Angewandte Chemie International Edition

Cover image for Vol. 45 Issue 46

November 27, 2006

Volume 45, Issue 46

Pages 7645–7853

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Book Reviews
    7. Highlights
    8. Review
    9. Communications
    10. Preview
    1. Cover Picture: Oxetanes as Promising Modules in Drug Discovery (Angew. Chem. Int. Ed. 46/2006) (page 7645)

      Georg Wuitschik, Mark Rogers-Evans, Klaus Müller, Holger Fischer, Björn Wagner, Franz Schuler, Liudmila Polonchuk and Erick M. Carreira

      Article first published online: 20 NOV 2006 | DOI: 10.1002/anie.200690158

      The oxetane ring is an orphan heterocycle in medicinal chemistry. In their Communication on page 7736 ff., M. Rogers-Evans, E. M. Carreira, and co-workers show that this structural motif can improve key physico- and pharmacochemical properties of an underlying scaffold. An “oxetane scan” within a series of lipophilic tertiary amine derivatives was performed to probe the influence of the oxetane ring on selected compound properties.

  2. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Book Reviews
    7. Highlights
    8. Review
    9. Communications
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    1. Graphical Abstract: Angew. Chem. Int. Ed. 46/2006 (pages 7648–7660)

      Article first published online: 20 NOV 2006 | DOI: 10.1002/anie.200690159

  3. Corrigendum

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Book Reviews
    7. Highlights
    8. Review
    9. Communications
    10. Preview
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      Switching On Cell Adhesion with Microelectrodes (page 7660)

      Chuan Zhao, Irene Witte and Gunther Wittstock

      Article first published online: 20 NOV 2006 | DOI: 10.1002/anie.200690160

      This article corrects:

      Switching On Cell Adhesion with Microelectrodes1

      Vol. 45, Issue 33, 5469–5471, Article first published online: 20 JUL 2006

  4. News

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Book Reviews
    7. Highlights
    8. Review
    9. Communications
    10. Preview
  5. Book Reviews

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Book Reviews
    7. Highlights
    8. Review
    9. Communications
    10. Preview
  6. Highlights

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Book Reviews
    7. Highlights
    8. Review
    9. Communications
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    1. Surfactant-Templated Mesoporous Materials: From Inorganic to Hybrid to Organic (pages 7664–7667)

      Yunfeng Lu

      Article first published online: 7 NOV 2006 | DOI: 10.1002/anie.200602489

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      Poring over materials: Over the past decade, surfactant-directed self-assembly (see scheme) has led to numerous inorganic and hybrid mesoporous materials. Recently, this process was extended to organic materials: mesoporous polymers were prepared from oligomers by using Pluronic surfactants. This approach allows the design of novel and functional materials for broad applications.

    2. Evolving Strategies for Protein Synthesis Converge on Native Chemical Ligation (pages 7668–7672)

      Derek Macmillan

      Article first published online: 8 NOV 2006 | DOI: 10.1002/anie.200602945

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      Build a bridge: Although used widely, certain limitations of popular protein assembly strategies such as native chemical ligation (NCL) have persisted. This highlight presents the results of recent reports that tackle these limitations (see picture). Aux=auxiliary.

  7. Review

    1. Top of page
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    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Book Reviews
    7. Highlights
    8. Review
    9. Communications
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    1. Recent Applications of Chiral Ferrocene Ligands in Asymmetric Catalysis (pages 7674–7715)

      Ramón Gómez Arrayás, Javier Adrio and Juan Carlos Carretero

      Article first published online: 20 NOV 2006 | DOI: 10.1002/anie.200602482

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      Pushing forward in asymmetric catalysis: Chiral ferrocene-based ligands have emerged as key structural motifs in transition-metal-mediated asymmetric catalysis because of their availability, unique stereochemical environment, and easy modulation of structural and electronic properties through a wide range of substituents and coordination modes. Recent results include novel types of ferrocene ligands and the development of innovative C[BOND]C and C[BOND]X bond-forming asymmetric processes.

  8. Communications

    1. Top of page
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    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Book Reviews
    7. Highlights
    8. Review
    9. Communications
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    1. DNA Logic Gates Based on Structural Polymorphism of Telomere DNA Molecules Responding to Chemical Input Signals (pages 7716–7719)

      Daisuke Miyoshi, Mamiko Inoue and Naoki Sugimoto

      Article first published online: 10 OCT 2006 | DOI: 10.1002/anie.200602404

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      Environmentally sensitive: Structural polymorphism of telomere DNA molecules, which may be useful for the construction of molecular devices, is affected by environmental factors. Based on the conversion of the telomere DNA molecules among four states, simple and robust DNA logic gates that respond to two chemical input signals (M+ and H+) and generate a change in fluorescence intensity as the output signal were developed.

    2. P88− Polyanion with Phosphorus Atoms in Three Different Formal Oxidation States Stabilized by a Combination of Ag+ and Hg2+ Cations (pages 7719–7722)

      Olga S. Oleneva, Tatiana A. Shestimerova, Evgeny V. Dikarev and Andrei V. Shevelkov

      Article first published online: 16 OCT 2006 | DOI: 10.1002/anie.200601155

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      Three “P”s in a pod: The polyanion P88− in Hg4Ag5P8Cl5 has been stabilized by the combination of Ag+ and Hg2+ ions, which are bound to the differently charged phosphorus atoms. Three different formal oxidation states of phosphorus are present in the structure.

    3. A Family of 3D Coordination Polymers Composed of Mn19 Magnetic Units (pages 7722–7725)

      Eleni E. Moushi, Theocharis C. Stamatatos, Wolfgang Wernsdorfer, Vassilios Nastopoulos, George Christou and Anastasios J. Tasiopoulos

      Article first published online: 30 OCT 2006 | DOI: 10.1002/anie.200603498

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      Singles networks: The use of 1,3-propanediol and of 2-methyl-1,3-propanediol in manganese carboxylate chemistry leads to two new 3D coordination polymers with an unprecedented Mn19 repeating unit. The polymers have open framework structures with nanometer-sized cavities (see picture; Na not visible, Mn blue, O red, C gray). The Mn19 units have a ground spin state of S=23/2 and behave as single-molecule magnets.

    4. De Novo Folding of the DNA-Binding ATF-2 Zinc Finger Motif in an All-Atom Free-Energy Forcefield (pages 7726–7728)

      Srinivasa M. Gopal and Wolfgang Wenzel

      Article first published online: 24 OCT 2006 | DOI: 10.1002/anie.200603415

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      Finger formation: Predictive all-atom folding of a DNA-binding αββ-zinc-finger motif in a free-energy forcefield has been demonstrated. The three models (shown in different shades of blue in the picture) show the lowest energy structures found in the simulation. The low-energy region of the free-energy surface and important steps of the folding pathway have been analyzed to help elucidate zinc-finger formation and function.

    5. From Vesicles to Helical Nanotubes: A Sergeant-and-Soldiers Effect in the Self-Assembly of Oligo(p-phenyleneethynylene)s (pages 7729–7732)

      Ayyappanpillai Ajayaghosh, Reji Varghese, Sankarapillai Mahesh and Vakayil K. Praveen

      Article first published online: 25 OCT 2006 | DOI: 10.1002/anie.200603238

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      Coassembly of short molecular wires OPE1 with chiral analogues OPE2, both of which are CD silent, exhibited a sergeant-and-soldiers effect that resulted in transformation of vesicular aggregates of OPE1 into CD-active helical nanotubes (see schematic picture), as revealed by CD, dynamic light scattering, and atomic force and transmission electron microscopies (TEM). OPE=oligo(p-phenyleneethynylene).

    6. Monodisperse Silica-Coated Polyvinylpyrrolidone/NaYF4 Nanocrystals with Multicolor Upconversion Fluorescence Emission (pages 7732–7735)

      Zhengquan Li and Yong Zhang

      Article first published online: 7 NOV 2006 | DOI: 10.1002/anie.200602975

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      In full color: Ultrafine lanthanide-doped polyvinylpyrrolidone/NaYF4 nanocrystals with narrow size distribution were synthesized and found to disperse well in water and many organic solvents. Silica was coated onto the nanocrystals to form a uniform thin layer. Highly efficient upconversion fluorescence was observed from both uncoated and silica-coated PVP/NaYF4 nanocrystals doped with Yb/Er or Yb/Tm (see picture).

    7. Oxetanes as Promising Modules in Drug Discovery (pages 7736–7739)

      Georg Wuitschik, Mark Rogers-Evans, Klaus Müller, Holger Fischer, Björn Wagner, Franz Schuler, Liudmila Polonchuk and Erick M. Carreira

      Article first published online: 2 OCT 2006 | DOI: 10.1002/anie.200602343

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      Ring the changes: Introduction of an oxetane ring results in remarkably improved physico- and biochemical properties of the underlying scaffold. The oxetane ring confers enhanced solubility, reduces the metabolic degredation, lipophilicity, and amphiphilicity, and modulates the basicity of a nearby amine group.

    8. Lead Chalcogenide Nanotubes Synthesized by Biomolecule-Assisted Self-Assembly of Nanocrystals at Room Temperature (pages 7739–7742)

      Hua Tong, Ying-Jie Zhu, Li-Xia Yang, Liang Li and Ling Zhang

      Article first published online: 24 OCT 2006 | DOI: 10.1002/anie.200602952

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      Natural help: PbE nanotubes (E=S, Se, Te; see picture) have been synthesized by a novel biomolecule-assisted method at room temperature. The precursor nanowires self-assembled from nanocrystals synthesized in the presence of cysteine play crucial roles as both the lead source and template in the formation of the nanotubes, which exhibit an obvious quantum confinement effect.

    9. Degradable Polyelectrolyte Capsules Filled with Oligonucleotide Sequences (pages 7743–7745)

      Alexander N. Zelikin, Qi Li and Frank Caruso

      Article first published online: 31 OCT 2006 | DOI: 10.1002/anie.200602779

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      To cap it all: A polycation-free encapsulation method is used to obtain high concentrations of uncomplexed, short oligonucleotide chains confined within monodisperse, degradable microcapsules. Oligonucleotide loadings of >104 chains per capsule are obtained, and more than 90 % of the capsules are filled with DNA. These capsules also undergo degradation under reducing conditions (such as those that occur in cells), releasing the encapsulated DNA.

    10. Iterative Saturation Mutagenesis on the Basis of B Factors as a Strategy for Increasing Protein Thermostability (pages 7745–7751)

      Manfred T. Reetz, José D. Carballeira and Andreas Vogel

      Article first published online: 31 OCT 2006 | DOI: 10.1002/anie.200602795

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      Efficiency counts: A new method of directed evolution for increasing the thermostability of proteins saves time and effort. In an illustrative study, iterative cycles of saturation mutagenesis were performed at those sites in a lipase that display high B factors.

    11. How Hydration Drastically Improves Adsorption Selectivity for CO2 over CH4 in the Flexible Chromium Terephthalate MIL-53 (pages 7751–7754)

      Philip L. Llewellyn, Sandrine Bourrelly, Christian Serre, Yaroslav Filinchuk and Gérard Férey

      Article first published online: 20 OCT 2006 | DOI: 10.1002/anie.200602278

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      Taking a deep breath: The hydrated form of the microporous metal organic framework MIL-53(Cr) performs better than the dehydrated form for the selectivity binding of carbon dioxide over methane (see graph). The polarity of the adsorbed gas is thought to play a role in inducing framework flexibility and the breathing of the pores.

    12. Designed Fabrication of Multifunctional Magnetic Gold Nanoshells and Their Application to Magnetic Resonance Imaging and Photothermal Therapy (pages 7754–7758)

      Jaeyun Kim, Sungjin Park, Ji Eun Lee, Seung Min Jin, Jung Hee Lee, In Su Lee, Ilseung Yang, Jun-Sung Kim, Seong Keun Kim, Myung-Haing Cho and Taeghwan Hyeon

      Article first published online: 30 OCT 2006 | DOI: 10.1002/anie.200602471

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      Targeting cancer: Multifunctional magnetic gold nanoshells (Mag-GNS) are prepared by coating silica spheres with gold nanoshells embedded with Fe3O4 nanoparticles. The Fe3O4 nanoparticles allow magnetic resonance imaging (MRI) for diagnosis, and the gold nanoshells enable photothermal therapy. By attaching an antibody to the Mag-GNS by a poly(ethylene glycol) (PEG) linker, cancer cells can be targeted.

    13. Synthesis of Tellurido-Bridged IrPt2, IrPd2, and IrPtPd Clusters by Inserting Zero-Valent Pt and Pd Centers into Te[BOND]C Bonds (pages 7758–7762)

      Takafumi Nakagawa, Hidetake Seino, Shoken Nagao and Yasushi Mizobe

      Article first published online: 19 OCT 2006 | DOI: 10.1002/anie.200602203

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      Te for two: A convenient method to prepare a series of tellurido-bridged mixed-metal clusters is demonstrated by the reactions of [Cp*Ir(CO)(TeTol)2] (Tol=p-CH3C6H4, Cp*=η5-C5Me5) with [Pt(PPh3)3] and [Pd(PPh3)4]. The Group 10 metal center inserts itself into the Te[BOND]C bond (see scheme). This method may be applied to the synthesis of a wide range of mixed-metal telluride cluster compounds.

    14. The Effects of Antibodies on Stilbene Excited-State Energetics (pages 7763–7765)

      Feng Tian, Erik W. Debler, David P. Millar, Ashok A. Deniz, Ian A. Wilson and Peter G. Schultz

      Article first published online: 7 NOV 2006 | DOI: 10.1002/anie.200602720

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      You light up my life! Antibodies, when bound to a donor–acceptor-substituted stilbene, strongly fluoresce with colors ranging from blue to green. Photophysical and structural analyses indicate that antibody binding alters the excited-state behavior of stilbene. Such complexes may find in vitro and in vivo application as fluorescent biosensors.

    15. Protein Structure Similarity Clustering: Dynamic Treatment of PDB Structures Facilitates Clustering (pages 7766–7770)

      Bradley D. Charette, Richard G. MacDonald, Stefan Wetzel, David B. Berkowitz and Herbert Waldmann

      Article first published online: 31 OCT 2006 | DOI: 10.1002/anie.200602125

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      In the family: The introduction of ligand docking, molecular dynamics, and the VAST algorithm into protein structure similarity clustering greatly streamlines the process and opens up otherwise unseen connections to new protein-cluster partners. VAST=vector alignment search tool.

    16. Isolated [Ni2H7]7− and [Ni4H12]12− Ions in La2MgNi2H8 (pages 7770–7773)

      Jean-Noël Chotard, Yaroslav Filinchuk, Bernard Revaz and Klaus Yvon

      Article first published online: 7 NOV 2006 | DOI: 10.1002/anie.200603651

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      Isolated and complex: La2MgNi2H8 contains isolated dinuclear [Ni2H7]7− and tetranuclear [Ni4H12]12− anions (see picture). These are the first polynuclear solid-state nickel hydride complexes. Their formation upon hydrogenation of the intermetallic compound La2MgNi2 is associated with a metal–insulator transition.

    17. SiO2/Ta2O5 Core–Shell Nanowires and Nanotubes (pages 7773–7778)

      Yu-Lun Chueh, Li-Jen Chou and Zhong Lin Wang

      Article first published online: 20 OCT 2006 | DOI: 10.1002/anie.200602228

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      Tantalizing silica: SiO2/Ta2O5 core–shell nanostructures were formed by reducing SiO2 nanowires under a Ta atmosphere at 950 °C. The diameter of the SiO2 nanowires inside the core–shell nanostructures could be manipulated by modifying the reduction time. Treatment of the core–shell structures in dilute HF solution yielded Ta2O5 nanotubes (see TEM image), whereas Ta2O5 nanowires were formed directly by increasing the reduction time.

    18. Surface Enrichment and Depletion Effects of Ions Dissolved in an Ionic Liquid: An X-ray Photoelectron Spectroscopy Study (pages 7778–7780)

      Florian Maier, J. Michael Gottfried, Jürgen Rossa, Dirk Gerhard, Peter Steffen Schulz, Wilhelm Schwieger, Peter Wasserscheid and Hans-Peter Steinrück

      Article first published online: 24 OCT 2006 | DOI: 10.1002/anie.200602756

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      Surfaces of ionic liquids: Angle-dependent X-ray photoelectron spectroscopy (XPS) shows that the surface composition of a solution of [Pt(NH3)4]Cl2 in the ionic liquid 1-ethyl-3-methylimidazolium ethyl sulfate ([EMIM][EtOSO3]) deviates considerably from the bulk composition. The [Pt(NH3)4]2+ cation is enriched on the surface at the expense of the [EMIM] cation (see picture), while the Cl anion is depleted to below the XPS detection limit.

    19. Palladium-Catalyzed Cross-Coupling Reactions of Diazine N-Oxides with Aryl Chlorides, Bromides, and Iodides (pages 7781–7786)

      Jean-Philippe Leclerc and Keith Fagnou

      Article first published online: 24 OCT 2006 | DOI: 10.1002/anie.200602773

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      New aspects ofN-oxides: Pyrazine, pyridazine, and pyrimidine N-oxides are regioselectively arylated with aryl iodides, bromides, and chlorides in the presence of a palladium catalyst (see scheme). The resulting products can be deoxygenated in high yield or further functionalized by making use of the N-oxide functionality. FG=functional group.

    20. Total Synthesis of Antibiotics GE2270A and GE2270T (pages 7786–7792)

      K. C. Nicolaou, Bin Zou, Dattatraya H. Dethe, Dong Bo Li and David Y.-K. Chen

      Article first published online: 24 OCT 2006 | DOI: 10.1002/anie.200602798

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      Beat the bugs: Total syntheses of the thiopeptide antibiotics GE2270A (X[BOND]Y=CH2[BOND]CH) and GE2270T (X[BOND]Y=CH[DOUBLE BOND]C) have been accomplished. The modular approach featured a hetero-Diels–Alder dimerization (A) to construct the trithiazolyl pyridine domain, and highly regioselective macrolactamizations (B) to furnish the macrocyclic core.

    21. A Ring-Expansion Methodology Involving Multicomponent Reactions: Highly Efficient Access to Polysubstituted Furan-Fused 1,4-Thiazepine Derivatives (pages 7793–7797)

      Cheng Ma, Hanfeng Ding, Yiping Zhang and Ming Bian

      Article first published online: 20 OCT 2006 | DOI: 10.1002/anie.200602836

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      Tri-ed and tested: Ring expansion processes were observed in the novel three-component reaction of thiazolium salts 1, 1,1-disubstituted ketenes 2 (generated in situ), and activated alkynes (see scheme, EWG=electron-withdrawing group). This protocol allows highly efficient assembly of unique furan-fused 1,4-thiazepine derivatives from simple and readily accessible starting materials.

    22. Soluble Poly(p-phenylenevinylene)s through Ring-Opening Metathesis Polymerization (pages 7797–7800)

      Chin-Yang Yu and Michael L. Turner

      Article first published online: 24 OCT 2006 | DOI: 10.1002/anie.200602863

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      Ring opening of substituted cyclophanedienes by ruthenium-based metathesis catalysts gives soluble phenylenevinylene homopolymers of well-defined molecular weight with an alternating cis-trans microstructure (see picture, R=OC8H17). The living character of this polymerization is demonstrated by controlled chain extension.

    23. Multifunctional Iridium Complexes Based on Carbazole Modules as Highly Efficient Electrophosphors (pages 7800–7803)

      Wai-Yeung Wong, Cheuk-Lam Ho, Zhi-Qiang Gao, Bao-Xiu Mi, Chin-Hsin Chen, Kok-Wai Cheah and Zhenyang Lin

      Article first published online: 24 OCT 2006 | DOI: 10.1002/anie.200602906

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      Getting the green light: Highly efficient organic light-emitting diodes (OLEDs) have been synthesized from robust green-electrophosphorescent IrIII complexes based on carbazole derivatives (see picture, HT=hole transporting, EL=electroluminescence). The combination of short triplet lifetime, high emission efficiency, and improved charge-transporting properties allows these OLEDs to achieve peak efficiencies of 12 % photons per electron and 38 cd A−1.

      Corrected by:

      Corrigendum: Multifunctional Iridium Complexes Based on Carbazole Modules as Highly Efficient Electrophosphors

      Vol. 46, Issue 10, 1558, Article first published online: 19 FEB 2007

    24. Synthesis of Nitrogen Heterocycles by the Ring Opening of Pyridinium Salts (pages 7803–7806)

      Aaron M. Kearney and Christopher D. Vanderwal

      Article first published online: 30 OCT 2006 | DOI: 10.1002/anie.200602996

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      The century-old ring-opening reaction of pyridinium salts with tethered nucleophiles has been harnessed for a synthesis of substituted indoles and related nitrogen heterocyles. Extension of this method could lead to oxygen- and sulfur-containing heterocycles and carbocycles, as well as to applications in natural product synthesis and medicinal chemistry.

    25. Noble-Metal/Cr2O3 Core/Shell Nanoparticles as a Cocatalyst for Photocatalytic Overall Water Splitting (pages 7806–7809)

      Kazuhiko Maeda, Kentaro Teramura, Daling Lu, Nobuo Saito, Yasunobu Inoue and Kazunari Domen

      Article first published online: 27 OCT 2006 | DOI: 10.1002/anie.200602473

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      Waterproofcoats: Rh/Cr2O3 (core/shell) nanoparticles supported on a (Ga1−xZnx)(N1−xOx) solid solution are synthesized by an in situ photodeposition method. These nanoparticles (see picture) are used as a promoter for overall water splitting upon visible-light irradiation (λ>400 nm). Without the Cr2O3 shell water is formed from H2 and O2 in an undesired back reaction.

    26. Stability and Polymerase Recognition of Pyridine Nucleobase Analogues: Role of Minor-Groove H-Bond Acceptors (pages 7809–7812)

      Yoonkyung Kim, Aaron M. Leconte, Yoshiyuki Hari and Floyd E. Romesberg

      Article first published online: 31 OCT 2006 | DOI: 10.1002/anie.200602579

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      In the groove: In an effort to develop unnatural base pairs, pyridyl nucleoside analogues were synthesized and characterized (see structures). An α-glycosidic nitrogen atom provides an H-bond acceptor that does not significantly facilitate pairing with natural nucleobases. However, it forms minor-groove H-bonds with water molecules and DNA polymerases that optimize the stability and replication, respectively, of the unnatural base pair.

    27. Reversibly Cross-Linked Surface-Grafted Polymer Brushes (pages 7812–7814)

      David M. Loveless, Nehal I. Abu-Lail, Marian Kaholek, Stefan Zauscher and Stephen L. Craig

      Article first published online: 25 OCT 2006 | DOI: 10.1002/anie.200602508

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      Detailed brushwork: Structurally and thermodynamically similar cross-linkers have opposite effects on the lateral resistance of grafted thin films of poly(4-vinylpyridine) brushes. The chemically reversible changes in mechanics are influenced by the dissimilar kinetics of the cross-linking interaction.

    28. Chemodosimeter for CuII Detection Based on Cyclic Peptide Nucleic Acids (pages 7815–7817)

      János Kovács, Thomas Rödler and Andriy Mokhir

      Article first published online: 24 OCT 2006 | DOI: 10.1002/anie.200603391

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      Copper-sensitive cycle: A cyclic peptide nucleic acid (PNA) that does not bind DNA and RNA can be prepared by placing an optimized linker between the termini. CuII ions, but not other tested metal ions, catalyze the transformation of the cyclic PNA into the linear PNA, which is a strong binder of nucleic acids (see picture). This effect is used for the fluorimetric detection of CuII. ssDNA=single-stranded DNA

    29. Highly Heteroselective Ring-Opening Polymerization of rac-Lactide Initiated by Bis(phenolato)scandium Complexes (pages 7818–7821)

      Haiyan Ma, Thomas P. Spaniol and Jun Okuda

      Article first published online: 26 OCT 2006 | DOI: 10.1002/anie.200603178

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      Tactical response: High heterotactic stereocontrol was observed from the ring-opening polymerization of rac-lactide on using a series of bis(phenolato)scandium complexes (see scheme). This stereocontrol appears to involve a dynamic monomer-recognition process as a result of the interconversion of the configuration from Λ into Δ.

    30. Acquisition Regime for High-Resolution Heteronuclear 2D NMR Spectra (pages 7821–7824)

      Igor Baskyr, Torsten Brand, Matthias Findeisen and Stefan Berger

      Article first published online: 30 OCT 2006 | DOI: 10.1002/anie.200603036

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      Double take: In the acquisition regime presented here, 1H,13C HSQC spectra are recorded twice with spectral widths of 5.8 and 6.2 ppm in the indirect dimension. The aliased signals are then unfolded to the full spectral width to yield an HSQC spectrum with 5 Hz per point in the 13C dimension without additional time requirements (see example of strychnine).

    31. Morphological Control of Catalytically Active Platinum Nanocrystals (pages 7824–7828)

      Hyunjoo Lee, Susan E. Habas, Sasha Kweskin, Derek Butcher, Gabor A. Somorjai and Peidong Yang

      Article first published online: 7 NOV 2006 | DOI: 10.1002/anie.200603068

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      Activity revived: Platinum nanoparticles (cuboctahedra, cubes, and porous particles, see picture, from left to right) capped with alkylammonium ions are synthesized by manipulating the reduction kinetics. The catalytic activity of these nanoparticles is superior to that of nanoparticles whose shape was controlled with a polymeric capping agent and foreign metal ions.

    32. An Extremely Long-Lived Singlet 4,4-Dimethoxy-3,5-diphenylpyrazolidine-3,5-diyl Derivative: A Notable Nitrogen-Atom Effect on Intra- and Intermolecular Reactivity (pages 7828–7831)

      Manabu Abe, Emi Kubo, Koichi Nozaki, Takashi Matsuo and Takashi Hayashi

      Article first published online: 24 OCT 2006 | DOI: 10.1002/anie.200603287

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      Life in the fast lane: An extremely long-lived singlet state of 4,4-dimethoxy-3,5-diphenylpyrazoline-3,5-diyl (1; τ=9.67 ms at room temperature) is reported, which affords intramolecularly the oxygen-migration product and reacts intermolecularly with 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD) to give the cycloaddition product. The diradical intermediate was characterized by its absorption band at 645 nm.

    33. Cooperative Coexistence: Effective Interplay of Two Brønsted Acids in the Asymmetric Synthesis of Isoquinuclidines (pages 7832–7835)

      Magnus Rueping and Cengiz Azap

      Article first published online: 2 NOV 2006 | DOI: 10.1002/anie.200603199

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      A Mannich–aza-Michael reaction in which both an electrophile and a nucleophile are activated provides a simple, highly enantioselective route to isoquinuclidines (1) from imines (2) and cyclohexenone (3). A feature of the reaction is the interplay of an achiral and a chiral Brønsted acid, which enable the asymmetric reaction process by cooperative activation of the enone and the imine.

    34. Photochemical Origin of the Immunosuppressive SNF4435C/D and Formation of Orinocin through “Polyene Splicing” (pages 7835–7838)

      Markus Müller, Björn Kusebauch, Guangxin Liang, Christopher M. Beaudry, Dirk Trauner and Christian Hertweck

      Article first published online: 25 OCT 2006 | DOI: 10.1002/anie.200602840

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      A splice from life: A photoinduced rearrangement cascade with alternating photochemical and thermal pericyclic steps leads to a novel pyrone compound with chain-contracted polyketide backbone (orinocin (2)). The excision of three propionate units from the polyene precursor, spectinabilin (1), proceeds via the immunosuppressive SNF4435C/D and yields an unusual triketide, mesitylene (see scheme).

    35. General Preparation of Primary, Secondary, and Tertiary Aryl Amines by the Oxidative Coupling of Polyfunctional Aryl and Heteroaryl Amidocuprates (pages 7838–7842)

      Vicente del Amo, Srinivas Reddy Dubbaka, Arkady Krasovskiy and Paul Knochel

      Article first published online: 31 OCT 2006 | DOI: 10.1002/anie.200603089

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      A tolerant reaction: Functionalized tertiary amines have been prepared by the oxidative coupling of amidocuprates with chloranil used as the oxidant (see Scheme). A high tolerance of functional groups and insensitivity to steric hindrance characterize this general amination reaction.

    36. On the Acceptor Substrate of C-Glycosyltransferase UrdGT2: Three Prejadomycin C-Glycosides from an Engineered Mutant of Streptomyces globisporus 1912 ΔlndE(urdGT2) (pages 7842–7846)

      Irfan Baig, Madan Kharel, Anton Kobylyanskyy, Lili Zhu, Yuriy Rebets, Bohdan Ostash, Andriy Luzhetskyy, Andreas Bechthold, Victor A. Fedorenko and Jürgen Rohr

      Article first published online: 24 OCT 2006 | DOI: 10.1002/anie.200603176

      Thumbnail image of graphical abstract

      The transfer of the geneurdGT2, which encodes a C-glycosyltransferase in the urdamycin pathway, into the lnd-minus mutant of the landomycin (lnd) biosynthetic pathway indicates the difference in the first glycosylation step in the urdamycin and landomycin pathways. It also reveals indirectly the acceptor substrate of UrdGT2 (see scheme) and gives evidence of greatly relaxed substrate specificity of all lnd glycosyltransferases except LndGT2.

    37. Unprecedented Insight into Diffusion by Monitoring the Concentration of Guest Molecules in Nanoporous Host Materials (pages 7846–7849)

      Jörg Kärger, Pavel Kortunov, Sergey Vasenkov, Lars Heinke, Dhananjai B. Shah, Rainer A. Rakoczy, Yvonne Traa and Jens Weitkamp

      Article first published online: 24 OCT 2006 | DOI: 10.1002/anie.200602892

      Thumbnail image of graphical abstract

      How many guests? Interference microscopy is used to monitor the concentration of guest molecules in a ferrierite zeolite. The micropore diffusivities are determined as a function of loading through the microscopic application of Fick's second law. This method can be used to study isotropic and anisotropic diffusion, as well as to locate and quantify surface barriers and internal defects.

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      Preview: Angew. Chem. Int. Ed. 46/2006 (page 7853)

      Article first published online: 20 NOV 2006 | DOI: 10.1002/anie.200690161

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