Chemistry - A European Journal

Cover image for Vol. 12 Issue 27

September 18, 2006

Volume 12, Issue 27

Pages 7007–7267

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    1. Cover Picture: Kinetic, Thermodynamic, and Mechanistic Patterns for Free (Unbound) Cytochrome c at Au/SAM Junctions: Impact of Electronic Coupling, Hydrostatic Pressure, and Stabilizing/Denaturing Additives (Chem. Eur. J. 27/2006) (page 7007)

      Dimitri E. Khoshtariya, Tina D. Dolidze, Stefan Seifert, David Sarauli, Geoffrey Lee and Rudi van Eldik

      Version of Record online: 6 SEP 2006 | DOI: 10.1002/chem.200690086

      The cross-testing of the CytC intrinsic ET mechanisms at the Au/SAM junctions (hydroxy-terminated n-alkanethiol self-assembled monolayers) in the freely diffusing regime revealed a gradual turnover from the adiabatic to nonadiabatic mechanism through the intermediate regime. In their Full Paper on page 7041 ff., R. van Eldik, D. E. Khoshtariya et al. describe their investigations involving variation of the SAM thickness (n=2, 3, 4, 6, 11, with n=4 found to be a turnover point), the relative solution viscosity, and the hydrostatic pressure (up to 150 MPa).

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    1. Structure and Reactivity of Radical Ions: New Twists on Old Concepts (pages 7018–7026)

      Patrick J. Donoghue and Olaf Wiest

      Version of Record online: 28 JUL 2006 | DOI: 10.1002/chem.200600554

      A single electron changes everything! Many fundamental concepts of organic chemistry, such as symmetry, aromaticity, or bonding, exhibit interesting variations in radical cations formed by one-electron oxidation of hydrocarbons. This paper reviews the role of state symmetry correlations, Jahn–Teller distortions, delocalization, and fractional bonding for the reaction pathways of these interesting reactive intermediates.

  4. Full Papers

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    1. Single-Chain Magnet Behavior in an Alternated One-Dimensional Assembly of a MnIII Schiff-Base Complex and a TCNQ Radical (pages 7028–7040)

      Hitoshi Miyasaka, Tomokura Madanbashi, Kunihisa Sugimoto, Yasuhiro Nakazawa, Wolfgang Wernsdorfer, Ken-ichi Sugiura, Masahiro Yamashita, Claude Coulon and Rodolphe Clérac

      Version of Record online: 7 AUG 2006 | DOI: 10.1002/chem.200600289

      Thumbnail image of graphical abstract

      A new one-dimensional ferrimagnetic arrangement of MnIII ions and the tetracyano-p-quinodimethane (TCNQ) radical has been obtained in [Mn(5-TMAMsaltmen)(TCNQ)](ClO4)2 (see picture) (5-TMAMsaltmen=N,N′-(1,1,2,2-tetramethylethylene) bis(5-trimethylammoniomethylsalicylideneiminato)), which exhibits single-chain magnet behavior as shown by the detailed analysis of its thermodynamic and dynamic properties.

    2. Kinetic, Thermodynamic, and Mechanistic Patterns for Free (Unbound) Cytochrome c at Au/SAM Junctions: Impact of Electronic Coupling, Hydrostatic Pressure, and Stabilizing/Denaturing Additives (pages 7041–7056)

      Dimitri E. Khoshtariya, Tina D. Dolidze, Stefan Seifert, David Sarauli, Geoffrey Lee and Rudi van Eldik

      Version of Record online: 3 AUG 2006 | DOI: 10.1002/chem.200600059

      Thumbnail image of graphical abstract

      Compare and understand: Combined kinetic and thermodynamic studies of intact (unbound) cytochrome c freely diffusing to gold electrodes modified by hydroxyl-terminated alkanethiol self-assembled monolayers (SAMs; see figure) revealed novel intrinsic links between local/global structural and functional characteristics and between dynamic effects of high pressure and solution viscosity, and demonstrated changeover of the charge-transfer mechanism with the variation of charge-transfer distance (SAM thickness).

    3. Carbonic Anhydrase Activators. Activation of Isozymes I, II, IV, VA, VII, and XIV with L- and D-Histidine and Crystallographic Analysis of Their Adducts with Isoform II: Engineering Proton-Transfer Processes within the Active Site of an Enzyme (pages 7057–7066)

      Claudia Temperini, Andrea Scozzafava, Daniela Vullo and Claudiu T. Supuran

      Version of Record online: 28 JUN 2006 | DOI: 10.1002/chem.200600159

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      Anchored at the entrance of the active site, l- and d-histidine residues activate carbonic anhydrases (isoforms hCA I, II, IV, VA, VII, and XIV) to different extents. X-ray crystallography showed that these activators participated in extended networks of hydrogen bonds with amino acid residues/water molecules present in the cavity, which explains their different efficacy and interaction patterns with various isozymes (see picture).

    4. Predicting the Activity of Single Isolated Lewis Acid Sites in Solid Catalysts (pages 7067–7077)

      Mercedes Boronat, Avelino Corma, Michael Renz and Pedro M. Viruela

      Version of Record online: 25 AUG 2006 | DOI: 10.1002/chem.200600478

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      Powerful quantum chemical calculations were combined with reaction rate measurements to elucidate the catalytic activity of Ti-, Zr- and Sn-beta zeolites for Lewis acid catalysed redox reactions. The difference in reactivity of the three materials is explained in terms of the molecular orbital distribution of the active sites and the adsorbed reactants.

    5. Flexibility of Inorganic Tennis Ball Structures Inducing Anion Selectivity (pages 7078–7083)

      Ki-Hyun Kim, Jung Su Park, Tae Yi Kang, Kyungeun Oh, Mi-Sook Seo, Youn Soo Sohn, Moo-Jin Jun, Wonwoo Nam and Kwan Mook Kim

      Version of Record online: 26 JUN 2006 | DOI: 10.1002/chem.200501626

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      Anions for tennis! Inorganic tennis balls (ITB) have been studied both in solution and the solid state. The cavity in an ITB is flexible and encapsulates various anions selectively. An example is shown here.

    6. Persilylated Phosphoranyl Radicals: The First Persistent Noncyclic Phosphoranyl Radicals (pages 7084–7094)

      Yves Berchadsky, Christiane Bernard-Henriet, Jean-Pierre Finet, Robert Lauricella, Sylvain R. A. Marque and Paul Tordo

      Version of Record online: 18 JUL 2006 | DOI: 10.1002/chem.200600299

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      Staying power: The persilylated phosphoranyl radicals 16 represent the first persistent noncyclic phosphoranyl radicals. EPR detection and kinetic studies of these new, very persistent (t1/2 = 45 min at room temperature) phosphoranyl radicals are presented. (EPR=electron paramagnetic resonance.)

    7. In Situ Synthesis of Trisubstituted Methanol Ligands and Their Potential as One-Pot Generators of Cubane-like Metal Complexes (pages 7095–7102)

      Brendan F. Abrahams, Timothy A. Hudson and Richard Robson

      Version of Record online: 11 JUL 2006 | DOI: 10.1002/chem.200600323

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      One-pot cubes: The assembly of targeted cubane-like metal complexes (for example, see figure) from simple building blocks can be achieved in one-pot reaction systems.

    8. Phane Properties of [2.2]Paracyclophane/Dehydrobenzoannulene Hybrids (pages 7103–7115)

      Heino Hinrichs, Andrew J. Boydston, Peter G. Jones, Kirsten Hess, Rainer Herges, Michael M. Haley and Henning Hopf

      Version of Record online: 7 AUG 2006 | DOI: 10.1002/chem.200600498

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      Global communication between the decks in the [2.2]paracyclophane unit is elucidated by comparison of the electronic absorption spectra of a series of compounds (see scheme) described herein.

    9. Chemical Synthesis of a Glycolipid Library by a Solid-Phase Strategy Allows Elucidation of the Structural Specificity of Immunostimulation by Rhamnolipids (pages 7116–7124)

      Jörg Bauer, Klaus Brandenburg, Ulrich Zähringer and Jörg Rademann

      Version of Record online: 17 AUG 2006 | DOI: 10.1002/chem.200600482

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      Structure–activity relationships in rhamnolipids: The first synthesis of a glycolipid library by hydrophobically assisted switching phase (HASP) synthesis is presented. The obtained rhamnolipids (RL) are potent stimulators of the innate immune system, acting through secretion of tumor necrosis factor α (TNFα), with high specificity regarding structural variations in the lipid part.

    10. A Novel Method for the In Situ Determination of Concentration Gradients in the Electrolyte of Li-Ion Batteries (pages 7125–7132)

      Jiang Zhou, Dmitry Danilov and Peter H. L. Notten

      Version of Record online: 18 JUL 2006 | DOI: 10.1002/chem.200600193

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      Battery powered: Measurement of the potential difference between two microreference electrodes placed in real Li-ion batteries allowed determination of the concentration gradient in the electrolyte. The diffusion coefficient of Li+ ions in the electrolyte and the diffusion overpotential from the electrolyte were also obtained (see scheme).

    11. Lanthanide Complexes of a Picolinate Ligand Derived from 1,4,7-Triazacyclononane with Potential Application in Magnetic Resonance Imaging and Time-Resolved Luminescence Imaging (pages 7133–7150)

      Aline Nonat, Christelle Gateau, Pascal H. Fries and Marinella Mazzanti

      Version of Record online: 6 JUN 2006 | DOI: 10.1002/chem.200501390

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      One ligand, two imaging probes: The inclusion of two picolinate groups on a triazacyclononane framework affords a new ligand leading to a mono-aquo gadolinium complex with favourable electronic relaxation properties for magnetic resonance imaging applications and to a terbium complex with high luminescence quantum yield (see scheme).

    12. Effect of Polarity and Structural Design on Molecular Photorefractive Properties of Heteroaromatic-Based Push–Pull Dyes (pages 7151–7160)

      Graziano Archetti, Alessandro Abbotto and Rüdiger Wortmann

      Version of Record online: 5 JUL 2006 | DOI: 10.1002/chem.200600037

      Thumbnail image of graphical abstract

      Optimizing photorefractive performance is expected to be facilitated by molecular design and host-matrix engineering. This study has established for the first time the strategic role of the polarity of the surrounding medium εr in determining photorefractive molecular performance (see picture). Complementary experimental and computational tools have been used to gain new insights into the photorefractive molecular properties of push–pull dipolar chromophores in terms of structural and media-polarity effects.

    13. Significantly Accelerated Direct Electron-Transfer Kinetics of Hemoglobin in a C60-MWCNT Nanocomposite Film (pages 7161–7166)

      Hua Zhang, Louzhen Fan and Shihe Yang

      Version of Record online: 28 JUN 2006 | DOI: 10.1002/chem.200600055

      Thumbnail image of graphical abstract

      Accelerated electron transfer: The heterogeneous electron-transfer rate constant ks of Hb/C60-MWCNT (MWCNT=multiple-walled carbon nanotube) was determined to be 0.39 s−1 (a), which is more than one order of magnitude greater than that of Hb/MWCNT (0.03 s−1) (c).

    14. Host–Guest Chemistry of Copper(II)–Histidine Complexes Encaged in Zeolite Y (pages 7167–7177)

      J. Gerbrand Mesu, Tom Visser, Andrew M. Beale, Fouad Soulimani and Bert M. Weckhuysen

      Version of Record online: 29 JUN 2006 | DOI: 10.1002/chem.200600087

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      Activation with zeolites: Zeolite Y was used to bring a copper–histidine complex into an activated, entactic form (see figure). A combination of different spectroscopic characterization techniques (XAS, UV/Vis/NIR, ESR, Raman, and IR spectroscopy) was used to identify the different copper–histidine species.

      Corrected by:

      Corrigendum: Corrigendum: Host-Guest Chemistry of Copper(II)–Histidine Complexes Encaged in Zeolite Y

      Vol. 17, Issue 12, 3312, Version of Record online: 4 MAR 2011

    15. Multicomponent Synthesis of Dihydropyrimidines and Thiazines (pages 7178–7189)

      Danielle J. Vugts, Manoe M. Koningstein, Rob F. Schmitz, Frans J. J. de Kanter, Marinus B. Groen and Romano V. A. Orru

      Version of Record online: 18 JUL 2006 | DOI: 10.1002/chem.200600168

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      Take four! A broad range of differently substituted dihydropyrimidines and thiazines can be efficiently prepared using a four-component reaction between phosphonates, nitriles, aldehydes, and iso(thio)cyanates (see scheme). The scope and limitations of this multicomponent reaction are fully described.

    16. Intramolecular Hetero-Michael Addition of β-Hydroxyenones for the Preparation of Highly Substituted Tetrahydropyranones (pages 7190–7203)

      Maud Reiter, Hazel Turner and Véronique Gouverneur

      Version of Record online: 3 JUL 2006 | DOI: 10.1002/chem.200600415

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      Pd catalysis: In the presence of a catalytic amount of [Pd(MeCN)4](BF4)2, syn- and anti-β-hydroxyenones undergo nonoxidative 6-endo-trig ring closure to form highly substituted tetrahydropyranones (see scheme). This palladium-mediated reaction is under kinetic control and operates with a high level of diastereocontrol.

    17. Affinity Adhesion of Carbohydrate Particles and Yeast Cells to Boronate-Containing Polymer Brushes Grafted onto Siliceous Supports (pages 7204–7214)

      Alexander E. Ivanov, Homayon Ahmad Panahi, Marina V. Kuzimenkova, Lars Nilsson, Björn Bergenståhl, Husain S. Waqif, Mohsen Jahanshahi, Igor Yu. Galaev and Bo Mattiasson

      Version of Record online: 18 JUL 2006 | DOI: 10.1002/chem.200600342

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      Cells adhere to boronate-containing copolymer brushes: Copolymers end-grafted onto solids enable sugar-specific adhesion and facile detachment of carbohydrate particles and cells (see picture). The grafted materials can be used for reversible immobilization and separation of cells.

    18. Resonance Structures of the Amide Bond: The Advantages of Planarity (pages 7215–7224)

      Jon I. Mujika, Jon M. Matxain, Leif A. Eriksson and Xabier Lopez

      Version of Record online: 28 JUN 2006 | DOI: 10.1002/chem.200600052

      Thumbnail image of graphical abstract

      Electron delocalization indexes derived from electron-pair densities have been demonstrated to be useful indicators of electron resonance in amides. A linear relation was found between the rotational barrier (ΔGrot) for the amides and the delocalization index (δON) between the nitrogen and oxygen atoms (see figure).

    19. Diastereoselective Multicomponent Cyclizations of Fischer Carbene Complexes, Lithium Enolates, and Allylmagnesium Bromide Leading to Highly Substituted Five- and Six-Membered Carbocycles (pages 7225–7235)

      José Barluenga, Iván Pérez-Sánchez, Marcos G. Suero, Eduardo Rubio and Josefa Flórez

      Version of Record online: 6 JUL 2006 | DOI: 10.1002/chem.200600491

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      Organometallic cyclizations: A novel one-pot synthetic sequence that transforms three/four simple starting materials into highly substituted and diastereomerically pure cyclopentanols or 1,4-cyclohexanediols has been developed (see scheme). These multicomponent cyclization reactions represent an efficient synthetic tool to introduce molecular complexity.

    20. De Novo Design, Synthesis, and Characterization of Quinoproteins (pages 7236–7245)

      Wen-Wu Li, Petra Hellwig, Michaela Ritter and Wolfgang Haehnel

      Version of Record online: 3 JUL 2006 | DOI: 10.1002/chem.200501212

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      Synthetic quinoproteins: Ubiquinone-0 and menaquinone-0 were bound through a thioether linkage to N-acetyl cysteine methyl ester and a de novo-designed synthetic four-helix bundle protein, and were characterized in detail (see picture). The redox potentials of the quinones in aqueous solution indicate a minor effect by the sulfur linkage but a substantial shift of 200–300 mV by the protein. Redox-induced Fourier transform infrared (FTIR) difference spectroscopy shows special features of the sulfur-substituted quinones.

    21. Unexpected Reactions of [60]Fullerene Involving Tertiary Amines and Insight into the Reaction Mechanisms (pages 7246–7253)

      Guan-Wu Wang, Xiao-Ping Chen and Xin Cheng

      Version of Record online: 20 JUL 2006 | DOI: 10.1002/chem.200600575

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      Stereoselective preparation of cyclopentafullerene derivatives: Novel fullerene products fused with full-carbon five-membered rings were obtained from reactions between C60 and tertiary amines in either the absence or the presence of an aldehyde (see scheme). Reaction mechanisms involving unusual carbon[BOND]nitrogen bond breaking in tertiary amines were proposed. ODCB=o-dichlorobenzene.

    22. Conformationally Restricted Aza-BODIPY: Highly Fluorescent, Stable Near-Infrared Absorbing Dyes (pages 7254–7263)

      Weili Zhao and Erick M. Carreira

      Version of Record online: 19 JUL 2006 | DOI: 10.1002/chem.200600527

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      Nitrogen makes all the difference! Novel NIR fluorescent, conformationally restricted aza-BODIPY dyes, such as that depicted here, were prepared by an efficient process. These dyes possess intense absorption, strong fluorescence, and high chemical and photostability.

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    1. You have free access to this content
      Preview: Chem. Eur. J. 27/2006 (page 7267)

      Version of Record online: 6 SEP 2006 | DOI: 10.1002/chem.200690088

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