ChemPhysChem

Cover image for Vol. 8 Issue 6

April 23, 2007

Volume 8, Issue 6

Pages 769–958

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Review
    6. Communications
    7. Articles
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    1. Cover Picture: Effect of Gramicidin on Phospholipid-Modified Monolayers and on Ion Transfer at a Liquid–Liquid Interface (ChemPhysChem 6/2007) (page 769)

      Hélder A. Santos, Sanna Carlsson, Lasse Murtomäki and Kyösti Kontturi

      Article first published online: 11 APR 2007 | DOI: 10.1002/cphc.200790013

      The cover picture shows a gramicidin embedded biomembrane that interacts with dextran sulfate (DS). These interactions affect drug transfer across the liquid–liquid interface. Langmuir–Blodgett and voltammetry techniques are used to study the interfacial and physicochemical properties of the system. A detailed characterization of the monolayers is presented, and drug transfer is discussed as a result of the modified surface charge and compactness of the lipid in the presence of gramicidin, calcium and DS. Further details can be found in the Article by H. A. Santos et al. on page 913.

  2. Graphical Abstract

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    3. Graphical Abstract
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    1. Graphical Abstract: ChemPhysChem 6/2007 (pages 771–778)

      Article first published online: 11 APR 2007 | DOI: 10.1002/cphc.200790014

  3. News

    1. Top of page
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    4. News
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    1. Spotlights on our Sister Journals (pages 780–781)

      Article first published online: 11 APR 2007 | DOI: 10.1002/cphc.200790015

  4. Review

    1. Top of page
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    4. News
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    1. ZnO: Material, Physics and Applications (pages 782–803)

      C. Klingshirn

      Article first published online: 11 APR 2007 | DOI: 10.1002/cphc.200700002

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      Clear as a bell: ZnO is presently experiencing a research boom, triggerd by hopes of practical applications of this cheap, transparent oxide as an alternative to materials such as GaN. This review covers aspects of the fundamental properties of ZnO and ZnO-based nanostructures as well as present and future applications, with emphasis on the electronic and optical properties. The picture shows deep-centre luminescence of various ZnO samples.

  5. Communications

    1. Top of page
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    3. Graphical Abstract
    4. News
    5. Review
    6. Communications
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    1. Direct Measurement of Size, Three-Dimensional Shape, and Specific Surface Area of Anatase Nanocrystals (pages 805–809)

      Armin Feldhoff, Cecilia Mendive, Thomas Bredow and Detlef Bahnemann

      Article first published online: 23 MAR 2007 | DOI: 10.1002/cphc.200700084

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      Little is different: The specific surface areas of individual crystal facets on anatase nanocrystals (see picture) are estimated quantitatively by the combination of transmission electron microscope measurements with a Wulff-type construction of the three-dimensional shape. The results demonstrate that the crystal facets that are most abundant for macroscopic crystals are not necessarily those that predominate in nanocrystals.

    2. Optical Gain Enhancement Using a Carbosiloxane Dendrimer in Dilute Solution of Rhodamine B (pages 810–814)

      Mei-Ling Zheng, Wei-Qiang Chen, Chun-Fang Li, Xian-Zi Dong and Xuan-Ming Duan

      Article first published online: 16 MAR 2007 | DOI: 10.1002/cphc.200600786

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      Enhancing emission: The addition of a carbosiloxane dendrimer to rhodamine B in methanol solution efficiently enhances emission by changing the microenvironment around rhodamine B molecules due to the site-isolation effect of the dendrimers (see picture). This effect results in a lower lasing threshold, a narrower width of the lasing peak and higher energy conversion.

    3. Separation of ortho- and para-Hydrogen in Van der Waals Complex Formation (pages 815–818)

      Timur A. Grinev, Alexei A. Buchachenko and Roman V. Krems

      Article first published online: 14 MAR 2007 | DOI: 10.1002/cphc.200700061

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      On the path to enrichment: Significant fractionation of ortho- and para-hydrogen occurs through the formation of van der Waals complexes in the gas phase (see figure). Two systems (Ar⋅⋅⋅H2 and Cl⋅⋅⋅H2) are evaluated which lead to the formation of complexes enriched by ortho-hydrogen.

    4. A New Approach for the Fabrication of Strongly Heterogeneous Mixed Self-Assembled Monolayers (pages 819–822)

      Nirmalya Ballav, Tobias Weidner, Katrin Rößler, Heinrich Lang and Michael Zharnikov

      Article first published online: 21 MAR 2007 | DOI: 10.1002/cphc.200700120

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      Thiol exchange: A new approach to fabricate strongly heterogeneous mixed self-assembled monolayers (SAMs) is presented. The mixing occurs by the exchange reaction between a one-component SAM and a suitable second component. The exchange reaction is promoted and precisely tuned by preliminary electron irradiation. As a validity test, mixed aliphatic–aromatic SAMs and templates comprised of active molecules and matrix molecules (see picture) are prepared.

  6. Articles

    1. Top of page
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    3. Graphical Abstract
    4. News
    5. Review
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    1. Power-Law Blinking in the Fluorescence of Single Organic Molecules (pages 823–833)

      Jacob P. Hoogenboom, Jordi Hernando, Erik M. H. P. van Dijk, Niek F. van Hulst and Maria F. García-Parajó

      Article first published online: 23 MAR 2007 | DOI: 10.1002/cphc.200600783

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      Blinking behavior in the emission of single perylene diimide molecules is found to obey power-law statistics over a large range of timescales (see figure). Marked differences and similarities between the power-law behavior in two different systems are observed. These findings are discussed in terms of several recently proposed models.

    2. Circumvention of Fluorophore Photobleaching in Fluorescence Fluctuation Experiments: a Beam Scanning Approach (pages 834–848)

      Dmitri Satsoura, Brian Leber, David W. Andrews and Cécile Fradin

      Article first published online: 30 MAR 2007 | DOI: 10.1002/cphc.200600589

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      Circular beam scanning is a convenient way to alleviate fluorophore photobleaching in single-molecule experiments. It reduces the photon exposure of individual fluorophores and helps prevent the formation of a photobleaching hole (see figure). Optimal beam scanning parameters are determined as a function of the fluorophore diffusion coefficient and photobleaching cross section.

    3. A Theoretical Study of Surface Reduction Mechanisms of CeO2(111) and (110) by H2 (pages 849–855)

      Hsin-Tsung Chen, Yong Man Choi, Meilin Liu and M. C. Lin

      Article first published online: 21 MAR 2007 | DOI: 10.1002/cphc.200600598

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      Reaction mechanisms for the interactions between CeO2(111) and (110) surfaces and H2 (see picture) are investigated using periodic density functional theory (DFT and DFT+U) calculations. It is found that the U correction method plays a significant role in energetics, especially for the partially reduced intermediates and products. The surface reduction reaction on CeO2(110) is energetically much more favorable than on the (111) surface.

    4. TiO2 Porous Electrodes with Hierarchical Branched Inner Channels for Charge Transport in Viscous Electrolytes (pages 856–861)

      Yong Zhao, Xianliang Sheng, Jin Zhai, Lei Jiang, Chunhe Yang, Zhongwei Sun, Yongfang Li and Daoben Zhu

      Article first published online: 21 MAR 2007 | DOI: 10.1002/cphc.200600664

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      Three-dimensional ion channels: Hierarchical branched inner channels were introduced into TiO2 photoanodes to assemble dye-sensitized solar cells. The picture shows a scanning electron microscope image (left) and a schematic depiction (right) of the photoanodes. A higher fill factor of 75.3 % and conversion efficiency of 7.1 % were obtained for a viscous ionic-liquid electrolyte compared to common nanostructured films.

    5. A Comprehensive Study of Concepts and Phenomena of the Nonspecific Adsorption of β-Lactoglobulin (pages 862–872)

      Michael Rabe, Dorinel Verdes, Michael Rankl, Georg R. J. Artus and Stefan Seeger

      Article first published online: 23 MAR 2007 | DOI: 10.1002/cphc.200600710

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      Protein adsorption kinetics: The nonspecific adsorption behavior of β-lactoglobulin on a solid interface is explored. On the basis of observations such as overshootings at a critical coverage or cooperative effects during the adsorption, a comprehensive kinetic model is developed (see picture).

    6. Computing the 1H NMR Spectrum of a Bulk Ionic Liquid from Snapshots of Car–Parrinello Molecular Dynamics Simulations (pages 873–881)

      Alessandro Bagno, Fabio D'Amico and Giacomo Saielli

      Article first published online: 16 MAR 2007 | DOI: 10.1002/cphc.200600725

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      Prediction of NMR spectra: The ability to predict the 1H NMR spectrum of a bulk ionic liquid phase is crucial in the understanding of such complex fluids. Acceptable accuracy must include the effect of the environment and its dynamics; this is accomplished through the analysis of clusters extracted from Car–Parrinello simulations in the case of 1-ethyl-3-methylimidazolium chloride (see figure).

    7. Characterisation of Nanocrystalline Magnesium Oxide by X-Ray Absorption Spectroscopy (pages 882–889)

      Shelley L. P. Savin, Alan V. Chadwick, Luke A. O'Dell and Mark E. Smith

      Article first published online: 23 MAR 2007 | DOI: 10.1002/cphc.200600750

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      Model system: MgO probes the relation between the preparative route and the microstructure of nanocrystalline materials. Pinned samples maintain a particle size of 11 nm, while a 23 nm ball-milled sample contains a significant fraction of amorphous material, illustrated by the greater reduction in EXAFS amplitude for this sample (see figure).

    8. Spin-Orbit Ab Initio Investigation of the Ultraviolet Photolysis of Diiodomethane (pages 890–898)

      Ya-Jun Liu, Luca De Vico, Roland Lindh and Wei-Hai Fang

      Article first published online: 12 MAR 2007 | DOI: 10.1002/cphc.200600737

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      Aim high: In this high-level ab initio study of the photolysis of diiodomethane, the authors show that the spin-orbit interaction is necessary in the theoretical description to correctly explain the experimentally observed processes. The results (see figure, where the C[BOND]I bond length is the reaction co-ordinate) clearly identify the relevant excited spin-mixed electronic states for the pathways.

    9. Long-Range Self-Governing Motion of Polymer Gel on a Gradiently Charged Insulating Substrate (pages 899–905)

      Songmiao Liang, Jian Xu, Lihui Weng, Lina Zhang, Xinglin Guo and Xiaoli Zhang

      Article first published online: 15 MAR 2007 | DOI: 10.1002/cphc.200600745

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      Electroresponsive behavior of poly(vinyl alcohol)/dimethylsulfoxide gel on the gradiently charged substrate is investigated using a noncontacted DC electric field. In response to the gradient change of the charge density and the charge polarity on the substrate, the gel shows a fast and self-governing linear motion in air. The figure shows the crawling velocity of the gel as a function of time at the constant electric field of 300 V mm−1.

    10. Controlled Aggregation of Functionalized Gold Nanoparticles with a Novel Conjugated Oligomer (pages 906–912)

      Xiaofeng Liu, Xiaorong He, Tonggang Jiu, Mingjian Yuan, Jialiang Xu, Jing Lv, Huibiao Liu and Yuliang Li

      Article first published online: 23 MAR 2007 | DOI: 10.1002/cphc.200600763

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      Tunable morphologies: The self-assembly behavior of pyridyl-ended π-conjugated ligands attached to gold nanoparticles is investigated in various solvents. Optical spectroscopy and TEM measurements show that branched rods, chains, and uniform particles (see figure) are obtained for these functionalized gold nanoparticles.

    11. Effect of Gramicidin on Phospholipid-Modified Monolayers and on Ion Transfer at a Liquid–Liquid Interface (pages 913–920)

      Hélder A. Santos, Sanna Carlsson, Lasse Murtomäki and Kyösti Kontturi

      Article first published online: 16 MAR 2007 | DOI: 10.1002/cphc.200600767

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      Monolayer models: Transport across membranes is a crucial process for drug uptake. The picture shows a schematic representation of the hybrid monolayer used to model such processes: phospholipids (white), gramicidin A (black), and dextran sulfate chains (grey) and calcium (black dots).

    12. Contribution of Charge-Transfer Mechanisms to Surface-Enhanced Raman Scattering with Near-IR Excitation (pages 921–925)

      Qun Zhou, Yanwen Chao, Yan Li, Wei Xu, Ying Wu and Junwei Zheng

      Article first published online: 16 MAR 2007 | DOI: 10.1002/cphc.200600776

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      When Au/PATP/Ag molecular junctions form on an ITO electrode (PATP=p-aminothiophenol; ITO=indium-doped tin oxide), much lower energy is required for the charge-transfer process between the metal nanoparticles due to the coupling with the vibrations of the PATP molecules (see picture). These effects are investigated using surface-enhanced Raman scattering (SERS).

    13. In Situ ESR and UV/Vis Spectroelectrochemical Study of Eosin Y Upon Reduction with and without Zn(II) Ions (pages 926–931)

      A. Goux, T. Pauporté, D. Lincot and L. Dunsch

      Article first published online: 15 MAR 2007 | DOI: 10.1002/cphc.200700009

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      A complex affair: A stable Eosin Y radical intermediate, which absorbs in the visible range, is detected for the first time by electron spin resonance (ESR, see spectra of Eosin Y radical, exptl — and simulated ••∥•). In the presence of Zn2+, however, no absorption or ESR signal is observed, as a complex is formed which is unable to stabilise the radical.

    14. Ethanol Adsorption, Decomposition and Oxidation on Ir(111): A High Resolution XPS Study (pages 932–937)

      Cornelis J. Weststrate, Wiebke Ludwig, Johan W. Bakker, Andreea C. Gluhoi and Bernard E. Nieuwenhuys 

      Article first published online: 16 MAR 2007 | DOI: 10.1002/cphc.200700055

      Thumbnail image of graphical abstract

      Molecular ethanol decomposes at 200 K into acetyl and adsorbed hydrogen, which then decomposes into CO, CH and H2 around 300 K. The picture shows a top view of the C 1s photoemission spectra during heating of a layer of ethanol adsorbed on an Ir(111) surface. The changes in the spectrum indicate a change in the nature and/or concentration of the adsorbate.

    15. The Importance of Tetrahedrally Coordinated Molecules for the Explanation of Liquid Water Properties (pages 938–943)

      Ralf Ludwig

      Article first published online: 16 MAR 2007 | DOI: 10.1002/cphc.200700067

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      Liquid water anomalies are accounted for when significant amounts of tetrahedrally coordinated water molecules as well as ring motifs (see picture) are included in computations. When both these species are included in the quantum cluster equilibrium model, the shift of the temperature maximum density as a function of pressure and isotopic substitution is reproduced correctly.

    16. Exploration on Regulating Factors for Proton Transfer along Hydrogen-Bonded Water Chains (pages 944–954)

      Shihai Yan, Liang Zhang, Robert I. Cukier and Yuxiang Bu

      Article first published online: 23 MAR 2007 | DOI: 10.1002/cphc.200600674

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      Five is favored: Proton transfer occurs along single-file H-bonded water wires which contain at most five water molecules. The authors investigate regulating factors (see figure), such as chain length, side water, solvent, temperature, and pressure for the model [ImH[BOND](H2O)n[BOND]ImH]+.

  7. Preview

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Review
    6. Communications
    7. Articles
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      Preview: ChemPhysChem 7/2007 (page 958)

      Article first published online: 11 APR 2007 | DOI: 10.1002/cphc.200790016

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