ChemPhysChem

Cover image for Vol. 8 Issue 14

October 8, 2007

Volume 8, Issue 14

Pages 2025–2142

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Review
    6. Minireview
    7. Communications
    8. Articles
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    1. Cover Picture: Two-Photon Microscopy and Spectroscopy of Lanthanide Bioprobes (ChemPhysChem 14/2007) (page 2025)

      Anthony D'Aléo, Guillaume Pompidor, Bénédicte Elena, Jean Vicat, Patrice L. Baldeck, Loïc Toupet, Richard Kahn, Chantal Andraud and Olivier Maury

      Article first published online: 26 SEP 2007 | DOI: 10.1002/cphc.200790045

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      The cover picture shows one- and two-photon excited fluorescence microscopy imaging pictures of crystals of lysozyme-containing terbium and europium tris-dipicolinate complexes. Whereas one-photon irradiation results in green (Tb) or red (Eu) luminescence of the whole crystal aggregate, two-photon excitation in the case of terbium gives a three-dimensionally resolved spot corresponding to the confocal excitation volume. In their article on page 2125, D'Aléo, Pompidor et al. describe the photophysical properties and particularly the linear and nonlinear fluorescence microscopy of these complexes in solution and in the crystalline state.

  2. Graphical Abstract

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    3. Graphical Abstract
    4. News
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    1. Graphical Abstract: ChemPhysChem 14/2007 (pages 2027–2033)

      Article first published online: 26 SEP 2007 | DOI: 10.1002/cphc.200790046

  3. News

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Review
    6. Minireview
    7. Communications
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  4. Review

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Review
    6. Minireview
    7. Communications
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    1. Intelligent Control of Surface Hydrophobicity (pages 2036–2050)

      Sally L. Gras, Tanveer Mahmud, Gary Rosengarten, Arnan Mitchell and Kourosh Kalantar-zadeh

      Article first published online: 27 AUG 2007 | DOI: 10.1002/cphc.200700222

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      Surface switches: The hydrophobicity of a switchable surface can be controlled by external stimuli, which alter interactions with liquids and biomolecules (see image). Six classes of external stimuli are discussed and recent progress towards their application in microsystems, materials science, biotechnology and medicine is explored.

  5. Minireview

    1. Top of page
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    3. Graphical Abstract
    4. News
    5. Review
    6. Minireview
    7. Communications
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    1. Dipole Moment Enhancement in Molecular Crystals from X-ray Diffraction Data (pages 2051–2063)

      Mark A. Spackman, Parthapratim Munshi and Birger Dittrich

      Article first published online: 6 AUG 2007 | DOI: 10.1002/cphc.200700339

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      Charge distribution in crystals: Experimental determinations of dipole moments in molecular crystals are collated to provide evidence that molecular dipole moments from X-ray diffraction data can provide a wealth of information on the change in the molecular charge distribution that results from crystal formation (see histograms of dipole moment enhancement, %ΔμX-ray). These experiments are unrivalled in their ability to provide such detailed information.

  6. Communications

    1. Top of page
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    3. Graphical Abstract
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    7. Communications
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    1. No Marked Kinetic Isotope Effect in the Peroxone (H2O2/D2O2+O3) Reaction: Mechanistic Consequences (pages 2065–2067)

      Myint Myint Sein, Alfred Golloch, Torsten C. Schmidt and Clemens von Sonntag

      Article first published online: 10 AUG 2007 | DOI: 10.1002/cphc.200700493

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      Radical species: Controversy surrounds the peroxone reaction mechanism; does the rate-determining step involve an electron-transfer or a hydride-transfer reaction? The authors re-investigate the peroxone reaction in D2O to resolve the issue (see figure).

    2. Size-Specific Chemistry on Bimetallic Surfaces: A Combined Experimental and Theoretical Study (pages 2068–2071)

      Martin Ruff, Naoki Takehiro, Ping Liu, Jens K. Nørskov and R. Jürgen Behm

      Article first published online: 5 SEP 2007 | DOI: 10.1002/cphc.200700070

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      Surface alloys: The chemical properties of bimetallic PdAu surface alloys are examined in terms of local properties of individual metal nanostructures during CO adsorption (see picture). These properties are quantitatively understood by electronic ligand effects, geometric ensemble effects and repulsive adsorbate–adsorbate interactions.

    3. Computing the Acidity of Liquids via Ab Initio Molecular Dynamics (pages 2072–2076)

      Christian Simon, Giovanni Ciccotti and Michael L. Klein

      Article first published online: 27 AUG 2007 | DOI: 10.1002/cphc.200700250

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      Virtual pH paper: A parameter-free method estimates the acidity of a liquid via ab initio molecular dynamics (AIMD). The idea, inspired by experiments, utilizes the concept of virtual pH paper. A series of colorimetric indicators (Hammet bases) are studied in the liquid of interest in their protonated form, using AIMD (see figure).

    4. Observation of Single-File Diffusion in Dipeptide Nanotubes by Continuous-Flow Hyperpolarized Xenon-129 NMR Spectroscopy (pages 2077–2081)

      Chi-Yuan Cheng and Clifford R. Bowers

      Article first published online: 31 AUG 2007 | DOI: 10.1002/cphc.200700336

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      Transported in single file: Expressions for the hyperpolarized NMR saturation recovery signals of single-file diffusion in L-alanyl-L-valine (AV) nanotubes are derived and compared to experiments. The distribution of hyperpolarized Xe inside a single channel with increasing observation time τ is shown schematically.

    5. A Cryptophane Biosensor for the Detection of Specific Nucleotide Targets through Xenon NMR Spectroscopy (pages 2082–2085)

      Vincent Roy, Thierry Brotin, Jean-Pierre Dutasta, Marie-Hélène Charles, Thierry Delair, François Mallet, Gaspard Huber, Hervé Desvaux, Yves Boulard and Patrick Berthault

      Article first published online: 21 AUG 2007 | DOI: 10.1002/cphc.200700384

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      DNA sensor: A xenon host composed of a cryptophane structure with a DNA strand (see picture) serves to detect its complementary strand in the micromolar range through laser-polarized 129Xe NMR spectroscopy.

    6. Assembly of Hexamolybdenum Metallic Clusters on Silicon Surfaces (pages 2086–2090)

      S. Ababou-Girard, S. Cordier, B. Fabre, Y. Molard and C. Perrin

      Article first published online: 11 SEP 2007 | DOI: 10.1002/cphc.200700499

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      Becoming attached: Mo6Ii8 (Ii=inner iodine) cluster cores are anchored in apical positions to monocrystalline silicon surfaces. The attachment occurs via pyridine groups, end-capping an alkyl monolayer which is covalently bound to the hydrogen-terminated silicon surface. Octahedral Mo6 clusters: orange; pyridine head groups of the monolayer: green; apical pyridine units: blue.

    7. Controllable Synthesis of CoO Nanosheets and their Magnetic Properties (pages 2091–2095)

      Wenli Zhang, Min Han, Ziyuan Jiang, You Song, Zhaoxiong Xie, Zheng Xu and Lansun Zheng

      Article first published online: 27 AUG 2007 | DOI: 10.1002/cphc.200700398

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      Superparamagnetic behaviour: CoO nanosheets synthesised by a surfactant-free wet chemical route (see high-resolution morphology image in figure), exhibit superparamagnetic features different from their bulk counterparts. No distinct antiferromagnetic transition around 300 K is observed in the nanosheets (see spectra).

    8. Endohedral Stannaspherenes Mn@Sn12 and its Dimer: Ferromagnetic or Antiferromagnetic? (pages 2096–2099)

      Jon M. Matxain, Mario Piris, Elena Formoso, Jose M. Mercero, Xabier Lopez and Jesus M. Ugalde

      Article first published online: 27 AUG 2007 | DOI: 10.1002/cphc.200700428

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      Intermetalloid clusters: A theoretical study describes a new endohedral stannaspherene Mn@Sn12 (left in figure) and its dimer. The Mn doping produces a neutral cluster with a very high spin. Three isomers are characterised for the dimer in which the antiferromagnetic coupling between the two manganese centres is favoured.

  7. Articles

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    3. Graphical Abstract
    4. News
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    1. The Reaction Mechanism of p-Toluenediamine Anodic Oxidation: An In Situ ESR-UV/Vis/NIR Spectroelectrochemical Study (pages 2101–2106)

      Aurélie Goux, Dominic Pratt and Lothar Dunsch

      Article first published online: 13 SEP 2007 | DOI: 10.1002/cphc.200700235

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      Medium acidity: The formation of intermediates in the anodic oxidation of p-toluenediamine is studied by in situ ESR-UV/Vis spectroelectrochemical methods. In the primary oxidation steps, no paramagnetic structures are observed at pH 2 and 10, whereas a radical cation is detected at medium pH values (see ESR spectrum).

    2. C[BOND]H Stretching Vibrational Shift of Benzene Dimer: Consistency of Experiment and Calculation (pages 2107–2111)

      Weizhou Wang, Michal Pitoňák and Pavel Hobza

      Article first published online: 31 AUG 2007 | DOI: 10.1002/cphc.200700415

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      Discrepency resolved: Computational studies of low-energy structures of the benzene dimer explain why a blue shift is never seen in experimental determinations of the vibrational shift. The blue shift is attributed to the C2v T-shaped structure TB1, which is unstable and transforms into a T-shaped (Cs ) structure TB2, the global minimum which gives rise to a small red shift.

    3. First Kinetic Determination of Partition Coefficients for Organic Compounds between the Three Microenvironments of AOT-Based Microemulsions (pages 2112–2118)

      Luis García-Río and María Méndez

      Article first published online: 13 SEP 2007 | DOI: 10.1002/cphc.200700318

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      Microemulsions: Kinetic analysis of organic reactions in microemulsions determines the two partition constants for incorporation of substrates from the water microdroplets and the continuous medium into the interface (see picture). The results reveal that three distinct regions in a microemulsion must always be considered, even at low water/surfactant ratios.

    4. Protein Side Chains Facilitate Mg/Al Exchange in Model Protein Binding Sites (pages 2119–2124)

      Elixabete Rezabal, Jose M. Mercero, Xabier Lopez and Jesus M. Ugalde

      Article first published online: 21 AUG 2007 | DOI: 10.1002/cphc.200700335

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      High affinity:The metal-exchange free energies of protein binding sites for MgII which have high affinity towards AlIII are determined by DFT calculations, taking into account solvent effects explicitly (see figure). The results show that thermodynamically favored exchange reactions can take place at a number of metal-binding sites.

    5. Two-Photon Microscopy and Spectroscopy of Lanthanide Bioprobes (pages 2125–2132)

      Anthony D'Aléo, Guillaume Pompidor, Bénédicte Elena, Jean Vicat, Patrice L. Baldeck, Loïc Toupet, Richard Kahn, Chantal Andraud and Olivier Maury

      Article first published online: 11 SEP 2007 | DOI: 10.1002/cphc.200700375

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      Lanthanide bioprobes: The first two-photon microscopy imaging experiments using tris-dipicolinate terbium complexes, as a probe were carried out on derivative protein crystals. Whereas one-photon irradiation results in green luminescence of the entire crystal aggregate, two-photon excitation gives a three-dimensionally resolved spot corresponding to the confocal volume (see picture).

    6. Label-Free Electrical Determination of Trypsin Activity by a Silicon-on-Insulator Based Thin Film Resistor (pages 2133–2137)

      Petra A. Neff, Andreas Serr, Bernhard K. Wunderlich and Andreas R. Bausch

      Article first published online: 27 AUG 2007 | DOI: 10.1002/cphc.200700279

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      Enzyme activity: The polyelectrolyte substrate poly-L-lysine is digested by trypsin directly at the sensor surface. The created fragments are released into the bulk solution which results in a measurable change of the surface potential allowing for the determination of trypsin (see figure).

  8. Preview

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    3. Graphical Abstract
    4. News
    5. Review
    6. Minireview
    7. Communications
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      Preview: ChemPhysChem 15/2007 (page 2142)

      Article first published online: 26 SEP 2007 | DOI: 10.1002/cphc.200790048

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