Angewandte Chemie International Edition

Cover image for Vol. 44 Issue 7

February 4, 2005

Volume 44, Issue 7

Pages 983–1141

    1. Cover Picture: Glycoviruses: Chemical Glycosylation Retargets Adenoviral Gene Transfer (Angew. Chem. Int. Ed. 7/2005) (page 983)

      Oliver M. T. Pearce, Kerry D. Fisher, Julia Humphries, Leonard W. Seymour, Alberto Smith and Benjamin G. Davis

      Version of Record online: 1 FEB 2005 | DOI: 10.1002/anie.200590021

      Sugar-specific mechanisms of cell transfection can be created by the controlled glycosylation of the surfaces of adenoviruses, which have an icosahedral structure, as depicted in the cover picture. In their Communication on page 1057 ff., L. W. Seymour, B. Davis, and co-workers describe how derivatives of adenoviruses with galactose or mannose selectively transfect human macrophages rather than the standard human endothelia and how this dramatic retargeting holds promise for gene therapy.

    2. Biophysical Chemistry. By Alan Cooper. (page 998)

      Martin Kahms

      Version of Record online: 1 FEB 2005 | DOI: 10.1002/anie.200485214

    3. Self-Assembled Molecular Capsules—Even More Than Nano-Sized Reaction Vessels (pages 1000–1002)

      Arne Lützen

      Version of Record online: 1 FEB 2005 | DOI: 10.1002/anie.200462272

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      Far from exhausted is the potential of molecular capsules (a tetranuclear gallium complex is shown as an example). Previously these self-assembled units served as receptors and tiny reaction vessels. In recent work they were used as sensitizers in photochemically induced reactions and as catalysts for rearrangements.

    4. All Science Is Interdisciplinary—From Magnetic Moments to Molecules to Men (Nobel Lecture) (pages 1004–1011)

      Paul C. Lauterbur

      Version of Record online: 20 JAN 2005 | DOI: 10.1002/anie.200462400

      Merely by chance, says Paul Lauterbur, one of the recipients of the Nobel Prize for Physiology or Medicine in 2003, were NMR imaging techniques his main research focus for many years. In his Nobel Lecture, he describes important facets of his life and his scientific carrier that led him from silicones to the clinical application of NMR spectroscopy and later to the question of how chemistry can help in explaining biology.

    5. Chasing Molecules That Were Never There: Misassigned Natural Products and the Role of Chemical Synthesis in Modern Structure Elucidation (pages 1012–1044)

      K. C. Nicolaou and Scott A. Snyder

      Version of Record online: 1 FEB 2005 | DOI: 10.1002/anie.200460864

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      It is a commonly held belief that the process of assigning structures to newly isolated natural products (see picture) is a relatively routine endeavor, one that offers little opportunity for adventure and does not require the art of chemical synthesis. This Review seeks to question the veracity of such a position and makes the case that there is plenty of room in the process of structural elucidation for intellectual challenge, chemical synthesis, and drama.

    6. Activity-Based High-Throughput Screening of Enzymes by Using a DNA Microarray (pages 1048–1053)

      Yi Hu, Grace Y. J. Chen and Shao Q. Yao

      Version of Record online: 19 NOV 2004 | DOI: 10.1002/anie.200461612

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      The expression display method is developed, which combines two techniques, ribosome display and DNA microarray, to express a mixture of proteins from their corresponding cDNA. Upon functional selection using an activity-based probe, multiple target enzymes are simultaneously isolated and subsequently identified by hybridization to a DNA microarray (see scheme; RT=reverse transcription, PCR=polymerase chain reaction).

    7. Dendrimer Folding in Aqueous Media: An Example of Solvent-Mediated Chirality Switching (pages 1053–1057)

      Amanda L. Hofacker and Jon R. Parquette

      Version of Record online: 5 JAN 2005 | DOI: 10.1002/anie.200460943

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      Staying in shape: The second and third generations of a new dendron system switch from left-handed to right-handed helical conformations upon a change in solvent from THF to water (picture; left). This inversion occurs in tandem with conformational shifts about the O[BOND]C[BOND]C[BOND]O bonds of a subset of terminating glycol chains, from gauche,gauche+,anti to anti,gauche,anti (picture; right).

    8. Glycoviruses: Chemical Glycosylation Retargets Adenoviral Gene Transfer (pages 1057–1061)

      Oliver M. T. Pearce, Kerry D. Fisher, Julia Humphries, Leonard W. Seymour, Alberto Smith and Benjamin G. Davis

      Version of Record online: 1 FEB 2005 | DOI: 10.1002/anie.200461832

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      A sugar-specific transfection mechanism is introduced by the glycosylation of adenoviruses (AVs, see picture), and manipulation of the glycosylation pattern allows the selective transfection of human macrophages in favor of the usual target. This dramatic retargeting holds promise for the fine-tuning of adenoviruses for applications such as gene therapy.

    9. In Vitro Selection of Structure-Switching Signaling Aptamers (pages 1061–1065)

      Razvan Nutiu and Yingfu Li

      Version of Record online: 11 JAN 2005 | DOI: 10.1002/anie.200461848

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      Picking out probes: A novel approach permits isolation of standard DNA aptamers by in vitro selection and conversion into fluorescence signaling probes. This method comprises the isolation of DNA aptamers capable of duplex-to-complex structure switching and labeling the derived aptamers with a pair of short DNA strands with a fluorophore F and a quencher Q to create a reporter system for real-time sensing (see picture).

    10. Stability of SIV gp32 Fusion-Peptide Single-Layer Protofibrils as Monitored by Molecular-Dynamics Simulations (pages 1065–1067)

      Patricia Soto, Josep Cladera, Alan E. Mark and Xavier Daura

      Version of Record online: 3 JAN 2005 | DOI: 10.1002/anie.200461935

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      Modeling the mechanisms of protofibril twisting: Molecular-dynamics simulations of simian viral peptide aggregates show that β sheets of 10 to 30 chains form left-handed helical ribbons with saddlelike curvature (see picture). These structures are highly dynamic, with oscillations around an average twist angle of 9–10°, and a pitch of 15–20 nm, depending on β-sheet length. The peptides studied are key to viral entry into host cells.

    11. Multifunctional Nanoparticles Possessing A “Magnetic Motor Effect” for Drug or Gene Delivery (pages 1068–1071)

      Tae-Jong Yoon, Jun Sung Kim, Byung Geol Kim, Kyeong Nam Yu, Myung-Haing Cho and Jin-Kyu Lee

      Version of Record online: 5 JAN 2005 | DOI: 10.1002/anie.200461910

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      Cells in motion: Multifunctional nanoparticles, with a unique combination of magnetic and fluorescent properties, coupled with biocompatibility are prepared. The uptake of the magnetic nanoparticles by cells is investigated, and an external “magnetic motor effect” on the cells containing the nanoparticles is observed (see scheme).

    12. Photorelease of an Organic Molecule in Solution: Light-Triggered Blockage of a Hydrogen-Bonding Receptor Site (pages 1072–1075)

      Yann Molard, Dario M. Bassani, Jean-Pierre Desvergne, Peter N. Horton, Michael B. Hursthouse and James H. R. Tucker

      Version of Record online: 11 JAN 2005 | DOI: 10.1002/anie.200461946

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      Bathed in light, the acyclic receptor 1 that binds a neutral guest molecule through hydrogen bonding (12) undergoes an intramolecular anthracene photodimerization reaction to yield a macrocyclic structure. The dramatic change in the structure of 1 from open to cyclic affects the binding properties of the receptor sites and leads to the exclusion of the guest molecule.

    13. Alkyne Carbonylation by Radicals: Tin-Radical-Catalyzed Synthesis of α-Methylene Amides from 1-Alkynes, Carbon Monoxide, and Amines (pages 1075–1078)

      Yoshitaka Uenoyama, Takahide Fukuyama, Osamu Nobuta, Hiroshi Matsubara and Ilhyong Ryu

      Version of Record online: 21 JAN 2005 | DOI: 10.1002/anie.200461954

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      A convergent synthesis of α-methylene amides exploits a hybrid radical/ionic concept in which radical carbonylation of alkynes is followed by ionic trapping of the resulting carbonyl-containing radical species with amines (see scheme). The reaction of substituted terminal alkynes with pressurized CO, Bu3SnH, and 2,2′-azobisisobutyronitrile in the presence of a large excess of amines gave good yields of the corresponding α-methylene amides.

    14. Aromatic Boron Wheels with More than One Carbon Atom in the Center: C2B8, C3B93+, and C5B11+ (pages 1078–1082)

      Stefan Erhardt, Gernot Frenking, Zhongfang Chen and Paul von Ragué Schleyer

      Version of Record online: 21 JAN 2005 | DOI: 10.1002/anie.200461970

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      Computational exploration of carboranes of formula CnBmq+ reveals that more than one hypercoordinated carbon atom can be enclosed by a peripheral ring comprising a suitable number of boron atoms. The C2B8, C3B93+, and C5B11+ species (the LUMO of the latter is shown) are stabilized by substantial Hückel π aromaticity. Furthermore, multicenter σ bonding helps bind the inner carbon units to the boron perimeters, though they can freely rotate relative to one another.

    15. One-Pot Conversion of Phospholide Ions into β-Functional Phosphinines (pages 1082–1084)

      Joanna Grundy and François Mathey

      Version of Record online: 20 JAN 2005 | DOI: 10.1002/anie.200462020

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      Only a few β-functional phosphinines are known. As a result, the reactivity of this class of compounds is almost unexplored. A straightforward access to such compounds from the readily available phospholide ions is described (see scheme) and the reaction mechanism is explored by theoretical methods.

    16. Atom-Transfer Radical Reactions under Mild Conditions with [{RuCl2(1,3,5-C6H3iPr3)}2] and PCy3 as the Catalyst Precursors (pages 1084–1088)

      Laurent Quebatte, Michel Haas, Euro Solari, Rosario Scopelliti, Quoc T. Nguyen and Kay Severin

      Version of Record online: 20 JAN 2005 | DOI: 10.1002/anie.200462037

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      Simply mixing the complex [{RuCl2(1,3,5-C6H3iPr3)}2] (1) with PCy3 is sufficient to generate a catalyst suitable for highly efficient atom-transfer radical addition and polymerization reactions at exceptionally low temperatures (see scheme). The steric congestion at the metal caused by the bulky ligands is thought to be essential for the reactivity of the catalyst.

    17. A Rock-Salt-Like Lattice Structure Consisting of Monocationic and Monoanionic AuIAgICuII Supramolecular Cages of D-Penicillaminate (pages 1088–1092)

      Atsushi Toyota, Tadashi Yamaguchi, Asako Igashira-Kamiyama, Tatsuya Kawamoto and Takumi Konno

      Version of Record online: 3 JAN 2005 | DOI: 10.1002/anie.200462205

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      All three coinage metals are present in the supramolecular compound created from D-penicillamine (D-H2pen) by stepwise reaction with AuI, AgI, and CuII in the presence of Cl. In this compound, 20-nuclear monocationic [Au6Ag8Cu6Cl(H2O)5(D-pen)12]+ and 21-nuclear monoanionic [Au6Ag9Cu6Cl4(H2O)6(D-pen)12] (see picture) supramolecular cages, each of which accommodates a Cl ion (green), are linked so as to form a giant rock-salt-like lattice structure.

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      Visualization of Membrane Processes in Living Cells by Surface-Attached Chromatic Polymer Patches (pages 1092–1096)

      Zulfiya Orynbayeva, Sofiya Kolusheva, Etta Livneh, Alexandra Lichtenshtein, Ilana Nathan and Raz Jelinek

      Version of Record online: 10 JAN 2005 | DOI: 10.1002/anie.200462393

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      Patch work: Through attachment of chromatic polydiacetylene (PDA) nanopatches onto the plasma membrane, real-time visualization of surface processes in living cells is possible (see picture; scale bar: 10 μm). The membrane-incorporated polymer patches did not adversely affect cell vitality for several hours and responded to structural perturbations of the plasma membrane both through induction of fluorescence as well as by undergoing blue–red color changes.

    19. “Grafting-From” Polymerization inside a Polyelectrolyte Hollow-Capsule Microreactor (pages 1096–1101)

      Won San Choi, Jeong-Ho Park, Hye Young Koo, Ju-Young Kim, B. K. Cho and Dong-Yu Kim

      Version of Record online: 3 JAN 2005 | DOI: 10.1002/anie.200460971

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      Interior decorating: Polymerization of styrene sulfonate monomers on the inner surface of polyelectrolyte hollow capsules results in polymers having molecular weights an order of magnitude higher than those produced in solution. The shape of the capsules after polymerization can be manipulated by varying the styrene sulfonate content (see SEM images; a: 25 wt %, b: 40 wt %).

    20. Highly Efficient Cobalt-Mediated Radical Polymerization of Vinyl Acetate (pages 1101–1104)

      Antoine Debuigne, Jean-Raphaël Caille and Robert Jérôme

      Version of Record online: 11 JAN 2005 | DOI: 10.1002/anie.200461333

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      Reversible end-capping of the growing polymer chains to form dormant species (see scheme) lowers the radical concentration. Thus, cobalt(II) acetylacetonate efficiently controls the bulk radical polymerization of vinyl acetate. The molar mass of the poly(vinyl acetate) increases linearly with monomer conversion, polydispersity is as low as 1.15, and polymerization can be resumed by preformed vinyl acetate oligomers. acac=acetylacetonate.

    21. GaAs–Polymer Hybrids Formed by Surface-Initiated Atom-Transfer Radical Polymerization of Methyl Methacrylate (pages 1104–1107)

      Qin Jia Cai, Guo Dong Fu, Fu Rong Zhu, En-Tang Kang and Koon-Gee Neoh

      Version of Record online: 11 JAN 2005 | DOI: 10.1002/anie.200461570

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      A sulfanylhexanol coupling agent is crucial for the preparation of GaAs–poly(methyl methacrylate) (PMMA) hybrids by surface-initiated atom-transfer radical polymerization (ATRP) of methyl methacrylate (see scheme) as it passivates the GaAs surface and also immobilizes the ATRP initiator. The surface states of GaAs are not significantly affected by the ATRP process.

    22. Remote Activation of Nickel Catalysts for Ethylene Oligomerization (pages 1108–1112)

      Yaofeng Chen, Gang Wu and Guillermo C. Bazan

      Version of Record online: 12 JAN 2005 | DOI: 10.1002/anie.200461630

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      Remote control: A novel molecular design is described and used to probe the activation of transition-metal-based ethylene polymerization and oligomerization initiators by the action of a Lewis acid across an electronically delocalized structural unit. Compound 1 which has a Lewis acid attached to a site removed from the trajectory of the incoming substrate, shows high activity for ethylene oligomerization.

    23. Perovskite Membranes in Ammonia Oxidation: Towards Process Intensification in Nitric Acid Manufacture (pages 1112–1115)

      Javier Pérez-Ramírez and Bent Vigeland

      Version of Record online: 13 JAN 2005 | DOI: 10.1002/anie.200462024

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      Intensified nitric acid production is possible when NH3 is oxidized with Ca- and Sr-substituted lanthanum ferrite perovskites in a membrane reactor with NO selectivities of up to 98 % (see picture). In this new process atmospheric N2 is rejected by the oxygen-conducting membrane, expensive noble metal catalysts are unnecessary, and no environmentally harmful N2O is produced.

    24. The Role of Gold in Gold–Titania Epoxidation Catalysts (pages 1115–1118)

      T. Alexander Nijhuis, Tom Visser and Bert M. Weckhuysen

      Version of Record online: 10 JAN 2005 | DOI: 10.1002/anie.200462043

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      Gold can activate propene or influence titania such that a reaction occurs in which bidentate propoxy species are formed on the catalyst (see picture). In the absence of gold this reaction is not possible. This observation brings the understanding of this unique catalyst system one step further.

    25. Highly Rigid Diphosphane Ligands with a Large Dihedral Angle Based on a Chiral Spirobifluorene Backbone (pages 1118–1121)

      Xu Cheng, Qi Zhang, Jian-Hua Xie, Li-Xin Wang and Qi-Lin Zhou

      Version of Record online: 21 JAN 2005 | DOI: 10.1002/anie.200462072

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      High and wide: The high rigidity and large dihedral angle of chiral, spirobifluorene-based diphosphane ligands lead to excellent reactivity and enantioselectivity in the ruthenium-catalyzed asymmetric hydrogenation of α,β-unsaturated carboxylic acids (see scheme).

    26. Enantioselective Reduction of β-Keto Acids with Engineered Streptomyces coelicolor (pages 1121–1125)

      Kevin I. Booker-Milburn, Rebecca Gillan, Meriel Kimberley, Takaaki Taguchi, Koji Ichinose, G. Richard Stephenson, Yutaka Ebizuka and David A. Hopwood

      Version of Record online: 11 JAN 2005 | DOI: 10.1002/anie.200462076

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      Compelling evidence for the intermediacy of the free β-keto acid 1, rather than the corresponding enzyme-bound thiolate as previously proposed, in the biosynthesis of the antibiotic actinorhodin (2) was obtained from studies of the enantioselective reduction of a range of β-keto acids by the engineered strain of S. coelicolor CH999/pIJ5675. This excellent whole-cell biotransformation system gave the desired S β-hydroxy acids with >95 % ee.

    27. A Trihydroxy Tin Group That Resists Oligomerization in the Trinuclear Nickel Cluster [Ni3(μ-P,P′-PPh2CH2PPh2)33-L)- (μ3-Sn(OH)3)] (pages 1125–1128)

      Eugenio Simón-Manso and Clifford P. Kubiak

      Version of Record online: 4 JAN 2005 | DOI: 10.1002/anie.200462129

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      Tin caps: A straightforward synthetic pathway leads to a series of trihydroxy tin capped trinuclear nickel clusters. The Sn(OH)3 groups of the clusters resist oligomerization. They display high nucleophilicity leading to reversible formation of an η2-carbonato tin capped cluster in the presence of CO2 (see scheme) and ring opening of 1,2-epoxybutane to the corresponding tin coordinated diolate.

    28. Palladium(0)-Catalyzed Hydroalkoxylation of Hexafluoropropene: Synthesis of Hydrofluoroethers under Neutral Conditions (pages 1128–1130)

      Yasuhisa Matsukawa, Junji Mizukado, Heng-dao Quan, Masanori Tamura and Akira Sekiya

      Version of Record online: 11 JAN 2005 | DOI: 10.1002/anie.200462200

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      No vinyl ether by-products are formed in the palladium(0)-complex catalyzed hydroalkoxylation of hexafluoropropene (see scheme). Saturated hydrofluoroethers are selectively synthesized with alcohols or phenols under neutral conditions in the presence of [Pd(PPh3)4]/dppb. dppb=1,4-bis(diphenylphosphanyl)butane.

    29. Stereocontrolled Total Synthesis of (−)-Aurisides A and B (pages 1130–1133)

      Ian Paterson, Gordon J. Florence, Annekatrin C. Heimann and Angela C. Mackay

      Version of Record online: 21 JAN 2005 | DOI: 10.1002/anie.200462267

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      An expedient total synthesis of aurisides A and B (1), unusual cytotoxic macrolide glycosides isolated from the Japanese sea hare D. auricularia, takes advantage of a highly convergent aldol-based route for the stereocontrolled construction of the common macrolide core. This is followed by α-selective glycosylation to introduce the sugar moieties.

    30. Nanoscale Tubules in Uranyl Selenates (pages 1134–1136)

      Sergey V. Krivovichev, Volker Kahlenberg, Reinhard Kaindl, Edgar Mersdorf, Ivan G. Tananaev and Boris F. Myasoedov

      Version of Record online: 11 JAN 2005 | DOI: 10.1002/anie.200462356

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      An inorganic oxo salt, K5[(UO2)3(SeO4)5](NO3)(H2O)3.5, forms a structure based on nanoscale uranyl selenate tubules (see picture; • {UO78−} bipyramids, ○ {SeO42−} tetrahedra). The interiors of the nanotubules are occupied by K+ ions and H2O molecules.

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