ChemPhysChem

Cover image for Vol. 14 Issue 16

November 11, 2013

Volume 14, Issue 16

Pages 3633–3842

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Concepts
    6. Communications
    7. Articles
    1. You have free access to this content
      Cover Picture: Global Reaction Pathways in the Photodissociation of I3 Ions in Solution at 267 and 400 nm Studied by Picosecond X-ray Liquidography (ChemPhysChem 16/2013) (page 3633)

      Dr. Kyung Hwan Kim, Hosung Ki, Key Young Oang, Prof. Shunsuke Nozawa, Dr. Tokushi Sato, Prof. Joonghan Kim, Prof. Tae Kyu Kim, Prof. Jeongho Kim, Prof. Shin-ichi Adachi and Prof. Hyotcherl Ihee

      Article first published online: 31 OCT 2013 | DOI: 10.1002/cphc.201390076

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      Time-resolved X-ray liquidography (TRXL) is a powerful tool for revealing the structural dynamics of chemical reactions in solution. By recording the difference scattering pattern at various time delays between ultrashort laser and X-ray pulses this technique allows to collect information on the structural change of the reacting molecules. This is shown by H. Ihee et al. on p. 3687, who elucidate the reaction mechanism of the photodissociation of I3 in solution. In addition to the reaction dynamics of the solute species, the transient structure of the solute/solvent cage and the changes in solvent density and temperature are revealed.

    2. You have free access to this content
      Inside Cover: Rotational and Translational Dynamics of Ras Proteins upon Binding to Model Membrane Systems (ChemPhysChem 16/2013) (page 3634)

      Alexander Werkmüller, Dr. Gemma Triola, Prof. Dr. Herbert Waldmann and Prof. Dr. Roland Winter

      Article first published online: 31 OCT 2013 | DOI: 10.1002/cphc.201390077

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      Using fluorescence anisotropy and correlation spectroscopy, R. Winter et al. show on p. 3698 how the diffusional mobility of Ras proteins changes upon membrane binding.

  2. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Concepts
    6. Communications
    7. Articles
    1. Graphical Abstract: ChemPhysChem 16/2013 (pages 3635–3642)

      Article first published online: 31 OCT 2013 | DOI: 10.1002/cphc.201390078

  3. News

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Concepts
    6. Communications
    7. Articles
    1. Editors' Selection: ChemPhysChem 16/2013 (page 3643)

      Article first published online: 31 OCT 2013 | DOI: 10.1002/cphc.201390079

    2. Nobel News (pages 3652–3653)

      Article first published online: 31 OCT 2013 | DOI: 10.1002/cphc.201300960

  4. Concepts

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Concepts
    6. Communications
    7. Articles
    1. Hard X-ray Spectroscopic Nano-Imaging of Hierarchical Functional Materials at Work (pages 3655–3666)

      Dr. Joy C. Andrews and Prof. Dr. Bert M. Weckhuysen

      Article first published online: 3 SEP 2013 | DOI: 10.1002/cphc.201300529

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      Big brother is X-raying you: Full-field hard X-ray spectroscopic nano-imaging is a powerful method to obtain single-pixel chemistry of hierarchical functional materials, such as catalytic solids, fuel cells, and batteries, during operation at realistic temperatures and pressures and with around 30 nm spatial resolution. Some technical aspects, as well as recent showcases, and future perspectives on the application of this characterization tool are presented.

    2. The Dissolution of Polyols in Salt Solutions and Ionic Liquids at Molecular Level: Ions, Counter Ions, and Hofmeister Effects (pages 3667–3671)

      Zakar Papanyan, Dr. Christian Roth, Kai Wittler, Sebastian Reimann and Prof. Dr. Ralf Ludwig

      Article first published online: 10 JUL 2013 | DOI: 10.1002/cphc.201300465

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      All good things come in threes! The dissolving power of traditional solvents and ionic liquids for polyols such as cellulose depends on three terms: sufficiently strong interacting anions, anion/cation combinations including small sized anions and large sized cations, as well as small water concentrations. The anions can only develop their disruption power if they are absorbed by smaller cations and not hydrated by water molecules (see picture). This behavior is related to Hofmeister effects.

  5. Communications

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Concepts
    6. Communications
    7. Articles
    1. Interactions of Imidazolium-Based Ionic Liquids with Oxide Surfaces Controlled by Alkyl Chain Functionalization (pages 3673–3677)

      Stefan Schernich, Dr. Mathias Laurin, Dr. Yaroslava Lykhach, Dr. Nataliya Tsud, Dr. Marek Sobota, Dr. Tomáš Skála, Dr. Kevin C. Prince, Dr. Nicola Taccardi, Valentin Wagner, Prof. Dr. Hans-Peter Steinrück, Prof. Dr. Vladimír Matolín, Prof. Dr. Peter Wasserscheid and Prof. Dr. Jörg Libuda

      Article first published online: 2 OCT 2013 | DOI: 10.1002/cphc.201300792

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      From a different angle: Thin films of functionalized ionic liquids are deposited on cerium oxides following a surface science approach. The functionalization of the alkyl chain changes its orientation with respect to the surface plane from normal to parallel. This then leads to a different surface chemistry at higher temperatures.

    2. The Influence of Reactive Side Products in Electrocatalytic Reactions: Methanol Oxidation as Case Study (pages 3678–3681)

      Robert Reichert, Dr. Johannes Schnaidt, Dr. Zenonas Jusys and Prof. Dr. R. Jürgen Behm

      Article first published online: 27 AUG 2013 | DOI: 10.1002/cphc.201300726

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      The role and impact of follow-up processes involving reactive side products in an electrocatalytic reaction is demonstrated for the electrooxidation of methanol at a Pt electrode. By using combined in situ infrared spectroscopy and online mass spectrometry and employing isotope-labeling techniques, it is shown that even small amounts of the incomplete oxidation products formaldehyde and formic acid have pronounced effects on the reaction.

    3. Determining the Critical Particle Size to Induce Enhanced Emission in Aggregates of a Highly Twisted Triarylamine (pages 3682–3686)

      Dr. Akshay Kokil, J. Matthew Chudomel, Dr. Boqian Yang, Prof. Michael D. Barnes, Prof. Paul M. Lahti and Prof. Jayant Kumar

      Article first published online: 2 OCT 2013 | DOI: 10.1002/cphc.201300667

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      Towards highly luminescent aggregates: A highly twisted triphenylamine displays aggregation-induced enhanced emission. A solvent-specific critical molecular aggregate size, once reached, gives rapid onset of enhanced emission in polar solvent mixtures that favor quenching of solvated individual molecule excited states.

  6. Articles

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Concepts
    6. Communications
    7. Articles
    1. Global Reaction Pathways in the Photodissociation of I3 Ions in Solution at 267 and 400 nm Studied by Picosecond X-ray Liquidography (pages 3687–3697)

      Dr. Kyung Hwan Kim, Hosung Ki, Key Young Oang, Prof. Shunsuke Nozawa, Dr. Tokushi Sato, Prof. Joonghan Kim, Prof. Tae Kyu Kim, Prof. Jeongho Kim, Prof. Shin-ichi Adachi and Prof. Hyotcherl Ihee

      Article first published online: 2 OCT 2013 | DOI: 10.1002/cphc.201300713

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      An eye for an I: By performing time-resolved X-ray liquidography measurements at two different excitation wavelengths, the wavelength dependence of the reaction mechanism of I3 photodissociation is elucidated (see picture). In addition to the reaction dynamics of solute species, the results reveal the transient structure of the solute/solvent cage and the changes in solvent density and temperature as a function of time.

    2. Rotational and Translational Dynamics of Ras Proteins upon Binding to Model Membrane Systems (pages 3698–3705)

      Alexander Werkmüller, Dr. Gemma Triola, Prof. Dr. Herbert Waldmann and Prof. Dr. Roland Winter

      Article first published online: 2 OCT 2013 | DOI: 10.1002/cphc.201300617

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      On the Ras: The diffusional mobility of N- and K-Ras signaling proteins attached to various lipid-bilayer membranes reveals high lipid-like rapid lateral diffusion and free rotation of the G-domain, determined by using fluorescence anisotropy and correlation spectroscopy experiments, respectively.

    3. Motion of Li+ in Nanoengineered LiBH4 and LiBH4:Al2O3 Comparison with the Microcrystalline Form (pages 3706–3713)

      Viktor Epp and Prof. Dr. Martin Wilkening

      Article first published online: 24 OCT 2013 | DOI: 10.1002/cphc.201300743

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      Nanoengineering of interfacial regions can be used to modify Li-ion transport in LiBH4 and two-phase LiBH4:Al2O3 composites. 7Li NMR spectroscopy, including spin–lattice relaxation and line-shape measurements, is useful for sensing influences on phase transitions and ion hopping (see picture).

    4. Quantifying the Nature of Lone Pair Domains (pages 3714–3725)

      Dr. Martin Rahm and Prof. Karl. O. Christe

      Article first published online: 9 SEP 2013 | DOI: 10.1002/cphc.201300723

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      Help, HELP! The first chemically relevant quantification of the lone pair domain by quantum chemical topology calculations is demonstrated. A novel partitioning of the electron localization function is introduced. The complementarity of density- and orbital-based analyses of chemistry is discussed. This measure of the lone pair domain correlates well with a range of molecular and atomic properties, and is predicted to be of general use.

    5. Temperature-Dependent Surface-Enrichment Effects of Imidazolium-Based Ionic Liquids (pages 3726–3730)

      Dr. Claudia Kolbeck, Dr. Alexey Deyko, Dr. Takashi Matsuda, Florian T. U. Kohler, Prof. Dr. Peter Wasserscheid, Dr. Florian Maier and Prof. Dr. Hans-Peter Steinrück

      Article first published online: 2 OCT 2013 | DOI: 10.1002/cphc.201300719

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      Loss of order! The surface enrichment of the alkyl chains of five imidazolium-based ionic liquids (ILs) at the liquid/vacuum interface is studied as a function of temperature by angle-resolved X-ray photoelectron spectroscopy; both the anion and the alkyl chain length at the cation are varied. At room temperature, the alkyl chains are enriched at the outer surface. Upon increasing the temperature, the degree of surface enrichment decreases.

    6. Two-Photon Solvatochromism II: Experimental and Theoretical Study of Solvent Effects on the Two-Photon Absorption Spectrum of Reichardt’s Dye (pages 3731–3739)

      Małgorzata Wielgus, Dr. Robert Zaleśny, Dr. N. Arul Murugan, Prof. Jacob Kongsted, Prof. Hans Ågren, Prof. Marek Samoc and Prof. Wojciech Bartkowiak

      Article first published online: 17 SEP 2013 | DOI: 10.1002/cphc.201300695

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      Polar opposites: Two-photon absorption (2PA) spectra of Reichardt's dye in diverse solvents are studied experimentally for the first time, and a hybrid quantum mechanics/molecular mechanics (QM/MM) approach is used to relate the changes of the 2PA cross-section to electronic-structure parameters (see picture).

    7. Predicting Low-Pressure O2 Adsorption in Nanoporous Framework Materials for Sensing Applications (pages 3740–3750)

      Dr. Todd R. Zeitler, Timothy Van Heest, Prof. David S. Sholl, Dr. Mark D. Allendorf and Dr. Jeffery A. Greathouse

      Article first published online: 2 OCT 2013 | DOI: 10.1002/cphc.201300682

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      Smaller is better: A set of 98 nanoporous framework material (NFM) structures was investigated by classical Grand canonical Monte Carlo simulations for low-pressure O2 adsorption properties. Structures without open metal sites that have very small pores (<2.5 Å) show increased O2/N2 selectivity. Additionally, O2/N2 mixture simulations show that in some cases, H2O or N2 can hinder O2 uptake for NFMs with small pores due to competitive adsorption.

    8. Kinetic Modeling of Hydrogen Abstractions Involving Sulfur Radicals (pages 3751–3771)

      Dr. Aäron G. Vandeputte, Prof. Dr. Marie-Françoise Reyniers and Prof. Dr. Guy B. Marin

      Article first published online: 31 OCT 2013 | DOI: 10.1002/cphc.201300661

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      A building kit for rate coefficients: The group additivity method for Arrhenius parameters is applied for hydrogen abstraction reactions involving sulfur radicals. The constructed model allows theoretical rate coefficients to be reproduced within a factor of three.

    9. Equilibrium Topology and Partial Inversion of Janus Drops: A Numerical Analysis (pages 3772–3776)

      Prof. Stig E. Friberg, Ildiko Kovach and Prof. Joachim Koetz

      Article first published online: 19 SEP 2013 | DOI: 10.1002/cphc.201300635

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      Drop tackle: A rigorous numerical calculation is made for the topology of equilibrium Janus drops, showing the importance of the interfacial tension equilibrium for the degree of coverage of the drop, with high interfacial tension towards water by the low energy drop.

    10. On the Regio- and Stereospecificity of Arachidonic Acid Peroxidation Catalyzed by Mammalian 15-Lypoxygenases: A Combined Molecular Dynamics and QM/MM Study (pages 3777–3787)

      Dr. Reynier Suardíaz, Dr. Laura Masgrau, Prof. Dr. José M. Lluch and Prof. Dr. Àngels González-Lafont

      Article first published online: 23 SEP 2013 | DOI: 10.1002/cphc.201300629

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      Cause and effect: The peroxidation of arachidonic acid catalyzed by rabbit 15-lipoxygenase-1 is analyzed at the molecular level by means of molecular dynamics and quantum mechanics/molecular mechanics calculations. The key to understanding the high C15/C11 (after hydrogen abstraction from C13) and C12/C8 (after hydrogen abstraction from C10) [n+2] regiospecificity for oxygen addition is the presence of steric-shielding residues.

    11. Temperature Dependence of the Properties of Water and Its Solutes, Including the Supercooled Region (pages 3788–3800)

      Prof. Dr. Jan H. Sluyters and Dr. Margaretha Sluyters-Rehbach

      Article first published online: 31 OCT 2013 | DOI: 10.1002/cphc.201300553

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      Dead stop! The conductivities of all ions in water converge at −30 °C. The picture shows, from top to bottom, plots for OH, Ca2+, Cl, Ag+, and Na+ versus temperature. Upon extrapolation, a wide variety of rate and equilibrium constants of processes and of physical properties become zero, and are thus arrested, at the very same temperature. Therefore, t0, the temperature of structural arrest, is a property of (supercooled) water.

    12. Kinetically Limited CO Adsorption: Spill-Over as a Highly Effective Adsorption Pathway on Bimetallic Surfaces (pages 3801–3805)

      Dr. Heinrich Hartmann, Dr. Thomas Diemant and Prof. Dr. R. Jürgen Behm

      Article first published online: 26 AUG 2013 | DOI: 10.1002/cphc.201300722

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      CO spill-over on bimetallic surfaces: The (locally) adsorbed carbon monoxide coverage, COad, on Pt-free areas of bimetallic Pt/Ru(0001) surfaces, a Ru(0001) substrate partly covered by Pt monolayer (ML) islands, can be increased well above the established usual saturation COad coverage of 0.68 ML, even under ultrahigh vacuum conditions, by using spill-over of CO adsorbed on the Pt islands to the Ru areas.

    13. A Novel Mechanism for the Extraction of Metals from Water to Ionic Liquids (pages 3806–3813)

      Dr. Camiel H. C. Janssen, Dr. Antonio Sánchez, Prof. Geert-Jan Witkamp and Prof. Mark N. Kobrak

      Article first published online: 31 OCT 2013 | DOI: 10.1002/cphc.201300686

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      Out of phase: A novel mechanism for the extraction of charged metal complexes from aqueous phases to ionic liquids is presented (see picture). The thermodynamics of the reaction are explored, and it is shown that the use of a suitable co-extraction agent can suppress the competing ion-exchange process. This method serves to drive the recovery of metals in high yield under relatively mild conditions.

    14. Composite Polymer Electrolytes for Fuel Cell Applications: Filler-Induced Effect on Water Sorption and Transport Properties (pages 3814–3821)

      Dr. Barbara Mecheri, Dr. Valeria Felice, Dr. Alessandra D'Epifanio, Prof. Dr. Ana C. Tavares and Prof. Silvia Licoccia

      Article first published online: 19 SEP 2013 | DOI: 10.1002/cphc.201300637

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      Materials for energy and sustainability: Composite membranes based on two different ionomers, Nafion and sulfonated polysulfone (SPS), can be used as electrolytes in polymer electrolyte membrane fuel cells (PEM-FCs). The analysis of water sorption and proton transport properties of composites illustrates the complex polymer–filler interaction, thus enabling the design of suitable electrolyte materials that operate in PEM-FC conditions.

    15. Flexible Polyester Cellulose Paper Supercapacitor with a Gel Electrolyte (pages 3822–3826)

      Prasannan Karthika, Dr. Natarajan Rajalakshmi and Dr. Kaveripatnam S. Dhathathreyan

      Article first published online: 23 OCT 2013 | DOI: 10.1002/cphc.201300622

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      Be flexible: A new form of energy-storage device that occupies minimum space and adapts to flexible shape and size requirements has been produced (see figure).

    16. Helical Self-Assembly of Optically Active Phthalocyanine Derivatives: Effect of Zn[BOND]O Coordination Bond on Morphology and Handedness of Nanostructures (pages 3827–3833)

      Congcong Zhang, Lu Jing, Sha Lin, Zijuan Hao, Jing Tian, Prof. Xiaomei Zhang and Prof. Peihua Zhu

      Article first published online: 14 OCT 2013 | DOI: 10.1002/cphc.201300604

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      Single-handed: Two optically active phthalocyanine derivatives with eight peripheral chiral (S)-4′-(2-methylbutoxy)biphenyl moieties on the β-position of the phthalocyanine ring are synthesized. A comparative investigation of the self-assembly behavior of these two compounds indicate the influence of the metal-coordination bond on the morphology and handedness of the self-assembled nanostructures.

    17. Atmospheric Chemistry and Environmental Assessment of Inhalational Fluroxene (pages 3834–3842)

      Dr. Iván Bravo, Dr. Ana Rodríguez, Dr. Diana Rodríguez, Dr. Yolanda Diaz-de-Mera, Dr. Alberto Notario and Dr. Alfonso Aranda

      Article first published online: 7 OCT 2013 | DOI: 10.1002/cphc.201300559

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      Anesthetics and global warming: Atmospheric lifetimes, infrared spectra, radiative efficiencies, and the reaction mechanism of fluroxene, an anesthetic, are elucidated to assess its environmental impact. Although the impact of fluroxene on global warming may be low, its cumulative effect is significantly increased by the secondary fluorinated esters that are formed during its atmospheric oxidation.

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