Angewandte Chemie International Edition

Cover image for Vol. 52 Issue 27

July 1, 2013

Volume 52, Issue 27

Pages 6787–7041

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Flashback
    5. News
    6. Author Profile
    7. News
    8. Highlight
    9. Review
    10. Communications
    1. You have free access to this content
      Cover Picture: Organocatalysis by Neutral Multidentate Halogen-Bond Donors (Angew. Chem. Int. Ed. 27/2013) (page 6787)

      Florian Kniep, Stefan H. Jungbauer, Qi Zhang, Sebastian M. Walter, Severin Schindler, Ingo Schnapperelle, Dr. Eberhardt Herdtweck and Dr. Stefan M. Huber

      Version of Record online: 5 JUN 2013 | DOI: 10.1002/anie.201304261

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      Neutral multidentate halogen-bond donors (halogen-based Lewis acids) can be used as organocatalysts in a halide abstraction reaction. In their Communication on page 7028 ff., S. M. Huber et al. describe the halogen-bond-catalyzed reaction of 1-chloroisochroman with ketene silyl acetals. The organocatalytic activity crucially depends on the iodine substituents of the halogen-bond donors, and hidden acid catalysts can be ruled out with high probability.

    2. You have free access to this content
      Inside Cover: Stereoselective Rearrangements with Chiral Hypervalent Iodine Reagents (Angew. Chem. Int. Ed. 27/2013) (page 6788)

      Umar Farid, Florence Malmedy, Romain Claveau, Lena Albers and Prof. Dr. Thomas Wirth

      Version of Record online: 31 MAY 2013 | DOI: 10.1002/anie.201304229

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      Iodine has made a long journey from being a table salt additive to the key element in efficient chiral reagents. In their Communication on page 7018 ff. T. Wirth and co-workers describe the utilization of such reagents in stereoselective oxidative rearrangements of alkenes. For the first time, rearrangements to α-arylated ketones can be performed in high enantioselectivities using chiral hypervalent iodine reagents based on lactic acid.

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      Inside Back Cover: Ultrafast Solvent-Assisted Electronic Level Crossing in 1-Naphthol (Angew. Chem. Int. Ed. 27/2013) (page 7043)

      Dr. Fabrizio Messina, Mirabelle Prémont-Schwarz, Dr. Olivier Braem, Dr. Dequan Xiao, Prof. Victor S. Batista, Dr. Erik T. J. Nibbering and Prof. Majed Chergui

      Version of Record online: 6 JUN 2013 | DOI: 10.1002/anie.201304256

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      Photoacidic properties of the prototypical molecule 1-naphthol have long been claimed to involve an inversion between the two first-excited singlet states, controlled by the polarity of the solvent. In their Communication on page 6871 ff., E. T. J. Nibbering, M. Chergui, et al. address the non-adiabatic excited-state dynamics of 1-naphthol with femtosecond time resolution and report the first direct experimental observation of the ultrafast level inversion.

    4. You have free access to this content
      Back Cover: Mix to Validate: A Facile, Reversible PEGylation for Fast Screening of Potential Therapeutic Proteins In Vivo (Angew. Chem. Int. Ed. 27/2013) (page 7044)

      Dr. Tae Hyung Kim, Dr. Magdalena Swierczewska, Dr. Yumin Oh, Dr. AeRyon Kim, Prof. Dr. Dong Gyu Jo, Prof. Dr. Jae Hyung Park, Prof. Dr. Youngro Byun, Prof. Dr. Scheherazade Sadegh-Nasseri, Prof. Dr. Martin G. Pomper, Prof. Dr. Kang Choon Lee and Prof. Dr. Seulki Lee

      Version of Record online: 6 JUN 2013 | DOI: 10.1002/anie.201304233

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      Increasing the half-life of therapeutic proteins in a specific, fast, and reliable way could greatly benefit the discovery of novel protein drugs. In their Communication on page 6880 ff., K. C. Lee, S. Lee, and co-workers conjugate Ni-NTA to poly(ethylene glycol) and then label oligohistidine-tagged therapeutic proteins to improve their stability in vivo without compromising bioactivity.

  2. Graphical Abstract

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

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Flashback
    5. News
    6. Author Profile
    7. News
    8. Highlight
    9. Review
    10. Communications
    1. 50 Years Ago ... (page 6802)

      Version of Record online: 21 JUN 2013 | DOI: 10.1002/anie.201303901

      Angewandte Chemie International Edition was first published in 1962, the mother journal first in 1888. In this monthly flashback, we feature some of the articles that appeared 50 years ago. This look back can open our eyes, stimulate discussion, or even raise a smile.

  4. News

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    9. Review
    10. Communications
  5. Author Profile

    1. Top of page
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    7. News
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    10. Communications
    1. Jieping Zhu (pages 6812–6813)

      Version of Record online: 5 FEB 2013 | DOI: 10.1002/anie.201210061

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      “I can never resist a delicious French dessert. My biggest motivation is to learn something new every day …” This and more about Jieping Zhu can be found on page 6812.

  6. News

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    3. Graphical Abstract
    4. Flashback
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    7. News
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    10. Communications
  7. Highlight

    1. Top of page
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    3. Graphical Abstract
    4. Flashback
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    7. News
    8. Highlight
    9. Review
    10. Communications
    1. Trifluoromethylthiolation

      Formation of C[BOND]SCF3 Bonds through Direct Trifluoromethylthiolation (pages 6818–6819)

      Dr. Anis Tlili and Dr. Thierry Billard

      Version of Record online: 9 MAY 2013 | DOI: 10.1002/anie.201301438

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      Modern chemistry with an old substituent: The introduction of the SCF3 group into organic substrates is a challenging task because of harsh or specific synthetic methods. However, recent advances in the formation of C[BOND]SCF3 bonds include the trifluoromethylthiolation with transition-metal-free systems or in the presence of palladium, nickel, or copper catalysts (see scheme).

  8. Review

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    10. Communications
    1. Non-natural Translation

      Reactions Templated by Nucleic Acids: More Ways to Translate Oligonucleotide-Based Instructions into Emerging Function (pages 6820–6843)

      Dr. Katarzyna Gorska and Prof. Nicolas Winssinger

      Version of Record online: 12 JUN 2013 | DOI: 10.1002/anie.201208460

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      Not lost in translation: The programmability of oligonucleotide recognition offers an attractive platform to direct the assembly of reactive partners so that a functional output is achieved. Recent progress in the type of transformations and their applications (such as the translation of oligonucleotide information in functional materials and novel architectures, bioactivity, or fluorescence) are summarized.

  9. Communications

    1. Top of page
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    3. Graphical Abstract
    4. Flashback
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    9. Review
    10. Communications
    1. Photochemistry

      Fabrication of Complex Three-Dimensional Polymer Brush Nanostructures through Light-Mediated Living Radical Polymerization (pages 6844–6848)

      Justin E. Poelma, Dr. Brett P. Fors, Dr. Gregory F. Meyers, Dr. John W. Kramer and Prof. Craig J. Hawker

      Version of Record online: 3 JUN 2013 | DOI: 10.1002/anie.201301845

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      A facile approach to unique 3D, patterned polymer brushes is based on visible-light-mediated controlled radical polymerization. The temporal and spatial control of the polymerization allows the patterning of polymer brushes from a uniform initiating layer using a simple photomask (see picture). Furthermore, gradient polymer brushes, patterned block copolymers, and complex 3D structures can be obtained by modulating light intensity.

    2. Host–Guest Systems

      Guest-Induced Unidirectional Dual Rotary and Twisting Motions of a Spiroborate-Based Double-Stranded Helicate Containing a Bisporphyrin Unit (pages 6849–6853)

      Shinya Yamamoto, Dr. Hiroki Iida and Prof. Dr. Eiji Yashima

      Version of Record online: 28 MAY 2013 | DOI: 10.1002/anie.201302560

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      Influential guests: The intercalation of an electron-deficient aromatic guest (shown in red) between the two porphyrin rings of an optically active, porphyrin-linked double-stranded spiroborate helicate triggered rotary motion of the porphyrin rings in one direction in conjunction with a unidirectional twisting motion of the spiroborate helix. This system has potential for the development of chirality-responsive molecular machines.

    3. DNA Nanocapsules

      Controlled Release of Encapsulated Cargo from a DNA Icosahedron using a Chemical Trigger (pages 6854–6857)

      Anusuya Banerjee, Dhiraj Bhatia, Anand Saminathan, Saikat Chakraborty, Shaunak Kar and Dr. Yamuna Krishnan

      Version of Record online: 28 MAY 2013 | DOI: 10.1002/anie.201302759

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      DNA Trojan horse: A DNA icosahedron (black, see scheme) held together with aptamers (red) was used to encapsulate molecular cargo such as fluorescent dextran (green). In the presence of a molecular trigger (gray hexagons), the aptamers fold back leading to opening of the icosahedron and simultaneous release of the encapsulated cargo.

    4. Nanostructures

      Synthesis of Enantiopure Carbonaceous Nanotubes with Optical Activity (pages 6858–6862)

      Shaohua Liu, Yingying Duan, Xuejiao Feng, Prof. Jun Yang and Prof. Shunai Che

      Version of Record online: 28 MAY 2013 | DOI: 10.1002/anie.201301199

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      In one step, self-assembled helical polypyrrole nanotubes were carbonized to enantiopure chiral carbonaceous nanotubes with a partially graphitized nanostructure (see picture). The ordered helical arrangement of the carbon nanostructure resulted in enantiomeric materials with distinct optical activity. Moreover, their unique structure endowed them with high reversible storage capacity of lithium ions.

    5. Liquid Crystals

      A General Method for the Enantioselective Formation of Helical Nanofilaments (pages 6863–6866)

      Takahiro Ueda, Shiori Masuko, Dr. Fumito Araoka, Prof. Ken Ishikawa and Prof. Hideo Takezoe

      Version of Record online: 28 MAY 2013 | DOI: 10.1002/anie.201300658

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      Controlling chirality: A general method to obtain homochiral helical nanofilaments (HNFs) based on a twisted nematic (TN) configuration was developed. By mixing bent-core molecules in the B4 phase with rod-like molecules in the nematic phase, the mixtures show the phase sequence of N–Bx(B4/N). Homochiral HNFs in the Bx phase were obtained from the mixtures when TN cells were cooled. The homochiral HNFs were observed by atomic force microscopy (see picture).

    6. Fuel Cells

      Optimized Synthesis of Fe/N/C Cathode Catalysts for PEM Fuel Cells: A Matter of Iron–Ligand Coordination Strength (pages 6867–6870)

      Dr. Juan Tian, Dr. Adina Morozan, Dr. Moulay Tahar Sougrati, Dr. Michel Lefèvre, Dr. Régis Chenitz, Prof. Jean-Pol Dodelet, Dr. Deborah Jones and Dr. Frédéric Jaouen

      Version of Record online: 29 MAY 2013 | DOI: 10.1002/anie.201303025

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      It's all in the detail: Highly active Fe/N/C catalysts for the oxygen-reduction reaction in polymer-electrolyte-membrane (PEM) fuel cells can be obtained from a precursor constructed from the zeolitic imidazolate framework ZIF-8 and an iron–ligand complex if, and only if, the displacement of ZnII ions from ZIF-8 by FeII ions is restricted (see picture; TPTZ=2,4,6-tris(2-pyridyl)-s-triazine).

    7. Femtochemistry

      Ultrafast Solvent-Assisted Electronic Level Crossing in 1-Naphthol (pages 6871–6875)

      Dr. Fabrizio Messina, Mirabelle Prémont-Schwarz, Dr. Olivier Braem, Dr. Dequan Xiao, Prof. Victor S. Batista, Dr. Erik T. J. Nibbering and Prof. Majed Chergui

      Version of Record online: 12 JUN 2013 | DOI: 10.1002/anie.201301931

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      Solvent effects: The nonadiabatic inversion dynamics of the energetic order of the electronic excited states of the photoacid 1-naphthol have been revealed by ultrafast spectroscopy on a femtosecond timescale (see picture; IC=internal conversion). The energetic order of the excited states La and Lb of 1-naphthol is reversed in 60 fs in polar dimethyl sulfoxide solvent.

    8. High-Nitrogen Compounds

      Electroactive Explosives: Nitrate Ester-Functionalized 1,2,4,5-Tetrazines (pages 6876–6879)

      Dr. David E. Chavez, Dr. Susan K. Hanson, Dr. Jacqueline M. Veauthier and Dr. Damon A. Parrish

      Version of Record online: 16 MAY 2013 | DOI: 10.1002/anie.201302128

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      Oxidation state control: The synthesis and characterization of two nitrate ester-functionalized electroactive tetrazine molecules (see example; N blue, Cl green, O red, C black) has been accomplished. The compounds are redox active and have desirable explosive properties. The reversible nature of their reduction could be utilized to control their chemical and physical properties.

    9. Protein Modifications

      Mix to Validate: A Facile, Reversible PEGylation for Fast Screening of Potential Therapeutic Proteins In Vivo (pages 6880–6884)

      Dr. Tae Hyung Kim, Dr. Magdalena Swierczewska, Dr. Yumin Oh, Dr. AeRyon Kim, Prof. Dr. Dong Gyu Jo, Prof. Dr. Jae Hyung Park, Prof. Dr. Youngro Byun, Prof. Dr. Scheherazade Sadegh-Nasseri, Prof. Dr. Martin G. Pomper, Prof. Dr. Kang Choon Lee and Prof. Dr. Seulki Lee

      Version of Record online: 5 JUN 2013 | DOI: 10.1002/anie.201302181

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      Happy TRAILs to you: PEGylation of proteins through complementary interactions between a His-tag and a Ni2+ complex of nitrilotriacetic acid (NTA, see picture), a well-established practice in protein research, was used to improve the half-life of therapeutic proteins in the blood following systemic administration in vivo. Animal models show that this site-specific modification improves the efficacy of modified TRAIL proteins.

    10. Metal Polycations

      A Tetrapositive Metal Ion in the Gas Phase: Thorium(IV) Coordinated by Neutral Tridentate Ligands (pages 6885–6888)

      Dr. Yu Gong, Dr. Han-Shi Hu, Dr. Guoxin Tian, Dr. Linfeng Rao, Prof. Dr. Jun Li and Dr. John K. Gibson

      Version of Record online: 6 MAY 2013 | DOI: 10.1002/anie.201302212

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      Sheltering thorium ions: A Th4+ ion supported by three neutral tetramethyl-3-oxaglutaramide ligands (L=TMOGA) is produced in the gas phase by electrospray ionization (see graph). The thorium in chiral Th(L)34+ is coordinated by nine oxygen atoms (see picture; O red, N blue, C gray). Quantum chemical studies revealed a decrease in Th[BOND]O binding energies and bond orders and an increase in bond lengths, as the number of coordinating ligands increases.

    11. Photoresponsive Nanowires

      Photoinduced Curling of Organic Molecular Crystal Nanowires (pages 6889–6893)

      Dr. Taehyung Kim, Dr. Muhanna K. Al-Muhanna, Dr. Salem D. Al-Suwaidan, Prof. Dr. Rabih O. Al-Kaysi and Prof. Dr. Christopher J. Bardeen

      Version of Record online: 16 MAY 2013 | DOI: 10.1002/anie.201302323

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      Molecular crystal nanowires composed of an anthracene-9-(1,3-butadiene) derivative exhibit a rapid transition from straight to highly coiled structures when exposed to a pulse of visible light. The curling does not depend on the direction of light illumination and occurs for nanowires composed of either the E or Z isomer. The shape change is driven by an EZ photoisomerization reaction that generates a mixture of isomers within a single nanowire.

    12. Supramolecular Medicine

      Supramolecular Iron Porphyrin/Cyclodextrin Dimer Complex that Mimics the Functions of Hemoglobin and Methemoglobin (pages 6894–6897)

      Dr. Kenji Watanabe, Dr. Hiroaki Kitagishi and Prof. Dr. Koji Kano

      Version of Record online: 27 MAY 2013 | DOI: 10.1002/anie.201302470

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      A real life saver: A supramolecule (met-hemoCD3, see scheme) was prepared by including a water-soluble porphinato iron(III) in a capsule of a cyclodextrin dimer (Py3OCD), which was synthesized in only two steps. The structure of met-hemoCD3 was determined by X-ray crystal analysis (see picture). Ferrous hemoCD3 showed functions similar to those of hemoglobin/myoglobin and also functioned as an antidote for cyanide poisoning.

    13. Supramolecular Chemistry

      Highly Cooperative Binding of Ion-Pair Dimers and Ion Quartets by a Bis(calix[4]pyrrole) Macrotricyclic Receptor (pages 6898–6902)

      Virginia Valderrey, Eduardo C. Escudero-Adán and Prof. Pablo Ballester

      Version of Record online: 27 MAY 2013 | DOI: 10.1002/anie.201302524

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      Connect four: A macrotricyclic receptor equipped with two convergent calix[4]pyrrole units features unprecedented binding properties towards two ion pairs. A highly cooperative binding process is observed for pairs of tetrabutylammonium (TBA) salts. MTOA=methyltrioctylammonium.

    14. POMcycles

      Template-Directed Assembly of Polyoxothiometalate Scaffolds into Nanomolecular Architectures (pages 6903–6906)

      Hong-Ying Zang, Dr. Haralampos N. Miras, Dr. De-Liang Long, Benjamin Rausch and Prof. Leroy Cronin

      Version of Record online: 28 MAY 2013 | DOI: 10.1002/anie.201300578

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      A new family of nanomolecular clusters was obtained by using the squarate anion as a template for the self-assembly of [Mo2O2S2(H2O)6]2+ (A) with the structure-directing anion [Mo5O18]6− (B) whose geometry dictates the formation of the polyoxothiometalate building blocks [(Mo2O2S2)3(OH)4(C4O4)] and [(Mo2O2S2)2(OH)2(C4O4)]. A gradual evolution in both symmetry and structural completeness is observed upon traversing the generations of the POMcycle family.

    15. Molecular Imprinting

      Thermo-Responsive Hydrogel Layers Imprinted with RGDS Peptide: A System for Harvesting Cell Sheets (pages 6907–6911)

      Dr. Guoqing Pan, Qianping Guo, Yue Ma, Prof. Dr. Huilin Yang and Prof. Dr. Bin Li

      Version of Record online: 28 MAY 2013 | DOI: 10.1002/anie.201300733

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      The efficient promotion of cell adhesion on a polymer surface and detachment of sheets of cells is possible with thermo-responsive cell culture substrates that are biofunctionalized through noncovalent molecular imprinting. The key is the thermo-responsive “specific binding” of the cell-adhesive peptide RGDS on the cell sheet harvest system (see picture).

    16. Phosphorylation

      Synthesis of Unsymmetric Diphospho-Inositol Polyphosphates (pages 6912–6916)

      Samanta Capolicchio, Divyeshsinh T. Thakor, Priv.-Doz. Dr. Anthony Linden and Dr. Henning J. Jessen

      Version of Record online: 27 MAY 2013 | DOI: 10.1002/anie.201301092

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      One to rule them all: A novel C2-symmetric phosphoramidite was developed that can be used to prepare all four unsymmetric diphospho inositol pentaphosphates (PP-InsP5). The target structures were synthesized in few steps and high enantiomeric ratios. With the obtained compounds, specificity of Ddp1 from yeast (a PP-InsP5 phosphatase) was studied.

    17. Fluorogenic Probes

      BODIPY–Tetrazine Derivatives as Superbright Bioorthogonal Turn-on Probes (pages 6917–6920)

      Dr. Jonathan C. T. Carlson, Dr. Labros G. Meimetis, Dr. Scott A. Hilderbrand and Prof. Ralph Weissleder

      Version of Record online: 27 MAY 2013 | DOI: 10.1002/anie.201301100

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      The fastest and the brightest: A new design that intimately connects tetrazine to a BODIPY fluorophore enables exceptionally efficient energy transfer and quenching. Upon reaction of the tetrazine, the brightness of the fluorophore increases more than a thousand-fold, which is a fluorogenic activation up to two orders of magnitude greater than previously described.

    18. Antitumor Agents

      The Two Faces of Potent Antitumor Duocarmycin-Based Drugs: A Structural Dissection Reveals Disparate Motifs for DNA versus Aldehyde Dehydrogenase 1 Affinity (pages 6921–6925)

      Tanja Wirth, Dr. Galina F. Pestel, Vanessa Ganal, Thomas Kirmeier, Dr. Ingrid Schuberth, Theo Rein, Professor Lutz F. Tietze and Professor Stephan A. Sieber

      Version of Record online: 16 MAY 2013 | DOI: 10.1002/anie.201208941

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      Duocarmycin-derived seco-cyclopropabenzindole (CBI) drugs have been shown to bind DNA and an aldehyde dehydrogenase (ALDH1A1) in lung cancer cells. The removal of the DNA-binding indole moiety results in a CBI compound that does not bind to DNA in whole cells but still exhibits remarkable cytotoxicity. This CBI compound has an increased affinity for ALDH1A1. Rh=rhodamine.

    19. Targeted Delivery

      A Reactive Oxygen Species (ROS)-Responsive Polymer for Safe, Efficient, and Targeted Gene Delivery in Cancer Cells (pages 6926–6929)

      Dr. Min Suk Shim and Prof. Younan Xia

      Version of Record online: 28 MAY 2013 | DOI: 10.1002/anie.201209633

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      Stimuli-responsive release: The high levels of reactive oxygen species (ROS) in prostate cancer cells can be exploited to trigger cancer-targeted gene delivery. A ROS-responsive thioketal-based cationic polymer was synthesized and functionalization with a cancer-targeting peptide led to selective and enhanced gene transfection in prostate cancer cells (see scheme).

    20. Lithium–Sulfur Batteries

      Highly Reversible Lithium/Dissolved Polysulfide Batteries with Carbon Nanotube Electrodes (pages 6930–6935)

      Dr. Yongzhu Fu, Yu-Sheng Su and Prof. Arumugam Manthiram

      Version of Record online: 29 MAY 2013 | DOI: 10.1002/anie.201301250

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      On paper: A lithium/dissolved polysulfide cell is developed utilizing a self-weaving, free-standing multiwalled carbon nanotube (MWCNT) “paper” as a host for the dissolved polysulfide active material and the reaction products. Exceptionally high capacities of 1600 mAh g−1 initially and 1411 mAh g−1 after 50 cycles (based on the mass of sulfur) are obtained at a rate of C/10.

    21. Gold Catalysts

      Resonant Photoemission Observations and DFT Study of s–d Hybridization in Catalytically Active Gold Clusters on Ceria Nanorods (pages 6936–6939)

      Yunyun Zhou, Neil J. Lawrence, Dr. Lu Wang, Dr. Lingmei Kong, Tai-Sing Wu, Dr. Jing Liu, Dr. Yi Gao, Dr. Joseph R. Brewer, Vivianna K. Lawrence, Prof. Dr. Renat F. Sabirianov, Prof. Dr. Yun-Liang Soo, Prof. Dr. Xiao Cheng Zeng, Prof. Dr. Peter A. Dowben, Prof. Dr. Wai Ning Mei and Prof. Dr. Chin Li Cheung

      Version of Record online: 28 MAY 2013 | DOI: 10.1002/anie.201301383

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      Up shift: 6s–5d hybridization and the up-shift of the 5d band to the Fermi level is demonstrated in catalytically active gold clusters on a cerium oxide nanorod support by using resonant photoemission spectroscopy and density functional theory modeling. These results help to explain the high catalytic activity of this system in CO oxidation.

    22. Expanded Porphyrins

      Palladium-Induced Pyrrolic Rearrangement of a Singly to a Doubly N-Confused [26]Hexaphyrin (pages 6940–6943)

      Dr. Sabapathi Gokulnath, Keiichi Nishimura, Dr. Motoki Toganoh, Dr. Shigeki Mori and Prof. Dr. Hiroyuki Furuta

      Version of Record online: 23 MAY 2013 | DOI: 10.1002/anie.201302955

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      A pyrrolic rearrangement reaction of singly N-confused [26]hexaphyrin mediated by PdCl2 afforded doubly N-confused [26]hexaphyrin bis(PdII) complex. The bis(PdII) complex is a rare example of an aromatic compound with definite non-degenerate HOMOs and LUMOs.

    23. Anticancer Nanofibers

      Disruption of the Dynamics of Microtubules and Selective Inhibition of Glioblastoma Cells by Nanofibers of Small Hydrophobic Molecules (pages 6944–6948)

      Yi Kuang and Prof. Bing Xu

      Version of Record online: 17 MAY 2013 | DOI: 10.1002/anie.201302658

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      Ganging up against the bad guys: Nanofibers of 1 efficiently inhibited the growth of glioblastoma cells but exhibited little acute toxicity toward a neuronal cell line. The selective cytotoxicity probably stems from the Warburg effect of cancer cells and the existence of microtubule-stabilizing proteins in neurons. Supramolecular nanofibers that can interrupt the self-organization of proteins may have potential as nanomedicines for the treatment of cancer.

    24. Soft Material Chemistry

      Tailoring Hydrogel Adhesion to Polydimethylsiloxane Substrates Using Polysaccharide Glue (pages 6949–6952)

      Chaenyung Cha, Eleni Antoniadou, Minkyung Lee, Jae Hyun Jeong, Wylie W. Ahmed, Prof. Taher A. Saif, Prof. Stephen A. Boppart and Prof. Hyunjoon Kong

      Version of Record online: 31 MAY 2013 | DOI: 10.1002/anie.201302925

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      Hydrogel meets silicone: The chemical functionalization of a polydimethylsiloxane (PDMS) surface with polysaccharide “glue” induces a strong, permanent adhesion between the hydrogel and PDMS. This hydrogel-coated silicone substrate was useful for controlling cellular organization under mechanical stretching (see picture) and also in fabricating microfluidic devices filled with the gel.

    25. Cycloaddition

      Silver-Catalyzed Isocyanide-Alkyne Cycloaddition: A General and Practical Method to Oligosubstituted Pyrroles (pages 6953–6957)

      Jianquan Liu, Zhongxue Fang, Prof. Qian Zhang, Prof. Qun Liu and Prof. Xihe Bi

      Version of Record online: 6 MAY 2013 | DOI: 10.1002/anie.201302024

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      Ag2CO3 is the key: The transition-metal-catalyzed cycloaddition of isocyanides and unactivated terminal alkynes has been realized with Ag2CO3 as a unique and robust catalyst (see scheme). The protocol is highly efficient, allowing a broad range of terminal and internal alkynes to react under base- and ligand-free conditions, generating synthetically useful oligosubstituted pyrroles in high yields.

    26. Synthesis of Pyrroles by Click Reaction: Silver-Catalyzed Cycloaddition of Terminal Alkynes with Isocyanides (pages 6958–6961)

      Meng Gao, Chuan He, Hongyi Chen, Ruopeng Bai, Ben Cheng and Prof. Aiwen Lei

      Version of Record online: 29 APR 2013 | DOI: 10.1002/anie.201302604

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      Just click with silver: Pyrroles are prepared by the co-cyclization of terminal alkynes and isocyanides in a silver-catalyzed click reaction. This route represents an extremely simple, efficient, and atom-economic approach to substituted pyrroles in good yields with high selectivity, thus complementing the click method for the rapid formation of multifunctional heterocycles.

    27. Trifluoromethylation

      Copper-Catalyzed Trifluoromethylation-Initiated Radical 1,2-Aryl Migration in α,α-Diaryl Allylic Alcohols (pages 6962–6966)

      Xiaowu Liu, Fei Xiong, Xuanping Huang, Liang Xu, Prof. Dr. Pengfei Li and Prof. Dr. Xiaoxing Wu

      Version of Record online: 27 MAY 2013 | DOI: 10.1002/anie.201302673

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      Not only symmetrical, but also unsymmetrical α,α-diaryl allylic alcohols are employed as substrates in the title reaction. A number of arenes and even heteroarenes underwent radical 1,2-aryl migration (“neophyl rearrangement”) to produce α-aryl β-trifluoromethyl ketones. The preferential migration of electron-deficient aryl groups over electron-rich ones in unsymmetrical substrates supports the radical mechanism, which was further confirmed by DFT calculations.

    28. Phosphorus Polymers

      Isomerization Polymerization of the Phosphaalkene MesP[DOUBLE BOND]CPh2: An Alternative Microstructure for Poly(methylenephosphine)s (pages 6967–6970)

      Paul W. Siu, Spencer C. Serin, Dr. Ivo Krummenacher, Dr. Thomas W. Hey and Prof. Dr. Derek P. Gates

      Version of Record online: 5 JUN 2013 | DOI: 10.1002/anie.201301881

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      Unique pathway: The radical-initiated addition polymerization of MesP=CPh2 propagates through the ortho-bound CH3 group of the Mes moiety after C[BOND]H bond activation (see scheme, Mes=2,4,6-trimethylphenyl, tht=tetrahydrothiophene, TEMPO=2,2,6,6-tetramethyl-l-piperidinoxyl). This unique isomerization polymerization mechanism contrasts the previously suggested head-to-tail enchainment typically observed for olefins.

    29. Natural Products

      Formal Enantioselective Synthesis of Aplykurodinone-1 (pages 6971–6973)

      Dr. Philippe A. Peixoto, Alexandre Jean, Dr. Jacques Maddaluno and Dr. Michaël De Paolis

      Version of Record online: 23 MAY 2013 | DOI: 10.1002/anie.201301465

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      Step economy and simplicity were combined in the asymmetric formal synthesis of aplykurodinone-1 (see scheme; TBS=tert-butyldimethylsilyl). The key features of the strategy involve a one-pot aerobic and directed oxidation/deoxygenation and a late-stage controlled epimerization to form the chiral architecture of the molecule.

    30. Ionic Silicon(II) Compounds

      Silicon(II) Coordination Chemistry: N-Heterocyclic Carbene Complexes of Si2+ and SiI+ (pages 6974–6978)

      Prof. Dr. Alexander C. Filippou, Dipl.-Chem. Yury N. Lebedev, Dr. Oleg Chernov, Dipl.-Chem. Martin Straßmann and Dr. Gregor Schnakenburg

      Version of Record online: 27 MAY 2013 | DOI: 10.1002/anie.201301363

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      Ligand swap: The exchange of N-heterocyclic carbene (NHC) ligands at SiII centers is shown to provide access to a dicationic NHC complex of silicon(II), and an NHC adduct of the iodosilyliumylidene cation SiI+, [SiI(IiPr2Me2)(IDipp)]+ (see picture). Characterization studies led to the discovery of an unprecedented C[BOND]H⋅⋅⋅Si anagostic interaction for [SiI(IiPr2Me2)(IDipp)]+.

    31. Peptide Nanoassemblies

      Towards Structure Determination of Self-Assembled Peptides Using Dynamic Nuclear Polarization Enhanced Solid-State NMR Spectroscopy (pages 6979–6982)

      Dr. Hiroki Takahashi, Bastien Viverge, Dr. Daniel Lee, Dr. Patrice Rannou and Dr. Gaël De Paëpe

      Version of Record online: 5 APR 2013 | DOI: 10.1002/anie.201210093

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      Supra-sensitivity: Dynamic nuclear polarization (DNP) enhanced solid-state NMR spectroscopy was performed on self-assembled peptide nanotubes. This approach yields significant experimental time savings (about five orders of magnitude; see picture) and was used to exemplify the feasibility of supramolecular structural studies of organic nanoassemblies at an atomic scale using DNP-enhanced solid-state NMR spectroscopy.

    32. Synthetic Methods

      Acceptorless Dehydrogenation of Nitrogen Heterocycles with a Versatile Iridium Catalyst (pages 6983–6987)

      Jianjun Wu, Dinesh Talwar, Steven Johnston, Prof. Ming Yan and Prof. Jianliang Xiao

      Version of Record online: 17 MAY 2013 | DOI: 10.1002/anie.201300292

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      Gas up: A cyclometalated iridium complex is found to catalyze the dehydrogenation of various benzofused N-heterocycles, thus releasing H2. Driven by as low as 0.1 mol % catalyst, the reaction affords quinolines, indoles, quinoxalines, isoquinolines, and β-carbolines in high yields.

    33. Asymmetric Synthesis

      You have full text access to this OnlineOpen article
      Methylene-Bridged Bis(imidazoline)-Derived 2-Oxopyrimidinium Salts as Catalysts for Asymmetric Michael Reactions (pages 6988–6991)

      Dr. Andrey E. Sheshenev, Ekaterina V. Boltukhina, Andrew J. P. White and King Kuok (Mimi) Hii

      Version of Record online: 27 MAY 2013 | DOI: 10.1002/anie.201300614

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      In nothing flat: The title salts, having planar nitrogen centers, were utilized successfully as phase-transfer catalysts for asymmetric Michael reactions of tert-butyl glycinate benzophenone Schiff base with vinyl ketone and chalcone derivatives, thus providing excellent levels of diastereo- and enantiocontrol (see scheme).

    34. Kinetics

      Model Studies of the Kinetics of Ester Hydrolysis under Stretching Force (pages 6992–6995)

      Dr. Sergey Akbulatov, Dr. Yancong Tian, Eugene Kapustin and Dr. Roman Boulatov

      Version of Record online: 17 MAY 2013 | DOI: 10.1002/anie.201300746

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      Experiments and computations are reported of how stretching a polymer containing an ester moiety affects the kinetics of its basic hydrolysis (see picture). DFT computations of complete conformational ensembles of three homologous esters suggest that a stretching force stabilizes the tetrahedral intermediate and the second transition state (TS) but has no effect on the relative energy of the first TS.

    35. Supported Catalysts

      Continuous Gas-Phase Hydroaminomethylation using Supported Ionic Liquid Phase Catalysts (pages 6996–6999)

      M. Sc. Martin Johannes Schneider, Martin Lijewski, Dr. René Woelfel, Dr. Marco Haumann and Prof. Dr. Peter Wasserscheid

      Version of Record online: 16 MAY 2013 | DOI: 10.1002/anie.201301365

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      Just SILP-ing through: Hydroaminomethylation of ethylene and diethylamine to diethylpropylamine is demonstrated as a continuous gas-phase reaction (see picture) using a supported ionic liquid phase (SILP) to immobilize the applied homogenous Rh-Xantphos catalyst. Highly selective and long-term stable (18 days) catalyst operation was obtained if the ionic liquid was of low basicity and lipophilicity combined with a porous activated carbon support.

    36. Autonomous Nanopropulsion

      Self-Propelled Polymer-Based Multilayer Nanorockets for Transportation and Drug Release (pages 7000–7003)

      Zhiguang Wu, Yingjie Wu, Wenping He, Dr. Xiankun Lin, Prof. Jianmin Sun and Prof. Qiang He

      Version of Record online: 23 MAY 2013 | DOI: 10.1002/anie.201301643

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      Nanotransporters: Self-assembled polymer multilayer nanorockets based on a template-assisted layer-by-layer technique can self-propel by chemical power, namely hydrogen peroxide degradation. They can perform drug loading, targeted transportation, and triggered drug release by an external physical stimuli in a controlled manner.

    37. Continuous Translation Reaction

      Rolling Circle Amplification in a Prokaryotic Translation System Using Small Circular RNA (pages 7004–7008)

      Naoko Abe, Dr. Michio Hiroshima, Hideto Maruyama, Dr. Yuko Nakashima, Dr. Yukiko Nakano, Prof. Dr. Akira Matsuda, Prof. Dr. Yasushi Sako, Prof. Dr. Yoshihiro Ito and Prof. Dr. Hiroshi Abe

      Version of Record online: 28 MAY 2013 | DOI: 10.1002/anie.201302044

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      Getting the runaround: Small circular RNA molecules containing an infinite open reading frame were synthesized and tested in an E. coli cell-free translation system. A circular RNA 126 nucleotides in length was found to produce more product than its linear counterpart by two orders of magnitude, because a ribosome can work more effectively towards the elongation on circular RNA than it can on linear RNA in this continuous peptide synthesis.

    38. Homogeneous Catalysis

      Triphenylene-Based Tris(N-Heterocyclic Carbene) Ligand: Unexpected Catalytic Benefits (pages 7009–7013)

      Sergio Gonell, Dr. Macarena Poyatos and Prof. Eduardo Peris

      Version of Record online: 3 JUN 2013 | DOI: 10.1002/anie.201302686

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      Triple play: A novel triphenylene-based tris(N-heterocyclic carbene) ligand with D3h symmetry and a highly π-delocalized system has been prepared and coordinated to palladium and gold (see figure). The catalytic activities of the new complexes have been compared with those of related benzimidazolylidene and a triptycene-based tris(N-heterocyclic carbene) complexes in three reactions.

    39. Stable Radicals

      An Air-Stable Oxyallyl Radical Cation (pages 7014–7017)

      Dr. David Martin, Dr. Curtis E. Moore, Arnold L. Rheingold and Prof. Guy Bertrand

      Version of Record online: 29 MAY 2013 | DOI: 10.1002/anie.201302841

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      Easy does it! Simply take two carbenes, add carbon monoxide, then HCl, and open the flask to air, and an oxyallyl radical cation is formed.

    40. Stereoselective Rearrangement

      Stereoselective Rearrangements with Chiral Hypervalent Iodine Reagents (pages 7018–7022)

      Umar Farid, Florence Malmedy, Romain Claveau, Lena Albers and Prof. Dr. Thomas Wirth

      Version of Record online: 7 MAY 2013 | DOI: 10.1002/anie.201302358

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      I likes rearrangements: Hypervalent iodine compounds can be used as environmentally friendly, mild, and selective reagents for highly enantioselective rearrangements of alkenes. For the first time, rearrangements to α-arylated ketones can be performed enantioselectively using lactic acid-based iodine(III) reagents.

    41. Sensor Particles

      Fluorescent Sensory Microparticles that “Light-up” Consisting of a Silica Core and a Molecularly Imprinted Polymer (MIP) Shell (pages 7023–7027)

      Wei Wan, Dr. Mustafa Biyikal, Dr. Ricarda Wagner, Prof. Dr. Börje Sellergren and Dr. Knut Rurack

      Version of Record online: 28 MAY 2013 | DOI: 10.1002/anie.201300322

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      From darkness came light: Incorporation of urea-based fluorescent dyes in an anion-imprinted thin polymer shell coated onto silica microparticles leads to a unique and highly enantioselective fluorescent “light-up” response to analytes (see scheme, MIP molecularly imprinted polymer).

    42. Halogen Bonds

      Organocatalysis by Neutral Multidentate Halogen-Bond Donors (pages 7028–7032)

      Florian Kniep, Stefan H. Jungbauer, Qi Zhang, Sebastian M. Walter, Severin Schindler, Ingo Schnapperelle, Dr. Eberhardt Herdtweck and Dr. Stefan M. Huber

      Version of Record online: 6 MAY 2013 | DOI: 10.1002/anie.201301351

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      I(n)organocatalysis: Neutral multidentate halogen-bond donors (halogen-based Lewis acids) catalyze the reaction of 1-chloroisochroman with ketene silyl acetals. The organocatalytic activity is linked to the presence (and number as well as orientation) of iodine substituents. As hidden acid catalysis can be ruled out with high probability, this case constitutes strong evidence for halogen-bond based organocatalysis. TBS=tert-butyldimethylsilyl.

    43. Pyrrolysine Biosynthesis

      Structure and Reaction Mechanism of Pyrrolysine Synthase (PylD) (pages 7033–7037)

      Felix Quitterer, Philipp Beck, Prof. Dr. Adelbert Bacher and Prof. Dr. Michael Groll

      Version of Record online: 29 MAY 2013 | DOI: 10.1002/anie.201301164

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      The final step in the biosynthesis of the 22nd genetically encoded amino acid, pyrrolysine, is catalyzed by PylD, a structurally and mechanistically unique dehydrogenase. This catalyzed reaction includes an induced-fit mechanism achieved by major structural rearrangements of the N-terminal helix upon substrate binding. Different steps of the reaction trajectory are visualized by complex structures of PylD with substrate and product.

    44. Boron Ligands

      An Electron-Precise, Tetrahedral μ3 Boride Complex (pages 7038–7041)

      Dipl.-Chem. Philipp Bissinger, Prof. Dr. Holger Braunschweig, Dipl.-Chem. Alexander Damme, Dr. Thomas Kupfer and Dr. Krzysztof Radacki

      Version of Record online: 3 JUN 2013 | DOI: 10.1002/anie.201302828

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      Boron at the top: Reaction of IMes⋅BBr3 (IMes=1,3-bis(2,4,6-trimethylphenyl) imidazol-2-ylidene) with Na[Co(CO)4] afforded the trimetalloboride [(CO)9Co33-B⋅IMes)] with high selectivity. This species has a tetrahedral geometry with an electron-precise bonding situation, which is uncommon for a μ3 boride complex. It can be considered the missing link between a tetrahedral μ3 borylene (nonclassical) and planar μ3 boride (electron-precise) complexes.

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