Angewandte Chemie International Edition

Cover image for Vol. 43 Issue 31

August 6, 2004

Volume 43, Issue 31

Pages 3983–4109

    1. Cover Picture: Molecular Lithography with DNA Nanostructures (Angew. Chem. Int. Ed. 31/2004) (page 3983)

      Zhaoxiang Deng and Chengde Mao

      Version of Record online: 2 AUG 2004 | DOI: 10.1002/anie.200490104

      Designed DNA nanostructures … can be accurately replicated into metal nanostructures by a molecular and a classic lithographic approach. The rational design and self-assembly of DNA motifs allows masks with sophisticated structures to be constructed. The cover picture shows one example, a gold film containing periodic, two-dimensional features that is replicated from a self-assembled, tetragonal DNA 2D array (repeating unit about 18 nm). More details can be found in the Communication by C. Mao and Z. Deng on page 4068 ff.

    2. Carbohydrate-Based Drug Discovery. 2 Volumes. Edited by Chi-Huey Wong. (pages 3995–3996)

      Oliver Plettenburg and Ulrich Stilz

      Version of Record online: 2 AUG 2004 | DOI: 10.1002/anie.200385089

    3. Small Molecules, Big Plans—Can Low-Molecular-Weight Compounds Control Human Regeneration? (pages 3998–4000)

      Claudia Gey and Athanassios Giannis

      Version of Record online: 8 JUL 2004 | DOI: 10.1002/anie.200460346

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      The name is the game. Reversine (1) is a low-molecular-weight compound that reverses the process of cell differentiation in mammals. Specialized muscle cells can be transformed into multipotent progenitor cells. This approach may have potential for targeted regeneration processes in humans.

    4. Reactions Between or Within Molecular Crystals (pages 4002–4011)

      Dario Braga and Fabrizia Grepioni

      Version of Record online: 21 JUN 2004 | DOI: 10.1002/anie.200301721

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      Weaning chemistry onto solids: reactions between solids (see picture) are often regarded as oddities and mechanical synthetic methods are felt to be fundamentally “nonchemical”. This attitude is changing as solvent-free conditions become more important in environmentally friendly processes. In addition, solid-state synthetic procedures are often viable alternative routes to known products and also to new compounds not obtainable by traditional solution chemistry.

    5. Function of the Antigen Transport Complex TAP in Cellular Immunity (pages 4014–4031)

      Silke Beismann-Driemeyer and Robert Tampé

      Version of Record online: 30 JUN 2004 | DOI: 10.1002/anie.200300642

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      Through the membrane: The antigen transporter complex TAP plays a pivotal role in the translocation machinery which pumps antigenic peptides from the cytosol into the ER, a requirement for entry into the secretory pathway and subsequent display on the cell surface. Structural and mechanistic aspects of this ABC transporter are of great interest in membrane biology, immunology, virology, and cell biology. The picture shows the nucleotide binding domain of human TAP1.

    6. Genetic Engineering of the Nanoscale Structure in Polyelectrolyte–Lipid Self-Assembled Systems (pages 4034–4037)

      Ilya Koltover, Sanjukta Sahu and Nicolynn Davis

      Version of Record online: 28 JUL 2004 | DOI: 10.1002/anie.200460164

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      Peptides sandwiched to order: Genetic engineering can be used to prepare charged polypeptides that self-assemble with oppositely charged surfactants into highly ordered multilayers (see diagram). Nanoscale order on three separate length scales can be controlled in the polyelectrolyte–surfactant self-assemblies by changing the peptide length, charge, and surfactant composition.

    7. How Do Clusters Grow? The Synthesis and Structure of Polynuclear Hydroxide Gallium(III) Clusters (pages 4037–4041)

      Jeremy C. Goodwin, Simon J. Teat and Sarah L. Heath

      Version of Record online: 2 AUG 2004 | DOI: 10.1002/anie.200353542

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      Three complexes from one reaction: The reaction of N-(2-hydroxyethyl)iminodiacetic acid with Ga(NO3)3 yields an alkoxo-bridged dimer, a Ga8 cluster (see picture), and a Ga13 cluster. The structures of these complexes and the structural relationships between them are reported, and the insight they may shed on the general mechanism of cluster formation is discussed.

    8. Inhibition of Amyloid Fibril Formation by Peptide Analogues Modified with α-Aminoisobutyric Acid (pages 4041–4044)

      Sharon Gilead and Ehud Gazit

      Version of Record online: 2 AUG 2004 | DOI: 10.1002/anie.200353565

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      Breaking up is not hard to do with an α-aminoisobutyric (Aib) acid β-breaker, which has a remarkably restricted conformation. A novel approach to the inhibition of amyloid formation was developed that uses peptides modified with Aib (see figure). The similarity of Aib to hydrophobic amino acids, often found in amyloidogenic sequences, allows its integration into recognition motifs.

    9. Investigation of Perylene Photonic Wires by Combined Single-Molecule Fluorescence and Atomic Force Microscopy (pages 4045–4049)

      Jordi Hernando, Pieter A. J. de Witte, Erik M. H.P van Dijk, Jeroen Korterik, Roeland J. M. Nolte, Alan E. Rowan, María F. García-Parajó and Niek F. van Hulst

      Version of Record online: 2 AUG 2004 | DOI: 10.1002/anie.200453745

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      Heterogeneous optical behavior of perylene polyisocyanides, which arises from different structures of the polymer backbone, is revealed by the combination of single-molecule fluorescence spectroscopy and atomic force microscopy. Short nonhelical perylene oligomers exhibit monomer-like fluorescence properties, whereas long helical perylene fiber emission arises from excimer sites after delocalization of the excitation along the polymer backbone (see picture).

    10. Stepwise Construction of Oligomeric 1,2-Diselenolene Platinum(IV) Complexes (pages 4049–4052)

      Xavi Ribas, João C. Dias, Jorge Morgado, Klaus Wurst, Manuel Almeida, Teodor Parella, Jaume Veciana and Concepció Rovira

      Version of Record online: 2 AUG 2004 | DOI: 10.1002/anie.200453761

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      Surrounded by selenium: Pulse field gradient spin-echo (PGSE) NMR diffusion studies of a mixture of oligomeric 1,2-diselenolene PtIV complexes are performed to characterize the species in solution (see structure: n=0 (1), n=1 (2), n=2 (3); red Pt, green Se, blue N, gray C). The results are in accord with the single-crystal X-ray diffraction structures obtained for the chiral complexes {PtIVSe6} (1) and {PtIV2Se10} (2).

    11. Simultaneous Identification of Multiple Protein Targets by Using Complementary-DNA Phage Display and a Natural-Product-Mimetic Probe (pages 4052–4055)

      Kathleen M. McKenzie, Elizabeth J. Videlock, Ute Splittgerber and David J. Austin

      Version of Record online: 2 AUG 2004 | DOI: 10.1002/anie.200454004

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      Putting on a good display: A novel selection protocol was devised for the simultaneous display cloning of three homologues of the FK506-binding protein (FKBP12, FKBP12.6, and FKBP13) by using AP1497 (see structure), a mimetic of FK506, and a T7 complementary-DNA phage-display library. A quantitative on-phage binding assay was also performed to evaluate the affinity of the isolated proteins.

    12. Carbopeptoid Folding: Effects of Stereochemistry, Chain Length, and Solvent (pages 4055–4059)

      Riccardo Baron, Dirk Bakowies and Wilfred F. van Gunsteren

      Version of Record online: 19 JUL 2004 | DOI: 10.1002/anie.200454114

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      Shaping up nicely: Carbopeptoids with THF rings in their backbone show distinct folding behavior depending on chain length, configuration, and solvent polarity. Molecular dynamics simulations of the folding yield averaged proton–proton distances in good agreement with experimental NOE data. They show, however, that a number of folds are important (b–d), whereas NOE data are usually interpreted in terms of single structures (a).

    13. Low-Dimensional Aggregates from Stilbazolium-Like Dyes (pages 4060–4063)

      Zhiyuan Tian, Yu Chen, Wensheng Yang, Jiannian Yao, Lingyun Zhu and Zhigang Shuai

      Version of Record online: 2 AUG 2004 | DOI: 10.1002/anie.200454131

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      Dye hard: Strong intermolecular interactions of stilbazolium-like dyes with different structures and conformations seem to act as the main driving force for the formation of nanostructures with distinct morphological and spectral properties. Nanorods and nanospheres (see picture) with well-defined shapes and uniform sizes are formed by changing the solvent quality during synthesis.

    14. Cycloisomerization Promoted by the Combination of a Ruthenium–Carbene Catalyst and Trimethylsilyl Vinyl Ether, and its Application in The Synthesis of Heterocyclic Compounds: 3-Methylene-2,3-dihydroindoles and 3-Methylene-2,3-dihydrobenzofurans (pages 4063–4067)

      Yukiyoshi Terada, Mitsuhiro Arisawa and Atsushi Nishida

      Version of Record online: 2 AUG 2004 | DOI: 10.1002/anie.200454157

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      Substituted N and O heterocycles have been synthesized by the cycloisomerization of dienes using a ruthenium-carbene catalyst. The products obtained with and without trimethylsilyl vinyl ether differ (see scheme, Cy=cyclohexyl, Mes=2,4,6-trimethylphenyl, Ts=p-toluenesulfonyl).

    15. Molecular Lithography with DNA Nanostructures (pages 4068–4070)

      Zhaoxiang Deng and Chengde Mao

      Version of Record online: 17 JUN 2004 | DOI: 10.1002/anie.200460257

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      Unmasking the potential: A DNA-templated nanofabrication approach is reported in which various 1D and 2D DNA nanostructures were assembled, and then these structures transformed into corresponding metal nanostructures through metal deposition (see schematic representation). The ease and flexibility of this technique offers a route to overcome the inabilities faced by traditional lithographic techniques.

    16. Post-Translational Modifications on Proteins: Facile and Efficient Procedure for the Identification of O-Glycosylation Sites by MALDI-LIFT-TOF/TOF Mass Spectrometry (pages 4071–4075)

      Masaki Kurogochi, Takahiko Matsushita and Shin-Ichiro Nishimura

      Version of Record online: 2 AUG 2004 | DOI: 10.1002/anie.200460020

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      We have LIFT-TOF! Transglycosylation of glycopeptides by β-galactosidase in the presence of lactose combined with tandem mass spectrometry using a 2,5-dihydroxybenzoic acid matrix enables the O-glycosylation sites to be identified (see scheme). The highly sensitive and ideal fragmentation patterns generated from glycopeptide precursor ion peaks can be readily used for precise and reliable structure analyses.

    17. Directed Evolution as a Method To Create Enantioselective Cyclohexanone Monooxygenases for Catalysis in Baeyer–Villiger Reactions (pages 4075–4078)

      Manfred T. Reetz, Birgit Brunner, Toni Schneider, Frank Schulz, Christopher M. Clouthier and Margaret M. Kayser

      Version of Record online: 2 AUG 2004 | DOI: 10.1002/anie.200460272

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      The direction and degree of enantioselectivity in the cyclohexanone monooxygenase catalyzed air-mediated Baeyer–Villiger reactions, such as the desymmetrization of 1, can be controlled by directed evolution.

    18. Directed Evolution of Cyclohexanone Monooxygenases: Enantioselective Biocatalysts for the Oxidation of Prochiral Thioethers (pages 4078–4081)

      Manfred T. Reetz, Franck Daligault, Birgit Brunner, Heike Hinrichs and Alfred Deege

      Version of Record online: 28 JUL 2004 | DOI: 10.1002/anie.200460311

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      Mutational changes in cyclohexanone monooxygenases (CHMOs), for example the introduction of serine at position 432, lead to surprisingly versatile enantioselective biocatalysts that perform particularly well in the air-mediated partial oxidation of prochiral thioethers (see scheme).

    19. Anchoring Molecular Magnets on the Si(100) Surface (pages 4081–4084)

      Guglielmo G. Condorelli, Alessandro Motta, Ignazio L. Fragalà, Filippo Giannazzo, Vito Raineri, Andrea Caneschi and Dante Gatteschi

      Version of Record online: 2 AUG 2004 | DOI: 10.1002/anie.200453933

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      Hydrosilylation by H-terminated silicon of the double bond of methyl 10-undecenoate with formation of a robust Si[BOND]C bond is the first step in a three-step procedure (see scheme) for anchoring the single-molecule magnet (SMM) [Mn12O12(OAc)16(H2O)4] (1) on the Si(100) surface.

    20. In Situ Formation of a Heterobimetallic Chiral [(Salen)TiIV]/[(Salen)VV] Catalyst for the Asymmetric Addition of TMSCN to Benzaldehyde (pages 4085–4089)

      Yuri N. Belokon, Michael North, Victor I. Maleev, Nikolay V. Voskoboev, Margarita A. Moskalenko, Alexander S. Peregudov, Andrey V. Dmitriev, Nikolai S. Ikonnikov and Henri B. Kagan

      Version of Record online: 2 AUG 2004 | DOI: 10.1002/anie.200454031

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      A mixed complex which results from two salen-derived VV and TiIV complexes (1 and 2), catalyzes the trimethylsilylcyanation of aldehydes. The reaction kinetics are largely determined by the titanium-derived portion, whereas the configuration of the mandelonitrile trimethylsilyl ether products is determined by the slower vanadium part of the catalyst. salen=N,N'-bis(salicylaldehydo)ethylenediamine.

    21. Readily Available Onio-Substituted Methyleneiminium Salts: Single Precursors for a Variety of Aminocarbenes (pages 4089–4093)

      Salvador Conejero, Yves Canac, Fook S. Tham and Guy Bertrand

      Version of Record online: 2 AUG 2004 | DOI: 10.1002/anie.200460045

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      From amides to carbenes: Phosphonio-substituted iminium salts are readily available from the corresponding amides in a one-pot reaction. Deprotonation followed by substitution reactions affords a variety of transient and stable amino carbenes (see scheme).

    22. “Naked” Phosphanediide Chains and their Fragmentation into Diphosphene Radical Anions (pages 4093–4097)

      Jens Geier, Jeffrey Harmer and Hansjörg Grützmacher

      Version of Record online: 2 AUG 2004 | DOI: 10.1002/anie.200460130

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      Encapsulation of the Na+ions of the [Na2(P4R4)] ion triple with a R,R or S,S configuration at the inner phosphorus atoms by cryptands has enabled cation-separated dianions to be obtained in a crystalline form. Fragmentation of the {Na([2.2.2]cryptand)}2(P4R4) into radical anions (P2R2).− occurs in solution (see scheme), as determined by EPR spectroscopy.

    23. Microencapsulated Chloroperoxidase as a Recyclable Catalyst for the Enantioselective Oxidation of Sulfides with Hydrogen Peroxide (pages 4097–4099)

      Valentina Trevisan, Michela Signoretto, Stefano Colonna, Vincenza Pironti and Giorgio Strukul

      Version of Record online: 2 AUG 2004 | DOI: 10.1002/anie.200460365

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      Bound to do the job: Sol–gel methods have been used to encapsulate chloroperoxidase (CPO) in microporous silica. The encapsulated CPO can then be used as an enantioselective catalyst for the oxidation of organic sulfides (see scheme) and can be recycled without appreciable loss of activity and enantioselectivity.

    24. Catalytic Hydrohydrazination of a Wide Range of Alkenes with a Simple Mn Complex (pages 4099–4102)

      Jérôme Waser and Erick M. Carreira

      Version of Record online: 2 AUG 2004 | DOI: 10.1002/anie.200460811

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      Enhanced activity, lower catalyst loading, shorter reaction times, and expanded substrate scope are the advantages of [Mn(dpm)3] over Co catalysts in the hydrohydrazination reaction of alkenes (see scheme). Thus, sterically hindered alkenes, including tetrasubstituted alkenes, can now also readily undergo this reaction.

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