Angewandte Chemie International Edition

Cover image for Vol. 54 Issue 32

August 3, 2015

Volume 54, Issue 32

Pages 9129–9418

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Author Profile
    8. News
    9. Highlight
    10. Review
    11. Communications
    1. You have free access to this content
      Cover Picture: Precise Molecular Fission and Fusion: Quantitative Self-Assembly and Chemistry of a Metallo-Cuboctahedron (Angew. Chem. Int. Ed. 32/2015) (page 9129)

      Dr. Ting-Zheng Xie, Dr. Kai Guo, Zaihong Guo, Wen-Yang Gao, Dr. Lukasz Wojtas, Dr. Guo-Hong Ning, Mingjun Huang, Dr. Xiaocun Lu, Jing-Yi Li, Dr. Sheng-Yun Liao, Dr. Yu-Sheng Chen, Dr. Charles N. Moorefield, Dr. Mary Jane Saunders, Prof. Stephen Z. D. Cheng, Prof. Chrys Wesdemiotis and Prof. George R. Newkome

      Article first published online: 26 JUN 2015 | DOI: 10.1002/anie.201505542

      Thumbnail image of graphical abstract

      Archimedean-based supramolecular cages are stoichiometrically synthesized from a bent, X-type, terpyridine-based ligand and Zn2+ or Cd2+ ions as described by G. R. Newkome, C. Wesdemiotis et al. in their Communication on page 9224 ff. Triggered by changing the concentration or the counterions, these unique materials undergo a fission–fusion process between a cuboctahedron and two octahedra that is reminiscent of the well-known biological processes observed in cell replication.

    2. You have free access to this content
      Inside Cover: Energetic Insight into the Formation of Solids from Aluminum Polyoxocations (Angew. Chem. Int. Ed. 32/2015) (page 9130)

      Dr. Dana Reusser, Prof. William H. Casey and Prof. Alexandra Navrotsky

      Article first published online: 30 JUN 2015 | DOI: 10.1002/anie.201505498

      Thumbnail image of graphical abstract

      In polluted streams aluminum-based amorphous solids (flocs) are formed via an intermediate, the ε-Keggin [AlO4Al12(OH)24(H2O)12]7+ ion (Al137+). In their Communication on page 9253 ff., A. Navrotsky et al. show the ε-Keggin Al137+ ion is energetically close to these aluminum flocs. Shown is a stream polluted with aluminum hydroxide flocs from Collar Gulch, Montana. Artwork design by Sharon Betterton, background photograph courtesy of Prof. Chris Gammons, Montana State University.

    3. You have free access to this content
      Inside Back Cover: Chemical Detoxification of Organomercurials (Angew. Chem. Int. Ed. 32/2015) (page 9419)

      Mainak Banerjee, Ramesh Karri, Kuber Singh Rawat, Karthick Muthuvel, Dr. Biswarup Pathak and Dr. Gouriprasanna Roy

      Article first published online: 23 JUL 2015 | DOI: 10.1002/anie.201506278

      Thumbnail image of graphical abstract

      Organomercurials including methylmercury are highly toxic to humans. In their Communication on page 9323 ff., G. Roy and co-workers describe a novel pathway to detoxify various organomercurials using N-methylimidazole-based thiones/selones. Less-toxic insoluble HgS and HgSe nanoparticles are formed under physiologically relevant conditions when organomercurials are treated with N-methylimidazole-based thiones/selones having an N-CH2CH2OH substituent.

    4. You have free access to this content
      Back Cover: Mercury under Pressure acts as a Transition Metal: Calculated from First Principles (Angew. Chem. Int. Ed. 32/2015) (page 9420)

      Dr. Jorge Botana, Dr. Xiaoli Wang, Dr. Chunju Hou, Prof. Dr. Dadong Yan, Prof. Dr. Haiqing Lin, Prof. Dr. Yanming Ma and Prof. Dr. Mao-sheng Miao

      Article first published online: 3 JUL 2015 | DOI: 10.1002/anie.201505500

      Thumbnail image of graphical abstract

      The 5d core electrons of Hg become active and involved in forming chemical bonds under high pressure. In their Communication on page 9280 ff., M.-S. Miao and co-workers show by means of first-principles calculations that Hg can form stable compounds of HgF4 and HgF3 under high pressure. The HgF4 molecular crystal consists of square-planar HgF4 molecules. HgF3 is an extended solid and exhibits exotic properties. It is metallic, ferromagnetic, and transparent to visible light.

  2. Frontispiece

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Author Profile
    8. News
    9. Highlight
    10. Review
    11. Communications
    1. You have free access to this content
      Frontispiece: Hybridization Gap and Dresselhaus Spin Splitting in EuIr4In2Ge4

      Nicholas P. Calta, Dr. Jino Im, Alexandra P. Rodriguez, Dr. Lei Fang, Dr. Daniel E. Bugaris, Dr. Thomas C. Chasapis, Prof. Arthur J. Freeman and Prof. Mercouri G. Kanatzidis

      Article first published online: 28 JUL 2015 | DOI: 10.1002/anie.201583261

      Thumbnail image of graphical abstract

      Intermetallic Phases M. G. Kanatzidis and co-workers describe in their Communication on page 9186 ff. an intermetallic semiconductor that adopts a non-centrosymmetric structure. The band gap in EuIr4In2Ge4 is a direct result of strong Ir[BOND]Ir bonding.

  3. Editorial

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Author Profile
    8. News
    9. Highlight
    10. Review
    11. Communications
    1. You have free access to this content
      The Graphene Flagship—A Giant European Research Project (pages 9132–9133)

      Prof. Andreas Hirsch

      Article first published online: 26 JUN 2015 | DOI: 10.1002/anie.201504842

      Thumbnail image of graphical abstract

      “…The European Commission decided to launch the Graphene Flagship Project in 2013. The project brings together leading research laboratories from all over Europe with a wide span of different expertise. The Graphene Flagship (together with the Human Brain Project) is the largest collaborative research project that has ever been set up in Europe …” Read more in the Editorial by Andreas Hirsch.

  4. Graphical Abstract

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

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

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Author Profile
    8. News
    9. Highlight
    10. Review
    11. Communications
    1. Marinella Mazzanti (page 9154)

      Article first published online: 13 APR 2015 | DOI: 10.1002/anie.201501564

      Thumbnail image of graphical abstract

      “If I won the lottery, I would open an art gallery. My biggest motivation is to keep learning new things …” This and more about Marinella Mazzanti can be found on page 9154.

  7. News

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

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Author Profile
    8. News
    9. Highlight
    10. Review
    11. Communications
    1. Universal Blood

      Towards the Production of Universal Blood by Structure-Guided Directed Evolution of Glycoside Hydrolases (pages 9158–9160)

      Dr. Zhoutong Sun, Dr. Adriana Ilie and Prof. Dr. Manfred T. Reetz

      Article first published online: 19 JUN 2015 | DOI: 10.1002/anie.201504318

      Thumbnail image of graphical abstract

      Coming closer to a vision: Directed evolution has been applied to a glycoside hydrolase for increased activity in the selective cleavage of A- and B-antigens from linkages on red blood cell surface glycans. The results are a major step forward in the challenging endeavor of producing universal blood.

  9. Review

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Author Profile
    8. News
    9. Highlight
    10. Review
    11. Communications
    1. Biomolecular NMR Spectroscopy

      Facing and Overcoming Sensitivity Challenges in Biomolecular NMR Spectroscopy (pages 9162–9185)

      Prof. Dr. Jan-Henrik Ardenkjaer-Larsen, Prof. Dr. Gregory S. Boebinger, Prof. Dr. Arnaud Comment, Prof. Dr. Simon Duckett, Prof. Dr. Arthur S. Edison, Dr. Frank Engelke, Prof. Dr. Christian Griesinger, Prof. Dr. Robert G. Griffin, Prof. Dr. Christian Hilty, Prof. Dr. Hidaeki Maeda, Prof. Dr. Giacomo Parigi, Prof. Dr. Thomas Prisner, Dr. Enrico Ravera, Prof. Dr. Jan van Bentum, Prof. Dr. Shimon Vega, Prof. Dr. Andrew Webb, Prof. Dr. Claudio Luchinat, Prof. Dr. Harald Schwalbe and Prof. Dr. Lucio Frydman

      Article first published online: 1 JUL 2015 | DOI: 10.1002/anie.201410653

      Thumbnail image of graphical abstract

      A new spin on bio-NMR: This Review presents a state-of-the-art description of the leading approaches being considered today to improve the sensitivity of NMR spectroscopy, particularly as applied in biomolecular settings. The focus is on the future of ultrahigh-field NMR systems, emerging NMR detection technologies, new approaches to nuclear hyperpolarization, and progress in sample preparation.

  10. Communications

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Author Profile
    8. News
    9. Highlight
    10. Review
    11. Communications
    1. Intermetallic Phases

      Hybridization Gap and Dresselhaus Spin Splitting in EuIr4In2Ge4 (pages 9186–9191)

      Nicholas P. Calta, Dr. Jino Im, Alexandra P. Rodriguez, Dr. Lei Fang, Dr. Daniel E. Bugaris, Dr. Thomas C. Chasapis, Prof. Arthur J. Freeman and Prof. Mercouri G. Kanatzidis

      Article first published online: 25 JUN 2015 | DOI: 10.1002/anie.201504315

      Thumbnail image of graphical abstract

      An intermetallic semiconductor with a non-centrosymmetric structure and the chemical formula EuIr4In2Ge4 is reported. The band gap is a direct result of strong Ir[BOND]Ir bonding, and strong spin–orbit coupling effects lead to spin splitting at the conduction- and valence-band edges, which is described by the Dresselhaus term.

    2. Molecular Logic Gates

      A Molecular Platform for Multistate Near-Infrared Electrochromism and Flip-Flop, Flip-Flap-Flop, and Ternary Memory (pages 9192–9197)

      Bin-Bin Cui, Jian-Hong Tang, Prof. Jiannian Yao and Prof. Yu-Wu Zhong

      Article first published online: 3 JUL 2015 | DOI: 10.1002/anie.201504584

      Thumbnail image of graphical abstract

      A diruthenium complex with a redox-active amine bridge shows three well-separated redox processes with exclusive near-infrared (NIR) absorbance at each redox state. The flip-flop, flip-flap-flop, and ternary memory have been realized by using the electropolymerized film (15–20 nm thick) of a related vinyl-functionalized complex with three electrochemical inputs and three NIR optical outputs.

    3. Boryl Radicals

      A Phosphine-Coordinated Boron-Centered Gomberg-Type Radical (pages 9198–9202)

      Dr. Amos J. Rosenthal, Dr. Marc Devillard, Dr. Karinne Miqueu, Dr. Ghenwa Bouhadir and Dr. Didier Bourissou

      Article first published online: 26 JUN 2015 | DOI: 10.1002/anie.201504502

      Thumbnail image of graphical abstract

      Radical action: A P-coordinated boryl radical with large spin density at the boron center is reported. The structure of the radical has been analyzed by EPR spectroscopy and using DFT calculations. The radical is found to undergo dimerization by a Gomberg-type dimerization process.

    4. Natural Products

      Total Synthesis and Structural Revision of Antibiotic CJ-16,264 (pages 9203–9208)

      Prof. Dr. K. C. Nicolaou, Dr. Akshay A. Shah, Dr. Henry Korman, Dr. Tabrez Khan, Dr. Lei Shi, Dr. Wisuttaya Worawalai and Prof. Dr. Emmanuel A. Theodorakis

      Article first published online: 19 JUN 2015 | DOI: 10.1002/anie.201504337

      Thumbnail image of graphical abstract

      CJ-16,264 demystified: A pursuit of the originally assigned structure of antibiotic CJ-16,264 through a novel strategy featuring a double transannular Diels–Alder reaction led to its first total synthesis and structural revision.

    5. Synthetic Methods

      Effective Formylation of Amines with Carbon Dioxide and Diphenylsilane Catalyzed by Chelating bis(tzNHC) Rhodium Complexes (pages 9209–9212)

      Thanh V. Q. Nguyen, Dr. Woo-Jin Yoo and Prof. Dr. Shū Kobayashi

      Article first published online: 19 JUN 2015 | DOI: 10.1002/anie.201504072

      Thumbnail image of graphical abstract

      Beyond the norm: Rhodium complexes bearing a strong electron-donating bis(1,2,3-triazol-5-ylidene) ligand were found to be excellent catalysts for the reductive formylation of amines with CO2 and Ph2SiH2 at ambient temperature. The catalyst system possesses a broad substrate scope which tolerates a variety of reducible functional groups and is suitable for the synthesis of bioactive compounds. Tf=trifuoromethanesulfonyl.

    6. Molecular Recognition

      Force Spectroscopy of Metal–Crown Ether Multivalency: Effect of Local Environments on Energy Landscape and Sensing Kinetics (pages 9213–9217)

      Dr. Ting-Yang Kuo, Dr. Wei-Hsiang Tseng and Prof. Dr. Chun-hsien Chen

      Article first published online: 18 JUN 2015 | DOI: 10.1002/anie.201503948

      Thumbnail image of graphical abstract

      Break it up! The mechanical strength of metal–crown ether multivalent interactions is unveiled quantitatively by single-molecule force spectroscopy. The rupture force is on the order of tens of pico-Newton. Dynamic force spectroscopy shows that the effect of local environments is distinct on affinity association yet relatively insignificant on the dissociation reaction.

    7. Nanomedicine

      Hydrophobic Cysteine Poly(disulfide)-based Redox-Hypersensitive Nanoparticle Platform for Cancer Theranostics (pages 9218–9223)

      Dr. Jun Wu, Dr. Lili Zhao, Dr. Xiaoding Xu, Dr. Nicolas Bertrand, Dr. Won II Choi, Dr. Basit Yameen, Prof. Jinjun Shi, Vishva Shah, Matthew Mulvale, James L. MacLean and Prof. Omid C. Farokhzad

      Article first published online: 26 JUN 2015 | DOI: 10.1002/anie.201503863

      Thumbnail image of graphical abstract

      Fatty diacid monomers were used to develop a hydrophobic cysteine poly(disulfide)-based redox-sensitive nanoparticle platform for cancer theranostics. With this model system, the relationships between polymer structure, nanoparticle hydrophobicity, and redox responsibility were demonstrated. In vitro and in vivo results showed excellent anticancer performance.

    8. Archimedean Polyhedra | Very Important Paper

      Precise Molecular Fission and Fusion: Quantitative Self-Assembly and Chemistry of a Metallo-Cuboctahedron (pages 9224–9229)

      Dr. Ting-Zheng Xie, Dr. Kai Guo, Zaihong Guo, Wen-Yang Gao, Dr. Lukasz Wojtas, Dr. Guo-Hong Ning, Mingjun Huang, Dr. Xiaocun Lu, Jing-Yi Li, Dr. Sheng-Yun Liao, Dr. Yu-Sheng Chen, Dr. Charles N. Moorefield, Dr. Mary Jane Saunders, Prof. Stephen Z. D. Cheng, Prof. Chrys Wesdemiotis and Prof. George R. Newkome

      Article first published online: 11 JUN 2015 | DOI: 10.1002/anie.201503609

      Thumbnail image of graphical abstract

      Bigger and bigger: A giant, 6 nm, shape-persistent, Archimedean-inspired cuboctahedron was quantitatively assembled and characterized by synchrotron X-ray analysis. The structure consists of one type of X-shaped, terpyridine-based ligand and 24 metal ions (Zn2+ or Cd2+). A fusion–fission switching process between a cuboctahedron and an octahedron could be induced by changing the concentration or the counterions.

    9. Electrocatalysis

      Designing a Highly Active Metal-Free Oxygen Reduction Catalyst in Membrane Electrode Assemblies for Alkaline Fuel Cells: Effects of Pore Size and Doping-Site Position (pages 9230–9234)

      Seonggyu Lee, Myounghoon Choun, Youngjin Ye, Prof. Dr. Jaeyoung Lee, Yeongdong Mun, Dr. Eunae Kang, Jongkook Hwang, Young-Ho Lee, Prof. Dr. Chae-Ho Shin, Prof. Dr. Seung-Hyeon Moon, Prof. Dr. Soo-Kil Kim, Prof. Dr. Eunsung Lee and Prof. Dr. Jinwoo Lee

      Article first published online: 18 JUN 2015 | DOI: 10.1002/anie.201501590

      Thumbnail image of graphical abstract

      Controlling the pore size and doping site position of metal-free catalysts is the key to the synthesis of highly active metal-free catalysts for membrane electrode assemblies. Both have a critical influence on the accessibility of reactants to doping sites. A metal-free catalyst with a large pore size and precisely controlled doping site positions provides highly accessible doping sites, resulting in an outstanding single-cell performance.

    10. 1,3-Dipolar Cycloaddition

      Region-Selective Deposition of Core–Shell Nanoparticles for 3 D Hierarchical Assemblies by the Huisgen 1,3-Dipolar Cycloaddition (pages 9235–9238)

      Sebastian H. Etschel, Luis Portilla, Johannes Kirschner, Martin Drost, Fan Tu, Priv.-Doz. Dr. Hubertus Marbach, Prof. Dr. Rik R. Tykwinski and Prof. Dr. Marcus Halik

      Article first published online: 18 JUN 2015 | DOI: 10.1002/anie.201501957

      Thumbnail image of graphical abstract

      Like a NP-needle in an azide-stack: Metal oxide nanoparticles functionalized with alkyne- and azide-bearing phosphonic acids were assembled in defined stacks with precise control over region-selectivity and layer composition by the Huisgen 1,3-dipolar cycloaddition. Incorporation of these stacks into capacitor devices shows the general applicability of our process for the fabrication of electronic devices.

    11. Nanosheets

      The Rapid Exfoliation and Subsequent Restacking of Layered Titanates Driven by an Acid–Base Reaction (pages 9239–9243)

      Huiyu Yuan, David Dubbink, Dr. Rogier Besselink and Prof. Johan E. ten Elshof

      Article first published online: 19 JUN 2015 | DOI: 10.1002/anie.201502539

      Thumbnail image of graphical abstract

      A fast and viable route to isolated nanosheets is presented that is based on exfoliation studies on the protonated layered titanate H1.07Ti1.73O4⋅H2O (HTO). Direct exfoliation of HTO occurs within seconds after mixing of the reactants, instead via a swollen state as previously thought. This route is promising for large-scale synthesis of exfoliated nanosheets.

    12. Cage Compounds

      A Porous Tricyclooxacalixarene Cage Based on Tetraphenylethylene (pages 9244–9248)

      Dr. Chun Zhang, Zhen Wang, Liangxiao Tan, Tian-Long Zhai, Dr. Sheng Wang, Prof. Bien Tan, Prof. Yan-Song Zheng, Prof. Xiang-Liang Yang and Prof. Hui-Bi Xu

      Article first published online: 18 JUN 2015 | DOI: 10.1002/anie.201502912

      Thumbnail image of graphical abstract

      Emissive porous cage: A tricyclooxacalixarene cage molecule based on triphenylethylene (TPE) was prepared. The porous internal structure of the system gave rise to a good CO2 uptake capacity and it showed a high selectivity for CO2 adsorption over N2. The cage molecule exhibited TPE fluorescence in solution and was used as a single-molecule platform to investigate the mechanism of aggregation-induced emission in TPE. Atom colors: C=gray; N=blue; O=red.

    13. Thiol-Induced Etching

      Radicals Are Required for Thiol Etching of Gold Particles (pages 9249–9252)

      Timothy A. Dreier and Dr. Christopher J. Ackerson

      Article first published online: 18 JUN 2015 | DOI: 10.1002/anie.201502934

      Thumbnail image of graphical abstract

      A radical new insight: The final step in the synthesis of atomically defined gold clusters has remained mechanistically obscure. A thiol-induced etching step is proposed that is initiated by the oxygen diradical.

    14. Aluminum Hydroxides

      Energetic Insight into the Formation of Solids from Aluminum Polyoxocations (pages 9253–9256)

      Dr. Dana Reusser, Prof. William H. Casey and Prof. Alexandra Navrotsky

      Article first published online: 30 JUN 2015 | DOI: 10.1002/anie.201503544

      Thumbnail image of graphical abstract

      Downhill: Calorimetric measurements on the ε-AlAl127+ ion and its heterometal-substituted forms provide the first enthalpy of formation (ΔH°f,el) values on these species in aqueous form independent of formation pathway. Data reveal the AlAl127+ ion lies closer in energy to solid aluminum (oxy)hydroxide phases than aqueous monomers, thus explaining its role as a precursor to amorphous aluminum hydroxides (flocs).

    15. Colloidal Crystals | Hot Paper

      Photonic Crystals with a Reversibly Inducible and Erasable Defect State Using External Stimuli (pages 9257–9261)

      Mao Chen, Yapeng Zhang, Siyu Jia, Lin Zhou, Prof. Dr. Ying Guan and Prof. Dr. Yongjun Zhang

      Article first published online: 23 JUN 2015 | DOI: 10.1002/anie.201503004

      Thumbnail image of graphical abstract

      Artificial defects: Doped microgel colloidal crystals were facilely assembled from two microgels with the same size. A defect state in the crystals could be reversibly induced and erased by external stimuli (see picture).

    16. Brønsted Superbases

      Basicity Limits of Neutral Organic Superbases (pages 9262–9265)

      Prof. Dr. Ivo Leito, Prof. Dr. Ilmar A. Koppel, Dr. Ivar Koppel, Dr. Karl Kaupmees, Sofja Tshepelevitsh and Jaan Saame

      Article first published online: 18 JUN 2015 | DOI: 10.1002/anie.201503345

      Thumbnail image of graphical abstract

      Touching the limits: The possible limits of superbasicity achievable with families of neutral bases by expanding the molecular framework are explored. A simple model connecting basicity to the extent of the framework is proposed, validated, and used for quantitative predictions. Some of the considered compound families are expected to reach a gas-phase basicity of 340–370 kcal mol−1, thus being among the most basic ever reported.

    17. Doped Materials

      Atomic-Layer-Confined Doping for Atomic-Level Insights into Visible-Light Water Splitting (pages 9266–9270)

      Fengcai Lei, Lei Zhang, Prof. Yongfu Sun, Liang Liang, Katong Liu, Jiaqi Xu, Prof. Qun Zhang, Prof. Bicai Pan, Prof. Yi Luo and Prof. Yi Xie

      Article first published online: 25 JUN 2015 | DOI: 10.1002/anie.201503410

      Thumbnail image of graphical abstract

      Cobalt doping confined in three atomic layers of In2S3 is implemented by a lamellar hybrid intermediate strategy. Ultrafast transient absorption spectroscopy shows that the ultrashort electron transfer time (ca. 1.6 ps) from the valence band to newly formed localized states is due to Co doping.

    18. Photoenergy Storage

      Integrating a Photocatalyst into a Hybrid Lithium–Sulfur Battery for Direct Storage of Solar Energy (pages 9271–9274)

      Dr. Na Li, Yarong Wang, Dr. Daiming Tang and Prof. Haoshen Zhou

      Article first published online: 10 JUN 2015 | DOI: 10.1002/anie.201503425

      Thumbnail image of graphical abstract

      A solar-driven chargeable Li-S battery has been developed by introducing a Pt/CdS photocatalyst in the aqueous polysulfide cathode. The most remarkable feature of this designed device is the simultaneous realization of both large-scale electrochemical storage and chemical fuel conversion of solar energy in one device, thus opening a new research area in pursuit of renewable clean energy.

    19. Porphyrinoids

      β,β-Diborylated Subporphyrinato Boron(III) Complexes as Useful Synthetic Precursors (pages 9275–9279)

      Masaaki Kitano, Yasuhiro Okuda, Dr. Eiji Tsurumaki, Dr. Takayuki Tanaka, Prof. Dr. Hideki Yorimitsu and Prof. Dr. Atsuhiro Osuka

      Article first published online: 18 JUN 2015 | DOI: 10.1002/anie.201503530

      Thumbnail image of graphical abstract

      Iridium-catalyzed borylation of B-aryl meso-free subporphyrinato boron(III) complexes with bis(pinacolato)diboron effectively produced 2,13-diborylated subporphyrins regioselectively in good yields. These borylated species serve as promising synthetic precursors for 2,13-diarylated subporphyrins and doubly β-to-β 1,3-butadiyne-bridged subporphyrin dimers.

    20. Theoretical Chemistry

      Mercury under Pressure acts as a Transition Metal: Calculated from First Principles (pages 9280–9283)

      Dr. Jorge Botana, Dr. Xiaoli Wang, Dr. Chunju Hou, Prof. Dr. Dadong Yan, Prof. Dr. Haiqing Lin, Prof. Dr. Yanming Ma and Prof. Dr. Mao-sheng Miao

      Article first published online: 1 JUL 2015 | DOI: 10.1002/anie.201503870

      Thumbnail image of graphical abstract

      Mercury rising: Thermodynamically stable forms of crystalline HgF3 and HgF4 have been identified by ab initio calculations using DFT and PSO structure search methods. The Hg is in a high oxidation state and its 5d electrons are involved in forming chemical bonds. HgF4 is a molecular crystal consisting of square-planar HgF4 molecules. HgF3 is an extended solid and exhibits exotic properties. It is metallic, ferromagnetic, and transparent to visible light.

    21. Metal–Organic Frameworks

      Organization and Energy Transfer of Fused Aromatic Hydrocarbon Guests within Anion-Confining Nanochannel MOFs (pages 9284–9288)

      Dr. Tae Hwan Noh, Haeri Lee, Jaeseong Jang and Prof. Dr. Ok-Sang Jung

      Article first published online: 18 JUN 2015 | DOI: 10.1002/anie.201503588

      Thumbnail image of graphical abstract

      Slotted into place: The direct inclusion and organization of fused aromatic hydrocarbons (FAHs) within the hydrophobic 1D nanochannels of 3D metal–organic frameworks (MOFs) [Zn3L4(CH3CN)6](X)6 (L=1,3,5-tris(isonicotinoyloxyethyl)cyanurate; X=BF4 and ClO4) is reported. Förster resonance energy transfer (FRET) with the nanochannels from one FAH derivative to another is described.

    22. Biocatalysis

      Creating Space for Large Acceptors: Rational Biocatalyst Design for Resveratrol Glycosylation in an Aqueous System (pages 9289–9292)

      Dr. Mareike E. Dirks-Hofmeister, Dr. Tom Verhaeghe, Karel De Winter and Prof. Dr. Tom Desmet

      Article first published online: 12 JUN 2015 | DOI: 10.1002/anie.201503605

      Thumbnail image of graphical abstract

      Biocatalyst design: Based on modeling and docking studies, a thermostable sucrose phosphorylase was engineered to enable access of large acceptor substrates. The site-specific loop variant R134A showed high transglycosylation activity on resveratrol in an aqueous system, requiring only sucrose as a cheap glycosyl donor. Significant promiscuity towards a range of other polyphenolic acceptors is also reported.

    23. Synthetic Methods

      Ruthenium-Catalyzed Monoalkenylation of Aromatic Ketones by Cleavage of Carbon–Heteroatom Bonds with Unconventional Chemoselectivity (pages 9293–9297)

      Hikaru Kondo, Nana Akiba, Dr. Takuya Kochi and Prof. Dr. Fumitoshi Kakiuchi

      Article first published online: 2 JUL 2015 | DOI: 10.1002/anie.201503641

      Thumbnail image of graphical abstract

      Smaller is better: The title reaction for ortho C[BOND]O and C[BOND]N bonds of aromatic ketones was achieved. Direct comparison of the cleavage of the carbon–heteroatom bonds suggested an unconventional chemoselectivity, where smaller, more-electron-donating groups are more easily cleaved. Selective monofunctionalization of C[BOND]O bonds in the presence of ortho C[BOND]H bonds was also achieved.

    24. DNA Repair

      Selenium-Mediated Dehalogenation of Halogenated Nucleosides and its Relevance to the DNA Repair Pathway (pages 9298–9302)

      Santanu Mondal, Dr. Debasish Manna and Prof. Dr. Govindasamy Mugesh

      Article first published online: 18 JUN 2015 | DOI: 10.1002/anie.201503598

      Thumbnail image of graphical abstract

      Saying goodbye to I: Selenium compounds are employed to mediate the dehalogenation of halogenated nucleobases and nucleosides in aqueous media under physiological conditions. These results may be important for the development of novel reagents for DNA modification and repair and suggest that Se derivatives may play a broader role in the metabolism of halogenated organic compounds in biology.

    25. Proton Transfer

      Complete Proton Transfer Cycle in GFP and Its T203V and S205V Mutants (pages 9303–9307)

      Dr. Sergey P. Laptenok, Prof. Andras Lukacs, Agnieszka Gil, Dr. Richard Brust, Dr. Igor V. Sazanovich, Dr. Gregory M. Greetham, Prof. Peter J. Tonge and Prof. Stephen R. Meech

      Article first published online: 18 JUN 2015 | DOI: 10.1002/anie.201503672

      Thumbnail image of graphical abstract

      Protein proton wires: Light-activated proton transport in green fluorescent protein (GFP), which acts as a model for protein proton wires, has been characterized by femto- to microsecond time domain IR spectroscopy and mutagenesis studies. The results provide a detailed picture of the dynamics of long-range proton transfer in a protein.

    26. Fused-Ring Systems

      Electron-Deficient Tetrabenzo-Fused Pyracylene and Conversions into Curved and Planar π-Systems Having Distinct Emission Behaviors (pages 9308–9312)

      Chaolumen, Dr. Michihisa Murata, Yasunori Sugano, Prof. Dr. Atsushi Wakamiya and Prof. Dr. Yasujiro Murata

      Article first published online: 18 JUN 2015 | DOI: 10.1002/anie.201503783

      Thumbnail image of graphical abstract

      Throw a curve: An efficient route for the synthesis of electron-deficient tetrabenzo-fused pyracylenes (TBPs) is reported. TBP was found to undergo unique addition reactions with n-butyllithium and benzyne to give fluorescent compounds with a curved and planar π-system, respectively. These compounds showed distinct emission colors in the solid state with high quantum yields.

    27. Nanobioanalysis | Hot Paper

      Real-time Monitoring of Discrete Synaptic Release Events and Excitatory Potentials within Self-reconstructed Neuromuscular Junctions (pages 9313–9318)

      Yu-Tao Li, Shu-Hui Zhang, Xue-Ying Wang, Xin-Wei Zhang, Dr. Alexander I. Oleinick, Prof. Dr. Irina Svir, Prof. Dr. Christian Amatore and Prof. Dr. Wei-Hua Huang

      Article first published online: 16 JUN 2015 | DOI: 10.1002/anie.201503801

      Thumbnail image of graphical abstract

      A microfluidic chip was developed taking advantage of a carbon fiber nanoelectrode (CFNE) and a robust platform for real-time monitoring of single intra-synaptic vesicular release events and of the subsequent generation of postsynaptic membrane excitatory potential (EJP) signals. By using this chip, the first in situ measurements of synaptic transmission in neuromuscular mimics are reported.

    28. Natural Product Synthesis

      Highly Efficient, Convergent, and Enantioselective Synthesis of Phthioceranic Acid (pages 9319–9322)

      Dr. Shiqing Xu, Akimichi Oda, Dr. Thomas Bobinski, Dr. Haijun Li, Yohei Matsueda and Prof. Dr. Ei-ichi Negishi

      Article first published online: 18 JUN 2015 | DOI: 10.1002/anie.201503818

      Thumbnail image of graphical abstract

      A step-economical synthesis of phthioceranic acid was achieved by using a conceptually new strategy. ZACA-Pd-catalyzed vinylation was used to prepare smaller deoxypropionate building blocks. Then two Cu-catalyzed stereospecific sp3–sp3 cross-couplings linked the smaller fragments together with full inversion of configuration to assemble large polydeoxypropionates in a stereoselective manner. ZACA=Zr-catalyzed asymmetric carboalumination of alkenes.

    29. Mercury Pollutants

      Chemical Detoxification of Organomercurials (pages 9323–9327)

      Mainak Banerjee, Ramesh Karri, Kuber Singh Rawat, Karthick Muthuvel, Dr. Biswarup Pathak and Dr. Gouriprasanna Roy

      Article first published online: 16 JUL 2015 | DOI: 10.1002/anie.201504413

      Thumbnail image of graphical abstract

      Getting rid of mercury: Insoluble HgE (E=S, Se) nanoparticles (NPs) are formed under physiologically relevant conditions when organomercurials are treated with N-methylimidazole-based thiones/selones having an N-CH2CH2OH substituent. Compounds lacking the N-CH2CH2OH substituent failed to produce HgE NPs upon treatment with organomercurials under identical reaction conditions. A novel pathway of detoxifying various organomercurials is described.

    30. Borohydride Hydrolysis

      A Family of High-Efficiency Hydrogen-Generation Catalysts Based on Ammonium Species (pages 9328–9332)

      Lilin Lu, Haijun Zhang, Shaowei Zhang and Faliang Li

      Article first published online: 18 JUN 2015 | DOI: 10.1002/anie.201500942

      Thumbnail image of graphical abstract

      The catalytic activities of inorganic ammonium ions for hydrogen generation by the hydrolysis of borohydrides and the corresponding mechanisms were investigated. The catalytic activities were higher than or comparable to those of typical noble-metal/transition-metal catalysts but the ammonium ions are considerably cheaper, more environmentally friendly, and more readily available.

    31. Chiral Polymer Catalysts

      Majority-Rules-Type Helical Poly(quinoxaline-2,3-diyl)s as Highly Efficient Chirality-Amplification Systems for Asymmetric Catalysis (pages 9333–9337)

      Dr. Yuan-Zhen Ke, Dr. Yuuya Nagata, Dr. Tetsuya Yamada and Prof. Dr. Michinori Suginome

      Article first published online: 11 JUN 2015 | DOI: 10.1002/anie.201502209

      Thumbnail image of graphical abstract

      Bowing to the majority: Poly(quinoxaline-2,3-diyl) containing PPh2 groups and chiral side chains derived from (R)-2-octanol with 23 % ee exhibited a single-handed-helical conformation and served as a highly enantioselective chiral ligand in palladium-catalyzed reactions (see scheme; se=screw-sense excess). The chirality of the polymer could be switched by a solvent effect to enable the synthesis of the enantiomeric products.

    32. Reactive Intermediates

      Olefin cis-Dihydroxylation and Aliphatic C[BOND]H Bond Oxygenation by a Dioxygen-Derived Electrophilic Iron–Oxygen Oxidant (pages 9338–9342)

      Sayanti Chatterjee and Dr. Tapan Kanti Paine

      Article first published online: 18 JUN 2015 | DOI: 10.1002/anie.201502229

      Thumbnail image of graphical abstract

      Lewis acid mediated O[BOND]O bond cleavage: A nucleophilic iron(II)–hydroperoxo oxidant, formed upon oxidative decarboxylation of an iron(II)–α-hydroxy acid complex, undergoes heterolytic O[BOND]O bond cleavage in the presence of a Lewis acid to generate an electrophilic iron(IV)–oxo–hydroxo oxidant. The electrophilic oxidant oxidizes sulfides to sulfoxides and alkenes to cis-diols, and it hydroxylates the strong C[BOND]H bonds of aliphatic substrates.

    33. Bioconjugation

      Development and Optimization of Glaser–Hay Bioconjugations (pages 9343–9346)

      Jessica S. Lampkowski, Jordan K. Villa, Dr. Travis S. Young and Dr. Douglas D. Young

      Article first published online: 18 JUN 2015 | DOI: 10.1002/anie.201502676

      Thumbnail image of graphical abstract

      A Glaser–Hay bioconjugation has been developed. This new bioconjugation method affords well-defined, linear, highly oxidized bioconjugates. This is the first reported aqueous Glaser–Hay reaction and first utilization of this reaction in the conjugation of proteins, small molecules, and solid supports.

    34. Synthetic Methods

      Copper-Catalyzed Regioselective Hydroalkylation of 1,3-Dienes with Alkyl Fluorides and Grignard Reagents (pages 9347–9350)

      Dr. Takanori Iwasaki, Ryohei Shimizu, Reiko Imanishi, Prof. Dr. Hitoshi Kuniyasu and Prof. Dr. Nobuaki Kambe

      Article first published online: 19 JUN 2015 | DOI: 10.1002/anie.201503288

      Thumbnail image of graphical abstract

      Making the switch: A copper–hydride species, generated by the treatment of a copper salt with alkyl Grignard reagents, catalyzes the 1,2-hydroalkylation of 1,3-dienes by alkyl fluorides and Grignard reagents. The alkyl group of the alkyl fluoride is selectively introduced to an internal carbon atom of the 1,3-diene and the Grignard reagent acts as hydride source to give the branched terminal alkene, even in the presence of alkenes and alkynes.

    35. Water Splitting

      NiSe Nanowire Film Supported on Nickel Foam: An Efficient and Stable 3D Bifunctional Electrode for Full Water Splitting (pages 9351–9355)

      Chun Tang, Ningyan Cheng, Zonghua Pu, Prof. Wei Xing and Prof. Xuping Sun

      Article first published online: 1 JUL 2015 | DOI: 10.1002/anie.201503407

      Thumbnail image of graphical abstract

      NiSe nanowire films grown hydrothermally in situ on nickel foam (NiSe/NF) were used as a 3D bifunctional electrode for both the oxygen evolution reaction and hydrogen evolution reaction in a strongly alkaline electrolyte. The films exhibit high catalytic activity and superior stability, and a cell voltage of only 1.63 V is required for the alkaline water electrolyzer to deliver 10 mA cm−2 water-splitting current.

    36. Synthetic Methods

      Copper-Catalyzed Trifluoromethylazidation of Alkynes: Efficient Access to CF3-Substituted Azirines and Aziridines (pages 9356–9360)

      Fei Wang, Na Zhu, Dr. Pinhong Chen, Prof. Dr. Jinxing Ye and Prof. Dr. Guosheng Liu

      Article first published online: 18 JUN 2015 | DOI: 10.1002/anie.201503412

      Thumbnail image of graphical abstract

      Az is: A novel method for convenient access to CF3-containing azirines has been developed, and involves a copper-catalyzed trifluoromethylazidation of alkynes and a photocatalyzed rearrangement. Both terminal and internal alkynes are compatible with this reaction and deliver azirines in moderate to good yields. The azirines can be further converted into various CF3-substituted aziridines. TMS=trimethylsilyl.

    37. Porous Polymer Materials

      Thiophene, Selenophene, and Tellurophene-based Three-Dimensional Organic Frameworks (pages 9361–9366)

      Dr. Peng-Fei Li, Tyler B. Schon and Prof. Dwight S. Seferos

      Article first published online: 19 JUN 2015 | DOI: 10.1002/anie.201503418

      Thumbnail image of graphical abstract

      Elements control properties: 3D frameworks consisting of adamantane vertices and diphenylheterocycle (S, Se, and Te) linkers have been synthesized and characterized. The specific surface area and pore width of frameworks depends on the element incorporated in the heterocycle. Optoelectronic properties are also element dependent. A supercapacitor was constructed to demonstrate electronic activity.

    38. Highly Energetic Compounds

      Combination of 1,2,4-Oxadiazole and 1,2,5-Oxadiazole Moieties for the Generation of High-Performance Energetic Materials (pages 9367–9371)

      Dr. Hao Wei, Dr. Chunlin He, Dr. Jiaheng Zhang and Prof. Dr. Jean'ne M. Shreeve

      Article first published online: 18 JUN 2015 | DOI: 10.1002/anie.201503532

      Thumbnail image of graphical abstract

      Bursting with energy: Two types of high-density energetic salts (see anion structures) were obtained by linking 1,2,4-oxadiazole and 1,2,5-oxadiazole precursors. The superior detonation performance and good thermal stability of the salts make them promising high-energy-density materials.

    39. Pincer Complexes | Hot Paper

      Reversible α-Hydrogen and α-Alkyl Elimination in PC(sp3)P Pincer Complexes of Iridium (pages 9372–9375)

      Dr. Klara J. Jonasson, Dr. Alexey V. Polukeev, Dr. Rocío Marcos, Prof. Mårten S. G. Ahlquist and Prof. Ola F. Wendt

      Article first published online: 26 JUN 2015 | DOI: 10.1002/anie.201503593

      Thumbnail image of graphical abstract

      An iridium pincer complex undergoes reversible α-alkyl elimination. Under certain conditions, this fundamentally new process for C(sp3)[BOND]C(sp3) bond cleavage has a low barrier that is comparable with that of well known α-hydrogen elimination reactions. Kinetic studies, activation parameters, and DFT calculations are also discussed.

    40. Supramolecular Chemistry | Very Important Paper

      Photocontrolled Reversible Conversion of Nanotube and Nanoparticle Mediated by β-Cyclodextrin Dimers (pages 9376–9380)

      He-Lue Sun, Dr. Yong Chen, Jin Zhao and Prof. Dr. Yu Liu

      Article first published online: 18 JUN 2015 | DOI: 10.1002/anie.201503614

      Thumbnail image of graphical abstract

      Photodriven interconversion: A photoswitchable supramolecular nanotube–nanoparticle system was constructed through secondary assembly of self-aggregates of amphiphilic porphyrin derivatives (see picture). These nanoassemblies repeatedly interconvert upon irradiation at 365 and 450 nm.

    41. Stereoselective Deuteration

      Catalytic Stereoinversion of L-Alanine to Deuterated D-Alanine (pages 9381–9385)

      Kimia Moozeh, Dr. Soon Mog So and Prof. Jik Chin

      Article first published online: 26 JUN 2015 | DOI: 10.1002/anie.201503616

      Thumbnail image of graphical abstract

      Deuteration of alanine with a combination of an achiral pyridoxal analogue and a chiral base as catalyst is stereoselective, but protonation is not. Thus a racemic mixture of alanine can be catalytically deuterated under mild conditions without the use of any protecting groups to give an enantiomeric excess of deuterated D-alanine.

    42. Uranium Complexes

      Investigation of Uranium Tris(imido) Complexes: Synthesis, Characterization, and Reduction Chemistry of [U(NDIPP)3(thf)3] (pages 9386–9389)

      Nickolas H. Anderson, Haolin Yin, John J. Kiernicki, Dr. Phillip E. Fanwick, Prof. Eric J. Schelter and Prof. Suzanne C. Bart

      Article first published online: 3 JUL 2015 | DOI: 10.1002/anie.201503771

      Thumbnail image of graphical abstract

      Reduced to dimers: [U(NDIPP)3(thf)3] was isolated upon treatment of [UI3(thf)4] with KC8 in the presence of 2,6-diisopropylphenylazide (N3DIPP). Crystallographic characterization shows an unprecedented fac-uranium tris(imido) species (see picture). Single-electron reduction of the complex formed the dimer [K(Et2O)]2[U(NDIPP)3]2, which was studied using variable-temperature/field magnetic measurements. Atom colors: U=pink; O=red; N=blue; C=black.

    43. Organocatalysis

      Enantioselective Synthesis of Quaternary Carbon Stereocenters: Addition of 3-Substituted Oxindoles to Vinyl Sulfone Catalyzed by Pentanidiums (pages 9390–9393)

      Dr. Lili Zong, Shubo Du, Kek Foo Chin, Dr. Chao Wang and Prof. Dr. Choon-Hong Tan

      Article first published online: 14 JUL 2015 | DOI: 10.1002/anie.201503844

      Thumbnail image of graphical abstract

      Efficiency of pentanidiums: Enantioselective conjugate addition between 3-alkyloxindoles and phenyl vinyl sulfone was achieved with a pentanidium phase-transfer catalyst. Various enantioenriched oxindole derivatives with versatile functional groups were synthesized. Gram-scale experiments also indicate the high efficiency and practicality of the current strategy.

    44. Electrocatalysis

      Irrelevance of Carbon Monoxide Poisoning in the Methanol Oxidation Reaction on a PtRu Electrocatalyst (pages 9394–9398)

      Dr. De-Jun Chen and Prof. Dr. YuYe J. Tong

      Article first published online: 6 JUL 2015 | DOI: 10.1002/anie.201503917

      Thumbnail image of graphical abstract

      The methanol oxidation reaction (MOR) on Ru/Pt thin film and commercial PtRu/C was studied by in situ attenuated total-reflection–surface-enhanced IR reflection absorption spectroscopy. A revised MOR enhancement mechanism is proposed in which CO on Pt sites is irrelevant but instead Pt–Ru boundary sites catalyze the oxygen insertion reaction that leads to the formation of bidentate formate (indicated as [DOUBLE BOND]OOCH) and enhances the direct reaction pathway.

    45. Biomass Conversion

      Porous Zirconium–Phytic Acid Hybrid: a Highly Efficient Catalyst for Meerwein–Ponndorf–Verley Reductions (pages 9399–9403)

      Dr. Jinliang Song, Baowen Zhou, Dr. Huacong Zhou, Lingqiao Wu, Dr. Qinglei Meng, Prof. Dr. Zhimin Liu and Prof. Dr. Buxing Han

      Article first published online: 14 JUL 2015 | DOI: 10.1002/anie.201504001

      Thumbnail image of graphical abstract

      All natural: Porous zirconium phosphonate (Zr-PhyA) was synthesized simply by reaction of natural phytic acid (PhyA) and ZrCl4 and applied as a very efficient catalyst for the Meerwein–Ponndorf–Verley reduction of various carbonyl compounds. Both the Zr element and phosphate groups contributed significantly to the excellent catalytic performance of Zr-PhyA.

    46. C[BOND]H Activation

      Rhodium(III)-Catalyzed Activation of C sp 3[BOND]H Bonds and Subsequent Intermolecular Amidation at Room Temperature (pages 9404–9408)

      Xiaolei Huang, Yan Wang, Prof. Dr. Jingbo Lan and Prof. Dr. Jingsong You

      Article first published online: 14 JUL 2015 | DOI: 10.1002/anie.201504507

      Thumbnail image of graphical abstract

      Giving direction: The title reaction leads to the successful functionalization of unreactive Cinline image[BOND]H bonds in the presence of directing groups (DGs). A rhodacycle having a SbF6 counterion was isolated and is proposed to be a plausible intermediate.

    47. Organocatalysis

      Asymmetric Construction of Spirooxindoles by Organocatalytic Multicomponent Reactions Using Diazooxindoles (pages 9409–9413)

      Ming-Yue Wu, Wei-Wei He, Prof. Dr. Xin-Yuan Liu and Prof. Dr. Bin Tan

      Article first published online: 2 JUL 2015 | DOI: 10.1002/anie.201504640

      Thumbnail image of graphical abstract

      Multiple players: The first highly stereoselective multicomponent reaction of diazooxindoles, nitrosoarenes, and nitroalkenes with a newly developed hydrogen-bond catalyst has been successfully developed. The spirooxindole products are isolated in excellent yields and stereoselectivities, and contain three contiguous stereogenic centers. R′′′=aryl or alkyl.

    48. Synergistic Catalysis

      Synergistic Catalysis: Metal/Proton-Catalyzed Cyclization of Alkynones Toward Bicyclo[3.n.1]alkanones (pages 9414–9418)

      Prof. Dr. Shifa Zhu, Qiaohui Zhang, Kai Chen and Prof. Dr. Huanfeng Jiang

      Article first published online: 3 JUL 2015 | DOI: 10.1002/anie.201504964

      Thumbnail image of graphical abstract

      A highly efficient and practical synergistically metal/proton-catalyzed Conia–ene reaction for the synthesis of bicyclo[3.n.1]alkanones has been developed. The reaction was successfully utilized in modifying natural compounds such as methyl dihydrojasmonate, α,β-thujone, and 5α-cholestan-3-one. Furthermore, the bicyclo[3.2.1]alkanones can be ring-opened by nucleophiles to give the corresponding products in excellent yields.

SEARCH

SEARCH BY CITATION