Chemistry - A European Journal

Cover image for Vol. 15 Issue 31

August 3, 2009

Volume 15, Issue 31

Pages 7507–7735

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Communications
    6. Full Papers
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    1. Cover Picture: Synthesis and EPR Studies of 2′-Deoxyuridines with Alkynyl, Rodlike Linkages (Chem. Eur. J. 31/2009) (page 7507)

      Adam Sniady, Michael D. Sevilla, Srinivasarao Meneni, Tadeusz Lis, Slawomir Szafert, Deepthi Khanduri, John M. Finke and Roman Dembinski

      Article first published online: 27 JUL 2009 | DOI: 10.1002/chem.200990116

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      Two different behaviors… of alkyne-tethered dinucleosides are described by M. D. Sevilla, R. Dembinski et al. in their Full Paper on page 7569 ff. In the reduced species the electron is localized on one ring only, whereas in the oxidized species the electron is delocalized over both rings. These structures essentially provide a gate that can separate hole and electron transport between strands in DNA systems. The cover is based on a photograph of the Markiezenhof Museum interior, Bergen op Zoom (The Netherlands) by Peter van Dijk. Art impression by Rien Slagter and graphical design by Peter van Dijk/Tomasz Sniady.

  2. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
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    1. Graphical Abstract: Chem. Eur. J. 31/2009 (pages 7508–7514)

      Article first published online: 27 JUL 2009 | DOI: 10.1002/chem.200990117

  3. News

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Communications
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  4. Communications

    1. Top of page
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    3. Graphical Abstract
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    1. Nanotube Composites

      Ionic Liquids on Photoinduced Nanotube Composite Arrays as a Reaction Medium (pages 7520–7525)

      Eijiro Miyako, Tamitake Itoh, Yoji Nara and Takahiro Hirotsu

      Article first published online: 30 JUN 2009 | DOI: 10.1002/chem.200901348

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      Attractive tubes: When triggered by very low powered near-infrared laser irradiation, photoimmobilized single-walled carbon nanotube composite arrays can provide ultrafast thermal control of room-temperature ionic liquids and quickly produce many poly(N-isopropylacrylamide) microspheres in water-in-ionic-liquid emulsions (see figure).

    2. Oligo(glyco–amino acid)s

      Synthesis of 2-C-Branched Oligo(glyco–amino acid)s (OGAAs) by Ring Opening of 1,2-Cyclopropanecarboxylated Sugar Donors (pages 7526–7529)

      Perali Ramu Sridhar, Patteti Venu Kumar, Kalapati Seshadri and Rayala Satyavathi

      Article first published online: 8 JUL 2009 | DOI: 10.1002/chem.200901022

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      Hybrid theory: 1,2-Cyclopropanecarboxylated sugars were used as glycosyl donors for the first time in the synthesis of 2-C-branched oligo(glyco–amino acid)s (OGAAs; see scheme) decorated with α-amino acids. The method was applied to an acceptor-reactivity-based stereo- and regioselective glycosylation reaction towards the preparation of several disaccharide-derived glyco–amino acid derivatives.

    3. Perylene Bisimides

      Regioselective Ru-Catalyzed Direct 2,5,8,11-Alkylation of Perylene Bisimides (pages 7530–7533)

      Satomi Nakazono, Yusuke Imazaki, Hyejin Yoo, Jaesung Yang, Takahiro Sasamori, Norihiro Tokitoh, Tassel Cédric, Hiroshi Kageyama, Dongho Kim, Hiroshi Shinokubo and Atsuhiro Osuka

      Article first published online: 2 JUL 2009 | DOI: 10.1002/chem.200901318

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      Regioselective direct alkylation of perylene bisimides at 2,5,8,11-positions has been achieved by reaction with terminal alkenes under ruthenium catalysis by the Murai–Chatani–Kakiuchi protocol (see scheme). Alkylation of perylene bisimides results in enhanced solubility and quantum efficiency in the solid state.

    4. Molecular Devices

      Electrochemically Induced Intermolecular Anion Transfer (pages 7534–7538)

      David Curiel, Paul D. Beer, Alberto Tárraga and Pedro Molina

      Article first published online: 2 JUL 2009 | DOI: 10.1002/chem.200900878

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      Electrochemical switching is applied to tune the relative anion-binding strength of two independent macrocyclic receptors (see figure) where the intermolecular anion transfer can be monitored by emission spectroscopy.

    5. Heterogeneous Catalysis

      Heterogeneously Catalyzed Efficient Alkyne–Alkyne Homocoupling by Supported Copper Hydroxide on Titanium Oxide (pages 7539–7542)

      Takamichi Oishi, Tatsuyori Katayama, Kazuya Yamaguchi and Noritaka Mizuno

      Article first published online: 30 JUN 2009 | DOI: 10.1002/chem.200901080

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      The supported copper hydroxide on titanium oxide (Cu(OH)x/TiO2) has been shown to act as an efficient heterogeneous catalyst for the oxidative alkyne–alkyne homocoupling. A wide variety of alkynes including aromatic, aliphatic, double-bond-containing, and silylacetylene derivatives were selectively converted into the corresponding diyne derivatives in high yields without any additives such as bases.

    6. Cascade Reactions

      Acid-Catalyzed Cascade Reactions of Arylvinylcyclopropenes with Acetals and Aldehydes for the Construction of Different Aromatic Systems (pages 7543–7548)

      Zhi-Bin Zhu, Yin Wei and Min Shi

      Article first published online: 30 JUN 2009 | DOI: 10.1002/chem.200900948

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      Catalyzed by acid, the reactions of arylvinylcycloproenes with acetals or aldehydes lead to different cascade additions to construct different aromatic systems (see scheme).

    7. Metal–Organic Frameworks

      Metal-Ion-Dependent Gas Sorptivity of Elastic Layer-Structured MOFs (pages 7549–7553)

      Atsushi Kondo, Ayako Chinen, Hiroshi Kajiro, Tomohiro Nakagawa, Kenichi Kato, Masaki Takata, Yoshiyuki Hattori, Fujio Okino, Tomonori Ohba, Katsumi Kaneko and Hirofumi Kanoh

      Article first published online: 30 JUN 2009 | DOI: 10.1002/chem.200901208

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      Elastic layers: By comparing the gas adsorptivities of N2, O2, CO2, and H2 on two elastic layer-structured metal–organic frameworks (MOFs) with different metal ions, definite differences could be observed in O2, CO2, and H2 despite their structural similarity. In most cases of MOFs, the metal ion has been considered as a connector. However, the metal ion clearly has the potential to regulate gas adsorptivity especially in flexible MOFs.

  5. Full Papers

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Communications
    6. Full Papers
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    1. Crystal Engineering

      Rational Modification of the Hierarchy of Intermolecular Interactions in Molecular Crystal Structures by Using Tunable Halogen Bonds (pages 7554–7568)

      Guillermo Mínguez Espallargas, Fiorenzo Zordan, Luis Arroyo Marín, Harry Adams, Kenneth Shankland, Jacco van de Streek and Lee Brammer

      Article first published online: 11 JUL 2009 | DOI: 10.1002/chem.200900410

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      Dial-in interaction strength: Tuning the strength of one type of intermolecular interaction affects the relative importance of different interactions in directing the crystal structure adopted. C[BOND]X⋅⋅⋅X′[BOND]M halogen bonds can be tuned in strength by changing either the organic (X) or inorganic (X′) halogen.

    2. Tethered Nucleosides

      Synthesis and EPR Studies of 2′-Deoxyuridines with Alkynyl, Rodlike Linkages (pages 7569–7577)

      Adam Sniady, Michael D. Sevilla, Srinivasarao Meneni, Tadeusz Lis, Slawomir Szafert, Deepthi Khanduri, John M. Finke and Roman Dembinski

      Article first published online: 16 JUL 2009 | DOI: 10.1002/chem.200900481

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      One of two ways: Alkyne-tethered dinucleosides have been shown to display two distinct behaviors; when reduced, the electron is localized on only one ring, whereas if they are oxidized the electron is delocalized across both rings (see figure). This effect could be used as a gate that separates hole and electron transport between strands in DNA systems.

    3. Dynamic Coordination Frameworks

      Temperature-Dependent Guest-Driven Single-Crystal-to-Single-Crystal Ligand Exchange in a Two-Fold Interpenetrated CdII Grid Network (pages 7578–7585)

      Chun-Feng Zhuang, Jianyong Zhang, Qing Wang, Zhao-Hua Chu, Dieter Fenske and Cheng-Yong Su

      Article first published online: 3 JUL 2009 | DOI: 10.1002/chem.200900552

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      Dynamic coordination polymers! Doubly interlaced CdII coordination grid networks show indirect recoverable single-crystal-to-single-crystal structural transformations through the water stabilization of the porous metastable structure involving Cd[BOND]O bond cleavage/formation in the coordination sphere and guest exchange in the framework cavity (see figure).

    4. Nanocomposites

      A Complete Multiscale Modelling Approach for Polymer–Clay Nanocomposites (pages 7586–7592)

      Giulio Scocchi, Paola Posocco, Jan-Willem Handgraaf, Johannes G. E. M. Fraaije, Maurizio Fermeglia and Sabrina Pricl

      Article first published online: 2 JUL 2009 | DOI: 10.1002/chem.200900995

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      Structural snapshots of polymer–clay nanocomposites are obtained by a mesoscopic bead–field hybrid simulation method in which the clay platelets and compatibiliser molecules are represented as soft-core beads and the polymer is represented by a field model (see picture; bead colors: brown, clay; blue/light green, compatibiliser; field colors: red, high density values; green, intermediate density values; blue, low density values).

    5. Hyperbranched Polymers

      Hybrid Polymerization of Vinyl and Hetero-Ring Groups of Glycidyl Methacrylate Resulting in Thermoresponsive Hyperbranched Polymers Displaying a Wide Range of Lower Critical Solution Temperatures (pages 7593–7600)

      Zhifeng Jia, Guolin Li, Qi Zhu, Deyue Yan, Xinyuan Zhu, Hao Chen, Jieli Wu, Chunlai Tu and Jian Sun

      Article first published online: 2 JUL 2009 | DOI: 10.1002/chem.200900345

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      Temperature-specific phase separation: Thermoresponsive hyperbranched polymers have been synthesized by hybrid polymerization of glycidyl methacrylate and oligo(ethylene glycol)s. Reversible abrupt phase separation at the LCST renders an aqueous solution of such a polymer opaque (see photographs, sjtu = Shanghai Jiao Tong University) by changing the hydrophilic/hydrophobic balance.

    6. Density Functional Theory

      Theoretical Study of the Stability of the DNA Duplexes Modified by a Series of Hydrophobic Base Analogues (pages 7601–7610)

      Lucie Zendlová, David Řeha, Michal Hocek and Pavel Hobza

      Article first published online: 30 JUN 2009 | DOI: 10.1002/chem.200802170

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      Pile up! The thermodynamic stability and selectivity of DNA duplexes modified by a series of base analogues was studied by molecular dynamics simulations and quantum chemical calculations based on the density functional theory. The effect of solvent was also included in the study by the continuum method. The results show the importance of stacking interactions, steric effects and solvation on the stability of a modified DNA duplex (see figure).

    7. Nanofibres

      New Blue-Light-Emitting Ultralong [Cd(L)(TeO3)] (L=polyamine) Organic–Inorganic Hybrid Nanofibre Bundles: Their Thermal Stability and Acidic Sensitivity (pages 7611–7618)

      Hong-Bin Yao, Xiao-Bo Li and Shu-Hong Yu

      Article first published online: 23 JUN 2009 | DOI: 10.1002/chem.200900610

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      Ultralong fibres: New blue-light-emitting ultralong [Cd(L)(TeO3)] nanofibre bundles (L=ethylenediamine, diethylenetriamine) have been synthesised under reflux in a mixed solvent (see figure). Their thermal stability, optical properties and acidic sensitivity have been investigated.

    8. Ionic Liquids

      Reversible Uptake of COS, CS2, and SO2: Ionic Liquids with O-Alkylxanthate, O-Alkylthiocarbonyl, and O-Alkylsulfite Anions (pages 7619–7627)

      David J. Heldebrant, Clement R. Yonker, Philip G. Jessop and Lam Phan

      Article first published online: 23 JUN 2009 | DOI: 10.1002/chem.200802602

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      Uptaking acid: CO2-binding organic liquid (BOL) systems are shown to chemically react with three sulfur-containing acid gases: COS, CS2, and SO2. These systems are the first to show reversible binding, and the uptake of the resulting acid gases yields viscous, colored ionic liquids (see image) that hold potential as chemical sensors for specific acid gases.

    9. Helical Structures

      Position-Dependent Effects of Fluorinated Amino Acids on the Hydrophobic Core Formation of a Heterodimeric Coiled Coil (pages 7628–7636)

      Mario Salwiczek, Sergey Samsonov, Toni Vagt, Elisabeth Nyakatura, Emanuel Fleige, Jorge Numata, Helmut Cölfen, M. Teresa Pisabarro and Beate Koksch

      Article first published online: 3 JUL 2009 | DOI: 10.1002/chem.200802136

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      Picking up the fluorine trail: The effects of amino acid side chain fluorination on the stability of protein folds are not easy to predict. The incorporation of fluorine substituents (in green) induces dipoles (arrows) in hydrophobic amino acid side chains. Whether or not the dipole interferes with the advantageous effects of increase in spatial demand and hydrophobicity highly depends on the orientation of the fluorinated side chain within the respective protein environment.

    10. Quinine Alkaloids

      Fluorinated Quinine Alkaloids: Synthesis, X-ray Structure Analysis and Antimalarial Parasite Chemotherapy (pages 7637–7647)

      Christoph Bucher, Christof Sparr, W. Bernd Schweizer and Ryan Gilmour

      Article first published online: 29 JUN 2009 | DOI: 10.1002/chem.200900505

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      Fluorine in focus! The synthesis of a series of C9-fluorinated quinine alkaloids is reported. Solid-state analysis of a number of the hydrochloride salts is documented and gives an intriguing insight into the consequence of introducing a fluorine atom at the C9 position. The first X-ray evidence of a vicinal fluorine atom at a stereogenic centre positioned anti to a substituted ammonium cation is disclosed.

    11. Magnetic Properties

      Diamond- and Graphite-Like Octacyanometalate-Based Polymers Induced by Metal Ions (pages 7648–7655)

      Ying Wang, Tian-Wei Wang, Hong-Ping Xiao, Yi-Zhi Li, You Song and Xiao-Zeng You

      Article first published online: 25 JUN 2009 | DOI: 10.1002/chem.200900578

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      Ferromagnetic graphite-like structures: By using cyclohexane-1,2-diamine as a ligand, and by adding metal ions, a 3D diamond-like framework and 2D graphite-like polymers (see figure) have been synthesised. The magnetic properties have been investigated and the more diffuse 5d orbitals lead to a stronger magnetic coupling interaction between the WV and CuII ions than MoV and CuII ions.

    12. Glycosylation

      Reliable Synthesis of Various Nucleoside Diphosphate Glycopyranoses (pages 7656–7664)

      Saskia Wolf, Tanja Zismann, Nathalie Lunau and Chris Meier

      Article first published online: 30 JUN 2009 | DOI: 10.1002/chem.200900572

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      A short and robust method for the synthesis of nucleoside diphosphate sugars (NDP-sugars) bearing natural nucleosides and sugars as well as analogues of both was developed. Yields up to 87 % were obtained using cycloSal-nucleotides as active esters. NDP-sugars play a key role in oligosaccharide synthesis and may be used in the future as drug targets.

    13. Diels–Alder Reactions

      An Alternative Mechanism for Diels–Alder Reactions of Evans Auxiliary Derivatives (pages 7665–7677)

      Snezhana M. Bakalova, Filipe J. S. Duarte, Miglena K. Georgieva, Eurico J. Cabrita and A. Gil Santos

      Article first published online: 1 JUL 2009 | DOI: 10.1002/chem.200900628

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      Stereoselectivity rationalization: The mechanism proposed by Evans for the Lewis acid promoted Diels–Alder reaction of cyclopentadiene (CPD) with α,β-unsaturated N-acyloxazolidinones was studied by theoretical and NMR spectroscopic methodologies. A new and more general model is proposed (see scheme).

    14. Electron Transfer

      Photophysics of an Intramolecular Hydrogen-Evolving Ru–Pd Photocatalyst (pages 7678–7688)

      Stefanie Tschierlei, Martin Presselt, Christian Kuhnt, Arkady Yartsev, Torbjörn Pascher, Villy Sundström, Michael Karnahl, Matthias Schwalbe , Bernhard Schäfer, Sven Rau , Michael Schmitt, Benjamin Dietzek  and Jürgen Popp 

      Article first published online: 25 JUN 2009 | DOI: 10.1002/chem.200900457

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      Electron transfer on the clock: Photoinduced electron transfer in the hydrogen-evolving photocatalyst [(tbbpy)2Ru(tpphz)PdCl2]2+ is found to take place on a sub-nanosecond timescale. Femtosecond time-resolved spectroscopy highlights the vectorial nature of electron transfer from the photoactive Ru center across the tpphz bridge to the catalytically active Pd center (see picture).

    15. Metal–Metal Interactions

      The Controlled Formation and Cleavage of an Intramolecular d8–d8 Pt–Pt Interaction in a Dinuclear Cycloplatinated Molecular “Pivot-Hinge” (pages 7689–7697)

      Chi-Kin Koo, Ka-Leung Wong, Kai-Cheung Lau, Wai-Yeung Wong and Michael Hon-Wah Lam

      Article first published online: 27 JUN 2009 | DOI: 10.1002/chem.200802703

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      An open and shut case: The “pivot-hinge”-like intramolecular motion of Pt2dppm was studied with the analogous complex Pt2dchpm (see picture). The reversible formation and cleavage of the Pt–Pt interaction in Pt2dppm is induced by π–π interactions between the phenyl moieties of the μ-dppm and the deprotonated pyrazolyl rings of the cyclometalated ligands.

    16. Porphyrin–Fullerene Dyads

      Synthesis, Conformational Interconversion, and Photophysics of Tethered Porphyrin–Fullerene Dyads with Parachute Topology (pages 7698–7705)

      Michael A. Fazio, Alexander Durandin, Nikolai V. Tkachenko, Marja Niemi, Helge Lemmetyinen and David I. Schuster

      Article first published online: 30 JUN 2009 | DOI: 10.1002/chem.200900587

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      Windshield-wiper-like motion: Previously proposed windshield-wiper-like conformational interconversion of parachute-shaped porphyrin–fullerene dyads (see picture), shown to be consistent with intramolecular electron-transfer dynamics at ambient temperatures and time-resolved electron paramagnetic resonance data at low temperatures, is supported by variable-temperature NMR studies on a newly synthesized dyad with the same topology.

    17. Coordination Modes

      Dirhodium(II) Compounds with Bridging Thienylphosphines: Studies on Reversible P,C/P,S Coordination (pages 7706–7716)

      Julio Lloret, Francisco Estevan, Pascual Lahuerta, Pipsa Hirva, Julia Pérez-Prieto and Mercedes Sanaú

      Article first published online: 30 JUN 2009 | DOI: 10.1002/chem.200900582

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      Heavy metalation: Switching from the P,C to P,S coordination mode of thienylphosphine to rhodium(II) occurs in a strong acidic medium (see image). Experimental and theoretical studies confirm that the main reaction pathway takes place without decoordination of the thienyl ring.

    18. Antioxidants

      A Mechanistic Study of the Effects of Antioxidants on the Formation of Malondialdehyde-Like Products in the Reaction of Hydroxyl Radicals with Deoxyribose (pages 7717–7723)

      Sandra Rachmilovich-Calis, Naomi Meyerstein and Dan Meyerstein

      Article first published online: 23 JUN 2009 | DOI: 10.1002/chem.200802272

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      Dependency: The antioxidant properties of R′SH compounds depend on the solution composition and the rate constants of the secondary reactions of the R′S. radicals (see scheme).

    19. Metal–Organic Frameworks

      Framework Breathing in the Vapour-Phase Adsorption and Separation of Xylene Isomers with the Metal–Organic Framework MIL-53 (pages 7724–7731)

      Vincent Finsy, Christine E. A. Kirschhock, Gill Vedts, Michael Maes, Luc Alaerts, Dirk E. De Vos, Gino V. Baron and Joeri F. M. Denayer

      Article first published online: 23 JUN 2009 | DOI: 10.1002/chem.200802672

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      Isomer separation on MIL-53: Framework breathing permits separation of xylene isomers (see picture). At low pressures (top), adsorption of C8 alkyl aromatic compounds induces contraction of the MIL-53 (Al) framework. Under these conditions, there is no difference in adsorption between the various isomers. No separation is possible. At higher pressures (bottom), the framework is reopened and additional molecules are adsorbed in a selective way.

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    4. News
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      Preview: Chem. Eur. J. 32/2009 (page 7735)

      Article first published online: 27 JUL 2009 | DOI: 10.1002/chem.200990119

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