Angewandte Chemie International Edition

Cover image for Vol. 53 Issue 48

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. Cover Pictures

    1. Thiophene-Based, Radial π-Conjugation: Synthesis, Structure, and Photophysical Properties of Cyclo-1,4-phenylene-2′,5′-thienylenes

      Dr. Hideto Ito, Yukari Mitamura, Prof. Dr. Yasutomo Segawa and Prof. Dr. Kenichiro Itami

      Article first published online: 21 NOV 2014 | DOI: 10.1002/anie.201410932

      Thumbnail image of graphical abstract

      Sulfur-containing carbon nanorings whose phenylene and thienylene units are alternately connected within the ring structure, such as in cyclo-1,4-phenylene-2′,5′-thienylene (CPT), show remarkable photophysical and crystallographic properties, as described by K. Itami et al. in their Communication (DOI: 10.1002/anie.201409389). The illustrated picture (provided by Haruko Hirukawa) represents a [4]CPT molecule, which forms a truncated cone shape and interesting tubular stacking in the solid state, similar to onion rings.

  2. Communications

    1. Membrane Recruitment

      Recruitment of SH-Containing Peptides to Lipid and Biological Membranes through the Use of a Palmitic Acid Functionalized with a Maleimide Group

      Ivan Haralampiev, Monique Mertens, Dr. Roland Schwarzer, Prof. Dr. Andreas Herrmann, Dr. Rudolf Volkmer, Prof. Dr. Pablo Wessig and Dr. Peter Müller

      Article first published online: 21 NOV 2014 | DOI: 10.1002/anie.201408089

      Thumbnail image of graphical abstract

      A lure for biomolecules: A palmitic acid derivative functionalized with a maleimide group serves to recruit sulfhydryl-containing biomolecules to membranes (see picture). The approach offers new possibilities for the preparation of biologically active liposomes and the manipulation of living cells.

    2. RNA Modifications

      Profiling of Ribose Methylations in RNA by High-Throughput Sequencing

      Ulf Birkedal, Mikkel Christensen-Dalsgaard, Nicolai Krogh, Radhakrishnan Sabarinathan, Jan Gorodkin and Prof. Henrik Nielsen

      Article first published online: 21 NOV 2014 | DOI: 10.1002/anie.201408362

      Thumbnail image of graphical abstract

      Composed of RNA and protein, ribosomes are the sites of protein synthesis in the cell. The RNA component is chemically modified at many residues close to the active site. A new sequencing method maps the most prominent modification, ribose methylation, across the entire ribosomal RNA in a single experiment. This method should aid in the study of fundamental aspects of ribosome function.

    3. LiNbO3-type Magnetic Oxynitride

      MnTaO2N: Polar LiNbO3-type Oxynitride with a Helical Spin Order

      Dr. Cédric Tassel, Yoshinori Kuno, Yoshihiro Goto, Dr. Takafumi Yamamoto, Dr. Craig M. Brown, Dr. James Hester, Dr. Koji Fujita, Dr. Masanobu Higashi, Prof. Ryu Abe, Prof. Katsuhisa Tanaka, Dr. Yoji Kobayashi and Prof. Hiroshi Kageyama

      Article first published online: 21 NOV 2014 | DOI: 10.1002/anie.201408483

      Thumbnail image of graphical abstract

      Under pressure: The first LiNbO3-type oxynitride, MnTaO2N, has been synthesized using a high-pressure technique (see picture). Contrary to conventional ammonolysis reaction, this approach allows to obtain an oxynitride with a middle-to-late transition metal. MnTaO2N is non-centrosymmetric unlike most oxynitrides and exhibits a nontrivial helical spin ordering below 25 K.

    4. Lipid Synthesis

      Phase Behavior of a Designed Cyclopropyl Analogue of Monoolein: Implications for Low-Temperature Membrane Protein Crystallization

      Livia Salvati Manni, Dr. Alexandru Zabara, Dr. Yazmin M. Osornio, Jendrik Schöppe, Dr. Alexander Batyuk, Prof. Dr. Andreas Plückthun, Prof. Dr. Jay S. Siegel, Prof. Dr. Raffaele Mezzenga and Prof. Dr. Ehud M. Landau

      Article first published online: 21 NOV 2014 | DOI: 10.1002/anie.201409791

      Thumbnail image of graphical abstract

      Membrane proteins: Lipidic cubic phases (LCPs) have been used as membrane-mimetic matrices to crystallize membrane proteins. A novel lipid, monodihydrosterculin (MDS; see picture) was designed and synthesized and its lipid molecular structure was correlated with the phase behavior of the ensuing mesophases. A particularly stable Pn3m cubic phase at low temperature was used to crystallize bacteriorhodopsin at 4 °C.

    5. Diblock Copolymers

      pH-Responsive Non-Ionic Diblock Copolymers: Ionization of Carboxylic Acid End-Groups Induces an Order–Order Morphological Transition

      Joseph R. Lovett, Dr. Nicholas J. Warren, Dr. Liam P. D. Ratcliffe, Dr. Marzena K. Kocik and Prof. Steven P. Armes

      Article first published online: 21 NOV 2014 | DOI: 10.1002/anie.201409799

      Thumbnail image of graphical abstract

      From worms to spheres: Ionization of a single terminal carboxylic acid on each stabilizer chain of gels containing non-ionic diblock copolymer worms confers unexpected pH-sensitivity; this subtle change in the packing parameter induces a reversible worm-to-sphere transformation with concomitant degelation.

    6. Natural Product Synthesis

      Total Synthesis of Indole Alkaloid Alsmaphorazine D

      Chenlong Zhu, Zhaobo Liu, Guanyu Chen, Kai Zhang and Prof. Dr. Hanfeng Ding

      Article first published online: 21 NOV 2014 | DOI: 10.1002/anie.201409827

      Thumbnail image of graphical abstract

      The total synthesis of (±)-alsmaphorazine D was achieved in a concise and efficient fashion. The key features of the strategy are based on a catalytic intramolecular oxidative cyclization, an oxidative cyclic aminal formation, a transannular radical cyclization, and a one-pot desilylation/double epimerization reaction. CAN=cerium(IV) ammonium nitrate.

    7. Reaction Mechanisms

      C[BOND]H Bond Activation by Metal–Superoxo Species: Magnetic Coupling Correlated to High Reactivity in Metal-Superoxo species

      Azaj Ansari, Dr. Prabha Jayapal and Prof. Gopalan Rajaraman

      Article first published online: 21 NOV 2014 | DOI: 10.1002/anie.201409844

      Thumbnail image of graphical abstract

      Superoxoman: The title reaction was investigated and the calculations reveal that Mn–O2.− and Fe–O2.− are stronger oxidants compared to either Cr–O2.− or Cu–O2.−, and the oxidative abilities are found to be correlated to the magnetic exchange parameter J. These findings have direct relevance to the functions of several metalloenzymes.

    8. Si,P Heterocycles

      Phosphide Delivery to a Cyclotrisilene

      Dr. Thomas P. Robinson, Dr. Michael J. Cowley, Prof. Dr. David Scheschkewitz and Prof. Dr. Jose M. Goicoechea

      Article first published online: 21 NOV 2014 | DOI: 10.1002/anie.201409908

      Thumbnail image of graphical abstract

      Addition of the 2-phosphoethynolate anion across the Si[BOND]Si double bond of a cyclic trisilene is presented. Photolysis of the resulting product affords a novel four-membered heterocycle exhibiting considerable allylic character. This latter species can be thought of as a congener of the cyclobutene anion.

    9. Biosynthesis

      Mechanistic Studies of the Radical S-Adenosylmethionine Enzyme DesII with TDP-D-Fucose

      Yeonjin Ko, Mark W. Ruszczycky, Sei-Hyun Choi and Prof. Dr. Hung-wen Liu

      Article first published online: 21 NOV 2014 | DOI: 10.1002/anie.201409540

      Thumbnail image of graphical abstract

      What dictates the substrate’s fate? DesII is a radical S-adenosylmethionine (SAM) enzyme that can catalyze either deamination or dehydrogenation depending on the substitution pattern of its substrate. By altering the stereochemistry of the dehydrogenation substrate, however, dehydration also becomes possible. This supports a model in which the fate of the substrate radical depends on its binding configuration in the enzyme active site.

  3. Cover Pictures

    1. Benzoxazolone Carboxamides: Potent and Systemically Active Inhibitors of Intracellular Acid Ceramidase

      Dr. Daniela Pizzirani, Dr. Anders Bach, Dr. Natalia Realini, Dr. Andrea Armirotti, Dr. Luisa Mengatto, Dr. Inga Bauer, Dr. Stefania Girotto, Dr. Chiara Pagliuca, Dr. Marco De Vivo, Dr. Maria Summa, Dr. Alison Ribeiro and Prof. Daniele Piomelli

      Article first published online: 21 NOV 2014 | DOI: 10.1002/anie.201410931

      Thumbnail image of graphical abstract

      The discovery of the first potent systemically active inhibitors of acid ceramidase (AC) are reported in the Communication (DOI: 10.1002/anie.201409042) by D. Piomelli and co-workers. This enzyme controls the levels of two key intracellular messengers: ceramide, which causes cell senescence and death, and sphingosine-1-phosphate (S1P), which has the opposite effect. By blocking AC, the new inhibitors tilt the balance between ceramide and S1P, thereby enhancing the pro-aging and pro-death effects of the former compound.

  4. Communications

    1. Boron Cage Clusters

      Endohedral and Exohedral Metalloborospherenes: M@B40 (M=Ca, Sr) and M&B40 (M=Be, Mg)

      Hui Bai, Qiang Chen, Prof. Dr. Hua-Jin Zhai and Prof. Dr. Si-Dian Li

      Article first published online: 21 NOV 2014 | DOI: 10.1002/anie.201408738

      Thumbnail image of graphical abstract

      Into higher spheres: The recently observed B40 borospherene is predicted to be capable of hosting a metal atom inside (M@B40; M=Ca, Sr) or coordinating one on its heptagonal surface (M&B40; M=Be, Mg). Metalloborospherenes are charge-transfer M2+B402− complexes, demonstrating the structural and electronic integrity of borospherene, akin to C60 buckyball.

    2. Photomagnetic Semiconductors

      Photomagnetic Response in Highly Conductive Iron(II) Spin-Crossover Complexes with TCNQ Radicals

      Hoa Phan, Shermane M. Benjamin, Eden Steven, Prof. James S. Brooks and Prof. Michael Shatruk

      Article first published online: 21 NOV 2014 | DOI: 10.1002/anie.201408680

      Thumbnail image of graphical abstract

      Multifunctional materials: Two cationic FeII complexes co-crystallized with partially charged TCNQ.δ radical anions exhibit temperature- and light-induced conversion between the high-spin and low-spin states of the FeII ion, as well as semiconductivity propagated by the TCNQ stacks. The conductivity of these materials is among the highest for all reported spin-crossover semiconductors.

    3. Molecular Dynamics

      Structure and Dynamics of Oligonucleotides in the Gas Phase

      Dr. Annalisa Arcella, Dr. Jens Dreyer, Dr. Emiliano Ippoliti, Ivan Ivani, Dr. Guillem Portella, Dr. Valérie Gabelica, Prof. Dr. Paolo Carloni and Prof. Dr. Modesto Orozco

      Article first published online: 21 NOV 2014 | DOI: 10.1002/anie.201406910

      Thumbnail image of graphical abstract

      Molecular dynamics calculations and mass spectrometry are combined to obtain an atomistic description of DNA under vacuum after electrospray vaporization under mild ionization conditions. After vaporization, gas-phase ions with different mass/charge (m/z) ratios are produced and for the most abundant charge state, the structure preserves a memory of the native conformation.

  5. Book Reviews

    1. Directed Selectivity in Organic Synthesis. A Practical Guide. By Tanja Gaich and Ekkehard Winterfeld.

      Tobias A. M. Gulder

      Article first published online: 20 NOV 2014 | DOI: 10.1002/anie.201410676

      Thumbnail image of graphical abstract

      Wiley-VCH, Weinheim, 2014. 368 pp., softcover, € 49.90.—ISBN 978-3527333752

  6. Communications

    1. Traceable Biogenic Nanovectors

      Transformation of Cell-Derived Microparticles into Quantum-Dot-Labeled Nanovectors for Antitumor siRNA Delivery

      Dr. Gang Chen, Jun-Yi Zhu, Prof. Zhi-Ling Zhang, Dr. Wei Zhang, Jian-Gang Ren, Min Wu, Zheng-Yuan Hong, Cheng Lv, Prof. Dai-Wen Pang and Prof. Yi-Fang Zhao

      Article first published online: 20 NOV 2014 | DOI: 10.1002/anie.201410223

      Thumbnail image of graphical abstract

      Illuminating biogenic microparticles: Cell-derived microparticles (MPs) are transformed to functionalized nanovectors by combining quantum dot (QD) labeling and efficient siRNA loading. This strategy not only reliably conferred excellent traceability and therapeutic potential on MPs, but also preserved their natural properties, thus facilitating the identification and further application of biogenic MPs. SA=streptavidin.

    2. Organocatalysis

      Phase-Transfer-Catalyzed Asymmetric SNAr Reaction of α-Amino Acid Derivatives with Arene Chromium Complexes

      Prof. Dr. Seiji Shirakawa, Kenichiro Yamamoto and Prof. Dr. Keiji Maruoka

      Article first published online: 20 NOV 2014 | DOI: 10.1002/anie.201409065

      Thumbnail image of graphical abstract

      Increased substrate scope in phase-transfer-catalyzed asymmetric SNAr reactions was achieved by the use of arene chromium complexes as electrophiles. An efficient asymmetric synthesis of α,α-disubstituted α-amino acids containing various aromatic substituents is shown. PTC=phase-transfer catalyst.

    3. Fullerenes

      Synthesis and Structure of LaSc2N@Cs(hept)-C80 with One Heptagon and Thirteen Pentagons

      Dr. Yang Zhang, Kamran B. Ghiassi, Qingming Deng, Nataliya A. Samoylova, Prof. Marilyn M. Olmstead, Prof. Alan L. Balch and Dr. Alexey A. Popov

      Article first published online: 20 NOV 2014 | DOI: 10.1002/anie.201409094

      Thumbnail image of graphical abstract

      An unanticipated discovery: The isomer of LaSc2N@C80 with a heptagonal ring and two pairs of adjacent pentagons has been isolated and characterized by single-crystal X-ray diffraction. Sc magenta, La orange, N blue.

    4. Supramolecular Catalysis

      Enantiotopos-Selective C[BOND]H Oxygenation Catalyzed by a Supramolecular Ruthenium Complex

      Dr. James R. Frost, Prof. Dr. Stefan M. Huber, Dr. Stefan Breitenlechner, M. Sc. Christoph Bannwarth and Prof. Dr. Thorsten Bach

      Article first published online: 20 NOV 2014 | DOI: 10.1002/anie.201409224

      Thumbnail image of graphical abstract

      Correctly addressed: Catalyst 1 allows for a selective oxygenation of spirocyclic oxindoles at one of two enantiotopic positions (•). Evidence was collected that hydrogen bonding (▪) is responsible for a perfect spatial overlap of the reactive centers in the transition state of the C[BOND]H activation reaction.

    5. DNA Nanotechnology

      Ion-Selective Formation of a Guanine Quadruplex on DNA Origami Structures

      Lydia Olejko, Dr. Piotr J. Cywinski and Prof. Dr. Ilko Bald

      Article first published online: 20 NOV 2014 | DOI: 10.1002/anie.201409278

      Thumbnail image of graphical abstract

      Right said FRET: Guanine (G) quadruplex structures are formed on DNA origami triangles in the presence of K+ ions, whereas G-quadruplex formation is completely suppressed when Na+ ions are present. This effect was studied with FRET measurements and ascribed to steric hindrance induced by the DNA origami platform. The systems may have potential for selective K+ sensing.

    6. Decarboxylative Coupling

      Transition-Metal-Free Formal Decarboxylative Coupling of α-Oxocarboxylates with α-Bromoketones under Neutral Conditions: A Simple Access to 1,3-Diketones

      Zhen He, Xiaotian Qi, Shiqing Li, Yinsong Zhao, Prof. Dr. Ge Gao, Prof. Dr. Yu Lan, Yiwei Wu, Prof. Dr. Jingbo Lan and Prof. Dr. Jingsong You

      Article first published online: 20 NOV 2014 | DOI: 10.1002/anie.201409361

      Thumbnail image of graphical abstract

      No metal needed: 1,3-Diketone compounds are synthesized from α-oxocarboxylates and α-bromoketones using a bromide-catalyzed, mild, neutral, and transition-metal-free procedure which tolerates a wide spectrum of functional groups. DFT calculations suggest a mechanism involving coupling followed by decarboxylation. NMP=N-methyl-2-pyrrolidone; TBAB=tetrabutylammonium bromide.

    7. Magnetic Resonance Imaging

      Activatable 19F MRI Nanoparticle Probes for the Detection of Reducing Environments

      Tatsuya Nakamura, Dr. Hisashi Matsushita, Dr. Fuminori Sugihara, Prof. Yoshichika Yoshioka, Dr. Shin Mizukami and Prof. Kazuya Kikuchi

      Article first published online: 20 NOV 2014 | DOI: 10.1002/anie.201409365

      Thumbnail image of graphical abstract

      Redox-sensitive MRI agents: Reducing-environment-responsive 19F magnetic resonance imaging (MRI) probes were developed. The 19F NMR/MRI signals of the probes are quenched by the paramagnetic relaxation enhancement effect of the Gd3+ complexes. A reductive reaction induced high signal enhancement of the probes (see picture).

    8. Macrocycles

      Thiophene-Based, Radial π-Conjugation: Synthesis, Structure, and Photophysical Properties of Cyclo-1,4-phenylene-2′,5′-thienylenes

      Dr. Hideto Ito, Yukari Mitamura, Prof. Dr. Yasutomo Segawa and Prof. Dr. Kenichiro Itami

      Article first published online: 20 NOV 2014 | DOI: 10.1002/anie.201409389

      Thumbnail image of graphical abstract

      Full circle: Cyclo-1,4-phenylene-2′,5′-thienylenes (CPTs) have been synthesized as the first example of a thiophene-based, radially π-conjugated system. X-ray crystal structures, UV-vis absorption and emission spectra, and theoretical studies revealed the unique structural and photophysical properties of CPTs based on their radial, cyclic π-conjugation.

    9. Self-Alignment of Pd8 Chains

      Self-Alignment of Low-Valent Octanuclear Palladium Atoms

      Kanako Nakamae, Dr. Yukie Takemura, Dr. Bunsho Kure, Prof. Takayuki Nakajima, Prof. Yasutaka Kitagawa and Prof. Tomoaki Tanase

      Article first published online: 20 NOV 2014 | DOI: 10.1002/anie.201409511

      Thumbnail image of graphical abstract

      Linear Pd8 chains were synthesized through self-alignment. Discrete molecules of [Pd8(μ-dpmppm)4](BF4)4 (1) and [Pd8(μ-dpmppm)4L2](BF4)4 [L=XylNC (2), acetonitrile (3), and dmf (4)] are stable in solution and exhibit interesting temperature-dependent photochemical properties in the near IR region. dpmppm=meso-bis[(diphenylphosphinomethyl)phenylphosphino]methane), XylNC=2,6-xylyl isocyanide, dmf=N,N-dimethylformamide.

    10. Direct Imine Formation

      Redox Properties of CeO2 at Low Temperature: The Direct Synthesis of Imines from Alcohol and Amine

      Dr. Masazumi Tamura and Prof. Dr. Keiichi Tomishige

      Article first published online: 20 NOV 2014 | DOI: 10.1002/anie.201409601

      Thumbnail image of graphical abstract

      The amazing redox property of CeO2 is utilized in the direct imine formation from alcohols and amines even at 303 K. The catalytic activity of CeO2 is more than 38-fold higher than that of other simple metal oxides. CeO2 is a reusable heterogeneous catalyst and can be applied to various alcohols and amines, resulting in high yields (75–98 %) and high selectivities (89–>99 %).

    11. Asymmetric Dearomatization | Hot Paper

      Asymmetric Dearomatization of β-Naphthols through an Amination Reaction Catalyzed by a Chiral Phosphoric Acid

      Shou-Guo Wang, Dr. Qin Yin, Dr. Chun-Xiang Zhuo and Prof. Dr. Shu-Li You

      Article first published online: 20 NOV 2014 | DOI: 10.1002/anie.201409756

      Thumbnail image of graphical abstract

      Useful skeletons: An electrophilic amination reaction catalyzed by chiral phosphoric acid is the basis for a highly efficient asymmetric dearomatization of naphthols. This protocol provides functionalized β-naphthalenone compounds with a chiral quaternary carbon center in excellent yields and enantioselectivity. These motifs are found in various biologically active natural products and therapeutic reagents.

    12. Flow Chemistry

      Chemical Assembly Systems: Layered Control for Divergent, Continuous, Multistep Syntheses of Active Pharmaceutical Ingredients

      Dr. Diego Ghislieri, Dr. Kerry Gilmore and Prof. Dr. Peter H. Seeberger

      Article first published online: 20 NOV 2014 | DOI: 10.1002/anie.201409765

      Thumbnail image of graphical abstract

      Single system, multiple medicines: A new paradigm in chemical synthesis is introduced, in which a systems-level approach to chemical synthesis allows access to a broad chemical space with a single process. The combination of five interchangeable reaction modules affords the continuous synthesis of β-amino acids, γ-lactams, and γ-amino acids, including the blockbuster drugs Gabapentin and Lyrica.

    13. Magnets | Very Important Paper

      Magnet Design by Integration of Layer and Chain Magnetic Systems in a π-Stacked Pillared Layer Framework

      Hiroki Fukunaga and Prof. Dr. Hitoshi Miyasaka

      Article first published online: 20 NOV 2014 | DOI: 10.1002/anie.201410057

      Thumbnail image of graphical abstract

      A pillared layer framework (PLF) was used to rationally design and fabricate a long-range ordered magnet with a phase transition temperature (Tc) of 82 K by integrating two low-dimensional magnetic materials, namely a layer magnetic system and a one-dimensional columnar magnetic system. Furthermore, Tc increased linearly with the applied pressure.

    14. Microsolvation

      Water–Water and Water–Solute Interactions in Microsolvated Organic Complexes

      Dr. Cristóbal Pérez, Dr. Justin L. Neill, Matthew T. Muckle, Dr. Daniel P. Zaleski, Dr. Isabel Peña, Prof. Juan C. Lopez, Prof. Jose L. Alonso and Prof. Brooks H. Pate

      Article first published online: 20 NOV 2014 | DOI: 10.1002/anie.201409057

      Thumbnail image of graphical abstract

      Water clusters: The microsolvated structures of BPL–(H2O)n (n=1–5; BPL= β-propiolactone) have been measured by chirped-pulse Fourier transform microwave spectroscopy. A delicate trade-off is found between maximizing the number of solute–H2O interactions and the minimum-energy structures of isolated clusters. The calculated and the experimentally derived dipole moments are shown by blue and green arrows, respectively (see picture).

    15. Drug Design

      Rational Design and Asymmetric Synthesis of Potent and Neurotrophic Ligands for FK506-Binding Proteins (FKBPs)

      Sebastian Pomplun, Dr. Yansong Wang, Dr. Alexander Kirschner, Dr. Christian Kozany, Dr. Andreas Bracher and Dr. Felix Hausch

      Article first published online: 20 NOV 2014 | DOI: 10.1002/anie.201408776

      Thumbnail image of graphical abstract

      Designed to be potent: An asymmetric synthesis with an HF-driven N-acyliminium cyclization as key step afforded (S)-C5-branched [4.3.1] aza-amide bicycles as a new class of highly potent and neurotrophic ligands for the psychiatric risk factor FKBP51. High resolution cocrystal structures confirmed the importance of the polar (S)-C5 substituents, which led to a more than 280-fold affinity increase. TMS=trimethylsilyl.

    16. Medicinal Chemistry | Hot Paper

      Design and Synthesis of High-Affinity Dimeric Inhibitors Targeting the Interactions between Gephyrin and Inhibitory Neurotransmitter Receptors

      Dr. Hans Michael Maric, Vikram Babu Kasaragod, Dr. Linda Haugaard-Kedström, Dr. Torben Johann Hausrat, Prof. Dr. Matthias Kneussel, Prof. Dr. Hermann Schindelin and Prof. Dr. Kristian Strømgaard

      Article first published online: 20 NOV 2014 | DOI: 10.1002/anie.201409043

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      Double-teaming: Dimeric peptide ligands were developed that target gephyrin, the central scaffolding protein for inhibitory neurotransmitter receptors in the brain, with unprecedented high affinity. Dimerization also substantially improved the serum stability, thus providing compounds with great promise for further studies of gephyrin–receptor interactions. The X-ray structure shows one of these peptides in complex with two monomers of the gephyrin E domain.

    17. Molecular Recognition

      Partitioning Solvophobic and Dispersion Forces in Alkyl and Perfluoroalkyl Cohesion

      Dr. Catherine Adam, Dr. Lixu Yang and Dr. Scott L. Cockroft

      Article first published online: 20 NOV 2014 | DOI: 10.1002/anie.201408982

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      In full force: The balance of solvophobic and van der Waals dispersion forces on the self-association of perfluoroalkyl and alkyl chains is examined in solution. The contributions of dispersion interactions in apolar cohesion were strongly attenuated in solution compared to the gas phase. In contrast, solvophobic effects were dominant in driving the association of apolar chains in aqueous solution.

    18. Peptide Monolayers

      The Influence of Two-Dimensional Organization on Peptide Conformation

      Dr. Simon J. White, Dr. Steven D. Johnson, Mark A. Sellick, Dr. Agnieszka Bronowska, Prof. Peter G. Stockley and Prof. Christoph Wälti

      Article first published online: 20 NOV 2014 | DOI: 10.1002/anie.201408971

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      Collective action: Molecular crowding in the high-molecular density environment of a 2D peptide monolayer is shown to govern peptide conformation and function. The results show that these collective interactions need to be accounted for in the design and interpretation of experimental studies involving surface-immobilized molecular systems.

    19. Spin Switching

      A Two-in-one Pincer Ligand and its Diiron(II) Complex Showing Spin State Switching in Solution through Reversible Ligand Exchange

      Dr. Subhas Samanta, Dr. Serhiy Demesko, Dr. Sebastian Dechert and Prof. Dr. Franc Meyer

      Article first published online: 20 NOV 2014 | DOI: 10.1002/anie.201408966

      Thumbnail image of graphical abstract

      A pyrazolate-bridged ligand with two {PNN} pincer-type compartments has been developed. Its diiron(II) complex LFe2(OTf)3(NCMe) shows a sequential, reversible, and complete spin state switching between the all-high-spin and all-low-spin states in solution, which correlates with a rapid multistep triflate/MeCN ligand exchange equilibrium. The spin transition temperature can be continuously tuned by varying the triflate concentration.

    20. Nanowire Orientation

      Large-Area Alignment of Tungsten Oxide Nanowires over Flat and Patterned Substrates for Room-Temperature Gas Sensing

      Wei Cheng, Yanrui Ju, Payam Payamyar, Dr. Darinka Primc, Dr. Jingyi Rao, Christoph Willa, Dr. Dorota Koziej and Prof. Dr. Markus Niederberger

      Article first published online: 20 NOV 2014 | DOI: 10.1002/anie.201408617

      Thumbnail image of graphical abstract

      Sensing, down to the wire: A facile solution route provides ultrathin tungsten oxide nanowires (see picture, left) which can be aligned over a large area by the Langmuir–Blodgett technique (middle). The aligned tungsten oxide nanowire thin films exhibit excellent sensitivity to H2 at room temperature (right).

    21. Reversible DNA Ligation

      Synthesis, Dynamic Combinatorial Chemistry, and PCR Amplification of 3′–5′ and 3′–6′ Disulfide-linked Oligonucleotides

      Dennis Jul Hansen, Ilenia Manuguerra, Michael Brøndum Kjelstrup and Prof. Kurt Vesterager Gothelf

      Article first published online: 20 NOV 2014 | DOI: 10.1002/anie.201405761

      Thumbnail image of graphical abstract

      Internucleosidic 3′–5′ and 3′–6′ disulfide linkages allows cleavage and template-directed formation of desired disulfides in the presence of mercaptoethanol. The artificial disulfide backbone is tolerated by polymerases and the sequences can be amplified by polymerase chain reaction.

    22. Redox-Switchable Catalysis

      Redox Control of a Dendritic Ferrocenyl-Based Homogeneous Catalyst

      M. Sc. Paul Neumann, Dr. Hanna Dib, Prof. Dr. Anne-Marie Caminade and Prof. Dr. Evamarie Hey-Hawkins

      Article first published online: 20 NOV 2014 | DOI: 10.1002/anie.201408314

      Thumbnail image of graphical abstract

      Under control: Both monomeric and dendritic (see picture) ferrocenylphosphane ruthenium(II) catalysts were reversibly switched off and on by chemical oxidation and reduction during isomerization of the allylic alcohol 1-octen-3-ol. This outcome is mainly due to electronic communication between the redox-active unit and the catalytic center. Such redox control could facilitate the development of catalysts with orthogonal activity for different substrates.

    23. High-Throughput Screening

      Direct Surface-Enhanced Raman Scattering Analysis of DNA Duplexes

      Dr. Luca Guerrini, Dr. Željka Krpetić, Dr. Danny van Lierop, Prof. Ramon A. Alvarez-Puebla and Prof. Duncan Graham

      Article first published online: 20 NOV 2014 | DOI: 10.1002/anie.201408558

      Thumbnail image of graphical abstract

      Accessing genomic information: A fast and affordable high-throughput screening method based on surface-enhanced Raman spectroscopy (SERS) is a low-cost and ultrasensitive genotyping strategy for gaining detailed genomic information on DNA duplexes. This method allows recognition of hybridization events, single-base mismatches, and base methylation.

    24. Photocatalysis | Hot Paper

      Metal-Free Carbonylations by Photoredox Catalysis

      Ing. Michal Majek and Prof. Dr. Axel Jacobi von Wangelin

      Article first published online: 20 NOV 2014 | DOI: 10.1002/anie.201408516

      Thumbnail image of graphical abstract

      A metal-free and base-free carbonylation has been developed which affords primary, secondary, and tertiary alkyl benzoates under irradiation with visible light in the presence of eosin Y as a photocatalyst. The mechanism has been studied by spectroscopic, theoretical, and preparative methods, and appears to involve intermediate aryl and aroyl radical species as well as a light-driven one-electron redox cycle without any sacrificial redox partner.

    25. Mesostructured Zeolites

      Co-development of Crystalline and Mesoscopic Order in Mesostructured Zeolite Nanosheets

      Dr. Robert J. Messinger, Dr. Kyungsu Na, Dr. Yongbeom Seo, Prof. Dr. Ryong Ryoo and Prof. Dr. Bradley F. Chmelka

      Article first published online: 20 NOV 2014 | DOI: 10.1002/anie.201408623

      Thumbnail image of graphical abstract

      Self-assembly of MFI-type crystal: The atomic and mesoscopic structural transformations that occur during hydrothermal syntheses of zeolite MFI nanosheets have been correlated and shown to proceed through initially mesostructured amorphous silica, followed by an intermediate nanolayered silicate phase. The results establish the transient processes by which coupled framework crystallization and surfactant self-assembly occur.

  7. Reviews

    1. Rare-Earth-Metal Hydrides

      Molecular Rare-Earth-Metal Hydrides in Non-Cyclopentadienyl Environments

      Dr. Waldemar Fegler, Dr. Ajay Venugopal, Dr. Mathias Kramer and Prof. Dr. Jun Okuda

      Article first published online: 20 NOV 2014 | DOI: 10.1002/anie.201406677

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      Beyond Cp: Molecular hydrides of rare-earth metals play an important role as homogeneous catalysts and as models of solid-state interstitial hydrides. This Review provides an overview of rare-earth-metal hydride complexes(without cyclopentadienyl ligands), with emphasis on the structural motifs and the effect of cationic charges on reactivity.

  8. Minireviews

    1. Cross-Coupling

      Stereospecific Couplings of Secondary and Tertiary Boronic Esters

      Dr. Daniele Leonori and Prof. Varinder K. Aggarwal

      Article first published online: 20 NOV 2014 | DOI: 10.1002/anie.201407701

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      Just couple it: In the past decade, highly efficient protocols have been developed to allow the stereospecific arylation of chiral organoborons. This Minireview documents the rapid development of this area, thus providing a clear overview of the various processes available together with mechanisms, as well as their scope and limitations.

  9. Communications

    1. Rhodium Complexes

      Terminal Phosphanido Rhodium Complexes Mediating Catalytic P[BOND]P and P[BOND]C Bond Formation

      Ana M. Geer, Ángel L. Serrano, Prof. Bas de Bruin, Prof. Miguel A. Ciriano and Dr. Cristina Tejel

      Article first published online: 19 NOV 2014 | DOI: 10.1002/anie.201407707

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      Oxidative addition of secondary phosphanes to a rhodium ethylene complex has led to mononuclear phosphanido rhodium complexes, which have been fully characterized (see picture). The terminal phosphanides are active catalysts for the “green synthesis” of phosphanes and diphosphanes under mild conditions through phosphane dehydrocoupling and olefin hydrophosphination reactions.

    2. Reaction Mechanisms

      Synthesis of a Stable Selenoaldehyde by Self-Catalyzed Thermal Dehydration of a Primary-Alkyl-Substituted Selenenic Acid

      Dr. Shohei Sase, Ryo Kakimoto and Prof. Dr. Kei Goto

      Article first published online: 19 NOV 2014 | DOI: 10.1002/anie.201409485

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      Selen’ it: A stable selenoaldehyde was synthesized by thermal dehydration of a selenenic acid bearing a nanosized primary-alkyl group. Intrinsic properties of a selenenic acid play a key role in this self-catalyzed β dehydration of an organic acid involving formation of an anhydride equivalent and subsequent β elimination of an acid. The selenoaldehyde showed remarkable stability and was characterized by crystallographic analysis.

  10. Highlights

    1. Light Emitting Diodes

      Let There Be Light—With Gallium Nitride: The 2014 Nobel Prize in Physics

      Paul Von Dollen, Dr. Siddha Pimputkar and Prof. Dr. James S. Speck

      Article first published online: 19 NOV 2014 | DOI: 10.1002/anie.201410693

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      Significant gains in energy savings now underway can be traced to a single invention—the blue light emitting diode. GaN-based blue LED technology not only resulted in efficient white light sources, but continues to enable a host of applications and scientific inquiries. The researchers primarily responsible for the development of the blue LED were awarded the 2014 Nobel Prize in Physics.

  11. Communications

    1. Dynamic Heterogeneity | Hot Paper

      Ionic Liquids: Not only Structurally but also Dynamically Heterogeneous

      Zhuan-Ping Zheng, Prof. Wen-Hui Fan, Soham Roy, Dr. Kamila Mazur, Andreas Nazet, Prof. Richard Buchner, Prof. Mischa Bonn and Dr. Johannes Hunger

      Article first published online: 19 NOV 2014 | DOI: 10.1002/anie.201409136

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      Size doesn′t matter: The equilibration of the ionic ammonium group in protic ionic liquids after an ultrafast temperature jump depends on the anion but not on the size of the hydrophobic side chain. This equilibration of the ionic domains is approximately two times slower than restructuring within the hydrophobic alkyl domains, which demonstrates the dynamic heterogeneity in ionic liquids.

    2. Heterocycle Synthesis

      Metal-Free Radical 5-exo-dig Cyclizations of Phenol-Linked 1,6-Enynes for the Synthesis of Carbonylated Benzofurans

      Ming Hu, Dr. Ren-Jie Song and Prof. Dr. Jin-Heng Li

      Article first published online: 19 NOV 2014 | DOI: 10.1002/anie.201408978

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      Benzofurans are obtained by the tBuONO-initiated radical 5-exo-dig cyclization of enynes under mild and metal-free conditions. The two oxygen atoms that constitute the newly formed carbonyl groups of the benzofuran system originate from O2 and 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO), respectively.

    3. Host–Guest Complexes

      Modulating the Binding of Polycyclic Aromatic Hydrocarbons Inside a Hexacationic Cage by Anion–π Interactions

      Dr. Nema Hafezi, Dr. James M. Holcroft, Dr. Karel J. Hartlieb, Edward J. Dale, Dr. Nicolaas A. Vermeulen, Charlotte L. Stern, Dr. Amy A. Sarjeant and Prof. J. Fraser Stoddart

      Article first published online: 19 NOV 2014 | DOI: 10.1002/anie.201408400

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      The ins and outs: A hexacationic macrobicyclic receptor comprised of pyridinium units fused together by electron-poor triazine rings has been shown to be a good receptor for polycyclic aromatic hydrocarbons. The lower than expected association constant for the PF6 salt with pyrene is attributed to the PF6 counterions fleetingly occupying the cavity. X-ray crystallography confirmed the presence of a PF6 ion in its cavity.

    4. Biocomputing

      Concatenated Logic Circuits Based on a Three-Way DNA Junction: A Keypad-Lock Security System with Visible Readout and an Automatic Reset Function

      Dr. Junhua Chen, Prof. Dr. Shungui Zhou and Junlin Wen

      Article first published online: 17 NOV 2014 | DOI: 10.1002/anie.201408334

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      Safe as houses: Concatenated logic circuits operating as a biocomputing keypad-lock security system with an automatic reset function were successfully constructed on the basis of toehold-mediated strand displacement and three-way-DNA-junction architecture. By the use of a split-G-quadruplex DNAzyme as the signal reporter, the output of the keypad lock was clearly recognized by the naked eye (see picture; MB=magnetic bead).

    5. Transparent Conducting Oxides

      A General One-Pot Strategy for the Synthesis of High-Performance Transparent-Conducting-Oxide Nanocrystal Inks for All-Solution-Processed Devices

      Jizhong Song, Sergei A. Kulinich, Jianhai Li, Yanli Liu and Prof. Haibo Zeng

      Article first published online: 17 NOV 2014 | DOI: 10.1002/anie.201408621

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      Nanocrystal inks: A series of transparent conducting oxide nanocrystals were prepared by a simple, generic, and easily scalable one-pot method. The formed NCs are of high crystallinity, uniform morphology, monodispersity, and high stability and could be employed for the assembly of high-quality electrodes.

    6. Native Chemical Ligation

      Traceless Purification and Desulfurization of Tau Protein Ligation Products

      Oliver Reimann, Dr. Caroline Smet-Nocca and Prof. Dr. Christian P. R. Hackenberger

      Article first published online: 17 NOV 2014 | DOI: 10.1002/anie.201408674

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      Fishing ligation products: Following a new method for traceless ligation, desulfurization, and purification, synthetic peptides equipped with photocleavable biotin are used in native chemical ligation (NCL) and expressed protein ligation (EPL) reactions. Pure, tag-free ligation products were obtained with a minimal time expenditure and used in an NCL-based synthesis of full-length human tau protein.

  12. Highlights

    1. Click Chemistry

      Enamine/Enolate-Mediated Organocatalytic Azide–Carbonyl [3+2] Cycloaddition Reactions for the Synthesis of Densely Functionalized 1,2,3-Triazoles

      Prof. Dr. Sripada S. V. Ramasastry

      Article first published online: 17 NOV 2014 | DOI: 10.1002/anie.201409410

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      Organocatalytic click! Recent advances in the metal-free enamine/enolate-mediated azide–carbonyl [3+2] cycloaddition reaction are discussed. These approaches require neither a metal catalyst nor alkyne substrates. Owing to the ready availability of carbonyl compounds, these methods thus offer excellent alternatives for the synthesis of 1,4-/1,5-disubstituted and 1,4,5-trisubstituted 1,2,3-triazoles.

  13. Communications

    1. Electrochemistry

      Photoelectrochemical Hydrogen Production in Alkaline Solutions Using Cu2O Coated with Earth-Abundant Hydrogen Evolution Catalysts

      Carlos G. Morales-Guio, Laurent Liardet, Dr. Matthew T. Mayer, Dr. S. David Tilley, Prof. Dr. Michael Grätzel and Prof. Dr. Xile Hu

      Article first published online: 17 NOV 2014 | DOI: 10.1002/anie.201410569

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      Amorphous molybdenum sulfide and nickel–molybdenum alloy efficiently catalyze the photoelectrochemical hydrogen evolution on a cuprous oxide photocathode in alkaline solutions.

    2. Grignard Reactions

      Catalytic Asymmetric Alkylation of Acylsilanes

      Jiawei Rong, Rik Oost, Dr. Alaric Desmarchelier, Prof. Adriaan J. Minnaard and Prof. Syuzanna R. Harutyunyan

      Article first published online: 17 NOV 2014 | DOI: 10.1002/anie.201409815

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      Chiral silanes: The highly enantioselective addition of Grignard reagents to acylsilanes is catalyzed by copper diphosphine complexes. This transformation affords tertiary aryl- and vinyl-substituted α-hydroxysilanes in up to 97 % yield and 98:2 enantiomeric ratio.

    3. NMR Spectroscopy

      Ligand-Detected Relaxation Dispersion NMR Spectroscopy: Dynamics of preQ1–RNA Binding

      Mag. Thomas Moschen, Mag. Christoph Hermann Wunderlich, Mag. Romana Spitzer, Mag. Jasmin Levic, Dr. Ronald Micura, Dr. Martin Tollinger and Dr. Christoph Kreutz

      Article first published online: 17 NOV 2014 | DOI: 10.1002/anie.201409779

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      Close interactions: Described is an NMR approach which gives access to two parameters of a ligand–receptor interaction. The off rate and the population of the small molecular–receptor complex can be determined. Ligand-detected NMR relaxation dispersion experiments represent a diagnostic tool for the characterization of binding mechanisms.

    4. Liquid Crystals | Hot Paper

      A Twist-Bend Nematic Phase Driven by Hydrogen Bonding

      Suzanne M. Jansze, Dr. Alfonso Martínez-Felipe, Prof. John M. D. Storey, Dr. Antonius T. M. Marcelis and Prof. Corrie T. Imrie

      Article first published online: 17 NOV 2014 | DOI: 10.1002/anie.201409738

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      Intriguing interplay: When the benzoic acid units in 4-[6-(4′-cyanobiphenyl-4-yl)hexyloxy]benzoic acid dimerize by hydrogen bonding (see picture), promesogenic liquid crystal trimers form. These supramolecular complexes show an enantiotropic nematic phase, which on cooling transforms into the twist-bend nematic phase in which the bent, achiral complexes spontaneously form helical structures.

    5. Structural Biology

      W2466.48 Opens a Gate for a Continuous Intrinsic Water Pathway during Activation of the Adenosine A2A Receptor

      Dr. Shuguang Yuan, Dr. Zhenquan Hu, Prof. Slawomir Filipek and Prof. Horst Vogel

      Article first published online: 17 NOV 2014 | DOI: 10.1002/anie.201409679

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      Water logged: Activation of G-protein-coupled receptors depends on the presence of water molecules inside the receptor. Microsecond molecular dynamics simulations revealed that agonist binding leads to structural fluctuations of the residue W6.48 inducing water influx and creation of a continuous water pathway (yellow dots, see structure) across the receptor.

    6. Noncovalent π Interactions

      Surfing π Clouds for Noncovalent Interactions: Arenes versus Alkenes

      Dr. Abil E. Aliev, Dr. Josephine R. T. Arendorf, Dr. Ilias Pavlakos, Dr. Rafael B. Moreno, Dr. Michael J. Porter, Prof. Henry S. Rzepa and Prof. William B. Motherwell

      Article first published online: 17 NOV 2014 | DOI: 10.1002/anie.201409672

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      Where do their affinities lie? In studies using molecular balances, noncovalent interactions with an arene dominated over those with an alkene, and a π-facial hydrogen bond from a hydroxy group to an arene was favored by about 1.2 kJ mol−1. Data for Y=CH2CH3, CHCH2, CCH, and CN groups indicated a long-range electrostatic C⋅⋅⋅π interaction between the Y substituent and the π system. The strongest interaction observed was with the cyano group.

    7. Gas Separation | Hot Paper

      Porous Liquids: A Promising Class of Media for Gas Separation

      Dr. Jinshui Zhang, Dr. Song-Hai Chai, Dr. Zhen-An Qiao, Dr. Shannon M. Mahurin, Dr. Jihua Chen, Dr. Youxing Fang, Dr. Shun Wan, Kimberly Nelson, Dr. Pengfei Zhang and Prof. Sheng Dai

      Article first published online: 17 NOV 2014 | DOI: 10.1002/anie.201409420

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      Perforated liquids: Functionalizing hollow silica spheres with suitable polymer species can produce a porous liquid containing empty silica cavities. Taking advantage of their liquid-like polymeric matrixes as the separation medium and the empty cavities as the gas transport pathway they can function as a promising candidates for gas separation.

    8. Conductive Materials

      High-Performance, Stretchable, Wire-Shaped Supercapacitors

      Dr. Tao Chen, Dr. Rui Hao, Prof. Huisheng Peng and Prof. Liming Dai

      Article first published online: 17 NOV 2014 | DOI: 10.1002/anie.201409385

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      Stretching out: Wire-shaped supercapacitors with more than 350 % elasticity have been developed by twisting two carbon-nanotube-wrapped elastic wires together with a polymer electrolyte between them. These newly developed wire devices exhibited high performance with a stability lasting for multiple stretching cycles.

    9. C[BOND]H Activation | Hot Paper

      Cobalt-Catalyzed C[BOND]H Cyanation of Arenes and Heteroarenes

      M. Sc. Jie Li and Prof. Dr. Lutz Ackermann

      Article first published online: 17 NOV 2014 | DOI: 10.1002/anie.201409247

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      As directed: The title reactions were accomplished with in situ generated cobalt(III) carboxylate complexes for highly efficient C[BOND]H activations. The direct cyanation proved viable with removable directing groups and displayed a broad substrate scope and mild reaction conditions.

    10. Synthetic Methods

      Copper-Catalyzed Stereoselective Aminoboration of Bicyclic Alkenes

      Ryosuke Sakae, Dr. Koji Hirano, Prof. Dr. Tetsuya Satoh and Prof. Dr. Masahiro Miura

      Article first published online: 17 NOV 2014 | DOI: 10.1002/anie.201409104

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      Have a nice ring: A copper-catalyzed aminoboration of bicyclic alkenes with diboron reagents and hydroxylamines has been developed. Subsequent oxidative transformations of the boryl group provide access to oxygen- and nitrogen-rich cyclic molecules. With a chiral bisphosphine ligand, (R,R)-Ph-BPE, the aminoboration could be conducted in an enantioselective fashion.

    11. Biradicaloids

      A Mixed Arsenic–Phosphorus Centered Biradicaloid

      Alexander Hinz, Prof. Dr. Axel Schulz and Dr. Alexander Villinger

      Article first published online: 17 NOV 2014 | DOI: 10.1002/anie.201408639

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      When you are two you cannot be too radical: The first biradicaloid with different radical centers, heteroatomic biradicaloid [P(μ-NR)2As], was obtained by reducing the corresponding dichloroarsaphosphadiazane with magnesium. Structure elucidation revealed a kite-shaped planar four-membered N2PAs ring with two equal P[BOND]N and As[BOND]N distances (see scheme, note in German the word for kite is Drachen, and dragon is Drache).

  14. Reviews

    1. Anti-Bredt Olefins

      Natural Products with Anti-Bredt and Bridgehead Double Bonds

      Dr. Jeffrey Y. W. Mak, Dr. Rebecca H. Pouwer and Assoc. Prof. Craig M. Williams

      Article first published online: 14 NOV 2014 | DOI: 10.1002/anie.201400932

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      Bend it like Bredt: Bredt’s rule, developed over a 100 years ago based on simple terpenes, states that the terminus of an olefin cannot exist at the bridgehead position of a bridged bicyclic system. For the first time, complex natural products containing bridgehead olefins and potential anti-Bredt systems are reviewed and evaluated, yet should they be considered anti-Bredt candidates at all?

  15. Communications

    1. Organocatalysis

      N-Heterocyclic Carbene Catalyzed Enantioselective α-Fluorination of Aliphatic Aldehydes and α-Chloro Aldehydes: Synthesis of α-Fluoro Esters, Amides, and Thioesters

      Dr. Xiuqin Dong, Dr. Wen Yang, Dr. Weimin Hu and Prof. Dr. Jianwei Sun

      Article first published online: 13 NOV 2014 | DOI: 10.1002/anie.201409961

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      Two roles for NFSI: The N-heterocyclic carbene (NHC) catalyzed asymmetric fluorination of readily available simple aliphatic aldehydes, α-chloro aldehydes, and even alcohols proceeds via azolium enolates and yields a wide range of α-fluoro esters, amides, and thioesters with excellent enantioselectivity. N-Fluorobenzenesulfonimide (NFSI) acts as both a fluorinating reagent and an oxidant in this transformation.

  16. Highlights

    1. Asymmetric Catalysis

      Building Up Quarternary Stereocenters of Chromans by Asymmetric Redox Organocatalysis: A New Entry to Vitamin E

      Dr. Thomas Netscher

      Article first published online: 13 NOV 2014 | DOI: 10.1002/anie.201409826

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      High-turnover catalysis offers a novel concept for the efficient chemo- and enantioselective preparation of chroman intermediates, which are useful for the synthesis of tocopherols (vitamin E components) and other biologically active compounds. A chiral ammonium iodide catalyst mediates the cycloetherification in combination with a cooxidant and an inorganic base in excellent yield and up to 93 % ee. OTs=para-toluenesulfonyl.

  17. Communications

    1. Nitrogen Fixation

      Low-Temperature N2 Binding to Two-Coordinate L2Fe0 Enables Reductive Trapping of L2FeN2 and NH3 Generation

      Dr. Gaël Ung and Prof. Jonas C. Peters

      Article first published online: 13 NOV 2014 | DOI: 10.1002/anie.201409454

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      An N2 fix: The title complex facilitates the conversion of N2 (1 atm) into NH3, but only at temperatures below −78 °C. The best yield (170 % relative to [L2Fe]) was measured at −95 °C. N2 binding becomes thermodynamically more favored at low temperature such that a sufficiently high concentration of [L2Fe(N2)] forms below −80 °C. This N2 binding event enables trapping and isolation (as a K+ adduct) of the reactive anionic three-coordinate complex [L2Fe−I(N2)].

    2. Porous Materials

      A Rod-Packing Microporous Hydrogen-Bonded Organic Framework for Highly Selective Separation of C2H2/CO2 at Room Temperature

      Peng Li, Dr. Yabing He, Dr. Yunfeng Zhao, Prof. Dr. Linhong Weng, Dr. Hailong Wang, Prof. Dr. Rajamani Krishna, Prof. Dr. Hui Wu, Prof. Dr. Wei Zhou, Prof. Dr. Michael O'Keeffe, Prof. Dr. Yu Han and Prof. Dr. Banglin Chen

      Article first published online: 13 NOV 2014 | DOI: 10.1002/anie.201410077

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      A 3D microporous rod-packing hydrogen-bonded organic framework was constructed from a trigonal building subunit with diaminotriazine functional groups. This framework exhibits highly selective separation of C2H2/CO2 at ambient temperature and pressure.

    3. Abramov Reaction

      The Catalytic Asymmetric Abramov Reaction

      Dr. Joyram Guin, Dr. Qinggang Wang, Manuel van Gemmeren and Prof. Dr. Benjamin List

      Article first published online: 13 NOV 2014 | DOI: 10.1002/anie.201409411

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      A chiral disulfonimide catalyst is used to achieve the first catalytic enantioselective Abramov reaction. Several functionalized α-hydroxy phosphonates were synthesized in good yields and with excellent enantiomeric ratios of up to >99:1. The process was shown to be scalable and up to 1 g of starting material could be employed under mild reaction conditions.

    4. Enzyme Inhibition | Hot Paper

      You have full text access to this OnlineOpen article
      Benzoxazolone Carboxamides: Potent and Systemically Active Inhibitors of Intracellular Acid Ceramidase

      Dr. Daniela Pizzirani, Dr. Anders Bach, Dr. Natalia Realini, Dr. Andrea Armirotti, Dr. Luisa Mengatto, Dr. Inga Bauer, Dr. Stefania Girotto, Dr. Chiara Pagliuca, Dr. Marco De Vivo, Dr. Maria Summa, Dr. Alison Ribeiro and Prof. Daniele Piomelli

      Article first published online: 13 NOV 2014 | DOI: 10.1002/anie.201409042

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      A key regulator of the sphingolipid metabolism is acid ceramidase (AC), which offers a molecular target in disorders such as cancer and inflammation, in which sphingolipid signaling might be dysfunctional. The shown compound is metabolically stable, inhibits AC activity both in vitro and in vivo, and can thus be used as a potent chemical probe to investigate the roles of ceramides in physiology and pathology.

    5. Organic–Inorganic Hybrid Composites

      Threading Chalcogenide Layers with Polymer Chains

      Dr. Wei-Wei Xiong, Jianwei Miao, Dr. Kaiqi Ye, Prof. Dr. Yue Wang, Prof. Dr. Bin Liu and Prof. Dr. Qichun Zhang

      Article first published online: 13 NOV 2014 | DOI: 10.1002/anie.201409653

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      Common thread: Inserting a polymer into a crystalline inorganic matrix to understand its structure, position, and the structure–property relationships of the resulting composites is important for designing new inorganic–organic materials and tuning their properties. Single crystals of polymer-chalcogenide composites were isolated by trapping polyethyleneglycol within a selenidostannate matrix under surfactant-thermal conditions.

    6. Amyloids | Hot Paper

      Atomic-Resolution Three-Dimensional Structure of Amyloid β Fibrils Bearing the Osaka Mutation

      Dr. Anne K. Schütz, Dr. Toni Vagt, Dr. Matthias Huber, Dr. Oxana Y. Ovchinnikova, Riccardo Cadalbert, Dr. Joseph Wall, Prof. Dr. Peter Güntert, Dr. Anja Böckmann, Prof. Dr. Rudi Glockshuber and Prof. Dr. Beat H. Meier

      Article first published online: 13 NOV 2014 | DOI: 10.1002/anie.201408598

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      A fold not observed before: The atomic-resolution fibril structure of the Aβ1-40 peptide with the Osaka mutation (E22Δ), which is associated with early-onset Alzheimer's disease, differs substantially from all previously proposed models. In this complex structure the deletion mutation is found in a β turn.

    7. Coordination Cages

      Stepwise Halide-Triggered Double and Triple Catenation of Self-Assembled Coordination Cages

      Rongmei Zhu, Jens Lübben, Priv.-Doz. Dr. Birger Dittrich and Prof. Dr. Guido H. Clever

      Article first published online: 13 NOV 2014 | DOI: 10.1002/anie.201408068

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      A ball-shaped self-assembled coordination cage [Pd2L4] based on a carbazole backbone and PdII cations is transformed into an interpenetrated double cage [3 X@Pd4L8] upon addition of 1.5 equiv of halide anions (X=Cl, Br). Surprisingly, further addition of the same halide anion triggered a second structural transformation to yield the L6n1-linked {trans-[(PdBr2)2L2]}3.

    8. Cellular Imaging

      Three-Dimensional Mid-Infrared Tomographic Imaging of Endogenous and Exogenous Molecules in a Single Intact Cell with Subcellular Resolution

      Dr. Luca Quaroni, Dr. Martin Obst, Prof. Dr. Marcus Nowak and Prof. Dr. Fabio Zobi

      Article first published online: 13 NOV 2014 | DOI: 10.1002/anie.201407728

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      Now in 3D: Conventional 2D cell imaging methods are limited in their ability to associate specific information on the sample composition with subcellular structures. A new method, in which tilt-series infrared tomography is used with a standard benchtop infrared microscopy, provides quantitative information on the 3D distribution of molecular components based on the intrinsic contrast provided by the sample.

    9. DNA Nanostructures

      Biocompatible Infinite-Coordination-Polymer Nanoparticle–Nucleic-Acid Conjugates for Antisense Gene Regulation

      Colin M. Calabrese, Dr. Timothy J. Merkel, William E. Briley, Pratik S. Randeria, Suguna P. Narayan, Dr. Jessica L. Rouge, Dr. David A. Walker, Alexander W. Scott and Prof. Chad A. Mirkin

      Article first published online: 13 NOV 2014 | DOI: 10.1002/anie.201407946

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      Iron it out: DNA-modified infinite-coordination-polymer (ICP) nanoparticles were constructed by a facile method to afford biocompatible gene-regulation agents. The iron(III)-based ICP nanoparticles were synthesized in water and conjugated directly to oligonucleotides by a copper-free click reaction. The resulting conjugates were capable of entering cells and effecting antisense gene regulation without transfection agents (see picture).

    10. Host–Guest Systems | Hot Paper

      Construction of Matryoshka-Type Structures from Supercharged Protein Nanocages

      Dr. Tobias Beck, Stephan Tetter, Matthias Künzle and Prof. Dr. Donald Hilvert

      Article first published online: 13 NOV 2014 | DOI: 10.1002/anie.201408677

      Thumbnail image of graphical abstract

      Cages within cages: By exploiting electrostatic interactions between two supercharged protein containers, namely supercharged lumazine synthase (red) and supercharged ferritin (blue) loaded with iron-oxide nanoparticles (black), nested Matryoshka-type structures were assembled. These cage-within-cage structures consist of two layers of protein surrounding iron oxide nanoparticles in a manner reminiscent of Russian dolls.

    11. Protein Binding to Nanoparticles

      Spherical Nucleic Acid Nanoparticle Conjugates Enhance G-Quadruplex Formation and Increase Serum Protein Interactions

      Alyssa B. Chinen, Chenxia M. Guan and Prof. Chad A. Mirkin

      Article first published online: 13 NOV 2014 | DOI: 10.1002/anie.201409211

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      Structure determines binding: Spherical nucleic acid nanoparticles (SNAs) adsorb proteins in a sequence-dependent fashion. G-rich SNAs adsorb more types and more total protein than poly-T SNAs, leading to increased macrophage uptake. This demonstrates that tertiary DNA structures can dictate nanoparticle protein corona formation, providing guidelines for the design of more efficacious therapeutic nucleic acid-based nanomaterials.

    12. Asymmetric Catalysis

      A Highly cis-Selective and Enantioselective Metal-Free Hydrogenation of 2,3-Disubstituted Quinoxalines

      Zhenhua Zhang and Prof. Dr. Haifeng Du

      Article first published online: 13 NOV 2014 | DOI: 10.1002/anie.201409471

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      At the core: A highly cis-selective and enantioselective metal-free hydrogenation of the title compounds was achieved using in situ generated chiral borane catalysts. The catalyst shown was generated from the chiral diene 1. The resulting tetrahydroquinoxalines products can be found as core structures for biologically active compounds.

    13. Zeolites

      Structure of Framework Aluminum Lewis Sites and Perturbed Aluminum Atoms in Zeolites as Determined by 27Al{1H} REDOR (3Q) MAS NMR Spectroscopy and DFT/Molecular Mechanics

      Dr. Jiří Brus, Libor Kobera, Dr. Wolfgang Schoefberger, Dr. Martina Urbanová, Petr Klein, Dr. Petr Sazama, Dr. Edyta Tabor, Dr. Stepan Sklenak, Dr. Anna V. Fishchuk and Dr. Jiří Dědeček

      Article first published online: 13 NOV 2014 | DOI: 10.1002/anie.201409635

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      Here’s where all the action is: The title studies indicate that tricoordinated framework (FR) (SiO)3Al atoms serve as electron-pair-acceptor AlFR Lewis sites in zeolites with the CHA and FER topology. These sites can be formed by the dehydroxylation of AlOH atoms tricoordinated to the framework (see picture). Both AlOH and AlFR Lewis species have broad 27Al NMR resonances, but they can be differentiated on the basis of their δi, CQ, and η values.

    14. Enzymatic Halogenation

      Enzymatic Halogenation of Tryptophan on a Gram Scale

      Marcel Frese and Prof. Dr. Norbert Sewald

      Article first published online: 12 NOV 2014 | DOI: 10.1002/anie.201408561

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      One for all, all for one: The combined immobilization of the tryptophan-7-halogenase RebH, a flavin reductase, and an alcohol dehydrogenase as a cross-linked enzyme aggregate leads to a solid multifunctional biocatalyst that can be used for an easily scalable regioselective synthesis of C7-halogenated tryptophan on a gram scale.

    15. Antitumor Agents

      Direct Cytosolic Delivery of siRNA Using Nanoparticle-Stabilized Nanocapsules

      Ying Jiang, Rui Tang, Bradley Duncan, Ziwen Jiang, Dr. Bo Yan, Rubul Mout and Prof. Dr. Vincent M. Rotello

      Article first published online: 12 NOV 2014 | DOI: 10.1002/anie.201409161

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      Special delivery: Nanoparticle-stabilized capsules (NPSCs) rapidly deliver small interfering RNA (siRNA) into the cytosol of a cell in a cholesterol-dependent manner, and the siRNA enters cells by membrane fusion. Such a platform effectively silenced model gene expression up to 90 %, thus highlighting NPSC-facilitated direct cytosolic siRNA delivery as a powerful tool for gene regulation and disease treatment.

    16. Mesoporous Carbon Spheres

      Synthesis of Nitrogen-Doped Mesoporous Carbon Spheres with Extra-Large Pores through Assembly of Diblock Copolymer Micelles

      Jing Tang, Dr. Jian Liu, Dr. Cuiling Li, Yunqi Li, Prof. Moses O. Tade, Prof. Sheng Dai and Prof. Yusuke Yamauchi

      Article first published online: 12 NOV 2014 | DOI: 10.1002/anie.201407629

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      Mesoporous materials: Nitrogen-doped mesoporous carbon spheres (NMCS) with extra-large pores were synthesized through assembly of diblock copolymer micelles. Polymerized dopamine (DA)/polystyrene-block-poly(ethylene oxide) (PS-b-PEO) composite spheres formed by self-polymerization of DA and spontaneous co-assembly with PS-b-PEO micelles. After carbonization and removal of the template, NMCS with large mesopores (up to 16 nm) were obtained.

    17. Zwitterionic Radicals

      Ambient Stable Zwitterionic Perylene Bisimide-Centered Radical

      Dr. David Schmidt, David Bialas and Prof. Dr. Frank Würthner

      Article first published online: 12 NOV 2014 | DOI: 10.1002/anie.201408067

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      A zwitterionic radical iPr2Im-PBI-Cl4 4 was isolated from the reaction of PBI-Cl4 1 with the N-heterocyclic carbene 1,3-di-iso-propyl-imidazolin-2-ylidene (iPr2Im 2). It is stable at ambient conditions and has been characterized by UV/Vis absorption, EPR and NMR spectroscopy as well as single-crystal X-ray diffraction.

    18. Green Chemistry

      Programmed Photodegradation of Polymeric/Oligomeric Materials Derived from Renewable Bioresources

      Dr. Saravanakumar Rajendran, Ramya Raghunathan, Dr. Ivan Hevus, Dr. Retheesh Krishnan, Dr. Angel Ugrinov, Prof. Dr. Mukund P. Sibi, Prof. Dr. Dean C. Webster and Prof. Dr. Jayaraman Sivaguru

      Article first published online: 12 NOV 2014 | DOI: 10.1002/anie.201408492

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      Biodegradable and recyclable: Renewable polymeric materials derived from biomass with built-in phototriggers were synthesized and evaluated for degradation under irradiation by UV light (see picture). Complete decomposition of the polymeric materials was observed with recovery of the monomer that was used to resynthesize the polymers.

    19. Photochemistry

      Sequential Control over Thiol Click Chemistry by a Reversibly Photoactivated Thiol Mechanism of Spirothiopyran

      Zhenzhen Liu, Dr. Tao Liu, Dr. Qiuning Lin, Prof. Chunyan Bao and Prof. Linyong Zhu

      Article first published online: 12 NOV 2014 | DOI: 10.1002/anie.201409097

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      On demand: The reversible photoactivated thiol mechanism of spirothiopyran confers spatiotemporal sequential control on the thiol click reaction. Thus, a specific sequence of events can be easily attained by using just one type of thiol click photochemical reaction.

  18. Reviews

    1. Argentophilicity

      Argentophilic Interactions

      Prof. Dr. Hubert Schmidbaur and Dr. Annette Schier

      Article first published online: 12 NOV 2014 | DOI: 10.1002/anie.201405936

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      Silver likes silver: Extensive evidence has accumulated in recent years that significant bonding interactions occur between seemingly closed-shell silver(I) centers of silver compounds. This argentophilic bonding appears to determine many structural details and important physical properties of silver(I) compounds in much the same way as aurophilic bonding is ubiquitously “at work” in gold chemistry.

  19. Communications

    1. Cycloaddition

      Highly Enantioselective Intramolecular 1,3-Dipolar Cycloaddition: A Route to Piperidino-Pyrrolizidines

      Dr. Srinivasa Rao Vidadala, Christopher Golz, Prof. Dr. Carsten Strohmann, Dr. Constantin-G. Daniliuc and Prof. Dr. Herbert Waldmann

      Article first published online: 12 NOV 2014 | DOI: 10.1002/anie.201409942

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      So selective: A highly enantioselective intramolecular 1,3-dipolar cycloaddition alone or in tandem with a highly diastereoselective intermolecular 1,3-dipolar cycloaddition provides efficient access to complex natural-product-inspired polycyclic scaffolds. Piperidino-pyrrolizidines with up to seven contiguous stereocenters were thus obtained.

    2. C[BOND]H Activation

      Cobalt-Catalyzed C(sp2)[BOND]H Alkoxylation of Aromatic and Olefinic Carboxamides

      Lin-Bao Zhang, Dr. Xin-Qi Hao, Shou-Kun Zhang, Zhan-Jiang Liu, Xin-Xiang Zheng, Dr. Jun-Fang Gong, Dr. Jun-Long Niu and Prof. Mao-Ping Song

      Article first published online: 12 NOV 2014 | DOI: 10.1002/anie.201409751

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      Alcohols in action: A wide range of alcohols and benzamide substrates functionalized with electron-rich or electron-poor substituents are tolerated in the title reaction. This practical reaction occurs under mild conditions.

    3. Fluorination

      AgF-Mediated Fluorinative Cross-Coupling of Two Olefins: Facile Access to α-CF3 Alkenes and β-CF3 Ketones

      Dr. Bing Gao, Dr. Yanchuan Zhao and Prof. Dr. Jinbo Hu

      Article first published online: 12 NOV 2014 | DOI: 10.1002/anie.201409705

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      The in situ formation of a trifluoromethyl moiety and an intermolecular alkenyl C[BOND]H functionalization were combined in a single reaction system. This AgF-mediated fluorination with a subsequent cross-coupling reaction between gem-difluoroolefins and non-fluorinated alkenes provides facile access to both α-CF3 alkenes and β-CF3 ketones.

    4. Natural Products

      Total Synthesis, Stereochemical Reassignment, and Biological Evaluation of (−)-Lyngbyaloside B

      Prof. Dr. Haruhiko Fuwa, Yuta Okuaki, Naoya Yamagata and Prof. Dr. Makoto Sasaki

      Article first published online: 12 NOV 2014 | DOI: 10.1002/anie.201409629

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      What I can create, I understand: Total synthesis of the proposed structure of (−)-lyngbyaloside B, a cytotoxic macrolide glycoside of marine origin, showed that the original stereochemical assignment needed to be reconsidered. The correct structure of this natural product was reassigned on the basis of spectroscopic and molecular modeling considerations and ultimately established by means of total synthesis.

    5. Boron Redox Chemistry | Hot Paper

      Boron as a Powerful Reductant: Synthesis of a Stable Boron-Centered Radical-Anion Radical-Cation Pair

      Dr. Philipp Bissinger, Prof. Dr. Holger Braunschweig, Dr. Alexander Damme, Dr. Christian Hörl, Dr. Ivo Krummenacher and Dr. Thomas Kupfer

      Article first published online: 11 NOV 2014 | DOI: 10.1002/anie.201409513

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      The tailor-made diborene IiPr⋅(iPr)B[DOUBLE BOND]B(iPr)⋅IiPr features an extremely electron-rich B–B double bond making it one of the most powerful neutral organic reductants known to date (E1/2=−1.95 V). Its reducing power was successfully exploited in the synthesis of a very rare boron-centered radical-anion radical-cation pair by one-electron reduction of a borole, MesBC4Ph4. IiPr=1,3-diisopropylimidazol-2-ylidene.

    6. NMR Spectroscopy

      Accelerated NMR Spectroscopy with Low-Rank Reconstruction

      Prof. Xiaobo Qu, Dr. Maxim Mayzel, Prof. Jian-Feng Cai, Prof. Zhong Chen and Prof. Vladislav Orekhov

      Article first published online: 11 NOV 2014 | DOI: 10.1002/anie.201409291

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      A low rank is an advantage: High-quality NMR spectra are reconstructed from a small number of non-uniformly sampled data points. Significant reduction in measurement time is obtained using the so far unexploited general property of NMR signal—its low rank (see picture; NUS=non-uniform sampling).

    7. Sustainable Chemistry | Hot Paper

      Green-Solvent-Processed Molecular Solar Cells

      Xiaofen Chen, Dr. Xiaofeng Liu, Mark A. Burgers, Dr. Ye Huang and Prof. Dr. Guillermo C. Bazan

      Article first published online: 11 NOV 2014 | DOI: 10.1002/anie.201409208

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      Molecular solar cells with high efficiencies can be fabricated from the green solvent 2-MeTHF. The light-harvesting semiconducting layer comprises a molecular donor with intermediate dimensions and a soluble fullerene derivative. No specific structural modifications are required on the semiconductors in order to use sustainable resources. PCE=power conversion efficiency.

  20. Author Profiles

    1. Varinder K. Aggarwal

      Article first published online: 10 NOV 2014 | DOI: 10.1002/anie.201409950

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      My favorite author (fiction) is V. S. Naipaul (A House for Mr. Biswas). I would have liked to have discovered the zipper—brilliant, flexible, versatile, and essential. Simple, yet intricate.

  21. Editorials

    1. You have free access to this content
      Chemistry: Interdisciplinary and International—and with a Sense of History

      Dr. Thomas Geelhaar

      Article first published online: 10 NOV 2014 | DOI: 10.1002/anie.201409939

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      We should not only honor the history of chemistry by commemorating anniversaries, but also acknowledge it as one of our disciplines. According to Wilhelm von Humboldt, it is only knowledge of the history of chemistry that gives us the best prerequisites for shaping the future of chemistry—from a stronger interdisciplinary and an international perspective … Read more in the Editorial by Thomas Geelhaar.

  22. Communications

    1. Anion Receptors

      A Bambusuril Macrocycle that Binds Anions in Water with High Affinity and Selectivity

      Dr. Mirza Arfan Yawer, Vaclav Havel and Prof. Vladimir Sindelar

      Article first published online: 10 NOV 2014 | DOI: 10.1002/anie.201409895

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      One ring binds them all: A bambusuril macrocycle is able to selectively capture a large number of different inorganic anions in water. The high stability of the resulting inclusion complexes is due to multiple C[BOND]H⋅⋅⋅anion hydrogen bonding interaction in hydrophobic cavity of the macrocycle.

    2. Cyclization

      Gold(I)-Catalyzed Diazo Cross-Coupling: A Selective and Ligand-Controlled Denitrogenation/Cyclization Cascade

      Guangyang Xu, Chenghao Zhu, Dr. Weijin Gu, Dr. Jian Li and Prof. Dr. Jiangtao Sun

      Article first published online: 10 NOV 2014 | DOI: 10.1002/anie.201409845

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      Old switcheroo: The title reaction proceeds through sequential denitrogenation and cyclization to afford N-substituted pyrazoles in a position-switchable mode. This novel transformation features selective decomposition of one diazo moiety and simultaneous preservation of the other one from two substrates. The choice of the ancillary ligand on the gold complex plays a pivotal role on the chemo- and regioselectivity of the reaction.

    3. Mass Spectrometry

      Development of Coated Blade Spray Ionization Mass Spectrometry for the Quantitation of Target Analytes Present in Complex Matrices

      M. Sc. German Augusto Gómez-Ríos and Prof. Janusz Pawliszyn

      Article first published online: 10 NOV 2014 | DOI: 10.1002/anie.201407057

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      There’s no hiding now: Coated blade spray is a technique based on solid-phase microextraction that has been designed for the quick extraction/cleanup of analytes from complex matrices and direct desorption/ionization under ambient MS conditions. The entire analytical process can be completed within 3 min (see picture; HV=high voltage, SRM=selected reaction monitoring) with limits of quantitation in the low picogram-per-millimeter region.

    4. Chemosensors

      Chiroptical Detection of Nonchromophoric, Achiral Guests by Enantiopure Alleno-Acetylenic Helicages

      Dr. Ori Gidron, Dr. Marc-Olivier Ebert, Dr. Nils Trapp and Prof. Dr. François Diederich

      Article first published online: 10 NOV 2014 | DOI: 10.1002/anie.201406585

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      Sensory perception: Enantiopure alleno-acetylenes can be assembled to form triple-stranded helicates having an internal cavity for the encapsulation of small cyclic guests. Guest-induced changes in the electronic circular dichroism (ECD) spectra of the helicate allowed the chiroptical detection of nonchromophoric, achiral solutes. Owing to the high affinity for 1,4-dioxane, this guest could be detected at low ppm levels.

  23. Reviews

    1. C[BOND]H Activation

      C[BOND]H Bond Activation by f-Block Complexes

      Prof. Dr. Polly L. Arnold, M. Chem. Max W. McMullon, M. Sc. Julia Rieb and Prof. Dr. Fritz E. Kühn

      Article first published online: 10 NOV 2014 | DOI: 10.1002/anie.201404613

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      Potential of transition metals: Numerous known lanthanide and actinide complexes are able to selectively activate C[BOND]H bonds of organic substrates. However, the challenge of establishing a closed catalytic cycle still remains. Many f-block complexes show great potential in this important area of chemistry.

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