Angewandte Chemie International Edition

Cover image for Vol. 55 Issue 41

Early View (Online Version of Record published before inclusion in an issue)

Editor: Peter Gölitz, Deputy Editors: Neville Compton, Haymo Ross

Online ISSN: 1521-3773

Associated Title(s): Angewandte Chemie, Chemistry - A European Journal, Chemistry – An Asian Journal, ChemistryOpen, ChemPlusChem, Zeitschrift für Chemie

  1. Communications

    1. Silylation

      Divergent and Stereoselective Synthesis of β-Silyl-α-Amino Acids through Palladium-Catalyzed Intermolecular Silylation of Unactivated Primary and Secondary C−H Bonds

      Yue-Jin Liu, Yan-Hua Liu, Zhuo-Zhuo Zhang, Sheng-Yi Yan, Kai Chen and Prof. Dr. Bing-Feng Shi

      Version of Record online: 28 SEP 2016 | DOI: 10.1002/anie.201607766

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      Good to Si you: A general and practical PdII-catalyzed intermolecular silylation of primary and secondary C−H bonds of α-amino acids and simple aliphatic acids is reported. This method provides divergent and stereoselective access to a variety of optical pure β-silyl-α-amino acids. Furthermore, the late-stage functionalization of biological small molecules such as (−)-santonin and β-cholic acid is demonstrated.

  2. Cover Pictures

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      Vacancy-Induced Electronic Structure Variation of Acceptors and Correlation with Proton Conduction in Perovskite Oxides

      Hye-Sung Kim, Ahreum Jang, Dr. Si-Young Choi, Prof. WooChul Jung and Prof. Sung-Yoon Chung

      Version of Record online: 28 SEP 2016 | DOI: 10.1002/anie.201607768

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      Proton trapping is a major cause of retardation of proton conduction in the bulk of perovskite oxides and is due to the strong electrostatic attraction between positively charged protons and negatively charged acceptors. In their Communication (DOI: 10.1002/anie.201603835), S.-Y. Chung and co-workers show that clustering of oxygen vacancies to acceptors can be induced by post-annealing and proton trapping is thereby suppressed. The impact of the oxygen vacancies and their effective charge on ionic conduction is shown.

  3. Minireviews

    1. Nanopore Sensors

      DNA-Based Nanopore Sensing

      Dr. Lei Liu and Prof. Hai-Chen Wu

      Version of Record online: 27 SEP 2016 | DOI: 10.1002/anie.201604405

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      DNA–analyte interactions: Conformational changes of rationally designed DNA probes in nanopores caused by the DNA–analyte interactions may induce distinct current changes during the DNA translocation process. The current signatures can be used to not only ascertain the existence of the analytes but also quantify their concentrations.

  4. Communications

    1. Lithium-Ion Mobility | Hot Paper

      Supertetrahedral Networks and Lithium-Ion Mobility in Li2SiP2 and LiSi2P3

      M. Sc. Arthur Haffner, Dr. Thomas Bräuniger and Prof. Dr. Dirk Johrendt

      Version of Record online: 27 SEP 2016 | DOI: 10.1002/anie.201607074

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      Mobile Li+ ions between supertetrahedra: The phosphidosilicates Li2SiP2 and LiSi2P3 form interpenetrating covalent networks of T2 or T4 and T5 supertetrahedra with diamond- or sphalerite-type topologies. 7Li solid-state MAS NMR analysis indicates the high mobility of the Li+ ions with small activation energies of 0.07–0.10 eV.

    2. Homogeneous Catalysis

      Controlling Proton Delivery through Catalyst Structural Dynamics

      Dr. Allan Jay P. Cardenas, Bojana Ginovska, Dr. Neeraj Kumar, Dr. Jianbo Hou, Dr. Simone Raugei, Dr. Monte L. Helm, Dr. Aaron M. Appel, Dr. R. Morris Bullock and Dr. Molly O'Hagan

      Version of Record online: 27 SEP 2016 | DOI: 10.1002/anie.201607460

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      Slower dynamics, faster catalysis: Dynamic processes that are key to catalysis can be controlled through remote substituents in the outer coordination sphere, in a manner similar to the role of the protein architecture in enzymes. This approach was used to increase the H2 production rates of nickel catalysts by three orders of magnitude with a minimal increase in overpotential.

    3. Heterogeneous Structures

      Fabrication of Hollow Materials by Fast Pyrolysis of Cellulose Composite Fibers with Heterogeneous Structures

      Dr. Yue Dong, Dr. Baoquan Jia, Dr. Feiya Fu, Dr. Heyou Zhang, Prof. Lina Zhang and Prof. Dr. Jinping Zhou

      Version of Record online: 27 SEP 2016 | DOI: 10.1002/anie.201607455

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      Hollow structural materials were fabricated from cuprammonium cellulose composite filaments by fast pyrolysis. The whole process could be completed within 100 s. The formation mechanism is related to the heterogeneous structure of the fibers and the gradient distribution of the metal oxides in the cellulose matrix.

    4. NMR Spectroscopy

      You have full text access to this OnlineOpen article
      1H-Detected Solid-State NMR Studies of Water-Inaccessible Proteins In Vitro and In Situ

      João Medeiros-Silva, Deni Mance, Mark Daniëls, Shehrazade Jekhmane, Dr. Klaartje Houben, Prof. Marc Baldus and Dr. Markus Weingarth

      Version of Record online: 27 SEP 2016 | DOI: 10.1002/anie.201606594

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      Within the membrane: An approach is presented that provides high-resolution 1H-detected solid-state NMR spectra of water-inaccessible proteins, even in complex environments such as cellular surfaces. This method was used for studying the molecular motion of the transmembrane section of an ion channel in liposomes and directly in native cell membranes.

    5. Microemulsions for CO2 Reduction

      Water-in-Supercritical CO2 Microemulsion Stabilized by a Metal Complex

      Tian Luo, Prof. Dr. Jianling Zhang, Xiuniang Tan, Chengcheng Liu, Dr. Tianbin Wu, Dr. Wei Li, Xinxin Sang, Prof. Buxing Han, Prof. Zhihong Li, Dr. Guang Mo, Dr. Xueqing Xing and Prof. Zhonghua Wu

      Version of Record online: 27 SEP 2016 | DOI: 10.1002/anie.201608695

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      Second that emulsion: For the first time the utilization of a metal complex leads to the formation of water-in-scCO2 microemulsions. Such a microemulsion provides a promising route for in situ CO2 reduction to produce formic acid at the water/scCO2 interface, in a process that provides a high efficiency, adjustable activity, and easy product and catalyst separation.

    6. Synthetic Methods

      Copper-Catalyzed Vicinal Diphosphination of Styrenes: Access to 1,2-Bis(diphenylphosphino)ethane-Type Bidentate Ligands from Olefins

      Yuto Okugawa, Prof. Dr. Koji Hirano and Prof. Dr. Masahiro Miura

      Version of Record online: 27 SEP 2016 | DOI: 10.1002/anie.201606976

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      Seeing double: A copper/N-heterocyclic carbene catalyzed oxidative vicinal diphosphination of styrenes with diphenyl(trimethylsilyl)phosphine proceeds to deliver the corresponding 1,2-bis(diphenylphosphino)ethanes in good yields. A pyridine N-oxide/MnO2 combined oxidant uniquely achieves the catalytic turnover of the copper.

    7. Polyoxometalates

      Closing Uranyl Polyoxometalate Capsules with Bismuth and Lead Polyoxocations

      Olivier Renier, Dr. Clément Falaise, Harrison Neal, Karoly Kozma and Prof. Dr. May Nyman

      Version of Record online: 27 SEP 2016 | DOI: 10.1002/anie.201607151

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      Heavy and heavier: Polyoxocations of the heavy metals bismuth and lead were nested inside uranyl polyoxoanion capsules, creating very distinctive X-ray scattering profiles. Matching symmetry and electrostatic attraction between the core and shell clusters enabled the formation of endohedral Pb@U24 and Bi@U24 in high yield and purity.

    8. Biosynthesis

      The Interplay between a Multifunctional Dehydratase Domain and a C-Methyltransferase Effects Olefin Shift in Ambruticin Biosynthesis

      Gesche Berkhan, Dr. Christian Merten, Claudia Holec and Prof. Dr. Frank Hahn

      Version of Record online: 27 SEP 2016 | DOI: 10.1002/anie.201607827

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      Three in one: In vitro testing of the recombinant polyketide synthase domain AmbDH4 and the C-methyltransferase AmbM reveals their interplay during olefin shift in ambruticin biosynthesis. The AmbDH4 domain shows a triple activity as a dehydratase, epimerase, and enoyl isomerase. Subtle changes in the domain structure probably enable olefin shift via a similar mechanism to that reported for enoyl isomerases.

    9. Phosphorus Heterocycles

      A Stable Crystalline Triarylphosphine Oxide Radical Anion

      Tobias A. Schaub, Eva M. Zolnhofer, Dominik P. Halter, Dr. Tatyana E. Shubina, Dr. Frank Hampel, Prof. Dr. Karsten Meyer and Dr. Milan Kivala

      Version of Record online: 27 SEP 2016 | DOI: 10.1002/anie.201605963

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      The spin within: A carefully designed triarylphosphine oxide scaffold with sterically demanding spirofluorenyl moieties undergoes chemical one-electron reduction at its phosphoryl moiety. The unique stability of the formed radical anion enables the isolation and X-ray crystallographic characterization of this hitherto elusive species.

    10. Synthesis Design

      Continuous Consecutive Reactions with Inter-Reaction Solvent Exchange by Membrane Separation

      Dr. Ludmila Peeva, Joao Da Silva Burgal, Zsofia Heckenast, Florine Brazy, Florian Cazenave and Prof. Andrew Livingston

      Version of Record online: 27 SEP 2016 | DOI: 10.1002/anie.201607795

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      High to low: Two processes that complicate the transition from batch to continuous operations in multistep synthesis are solvent exchange (especially high-boiling- to low-boiling-point solvent) and catalyst separation. Described herein is membrane technology as an enabling platform for coupling these processes in a continuous operation.

  5. Highlights

    1. Nanoparticle Catalysts

      Excavation of Precious-Metal-Based Alloy Nanoparticles for Efficient Catalysis

      Prof. Dr. Franklin (Feng) Tao

      Version of Record online: 27 SEP 2016 | DOI: 10.1002/anie.201606324

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      Methods have recently been developed for the synthesis of excavated alloy nanoparticles. However, various challenges still need to be overcome for a broad range of excavated nanoparticles with different sizes, surface structures, compositions, and constituent elements to be available for chemical and energy transformations through thermal catalysis and electrocatalysis.

  6. Communications

    1. Helicenes

      Electron Delocalization in Perylene Diimide Helicenes

      Nathaniel J. Schuster, Dr. Daniel W. Paley, Dr. Steffen Jockusch, Dr. Fay Ng, Dr. Michael L. Steigerwald and Prof. Colin Nuckolls

      Version of Record online: 26 SEP 2016 | DOI: 10.1002/anie.201607878

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      Two helicenes were synthesized by double fusion of an acene with two perylene diimide (PDI) subunits. These PDI-helicene homologs show different structural and electronic properties, despite differing by only a single ring in the link between the PDI units. The shorter link brings the two PDI subunits closer together, and this results in the collision of their respective π-electron clouds.

    2. Inhibitors

      You have full text access to this OnlineOpen article
      Mirror-Image Packing Provides a Molecular Basis for the Nanomolar Equipotency of Enantiomers of an Experimental Herbicide

      Dr. Claudine Bisson, Dr. K. Linda Britton, Dr. Svetlana E. Sedelnikova, H. Fiona Rodgers, Dr. Thomas C. Eadsforth, Dr. Russell C. Viner, Dr. Tim R. Hawkes, Dr. Patrick J. Baker and Prof. David W. Rice

      Version of Record online: 26 SEP 2016 | DOI: 10.1002/anie.201607185

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      Chiral promiscuity: During a structure-led herbicide development program, both enantiomers of the lead compound were found to bind at the active site of the target with equal nanomolar potency. The main substituent groups lie in a plane, thus facilitating their equivalent interactions with the chiral surface of the enzyme by mirror-image packing, thus mimicking an achiral reaction intermediate.

    3. Soft Matter

      One-Step Microfluidic Fabrication of Polyelectrolyte Microcapsules in Aqueous Conditions for Protein Release

      Dr. Liyuan Zhang, Dr. Li-Heng Cai, Dr. Philipp S. Lienemann, Dr. Torsten Rossow, Dr. Ingmar Polenz, Queralt Vallmajo-Martin, Dr. Martin Ehrbar, Dr. Hui Na, Dr. David J. Mooney and Dr. David A. Weitz

      Version of Record online: 26 SEP 2016 | DOI: 10.1002/anie.201606960

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      Polyelectrolyte (PE) capsules: Using two immiscible aqueous solutions, dextran and PEG, transient double emulsions were created in a microfluidic system and used as templates to fabricate PE capsules. The capsule shell was formed by complexation of oppositely charged PEs, PE+ and PE−, at the interface of the two aqueous phases. This platform enables encapsulation and release of proteins without impairing their activity.

    4. Methane Oxidation

      Low-Temperature Transformation of Methane to Methanol on Pd1O4 Single Sites Anchored on the Internal Surface of Microporous Silicate

      Weixin Huang, Dr. Shiran Zhang, Yu Tang, Yuting Li, Dr. Luan Nguyen, Dr. Yuanyuan Li, Dr. Junjun Shan, Prof. Dr. Dequan Xiao, Raphael Gagne, Prof. Dr. Anatoly I. Frenkel and Prof. Dr. Franklin (Feng) Tao

      Version of Record online: 26 SEP 2016 | DOI: 10.1002/anie.201604708

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      Single site Pd1O4 anchored in microspores of zeolite with 2.0 w % CuO is active for transforming of CH4 to CH3OH in aqueous solution in the temperature range of 50–95 °C. Selectivity for production of CH3OH in this temperature range was found to be 78 %-86 % at 50–95 °C, offering an obvious improvement over harsh alternative conditions.

    5. Anti-Cancer Complexes

      A Macrocyclic Ruthenium(III) Complex Inhibits Angiogenesis with Down-Regulation of Vascular Endothelial Growth Factor Receptor-2 and Suppresses Tumor Growth In Vivo

      Dr. Wai-Lun Kwong, Dr. Kar-Yee Lam, Dr. Chun-Nam Lok, Dr. Yau-Tsz Lai, Dr. Pui-Yan Lee and Prof. Dr. Chi-Ming Che

      Version of Record online: 26 SEP 2016 | DOI: 10.1002/anie.201608094

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      Anti-angiogenic Ru(III): A macrocyclic ruthenium(III) complex is found to inhibit endothelial cell angiogenesis and cancer cell invasiveness, to suppress the protein and mRNA expression of VEGFR2 and the VEGFR downstream signaling pathways and to display in vivo anti-tumor activities.

  7. Cover Pictures

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      Graphane Nanostripes

      Dr. Lu Wang, Prof. Dr. Zdeněk Sofer, Daniel Bouša, Prof. Dr. David Sedmidubský, Dr. Štěpán Huber, Dr. Stanislava Matějková, Dr. Alena Michalcová and Prof. Dr. Martin Pumera

      Version of Record online: 26 SEP 2016 | DOI: 10.1002/anie.201608909

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      The interplay of metallic nanoparticles and defects in hydrogenated carbon nanostripes leads to spin polarization and induction of a ferromagnetic moment. In their Communication (DOI: 10.1002/anie.201606852), M. Pumera and co-workers show that the presence of metallic nanoparticles incorporated into graphane nanostripes has a positive effect on electrocatalytic properties towards the hydrogen evolution reaction.