Angewandte Chemie International Edition

Cover image for Vol. 54 Issue 23

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. Synthetic Methods

      An Iodine-Catalyzed Hofmann–Löffler Reaction

      Dr. Claudio Martínez and Prof. Dr. Kilian Muñiz

      Article first published online: 28 MAY 2015 | DOI: 10.1002/anie.201501122

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      Iodine does it! The first catalytic Hofmann–Löffler reaction proceeds with a combination of catalytic amounts of molecular iodine and a modified hypervalent iodine(III) reagent. The reaction proceeds under mild catalytic conditions and the intramolecular C[BOND]H amination addresses primary, secondary, and tertiary C[BOND]H groups.

    2. Cross-Coupling

      Ligand-Free Copper-Catalyzed Negishi Coupling of Alkyl-, Aryl-, and Alkynylzinc Reagents with Heteroaryl Iodides

      Surendra Thapa, Arjun Kafle, Dr. Santosh K. Gurung, Adam Montoya, Patrick Riedel and Prof. Ramesh Giri

      Article first published online: 28 MAY 2015 | DOI: 10.1002/anie.201502379

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      Simply copper: Primary, secondary, and tertiary alkylzinc reagents couple with heteroaryl iodides in the presence of ligand-free CuI without complications arising from β-hydride elimination and rearrangement. The reactions can be extended to the couplings of aryl- and alkynylzinc reagents as well. DMF=N,N-dimethylformamide.

    3. Organocatalysis

      Organocatalytic Activation of the Leaving Group in the Intramolecular Asymmetric SN2′ Reaction

      Yusuke Kuroda, Dr. Shingo Harada, Akinori Oonishi, Dr. Yousuke Yamaoka, Prof. Dr. Ken-ichi Yamada and Prof. Dr. Kiyosei Takasu

      Article first published online: 28 MAY 2015 | DOI: 10.1002/anie.201502831

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      Leaving-group activation: A Brønsted-acid-catalyzed intramolecular enantioselective SN2′ reaction was developed utilizing trichloroacetimidate as a leaving group. The findings indicated that dual activation of the substrates is operative. This metal-free allylic alkylation allows highly enantioselective access to 2-vinylpyrrolidines bearing various substituents.

    4. Microfluidics

      Microfluidic Formation of Membrane-Free Aqueous Coacervate Droplets in Water

      Dirk van Swaay, Dr. T.-Y. Dora Tang, Prof. Dr. Stephen Mann and Prof. Dr. Andrew de Mello

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201502886

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      Stable dispersions of polymer/nucleotide or polymer/polysaccharide coacervate droplets with a narrow size distribution are prepared in water using microfluidic flow focusing. Two distinct populations of co-located coacervate droplets containing different DNA oligonucleotides are produced simultaneously, and shown to coexist in close proximity without exchange of genetic information for over six days.

    5. Electrochemistry

      Extraordinary Supercapacitor Performance of a Multicomponent and Mixed-Valence Oxyhydroxide

      Dr. Jianli Kang, Akihiko Hirata, Luyang Chen, Shengli Zhu, Takeshi Fujita and Prof. Mingwei Chen

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201500133

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      Electrochemical polarization of a de-alloyed nanoporous NiCuMn alloy was employed to synthesize a novel multicomponent mixed-valence oxyhydroxide based electrode. The oxyhydroxide/metal electrode possesses both high specific capacitance (627 F cm−3) at a current density of 0.25 A cm−3 and wide working-potential window (1.8 V) in aqueous electrolyte, resulting in a high energy and power densities with excellent cyclic stability.

    6. Surface Chemistry

      The Magic Au60 Nanocluster: A New Cluster-Assembled Material with Five Au13 Building Blocks

      Yongbo Song, Fangyu Fu, Dr. Jun Zhang, Jinsong Chai, Xi Kang, Prof. Peng Li, Prof. Shengli Li, Prof. Hongping Zhou and Prof. Manzhou Zhu

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201501830

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      The X-ray crystallographic structure of the [Au60Se2(SePh)15(Ph3P)10]+ nanocluster exhibits a closed gold ring that contains five icosahedral Au13 building blocks, which are clipped together by Au–Se–Au linkages. This new material can be used for optical limiting. These results offer a basis for a deeper understanding of how to control cluster-assembled materials for tailoring their functionalities.

    7. Photocatalysis

      A Ruthenium(II)–Copper(II) Dyad for the Photocatalytic Oxygenation of Organic Substrates Mediated by Dioxygen Activation

      Dr. Wissam Iali, Dr. Pierre-Henri Lanoe, Dr. Stéphane Torelli, Dr. Damien Jouvenot, Prof. Frédérique Loiseau, Colette Lebrun, Dr. Olivier Hamelin and Dr. Stéphane Ménage

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201501180

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      O2 activation oxidation: A new Ru-Cu dyad has been isolated and confirmed to be efficient for the photocatalytic oxygenation of organic substrates. Mechanistic investigations confirmed a photoinduced electron transfer from the photosensitizer to the copper catalytic center prior to O2 activation. X=substrate (sulfides, alkenes, phosphines).

    8. Heterogeneous Catalysis

      A Catalyst Platform for Unique Cationic (Co)Polymerization in Aqueous Emulsion

      Dr. Irina V. Vasilenko, Dr. Hui Yee Yeong, Dr. Marco Delgado, Dr. Samira Ouardad, Dr. Frédéric Peruch, Prof. Dr. Brigitte Voit, Dr. François Ganachaud and Dr. Sergei V. Kostjuk

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201501157

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      Old pot, best cooking! Well-known hyperbranched anionic surfactants (hard DBSNa) mixed together with rare earth metal salts, generate Lewis acid surfactant complexes. These complexes show remarkable efficiency in the (co)polymerization of, for example, styrene and isoprene into long and linear chains.

    9. Host–Guest Complexes

      Halogen-Bond-Assisted Guest Inclusion in a Synthetic Cavity

      Dr. Hiroki Takezawa, Dr. Takashi Murase, Prof. Dr. Giuseppe Resnati, Prof. Dr. Pierangelo Metrangolo and Prof. Dr. Makoto Fujita

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201500994

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      Close but comfortable: Iodoperfluorocarbons were efficiently included in a self-assembled cage owing to halogen bonding (XB) with NO3 anions or H2O molecules (see picture: C gray, N blue, O red, F green, I purple, Pd brown). The confined cavity of the cage enhanced XB, as confirmed by NMR spectroscopy in solution and X-ray crystallography in the solid state. Pairwise selective XB between C6F3I3 and C6H5NMe2 within the cavity was also observed.

    10. Perovskites

      The Role of Oxygen in the Degradation of Methylammonium Lead Trihalide Perovskite Photoactive Layers

      Nicholas Aristidou, Dr. Irene Sanchez-Molina, Thana Chotchuangchutchaval, Dr. Michael Brown, Dr. Luis Martinez, Dr. Thomas Rath and Prof. Saif A. Haque

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201503153

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      The influence of light and oxygen on the stability of CH3NH3PbI3 perovskite-based photoactive layers is investigated. Upon exposure to both light and dry air the mesoporous (mp) Al2O3/CH3NH3PbI3 layers decompose to methylamine, PbI2, and I2. This degradation is initiated by the reaction of superoxide (O2) with the methylammonium moiety of the perovskite absorber. MA=methyl ammonium, CB=conduction band, VB=valence band.

    11. Homogeneous Catalysis

      Oxygen Evolution Catalyzed by a Mononuclear Ruthenium Complex Bearing Pendant SO3 Groups

      Dr. Masaki Yoshida, Dr. Mio Kondo, Sena Torii, Prof. Ken Sakai and Prof. Shigeyuki Masaoka

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201503365

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      Lucky pendant: Ce4+-driven water oxidation catalyzed by a mononuclear ruthenium complex was observed to be accelerated following the introduction of pendant SO3 groups to the catalyst, which are able to capture Ce4+ ions. The results of this work indicate that modification of the secondary coordination sphere is an effective strategy for the development of catalysts for water oxidation.

    12. Nanostructures

      Rapid Cationization of Gold Nanoparticles by Two-Step Phase Transfer

      M. Sc. Jukka Hassinen, M. Sc. Ville Liljeström, Prof. Mauri A. Kostiainen and Prof. Robin H. A. Ras

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201503655

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      Be positive! Cationic gold nanoparticles with tunable sizes from 8 to 20 nm can be prepared by a rapid and scalable two-step phase-transfer protocol that starts from simple citrate-capped particles and proceeds via neutral octadecylamine-capped nanoparticles (see figure). The cationic gold nanoparticles form ordered self-assembled structures with negatively charged biological components through electrostatic interactions.

    13. Organic–Inorganic Hybrids

      Amphiphilic Organic–Inorganic Hybrid Zeotype Aluminosilicate like a Nanoporous Crystallized Langmuir–Blodgett Film

      Dr. Takuji Ikeda, Dr. Norihito Hiyoshi, Dr. Shun-ichi Matsuura, Dr. Tetsuya Kodaira, Takuma Nakaoka, Ami Irisa, Miki Kawano and Dr. Katsutoshi Yamamoto

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201503661

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      Crystallized film: A novel organic–inorganic hybrid nanoporous material with alternately laminated lipophilic and hydrophilic nanospaces was synthesized. It shows microporous adsorption for both hydrophilic and lipophilic adsorptives, and its outer surface tightly adsorbs lysozyme.

  2. Cover Pictures

    1. You have free access to this content
      Organic Light-Emitting Diodes Using a Neutral π Radical as Emitter: The Emission from a Doublet

      Qiming Peng, Ablikim Obolda, Prof. Dr. Ming Zhang and Prof. Dr. Feng Li

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201504417

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      Open-shell molecules as emitters offer a new route to realize highly efficient organic light-emitting diodes (OLEDs). In their Communication (DOI: 10.1002/anie.201500242), F. Li et al. report a new kind of OLED in which a neutral π radical is used as the emitter. The emission of the radical is the radiative decay from doublet excitons, which is spin-allowed. The key challenge of how to harvest triplets in an OLED is thus circumvented.

    2. You have free access to this content
      Photoinduced Charge-Carrier Generation in Epitaxial MOF Thin Films: High Efficiency as a Result of an Indirect Electronic Band Gap?

      Dr. Jinxuan Liu, Wencai Zhou, Jianxi Liu, Dr. Ian Howard, Dr. Goran Kilibarda, Dr. Sabine Schlabach, Damien Coupry, Dr. Matthew Addicoat, Satoru Yoneda, Yusuke Tsutsui, Dr. Tsuneaki Sakurai, Prof. Dr. Shu Seki, Dr. Zhengbang Wang, Peter Lindemann, Dr. Engelbert Redel, Prof. Thomas Heine and Prof. Dr. Christof Wöll

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201504133

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      Strictly periodic assemblies of porphyrin-units deposited on functionalized substrates can be used to realize solar cells with remarkable efficiency. In their Communication (10.1002/anie.201501862) J. Liu, C. Wöll and co-workers show by electronic-structure calculations that ordered arrays of porphyrins have a small dispersion of occupied and unoccupied bands leading to the formation of a small indirect band gap. Such ordered porphyrin metal–organic frameworks (MOFs) are then grown using a layer-by-layer liquid-phase epitaxy.

  3. Communications

    1. Asymmetric Synthesis

      Organocatalytic Asymmetric 1,6-Addition/1,4-Addition Sequence to 2,4-Dienals for the Synthesis of Chiral Chromans

      Pernille H. Poulsen, Karla Santos Feu, Bruno Matos Paz, Prof. Dr. Frank Jensen and Prof. Dr. Karl Anker Jørgensen

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201503370

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      One six one four: Based on a 1,6-Friedel–Crafts/1,4-oxa-Michael sequence, an organocatalyst directs the reaction of hydroxyarenes with a vinylogous iminium-ion intermediate to give only one out of four possible regioisomers. The reaction provides optically active chromans in high yields with up to 99 % ee.

    2. Hydrogenation Reactions

      Pd–Pb Alloy Nanocrystals with Tailored Composition for Semihydrogenation: Taking Advantage of Catalyst Poisoning

      Dr. Wenxin Niu, Dr. Yongjun Gao, Dr. Weiqing Zhang, Prof. Ning Yan and Prof. Xianmao Lu

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201503148

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      Taking advantage of poisons: The poisoning effect of lead(II) ions can alter the shapes of Pd–Pb alloy nanocrystals. It endows the alloy nanocrystals with superior selectivity for the semihydrogenation of alkynes.

    3. Asymmetric Synthesis

      Catalytic Enantioselective Reaction of α-Aminoacetonitriles Using Chiral Bis(imidazoline) Palladium Catalysts

      Masaru Kondo, Tomoki Nishi, Prof. Dr. Tsubasa Hatanaka, Prof. Dr. Yasuhiro Funahashi and Prof. Dr. Shuichi Nakamura

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201503098

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      Good yields and diastereo- and enantioselectivities were observed for the title reaction with various imines using chiral bis(imidazoline)/Pd catalysts. The reaction of α-aminonitriles with di-tert-butyl azodicarboxylate afforded chiral α,α-diaminonitrile in high yield with high enantioselectivity. acac=acetylacetonate, Boc=tert-butoxycarbonyl.

    4. Breath Analysis

      Drug Pharmacokinetics Determined by Real-Time Analysis of Mouse Breath

      Dr. Xue Li, Dr. Pablo Martinez-Lozano Sinues, Dr. Robert Dallmann, Lukas Bregy, Dr. Maija Hollmén, Dr. Steven Proulx, Prof. Steven A. Brown, Prof. Michael Detmar, Prof. Malcolm Kohler and Prof. Renato Zenobi

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201503312

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      A noninvasive in vivo method based on secondary electrospray ionization mass spectrometry was used to determine the pharmacokinetics of drugs and their metabolites from the breath of a single mouse in real time. As an example, the pharmacokinetics of the antidepressant and anaesthetic drug ketamine and its metabolites was studied with a time resolution of 10 s per data point.

  4. News

  5. Communications

    1. Prometabolites | Hot Paper

      Prometabolites of 5-Diphospho-myo-inositol Pentakisphosphate

      Igor Pavlovic, Divyeshsinh T. Thakor, Priv.-Doz. Dr. Laurent Bigler, Dr. Miranda S. C. Wilson, Debabrata Laha, Dr. Gabriel Schaaf, Prof. Dr. Adolfo Saiardi and Prof. Dr. Henning J. Jessen

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201503094

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      Precursors of 5-diphospho-myo-inositol pentakisphosphate with biolabile protecting groups were synthesized, and their in vitro/in cellulo metabolism was studied. Acetoxybenzyl phosphates and phosphoanhydrides were rapidly removed in mammalian tissue and cell homogenates. This process was analyzed by polyacrylamide gel electrophoresis, which also led to the identification of unexpected side products.

    2. Structure Elucidation

      A Triphenylamine with Two Phenoxy Radicals Having Unusual Bonding Patterns and a Closed-Shell Electronic State

      Dr. Daisuke Sakamaki, Soichiro Yano, Toshiyuki Kobashi, Prof. Dr. Shu Seki, Dr. Takuya Kurahashi, Prof. Dr. Seijiro Matsubara, Dr. Akihiro Ito and Prof. Dr. Kazuyoshi Tanaka

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201502949

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      In a (closed)nut shell: A novel triphenylamine derivative having two phenoxy radicals appended to the amino nitrogen atom has been prepared. This molecule has an unexpected closed-shell electronic state, even at room temperature, in spite of its structural similarity to the galvinoxyl radical. The molecule features two C[BOND]N bonds with multiple-bond character and a remarkably low HOMO–LUMO gap.

    3. Peptide Therapeutics

      Targeting the Two Oncogenic Functional Sites of the HPV E6 Oncoprotein with a High-Affinity Bivalent Ligand

      Dr. Juan Ramirez, Juline Poirson, Clémence Foltz, Dr. Yassmine Chebaro, Maxime Schrapp, Amandine Meyer, Dr. Anaëlle Bonetta, Anne Forster, Dr. Yves Jacob, Dr. Murielle Masson, Dr. François Deryckère and Dr. Gilles Travé

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201502646

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      Double duty: A bifunctional inhibitory ligand of human papillomaviruses (HPV) E6 oncoproteins was developed by combining the minimal E6-binding regions of two key cellular targets of E6: a PDZ domain from the polarity protein MAGI1, and an LxxLL motif from the ubiquitin ligase E6AP. The PDZ-LxxLL chimera binds high-risk mucosal HPV E6 proteins with nanomolar affinity and induces apoptotic death in HPV-positive cells derived from cervical tumors.

    4. Polycycles | Hot Paper

      Tetrabenzoperipentacene: Stable Five-Electron Donating Ability and a Discrete Triple-Layered β-Graphite Form in the Solid State

      Akinobu Matsumoto, Dr. Mitsuharu Suzuki, Dr. Daiki Kuzuhara, Dr. Hironobu Hayashi, Prof. Dr. Naoki Aratani and Prof. Dr. Hiroko Yamada

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201502466

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      Triple the fun: Synthesis of an all-carbon conjugated tetrabenzoperipentacene was achieved. The single-crystal X-ray structure revealed that the molecules form a triple-layered cluster-like β-graphite. The remarkably rigid carbon framework results in a small Stokes shift and fully reversible five-electron oxidation potentials.

  6. Reviews

    1. Blue LEDs

      Blue Light: A Fascinating Journey (Nobel Lecture)

      Prof. Isamu Akasaki

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201502664

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      In the beginning there was light: Mankind has pursued light sources since ancient times, starting with flames, then the development of electric light bulbs much later, and most recently the production of light-emitting diodes. Isami Akasaki describes the historical progress that led to the invention of the first blue LED and related optical devices.

  7. Highlights

    1. Water Splitting

      Solar Water Splitting at λ=600 nm: A Step Closer to Sustainable Hydrogen Production

      Dr. Jinshui Zhang and Prof. Xinchen Wang

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201502659

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      Overall water splitting with a semiconductor photocatalyst under visible-light irradiation is considered as a “dream reaction” in chemistry. The development of a 600 nm photocatalyst for solar water splitting highlighted here is not only an important milestone towards sustainable hydrogen production, but also a new starting point for artificial photosynthesis. STH=solar-to-hydrogen energy conversion efficiency.

  8. Communications

    1. Epigenetics | Hot Paper

      Epigenetic Genome Mining of an Endophytic Fungus Leads to the Pleiotropic Biosynthesis of Natural Products

      Dr. Xu-Ming Mao, Dr. Wei Xu, Dr. Dehai Li, Dr. Wen-Bing Yin, Dr. Yit-Heng Chooi, Dr. Yong-Quan Li, Dr. Yi Tang and Dr. Youcai Hu

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201502452

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      The endophytic fungus­ Calcarisporium arbuscula is rich in cryptic gene clusters for natural product biosynthesis. Removal of a global epigenetic repressor HdaA, the histone H3 deacetylase, activates the expression of over 75 % of the silenced gene clusters and enables the isolation of new natural products.

    2. Heterocycles

      Zinc-Catalyzed Alkyne Oxidation/C[BOND]H Functionalization: Highly Site-Selective Synthesis of Versatile Isoquinolones and β-Carbolines

      Long Li, Bo Zhou, Yong-Heng Wang, Chao Shu, Yi-Fei Pan, Prof. Dr. Xin Lu and Prof. Dr. Long-Wu Ye

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201502553

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      Swap gold for zinc: The title reaction was achieved by a zinc(II)-catalyzed alkyne oxidation/C[BOND]H functionalization sequence. In contrast to the well-established gold-catalyzed intermolecular alkyne oxidation, the over-oxidation can be suppressed in this system and the reaction most likely proceeds by a Friedel–Crafts-type pathway. Tf=trifluoromethanesulfonyl, PG=protecting group.

    3. Lithium Amides in Solution

      The Donor-Base-Free Aggregation of Lithium Diisopropyl Amide in Hydrocarbons Revealed by a DOSY Method

      M.Sc. Roman Neufeld, Dr. Michael John and Prof.Dr. Dietmar Stalke

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201502576

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      An important reagent: Lithium diisopropyl amide plays a key role in organic synthesis, serving as a base par excellence for a broad range of deprotonation reactions. However, its state of aggregation in solution in the absence of donor bases was unclear. This problem has been solved by application of a new DOSY NMR experiment.

    4. Photoelectrochemical Cells

      A Photoelectrochemical Solar Cell Consisting of a Cadmium Sulfide Photoanode and a Ruthenium–2,2′-Bipyridine Redox Shuttle in a Non-aqueous Electrolyte

      Yosuke Kageshima, Hiromu Kumagai, Tsutomu Minegishi, Prof. Jun Kubota and Prof. Kazunari Domen

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201502586

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      A CdS photoanode and Pt counter electrode as a photoelectrochemical cell with the redox shuttle of the ruthenium–2,2′-bipyridine complex [Ru(bpy)3]2+/3+ in a non-aqueous electrolyte was studied. An open-circuit voltage of 1.48 V, short-circuit current of 3.88 mA cm−2, and fill factor of 0.49 were obtained. TBA=tetra-n-butylammonium.

    5. Synthetic Methods

      Barium-Mediated Cross-Dehydrocoupling of Hydrosilanes with Amines: A Theoretical and Experimental Approach

      Clément Bellini, Prof. Dr. Jean-François Carpentier, Dr. Sven Tobisch and Dr. Yann Sarazin

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201502956

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      Raising the bar(ium): Alkaline-earth complexes of the type [Ae{N(SiMe3)2}2⋅(THF)x] and [{N^N}Ae{N(SiMe3)2}⋅(THF)x] are very active, productive, and chemoselective precatalysts for the N[BOND]H/H[BOND]Si cross-dehydrocoupling of (di)amines with (di)hydrosilanes. The mechanisms have been elucidated by combining DFT and experimental data. THF=tetrahydrofuran, TOF=turnover frequency, TON=turnover number.

    6. Surface Chemistry | Hot Paper

      Size-Dependent Ligand Layer Dynamics in Semiconductor Nanocrystals Probed by Anisotropy Measurements

      Ido Hadar, Tsafrir Abir, Shira Halivni, Adam Faust and Prof. Uri Banin

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201502999

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      Dynamic properties of a ligand shell: The size-dependent dynamic properties of an organic ligand shell, capping the surface of colloidal nanocrystals, have been studied by probing polarized emission of surface-bound organic dyes (see picture). These properties impact the synthesis, dispersibility, and optoelectronic features of colloidal nanocrystals.

    7. Cluster Compounds

      Attenuated Organomagnesium Activation of White Phosphorus

      Dr. Merle Arrowsmith, Prof. Michael S. Hill, Dr. Andrew L. Johnson, Dr. Gabriele Kociok-Köhn and Dr. Mary F. Mahon

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201503065

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      Taking the P: The controlled, sequential activation of white phosphorus (P4) can be mediated by organomagnesium compounds with appropriate supporting ligands. The activation leads to the highly discriminating synthesis of unusual [nBu2P4]2− and [nBu2P8]2− cluster dianions.

    8. Hypervalent Iodine/Photoredox

      Dual Hypervalent Iodine(III) Reagents and Photoredox Catalysis Enable Decarboxylative Ynonylation under Mild Conditions

      Hanchu Huang, Guojin Zhang and Prof. Dr. Yiyun Chen

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201502369

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      Cool cats: Ynones, ynamides, and ynoates have been constructed at room temperature from substrates with various sensitive and reactive functional groups by using a combination of hypervalent iodine(III) reagents (HIRs) and photoredox catalysis with visible light. The reaction proceeds by formation of an acyl radical from α-ketoacids followed by an unprecedented acyl radical addition to HIR-bound alkynes.

    9. Charge Transfer | Hot Paper

      Carbon Nanodots: Supramolecular Electron Donor–Acceptor Hybrids Featuring Perylenediimides

      Volker Strauss, Johannes T. Margraf, Konstantin Dirian, Dr. Zois Syrgiannis, Prof. Dr. Maurizio Prato, Dr. Cordula Wessendorf, Prof. Dr. Andreas Hirsch, Prof. Dr. Timothy Clark and Prof. Dr. Dirk M. Guldi

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201502482

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      Long-term separation: Charge-transfer complexes formed by electron-donating carbon nanodots and electron-accepting perylenediimides are prepared. In ultrafast pump-probe experiments (see picture) the charge-separated state with a lifetime of 210 ps was found.

    10. Polyoxometalates

      Following the Reaction of Heteroanions inside a {W18O56} Polyoxometalate Nanocage by NMR Spectroscopy and Mass Spectrometry

      Qi Zheng, Dr. Laia Vilà-Nadal, Dr. Christoph Busche, Dr. Jennifer S. Mathieson, Dr. De-Liang Long and Prof. Dr. Leroy Cronin

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201502295

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      Caught in a trap: A tungsten-based Dawson-like polyoxometalate cluster [W18O56(HPIIIO3)2(H2O)2]8− has been isolated. NMR spectroscopy and ESI-MS show that in solution, the cluster undergoes a structural rearrangement whereby the {HPO3} moieties dimerize through interphosphite interactions. In the solid state, the cluster underwent a temperature-dependent intramolecular redox reaction (PIII[RIGHTWARDS ARROW]PV). Atom colors: W=gray; O=red; P=orange; H=light gray.

    11. Electrocatalysis

      Iron Carbide Nanoparticles Encapsulated in Mesoporous Fe-N-Doped Carbon Nanofibers for Efficient Electrocatalysis

      Zhen-Yu Wu, Xing-Xing Xu, Bi-Cheng Hu, Dr. Hai-Wei Liang, Dr. Yue Lin, Dr. Li-Feng Chen and Prof. Dr. Shu-Hong Yu

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201502173

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      Nanocomposite electrocatalyst: A high performance electrocatalyst for oxygen reduction reaction (ORR) is based on Fe3C nanoparticles encapsulated in mesoporous Fe-N-doped carbon nanofibers. It can be synthesized from low-cost and abundant precursors and exhibits excellent electrocatalytic performance for ORR in both alkaline and acidic media.

    12. Conformational Analysis

      Noncovalent Lone Pair⋅⋅⋅(No-π!)-Heteroarene Interactions: The Janus-Faced Hydroxy Group

      Dr. Ilias Pavlakos, Dr. Tanzeel Arif, Dr. Abil E. Aliev, Prof. William B. Motherwell, Dr. Graham J. Tizzard and Dr. Simon J. Coles

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201502103

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      Fatal attraction: The noncovalent interaction of a hydroxy group with pyrazines and quinoxalines involves a lone pair (lp)–heteroarene attraction which is stronger and solvent independent when measured relative to the π-facial hydrogen bond to a benzene ring. Organic fluorides also prefer the heteroarene ring over benzene. The attraction between a quinoxaline and a terminal alkyne is stronger than an OH–arene interaction.

    13. Synthetic Methods

      Copper-Catalyzed Oxy-Alkenylation of Homoallylic Alcohols to Generate Functional syn-1,3-Diol Derivatives

      Dean Holt and Prof. Matthew J. Gaunt

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201501995

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      Polyols: The reported copper-catalyzed oxy-alkenylation strategy works well for a range of readily available, substituted homoallylic alcohol derivatives and alkenyl(aryl) iodonium salts to form syn-1,3-carbonates in excellent yield and high selectivity. Furthermore, the products formed are amenable to an iterative reaction sequence, thus affording highly complex polyketide-like fragments.

    14. Self-Assembly

      Self-Assembled Spherical Complex Displaying a Gangliosidic Glycan Cluster Capable of Interacting with Amyloidogenic Proteins

      Dr. Sota Sato, Yutaka Yoshimasa, Dr. Daishi Fujita, Dr. Maho Yagi-Utsumi, Dr. Takumi Yamaguchi, Prof. Dr. Koichi Kato and Prof. Dr. Makoto Fujita

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201501981

      Thumbnail image of graphical abstract

      A pentasaccharide cluster derived from natural ganglioside was synthesized by chemical modification of self-assembled spherical scaffolds. The cluster interacts with amyloidogenic proteins, amyloid β (Aβ), or α-synuclein, demonstrating its inherent recognition abilities through clustering effect. This discrete cluster allows characterizing the early encounter stage of biomolecular interactions of pathological interest using NMR spectroscopy.

    15. Solid-State Structures

      Frenkel-Defect-Mediated Chemical Ordering Transition in a Li–Mn–Ni Spinel Oxide

      Hyewon Ryoo, Hyung Bin Bae, Dr. Young-Min Kim, Dr. Jin-Gyu Kim, Dr. Seongsu Lee and Prof. Sung-Yoon Chung

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201502320

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      Defective mediators: B-site configurational ordering in an AB2O4-type spinel oxide takes place by the formation of Frenkel-type defects which form the crucial transient state. A precise suggestion of the transient states (see picture) and the resulting kinetic pathway during the ordering transition is provided.

    16. CO2 Absorption | Hot Paper

      Computer-Aided Design of Ionic Liquids as CO2 Absorbents

      Dzmitry S. Firaha, Dr. Oldamur Hollóczki and Prof. Dr. Barbara Kirchner

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201502296

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      Better by design: Using a continuum model makes it possible to distinguish between the chemical and physical absorption of CO2 in ionic liquids. The ionic liquids showing chemical adsorption were further narrowed down to “good” candidates, in which a facile desorption is feasible according to a calculated energy criterion. This criterion was determined by correlating the calculated Gibbs free energies with experimental capacities.

    17. Homogeneous Gold Catalysis

      Gold-Catalyzed Cascade Cyclization of 2-Alkynyl-N-Propargylanilines by Rearrangement of a Propargyl Group

      Yusuke Tokimizu, Dr. Shinya Oishi, Prof. Dr. Nobutaka Fujii and Prof. Dr. Hiroaki Ohno

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201502256

      Thumbnail image of graphical abstract

      Heart of gold: A rapid access to fused three-dimensional indolines has been developed in which four bonds and three rings are formed in a single operation. Under gold catalysis, a propargyl substituent migrates from an aniline nitrogen atom to the C3-position of an indole from 2-alkynyl-N-propargylanilines to give the tetracyclic fused indolines directly (see scheme).

    18. Lithium–Air Battery

      Direct Detection of the Superoxide Anion as a Stable Intermediate in the Electro-Reduction of Oxygen in a Non-Aqueous Electrolyte Containing Phenol as a Proton Source

      Prof. Zhangquan Peng, Dr. Yuhui Chen, Prof. Peter G. Bruce and Prof. Ye Xu

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201502039

      Thumbnail image of graphical abstract

      Stable superoxide found in Gold ORR: An in situ spectroscopic study of the oxygen reduction reaction (ORR) on gold in a DMSO electrolyte containing phenol as a proton source shows that the ORR can begin with 1e transfer to O2. Thus O2, not HO2, is the first stable intermediate during the ORR to hydrogen peroxide. The unusual stability of O2 is explained using DFT calculations.

    19. Supramolecular Hydrogels

      Multistimuli-Responsive, Moldable Supramolecular Hydrogels Cross-Linked by Ultrafast Complexation of Metal Ions and Biopolymers

      Zhifang Sun, Fucong Lv, Lujie Cao, Dr. Lin Liu, Prof. Dr. Yi Zhang and Prof. Dr. Zhouguang Lu

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201502228

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      Turning to jelly: A series of metal–biopolymer hydrogels is obtained by ultrafast supramolecular complexation. The hydrogels are easily prepared, have high water content, and are stable at room temperature. The multistimuli-responsive Ag-based hydrogel can be molded to form shape-persistent, free-standing objects.

    20. Systems Chemistry

      Controlling the Structure and Length of Self-Synthesizing Supramolecular Polymers through Nucleated Growth and Disassembly

      Dr. Asish Pal, Dr. Morteza Malakoutikhah, Giulia Leonetti, Meniz Tezcan, Mathieu Colomb-Delsuc, Dr. Van Duc Nguyen, Prof. Jasper van der Gucht and Prof. Sijbren Otto

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201501965

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      Planting the right seeds: Combining dynamic covalent chemistry with seeded self-assembly allows access to self-synthesizing fibers and block co-fibers with excellent control over length and polydispersity. Kinetically controlled assembly of self-synthesizing peptide-functionalized macrocycles occurs through a nucleation and growth mechanism when a seed is present.

    21. Organocatalysis

      Brønsted Acid Catalyzed Asymmetric Hydroamination of Alkenes: Synthesis of Pyrrolidines Bearing a Tetrasubstituted Carbon Stereocenter

      Dr. Jin-Shun Lin, Peng Yu, Lin Huang, Pan Zhang, Prof. Dr. Bin Tan and Prof. Dr. Xin-Yuan Liu

      Article first published online: 26 MAY 2015 | DOI: 10.1002/anie.201501762

      Thumbnail image of graphical abstract

      The enantioselective Brønsted acid catalyzed intramolecular hydroamination of alkenes is enabled by the use of a thiourea group that acts as both the activating and directing group by cooperative multiple hydrogen bonding. This method can be employed for the efficient construction of a series of chiral (spirocyclic) pyrrolidines and tricyclic amines with α-tetrasubstituted carbon stereocenters.

    22. Glycoproteins

      Chemical Synthesis of O-Glycosylated Human Interleukin-2 by the Reverse Polarity Protection Strategy

      Dr. Yuya Asahina, Shinobu Komiya, Ami Ohagi, Rina Fujimoto, Dr. Hiroko Tamagaki, Katsuhiro Nakagawa, Dr. Takashi Sato, Prof. Dr. Shizuo Akira, Prof. Dr. Toshifumi Takao, Dr. Akira Ishii, Prof. Dr. Yoshiaki Nakahara and Prof. Dr. Hironobu Hojo

      Article first published online: 26 MAY 2015 | DOI: 10.1002/anie.201501847

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      Take your Pic: Total synthesis of the glycosylated human interleukin-2 (IL-2) was achieved. The poor solubility of the C-terminal half during purification and ligation was overcome by using the reverse polarity protection of the carboxylic acid by a picolyl (Pic) ester. Together with a new prolyl thioester synthesis for the (28–65) segment, the desired IL-2, having full biological activity, was successfully prepared.

    23. Rare-Earth Elements

      An Operationally Simple Method for Separating the Rare-Earth Elements Neodymium and Dysprosium

      Justin A. Bogart, Connor A. Lippincott, Dr. Patrick J. Carroll and Prof. Eric J. Schelter

      Article first published online: 26 MAY 2015 | DOI: 10.1002/anie.201501659

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      Reuse and recycle: A tripodal nitroxide ligand is used in the separation of Nd and Dy giving good recoveries from Nd/Dy(OTf)3 mixtures. The separation factor SNd/Dy=359 achieved is an improvement over conventional separation methods involving liquid–liquid extractions. This method will contribute to incentivizing recycling of Nd/Dy permanent magnetic materials.

    24. Chiral Borospherenes

      Cage-like B41+ and B422+: New Chiral Members of the Borospherene Family

      Qiang Chen, Su-Yan Zhang, Hui Bai, Wen-Juan Tian, Ting Gao, Hai-Ru Li, Chang-Qing Miao, Dr. Yue-Wen Mu, Hai-Gang Lu, Prof. Dr. Hua-Jin Zhai and Prof. Dr. Si-Dian Li

      Article first published online: 26 MAY 2015 | DOI: 10.1002/anie.201501588

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      Chiral cations: Following the recently observed C3/C2 B39 and D2d B40, two new chiral members C1 B41+ and C2 B422+ are presented to the borospherene family. These chiral borospherene cations are composed of twelve interwoven boron double chains with six hexagonal and heptagonal faces and exhibit σ plus π double delocalization, which can be viewed as cuborenes analogous to cubane (C8H8).

    25. Synthetic Methods | Hot Paper

      A Versatile Room-Temperature Route to Di- and Trisubstituted Allenes Using Flow-Generated Diazo Compounds

      Jian-Siang Poh, Dr. Duc N. Tran, Dr. Claudio Battilocchio, Dr. Joel M. Hawkins and Prof. Steven V. Ley

      Article first published online: 26 MAY 2015 | DOI: 10.1002/anie.201501538

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      Well tolerated: A mild copper-catalyzed coupling reaction between unstabilized diazo compounds (generated in flow) and terminal alkynes is reported. The method provides di- and trisubstituted allenes with high functional-group tolerance.

    26. Dual Catalysis | Very Important Paper

      Merging Photoredox and Nickel Catalysis: The Direct Synthesis of Ketones by the Decarboxylative Arylation of α-Oxo Acids

      Dr. Lingling Chu, Jeffrey M. Lipshultz and Prof. Dr. David W. C. MacMillan

      Article first published online: 26 MAY 2015 | DOI: 10.1002/anie.201501908

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      The direct decarboxylative arylation of α-oxo acids has been achieved by synergistic visible-light-mediated photoredox and nickel catalysis. This method offers rapid entry to aryl and alkyl ketone architectures from simple α-oxo acid precursors via an acyl radical intermediate. Significant substrate scope is observed with respect to both the oxo acid and arene coupling partners.

    27. Heterogeneous Catalysis

      Size of Gold Nanoparticles Driving Selective Amide Synthesis through Aerobic Condensation of Aldehydes and Amines

      Dr. Hiroyuki Miyamura, Hyemin Min, Dr. Jean-François Soulé and Prof. Dr. Shū Kobayashi

      Article first published online: 26 MAY 2015 | DOI: 10.1002/anie.201501795

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      Superior activity and selectivity of gold nanoparticles (Au-NPs) of medium size (4.5–11 nm) were found for the direct and selective aerobic oxidative amide synthesis from various combinations of aldehydes and amines. This is an example of an unusual correlation between the size of NPs and their activity/selectivity. These catalysts could be recovered and reused several times without loss of activity.

    28. Drug Discovery

      DNA-Encoded Dynamic Combinatorial Chemical Libraries

      Francesco V. Reddavide, Weilin Lin, Sarah Lehnert and Dr. Yixin Zhang

      Article first published online: 26 MAY 2015 | DOI: 10.1002/anie.201501775

      Thumbnail image of graphical abstract

      Selection goes dynamic: Dynamic combinatorial chemistry explores the thermodynamic equilibrium of reversible reactions. DNA-encoded chemical libraries enable the selection of binders from compound mixtures. Now the advantages of DNA-encoded dynamic combinatorial chemical libraries for the selection of protein binders from a myriad of compounds (see picture) and for DNA-templated reactions are demonstrated.

    29. Electrochemistry

      Thin-Layer Chemical Modulations by a Combined Selective Proton Pump and pH Probe for Direct Alkalinity Detection

      Dr. Majid Ghahraman Afshar, Dr. Gastón A. Crespo and Prof. Eric Bakker

      Article first published online: 26 MAY 2015 | DOI: 10.1002/anie.201500797

      Thumbnail image of graphical abstract

      A chemically selective electrochemical proton pump creates a concentration perturbation in a thin-layer sample that is detected by a pH probe placed opposite. The proposed methodology is applicable for a range of ions and is demonstrated here for direct alkalinity measurements. L=ionophore; R=cation exchanger; Jinline image=proton flux; IFS=inner filling solution.

    30. DNA Self-Assembly

      Hyper-Branched Hybridization Chain Reaction for Triggered Signal Amplification and Concatenated Logic Circuits

      Dr. Sai Bi, Min Chen, Xiaoqiang Jia, Ying Dong and Prof. Dr. Zonghua Wang

      Article first published online: 26 MAY 2015 | DOI: 10.1002/anie.201501457

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      DNA branches out: A hyper-branched hybridization chain reaction is reported for the self-assembly of dendritic DNA structures triggered by an initiator DNA strand. Using this method, ultrasensitive detection of target DNA was achieved and three-input concatenated logic circuits have been constructed which can operate as keypad locks for biocomputing security systems at the molecular level.

    31. Multivalent Polymer Nanocomplex

      Multivalent Polymer Nanocomplex Targeting Endosomal Receptor of Immune Cells for Enhanced Antitumor and Systemic Memory Response

      Sun-Young Kim, Min Beom Heo, Dr. Geum-Sook Hwang, Youngae Jung, Dr. Do Yeol Choi, Prof. Dr. Yeong-Min Park and Prof. Dr. Yong Taik Lim

      Article first published online: 26 MAY 2015 | DOI: 10.1002/anie.201501380

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      Enhanced immunostimulation: A multivalent polymer nanocomplex for the effective intracellular delivery and subsequent multivalent display of immunostimulatory cytosine-phosphate-guanine oligodeoxynucleotides (CpG ODNs) in antigen-presenting cells is described. Mice vaccinated with dendritic cells treated with the nanocomplex exhibited tumor growth inhibition as well as a strong antitumor memory response. HA=hyaluronic acid, PLL=poly(L-lysine).

    32. Semiconducting Nanostructures

      Unambiguous Diagnosis of Photoinduced Charge Carrier Signatures in a Stoichiometrically Controlled Semiconducting Polymer-Wrapped Carbon Nanotube Assembly

      Dr. Jean-Hubert Olivier, Dr. Jaehong Park, Dr. Pravas Deria, Dr. Jeff Rawson, Yusong Bai, Dr. Amar S. Kumbhar and Prof. Michael J. Therien

      Article first published online: 26 MAY 2015 | DOI: 10.1002/anie.201501364

      Thumbnail image of graphical abstract

      Nanohybrid compositions based on (6,5) chirality-enriched SWNTs and a chiral n-type polymer (S-PBN(b)-Ph4PDI) that exploits a perylenediimide-containing repeat unit undergo light-driven electron–hole pair generation. Rigorously controlled SWNT:electron acceptor stoichiometry and organization enable spectroscopic characterization of the photoinduced charge carrier signatures and evaluation of the associated charge separation and charge migration dynamics via pump-probe transient absorption spectroscopy.

    33. Protein Dynamics

      Kinetic Cooperativity in Human Pancreatic Glucokinase Originates from Millisecond Dynamics of the Small Domain

      Dr. Mioara Larion, Dr. Alexandar L. Hansen, Dr. Fengli Zhang, Dr. Lei Bruschweiler-Li, Dr. Vitali Tugarinov, Prof. Dr. Brian G. Miller and Prof. Dr. Rafael Brüschweiler

      Article first published online: 26 MAY 2015 | DOI: 10.1002/anie.201501204

      Thumbnail image of graphical abstract

      Distant but decisive: Kinetic cooperativity is an intrinsic property of glucokinase that enables it to maintain whole-body glucose homeostasis. The small-domain dynamics of glucokinase on the millisecond timescale have now been quantified by NMR spectroscopic experiments and found to be responsible for this effect by interfering with the turnover rate constant and generating non-Michaelis–Menten kinetics (see picture).

    34. Synthetic Methods

      Remote Hydroxylation through Radical Translocation and Polar Crossover

      Kyle A. Hollister, Elizabeth S. Conner, Mark L. Spell, Kristina Deveaux, Léa Maneval, Michael W. Beal and Prof. Dr. Justin R. Ragains

      Article first published online: 26 MAY 2015 | DOI: 10.1002/anie.201500880

      Thumbnail image of graphical abstract

      Mild conditions have been developed for the remote functionalization of aliphatic C[BOND]H bonds through radical translocation and oxidation of the resulting radical to the carbocation as a prerequisite to nucleophilic attack. The employment of fac-[Ir(ppy)3] together with the Tzo group facilitates the site-selective replacement of inert C[BOND]H bonds with a C[BOND]OH group.

    35. Biocatalytic Self-Assembly

      Biocatalytic Pathway Selection in Transient Tripeptide Nanostructures

      Charalampos G. Pappas, Ivan R. Sasselli and Prof. Rein V. Ulijn

      Article first published online: 26 MAY 2015 | DOI: 10.1002/anie.201500867

      Thumbnail image of graphical abstract

      Off the beaten track: Sequence-dependent kinetic pathway selection in chemically fueled catalytic self-assembly of tripeptides is demonstrated, in which the control of the lifetime of the nanostructures is dictated by chemical design. Mimicking the unique features of these systems may open up opportunities to create supramolecular systems for non-equilibrium motility and shape control.

    36. Rattle-Structured Nanoprobe

      Multifunctional Nano-Bioprobes Based on Rattle-Structured Upconverting Luminescent Nanoparticles

      Dr. Shan Lu, Dr. Datao Tu, Ping Hu, Jin Xu, Renfu Li, Dr. Meng Wang, Dr. Zhuo Chen and Prof. Dr. Xueyuan Chen

      Article first published online: 26 MAY 2015 | DOI: 10.1002/anie.201501468

      Thumbnail image of graphical abstract

      Rattle-structured nano-bioprobes featuring a β-NaLuF4:Gd/Yb/Er core and a benzene-bridged organosilica shell exhibit a high loading capacity and the disaggregation effect of photosensitizers, providing enhanced photodynamic therapy. Together with the functions of upconversion/X-ray computed tomography (UC/CT) dual-modal imaging and tumor-targeting, these nanoprobes are highly promising for cancer theranostics.

    37. CO2 Activation | Hot Paper

      Carbon Dioxide Activation and Reaction Induced by Electron Transfer at an Oxide–Metal Interface

      Dr. Florencia Calaza, Christian Stiehler, Yuichi Fujimori, Prof. Dr. Martin Sterrer, Sebastian Beeg, Dr. Miguel Ruiz-Oses, Prof. Dr. Niklas Nilius, Dr. Markus Heyde, Teemu Parviainen, Dr. Karoliina Honkala, Prof. Dr. Hannu Häkkinen and Prof. Dr. Hans-Joachim Freund

      Article first published online: 26 MAY 2015 | DOI: 10.1002/anie.201501420

      Thumbnail image of graphical abstract

      Electrons are shuttled back and forth between CO2 and a metal–insulator–metal model system, enabling the activation of CO2 and its reaction to oxalate. This may either react further or reversibly decompose to CO2.

    38. Hydrogen Separation | Hot Paper

      Inverted Fuel Cell: Room-Temperature Hydrogen Separation from an Exhaust Gas by Using a Commercial Short-Circuited PEM Fuel Cell without Applying any Electrical Voltage

      Sebastian Friebe, Benjamin Geppert and Prof. Dr. Jürgen Caro

      Article first published online: 26 MAY 2015 | DOI: 10.1002/anie.201500751

      Thumbnail image of graphical abstract

      Fuel cell turned on its head: A short-circuited PEM fuel cell with a Nafion membrane can separate hydrogen from exhaust gases of different compositions at room temperature. The permeated hydrogen can either be obtained using an inert flushing gas or used directly in catalytic hydrogenations or combustion processes with reactive flushing gases.

    39. Organocatalysis

      The Organocatalytic Asymmetric Prins Cyclization

      Dr. Gavin Chit Tsui, Luping Liu and Prof. Dr. Benjamin List

      Article first published online: 26 MAY 2015 | DOI: 10.1002/anie.201500219

      Thumbnail image of graphical abstract

      A bulky cat.: In an organocatalytic asymmetric Prins cyclization, salicylaldehydes react with 3-methyl-3-buten-1-ol in the presence of a chiral imidodiphosphoric acid catalyst to afford highly functionalized 4-methylenetetrahydropyrans in excellent regio- and enantioselectivities (see scheme).

    40. Radical Anions

      An Isolable Radical Anion of an Organosilicon Cluster Containing Only σ Bonds

      Dr. Kyohei Otsuka, Naozumi Matsumoto, Dr. Shintaro Ishida and Prof. Dr. Soichiro Kyushin

      Article first published online: 26 MAY 2015 | DOI: 10.1002/anie.201500523

      Thumbnail image of graphical abstract

      The radical anion of octa-tert-butyloctasilacubane was generated and isolated (see picture). The X-ray crystallographic analysis showed that the Si[BOND]Si bonds are shortened and the Si[BOND]C bonds are elongated compared with those of octa-tert-butyloctasilacubane. These results are well explained by the distribution of an unpaired electron in the singly occupied molecular orbital (SOMO).

    41. Nanotechnology

      Hypoxia Induced by Upconversion-Based Photodynamic Therapy: Towards Highly Effective Synergistic Bioreductive Therapy in Tumors

      Dr. Yanyan Liu, Prof. Yong Liu, Prof. Wenbo Bu, Dr. Chao Cheng, Dr. Changjing Zuo, Dr. Qingfeng Xiao, Yong Sun, Dr. Dalong Ni, Dr. Chen Zhang, Dr. Jianan Liu and Prof. Jianlin Shi

      Article first published online: 26 MAY 2015 | DOI: 10.1002/anie.201500478

      Thumbnail image of graphical abstract

      Synergetic therapy: Strong hypoxia created by upconversion photodynamic therapy (UC-PDT) activates bioreductive pro-drugs co-delivered to form cytotoxic species, thereby potentiating the synergetic anticancer efficacy of UC-PDT. This process was accomplished by using upconversion-based nanoparticles designed to simultaneously deliver photosensitizer molecules and bioreductive pro-drugs in silica layers.

    42. Plant Polyphenols

      Gallotannins and Tannic Acid: First Chemical Syntheses and In Vitro Inhibitory Activity on Alzheimer’s Amyloid β-Peptide Aggregation

      Dr. Tahiri Sylla, Prof. Laurent Pouységu, Dr. Grégory Da Costa, Dr. Denis Deffieux, Prof. Jean-Pierre Monti and Prof. Stéphane Quideau

      Article first published online: 26 MAY 2015 | DOI: 10.1002/anie.201411606

      Thumbnail image of graphical abstract

      Hexa- and decagalloylglucoses, which belong to the gallotannin plant polyphenols, were chemically synthesized for the first time, and a method for the selective synthesis of the monogalloylglucoses α- and β-glucogallin was developed. An in vitro evaluation showed that the non-natural α-glucogallin and a natural β-hexagalloylglucose are potent inhibitors of amyloid β-peptide aggregation.

    43. Heterocycles

      Construction of an Internally B3N3-Doped Nanographene Molecule

      Dr. Matthias Krieg, Florian Reicherter, Dr. Peter Haiss, Dr. Markus Ströbele, Dr. Klaus Eichele, Michael-John Treanor, Prof. Dr. Renald Schaub and Prof. Dr. Holger F. Bettinger

      Article first published online: 26 MAY 2015 | DOI: 10.1002/anie.201412165

      Thumbnail image of graphical abstract

      A change of heart: The borazine derivative of hexa-peri-hexabenzocoronene was produced in a high-temperature reaction through multiple dehydrogenation of a borazine. The solid-state structure of this BN-doped HBC (BN-HBC) is isotypic with that of the parent HBC. Scanning tunneling microscopy shows that BN-HBC lies flat on Au(111) in a two-dimensional pattern.

    44. Magnesium Batteries

      An Efficient Halogen-Free Electrolyte for Use in Rechargeable Magnesium Batteries

      Dr. Oscar Tutusaus, Dr. Rana Mohtadi, Dr. Timothy S. Arthur, Dr. Fuminori Mizuno, Dr. Emily G. Nelson and Prof. Yulia V. Sevryugina

      Article first published online: 26 MAY 2015 | DOI: 10.1002/anie.201412202

      Thumbnail image of graphical abstract

      A simple yet multifaceted magnesium monocarborane (MMC) based electrolyte was prepared. This remarkable halogen-free and benign system is compatible with Mg metal and displays the highest anodic stability reported to date. The non-corrosive nature of the MMC electrolyte enabled the examination of high-voltage cathodes in a coin cell, which is a critical step forward in realizing practical rechargeable Mg batteries.

    45. Host–Guest Systems

      Halogen Bonding Molecular Capsules

      Oliver Dumele, Dr. Nils Trapp and Prof. Dr. François Diederich

      Article first published online: 26 MAY 2015 | DOI: 10.1002/anie.201502960

      Thumbnail image of graphical abstract

      Time for halogens: Self-assembly of supramolecular capsules solely by halogen bonding (XB) is realized on the platform of resorcin[4]arene cavitands. The halogenated donor hemisphere binds in a 180° fashion through tetradentate XB to the acceptor hemisphere for capsule formation in solution. Guest inclusion inside the XB capsule is demonstrated and quantified.

    46. Platinum Complexes

      The Role of Substituent Effects in Tuning Metallophilic Interactions and Emission Energy of Bis-4-(2-pyridyl)-1,2,3-triazolatoplatinum(II) Complexes

      M. R. Ranga Prabhath, Dr. Julia Romanova, Prof. Richard J. Curry, Prof. S. Ravi P. Silva and Dr. Peter D. Jarowski

      Article first published online: 26 MAY 2015 | DOI: 10.1002/anie.201502390

      Thumbnail image of graphical abstract

      Turn-on tunability: A series of bis-4-(2-pyridyl)-1,2,3-triazolatoplatinum(II) complexes display variable emission tunability. At low concentration, the emission can be tuned only slightly by changing the nature of the substituent but at higher concentrations tunability is enhanced. This “turn-on” sensitivity in the excimeric emission is attributed to strong Pt–Pt metallophilic interactions and a change in the excited-state character.

  9. Cover Pictures

    1. You have free access to this content
      Deciphering a Nanocarbon-Based Artificial Peroxidase: Chemical Identification of the Catalytically Active and Substrate-Binding Sites on Graphene Quantum Dots

      Hanjun Sun, Andong Zhao, Dr. Nan Gao, Dr. Kai Li, Prof. Jinsong Ren and Prof. Xiaogang Qu

      Article first published online: 21 MAY 2015 | DOI: 10.1002/anie.201504212

      Thumbnail image of graphical abstract

      Graphene quantum dots (GQDs) can act as nanocarbon-based artificial peroxidases. In their Communication (DOI: 10.1002/anie.201500626), X. Qu et al. obtain various GQD derivatives by the selective deactivation of oxygen-containing groups. A comparison of their catalytic activities shows that ketone groups are the catalytically active sites, whereas carboxylic groups act as substrate-binding sites, and hydroxy groups can inhibit the activity of the GQDs.

    2. You have free access to this content
      Determination of Enantiomeric Excess in Amine Derivatives with Molecular Self-Assemblies

      Elena G. Shcherbakova, Dr. Tsuyoshi Minami, Dr. Valentina Brega, Prof. Dr. Tony D. James and Prof. Dr. Pavel Anzenbacher Jr.

      Article first published online: 21 MAY 2015 | DOI: 10.1002/anie.201504210

      Thumbnail image of graphical abstract

      Orthogonal dynamic covalent self-assembly has been used for high-throughput determination of the enantiomeric purity of chiral amines. The method, described by P. Anzenbacher and co-workers in their Communication (DOI: 10.1002/anie.201501736) is based on the self-assembly of 2-formylphenylboronic acid with a chiral diol auxiliary and a chiral amine of unknown chirality to produce two diastereomeric iminoboronates that differ in their fluorescence, as measured using a microplate reader. The approach allows accurate determination of the ee value of chiral amines with errors below 2%.

    3. You have free access to this content
      Electrokinetic Size and Mobility Traps for On-site Therapeutic Drug Monitoring

      Aliaa I. Shallan, Dr. Rosanne M. Guijt and Prof. Michael C. Breadmore

      Article first published online: 21 MAY 2015 | DOI: 10.1002/anie.201504134

      Thumbnail image of graphical abstract

      Two nanojunctions with different pore sizes are the key parts of size and mobility traps described by M. C. Breadmore and co-workers in their Communication (DOI: 10.1002/anie.201501794). The traps were developed to extract, concentrate, and purify pharmaceuticals from body fluids prior to their separation by microchip electrophoresis. Therapeutic levels of the antibiotic ampicillin could be detected in blood samples within five minutes.

  10. Book Reviews

    1. Comets and their Origin. The Tools to Decipher a Comet. By Uwe Meierhenrich.

      Guillermo Manuel Muñoz Caro

      Article first published online: 21 MAY 2015 | DOI: 10.1002/anie.201503887

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      Wiley-VCH, Weinheim 2014. 352 pp., hardcover, € 125.00—ISBN 978-3527412815

  11. Communications

    1. Fluorescence Memory

      Multicolor Fluorescence Writing Based on Host–Guest Interactions and Force-Induced Fluorescence-Color Memory

      Dr. Yuki Matsunaga and Prof. Jye-Shane Yang

      Article first published online: 15 MAY 2015 | DOI: 10.1002/anie.201503406

      Thumbnail image of graphical abstract

      Memorable art: Multicolor fluorescence writing was possible on thin solid films of a pentiptycene–anthracene conjugated system (see picture). This technique relies on the formation of fluorescent exciplexes with aniline vapors and on force-induced fluorescence color memory. The drawings were erased by blowing air over the surface and by exposure to dichloromethane fumes.

  12. Book Reviews

    1. Molecular Aesthetics. Edited by Peter Weibel and Ljiljana Fruk.

      Dirk Trauner

      Article first published online: 15 MAY 2015 | DOI: 10.1002/anie.201502654

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      MIT Press, Cambridge, 2013. 400 pp., hardcover, $ 55.00.—ISBN 978-0262018784

  13. Communications

    1. Perovskite Solar Cells

      The Significance of Ion Conduction in a Hybrid Organic–Inorganic Lead-Iodide-Based Perovskite Photosensitizer

      Dr. Tae-Youl Yang, Dr. Giuliano Gregori, Norman Pellet, Prof. Michael Grätzel and Prof. Joachim Maier

      Article first published online: 15 MAY 2015 | DOI: 10.1002/anie.201500014

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      In alkyl ammonium iodide ion conduction turns out to be substantial. The resulting stoichiometric polarization can explain anomalous features in perovskite solar cells: huge apparent low-frequency permittivity and hysteretic current–voltage behavior in cyclic sweep experiments.

    2. DNA Nanostructures | Hot Paper

      One-Step Formation of “Chain-Armor”-Stabilized DNA Nanostructures

      Valentina Cassinelli, Dr. Birgit Oberleitner, Jessica Sobotta, Philipp Nickels, Guido Grossi, Dr. Susanne Kempter, Dr. Thomas Frischmuth, Prof. Tim Liedl and Dr. Antonio Manetto

      Article first published online: 15 MAY 2015 | DOI: 10.1002/anie.201500561

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      Interlocked catenane rings consisting of 24 single-stranded DNA molecules (“chain-armor DNA”) were built from six helix tubes containing 3′-alkyne- and 5′-azide-modified single-stranded tiles (SST) that were covalently closed by click chemistry. Intramolecular cyclization stabilized these DNA nanotubes efficiently against enzymatic and thermal degradation.

    3. Aggregation-Induced Emission

      Aggregation-Induced Photon Upconversion through Control of the Triplet Energy Landscapes of the Solution and Solid States

      Dr. Pengfei Duan, Dr. Nobuhiro Yanai, Dr. Yuki Kurashige and Prof. Dr. Nobuo Kimizuka

      Article first published online: 15 MAY 2015 | DOI: 10.1002/anie.201501449

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      Affairs of state: Whereas a cyano-substituted 1,4-distyrylbenzene derivative shows no upconverted (UC) emission in solution, a clear upconverted emission is observed for solution-cast crystals (see picture). The difference is attributed to immediate decay of excited triplets through conformational twisting and isomerization being possible in solution but not in the solid state.

    4. Carbenes | Hot Paper

      Rhodium(I)-Catalyzed Sequential C(sp)[BOND]C(sp3) and C(sp3)[BOND]C(sp3) Bond Formation through Migratory Carbene Insertion

      Ying Xia, Sheng Feng, Zhen Liu, Dr. Yan Zhang and Prof. Dr. Jianbo Wang

      Article first published online: 15 MAY 2015 | DOI: 10.1002/anie.201503140

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      All on C: A sequential RhI-catalyzed alkyl and alkynyl coupling on a carbene successively establishes a C(sp)[BOND]C(sp3) and then a C(sp3)[BOND]C(sp3) bond on the original carbenic carbon center. The reaction results in the formation of an all-carbon quaternary center in high efficiency. A rhodium–carbene migratory insertion is proposed as the key step in this transformation.

    5. Diastereoselectivity

      Mechanistic Insight into the Stereochemical Control of Lactide Polymerization by Salan–Aluminum Catalysts

      Konstantin Press, Prof. Israel Goldberg and Prof. Moshe Kol

      Article first published online: 15 MAY 2015 | DOI: 10.1002/anie.201503111

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      The importance of being (diastereomerically) earnest: Chiral 2,2′-bipyrrolidine-based salan ligands give Al complexes as single diastereomers, which are active catalysts for stereoselective polymerization of racemic lactide. The heterotacticity of the obtained poly(lactic acid) increased dramatically upon increasing the enantiomeric impurity of the catalyst as the result of an insertion/auto-inhibition/exchange mechanism.

    6. Metal–Organic Polyhedra

      Cooperative Crystallization of Heterometallic Indium–Chromium Metal–Organic Polyhedra and Their Fast Proton Conductivity

      Dr. Quan-Guo Zhai, Chengyu Mao, Dr. Xiang Zhao, Dr. Qipu Lin, Fei Bu, Xitong Chen, Prof. Dr. Xianhui Bu and Prof. Dr. Pingyun Feng

      Article first published online: 15 MAY 2015 | DOI: 10.1002/anie.201503095

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      In3+ befriending Cr3+: Indium and chromium ions drag each other into unprecedented heterometallic In-Cr-MOP (metal–organic polyhedra) crystals. These have a high proton conductivity (5.8×10−2 S cm−1) at 22.5 °C and 98 % relative humidity for a single crystal.

    7. Porphyrinoids

      Synthesis of Meso-Substituted Subphthalocyanine–Subporphyrin Hybrids: Boron Subtribenzodiazaporphyrins

      Sonia Remiro-Buenamañana, Dr. Alejandro Díaz-Moscoso, Dr. David L. Hughes, Prof. Manfred Bochmann, Dr. Graham J. Tizzard, Dr. Simon J. Coles and Prof. Andrew N. Cammidge

      Article first published online: 15 MAY 2015 | DOI: 10.1002/anie.201502662

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      The first syntheses of subphthalocyanine–subporphyrin hybrid structures are reported. The new hybrids are isolated as robust, pure materials that display intense absorption and emission in the mid-visible region, and are further characterized in solution and solid state by variable-temperature NMR spectroscopy and X-ray crystallography, respectively.

    8. Synthetic Methods

      Synthesis of Phosphabenzenes by an Iron-Catalyzed [2+2+2] Cycloaddition Reaction of Diynes with Phosphaalkynes

      Dr. Kazunari Nakajima, Shohei Takata, Prof. Dr. Ken Sakata and Prof. Dr. Yoshiaki Nishibayashi

      Article first published online: 15 MAY 2015 | DOI: 10.1002/anie.201502531

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      Ironing out any difficulties: Unlike complexes of other transition metals, an iron catalyst enabled the synthesis of phosphabenzenes from 1,6-diynes and phosphaalkynes (see scheme). A variety of phosphabenzene derivatives were formed in good to high yield by FeI2-catalyzed [2+2+2] cycloaddition reactions of these substrates in m-xylene.

    9. Peptide Linkage

      A PEGylated Photocleavable Auxiliary Mediates the Sequential Enzymatic Glycosylation and Native Chemical Ligation of Peptides

      Dr. Claudia Bello, Dr. Shuo Wang, Dr. Lu Meng, Prof. Dr. Kelley W. Moremen and Prof. Dr. Christian F. W. Becker

      Article first published online: 15 MAY 2015 | DOI: 10.1002/anie.201501517

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      Two in one: An efficient approach for the preparation of modified peptides has been applied to the synthesis of O-glycosylated MUC1 repeats. A photocleavable PEGylated auxiliary mediates the sequential O-glycosylation and subsequent ligation of MUC1 peptides.

  14. Author Profiles

    1. Ryan Gilmour

      Article first published online: 14 MAY 2015 | DOI: 10.1002/anie.201503503

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      If I could be anyone for a day, I would be James Bond … because … If I were a car I would be an Aston Martin DB5.

  15. Communications

    1. Heterogeneous Catalysis

      Graphitic-Carbon Layers on Oxides: Toward Stable Heterogeneous Catalysts for Biomass Conversion Reactions

      Dr. Haifeng Xiong, Thomas J. Schwartz, Nalin I. Andersen, Prof. James A. Dumesic and Prof. Abhaya K. Datye

      Article first published online: 14 MAY 2015 | DOI: 10.1002/anie.201502206

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      Protected catalyst support: Depositing graphitic carbon onto oxides can effectively protect the oxide surface from attack by water under harsh conditions. The graphitic carbon/oxide composite supported catalysts exhibit excellent stability (even under acidic conditions) for biomass conversion reactions. CVD=chemical vapor deposition.

    2. Synthetic Methods

      Practical Continuous-Flow Trapping Metalations of Functionalized Arenes and Heteroarenes Using TMPLi in the Presence of Mg, Zn, Cu, or La Halides

      Matthias R. Becker and Prof. Dr. Paul Knochel

      Article first published online: 14 MAY 2015 | DOI: 10.1002/anie.201502393

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      Flow makes the difference: In situ trapping transmetalations in which functionalized arenes or heterocycles are mixed with metal salts proceed at 0 °C within 40 s in a continuous flow apparatus. Subsequent batch quenching of the resulting Mg, Zn, Cu, or La organic species with various electrophiles proceeds in high yields (see example).

    3. Proteasome Inhibitors

      A Minimal β-Lactone Fragment for Selective β5c or β5i Proteasome Inhibitors

      Prof. Dr. Michael Groll, Dr. Vadim S. Korotkov, Dr. Eva M. Huber, Prof. Dr. Armin de Meijere and Dr. Antje Ludwig

      Article first published online: 14 MAY 2015 | DOI: 10.1002/anie.201502931

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      Every little counts: Proteasome inhibitors are potent drugs for cancers. X-ray analysis and activity assays revealed that nonpeptide belactosine derivatives target the S1 and primed sites of β5 subunits with high affinity. These β-lactones are less cytotoxic than currently applied proteasome inhibitors and analogues varying only in one methyl group show a six-fold difference in their affinity for the immunoproteasome.

    4. Crystallization

      In Situ Microscopic Observation of the Crystallization Process of Molecular Microparticles by Fluorescence Switching

      Xin Ye, Prof. Yang Liu, Yun Lv, Guangfeng Liu, Xiaoxin Zheng, Quanxiang Han, Kenneth A. Jackson and Prof. Xutang Tao

      Article first published online: 14 MAY 2015 | DOI: 10.1002/anie.201503052

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      Crystallization of microparticles can be observed in situ and in real time by fluorescence microscopy by utilizing a novel organic chromophore with morphology-dependent fluorescence. Perfectly spherical microparticles nucleate at the interior and growth is confined to the inner part, ending with a core–shell structure (see picture, top). Defects of the surface prior to crystallization can lead to a complete crystal (bottom).

    5. Metabolic Labeling

      A Bioorthogonal Chemical Reporter of Viral Infection

      Dr. Anne B. Neef, Dr. Lucile Pernot, Verena N. Schreier, Prof. Dr. Leonardo Scapozza and Prof. Dr. Nathan W. Luedtke

      Article first published online: 14 MAY 2015 | DOI: 10.1002/anie.201500250

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      Pathogen-induced metabolic labeling: Cells infected by Herpes Simplex Virus-1 (HSV-1) were selectively labeled with the gemcitabine metabolite analogue dF-EdU and an azide-conjugated fluorophore. Labeling selectivity is due to the phosphorylation of dF-EdU by viral but not human thymidine kinases. These results establish a new approach for pathogen-specific bioorthogonal chemical labeling.

    6. Natural Products

      Synthesis and Applications of Hajos–Parrish Ketone Isomers

      James M. Eagan, Masahiro Hori, Dr. Jianbin Wu, Dr. Kyalo Stephen Kanyiva and Prof. Dr. Scott A. Snyder

      Article first published online: 14 MAY 2015 | DOI: 10.1002/anie.201500925

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      Moving methyl groups: Hajos–Parrish ketone isomers with a transposed methyl group, termed “iso-Hajos–Parrish ketones”, are useful building blocks for diverse targets. A new synthetic method to cyclopentenones is used in a three-step approach to several of these compounds. Furthermore, a natural product that was previously accessed in 18 steps was now synthesized in 10 steps using an iso-Hajos–Parrish ketone.

    7. Silver Clusters

      Ag2 and Ag3 Clusters: Synthesis, Characterization, and Interaction with DNA

      Dr. David Buceta, Dr. Natalia Busto, Dr. Giampaolo Barone, Prof. Dr. José M. Leal, Prof. Dr. Fernando Domínguez, Dr. Lisandro J. Giovanetti, Prof. Dr. Félix G. Requejo, Prof. Dr. Begoña García and Prof. Dr. M. Arturo López-Quintela

      Article first published online: 12 MAY 2015 | DOI: 10.1002/anie.201502917

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      Sandwiching silver in DNA: Subnanometric silver clusters (Ag2 and Ag3) were synthesized using a kinetic control procedure. Interaction studies of the clusters with DNA have demonstrated that Ag2 clusters interact only by covalent binding, whereas Ag3 clusters intercalate between the base pairs in DNA (see picture) and induce strong conformational changes.

    8. Solar Cells | Very Important Paper

      Pseudohalide-Induced Moisture Tolerance in Perovskite CH3NH3Pb(SCN)2I Thin Films

      Qinglong Jiang, Dominic Rebollar, Jue Gong, Elettra L. Piacentino, Prof. Chong Zheng and Prof. Tao Xu

      Article first published online: 12 MAY 2015 | DOI: 10.1002/anie.201503038

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      The replacement of two iodides by two pseudohalide thiocyanate ions in CH3NH3PbI3 results in a perovskite material with superior tolerance to moisture when used as the active material of a solar cell. For the CH3NH3Pb(SCN)2I perovskite films, no significant degradation was observed after the film had been exposed to air with a relative humidity of 95 % for over four hours, whereas the CH3NH3PbI3 films degraded in less than 1.5 hours.

    9. Asymmetric Catalysis

      Copper-Catalyzed Intermolecular Asymmetric Propargylic Dearomatization of Indoles

      Wen Shao, He Li, Chuan Liu, Prof. Dr. Chen-Jiang Liu and Prof. Dr. Shu-Li You

      Article first published online: 12 MAY 2015 | DOI: 10.1002/anie.201503042

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      New sub: The title reaction provides a highly efficient synthesis of versatile furoindoline and pyrroloindoline derivatives containing a quaternary carbon stereogenic center and a terminal alkyne moiety with up to 86 % yield and 98 % ee by an asymmetric propargylic substitution reaction .

  16. Cover Pictures

    1. You have free access to this content
      Revisiting the Solution Structure of Ceric Ammonium Nitrate

      Dr. Thomas J. Demars, Dr. Mrinal K. Bera, Dr. Soenke Seifert, Dr. Mark R. Antonio and Dr. Ross J. Ellis

      Article first published online: 12 MAY 2015 | DOI: 10.1002/anie.201503958

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      A half-century-old assertion about the structure of ceric ammonium nitrate (CAN) in solution is challenged. In their Communication (DOI: 10.1002/anie.201502336), R. J. Ellis and co-workers show that in HNO3, CAN is a dinuclear Ce[BOND]O[BOND]Ce complex. The bridging oxygen (the guy with the hat) would usually be attacked and devoured by the HNO3 sharks. However, he is protected by the Ce “life rings” on either side and so he is safe. The structure suggests that CAN can act as a two-electron transfer reagent, and not as generally assumed, a one-electron transfer reagent.

    2. You have free access to this content
      DNA-Grafted Supramolecular Polymers: Helical Ribbon Structures Formed by Self-Assembly of Pyrene–DNA Chimeric Oligomers

      Yuliia Vyborna, Mykhailo Vybornyi, Dr. Alexander V. Rudnev and Prof. Dr. Robert Häner

      Article first published online: 12 MAY 2015 | DOI: 10.1002/anie.201504048

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      DNA-grafted supramolecular polymers combine the intrinsic properties of self-assembled materials with the potential of sequence-specific functionalization. In their Communication (DOI: 10.1002/anie.201502066), R. Häner and co-workers describe the supramolecular polymerization of chimeric pyrene–DNA oligomers. The formation of helical ribbon structures is driven by pyrene stacking interactions and enables the controlled arrangement of oligonucleotide strands along the edges of the supramolecular polymers.

  17. Communications

    1. Bioorganic Chemistry

      Remarkable Effect of Chalcogen Substitution on an Enzyme Mimetic for Deiodination of Thyroid Hormones

      Karuppusamy Raja and Prof. Dr. Govindasamy Mugesh

      Article first published online: 12 MAY 2015 | DOI: 10.1002/anie.201502762

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      It’s hormonal: The replacement of sulfur/selenium atoms in deiodinase mimetics by tellurium atoms remarkably alters the reactivity as well as regioselectivity toward thyroxine (T4). Sequential deiodinations of T4 by tellurium compounds produces all the thyroid hormone derivatives.