ChemPhysChem

Cover image for Vol. 9 Issue 12

August 25, 2008

Volume 9, Issue 12

Pages 1653–1802

  1. Cover Picture

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    2. Cover Picture
    3. Graphical Abstract
    4. News
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    1. Cover Picture: Oxygen Microscopy by Two-Photon-Excited Phosphorescence (ChemPhysChem 12/2008) (page 1653)

      Olga S. Finikova, Artem Y. Lebedev, Alexey Aprelev, Thomas Troxler, Feng Gao, Carmen Garnacho, Silvia Muro, Robin M. Hochstrasser and Sergei A. Vinogradov

      Article first published online: 15 AUG 2008 | DOI: 10.1002/cphc.200890048

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      The cover picture illustrates the chemical structure of a dendritic phosphorescent nanoprobe for two-photon microscopy of oxygen. Several antenna chromophores (yellow) capture the excitation energy from a pulsed femtosecond laser and channel it to the central platinum porphyrin (orange) via intramolecular Förster-type energy transfer. In their manuscript on page 1673, S. A. Vinogradov et al., show that oxygen has to diffuse through the dendritic layer in order to quench the porphyrin phosphorescence. Images of intracellular pO2 are obtained using the newly developed method.

  2. Graphical Abstract

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  3. News

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  4. Communications

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    1. Resonance Raman Spectra and Raman Excitation Profiles of Rhodamine 6G from Time-Dependent Density Functional Theory (pages 1667–1669)

      Julien Guthmuller and Benoît Champagne

      Article first published online: 10 JUL 2008 | DOI: 10.1002/cphc.200800253

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      Modeling spectra: Theoretical approaches are employed to reproduce and interpret the resonant Raman spectra of Rhodamine 6G (see figure) and evidence the impact of the ground to excited state geometry modifications on the excitation profiles via vibronic coupling mechanisms.

    2. Model Studies of the Interfacial Ordering of Oleanolic Acid in the Cuticula (pages 1670–1672)

      Gerald Brezesinski and Dieter Vollhardt

      Article first published online: 4 AUG 2008 | DOI: 10.1002/cphc.200800329

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      2D-ordering: The specific interfacial ordering and structural characteristics of well-defined model monolayers (see figure), obtained with highly sophisticated methods, allow the understanding of the oleanoic acid's location exclusively in the cuticula; although its chemical multicyclic planar structure deviates considerably from the typical amphiphile's structure.

  5. Articles

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Communications
    6. Articles
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    1. Oxygen Microscopy by Two-Photon-Excited Phosphorescence (pages 1673–1679)

      Olga S. Finikova, Artem Y. Lebedev, Alexey Aprelev, Thomas Troxler, Feng Gao, Carmen Garnacho, Silvia Muro, Robin M. Hochstrasser and Sergei A. Vinogradov

      Article first published online: 28 JUL 2008 | DOI: 10.1002/cphc.200800296

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      Oxygen distributions are imaged by two-photon laser scanning microscopy (2P LSM) using a newly developed two-photon-enhanced phosphorescent nanoprobe (see figure). 2P LSM allows visualization of oxygen gradients in 3D with near diffraction-limited resolution, and lifetime-based measurements eliminate dependence on the local probe concentration.

    2. Fabrication and Visualization of Metal-Ion Patterns on Glass by Dip-Pen Nanolithography (pages 1680–1687)

      Lourdes Basabe-Desmonts, Chien-Ching Wu, Kees O. van der Werf, Maria Peter, Martin Bennink, Cees Otto, Aldrik H. Velders, David N. Reinhoudt, Vinod Subramaniam and Mercedes Crego-Calama

      Article first published online: 21 JUL 2008 | DOI: 10.1002/cphc.200700853

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      Metal ion patterns: Patterns of metal ions on glass slides coated with fluorescent self-assembled monolayers (SAMs) are fabricated. Different degrees of fluorescence enhancement occur with different metal ions (see schematic). The use of an atomic force fluorescence microscope (AFFM) and the sensing properties of the fluorescent SAMs, permit writing and the immediate visualization of submicrometer-scale metal-ion patterns on glass.

    3. Discrete Arrays of Liquid-Crystal-Supported Proteolipid Monolayers as Phantom Cell Surfaces (pages 1688–1692)

      Amber R. Wise, Jeffrey A. Nye and Jay T. Groves

      Article first published online: 24 JUL 2008 | DOI: 10.1002/cphc.200800257

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      Perfect support: Microfabrication techniques to create arrays of identical liquid-crystalline areas for membrane support and protein display are demonstrated. A new method using a network of small proteins is employed to stabilize the liquid–liquid interface and make it biofunctional. The obtained surface is then used as a support for an immunological T cell synapse (see figure).

    4. C[BOND]H bonds with a Positive Dipole Gradient Can Form Blue-Shifting Hydrogen Bonds: The Complex of Halothane with Methyl Fluoride (pages 1693–1701)

      Bart Michielsen, Wouter A. Herrebout and Benjamin J. van der Veken

      Article first published online: 11 JUL 2008 | DOI: 10.1002/cphc.200800263

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      In the 1:1 complex of halothane (CF3CCBrClH) with methyl fluoride the C[BOND]H bond of the former interacts with the fluorine atom of the latter (see picture) according to infrared spectroscopic results and ab initio calculations. With an observed complexation shift of +15.4 cm−1 of the halothane C[BOND]H stretching mode, this complex provides a new example of a blue-shifting hydrogen bond.

    5. Investigation of the Benzene–Naphthalene and Naphthalene–Naphthalene Potential Energy Surfaces: DFT/CCSD(T) Correction Scheme (pages 1702–1708)

      Miroslav Rubeš, Ota Bludský and Petr Nachtigall

      Article first published online: 23 JUL 2008 | DOI: 10.1002/cphc.200800274

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      Parallel-displaced vs T-shaped: The potential energy surfaces of the naphthalene dimer and the benzene–naphthalene complex (see figure) are investigated using the DFT/CCSD(T) correction scheme. The larger the size of the aromatic molecule involved in complex formation, the higher the stability of the parallel-displaced structures with respect to the T-shaped structures. Only the benzene dimer shows a stable T-shaped structure.

    6. Photodissociation Spectroscopy of CD3I+ Generated by Mass-Analyzed Threshold Ionization for Structure Determination (pages 1709–1714)

      Yong Jin Bae and Myung Soo Kim

      Article first published online: 9 JUL 2008 | DOI: 10.1002/cphc.200800207

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      Excited molecular cation: High-resolution rotational spectra of CH3I+ and CD3I+ in the first excited electronic state are measured by photodissociation of the ground-state cations generated by mass-analyzed threshold ionization. Spectroscopic constants and geometries of the cations in the ground (equation image2E3/2) and excited states (Ã2A1) are determined (see picture).

    7. Why Are Selenouracils as Basic as but Stronger Acids than Uracil in the Gas Phase? (pages 1715–1720)

      Cristina Trujillo, Otilia Mó and Manuel Yáñez

      Article first published online: 10 JUL 2008 | DOI: 10.1002/cphc.200800215

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      The acid test: Selenouracils are predicted to be stronger acids than uracil. This acidity enhancement is due to a specific stabilization of the anion when O is replaced by Se, because of a significant aromatization of the ring upon deprotonation, and to a better dispersion of the excess electron density when the system contains third-row atoms, as reflected in the electron localization function (see picture).

    8. Photodissociation of Dibromobenzenes at 266 nm by the Velocity Imaging Technique (pages 1721–1728)

      Xiao-Peng Zhang, Zheng-Rong Wei, Wei-Bin Lee, Ting-Jung Chao and King-Chuen Lin

      Article first published online: 15 JUL 2008 | DOI: 10.1002/cphc.200800180

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      Up to speed: Resonance-enhanced multiphoton ionization combined with a velocity imaging technique indicates that the photodissociation of o-, m-, and p-dibromobenzene (see ion image) gives rise to the primary Br(2P3/2) product through two dissociation channels. One channel is initiated from the lowest excited singlet state coupled to a repulsive triplet state, while the other is attributed to a bound triplet state.

    9. Micelles as Containers for Self-Assembled Nanodevices: A Fluorescent Sensor for Lipophilicity (pages 1729–1737)

      Giuseppe Chirico, Maddalena Collini, Laura D'Alfonso, Franck Denat, Yuri A. Diaz-Fernandez, Luca Pasotti, Yoann Rousselin, Nicolas Sok and Piersandro Pallavicini

      Article first published online: 23 JUL 2008 | DOI: 10.1002/cphc.200800292

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      Sensors included: The interaction of 1-pyrenecarboxylate with the Zn2+ complex of a lipophilized cyclen is dramatically promoted by micellar inclusion, which results in a strong increase in fluorescence (see picture). The system works as a self-assembled nanodevice capable of sensing the lipophilicity of added molecules, which is reported by means of fluorescence variation.

    10. Microstructuring of Polystyrene Surfaces with Nonsolvent Sessile Droplets (pages 1738–1746)

      Ramon Pericet-Camara, Elmar Bonaccurso and Karlheinz Graf

      Article first published online: 23 JUL 2008 | DOI: 10.1002/cphc.200800098

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      A characteristic microstructure remains on a polymer surface after evaporation of a sessile water droplet in a solvent-rich environment. Regular arrays of size-controlled microvessels are fabricated in this way (see picture). The resulting height profiles are modeled by using a recent elastic theory that is based on the interplay between the interfacial tension γLV and the Laplace pressure ΔP of the liquid.

    11. Variable-Temperature Infrared Spectroscopy Studies on the Thermodynamics of CO Adsorption on the Zeolite Ca–Y (pages 1747–1751)

      Barbara Bonelli, Carlos Otero Areán, Marco Armandi, Montserrat Rodríguez Delgado and Edoardo Garrone

      Article first published online: 11 JUL 2008 | DOI: 10.1002/cphc.200800238

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      Gas adsorption: An IR cell that operates above ambient temperature, and which enables IR absorbance, temperature and equilibrium pressure to be simultaneously recorded, gives precise thermodynamic data for the CO/Ca–Y system. In the range of 298–380 K and 5–8 mbar, CO adsorbed on Ca–Y gives rise to monocarbonyl (Ca2+⋅⋅⋅CO) and isocarbonyl (Ca2+⋅⋅⋅OC) species (see figure).

    12. Comparison of the Electrochemical and Luminescence Properties of Two Carbazole-Based Phosphine Oxide EuIII Complexes: Effect of Different Bipolar Ligand Structures (pages 1752–1760)

      Hui Xu, Kun Yin and Wei Huang

      Article first published online: 18 JUN 2008 | DOI: 10.1002/cphc.200800125

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      Inner space: The electrochemical and photophysical properties of two EuIII ternary complexes (see figure) provide important insights into the development of red component emitters for OLEDs. The insertion of a π-spacer (an ambipolar phosphine oxide) in the donor–acceptor system strongly improves coordination, which facilitates the modification of the complexes by designing multifunctional ligands purposefully.

    13. Photothermal Detection of Individual Gold Nanoparticles: Perspectives for High-Throughput Screening (pages 1761–1766)

      Florian Kulzer, Niels Laurens, Jaya Besser, Thomas Schmidt, Michel Orrit and Herman P. Spaink

      Article first published online: 30 JUL 2008 | DOI: 10.1002/cphc.200800127

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      Enlarged detection volume: Photothermal microscopy allows the detection of individual gold nanoparticles with high signal-to-noise ratio (see picture) in an enlarged detection volume, thus promising increased throughput in screening applications.

    14. Associative Versus Dissociative Mechanisms of Phosphate Monoester Hydrolysis: On the Interpretation of Activation Entropies (pages 1767–1773)

      Shina C. L. Kamerlin, Jan Florián and Arieh Warshel

      Article first published online: 30 JUL 2008 | DOI: 10.1002/cphc.200800356

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      Tattletale activation entropies: The first comprehensive theoretical study of the activation entropies for phosphate hydrolysis using Langevin dipole methods and the restraint release approach demonstrates that associative and dissociative pathways have virtually identical activation entropies (see figure). This is contrary to the traditional assumption that a near-zero activation entropy indicates a dissociative pathway.

    15. Photo-Induced Hydrogen Exchange Reaction between Methanol and Glyoxal: Formation of Hydroxyketene (pages 1774–1780)

      Zofia Mielke, Małgorzata Mucha, Andrzej Bil, Barbara Golec, Stephane Coussan and Pascale Roubin

      Article first published online: 9 JUL 2008 | DOI: 10.1002/cphc.200800249

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      Methanol please! The molecular glyoxal–methanol complex, isolated in solid argon and irradiated with a mercury lamp (λ>370 nm), converts into a hydroxyketene–methanol complex (see scheme). The reaction involves exchange of two hydrogen atoms between the two complex subunits.

    16. Adsorption of 1,3-Benzenedithiol and 1,3-Benzenedimethanethiol on Gold Surfaces (pages 1781–1787)

      Jong Kuk Lim, Youngmin Kim, Ohyun Kwon and Sang-Woo Joo

      Article first published online: 30 JUL 2008 | DOI: 10.1002/cphc.200800175

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      Going for gold: In contrast to 1,3-benzenedimethanethiol (1,3-BDMT), 1,3-benzenedithiol (1,3-BDT) appears not to self-assemble efficiently on Au surfaces due to the absence of the methylene unit. DFT calculations on the basis of an adsorption model using an Au8 cluster indicate single- and double-thiol anchoring geometries (see picture) of 1,3-BDT and 1,3-BDMT on Au surfaces.

    17. Tunneling Splittings in the S0 and S1 States of the Benzoic Acid Dimer Determined by High-Resolution UV Spectroscopy (pages 1788–1797)

      Ivo Kalkman, Chau Vu, Michael Schmitt and W. Leo Meerts

      Article first published online: 28 JUL 2008 | DOI: 10.1002/cphc.200800214

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      How the barrier changes: The amount by which both the S0 and S1 energy levels of the benzoic acid dimer are split due to concerted proton tunneling are determined. The exact structure of the dimer in both states is also derived by means of rotationally resolved UV spectroscopy. In the picture the structure of the benzoic acid dimer is superimposed on a rotationally resolved UV spectrum.

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      Preview: ChemPhysChem 13/2008 (page 1802)

      Article first published online: 15 AUG 2008 | DOI: 10.1002/cphc.200890051

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