity for phenylalanine residues, which are crucial to the hydrophobic interactions formed during amyloid fibrillation. This supramolecular strategy has potential for the development of a therapeutic agent for amyloidosis.

    4. You have free access to this content
      Back Cover: Co-existence of Two Different α-Synuclein Oligomers with Different Core Structures Determined by Hydrogen/Deuterium Exchange Mass Spectrometry (Angew. Chem. Int. Ed. 29/2014) (page 7676)

      Dr. Wojciech Paslawski, Simon Mysling, Karen Thomsen, Dr. Thomas J. D. Jørgensen and Prof. Dr. Daniel E. Otzen

      Article first published online: 14 JUL 2014 | DOI: 10.1002/anie.201401153

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      α-Synuclein oligomers are widely accepted to be cytotoxic species in Parkinson's disease. There is debate as to whether they are intermediate species of fibril formation or the end product of aggregation. In their Communication on page 7560 ff., D. Otzen, T. J. D. Jørgensen, and co-workers show that both are correct, and two types of α-synuclein oligomers are formed: one that can be elongated by monomers to form fibrils and a second that stacks together to form more amorphous structures.

  2. Frontispiece

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlight
    11. Minireview
    12. Review
    13. Communications
    1. You have free access to this content
      Frontispiece: Triazine-Based Graphitic Carbon Nitride: a Two-Dimensional Semiconductor

      Gerardo Algara-Siller, Dr. Nikolai Severin, Samantha Y. Chong, Dr. Torbjörn Björkman, Dr. Robert G. Palgrave, Andrea Laybourn, Prof. Dr. Markus Antonietti, Prof. Yaroslav Z. Khimyak, Dr. Arkady V. Krasheninnikov, Prof. Dr. Jürgen P. Rabe, Prof. Dr. Ute Kaiser, Prof. Andrew I. Cooper, Prof. Dr. Arne Thomas and Dr. Michael J. Bojdys

      Article first published online: 14 JUL 2014 | DOI: 10.1002/anie.201482971

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      Graphitic Carbon Nitride

      In their Communication on page 7450 ff., A. I. Cooper, M. J. Bojdys, et al. report crystalline thin films of triazine-based graphitic carbon nitride (TGCN). TGCN is structurally similar to graphite but it is a semiconductor, and the thin films display a direct bandgap between 1.6 and 2.0 eV.

  3. Graphical Abstract

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

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

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

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlight
    11. Minireview
    12. Review
    13. Communications
    1. Yi Xie (page 7396)

      Article first published online: 25 MAR 2014 | DOI: 10.1002/anie.201402434

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      “My favorite saying is “the devil is in the detail”. The principal aspects of my personality are modesty and optimism …” This and more about Yi Xie can be found on page 7396.

  7. News

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

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

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlight
    11. Minireview
    12. Review
    13. Communications
    1. CO2 Copolymers

      Preparation of CO2/Diene Copolymers: Advancing Carbon Dioxide Based Materials (pages 7402–7404)

      Dr. Giulia Fiorani and Prof. Dr. Arjan W. Kleij

      Article first published online: 18 JUN 2014 | DOI: 10.1002/anie.201403969

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      CO2-based materials: Metastable CO2/diene-based lactones, which were prepared by the palladium-catalyzed telomerization of CO2 and dienes, easily undergo aerobic radical homo-polymerization to give novel CO2-rich polymers. This two-step reaction set-up expands the potential applications of CO2-based copolymers by adding innovative compositions, structures, and properties.

  10. Minireview

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlight
    11. Minireview
    12. Review
    13. Communications
    1. Synthetic Methods

      Asymmetric Organocatalytic Epoxidations: Reactions, Scope, Mechanisms, and Applications (pages 7406–7426)

      Dr. Rebecca L. Davis, Dr. Julian Stiller, Dr. Tricia Naicker, Dr. Hao Jiang and Prof. Dr. Karl Anker Jørgensen

      Article first published online: 11 JUN 2014 | DOI: 10.1002/anie.201400241

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      Pick your type: In the past several decades, highly useful epoxidation protocols have been developed with a variety of activation modes using a wide range of asymmetric organocatalysts. This review documents the rapid and expansive development in this area, thus providing a clear overview of the various catalyst types available for asymmetric organocatalytic epoxidations, as well as their mechanisms and applications.

  11. Review

    1. Top of page
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    3. Frontispiece
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlight
    11. Minireview
    12. Review
    13. Communications
    1. Dyes/Pigments

      Strategies for the Synthesis of Functional Naphthalene Diimides (pages 7428–7448)

      Dr. Sabin-Lucian Suraru and Prof. Dr. Frank Würthner

      Article first published online: 24 JUN 2014 | DOI: 10.1002/anie.201309746

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      Core competence: The structural modification of naphthalene diimides has undergone significant development in the last few years, which has culminated in a broad range of new derivatives with different adjustable electronic properties. This Review describes the synthetic strategies towards core-substituted as well as core-expanded naphthalene diimides.

  12. Communications

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlight
    11. Minireview
    12. Review
    13. Communications
    1. Carbon Nitride | Hot Paper

      Triazine-Based Graphitic Carbon Nitride: a Two-Dimensional Semiconductor (pages 7450–7455)

      Gerardo Algara-Siller, Dr. Nikolai Severin, Samantha Y. Chong, Dr. Torbjörn Björkman, Dr. Robert G. Palgrave, Andrea Laybourn, Prof. Dr. Markus Antonietti, Prof. Yaroslav Z. Khimyak, Dr. Arkady V. Krasheninnikov, Prof. Dr. Jürgen P. Rabe, Prof. Dr. Ute Kaiser, Prof. Andrew I. Cooper, Prof. Dr. Arne Thomas and Dr. Michael J. Bojdys

      Article first published online: 18 MAY 2014 | DOI: 10.1002/anie.201402191

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      Only five non-metallic materials of the graphene family were known up to date: graphene, hBN, BCN, fluorographene, and graphene oxide. For the first time, crystalline thin films of triazine-based graphitic carbon nitride (TGCN) are now presented. TGCN is structurally similar to graphite but it is a semiconductor. The thin films are a few to several hundreds of atomic layers thick and display a direct bandgap between 1.6 and 2.0 eV.

    2. Exciton Dissociation

      Organic Photovoltaics: Elucidating the Ultra-Fast Exciton Dissociation Mechanism in Disordered Materials (pages 7456–7460)

      Henry M. Heitzer, Brett M. Savoie, Prof. Tobin J. Marks and Prof. Mark A. Ratner

      Article first published online: 14 MAY 2014 | DOI: 10.1002/anie.201402568

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      An exciting model: An exciton dissociation model that captures both ultra-fast and diffusion-limited behavior in bulk-heterojunction organic photovoltaic (OPV) systems is proposed. The model examines the disparate mechanisms for ultra-fast exciton delocalization: exciton delocalization and impure domains.

    3. Amyloids

      Supramolecular Inhibition of Amyloid Fibrillation by Cucurbit[7]uril (pages 7461–7465)

      Hong Hee Lee, Tae Su Choi, Shin Jung C. Lee, Jong Wha Lee, Junghong Park, Dr. Young Ho Ko, Prof. Dr. Won Jong Kim, Prof. Dr. Kimoon Kim and Prof. Dr. Hugh I. Kim

      Article first published online: 19 MAY 2014 | DOI: 10.1002/anie.201402496

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      Supramolecular strategy: Amyloid fibrillation of insulin and β-amyloid was modulated by using cucurbit[7]uril (CB[7]). CB[7] exhibits high binding affinity for phenylalanine residues, which are crucial to the hydrophobic interactions formed during amyloid fibrillation. This supramolecular strategy based on a residue-specific interaction has potential for the development of a therapeutic agent for amyloidosis.

    4. Inorganic Interfaces

      All-Inorganic Nanocrystals as a Glue for BiSbTe Grains: Design of Interfaces in Mesostructured Thermoelectric Materials (pages 7466–7470)

      Dr. Jae Sung Son, Hao Zhang, Dr. Jaeyoung Jang, Dr. Bed Poudel, Al Waring, Luke Nally and Prof. Dr. Dmitri V. Talapin

      Article first published online: 22 MAY 2014 | DOI: 10.1002/anie.201402026

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      The interfaces in thermoelectric materials can be formed by using bismuth nanocrystals (NCs) capped with (N2H5)4Sb2Te7 ligands that serve as a “glue” for mesoscopic grains, which are joined in hot-pressed pellets or solution-processed thin films. The design of the NC glue allows selective enhancement or decrease of the majority-carrier concentration near the grain boundaries.

    5. Materials for Carbon Sequestration

      Carbon Dioxide Sensitivity of Zeolitic Imidazolate Frameworks (pages 7471–7474)

      Cristina Mottillo and Prof. Tomislav Friščić

      Article first published online: 30 MAY 2014 | DOI: 10.1002/anie.201402082

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      ZIF today, carbonate tomorrow: The sensitivity of zeolitic imidazolate frameworks (ZIFs) to CO2 in humid environments, which was previously not recognized, leads to degradation of porous and non-porous Zn-, Co-, and Cd-based ZIFs into complex carbonates. Only one of the five tested ZIFs was resistant to chemical attack by CO2.

    6. DNA Architectures

      Complex Reconfiguration of DNA Nanostructures (pages 7475–7479)

      Dr. Bryan Wei, Luvena L. Ong, Jeffrey Chen, Alexander S. Jaffe and Prof. Dr. Peng Yin

      Article first published online: 4 JUN 2014 | DOI: 10.1002/anie.201402437

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      Carving out a shape-changing strategy: The modularly interconnected architecture of single-stranded DNA tile and brick structures was used to develop a general method for structural reconfiguration. The removal of one component strand (see picture) revealed a newly exposed toehold on a neighboring strand, thus enabling the removal of regions of connected component strands without the need to modify the strands with predesigned external toeholds.

    7. Zeolite Structures

      An Aluminophosphate Molecular Sieve with 36 Crystallographically Distinct Tetrahedral Sites (pages 7480–7483)

      Jun Kyu Lee, Alessandro Turrina, Liangkui Zhu, Seungwan Seo, Dr. Daliang Zhang, Dr. Paul A. Cox, Prof. Paul A. Wright, Prof. Shilun Qiu and Prof. Suk Bong Hong

      Article first published online: 26 MAY 2014 | DOI: 10.1002/anie.201402495

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      Structure elucidation: The structure of the new medium-pore aluminophosphate molecular sieve PST-6 (see picture) with 36 crystallographically distinct tetrahedral sites and thus with the most complex zeolite structure known to date, has been solved by combining X-ray diffraction, electron crystallography, and computer modeling.

    8. DNA Nanostructure

      Helical DNA Origami Tubular Structures with Various Sizes and Arrangements (pages 7484–7490)

      Prof. Dr. Masayuki Endo, Seigi Yamamoto, Tomoko Emura, Kumi Hidaka, Dr. Nobuhiro Morone, Prof. Dr. John E. Heuser and Prof. Dr. Hiroshi Sugiyama

      Article first published online: 30 MAY 2014 | DOI: 10.1002/anie.201402973

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      Tubular structures were constructed in a size-controlled fashion by a new DNA origami method and analyzed by atomic force microscopy. The formation of unexpectedly long tubes with different helical properties was observed in addition to that of the expected short ones. Analysis of the content of short and long tubes allows an estimation of the folding pathways.

    9. Protein Modifications

      Allenamides as Orthogonal Handles for Selective Modification of Cysteine in Peptides and Proteins (pages 7491–7494)

      Ata Abbas, Prof. Bengang Xing and Prof. Teck-Peng Loh

      Article first published online: 30 MAY 2014 | DOI: 10.1002/anie.201403121

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      Tagged: Allenamides add selectively to the thiol group of cysteine and does not react with the other functional groups on the unprotected peptide or protein under physiological conditions.

    10. NMR Spectroscopy

      Heterogeneous Solution NMR Signal Amplification by Reversible Exchange (pages 7495–7498)

      Fan Shi, Aaron M. Coffey, Assist. Prof. Kevin W. Waddell, Assist. Prof. Eduard Y. Chekmenev and Assoc. Prof. Boyd M. Goodson 

      Article first published online: 30 MAY 2014 | DOI: 10.1002/anie.201403135

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      Sending a signal: A novel variant of an iridium-based organometallic catalyst was synthesized and immobilized on polymer microbeads. Upon administration of parahydrogen (pH2) gas to a solution containing the catalyst and pyridine, up to a fivefold enhancement is observed in the 1H NMR spectra owing to the title process (HET-SABRE). The catalyst is easy to recycle and holds potential for applications varying from spectroscopic studies of catalysis to imaging metabolites.

    11. DNA Machines

      Switchable Reconfiguration of an Interlocked DNA Olympiadane Nanostructure (pages 7499–7503)

      Dr. Chun-Hua Lu, Xiu-Juan Qi, Alessandro Cecconello, Dr. Stefan-Sven Jester, Prof. Michael Famulok and Prof. Itamar Willner

      Article first published online: 30 MAY 2014 | DOI: 10.1002/anie.201403202

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      A feat worthy of a medal: A five-ring interlocked DNA catenane underwent programmed and switchable reconfiguration across four states (see picture). The dynamics of transitions between the states were monitored by fluorescence spectroscopy. By the tethering of gold nanoparticles to the five-ring catenane scaffold, reconfiguration of the nanoparticles was demonstrated.

    12. Microfluidics

      Versatile Preparation of Nonspherical Multiple Hydrogel Core PAM/PEG Emulsions and Hierarchical Hydrogel Microarchitectures (pages 7504–7509)

      Song Guo, Tong Yao, Xiaobo Ji, Prof. Changfeng Zeng, Prof. Chongqing Wang and Prof. Lixiong Zhang

      Article first published online: 4 JUN 2014 | DOI: 10.1002/anie.201403256

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      Mix and match: Emulsions of nonspherical multicore PAM/PEG droplets and hierarchical PAM/PEG hydrogel microarchitectures (see figure) are prepared by combining polymerization-induced phase separation with droplet coalescence in microdevices. This enables the fine-tuning of their morphology and inner structure.

    13. Synthetic Methods

      Practical, Modular, and General Synthesis of Benzofurans through Extended Pummerer Annulation/Cross-Coupling Strategy (pages 7510–7513)

      Prof. Dr. Kei Murakami, Prof. Dr. Hideki Yorimitsu and Prof. Dr. Atsuhiro Osuka

      Article first published online: 12 JUN 2014 | DOI: 10.1002/anie.201403288

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      It's simple: Operationally simple, efficient, and widely applicable Pummerer annulations of simple phenols with ketene dithioacetal monoxides provide a variety of benzofurans with a methylthio group at the 2-position. Subsequent nickel-catalyzed arylation culminates in diversity-oriented synthesis of multisubstituted benzofurans. The title sequence was used in the synthesis of biologically active natural products and highly fluorescent benzofurans.

    14. Reaction Cascades

      A Bioinspired Catalytic Oxygenase Cascade to Generate Complex Oxindoles (pages 7514–7518)

      Dr. Yao Wang, Dipl.-Chem. Jonathan O. Bauer, Prof. Dr. Carsten Strohmann and Dr. Kamal Kumar

      Article first published online: 30 MAY 2014 | DOI: 10.1002/anie.201403415

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      O2 cascades: The first one-pot oxygenase cascade is presented, wherein a copper-catalyzed oxygenase reaction transforms the allylic CH3 of 3-methylidene oxindole into an aldehyde, which then undergoes an aldol–oxa-Michael addition reaction with β-ketoesters to give dihydrofuran-bearing oxindoles.

    15. Natural Product Biosynthesis

      The Biosynthesis and Catabolism of the Maleic Anhydride Moiety of Stipitatonic Acid (pages 7519–7523)

      Dr. Ahmed al Fahad, Amira Abood, Prof. Dr. Thomas J. Simpson and Prof. Dr. Russell J. Cox

      Article first published online: 26 MAY 2014 | DOI: 10.1002/anie.201403450

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      Building and demolition: The biochemical steps leading from the first-formed tropolone of the stipitatic acid pathway in the fungus Talaromyces stipitatus via the maleic anhydride containing stipitatonic acid have been determined by coordinated gene knockout and in vitro assays. The formation of shunt products including cordytropolone and talaroditropolone sheds light on the metabolism in other fungal organisms.

    16. Natural Products

      Iterative Assembly of Two Separate Polyketide Chains by the Same Single-Module Bacterial Polyketide Synthase in the Biosynthesis of HSAF (pages 7524–7530)

      Dr. Yaoyao Li, Haotong Chen, Yanjiao Ding, Yunxuan Xie, Dr. Haoxin Wang, Prof. Dr. Ronald L. Cerny, Prof. Dr. Yuemao Shen and Prof. Dr. Liangcheng Du

      Article first published online: 30 MAY 2014 | DOI: 10.1002/anie.201403500

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      Only a single-module hybrid polyketide synthase–nonribosomal peptide synthetase (PKS-NRPS) is found in the biosynthetic gene cluster of the broad-spectrum antifungal polycyclic tetramate macrolactam HSAF (see picture), although two separate hexaketide chains are required to assemble the HSAF skeleton. Heterologous production and in vitro reconstitution by using purified PKS and NRPS demonstrated the iterative polyketide biosynthetic mechanism.

    17. Fluorogenic Probes

      Ultrafluorogenic Coumarin–Tetrazine Probes for Real-Time Biological Imaging (pages 7531–7534)

      Dr. Labros G. Meimetis, Dr. Jonathan C. T. Carlson, Dr. Randy J. Giedt, Dr. Rainer H. Kohler and Prof. Ralph Weissleder

      Article first published online: 10 JUN 2014 | DOI: 10.1002/anie.201403890

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      Fiercely fluorogenic: Brightness enhancement of greater than 10000-fold is detected in a series of coumarin–tetrazine probes, the largest to date of any bioorthogonal fluorogenic platform. This enhancement is achieved by the logical use of through-bond energy transfer (TBET) in molecular design. High-spatial-resolution “no-wash” images of extra- and intracellular targets were obtained with negligible background signal.

    18. Artificial Cells

      In Vitro Synthesis of the E. coli Sec Translocon from DNA (pages 7535–7538)

      M. Sc. Hideaki Matsubayashi, Dr. Yutetsu Kuruma and Prof. Dr. Takuya Ueda

      Article first published online: 4 JUN 2014 | DOI: 10.1002/anie.201403929

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      Cell free: The E.coli Sec translocon, which mediates the insertion of membrane proteins into the plasma membrane, was successfully reconstructed by synthesizing its component proteins in vitro. The synthesized SecYEG components were spontaneously inserted into a liposome membrane and formed a functional complex. The synthesized Sec translocon was able to mediate the membrane translocation of single- and multi-span membrane proteins (MPs).

    19. Spin Crossover

      Structure-Driven Orientation of the High-Spin–Low-Spin Interface in a Spin-Crossover Single Crystal (pages 7539–7542)

      Mouhamadou Sy, Prof. em. François Varret, Prof. Kamel Boukheddaden, Guillaume Bouchez, Ing. Jérôme Marrot, Prof. Santoshi Kawata and Prof. em. Sumio Kaizaki

      Article first published online: 4 JUN 2014 | DOI: 10.1002/anie.201403971

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      Elastic interfaces: The orientations of high-spin–low-spin (HS–LS) interfaces at the thermal transition of thin Fe(NCSe) spin-crossover crystals, observed by optical microscopy (see picture) are explained by considering the structural mismatch between the LS and HS phases in 2D models. The orientations correspond to mismatch-free situations which also explain the resilience of the crystals upon repeated switching.

    20. Multicomponent Coupling

      A Highly Modular One-Pot Multicomponent Approach to Functionalized Benzo[b]phosphole Derivatives (pages 7543–7546)

      Bin Wu, Dr. Mithun Santra and Prof. Naohiko Yoshikai

      Article first published online: 30 MAY 2014 | DOI: 10.1002/anie.201404019

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      All the pieces in one pot: A novel one-pot sequential coupling of readily available reaction components allows the construction of a library of benzo[b]phosphole derivatives. The method employs an arylzinc reagent, an alkyne, dichlorophenylphosphine (or phosphorus trichloride and a Grignard reagent), and an oxidant, and features the cobalt-catalyzed migratory arylzincation of the alkyne and electrophilic phosphacyclization as key steps.

    21. Metal Oxide Catalysts | Very Important Paper

      A Reliable Aerosol-Spray-Assisted Approach to Produce and Optimize Amorphous Metal Oxide Catalysts for Electrochemical Water Splitting (pages 7547–7551)

      Long Kuai, Jing Geng, Changyu Chen, Erjie Kan, Yadong Liu, Qing Wang and Prof. Dr. Baoyou Geng

      Article first published online: 4 JUN 2014 | DOI: 10.1002/anie.201404208

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      Spraying out catalysts: An aerosol-spray-assisted route with metal salts is a reliable route to identify amorphous metal oxide catalysts for electrochemical water splitting. The composition of the products can be precisely controlled from the precursor solution. The catalysts can be continuously collected at a rate of about 0.1 g h−1 from a single home-made device, and this method is thus scalable and suitable for industrial applications.

    22. Functionalized DNA | Hot Paper

      7-Aryl-7-deazaadenine 2′-Deoxyribonucleoside Triphosphates (dNTPs): Better Substrates for DNA Polymerases than dATP in Competitive Incorporations (pages 7552–7555)

      Pavel Kielkowski, Dr. Jindřich Fanfrlík and Prof. Dr. Michal Hocek

      Article first published online: 30 MAY 2014 | DOI: 10.1002/anie.201404742

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      More is more! Bulky functionalized 7-aryl-7-deazaadenine 2′-deoxyribonucleoside triphosphates (dNTPs) are better substrates than their natural counterparts in competitive primer extensions with DNA polymerases (see picture). This ability is important for the possible in vivo enzymatic synthesis of functionalized DNA.

    23. Oxide–Hydrides | Very Important Paper

      Strontium Vanadium Oxide–Hydrides: “Square-Planar” Two-Electron Phases (pages 7556–7559)

      Dr. Fabio Denis Romero, Alice Leach, Dr. Johannes S. Möller, Francesca Foronda, Prof. Stephen J. Blundell and Prof. Michael A. Hayward

      Article first published online: 24 JUN 2014 | DOI: 10.1002/anie.201403536

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      Exchanging anions makes vanadium square: Reaction with CaH2 leads to oxide-for-hydride ion exchange in Srn+1VnO3n+1 (n=∞, 1, 2) strontium vanadium oxides. The resulting oxide–hydride phases, SrVO2H, Sr2VO3H, and Sr3V2O5H2, contain arrays of apex-linked V3+O4 squares stacked with SrH layers/chains, such that SrVO2H can be considered to be analogous to infinite-layer oxide phases but with a d2 electron count.

    24. Protein Aggregation | Hot Paper

      Co-existence of Two Different α-Synuclein Oligomers with Different Core Structures Determined by Hydrogen/Deuterium Exchange Mass Spectrometry (pages 7560–7563)

      Dr. Wojciech Paslawski, Simon Mysling, Karen Thomsen, Dr. Thomas J. D. Jørgensen and Prof. Dr. Daniel E. Otzen

      Article first published online: 16 APR 2014 | DOI: 10.1002/anie.201400491

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      On-pathway or off-pathway? α-Synuclein oligomers are widely accepted to be cytotoxic species in Parkinson's disease. There is debate as to whether they are intermediate species of fibril formation or the distinct end product of aggregation. Data indicate that both are correct and two different types of α-synuclein oligomers are formed: one that can be elongated by monomers and form fibrils and a second that stacks together to form more amorphous structures.

    25. C[BOND]F Bond Activation

      Double C[BOND]F Bond Activation through β-Fluorine Elimination: Nickel-Mediated [3+2] Cycloaddition of 2-Trifluoromethyl-1-alkenes with Alkynes (pages 7564–7568)

      Tomohiro Ichitsuka, Dr. Takeshi Fujita, Tomohiro Arita and Prof. Dr. Junji Ichikawa

      Article first published online: 18 MAY 2014 | DOI: 10.1002/anie.201402695

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      Clear-cut: The nickel-mediated [3+2] cycloaddition of 2-trifluoromethyl-1-alkenes with alkynes afforded fluorine-containing multi-substituted cyclopentadienes. This reaction involves the consecutive and regioselective double C[BOND]F bond cleavage of a trifluoromethyl and a pentafluoroethyl group by β-fluorine elimination.

    26. Ligand Design

      B[BOND]H, C[BOND]H, and B[BOND]C Bond Activation: The Role of Two Adjacent Agostic Interactions (pages 7569–7573)

      Audrey Cassen, Yann Gloaguen, Laure Vendier, Carine Duhayon, Amalia Poblador-Bahamonde, Christophe Raynaud, Eric Clot, Gilles Alcaraz and Sylviane Sabo-Etienne

      Article first published online: 2 JUL 2014 | DOI: 10.1002/anie.201404753

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      Bond activity: A new phosphinoborane ruthenium complex was isolated. This complex exhibits two adjacent δ-Csp3[BOND]H and ε-Bsp2[BOND]H agostic interactions involving directly connected σ-bonds of different polarity, which can either be displaced or lead selectively to B[BOND]C or C[BOND]H bond cleavage, depending on the experimental conditions.

    27. Structure Elucidation

      Iron Porphyrin Carbenes as Catalytic Intermediates: Structures, Mössbauer and NMR Spectroscopic Properties, and Bonding (pages 7574–7578)

      Rahul L. Khade, Wenchao Fan, Dr. Yan Ling, Liu Yang, Prof. Dr. Eric Oldfield and Prof. Dr. Yong Zhang

      Article first published online: 6 JUN 2014 | DOI: 10.1002/anie.201402472

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      Doubled up: This work describes the first accurate predictions of the Mössbauer and 13C NMR spectra, local geometries, and Fe[BOND]C bonding of iron porphyrin carbenes (IPCs). Unlike the previously assumed picture of a double bond between iron and carbon [FeIV={C(X)Y}2−], analogous to the catalytic intermediates in conventional P450 reactions (FeIV[DOUBLE BOND]O2−), IPC complexes are best described as FeII[LEFTWARDS ARROW]{:C(X)Y}0.

    28. Heterocycle Synthesis

      Base-Controlled Selectivity in the Synthesis of Linear and Angular Fused Quinazolinones by a Palladium-Catalyzed Carbonylation/Nucleophilic Aromatic Substitution Sequence (pages 7579–7583)

      Jianbin Chen, Dr. Kishore Natte, Dr. Anke Spannenberg, Dr. Helfried Neumann, Prof. Dr. Peter Langer, Prof. Dr. Matthias Beller and Prof. Dr. Xiao-Feng Wu

      Article first published online: 30 MAY 2014 | DOI: 10.1002/anie.201402779

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      First base, second base… home run! A base-controlled palladium-catalyzed carbonylation/intramolecular nucleophilic aromatic substitution reaction gave linear and angular fused pyridoquinazolones: 1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU) yielded the linear products, whereas NEt3 gave the angular derivatives (see scheme; Ad=adamantyl, DMA=dimethylacetamide). A light-induced Diels–Alder reaction of the product was also observed.

    29. Oxygen Evolution Catalysts

      A Strongly Coupled Graphene and FeNi Double Hydroxide Hybrid as an Excellent Electrocatalyst for the Oxygen Evolution Reaction (pages 7584–7588)

      Xia Long, Jinkai Li, Shuang Xiao, Keyou Yan, Zilong Wang, Haining Chen and Shihe Yang

      Article first published online: 6 JUN 2014 | DOI: 10.1002/anie.201402822

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      A low-cost and highly active electrochemical catalyst for the oxygen evolution reaction is created by alternatively stacking FeNi double hydroxide cation layers with GO anionic sheets. The advanced performance of the catalyst stems from the intrinsic catalytic activity of the layered FeNi double hydroxide and is boosted by the high electric conductivity of the adjoining graphene sheets.

    30. C[BOND]H Borylation

      Phosphine-Directed C[BOND]H Borylation Reactions: Facile and Selective Access to Ambiphilic Phosphine Boronate Esters (pages 7589–7593)

      Kristina M. Crawford, Timothy R. Ramseyer, Christopher J. A. Daley and Timothy B. Clark

      Article first published online: 4 JUN 2014 | DOI: 10.1002/anie.201402868

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      Directed borylation: Ambiphilic phosphine boronate esters are accessed by a phosphine-directed C[BOND]H borylation reaction. The Lewis basic phosphine directs the borylation to the adjacent C[BOND]H bond, providing access to intriguing ligand and catalyst scaffolds.

    31. Asymmetric Catalysis

      A Cooperative N-Heterocyclic Carbene/Chiral Phosphate Catalysis System for Allenolate Annulations (pages 7594–7598)

      Dr. Anna Lee and Prof. Karl A. Scheidt

      Article first published online: 4 JUN 2014 | DOI: 10.1002/anie.201403446

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      Cooperation: A highly enantioselective NHC-catalyzed [3+2] annulation of α,β-alkynals and α-ketoesters generates the desired γ-crotonolactones in high yields. The reaction is based on the cooperative catalysis of a chiral Brønsted acid and a precatalyst consisting of a C1-symmetric biaryl and a saturated imidazolium moiety.

    32. Metallopeptide Design | Hot Paper

      Conformationally Constrained Cyclic Peptides: Powerful Scaffolds for Asymmetric Catalysis (pages 7599–7603)

      Lifei Zheng, Alessio Marcozzi, Dr. Jennifer Y. Gerasimov and Prof. Dr. Andreas Herrmann

      Article first published online: 4 JUN 2014 | DOI: 10.1002/anie.201403829

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      Ligand development: A cyclic peptide, containing only natural amino acids along with an intramolecular disulfide bridge, was identified as a simple and versatile coordination sphere for asymmetric catalysis. “Alanine scanning” provided mechanistic insights and assisted in systematic optimizations for the peptide ligands.

    33. Acyltrifluoroborate Reagents | Hot Paper

      A Reagent for the One-Step Preparation of Potassium Acyltrifluoroborates (KATs) from Aryl- and Heteroarylhalides (pages 7604–7607)

      Dr. Gábor Erős, Yo Kushida and Prof. Dr. Jeffrey W. Bode

      Article first published online: 30 MAY 2014 | DOI: 10.1002/anie.201403931

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      Bring it on! The challenge of forming acyl boranes by trapping acyl anion equivalents is avoided by the design and development of an electrophilic source of the acyltrifluoroborate group. This novel reagent makes possible the one-step transformation of aryl and heteroaryl halides into the corresponding potassium acyltrifluoroborates via organolithium intermediates.

    34. Cyclization

      Rhodium(I)-Catalyzed Cycloisomerization of Benzylallene-Alkynes through C[BOND]H Activation (pages 7608–7612)

      Yasuaki Kawaguchi, Dr. Shigeo Yasuda, Akira Kaneko, Yuki Oura and Prof. Dr. Chisato Mukai

      Article first published online: 30 MAY 2014 | DOI: 10.1002/anie.201403990

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      Vinylidene complex: An efficient RhI-catalyzed cycloisomerization of benzylallene-alkynes produced the tricyclo[9.4.0.03,8]pentadecapentaene skeleton through Cinline image[BOND]H bond activation. Based on deuteration and competition experiments, a reaction mechanism was proposed, which proceeds via a vinylidenecarbene–RhI intermediate.

    35. Graphene Oxide

      Sulfur-Functionalized Graphene Oxide by Epoxide Ring-Opening (pages 7613–7618)

      Helen R. Thomas, Alexander J. Marsden, Dr. Marc Walker, Dr. Neil R. Wilson and Dr. Jonathan P. Rourke

      Article first published online: 4 JUN 2014 | DOI: 10.1002/anie.201404002

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      GO for gold: Potassium thioacetate was used to selectively open the epoxides present on a graphene oxide (GO) surface. This new route into functionalization of GO was exploited to attach gold nanoparticles on a GO surface (see picture).

    36. Carbocycle Synthesis

      Highly Diastereodivergent Synthesis of Tetrasubstituted Cyclohexanes Catalyzed by Modularly Designed Organocatalysts (pages 7619–7623)

      Dr. Nirmal K. Rana, Dr. Huicai Huang and Prof. Dr. John C.-G. Zhao

      Article first published online: 12 JUN 2014 | DOI: 10.1002/anie.201404072

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      Stereoisomer made to order: Diastereodivergence is realized through controlling the stereoselectivity of the individual steps of a tandem Michael/Michael reaction. Up to 8 of the 16 possible stereoisomers have been successfully obtained in high enantio- and diastereoselectivities using modularly designed organocatalysts for the tandem reaction and an ensuing epimerization. QDT=quinidine thiourea, QNT=quinine thiourea.

    37. Supported Catalysts

      Gold-Catalyzed Direct Hydrogenative Coupling of Nitroarenes To Synthesize Aromatic Azo Compounds (pages 7624–7628)

      Xiang Liu, Hai-Qian Li, Sen Ye, Dr. Yong-Mei Liu, Prof. Dr. He-Yong He and Prof. Dr. Yong Cao

      Article first published online: 6 JUN 2014 | DOI: 10.1002/anie.201404543

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      Game of rates: A general approach for the chemoselective hydrogenative coupling of nitroarenes to give the corresponding azo compounds, using a heterogeneous gold catalyst, has been developed. As a result of the remarkable synergy between the metal and support, a facile condensation of transient nitroso and hydroxylamine intermediates proceeds. The desired transformation is highly selective under mild reaction conditions.

    38. Trifluoromethylation

      Copper-Catalyzed One-Pot Trifluoromethylation/Aryl Migration/Carbonyl Formation with Homopropargylic Alcohols (pages 7629–7633)

      Dr. Pin Gao, Yong-Wen Shen, Ran Fang, Xin-Hua Hao, Zi-Hang Qiu, Fan Yang, Xiao-Biao Yan, Qiang Wang, Xiang-Jun Gong, Prof. Dr. Xue-Yuan Liu and Prof. Dr. Yong-Min Liang

      Article first published online: 18 JUN 2014 | DOI: 10.1002/anie.201403383

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      A copper-catalyzed one-pot reaction of homopropargylic alcohols involves trifluoromethylation, aryl migration, and formation of a carbonyl group. A series of 3-butenal and 3-buten-1-one derivatives with a trifluoromethyl-substituted olefin were obtained in moderate to good yields with high regioselectivity. The mechanism is proposed to involve a 5-ipso cyclization.

    39. Cascade Reactions

      Asymmetric Cascade Reaction to Allylic Sulfonamides from Allylic Alcohols by Palladium(II)/Base-Catalyzed Rearrangement of Allylic Carbamates (pages 7634–7638)

      Dipl.-Chem. Johannes Moritz Bauer, Dr. Wolfgang Frey and Prof. Dr. René Peters

      Article first published online: 4 JUN 2014 | DOI: 10.1002/anie.201403090

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      Going through changes: Highly enantioenriched allylic amines have been prepared by a cascade reaction capable of transforming allylic alcohols into chiral sulfonyl-protected allylic amines. This process is catalyzed by the combination of a chiral palladacycle and a tertiary amine base and merges high step-economy with operational simplicity. Mechanistic studies suggest that the key step is a [3,3] rearrangement of a deprotonated N-sulfonylcarbamate.

    40. Phosphorus Activation

      Selective Functionalization of P4 by Metal-Mediated C[BOND]P Bond Formation (pages 7639–7642)

      Sebastian Heinl, Sabine Reisinger, Dr. Christoph Schwarzmaier, Dr. Michael Bodensteiner and Prof. Dr. Manfred Scheer

      Article first published online: 30 MAY 2014 | DOI: 10.1002/anie.201403295

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      New wings for the P4 butterfly: Using two methods starting from white phosphorus, the carbon-substituted bicyclic P4 butterfly compounds CpR2P4 (CpR=C5(4-nBuC6H4)5, C5H2tBu3, C5Me5, C5HiPr4) were generated. The methods involve the intermediary formation of {CpR} radicals that selectively open one P[BOND]P bond of the P4 tetrahedron. The simple procedures and the broad variety of suitable CpR substituents open new ways in the carbon-based P4 activation.

    41. Phosphaferrocenes

      Functionalization of a cyclo-P5 Ligand by Main-Group Element Nucleophiles (pages 7643–7646)

      Eric Mädl, Dr. Mikhail V. Butovskii, Dr. Gábor Balázs, Dr. Eugenia V. Peresypkina, Dr. Alexander V. Virovets, Michael Seidl and Prof. Dr. Manfred Scheer

      Article first published online: 4 JUN 2014 | DOI: 10.1002/anie.201403581

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      Pentaphosphaferrocene [Cp*Fe(η5-P5)] reacts with different nucleophiles, leading to the formation of unprecedented mono-, di-, or trianionic species. These compounds show a dissimilarity to its carbonaceous relative ferrocene.

    42. Functionalized Terpyridines

      Unprecedented Strong Lewis Bases—Synthesis and Methyl Cation Affinities of Dimethylamino-Substituted Terpyridines (pages 7647–7651)

      Dr. Paul Hommes, Christina Fischer, Dr. Christoph Lindner, Prof. Dr. Hendrik Zipse and Prof. Dr. Hans-Ulrich Reissig

      Article first published online: 4 JUN 2014 | DOI: 10.1002/anie.201403403

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      Super Lewis bases! The hitherto unknown 4,4′′-bis(dimethylamino)- and 4,4′,4′′-tris(dimethylamino)terpyridines have been prepared by a simple and flexible synthesis. Nonafloxy-substituted terpyridine intermediates allow smooth introduction of dimethylamino groups or palladium-catalyzed coupling reactions. The calculated methyl cation affinities of the novel terpyridines promise unprecedented high Lewis basicities and excellent ligand properties.

    43. Enzyme Models

      Induced-Fit Mechanism in Class I Terpene Cyclases (pages 7652–7656)

      Philipp Baer, Patrick Rabe, Katrin Fischer, Christian A. Citron, Tim A. Klapschinski, Prof. Dr. Michael Groll and Prof. Dr. Jeroen S. Dickschat

      Article first published online: 30 MAY 2014 | DOI: 10.1002/anie.201403648

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      A class act: The open and closed (ligand-bound) conformations of selinadiene synthase reveal an induced-fit mechanism, and give insights into carbocation formation and regulation in class I terpene cyclases. The substrate turnover is accomplished by an effector triad on the G1 helix, comprising the pyrophosphate sensor Arg178, the linker Asp181, and the effector Gly182. This structural motif is strictly conserved in all class I terpene cyclases.

    44. Photopharmacology

      Optical Control of Acetylcholinesterase with a Tacrine Switch (pages 7657–7660)

      Dipl.-Chem. Johannes Broichhagen, Innokentij Jurastow, Katharina Iwan, Prof. Dr. Wolfgang Kummer and Prof. Dr. Dirk Trauner

      Article first published online: 4 JUN 2014 | DOI: 10.1002/anie.201403666

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      Taming an enzyme with light: Acetylcholinesterase (AChE) is one of the most active enzymes and an essential component of synaptic transmission in cholinergic systems. Based on the well-known drug tacrine, a photoswitchable inhibitor that can optically control the enzymatic activity of AChE was developed, and its inhibitory effect was shown by tracheal tensometry. The molecule is a weak inhibitor in the dark, but gains full activity when irradiated with UV light.

    45. Photochemistry | Very Important Paper

      Enantioselective Catalysis of the Intermolecular [2+2] Photocycloaddition between 2-Pyridones and Acetylenedicarboxylates (pages 7661–7664)

      M. Sc. Mark M. Maturi and Prof. Dr. Thorsten Bach

      Article first published online: 2 JUN 2014 | DOI: 10.1002/anie.201403885

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      Unprecedented heights: Although the triplet state of pyridones (which is populated through sensitizer 1) lies more than 250 kJ mol−1 above the ground state, the enantioselective control of an intermolecular [2+2] photocycloaddition has been achieved for the first time, using only low catalyst loadings.

    46. DNA Nanotechnology | Hot Paper

      Surface-Assisted Large-Scale Ordering of DNA Origami Tiles (pages 7665–7668)

      Ali Aghebat Rafat, Dr. Tobias Pirzer, Max B. Scheible, Anna Kostina and Prof. Dr. Friedrich C. Simmel

      Article first published online: 4 JUN 2014 | DOI: 10.1002/anie.201403965

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      Molecular tessellation: Electrostatic control of adhesion and mobility of DNA origami structures on mica surfaces using monovalent cations facilitates formation of large, ordered 2D arrays of origami tiles. The lattices can be formed either by close-packing of symmetric, non-interacting DNA origami structures, or by utilizing blunt-end stacking interactions between the origami units. The resulting crystalline lattices are readily utilized as templates for the ordered arrangement of proteins.

    47. Tumor Diagnosis

      You have full text access to this OnlineOpen article
      In Vivo Imaging of Mouse Tumors by a Lipidated Cathepsin S Substrate (pages 7669–7673)

      Dr. Hai-Yu Hu, Dr. Divya Vats, Matej Vizovisek, Lovro Kramer, Catherine Germanier, Dr.  K. Ulrich Wendt, Prof. Markus Rudin, Prof. Boris Turk, Dr. Oliver Plettenburg and Priv.-Doz. Dr. Carsten Schultz

      Article first published online: 30 MAY 2014 | DOI: 10.1002/anie.201310979

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      Lipidated protease FRET probes were previously shown to be internalized by target cells releasing the protease of interest. A lipidated, non-peptidic FRET probe is presented for cathepsin S, a protease secreted by macrophages in the tumor environment. In cultured cells and in a grafted tumor mouse model, the probe is successfully cleaved and in the mouse is accumulated in the tumor tissue with little signal in organs such as liver and lung.

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