Angewandte Chemie International Edition

Cover image for Vol. 53 Issue 26

June 23, 2014

Volume 53, Issue 26

Pages 6571–6826

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Highlight
    9. Review
    10. Communications
    1. You have free access to this content
      Cover Picture: Improved Cyclopropanation Activity of Histidine-Ligated Cytochrome P450 Enables the Enantioselective Formal Synthesis of Levomilnacipran (Angew. Chem. Int. Ed. 26/2014) (page 6571)

      Dr. Z. Jane Wang, Dr. Hans Renata, Nicole E. Peck, Christopher C. Farwell, Dr. Pedro S. Coelho and Prof. Dr. Frances H. Arnold

      Article first published online: 20 MAY 2014 | DOI: 10.1002/anie.201404337

      Thumbnail image of graphical abstract

      Mutation of the axial ligand can be used to tune the carbenoid activity of cytochrome P450 from Bacillus megaterium. In their Communication on page 6810 ff., F. Arnold and co-workers report the engineering of a histidine-ligated P450 enzyme that shows high catalytic activity for in vivo cyclopropanation using diazo compounds. This enzyme enables the enantioselective synthesis of a key precursor of levomilnacipran under aerobic conditions on a preparative scale. Image: Liang Zong and Yan Liang (L2Molecule.com).

    2. You have free access to this content
      Inside Cover: An Isolated Nitridyl Radical-Bridged {Rh(N.)Rh} Complex (Angew. Chem. Int. Ed. 26/2014) (page 6572)

      Dr. Yann Gloaguen, Christophe Rebreyend, Dr. Martin Lutz, Pravin Kumar, Dr. Martina Huber, Dr. Ir. Jarl Ivar van der Vlugt, Prof. Dr. Sven Schneider and Prof. Dr. Bas de Bruin

      Article first published online: 18 MAY 2014 | DOI: 10.1002/anie.201404169

      Thumbnail image of graphical abstract

      Breaking news: The first example of an isolated “nitridyl radical” (.N2−) complex is described by S. Schneider, B. de Bruin, and co-workers in their Communication on page 6814 ff. Formally, the paramagnetic, binuclear [(PNN)Rh

      • thumbnail image

      Rh(PNN)] complex is also a rare example of a Group 9 transition-metal (bridging) nitrido complex. Its spin density is delocalized over the Rh

      • thumbnail image

      Rh moiety, but the complex has a prevailing nitridyl radical character.

    3. You have free access to this content
      Inside Back Cover: Excited-State Dynamics of Pentacene Derivatives with Stable Radical Substituents (Angew. Chem. Int. Ed. 26/2014) (page 6827)

      Dr. Akitaka Ito, Akihiro Shimizu, Noriaki Kishida, Yusuke Kawanaka, Dr. Daisuke Kosumi, Prof. Dr. Hideki Hashimoto and Prof. Dr. Yoshio Teki

      Article first published online: 2 MAY 2014 | DOI: 10.1002/anie.201401150

      Thumbnail image of graphical abstract

      More than one pentacene triplet is produced from the absorption of one photon. In their Communication on page 6715 ff., Y. Teki et al. describe how transient absorption measurements performed on pentacene derivatives with stable radical substituents in dilute solution demonstrate that the ultrafast formation of a triplet excited state in the pentacene moiety (violet) from a photoexcited singlet state (green) occurs through contributions of enhanced intersystem crossing and singlet fission.

    4. You have free access to this content
      Back Cover: Regulated Incorporation of Two Different Metal Ions into Programmed Sites in a Duplex by DNA Polymerase Catalyzed Primer Extension (Angew. Chem. Int. Ed. 26/2014) (page 6828)

      Tatsuya Funai, Junko Nakamura, Yuki Miyazaki, Risa Kiriu, Dr. Osamu Nakagawa, Dr. Shun-ichi Wada, Prof. Akira Ono and Prof. Hidehito Urata

      Article first published online: 2 MAY 2014 | DOI: 10.1002/anie.201401152

      Thumbnail image of graphical abstract

      HgII and AgI ions were found to specifically trigger DNA polymerase catalyzed primer extension in the absence of a Watson–Crick matched nucleotide through the formation of the T–HgII–T and newly discovered C–AgI–T base pairs. In their Communication on page 6624 ff., H. Urata and co-workers show that the strict base recognition of these metal ions enables the regulated incorporation of the two different metal ions into programmed sites in the DNA duplex.

  2. Frontispiece

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Highlight
    9. Review
    10. Communications
    1. You have free access to this content
      Frontispiece: Three-Dimensional Ordered Assembly of Thin-Shell Au/TiO2 Hollow Nanospheres for Enhanced Visible-Light-Driven Photocatalysis

      Cao-Thang Dinh, Hoang Yen, Prof. Freddy Kleitz and Prof. Trong-On Do

      Article first published online: 20 JUN 2014 | DOI: 10.1002/anie.201482671

      Thumbnail image of graphical abstract

      T.-O. Do and co-workers report a three-dimensional ordered assembly of thin-shell Au/TiO2 hollow nanospheres in their Communication on page 6618 ff. These materials have a significantly enhanced photocatalytic activity compared to conventional nanopowders.

  3. Graphical Abstract

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

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

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Highlight
    9. Review
    10. Communications
    1. Carsten Bolm (pages 6596–6597)

      Article first published online: 19 FEB 2014 | DOI: 10.1002/anie.201400646

      Thumbnail image of graphical abstract

      “My worst nightmare is to have to suffer from more administrative nonsense. My biggest motivation is not the h-index, for sure. …” This and more about Carsten Bolm can be found on page 6596–6597.

  6. News

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

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

      Encoding Optical Signals (pages 6600–6601)

      Prof. Dr. Juyoung Yoon

      Article first published online: 6 JUN 2014 | DOI: 10.1002/anie.201402846

      Thumbnail image of graphical abstract

      Light up tomorrow: A photochromic material with excellent fatigue resistance, high thermal stability, and quantitative photoswitching can be used as a linear photoswitching material to replace nonlinear optical materials for encoding optical signals. Therefore, information in one light ray can be directly transmitted to another light ray without converting back to the electronic format.

  8. Review

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

      Thiopeptide Engineering: A Multidisciplinary Effort towards Future Drugs (pages 6602–6616)

      Xavier Just-Baringo, Prof. Fernando Albericio and Prof. Mercedes Álvarez

      Article first published online: 23 MAY 2014 | DOI: 10.1002/anie.201307288

      Thumbnail image of graphical abstract

      Making a complement: Modification of the structure of thiopeptides has produced numerous analogues that overcome some of their inherent limitations. The combined use of chemical synthesis, semisynthesis, and biosynthetic pathway engineering will allow the development of future thiopeptide-based drugs.

  9. Communications

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

      Three-Dimensional Ordered Assembly of Thin-Shell Au/TiO2 Hollow Nanospheres for Enhanced Visible-Light-Driven Photocatalysis (pages 6618–6623)

      Cao-Thang Dinh, Hoang Yen, Prof. Freddy Kleitz and Prof. Trong-On Do

      Article first published online: 15 APR 2014 | DOI: 10.1002/anie.201400966

      Thumbnail image of graphical abstract

      Order makes a difference: A three-dimensional ordered assembly of thin-shell Au/TiO2 hollow nanospheres exhibits not only a very high surface area but also photonic behavior and multiple light scattering. The designed materials show significantly enhanced visible-light absorption and a visible-light-driven photocatalytic activity several times higher than those of conventional Au/TiO2 nanopowders.

    2. Bioinorganic Chemistry

      Regulated Incorporation of Two Different Metal Ions into Programmed Sites in a Duplex by DNA Polymerase Catalyzed Primer Extension (pages 6624–6627)

      Tatsuya Funai, Junko Nakamura, Yuki Miyazaki, Risa Kiriu, Dr. Osamu Nakagawa, Dr. Shun-ichi Wada, Prof. Akira Ono and Prof. Hidehito Urata

      Article first published online: 9 APR 2014 | DOI: 10.1002/anie.201311235

      Thumbnail image of graphical abstract

      (Quick) silver DNA: HgII and AgI ions were found to specifically trigger DNA polymerase catalyzed primer extension in the absence of a Watson–Crick matched nucleotide through the formation of T–HgII–T and newly discovered C–AgI–T base pairs. The strict base recognition by the metal ions enabled regulated incorporation of the two different metal ions into programmed sites in duplex DNA.

    3. Antitumor Agents

      Pharmacophore Reassignment for Induction of the Immunosurveillance Cytokine TRAIL (pages 6628–6631)

      Nicholas T. Jacob, Dr. Jonathan W. Lockner, Prof.Dr. Vladimir V. Kravchenko and Prof. Dr. Kim D. Janda

      Article first published online: 18 MAY 2014 | DOI: 10.1002/anie.201402133

      Thumbnail image of graphical abstract

      Setting the record straight: An investigation of an imidazolinopyrimidinone (TIC10) reported to induce expression of the immunosurveillance cytokine TRAIL led to a constitutional reassignment of the active pharmacophore. Analysis of TRAIL induction in macrophages revealed the reported structure to be inactive. The structural identity of the active compound was established. The active compound was then synthesized and its activity confirmed.

    4. Anion Coordination

      Anion-Coordination-Induced Turn-On Fluorescence of an Oligourea-Functionalized Tetraphenylethene in a Wide Concentration Range (pages 6632–6636)

      Jie Zhao, Dong Yang, Dr. Yanxia Zhao, Prof. Xiao-Juan Yang, Prof. Yao-Yu Wang and Prof. Biao Wu

      Article first published online: 18 MAY 2014 | DOI: 10.1002/anie.201402169

      Thumbnail image of graphical abstract

      Phosphate ions in a bind: The tetrakis(bisurea)-decorated tetraphenylethene (TPE) displays fluorescence “turn-on” over a wide concentration range upon phosphate coordination. The fluorescence enhancement can be attributed to the restriction of the intramolecular rotation of TPE by anion coordination. This “anion-coordination-induced emission” (ACIE) is another approach for fluorescence turn-on.

    5. Sulfur Oxoacids | Hot Paper

      Straightforward Synthesis of the Brønsted Acid hfipOSO3H and its Application for the Synthesis of Protic Ionic Liquids (pages 6637–6640)

      Dr. Witali Beichel, Dipl.-Chem. Johann M. U. Panzer, B. Sc. Julian Hätty, Dipl.-Chem. Xiaowei Ye, Dr. Daniel Himmel and Prof. Dr. Ingo Krossing

      Article first published online: 26 MAY 2014 | DOI: 10.1002/anie.201402577

      Thumbnail image of graphical abstract

      A new Superacid? The novel Brønsted acid hfipOSO3H (hfip=C(H)(CF3)2) was prepared on the kilogram scale. In the gas phase, it is more acidic than sulfuric acid by ten orders of magnitude. Furthermore, this acid may be used for the synthesis of air- and moisture-stable protic ionic liquids of low viscosity and high conductivity.

    6. Enzyme Catalysis

      A Smart Library of Epoxide Hydrolase Variants and the Top Hits for Synthesis of (S)-β-Blocker Precursors (pages 6641–6644)

      Xu-Dong Kong, Qian Ma, Jiahai Zhou, Bu-Bing Zeng and Jian-He Xu

      Article first published online: 19 MAY 2014 | DOI: 10.1002/anie.201402653

      Thumbnail image of graphical abstract

      Hot pockets: Microtuning of the enzyme active pocket gives a smart library of epoxide hydrolase variants with an expanded substrate spectrum covering a series of typical β-blocker precursors. Improved activities of 6- to 430-fold were achieved by redesigning the active site at two predicted hot spots, and enhanced activity toward bulky substrates was found.

    7. Nitrogen Heterocycles

      Rhodium(II)-Catalyzed Intramolecular Cycloisomerizations of Methylenecyclopropanes with N-Sulfonyl 1,2,3-Triazoles (pages 6645–6649)

      Kai Chen, Zi-Zhong Zhu, Yong-Sheng Zhang, Dr. Xiang-Ying Tang and Prof. Min Shi

      Article first published online: 18 MAY 2014 | DOI: 10.1002/anie.201402803

      Thumbnail image of graphical abstract

      The azavinyl rhodium carbenes derived from N-sulfonyltriazole methylenecyclopropanes were found to be very reactive in the divergent synthesis of N-containing heterocycles. Different types of cycloisomerizations were observed depending on the substrates. Derivatization of the products easily gave a series of diazabicyclo[3.2.1]octane derivatives. Bs=bromobenzenesulfonyl, Ms=methanesulfonyl, Piv=pivalate, Ts=4-toluenesulfonyl.

    8. Cross-Coupling

      Palladium-Catalyzed Oxidative Difunctionalization of Alkenes with α-Carbonyl Alkyl Bromides Initiated through a Heck-type Insertion: A Route to Indolin-2-ones (pages 6650–6654)

      Jian-Hong Fan, Wen-Ting Wei, Ming-Bo Zhou, Dr. Ren-Jie Song and Prof. Dr. Jin-Heng Li

      Article first published online: 21 MAY 2014 | DOI: 10.1002/anie.201402893

      Thumbnail image of graphical abstract

      Indolinone synthesis: A new palladium-catalyzed oxidative difunctionalization reaction of N-arylalkenes with primary, secondary, and tertiary α-carbonyl alkyl bromides proceeds through a radical process and provides indolin-2-ones in moderate to excellent yields. The reaction is initiated by a Heck insertion followed by interception of the σ-alkyl palladium(II) intermediate with aryl C(sp2)[BOND]H bonds. dppe=1,2-bis(diphenylphosphino)ethane.

    9. Detecting H2O2 from Mitochondria

      Electrochemical Monitoring of the Early Events of Hydrogen Peroxide Production by Mitochondria (pages 6655–6658)

      Dr. Emmanuel Suraniti, Salem Ben-Amor, Pauline Landry, Prof. Michel Rigoulet, Prof. Eric Fontaine, Prof. Serge Bottari, Dr. Anne Devin, Prof. Neso Sojic, Dr. Nicolas Mano and Dr. Stéphane Arbault

      Article first published online: 22 MAY 2014 | DOI: 10.1002/anie.201403096

      Thumbnail image of graphical abstract

      Ultrasensitive biosensors for H2O2 (1 nM limit of detection) have been developed based on peroxidase-redox polymer modified carbon electrodes (see figure; Os= polymer-bound osmium complex). They allow the monitoring of several regimes of H2O2 release by mitochondria. In particular, unprecedented nanomolar-amplitude bursts of H2O2 have been detected. The results offer opportunities to study the role of mitochondria as a hub of redox signaling in cells.

    10. Oxygen Reduction

      Covalent Grafting of Carbon Nanotubes with a Biomimetic Heme Model Compound To Enhance Oxygen Reduction Reactions (pages 6659–6663)

      Dr. Ping-Jie Wei, Guo-Qiang Yu, Prof.Dr. Yoshinori Naruta and Prof.Dr. Jin-Gang Liu

      Article first published online: 19 MAY 2014 | DOI: 10.1002/anie.201403133

      Thumbnail image of graphical abstract

      Bio-inspired catalyst defeats Pt: A biomimetic electrocatalyst for the oxygen reduction reaction (ORR) has been covalently grafted onto multiwalled carbon nanotubes. Without pyrolysis, this bio-inspired catalyst, in which an axial imidazole-coordinated porphyrin mimics the active site of O2-activating heme-containing enzymes, shows superior ORR activity and stability compared to the state-of-the-art Pt/C catalyst in both acidic and alkaline solutions.

    11. Energy Conversion

      A Twisted Wire-Shaped Dual-Function Energy Device for Photoelectric Conversion and Electrochemical Storage (pages 6664–6668)

      Hao Sun, Xiao You, Jue Deng, Xuli Chen, Zhibin Yang, Peining Chen, Xin Fang and Prof. Huisheng Peng

      Article first published online: 16 APR 2014 | DOI: 10.1002/anie.201403168

      Thumbnail image of graphical abstract

      Twisted: A wire-shaped energy device that can perform photoelectric conversion and electrochemical storage was developed through a simple but effective twisting process. The energy wire exhibited a high energy conversion efficiency of 6.58 % and specific capacitance of 85.03 μF cm−1 or 2.13 mF cm−2, and the two functions were alternately realized without sacrificing either performance.

    12. Oxygen Reduction

      Dramatic Increase in the Oxygen Reduction Reaction for Platinum Cathodes from Tuning the Solvent Dielectric Constant (pages 6669–6672)

      Alessandro Fortunelli, William A. Goddard, Yao Sha, Ted H. Yu, Luca Sementa, Giovanni Barcaro and Oliviero Andreussi

      Article first published online: 14 MAY 2014 | DOI: 10.1002/anie.201403264

      Thumbnail image of graphical abstract

      Hydrogen fuel cell: The oxygen reduction reaction (ORR) kinetics can be strongly accelerated by changing the solvent and its dielectric constant, a possibly general effect in electrochemical systems. The influence of the solvent dielectric constant on the reaction barriers of the ORR is studied by density functional theory (see picture).

    13. Asymmetric Catalysis

      Rhodium-Catalyzed Asymmetric Arylation of β,γ-Unsaturated α-Ketoamides for the Construction of Nonracemic γ,γ-Diarylcarbonyl Compounds (pages 6673–6677)

      Dr. Juanjuan Wang, Dr. Min Wang, Prof. Dr. Peng Cao, Liyin Jiang, Dr. Guihua Chen and Prof. Dr. Jian Liao

      Article first published online: 18 MAY 2014 | DOI: 10.1002/anie.201403325

      Thumbnail image of graphical abstract

      Constructing chiral carbonyls: A simple new chiral sulfinylphosphine ligand L was developed, which promoted excellent 1,4-selectivities and enantioselectivities in the rhodium-catalyzed conjugate addition of arylboronic acids to β,γ-unsaturated α-ketoamides. The desired γ,γ-diaryl-α-ketocarbonyl compounds were afforded with high yields and high optical purities.

    14. Antiaromaticity

      Reversible Redox Reaction Between Antiaromatic and Aromatic States of 32π-Expanded Isophlorins (pages 6678–6682)

      Tullimilli Y. Gopalakrishna and Prof. Dr. Venkataramanarao G. Anand

      Article first published online: 14 MAY 2014 | DOI: 10.1002/anie.201403372

      Thumbnail image of graphical abstract

      Pi redox: Expanded isophlorins can undergo reversible two-electron redox reactions to interconvert between 32π-antiaromatic and 30π-aromatic states. trifluoroacetic acid, Et3O+SbCl6, or NOBF4 and triethylamine, zinc, or FeCl2 can be employed as oxidizing and reducing agents, respectively. This reversible redox process can also regulate the topology between a figure-eight and planar conformation.

    15. Polymerization | Very Important Paper

      Polymerization of Ethylene through Reversible Addition–Fragmentation Chain Transfer (RAFT) (pages 6683–6686)

      Dr. Cédric Dommanget, Dr. Franck D'Agosto and Dr. Vincent Monteil

      Article first published online: 22 MAY 2014 | DOI: 10.1002/anie.201403491

      Thumbnail image of graphical abstract

      Controlled growth: Xanthates were employed as controlling agents in the radical polymerization of ethylene (see scheme). The reversible addition–fragmentation chain-transfer technique proceeds under relatively mild reaction conditions (T = 70 °C, P = 200 bar). AIBN=2,2′-azobisisobutyronitrile.

    16. Enzymatic Synthesis

      Synthetic Disialyl Hexasaccharides Protect Neonatal Rats from Necrotizing Enterocolitis (pages 6687–6691)

      Dr. Hai Yu, Kam Lau, Dr. Vireak Thon, Chloe A. Autran, Dr. Evelyn Jantscher-Krenn, Mengyang Xue, Dr. Yanhong Li, Dr. Go Sugiarto, Dr. Jingyao Qu, Shengmao Mu, Dr. Li Ding, Prof. Dr. Lars Bode and Prof. Dr. Xi Chen

      Article first published online: 21 MAY 2014 | DOI: 10.1002/anie.201403588

      Thumbnail image of graphical abstract

      Sweet protection: Two novel synthetic disialyl hexaoses obtained by highly efficient one-pot multienzyme (OPME) reactions were shown to protect neonatal rats from necrotizing enterocolitis (see scheme; GlcNAC: N-acetylglucosamine; Gal: galactose; Neu5Ac: N-acetylneuraminic acid; DSLNnT: disialyllacto-N-neotetraose; LNT: lacto-N-tetraose; DS'LNT: α2—6-linked disialyllacto-N-tetraose).

    17. Cascade C-H Activation | Hot Paper

      Ligand-Enabled Triple C[BOND]H Activation Reactions: One-Pot Synthesis of Diverse 4-Aryl-2-quinolinones from Propionamides (pages 6692–6695)

      Dr. Youqian Deng, Dr. Wei Gong, Jian He and Prof. Dr. Jin-Quan Yu

      Article first published online: 14 MAY 2014 | DOI: 10.1002/anie.201403878

      Thumbnail image of graphical abstract

      Building complexity: Diverse 4-aryl-2-quinolinones such as 1 are prepared from propionamides in one pot by pyridine ligand-promoted triple sequential C[BOND]H activation reactions and a stereospecific Heck reaction. In these cascade reactions, three new C[BOND]C bonds and one C[BOND]N bond are formed to rapidly build molecular complexity from propionic acid.

    18. Metal–Ligand Multiple Bonds

      You have full text access to this OnlineOpen article
      Synthesis, Characterization, and Reactivity of a Uranium(VI) Carbene Imido Oxo Complex (pages 6696–6700)

      Dr. Erli Lu, Dr. Oliver J. Cooper, Dr. Jonathan McMaster, Dr. Floriana Tuna, Prof. Eric J. L. McInnes, Dr. William Lewis, Prof. Alexander J. Blake and Prof. Stephen T. Liddle

      Article first published online: 19 MAY 2014 | DOI: 10.1002/anie.201403892

      Thumbnail image of graphical abstract

      Three not of a kind: An unprecedented arrangement of three formal multiply bonded ligands to one metal center, where the coordinated heteroatoms derive from different element groups, is found in the uranium(VI) carbene imido oxo complex [U(BIPMTMS)(NMes)(O)(DMAP)2] (Mes=2,4,6-Me3C6H2).

    19. Total Synthesis

      Total Syntheses of Hyperforin and Papuaforins A–C, and Formal Synthesis of Nemorosone through a Gold(I)-Catalyzed Carbocyclization (pages 6701–6704)

      Gabriel Bellavance and Prof. Louis Barriault

      Article first published online: 18 MAY 2014 | DOI: 10.1002/anie.201403939

      Thumbnail image of graphical abstract

      Five gold rings: The concise total syntheses of the polyprenylated polycyclic acylphloroglucinols (PPAPs) hyperforin and papuaforins A–C, and the formal synthesis of nemorosone have been realized in 17 steps. Key to the realization of these syntheses is the short and scalable assembly of densely substituted PPAP scaffolds through a gold(I)-catalyzed 6-endo-dig carbocyclization of cyclic silylenol ethers.

    20. Heterogeneous Catalysis

      Molybdenum Carbide as Alternative Catalysts to Precious Metals for Highly Selective Reduction of CO2 to CO (pages 6705–6709)

      Marc D. Porosoff, Dr. Xiaofang Yang, Dr. J. Anibal Boscoboinik and Prof. Dr. Jingguang G. Chen

      Article first published online: 19 MAY 2014 | DOI: 10.1002/anie.201404109

      Thumbnail image of graphical abstract

      Active, selective, and cheap: Mo2C and cobalt-modified Mo2C were both shown to be effective catalysts for CO2 conversion by hydrogen in flow reactor experiments over powder catalysts. In-situ XANES measurements verified that Mo2C can undergo an oxidation-carburization cycle. Modifying Mo2C with small amounts of cobalt further improved catalytic performance.

    21. Hydrogen-Evolution Catalysts

      Carbon Nanotubes Decorated with CoP Nanocrystals: A Highly Active Non-Noble-Metal Nanohybrid Electrocatalyst for Hydrogen Evolution (pages 6710–6714)

      Qian Liu, Dr. Jingqi Tian, Wei Cui, Dr. Ping Jiang, Ningyan Cheng, Prof. Abdullah M. Asiri and Prof. Xuping Sun

      Article first published online: 20 MAY 2014 | DOI: 10.1002/anie.201404161

      Thumbnail image of graphical abstract

      A nanohybrid that consists of carbon nanotubes decorated with CoP nanocrystals (CoP/CNT) was prepared by the low-temperature phosphidation of a Co3O4/CNT precursor. As a novel non-noble-metal hydrogen-evolution electrocatalyst that operates in acidic media, this nanohybrid exhibits an onset overpotential of only 40 mV and maintained its catalytic activity for at least 18 hours.

    22. Photophysics

      Excited-State Dynamics of Pentacene Derivatives with Stable Radical Substituents (pages 6715–6719)

      Dr. Akitaka Ito, Akihiro Shimizu, Noriaki Kishida, Yusuke Kawanaka, Dr. Daisuke Kosumi, Prof. Dr. Hideki Hashimoto and Prof. Dr. Yoshio Teki

      Article first published online: 30 APR 2014 | DOI: 10.1002/anie.201310291

      Thumbnail image of graphical abstract

      The state of play: Enhanced intersystem crossing (ISC) and singlet fission have been shown to occur in pentacene (Pn) derivatives with stable radical substituents. These effects result in the ultrafast formation of a triplet excited state in the pentacene moiety from a photoexcited singlet state, even in dilute solution. The excited-state dynamics of the derivatives were evaluated in detail through transient absorption measurements.

    23. Molecular Switches | Very Important Paper

      A Rapidly Reversible Chemical Dimerizer System to Study Lipid Signaling in Living Cells (pages 6720–6723)

      Suihan Feng, Dr. Vibor Laketa, Frank Stein, Dr. Anna Rutkowska, Dr. Aidan MacNamara, Dr. Sofia Depner, Prof. Ursula Klingmüller, Dr. Julio Saez-Rodriguez and Priv.-Doz. Dr. Carsten Schultz

      Article first published online: 19 MAY 2014 | DOI: 10.1002/anie.201402294

      Thumbnail image of graphical abstract

      Little helper: Chemical dimerizers are powerful tools for manipulation of enzyme activities in intact cells. The first rapidly reversible chemical dimerization system is introduced, which permits to determine kinetics of lipid metabolizing enzymes in living cells. This new method was applied to induce and stop phosphatidylinositol 3-kinase activity, allowing to quantitatively measure 3,4,5-trisphosphate turnover.

    24. Coordination Distortion

      A Displacive-Type Metal Crown Ether Ferroelectric Compound: Ca(NO3)2(15-crown-5) (pages 6724–6729)

      Dr. Heng-Yun Ye, Dr. Yi Zhang, Dr. Da-Wei Fu and Prof. Ren-Gen Xiong

      Article first published online: 20 MAY 2014 | DOI: 10.1002/anie.201402339

      Thumbnail image of graphical abstract

      Following the Curie symmetry principle and Aizu rule, it was discovered there is a paraelectric-to-ferroelectric phase transition in Ca(NO3)2(15-crown-5) at Tc=205 K, which was confirmed by calorimetry and second harmonic generation measurements. The ferroelectric mechanism is attributable to distortion of the coordination of the central Ca atom.

    25. Single-Cell Proteomics

      Single-Cell Chemical Proteomics with an Activity-Based Probe: Identification of Low-Copy Membrane Proteins on Primary Neurons (pages 6730–6733)

      Fei Xu, Han Zhao, Dr. Xiaojun Feng, Dr. Linhai Chen, Dongjuan Chen, Yang Zhang, Prof. Fajun Nan, Prof. Jianfeng Liu and Prof. Bi-Feng Liu

      Article first published online: 21 MAY 2014 | DOI: 10.1002/anie.201402363

      Thumbnail image of graphical abstract

      Singles only: A single-cell chemical proteomics strategy with an activity-based probe (ABP) enables observation of low-abundance membrane receptors at the single-cell level by discriminating them from the whole proteome. The strategy avoids problems associated with cytometry-based techniques, and could be used to identify low-copy receptors on the primary neurons of animals.

    26. Photocaged DNA

      Polymerase Synthesis of Photocaged DNA Resistant against Cleavage by Restriction Endonucleases (pages 6734–6737)

      Zuzana Vaníková and Prof. Dr. Michal Hocek

      Article first published online: 21 MAY 2014 | DOI: 10.1002/anie.201402370

      Thumbnail image of graphical abstract

      Stability: A modified nucleoside triphosphate is incorporated into DNA sequences using polymerase. The resulting photocaged DNA is resistant against cleavage by restriction endonucleases (REs) and fully replicable by polymerase chain reaction (PCR) or primer extension (PEX).

    27. Photoreconstructions

      Following a Photoinduced Reconstructive Phase Transformation and its Influence on the Crystal Integrity: Powder Diffraction and Theoretical Study (pages 6738–6742)

      Tomče Runčevski, Dr. Marina Blanco-Lomas, Dr. Marco Marazzi, Marcos Cejuela, Dr. Diego Sampedro and Prof. Robert E. Dinnebier

      Article first published online: 21 MAY 2014 | DOI: 10.1002/anie.201402515

      Thumbnail image of graphical abstract

      Changing phases: In the course of solid-state photoreactions, the single crystal of a reactant can be transformed into a single crystal of the product or it can become amorphous. Between these scenarios exist the reconstructive phase transformations, where the single crystal becomes a powder. A detailed description of the latter is given.

    28. Nanostructures

      Photocatalytic Au–Bi2S3 Heteronanostructures (pages 6743–6746)

      Goutam Manna, Riya Bose and Dr. Narayan Pradhan

      Article first published online: 20 MAY 2014 | DOI: 10.1002/anie.201402709

      Thumbnail image of graphical abstract

      Promising returns of gold on the side: In a designed Au–Bi2S3 heteronanostructure photocatalyst, Au nanoparticles were located at the center of the semiconductor nanorods (see picture), rather than at the tip, as usually reported. These nanostructures were found to be efficient visible-light photocatalysts and to have excellent photocurrent and photoresponse properties.

    29. Natural Product Synthesis | Very Important Paper

      Harnessing Quinone Methides: Total Synthesis of (±)-Vaticanol A (pages 6747–6751)

      Tue H. Jepsen, Stephen B. Thomas, Yunqing Lin, Dr. Christos I. Stathakis, Irene de Miguel and Prof. Dr. Scott A. Snyder

      Article first published online: 19 MAY 2014 | DOI: 10.1002/anie.201402858

      Thumbnail image of graphical abstract

      Three's Company: The resveratrol trimer vaticanol A, along with a number of diastereomeric congeners, has been synthesized for the first time through an effective strategy utilizing three reactive quinone methide intermediates to forge three critical bonds (highlighted in pink). These events, one of which succeeded only under very specific conditions, expediently generated its [7,5]-carbocyclic core and afforded a unique sequence for dihydrobenzofuran formation.

    30. Anticancer Drugs

      Immuno-Chemotherapeutic Platinum(IV) Prodrugs of Cisplatin as Multimodal Anticancer Agents (pages 6752–6756)

      Daniel Yuan Qiang Wong, Charmian Hui Fang Yeo and Prof. Wee Han Ang

      Article first published online: 20 MAY 2014 | DOI: 10.1002/anie.201402879

      Thumbnail image of graphical abstract

      Two-pronged attack: A cisplatin prodrug was developed with the ability to induce cancer cell death through two distinct pathways, targeted direct cytotoxicity and activation of innate immune cells for cell-mediated cytotoxicity, to realize the concept of a multimodal immuno-chemotherapeutic approach (see figure; m: D-Met).

    31. Phosphorus Heterocycles

      Redox-Triggered Reversible Interconversion of a Monocyclic and a Bicyclic Phosphorus Heterocycle (pages 6757–6761)

      Dr. Dominikus Heift, Dr. Zoltán Benkő and Prof. Dr. Hansjörg Grützmacher

      Article first published online: 19 MAY 2014 | DOI: 10.1002/anie.201402884

      Thumbnail image of graphical abstract

      Turning a negative into a positive: The fully reversible conversion between an anionic six-membered phosphorus–nitrogen heterocycle and a bicyclic diazaphospholenium cation as stable redox states leads to an “umpolung” of the electronic properties which is of interest for smart materials.

    32. Rotaxanes

      Small-Molecule Recognition for Controlling Molecular Motion in Hydrogen-Bond-Assembled Rotaxanes (pages 6762–6767)

      Dr. Alberto Martinez-Cuezva, Dr. Jose Berna, Dr. Raul-Angel Orenes, Dr. Aurelia Pastor and Prof. Dr. Mateo Alajarin

      Article first published online: 20 MAY 2014 | DOI: 10.1002/anie.201402962

      Thumbnail image of graphical abstract

      A “narcotic” effect of barbital on the Brownian motion of novel [2]rotaxanes with two di(acylamino)pyridine binding sites was observed: The establishment of hydrogen-bond arrays with barbital caused dynamic restraint of the ring shuttling (see picture). The original translational motion was reestablished by a competitive recognition event with an external barbital binder.

    33. DNA Replication

      You have full text access to this OnlineOpen article
      Loading Dynamics of a Sliding DNA Clamp (pages 6768–6771)

      Dr. Won-Ki Cho, Dr. Slobodan Jergic, Daehyung Kim, Prof. Nicholas E. Dixon and Prof. Jong-Bong Lee

      Article first published online: 22 MAY 2014 | DOI: 10.1002/anie.201403063

      Thumbnail image of graphical abstract

      When one clamp closes… Single-molecule Förster resonance energy transfer and single-molecule fluorescence polarization were used to monitor the loading of a sliding DNA clamp onto double-stranded DNA by the clamp loader (see picture). Thus, the dynamic features of a DNA clamp in the DNA/DNA-clamp/clamp-loader ternary complex were revealed.

    34. Targeted Cell Ablation

      Selective Ablation of β-Galactosidase-Expressing Cells with a Rationally Designed Activatable Photosensitizer (pages 6772–6775)

      Dr. Yuki Ichikawa, Dr. Mako Kamiya, Dr. Fumiaki Obata, Prof. Masayuki Miura, Dr. Takuya Terai, Dr. Toru Komatsu, Dr. Tasuku Ueno, Dr. Kenjiro Hanaoka, Prof. Tetsuo Nagano and Prof. Yasuteru Urano

      Article first published online: 21 MAY 2014 | DOI: 10.1002/anie.201403221

      Thumbnail image of graphical abstract

      Bull's eye! An activatable photosensitizer capable of specifically inducing the death of β-galactosidase-expressing cells in response to light irradiation was developed. Reaction with the enzyme resulted in a dynamic structural change to the phototoxic open form (see scheme), thus enabling the specific ablation of cells of interest in living tissues.

    35. Homogeneous Catalysis

      Palladium-Catalyzed Allylic Alkylation of Simple Ketones with Allylic Alcohols and Its Mechanistic Study (pages 6776–6780)

      Xiaohong Huo, Dr. Guoqiang Yang, Prof. Delong Liu, Prof. Yangang Liu, Prof. Ilya D. Gridnev and Prof. Wanbin Zhang

      Article first published online: 21 MAY 2014 | DOI: 10.1002/anie.201403410

      Thumbnail image of graphical abstract

      Concerted action: Allylic alcohols were directly used in the title reaction under mild conditions. The reaction smoothly proceeds by the concerted action of a Pd catalyst, a pyrrolidine co-catalyst, and a hydrogen-bonding solvent, and does not require any additional reagents. A computational study suggested that methanol plays a crucial role in the formation of the π-allylpalladium complex by lowering the activation barrier.

    36. Dynamic Covalent Bonds | Hot Paper

      Dynamic Diselenide Bonds: Exchange Reaction Induced by Visible Light without Catalysis (pages 6781–6785)

      Shaobo Ji, Wei Cao, Ying Yu and Prof. Huaping Xu

      Article first published online: 19 MAY 2014 | DOI: 10.1002/anie.201403442

      Thumbnail image of graphical abstract

      Diselenide bonds are dynamic covalent bonds. Their metathesis can be induced by irradiation with visible light and likely proceeds through a radical mechanism, as the exchange reaction between two different diselenides was suppressed by the addition of the radical scavenger 2,2,6,6-tetramethylpiperidine N-oxide (TEMPO).

    37. Conjugated Polycycles

      Heptagon-Embedded Pentacene: Synthesis, Structures, and Thin-Film Transistors of Dibenzo[d,d′]benzo[1,2-a:4,5-a′]dicycloheptenes (pages 6786–6790)

      Xuejin Yang, Danqing Liu and Prof. Qian Miao

      Article first published online: 20 MAY 2014 | DOI: 10.1002/anie.201403509

      Thumbnail image of graphical abstract

      All sixes and sevens: A new class of conjugated polycyclic molecules have a nearly flat C6-C7-C6-C7-C6 polycyclic framework with a p-quinodimethane core. With a field-effect mobility of up to 0.76 cm2 V−1 s−1 as measured from solution-processed thin-film transistors, these molecules are alternatives to the pentacene analogues for application in organic electronic devices.

    38. C[BOND]O Activation

      Nickel-Catalyzed α-Arylation of Ketones with Phenol Derivatives (pages 6791–6794)

      Ryosuke Takise, Kei Muto, Prof. Dr. Junichiro Yamaguchi and Prof. Dr. Kenichiro Itami

      Article first published online: 20 MAY 2014 | DOI: 10.1002/anie.201403823

      Thumbnail image of graphical abstract

      The nickel-catalyzed α-arylation of ketones with readily available phenol derivatives (esters and carbamates) provides access to useful α-arylketones. The use of 3,4-bis(dicyclohexylphosphino)thiophene (dcypt) as an air-stable ligand enables this transformation. The intermediate of an assumed C[BOND]O oxidative addition was isolated and characterized by X-ray crystal-structure analysis.

    39. BN Heterocycles

      Monobenzofused 1,4-Azaborines: Synthesis, Characterization, and Discovery of a Unique Coordination Mode (pages 6795–6799)

      Dr. Senmiao Xu, Dr. Fredrik Haeffner, Dr. Bo Li, Dr. Lev N. Zakharov and Prof. Dr. Shih-Yuan Liu

      Article first published online: 18 MAY 2014 | DOI: 10.1002/anie.201403903

      Thumbnail image of graphical abstract

      Breaking N-BC News: The first general synthesis of boron-substituted monobenzofused 1,4-azaborines has been developed. As part of the synthetic investigations, a unique κ2-N2-BC coordination mode was discovered and investigated.

    40. Chemicals from Algae | Hot Paper

      Synthetic Polyester from Algae Oil (pages 6800–6804)

      M. Sc. Philipp Roesle, M. Sc. Florian Stempfle, B. Sc. Sandra K. Hess, B. Sc. Julia Zimmerer, Dr. Carolina Río Bártulos, Dr. Bernard Lepetit, Angelika Eckert, Prof. Dr. Peter G. Kroth and Prof. Dr. Stefan Mecking

      Article first published online: 20 MAY 2014 | DOI: 10.1002/anie.201403991

      Thumbnail image of graphical abstract

      Algae as feedstock: Crude algae oil from the strain Phaeodactylum tricornutum was transformed into polycondensation-grade purity monomers and thus utilized as feedstock for the production of an algae oil based polyester.

    41. Synthetic Methods

      Direct Assembly of 3,4-Difunctionalized Benzofurans and Polycyclic Benzofurans by Phenol Dearomatization and Palladium-Catalyzed Domino Reaction (pages 6805–6809)

      Zhaomeng Han, Liang Zhang, Prof. Dr. Zhiming Li and Prof. Dr. Renhua Fan

      Article first published online: 20 MAY 2014 | DOI: 10.1002/anie.201404155

      Thumbnail image of graphical abstract

      Destruction and reconstruction: The combination of a hypervalent-iodine-mediated oxidative dearomatization and palladium-catalyzed domino reaction provides a practical approach to 3,4-difunctionalized benzofurans and polycyclic benzofurans from 2-alkynylphenols.

    42. Biocatalysis | Hot Paper

      Improved Cyclopropanation Activity of Histidine-Ligated Cytochrome P450 Enables the Enantioselective Formal Synthesis of Levomilnacipran (pages 6810–6813)

      Dr. Z. Jane Wang, Dr. Hans Renata, Nicole E. Peck, Christopher C. Farwell, Dr. Pedro S. Coelho and Prof. Dr. Frances H. Arnold

      Article first published online: 6 MAY 2014 | DOI: 10.1002/anie.201402809

      Thumbnail image of graphical abstract

      Old cytochrome, new tricks: Mutation of the proximal Cys residue in the cytochrome P450 enzyme from Bacillus megaterium (P450-BM3) leads to highly active, oxygen tolerant, and enantioselective catalysts for the cyclopropanation of N,N-diethyl-2-phenylacrylamide. Directed evolution of a histidine-ligated P450-BM3 enabled the enantioselective formal synthesis of levomilnacipran.

    43. Rhodium–Nitridyl Complex | Hot Paper

      An Isolated Nitridyl Radical-Bridged {Rh(N.)Rh} Complex (pages 6814–6818)

      Dr. Yann Gloaguen, Christophe Rebreyend, Dr. Martin Lutz, Pravin Kumar, Dr. Martina Huber, Dr. Ir. Jarl Ivar van der Vlugt, Prof. Dr. Sven Schneider and Prof. Dr. Bas de Bruin

      Article first published online: 19 MAY 2014 | DOI: 10.1002/anie.201403445

      Thumbnail image of graphical abstract

      The first isolated nitridyl radical (.N2−) complex was obtained by photochemical activation of the rhodium–azide complex [(PNNH)Rh(N3)] (1), producing N2, H2, and the paramagnetic complex 2. Complex 2 reacts selectively with CO to produce complex 3, presumably by N,N-coupling of nitridyl radicals.

    44. Electrochemical CO2 Capture

      You have full text access to this OnlineOpen article
      Direct Electrochemical Capture and Release of Carbon Dioxide Using an Industrial Organic Pigment: Quinacridone (pages 6819–6822)

      Dogukan Hazar Apaydin, Dr. Eric Daniel Głowacki, Dr. Engelbert Portenkirchner and Prof. Niyazi Serdar Sariciftci

      Article first published online: 21 MAY 2014 | DOI: 10.1002/anie.201403618

      Thumbnail image of graphical abstract

      Capture and release: The established industrial colorant quinacridone reacts with CO2 following electrochemical reduction, with an uptake efficiency of 4.6 mmol CO2/g quinacridone at room temperature. The CO2 can be released by electrochemical oxidation.

    45. BaTiO3 Aerogels

      Assembly of BaTiO3 Nanocrystals into Macroscopic Aerogel Monoliths with High Surface Area (pages 6823–6826)

      Felix Rechberger, Florian J. Heiligtag, Martin J. Süess and Prof. Dr. Markus Niederberger

      Article first published online: 22 MAY 2014 | DOI: 10.1002/anie.201402164

      Thumbnail image of graphical abstract

      Bridging length scales: A powerful strategy of assembling surface-functionalized nanocrystalline BaTiO3 particles into a highly porous macroscopic framework is presented. After supercritical drying, the obtained structures show a large surface area and a low density. By starting off with functional building blocks on the nanoscale and ending with a body in the centimeter range, over seven orders of magnitude in length scales are addressed.

SEARCH

SEARCH BY CITATION