Angewandte Chemie International Edition

Cover image for Vol. 53 Issue 31

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, Zeitschrift für Chemie

Upcoming VIPs

The following papers are very important in the opinion of two referees. They will be published as soon as possible.

You are invited to comment on published VIPs. Please use the link given at the end of each such abstract. Scientific comments may be forwarded to the authors by the editorial office and may be posted on this page. Kindly let us know if your comments are for the editorial office only, the author, or the public as well.

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Reprogramming Nonribosomal Peptide Synthetases for “Clickable” Amino Acids

Dr. Hajo Kries, Rudolf Wachtel, Anja Pabst, Benedikt Wanner, David Niquille and Prof. Dr. Donald Hilvert

Reprogramming Nonribosomal Peptide Synthetases for “Clickable” Amino AcidsPocketed: A single active site mutation reprograms the substrate specificity of nonribosomal peptide synthetase adenylation domains, enabling efficient incorporation of non-natural aromatic amino acids containing unique chemical functionality for bioorthogonal labeling.

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An Easy Way To Prepare Monolithic Inorganic Oxide Aerogels

Dr. Lili Ren, Sumin Cui, Fengchao Cao and Qinghui Guo

An Easy Way To Prepare Monolithic Inorganic Oxide AerogelsNot cracking up: A drying method based on the sublimation of organic solvent allows the rapid synthesis of the monolithic inorganic oxide aerogels without cracks from wet gels. The method proceeds by endothermic evaporation of organic solvent at the outer surface followed by sublimation of solidified solvent (see picture).

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Monitoring Morphology and Hydrogen Coverage of Nanometric Pt/γ-Al2O3 Particles by In Situ HERFD–XANES and Quantum Simulations

Agnes Gorczyca, Dr. Virginie Moizan, Dr. Celine Chizallet, Dr. Olivier Proux, William Del Net, Eric Lahera, Dr. Jean-Louis Hazemann, Dr. Pascal Raybaud and Dr. Yves Joly

Monitoring Morphology and Hydrogen Coverage of Nanometric Pt/γ-Al2O3 Particles by In Situ HERFD–XANES and Quantum SimulationsIdentifying the morphology of platinum nanoclusters supported on γ-alumina and the hydrogen coverage at a given temperature and hydrogen pressure is possible. The use of state-of-the-art methodologies combining high-resolution X-ray absorption near edge structure (XANES) in situ experiments, quantum molecular dynamics calculations, and XANES simulations gives unrivalled insights into catalyst characterization.

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Integrating Perovskite Solar Cells into a Flexible Fiber

Longbin Qiu, Jue Deng, Xin Lu, Zhibin Yang and Prof. Huisheng Peng

Integrating Perovskite Solar Cells into a Flexible FiberWearable perovskite solar cells with a fiber structure are synthesized by continuously winding an aligned carbon nanotube (CNT) sheet onto a stainless-steel wire; photoactive materials are incorporated in between them through a solution process. The fiber-shaped perovskite solar cell exhibits an energy conversion efficiency of 3.3 % and may be woven into electronic textiles.

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Bonding Nature of Local Structural Motifs in Amorphous GeTe

Dipl.-Chem. Volker L. Deringer, Dr. Wei Zhang, Dr. Marck Lumeij, Dipl.-Chem. Stefan Maintz, Prof. Dr. Matthias Wuttig, Prof. Dr. Riccardo Mazzarello and Prof. Dr. Richard Dronskowski

Bonding Nature of Local Structural Motifs in Amorphous GeTeAmorphous—no problem! Analyzing a crystalline structure by breaking it down into local fragments and covalent bonds is a technique that chemists have long perfected. With new tools at hand, this chemical language can be extended to amorphous solid-state materials—in this case, to the phase-change memory alloy germanium telluride.

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Stereocontrolled Synthesis of 1,5-Stereogenic Centers through Three-Carbon Homologation of Boronic Esters

Phillip J. Unsworth, Dr. Daniele Leonori and Prof. Varinder K. Aggarwal

Stereocontrolled Synthesis of 1,5-Stereogenic Centers through Three-Carbon Homologation of Boronic EstersThree more: The 3C homologation of chiral pinacol boronic esters gives di- or trisubstituted allylic boronic esters with high yield and E selectivities. The combination of this method with lithiation–borylation enables the synthesis of alkyl chains that bear 1,5-stereogenic centers. The utility of the process was demonstrated in a formal synthesis of (+)-jasplakinolide.

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In Situ Quantification and Visualization of Lithium Transport with Neutrons

Danny X. Liu, Jinghui Wang, Ke Pan, Dr. Jie Qiu, Prof. Marcello Canova, Prof. Lei R. Cao and Prof. Anne C. Co

In Situ Quantification and Visualization of Lithium Transport with NeutronsAn in-depth study: In situ neutron depth profiling has been demonstrated to provide temporal and spatial measurement of Li concentration and visualization of its transposition upon charging and discharging of a Li-ion cell (see picture). The delithiation process shows the removal of Li near the surface, which leads to a decreased coulombic efficiency.

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High Correlation between Oxidation Loci on Graphene Oxide

Jinrong Yang, Dr. Guosheng Shi, Dr. Yusong Tu and Prof. Haiping Fang

High Correlation between Oxidation Loci on Graphene OxideA reaction mechanism and a kinetic profile for graphene oxidation are proposed. Graphene oxidation proceeds with high correlation between oxidation loci, which is due to three crucial factors: 1) breaking of delocalized π bonds, 2) steric hindrance, and 3) hydrogen-bond formation.

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Membrane Deformation by Neolectins with Engineered Glycolipid Binding Sites

Julie Arnaud, Kevin Tröndle, Dr. Julie Claudinon, Dr. Aymeric Audfray, Dr. Annabelle Varrot, Prof. Winfried Römer and Dr. Anne Imberty

Membrane Deformation by Neolectins with Engineered Glycolipid Binding SitesNeolectins, which are based on a β-propeller architecture, have been designed with controlled number and position of binding sites to decipher the role of multivalency on avidity to a glycosylated surface and on membrane dynamics of glycolipids. Whereas the avidity only depends on the presence of at least two binding sites, the ability to bend and invaginate membranes critically depends on the distance between two adjacent binding sites.

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A Protein-Based Pentavalent Inhibitor of the Cholera Toxin B-Subunit

Dr. Thomas R. Branson, Dr. Tom E. McAllister, Jaime Garcia-Hartjes, Dr. Martin A. Fascione, Dr. James F. Ross, Dr. Stuart L. Warriner, Dr. Tom Wennekes, Prof. Han Zuilhof and Dr. W. Bruce Turnbull

A Protein-Based Pentavalent Inhibitor of the Cholera Toxin B-SubunitCholera versus cholera: The inhibition of multivalent protein/carbohydrate interactions between toxins and glycolipids in cell membranes can prevent the toxins from entering cells. The site-specific modification of a protein scaffold, matched in both size and valency to the target toxin, led to a multivalent inhibitor with an IC50 value of 104 pM for the cholera toxin B-subunit.

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Search for a Strong, Virtually “No-Shift” Hydrogen Bond: A Cage Molecule with an Exceptional OH⋅⋅⋅F Interaction

Mark D. Struble, Courtney Kelly, Dr. Maxime A. Siegler and Prof. Thomas Lectka

Search for a Strong, Virtually “No-Shift” Hydrogen Bond: A Cage Molecule with an Exceptional OH⋅⋅⋅F InteractionClose encounters: The spectroscopic properties of a caged fluorine molecule with a strong C[BOND]F⋅⋅⋅H[BOND]O interaction were studied. While computations and NMR data afford evidence for a strong interaction, almost no shift of the OH stretch in the IR spectrum was detected. These data point to a rare no-shift hydrogen bond, in which the bond’s red- and blue-shift character cancels.

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A High-Pressure NMR Probe for Aqueous Geochemistry

Dr. Brent G. Pautler, Christopher A. Colla, Dr. Rene L. Johnson, Peter Klavins, Dr. Stephen J. Harley, Dr. C. André Ohlin, Prof. Dimitri A. Sverjensky, Dr. Jeffrey H. Walton and Prof. William H. Casey

A High-Pressure NMR Probe for Aqueous GeochemistryA non-magnetic piston-cylinder pressure cell has been developed for solution-state NMR spectroscopy up to 20 kbar for aqueous geochemical applications. 11B NMR spectroscopic investigations into the H3BO3–catechol equilibrium demonstrates a large pressure-driven exchange rate. The success of these experiments suggests that this probe design can be applied to a wide variety of NMR-active nuclei.

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Synthesis of Two-Dimensional Transition-Metal Phosphates with Highly Ordered Mesoporous Structures for Lithium-Ion Battery Applications

Dan Yang, Dr. Ziyang Lu, Dr. Xianhong Rui, Xiao Huang, Dr. Hai Li, Dr. Jixin Zhu, Wenyu Zhang, Prof. Yeng Ming Lam, Prof. Huey Hoon Hng, Prof. Hua Zhang and Prof. Qingyu Yan

Synthesis of Two-Dimensional Transition-Metal Phosphates with Highly Ordered Mesoporous Structures for Lithium-Ion Battery ApplicationsUltrathin two-dimensional (2D) nanoflakes of transition-metal phosphates, including FePO4 (see TEM image), Mn3(PO4)2, and Co3(PO4)2, with highly ordered mesoporous structures have been successfully synthesized in a nonpolar solvent. The use of the 2D mesoporous FePO4 nanoflake as a cathode in a lithium-ion battery resulted in excellent stability and high rate capabilities.

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Alkene–Tetrazine Ligation for Imaging Cellular DNA

Dr. Ulrike Rieder and Prof. Dr. Nathan W. Luedtke

Alkene–Tetrazine Ligation for Imaging Cellular DNADiels–Alder on DNA: 5-Vinyl-2′-deoxyuridine (VdU) is metabolically incorporated into cellular DNA where it can be visualized by using inverse electron demand Diels–Alder reactions with fluorescent tetrazines. VdU–tetrazine ligation reactions are rapid (k≈0.02 M−1 s−1) and chemically orthogonal to alkyne–azide “click” reactions, thereby enabling time-resolved, multicolor labeling of DNA synthesis in individual cells.

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EarlyViewAqueous Heterogeneity at the Air/Water Interface Revealed by Two-Dimensional Phase-Sensitive Sum-Frequency Generation Spectroscopy

Cho-Shuen Hsieh, Masanari Okuno, Johannes Hunger, Ellen H. G. Backus, Yuki Nagata, and Mischa Bonn*

Water molecules interact strongly with each other through hydrogen bonds resulting in efficient intermolecular coupling. Using surface-specific femtosecond vibrational spectroscopy, it is found that at the air/water interface the intermolecular coupling is significantly reduced compared to bulk water and varies strongly for different interfacial water molecules—in contrast to bulk water, where the coupling is the same for all water molecules. The weakest intermolecular coupling is observed for the topmost, weakly hydrogen-bonded OH groups, despite the reduced structural constraints imposed on these OH groups by the interfacial hydrogen-bond environment.

Received February 18, 2014, published online June 24, 2014, DOI: 10.1002/anie.201402566 – read now. No. 31/2014.

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EarlyViewDecay of FeV Nitride Complexes by a N–N Bond Coupling Reaction in Solution: A Combined Spectroscopic and Theoretical Analysis

Oliver Krahe, Eckhard Bill, and Frank Neese*

Cryogenically trapped FeV–nitride complexes with cyclam-based ligands were found to decay by bimolecular reactions, forming exclusively FeII compounds. Characterization of educts and products by Mössbauer spectroscopy, mass spectrometry, and spectroscopy-oriented DFT calculations showed that the reaction mechanism is reductive nitride coupling and release of dinitrogen (2FeV≡N[RIGHTWARDS ARROW]FeII-N=N-FeII[RIGHTWARDS ARROW]2FeII+N2). The reaction pathways, representing an "inverse" of the Haber–Bosch reaction, were computationally explored in detail, also to judge the feasibility that the converse would yield catalytically competent FeV(N). Implications for the photolytic cleavage of FeIII–azides used to generate high-valent Fe nitrides could be discussed.

Received March 20, 2014, published online May 18, 2014, DOI: 10.1002/anie.201403402 – read now.

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EarlyViewThreshold Sensing by a Synthetic Enzymatic Reaction–Diffusion Network

Sergey Semenov, Albert J. Markvoort, Tom F. A. de Greef, and Wilhelm T. S. Huck

A wet stamping method is reported to precisely control concentrations of enzymes and inhibitors in place and time inside layered gels. By combining enzymatic reactions such as autocatalysis and inhibition with spatial delivery of components through soft-lithographic techniques the biochemical reaction network can filter out certain aspects of a pattern (density of pillars, size of features on the stamp) and translate this information into a fluorescent signal because of the local autocatalytic activation of trypsin. The experimental method can be used to assess fundamental principles of spatiotemporal order formation in chemical reaction networks.

Received February 12, 2014, published online April 02, 2014, DOI: 10.1002/anie.201402327 – read now. No. 31/2014.

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EarlyViewRate Coefficients of Criegee Intermediate (CH2OO and CH3CHOO) Reactions with Formic and Acetic Acid Are Close to Their Collision Limit: Direct Kinetics Measurements and Atmospheric Implications

Oliver Welz, Arkke J. Eskola, Leonid Sheps, Brandon Rotavera, John D. Savee, Adam M. Scheer, David L. Osborn, Douglas Lowe, A. Murray Booth, Ping Xiao, M. Anwar H. Khan, Carl J. Percival,* Dudley E. Shallcross,* and Craig A. Taatjes*

Rate coefficients for reactions of Criegee intermediates (carbonyl oxides, CI) with organic acids are in excess of 1x10-10 cm3 s-1, suggesting that reaction with carboxylic acids is a substantially more important loss process for CI than has been assumed. Implementing these rate coefficients in global atmospheric models shows that reactions between CI and organic acids make a substantial contribution to removal of these acids in terrestrial equatorial areas and in other regions where high CI concentrations occur such as high northern latitudes, and implies that sources of acids in these areas are larger than previously recognized.

Received January 28, 2014, published online March 25, 2014, DOI: 10.1002/anie.201400964 – read now.

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