ChemPlusChem

Cover image for Vol. 77 Issue 8

Special Issue: Board Members Issue

August 2012

Volume 77, Issue 8

Pages 599–726

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Masthead
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Full Papers
    1. Cover Picture: Counterion-Induced Inversion of Conformer Stability of a [5]Helquat Dication (ChemPlusChem 8/2012) (page 599)

      Lukáš Severa, Michael Jirásek, Pavel Švec, Dr. Filip Teplý, Dr. Ágnes Révész, Dr. Detlef Schröder, Dr. Dušan Koval, Dr. Václav Kašička, Dr. Ivana Císařová and Dr. David Šaman

      Article first published online: 9 AUG 2012 | DOI: 10.1002/cplu.201290033

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      The cover picture shows different approaches used by chemists in Prague to investigate the conformations of a pentacyclic bispyridinium ion in the gas phase, in solution, and in the solid state. The title heterocycle has two conformers of which one is helical (helquat, HQ2+) and the other looks like a horse-saddle (saddlequat, SQ2+). For the free dication in the gas phase, the neutral salt in solution, and the crystal, the helical form is preferred. However, in the singly charged binary ion pairs [HQ2+ ⋅ X] and [SQ2+ ⋅ X], subtle effects of the counterions X determine the relative stabilities of conformers, and with several counterions the saddle forms are in fact more stable than the helical ones. A full account can be found in the Full Paper by D. Schröder and co-workers on page 624 ff.

    2. Back Cover Picture: Extended DNA Tile Actuators (ChemPlusChem 8/2012) (page 730)

      Dr. Martin Kristiansen, Mille B. L. Kryger, Dr. Zhao Zhang, Dr. Niels V. Voigt, Assoc. Prof. Victoria Birkedal and Prof. Kurt V. Gothelf

      Article first published online: 9 AUG 2012 | DOI: 10.1002/cplu.201290037

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      The back cover picture shows three types of extended actuators having unprecedented size and complexity. In their Full Paper on page^^636^^ff., K. V. Gothelf and co-workers outline the construction of mechanical actuators based on DNA sliding through sequence homologogy. These linear, triangular, and quadrilateral DNA structures were characterized by gel electrophoresis and Förster resonance energy transfer spectroscopy to clearly demonstrate the designed motion for each actuator.

  2. Masthead

    1. Top of page
    2. Cover Pictures
    3. Masthead
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Full Papers
    1. Masthead: ChemPlusChem 8/2012 (page 600)

      Article first published online: 9 AUG 2012 | DOI: 10.1002/cplu.201290034

  3. Editorial

    1. Top of page
    2. Cover Pictures
    3. Masthead
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Full Papers
    1. You have free access to this content
      High-Quality Multidisciplinary Research (pages 601–603)

      Dr. Marisa Spiniello

      Article first published online: 9 AUG 2012 | DOI: 10.1002/cplu.201200169

      Board Members Special Issue: Multidisciplinary contributions from the three Chairmen and selected Board Members.

  4. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Masthead
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Full Papers
    1. Graphical Abstract: ChemPlusChem 8/2012 (pages 604–608)

      Article first published online: 9 AUG 2012 | DOI: 10.1002/cplu.201290035

  5. News

    1. Top of page
    2. Cover Pictures
    3. Masthead
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Full Papers
  6. Full Papers

    1. Top of page
    2. Cover Pictures
    3. Masthead
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Full Papers
    1. A Family of Discrete Magnetically Switchable Nanoballs (pages 616–623)

      Dr. Martin B. Duriska, Dr. Suzanne M. Neville, Dr. Boujemaa Moubaraki, Prof. Keith S. Murray, Dr. Chérif Balde, Dr. Jean-François Létard, Prof. Cameron J. Kepert and Prof. Stuart R. Batten

      Article first published online: 30 JUL 2012 | DOI: 10.1002/cplu.201200123

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      Nanoswitches: A family of 3 nm sized metallosupramolecular “nanoballs” can be switched between high spin and low spin states by change in temperature or irradiation by light, and they are the largest discrete spin-crossover molecules reported to date (see structure). Variation of axial iron-bound NCX ligands leads to increasing transition temperatures and more complete spin transitions in the order X=S<Se<BH3.

    2. Counterion-Induced Inversion of Conformer Stability of a [5]Helquat Dication (pages 624–635)

      Lukáš Severa, Michael Jirásek, Pavel Švec, Dr. Filip Teplý, Dr. Ágnes Révész, Dr. Detlef Schröder, Dr. Dušan Koval, Dr. Václav Kašička, Dr. Ivana Císařová and Dr. David Šaman

      Article first published online: 19 APR 2012 | DOI: 10.1002/cplu.201200009

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      Subtle counterion effects in the gas phase determine the relative stabilities of different conformers of a [5]helquat dication HQ2+ in their singly charged binary ion pairs [HQ2+X] with various counterions X. With several counterions, the saddle conformers [SQ2+X] are more stable than the helical ones. By contrast to the variable situation in the ion pairs, in the free gaseous dications as well as in the condensed-phase salts the helical forms HQ2+ and [HQ2+2X] are strongly energetically preferred over the saddle forms.

    3. Extended DNA Tile Actuators (pages 636–642)

      Dr. Martin Kristiansen, Mille B. L. Kryger, Dr. Zhao Zhang, Dr. Niels V. Voigt, Assoc. Prof. Victoria Birkedal and Prof. Kurt V. Gothelf

      Article first published online: 3 AUG 2012 | DOI: 10.1002/cplu.201200149

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      Multiple states: Modular linear, triangular, and quadrilateral DNA nanostructures which can obtain up to 12 different states have been designed (see figure). The ability to switch between different states is obtained by introducing sequence homology around all crossover junctions. The structures can be fixed in each of the states by using specific lock strands for each state.

    4. [TeX3]+ Cations Stabilized by the Weakly Coordinating [Al(ORF)4] Anion: FIR Spectra, Raman Spectra, and Evaluation of an Abnormal Halogen Dependence of the 125Te NMR Chemical Shifts (pages 643–651)

      Dipl.-Chem. Tobias A. Engesser, Dr. Peter Hrobárik, Dr. Nils Trapp, Dr. Philipp Eiden, Dr. Harald Scherer, Prof. Dr. Martin Kaupp and Prof. Dr. Ingo Krossing

      Article first published online: 18 APR 2012 | DOI: 10.1002/cplu.201200025

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      TeX3[Al(ORF)4] have been synthesized and characterized by 125Te NMR in solution and by X-ray diffraction, Raman, and IR spectroscopy in the solid state (X=Cl, Br, I; RF=C(CF3)3). The vibrational analysis shows a very weak contact of [TeX3]+ to the anion. The observed “abnormal halogen dependence” of the 125Te NMR chemical shifts results from an interplay of relativistic and solvent effects.

    5. Synthesis of Hydrazone-Modified Nucleotides and Their Polymerase Incorporation onto DNA for Redox Labeling (pages 652–662)

      Veronika Raindlová, Dr. Radek Pohl, Dr. Blanka Klepetářová, Dr. Luděk Havran, Eva Šimková, Dr. Petra Horáková, Dr. Hana Pivoňková, Prof.Dr. Miroslav Fojta and Prof.Dr. Michal Hocek

      Article first published online: 30 APR 2012 | DOI: 10.1002/cplu.201200056

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      Redox labeling of DNA through nitroarylhydrazone modification has been achieved either by polymerase incorporation of hydrazone-modified dNTPs or by incorporation of aldehydes and subsequent hydrazone formation (see figure). Electrochemical studies revealed the potential utility of different redox-active groups for DNA labeling for bioanalysis.

    6. From Molecular Gallium and Indium Siloxide Precursors to Amorphous Semiconducting Transparent Oxide Layers for Applications in Thin-Film Field-Effect Transistors (pages 663–674)

      Dr. Kerim Samedov, Dr. Yilmaz Aksu and Prof. Dr. Matthias Driess

      Article first published online: 16 JUL 2012 | DOI: 10.1002/cplu.201200086

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      Metalorganics for supreme linkages: New molecular precursors for low-temperature synthesis of amorphous indium and gallium oxide for electronic applications have been synthesized and probed successfully for applications as thin-film field-effect transistors (FET; see figure). These films exhibit very good FET performance with a high field-effect mobility of 3.0×10−1 cm2 V−1 s and on/off current ratio of 108.

    7. Adsorption of Carbon Dioxide on Sodium and Potassium Forms of STI Zeolite (pages 675–681)

      Dr. Arnošt Zukal, Prof. Stacey I. Zones, Dr. Martin Kubů, Dr. Tracy M. Davis and Prof. Jiří Čejka

      Article first published online: 6 JUN 2012 | DOI: 10.1002/cplu.201200089

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      The heat is on! To obtain detailed information on the effect of alkali metal cations on CO2 adsorption on high-silica STI zeolite, the temperature dependence of CO2 isotherms was investigated in the temperature range 273–333 K. Based on these data, isosteric heats of adsorption of CO2 were determined, discussed, and compared in detail with those of FER, MFI, MEL, TUN, and IMF structural types (see figure of isosteric heat of CO2 adsorption on zeolites).

    8. Dimerization Reaction of Regioisomeric Bis(phenylethynyl)benzene Radical Anions during Pulse Radiolysis (pages 682–687)

      Prof. Dr. Mamoru Fujitsuka, Dr. Shingo Samori, Sachiko Tojo, Prof. Dr. Michael M. Haley and Prof. Dr. Tetsuro Majima

      Article first published online: 3 JUL 2012 | DOI: 10.1002/cplu.201200110

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      Pulse radiolysis for dimerization: Dimerization of a series of regioisomeric 1,4-, 1,3-, and 1,2-bis(phenylethynyl)benzene radical anions substituted by various electron-donor and/or electron-acceptor groups was studied during pulse radiolysis (see scheme; DMF=N,N-dimethylformamide). The rate constant of dimerization depends largely on substitution pattern and electronic nature of substituents.

    9. Enhanced Optical Nonlinearity in Noncovalently Functionalized Amphiphilic Graphene Composites (pages 688–693)

      Tingchao He, Dr. Xiaoying Qi, Rui Chen, Dr. Jun Wei, Prof. Hua Zhang and Prof. Handong Sun

      Article first published online: 10 JUL 2012 | DOI: 10.1002/cplu.201200113

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      No limit! Broadband optical limiting (OL) characteristics were explored in the amphiphilic graphene composite (PEG-OPE-rGO) for the first time (see figure). It was found that the PEG-OPE-rGO nanocomposite presents excellent OL effects in various solvents and in highly transparent thin films from the nanosecond visible to near-infrared pulses, which makes this composite a very promising material for use in practical OL devices.

    10. Biomimetic Mineralization of Calcium Phosphate on a Functionalized Porous Silicon Carbide Biomaterial (pages 694–699)

      Dr. Archan Dey, Chris. J. van den Hoogen, Dr. Michel Rosso, Niek Lousberg, Marco M. R. M. Hendrix, Dr. Heiner Friedrich, Joaquín Ramírez-Rico, Prof. Han Zuilhof, Prof. Gijsbertus de With and Dr. Nico A. J. M. Sommerdijk

      Article first published online: 23 JUL 2012 | DOI: 10.1002/cplu.201200118

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      Make no bones about it: To achieve porous bioactive implant materials for load-bearing bone, a new strategy towards biomimetic calcium phosphate coatings has been investigated. The surface of the porous silicon carbide is modified with a covalently bound monolayer exposing carboxylic acid groups that promote the selective deposition of a very well-defined fully crystalline layer of oriented mixed octacalcium phosphate/hydroxyapatite crystals on substrates with complex geometry (see figure).

    11. Postfunctionalization of Helical Polyisocyanopeptides with Phthalocyanine Chromophores by “Click Chemistry” (pages 700–706)

      Dr. Ismael López-Duarte, Dr.  M. Victoria Martínez-Díaz, Dr. Erik Schwartz, Dr. Matthieu Koepf, Dr. Paul H. J. Kouwer, Prof. Alan E. Rowan, Prof. Roeland J. M. Nolte and Prof. Tomás Torres

      Article first published online: 25 JUN 2012 | DOI: 10.1002/cplu.201200087

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      Rigid rod polyisocyanopeptides bearing phthalocyanines as pendant groups, arranged in a helical fashion along the polymer backbone, have been prepared by “click chemistry” reaction of polyisocyanopeptides containing acetylene side-arms with zinc(II) phthalocyanine azide, resulting in the longest well-defined phthalocyanine assembly reported to date (see scheme).

    12. Investigation of Copper Corrosion Inhibition with Frequency-Dependent Alternating-Current Scanning Electrochemical Microscopy (pages 707–712)

      Dr. Juan José Santana, Dr. Maike Pähler, Prof. Wolfgang Schuhmann and Prof. Ricardo M. Souto

      Article first published online: 21 MAY 2012 | DOI: 10.1002/cplu.201200091

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      Corrosion science: The inhibition of copper corrosion by the organic inhibitors benzotriazole (BTAH), 5-methyl-benzotriazole (MBTAH), 2-mercaptobenzimidazole (MBI), and ethyl xanthate (EX) was investigated by alternating-current scanning electrochemical microscopy (AC-SECM; see figure). These inhibitors form a thin passivating layer on the copper surface, which can be analysed by measuring the local electrochemical activity with AC-SECM.

    13. Visible-Light-Induced Sulfoxidation of Alkanes in the Presence of Titania (pages 713–720)

      Francesco Parrino, Ayyappan Ramakrishnan, Cornelia Damm and Prof. Dr. Horst Kisch

      Article first published online: 10 JUL 2012 | DOI: 10.1002/cplu.201200097

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      Visible-light photosulfoxidation: Titanium dioxide photocatalyzes visible-light-induced sulfoxidation of alkanes through an optical charge-transfer excitation of a titania–sulfur dioxide complex (see proposed mechanism). The reaction exhibits typical features of a photoinduced radical chain reaction.

    14. Application of a Versatile Nanoparticle Stabilizer in Phase Transfer and Catalysis (pages 721–726)

      Dr. Ilaria Biondi, Dr. Vincent Laporte and Prof. Paul J. Dyson

      Article first published online: 10 JUL 2012 | DOI: 10.1002/cplu.201200108

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      Polymer coated: Metal nanoparticles coated with an ionic polymer may be readily dispersed in a wide range of solvents including ionic liquids (see figure). In catalysis the nature of the solvent strongly influences the outcome of the reaction and consequently the solvent can be used to fine-tune the surface features of the nanoparticles and their corresponding catalytic properties.

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