ChemPhysChem

Cover image for Vol. 9 Issue 15

October 24, 2008

Volume 9, Issue 15

Pages 2125–2274

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Review
    6. Concept
    7. Communications
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    1. Cover Picture: Interaction of NO2 with Model NSR Catalysts: Metal–Oxide Interaction Controls Initial NOx Storage Mechanism (ChemPhysChem 15/2008) (page 2125)

      Aine Desikusumastuti, Thorsten Staudt, Zhihui Qin, Markus Happel, Mathias Laurin , Yaroslava Lykhach, Shamil Shaikhutdinov, Friedemann Rohr and Jörg Libuda

      Version of Record online: 17 OCT 2008 | DOI: 10.1002/cphc.200890060

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      The cover picture shows a time-resolved infrared reflection absorption spectroscopy experiment during NOx uptake on a single-crystal-based NSR (NOx storage and reduction) model catalyst. By correlation of structural properties (scanning tunneling microscopy, figure background) and in-situ surface spectroscopy, J. Libuda et al. in their paper on page 2191–2197, obtain detailed insights into the mechanism of nitrite and nitrate formation.

  2. Graphical Abstract

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    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Review
    6. Concept
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  3. News

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    4. News
    5. Review
    6. Concept
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  4. Review

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    1. Microfluidics for Miniaturized Laboratories on a Chip (pages 2140–2156)

      Thomas A. Franke and Achim Wixforth

      Version of Record online: 17 OCT 2008 | DOI: 10.1002/cphc.200800349

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      Hi-tech comes in small packages: Current state-of-the-art lab-on-a-chip technology is presented in this Review. On these small length scales the fluidics differ significantly from the macroscopic world. Actuation and mixing of fluids by surface acoustic waves are emphasized, with blood flow on a chip (see picture) providing a striking example of the potential of the lab-on-a-chip.

  5. Concept

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    1. Strategies for the Improvement of the Hydrogen Storage Properties of Metal Hydride Materials (pages 2157–2162)

      Hui Wu

      Version of Record online: 26 SEP 2008 | DOI: 10.1002/cphc.200800498

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      Ions on the move: Layered crystals of Li2Ca(NH)2 promote Li+ ions in 2D channels defined by slabs of Ca[NH]6 octahedra (see picture). This facilitates hydrogenation, which results in a significantly lowered hydrogen-absorption temperature compared to pure Li2NH. The enhanced ion mobility improves the dehydrogenation performance of this system, thus leading to lowered desorption temperatures and accelerated kinetics.

  6. Communications

    1. Top of page
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    1. SERS and Multiphoton-Induced Luminescence of Gold Micro- and Nanostructures Fabricated by NIR Femtosecond-Laser Irradiation (pages 2163–2167)

      Maik Eichelbaum, Janina Kneipp, Bruno E. Schmidt, Ulrich Panne and Klaus Rademann

      Version of Record online: 22 SEP 2008 | DOI: 10.1002/cphc.200800417

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      Two in one fell swoop: With a confocal microscope and a Ti:Sa fs-laser, gold nanoparticle-containing micro- and nano-sized patterns can be written into 350 nm thin sol–gel derived silicate-titanate films (see figure). The nanoparticles are characterized by a multiphoton-induced luminescence and enhance the Raman scattering of adsorbed adenine molecules by the SERS effect.

    2. Fluoride Binding in Water: A New Environment for a Known Receptor (pages 2168–2171)

      Massimo Cametti, Antonella Dalla Cort and Kristin Bartik

      Version of Record online: 22 SEP 2008 | DOI: 10.1002/cphc.200800412

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      Binding in a micelle: In the presence of CTABr micelles (see picture), the salophen–UO2 complex 1 binds fluoride in water with the highest affinity ever recorded for a neutral receptor (K≈ ca. 104M−1). The receptor's location and its orientation within the micellar system are determined by PRE and NOE NMR experiments.

    3. Protic Ionic Liquids with Unusually High Dielectric Permittivities (pages 2172–2173)

      Mian-Mian Huang and Hermann Weingärtner

      Version of Record online: 15 SEP 2008 | DOI: 10.1002/cphc.200800523

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      Highly polar ionic media: Ionic liquids have fairly low relative dielectric permittivities which at 25 °C are of the order of 10–15, classifying ionic liquids as moderately polar solvents. However, protic ionic liquids composed of Brønsted acids and Brønsted bases show substantially higher dielectric constants, thus providing highly polar ionic media (see figure).

    4. Photoinduced Surface Relief Grating Formation on a Co-crystal of 4-[Bis(9,9-dimethylfluoren-2-yl)amino]azobenzene and Ethyl Acetate (pages 2174–2176)

      Hideyuki Nakano

      Version of Record online: 2 SEP 2008 | DOI: 10.1002/cphc.200800419

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      Corrugation of the surface: A co-crystal of 4-[bis(9,9-dimethylfluoren-2-yl)amino]azobenzene and ethyl acetate (picture, left) is obtained and a photoinduced surface relief grate (SRG) is formed on its surface (picture, right)—a first for a co-crystal. The effect of the polarization of the writing beams on SRG formation is different from that observed for a 4-(dimethylamino)azoben- zene single crystal.

    5. Calculated Raman Optical Activity Signatures of Tryptophan Side Chains (pages 2177–2180)

      Christoph R. Jacob, Sandra Luber and Markus Reiher

      Version of Record online: 22 SEP 2008 | DOI: 10.1002/cphc.200800448

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      Raman optical activity: The different local chirality of an adjacent group can cause a different sign of the ROA intensity of an amino-acid side chain (here tryptophan, see picture centre), even though the normal mode is unchanged. Calculated spectra clearly confirm that ROA spectroscopy can be utilized to determine the absolute conformation of tryptophan side chains in proteins (see figure, left and right).

    6. Heat of Adsorption for Hydrogen in Microporous High-Surface-Area Materials (pages 2181–2184)

      Barbara Schmitz, Ulrich Müller, Natalia Trukhan, Markus Schubert, Gérard Férey and Michael Hirscher

      Version of Record online: 26 SEP 2008 | DOI: 10.1002/cphc.200800463

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      Pore size matters: The heat of adsorption for hydrogen is determined over a wide range of surface coverages for activated carbon and several metal–organic frameworks. Heat determination is based on hydrogen adsorption measurements performed at temperatures between 77 and 296 K (see figure, BTC=benzene-1,3,5-tricarboxylate). The materials with smaller cavities show a higher heat of adsorption for hydrogen.

  7. Articles

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Review
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    1. Physical Vapor Deposition of [EMIM][Tf2N]: A New Approach to the Modification of Surface Properties with Ultrathin Ionic Liquid Films (pages 2185–2190)

      Till Cremer, Manuela Killian, J. Michael Gottfried, Natalia Paape, Peter Wasserscheid, Florian Maier and Hans-Peter Steinrück

      Version of Record online: 8 OCT 2008 | DOI: 10.1002/cphc.200800300

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      Preferential ionic distribution: Nanometer-thick ionic liquid films produced on planar glass substrates by means of thermal evaporation and recondensation under ultrahigh-vacuum conditions exhibit a bilayered structure within the first molecular layer (see picture).

    2. Interaction of NO2 with Model NSR Catalysts: Metal–Oxide Interaction Controls Initial NOx Storage Mechanism (pages 2191–2197)

      Aine Desikusumastuti, Thorsten Staudt, Zhihui Qin, Markus Happel, Mathias Laurin , Yaroslava Lykhach, Shamil Shaikhutdinov, Friedemann Rohr and Jörg Libuda

      Version of Record online: 8 OCT 2008 | DOI: 10.1002/cphc.200800550

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      Model catalyst: Nitrite formation during the initial stages of NOx uptake on a nitrogen storage and reduction (NSR) catalyst is critically controlled by the interaction between the barium based NOx storage material and the supported noble metal nanoparticles. This effect is due to reverse spillover of activated oxygen species, as demonstrated by experiments on a NSR model catalyst.

    3. Ion-Responsive Behavior of Ionic-Liquid Surfactant Aggregates with Applications in Controlled Release and Emulsification (pages 2198–2202)

      Yanfei Shen, Yuanjian Zhang, Daniel Kuehner, Guifu Yang, Fuyu Yuan and Li Niu

      Version of Record online: 17 OCT 2008 | DOI: 10.1002/cphc.200800449

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      Control over aggregates: A simple but efficient, rapid, and quantitative ion-responsive micelle system, based on counter-anion exchange of a surfactant containing an imidazolium unit (see figure), is successfully applied to controlled release and emulsification. The proposed design offers a novel way to control these smart physical aggregates.

    4. Circular Dichroism Study of the Mechanism of Formation of DNA Templated Nanowires (pages 2203–2206)

      Hamsa Jaganathan, Joseph M. Kinsella and Albena Ivanisevic

      Version of Record online: 26 SEP 2008 | DOI: 10.1002/cphc.200800509

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      Structural changes: Metallic (Au) and magnetic (Fe2O3 and CoFe2O4) nanoparticles (NP) aligned along the DNA strand are compared to the structure of B-form double-stranded DNA through circular dichroism experiments (see figure). Absorbance and thermal melting tests confirm the structural changes of the DNA-templated nanowires.

    5. Infrared Spectroscopy of a Wilkinson Catalyst in a Room-Temperature Ionic Liquid (pages 2207–2213)

      Johannes Kiefer, Katharina Obert, Simone Himmler, Peter S. Schulz, Peter Wasserscheid and Alfred Leipertz

      Version of Record online: 12 SEP 2008 | DOI: 10.1002/cphc.200800450

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      Ionic liquid structure: IR spectra of the ionic liquid (IL) 1-ethyl-3-methylimidazolium acetate containing different concentrations of the Wilkinson catalyst RhCl(PPh3)3 are studied. The Rh complex exerts influence on the bending vibration of the imidazolium ring, probably due to hydrogen-bond formation (see figure). Quantitative spectroscopic analysis of the mixtures is achieved.

    6. Picosecond Structural Relaxation of Abietic Acid Based Amine End Capped Para-Phenylenevinylene Trimers in Solution (pages 2214–2220)

      Roberto E. Di Paolo, Barbara Gigante, Maria A. Esteves, Natércia Pires, Célia Santos, Maria H. Lameiro, João Seixas de Melo, Hugh D. Burrows and António L. Maçanita

      Version of Record online: 1 OCT 2008 | DOI: 10.1002/cphc.200800374

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      Torsional relaxation: After excitation, the backbone of abietic acid-based PPV trimers follows a fast conformational relaxation process, leading to more planar conformers (see figure). The conformational relaxation is affected by both side chain and the amine groups of the compounds. A linear relationship is found between the volume of these groups and the relaxation times.

    7. Cyano Analogues of 7-Azaindole: Probing Excited-State Charge-Coupled Proton Transfer Reactions in Protic Solvents (pages 2221–2229)

      Cheng-Chih Hsieh, Kew-Yu Chen, Wan-Ting Hsieh, Chin-Hung Lai, Jiun-Yi Shen, Chang-Ming Jiang, Hsin-Sheng Duan and Pi-Tai Chou

      Version of Record online: 26 SEP 2008 | DOI: 10.1002/cphc.200800352

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      Systematic study: A series of new 7-azaindole derivatives are designed and synthesized to study the excited-state charge-coupled proton transfer reactions in protic solvents (see figure). The results conclude that solvent-polarity induced barrier plays a key role for the excited state proton transfer of 7-azaindoles in methanol.

    8. Pluronics-Stabilized Gold Nanoparticles: Investigation of the Structure of the Polymer–Particle Hybrid (pages 2230–2236)

      Kamil Rahme, Julian Oberdisse, Ralf Schweins, Cédric Gaillard, Jean-Daniel Marty, Christophe Mingotaud and Fabienne Gauffre

      Version of Record online: 26 SEP 2008 | DOI: 10.1002/cphc.200800358

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      Hybrid gold–polymer nanoparticles are obtained by self-assembly of amphiphilic poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) triblock copolymers in solutions containing preformed gold nanoparticles (see schematic). Gold nanoparticles are individually embedded within globules of polymer (see TEM image), even under conditions for which polymer micelles do not form in solution.

    9. Experimental and Theoretical Study of Helium Broadening and Shift of HCO+ Rotational Lines (pages 2237–2244)

      Giovanni Buffa, Luca Dore, Francesca Tinti and Markus Meuwly

      Version of Record online: 22 SEP 2008 | DOI: 10.1002/cphc.200800369

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      Collisions: An experimental and theoretical study of pressure broadening and pressure shift of HCO+ rotational lines perturbed by collisions with He is presented. Results from the quantum treatment agree well with experiments, whereas the semiclassical approach lead to appreciable differences [see PES, black: CCSD(T), red: HF]. The line width is particularly sensitive to the long-range part of the potential energy surface.

    10. Host–Guest Interaction of Chaperonin GroEL and Water-Soluble CdTe Quantum Dots and its Size-Selective Inclusion (pages 2245–2251)

      Chaoqing Dong, Liwen Shao, Jiacheng Guo and Jicun Ren

      Version of Record online: 26 SEP 2008 | DOI: 10.1002/cphc.200800398

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      Dots included: Water-soluble quantum dots (QDs) can enter the inner cavity of GroEL to form an inclusion complex. The inclusion of GroEL is size-selective to QDs and only small QDs are able to enter the cavity, as observed by fluorescence correlation spectroscopy (see picture).

    11. Charge Transport through Molecular Rods with Reduced π-Conjugation (pages 2252–2258)

      Emanuel Lörtscher, Mark Elbing, Meinrad Tschudy, Carsten von Hänisch, Heiko B. Weber, Marcel Mayor and Heike Riel

      Version of Record online: 8 OCT 2008 | DOI: 10.1002/cphc.200800388

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      Molecular electronics: The influence of reduced π-conjugation on the resonant charge transport along oligophenylene rods of different lengths is studied at the single-molecule level (see picture). Charge transport through the first molecular orbital is dominated by charge-carrier injection into the molecule, rather than by the intrinsic resistance of the molecular wire.

    12. Theoretical Study on the Spectroscopic Properties of CO3.−.nH2O Clusters: Extrapolation to Bulk (pages 2259–2264)

      Arup K. Pathak, Tulsi Mukherjee and Dilip K. Maity

      Version of Record online: 26 SEP 2008 | DOI: 10.1002/cphc.200800429

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      Cluster to bulk: Simulated annealing with Monte Carlo sampling is applied to locate the global minimum energy structure of small hydrated CO3.− clusters. The bulk vertical detachment energy of CO3.− (aq) is predicted to be 10.6 eV. The simulated UV/Vis spectrum of the CO3.−.8 H2O cluster shows key features of the experimental spectrum of CO3.− (aq) (see figure).

    13. Cooperativity between the Halogen Bond and the Hydrogen Bond in H3N⋅⋅⋅XY⋅⋅⋅HF Complexes (X, Y=F, Cl, Br) (pages 2265–2269)

      Qingzhong Li, Qingquan Lin, Wenzuo Li, Jianbo Cheng, Baoan Gong and Jiazhong Sun

      Version of Record online: 22 SEP 2008 | DOI: 10.1002/cphc.200800467

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      Different, but working together: MP2 calculations provide information on H3N⋅⋅⋅XY⋅⋅⋅HF triads (X, Y=F, Cl, Br, see picture) each having a halogen bond and a hydrogen bond. The results indicate significant cooperativity between the halogen and hydrogen bonds of these complexes.

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    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Review
    6. Concept
    7. Communications
    8. Articles
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      Preview: ChemPhysChem 16/2008 (page 2274)

      Version of Record online: 17 OCT 2008 | DOI: 10.1002/cphc.200890063

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