ChemPhysChem

Cover image for Vol. 14 Issue 9

June 24, 2013

Volume 14, Issue 9

Pages 1749–2001

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Editors' Selection
    5. News
    6. Concepts
    7. Communications
    8. Articles
    1. You have free access to this content
      Cover Picture: Theoretical Investigation of Generator–Collector Microwell Arrays for Improving Electroanalytical Selectivity: Application to Selective Dopamine Detection in the Presence of Ascorbic Acid (ChemPhysChem 9/2013) (page 1749)

      Dr. Alexander Oleinick, Feng Zhu, Dr. Jiawei Yan, Prof. Dr. Bingwei Mao, Prof. Dr. Irina Svir  and Prof. Dr. Christian Amatore

      Article first published online: 14 JUN 2013 | DOI: 10.1002/cphc.201390041

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      Generator–collector microwell arrays show excellent performance for selective and sensitive detection of an analyte of interest in the presence of interferents, with redox waves occurring before that of the analyte. Due to the specific geometry of the array and the adequate control of each electrode potential, the analyte signal is increased by redox cycling, while that of the interferent is drastically reduced. The theory and simulations presented on p. 1887 by I. Svir, C. Amatore et al. not only allow proper modeling of the experimental results, but also open up new operating possibilities.

    2. You have free access to this content
      Inside Cover: Printable Magnetoelectronics (ChemPhysChem 9/2013) (page 1750)

      Dr. Denys Makarov, Daniil Karnaushenko and Prof. Dr. Oliver G. Schmidt

      Article first published online: 14 JUN 2013 | DOI: 10.1002/cphc.201390042

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      Printable magnetoelectronics has recently been realized. On p. 1771 D. Makarov et al. position the topic of printable magnetic sensorics in a family of printable electronics and highlight possible applications of this technology.

  2. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Editors' Selection
    5. News
    6. Concepts
    7. Communications
    8. Articles
  3. Editors' Selection

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Editors' Selection
    5. News
    6. Concepts
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    8. Articles
    1. Editors' Selection: ChemPhysChem 9/2013 (page 1761)

      Article first published online: 14 JUN 2013 | DOI: 10.1002/cphc.201390044

  4. News

    1. Top of page
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    3. Graphical Abstract
    4. Editors' Selection
    5. News
    6. Concepts
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    8. Articles
    1. Materials and Methods (page 1769)

      Article first published online: 14 JUN 2013 | DOI: 10.1002/cphc.201300523

  5. Concepts

    1. Top of page
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    3. Graphical Abstract
    4. Editors' Selection
    5. News
    6. Concepts
    7. Communications
    8. Articles
    1. You have full text access to this OnlineOpen article
      Printable Magnetoelectronics (pages 1771–1776)

      Dr. Denys Makarov, Daniil Karnaushenko and Prof. Dr. Oliver G. Schmidt

      Article first published online: 8 APR 2013 | DOI: 10.1002/cphc.201300162

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      Man the presses! A large variety of electronic components assembled as printable optoelectronic devices and communication modules are already commercially available. However, an element that responds to a magnetic field has been realized only recently. Here, the printable magnetic sensorics is positioned in a family of printable electronics and possible application directions of this technology are highlighted.

    2. Integrated Devices to Realize Energy Conversion and Storage Simultaneously (pages 1777–1782)

      Tao Chen, Zhibin Yang and Prof. Huisheng Peng

      Article first published online: 5 APR 2013 | DOI: 10.1002/cphc.201300032

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      Live wire: Novel integrated devices are described for the simultaneous realization of photoelectric conversion and energy storage with an emphasis on a wire format. The wire structure enables unique and promising applications, for example being woven into clothes or other complex flexible equipment by conventional textile technology.

  6. Communications

    1. Top of page
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    3. Graphical Abstract
    4. Editors' Selection
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    6. Concepts
    7. Communications
    8. Articles
    1. Direct 2H NMR Observation of the Proton Mobility of the Acidic Sites of Anhydrous 12-Tungstophosphoric Acid (pages 1783–1786)

      Dr. Daniil I. Kolokolov, Maxim S. Kazantsev, Dr. Mikhail V. Luzgin, Prof. Hervé Jobic and Prof. Alexander G. Stepanov

      Article first published online: 16 APR 2013 | DOI: 10.1002/cphc.201300291

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      Flip and hop before you′re caught! The proton dynamics of solid 12-tungstophosphoric acid (TPA) is probed by solid-state 2H NMR in a temperature range from 293–503 K. Protons of TPA are shown to be involved in two types of molecular motion (see picture): the anisotropic local two-site flipping between the two possible orientations of the O[BOND]H bond at bridged oxygens of the Keggin anion, and the isotropic diffusion by hopping between neighboring surface oxygens of the anion.

    2. Band Gap Engineering of BN Sheets by Interlayer Dihydrogen Bonding and Electric Field Control (pages 1787–1792)

      Qing Tang, Prof. Dr. Zhen Zhou, Prof. Panwen Shen and Prof. Dr. Zhongfang Chen

      Article first published online: 19 APR 2013 | DOI: 10.1002/cphc.201300141

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      An unconventional bonding: The presence of interlayer B[BOND]H⋅⋅⋅H[BOND]N dihydrogen bonds in hydrogenated bilayer BN nanosheets reduces the intrinsic large band gap of the chair-type BN conformation owing to interlayer charge transfer. In contrast, the insulating properties of the thermodynamically more stable stirrup-type bilayer BN can be engineered by applying an electric field. These results illuminate a new pathway for band gap engineering of 2D BN nanomaterials.

    3. One-Pot in Situ Mixed Film Formation by Azo Coupling and Diazonium Salt Electrografting (pages 1793–1796)

      Dr. Charles Esnault, Dr. Nicolas Delorme, Prof. Guy Louarn and Prof. Jean-François Pilard

      Article first published online: 23 APR 2013 | DOI: 10.1002/cphc.201300007

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      So simple: The in situ synthesis of an aryldiazonium salt and an azo-aryldiazonium salt by azo coupling from sulfanilic acid and aniline is reported. Formation of a mixed organic layer is monitored by cyclic voltammetry and atomic force microscopy. A compact mixed layer is obtained with a global roughness of 0.4 nm and 10–15 % vertical extension in the range 1.5–6 nm.

    4. Stacking Interactions of Ni(acac) Chelates with Benzene: Calculated Interaction Energies (pages 1797–1800)

      Dr. Dušan N. Sredojević, Dragan B. Ninković, Dr. Goran V. Janjić, Dr. Jia Zhou, Prof. Michael B. Hall and Prof. Snežana D. Zarić

      Article first published online: 16 APR 2013 | DOI: 10.1002/cphc.201201062

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      Piling ′em up: The stacking energy of the [Ni(acac)2]/benzene system is calculated at local CCSD(T) level and is in good agreement with the values obtained with the SCS-MP2 method. Energies calculated with several DFT-D methods are somewhat overestimated. The calculated stacking energy of the [Ni(acac)2]/benzene system is significantly stronger than that of the benzene dimer.

    5. AFM Study of Gibbs Films of Semifluorinated Alkanes at Liquid Crystal/Air Interfaces (pages 1801–1805)

      Dr. Xunda Feng, Dr. Ahmed Mourran, Prof. Dr. Martin Möller and Dr. Christian Bahr

      Article first published online: 14 MAY 2013 | DOI: 10.1002/cphc.201300173

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      Forming micelles: The first in situ AFM study of Gibbs films of semifluorinated alkanes at liquid crystal/air interfaces is presented. The Gibbs films self-organize in a hexagonal close packing of surface micelles with shapes and lateral dimensions that are similar to micelles forming on aqueous and solid surfaces. It is concluded that he formation of surfaces micelles and their self-organization in large-area dense hexagonal arrays are intrinsic properties of semifluorinated alkane molecules.

  7. Articles

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Editors' Selection
    5. News
    6. Concepts
    7. Communications
    8. Articles
    1. Structural Principles and Thermoelectric Properties of Polytypic Group 14 Clathrate-II Frameworks (pages 1807–1817)

      Dr. Antti J. Karttunen and Prof. Dr. Thomas F. Fässler

      Article first published online: 22 APR 2013 | DOI: 10.1002/cphc.201300133

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      Anisotropic clathrates: Quantum chemical investigation shows the highly anisotropic hexagonal clathrate polytypes to be practically as stable as the experimentally known cubic member of the same structural family. The semiconducting group 14 clathrates are known to be efficient thermoelectric materials and the structural anisotropy of the novel hexagonal clathrate polytypes significantly affects their thermoelectric properties.

    2. Controlling the π-Stacking Behavior of Pyrene Derivatives: Influence of H-Bonding and Steric Effects in Different States of Aggregation (pages 1818–1829)

      Andreas T. Haedler, Holger Misslitz, Christian Buehlmeyer, Prof. Dr. Rodrigo Q. Albuquerque, Prof. Dr. Anna Köhler and Prof. Dr. Hans-Werner Schmidt

      Article first published online: 25 APR 2013 | DOI: 10.1002/cphc.201300242

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      The Influence of H-bonding and steric hindrance on the optical properties and the π-stacking of pyrene derivatives is investigated and described in dilute solution, as supramolecular aggregates and in the crystalline state.

    3. The Distorted Tropane of Scopoline (pages 1830–1835)

      Dr. Patricia Écija, Dr. Emilio J. Cocinero, Prof. Alberto Lesarri, Dr. Francisco J. Basterretxea, Dr. José A. Fernández and Prof. Fernando Castaño

      Article first published online: 2 MAY 2013 | DOI: 10.1002/cphc.201300199

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      Live isomerization: The uncommon three-ring structure of scopoline (oscine), an alkaloid, is revealed from gas-phase isomerization of scopine using rotational spectroscopy.

    4. Single-Step Sulfo-Selenization Method to Synthesize Cu2ZnSn(SySe1−y)4 Absorbers from Metallic Stack Precursors (pages 1836–1843)

      Andrew Fairbrother, Xavier Fontané, Dr. Victor Izquierdo-Roca, Moises Espindola-Rodriguez, Simon López-Marino, Dr. Marcel Placidi, Dr. Juan López-García, Prof. Alejandro Pérez-Rodríguez and Dr. Edgardo Saucedo

      Article first published online: 10 APR 2013 | DOI: 10.1002/cphc.201300157

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      Not an ordinary pentenary! A straightforward sulfo-selenization process for the formation of pentenary Cu2ZnSn(SySe1−y) solar-cell absorber films permits the tuning of the absorber composition from sulfur-rich to selenium-rich in a single annealing process. The resulting films, with compositions in the whole range of S/(S+Se) ratios, aim at pentenary-based solar cells of superior efficiency, which to date have been mostly limited to chalcogen-containing precursors.

    5. Computational Studies on Non-covalent Interactions of Carbon and Boron Fullerenes with Graphene (pages 1844–1852)

      Arun K. Manna and Prof. Swapan K. Pati

      Article first published online: 24 APR 2013 | DOI: 10.1002/cphc.201300155

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      Bound by choice: Energetic and optoelectronic properties of various graphene–fullerene composites are investigated by DFT calculations (see picture). Both van der Waals and charge-transfer interactions need to be considered to assess the correct stability order of these weakly bound complexes. The composites show diverse electronic and optical properties, which suggest their potential in optoelectronic and photovoltaic devices applications.

      Corrected by:

      Corrigendum: Corrigendum: Computational Studies on Non-Covalent Interactions of Carbon and Boron Fullerenes with Graphene

      Vol. 14, Issue 13, 2881, Article first published online: 12 SEP 2013

    6. Deposition and Characterization of Luminescent Eu(tta)3phen-Doped Parylene-Based Thin-Film Materials (pages 1853–1863)

      Dr. Gianluigi Maggioni, Antonio Campagnaro, Dr. Michele Tonezzer, Dr. Sara Carturan and Prof. Alberto Quaranta

      Article first published online: 3 MAY 2013 | DOI: 10.1002/cphc.201300151

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      Let there be light! Luminescent host–guest films are produced by finely dispersing Eu(tta)3phen [tta = tris(2-thenoyl trifluoroacetone), phen = 1,10-phenantroline] in a parylene matrix by using a new coarse vacuum cosublimation technique. Fine dispersion of the Eu complex molecules and energy transfer between parylene and the Eu complex afford emitted light that is five times more intense than the light emitted by films of the Eu complex alone.

    7. Solid-State NMR Correlation Experiments and Distance Measurements in Paramagnetic Metalorganics Exemplified by Cu-Cyclam (pages 1864–1870)

      Shashi K. Kumara Swamy, Agnieszka Karczmarska, Prof. Malgorzata Makowska-Janusik, Prof. Abdelhadi Kassiba and Prof. Jens Dittmer

      Article first published online: 14 JUN 2013 | DOI: 10.1002/cphc.201300119

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      Paramagnetic metalorganics in the solid phase are accessible to NMR by particular pulse sequences. They even provide advantages compared to diamagnetic systems, as the hyperfine shift improves hydrogen resolution, thus allowing for the recording of 1H-1H correlation experiments. The paramagnetic relaxation can then be exploited in order to obtain metal–carbon distances even in the close environment of the metal center.

    8. Large-Area Plasmonic Substrate of Silver-Coated Iron Oxide Nanorod Arrays for Plasmon-Enhanced Spectroscopy (pages 1871–1876)

      Waldemir Moura Carvalho Jr., Dr. Diogo Volpati, Vitor A. Nunes Carvalho, Prof. Ricardo F. Aroca, Prof. Carlos J. L. Constantino and Prof. Flavio L. Souza

      Article first published online: 6 MAY 2013 | DOI: 10.1002/cphc.201300054

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      Stand up straight! Vertically oriented α-Fe2O3 nanorod arrays are synthesized under hydrothermal conditions over a large area, as an active platform for surface-enhanced resonance Raman scattering (SERRS) and surface-enhanced fluorescence (SEF, see picture; LB=Langmuir–Blodgett layer of probe molecule). The morphology of the arrays is preserved after the surface is covered with a 6 nm Ag layer deposited by physical vapor deposition (PVD).

    9. A Monolayer Assay Tailored to Investigate Lipid–Protein Systems (pages 1877–1881)

      Grzegorz Chwastek and Prof. Petra Schwille

      Article first published online: 18 APR 2013 | DOI: 10.1002/cphc.201300035

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      Small and handy: A new simple miniaturized monolayer assay (see picture, monolayer in miniaturized chamber) is proposed to investigate specific features of cellular membranes. The method can be easily combined with standard analytical techniques such as confocal fluorescence microscopy and fluorescence correlation spectroscopy (FCS).

    10. Strong Light-Molecule Coupling on Plasmonic Arrays of Different Symmetry (pages 1882–1886)

      Dr. Adi Salomon, Shaojun Wang, Dr. James A. Hutchison, Dr. Cyriaque Genet and Prof. Thomas W. Ebbesen

      Article first published online: 10 APR 2013 | DOI: 10.1002/cphc.201200914

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      The strong coupling of porphyrin J-aggregates to plasmonic nanostructures of different symmetry is investigated. The nanostructures of higher symmetry show the strongest interaction with the molecular layer. At high coupling strengths a new, weakly dispersive mode appears. These findings point to new ways for optimizing strong coupling and thereby realize its full potential for molecular and material science.

    11. Theoretical Investigation of Generator–Collector Microwell Arrays for Improving Electroanalytical Selectivity: Application to Selective Dopamine Detection in the Presence of Ascorbic Acid (pages 1887–1898)

      Dr. Alexander Oleinick, Feng Zhu, Dr. Jiawei Yan, Prof. Dr. Bingwei Mao, Prof. Dr. Irina Svir  and Prof. Dr. Christian Amatore

      Article first published online: 10 APR 2013 | DOI: 10.1002/cphc.201300134

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      Well separated: A microwell array integrating collector–generator amplification into a diffusional faradaic cage virtually eliminates irreversible redox interferences, for example, in dopamine (DA) detection in the presence of ascorbic acid (AA). Thus, AA is scavenged but DA enters the nanocavities for oxidation at the disk electrodes, and its signal is further amplified by redox cycling (see picture).

    12. Recombination of Lophyl Radicals in Pyrrolidinium-Based Ionic Liquids (pages 1899–1908)

      Stefan Berdzinski, Joachim Horst, Petra Straßburg and Prof. Dr. Veronika Strehmel

      Article first published online: 6 MAY 2013 | DOI: 10.1002/cphc.201300098

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      Rate increases: Long alkyl chains bound at the cation of 1-alkyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ionic liquids change the steric requirements on the transition state of the bimolecular lophyl radical recombination reaction (see picture). Recombination of the photolytically generated radicals is faster in the ionic liquids than in traditional organic solvents.

    13. Evaluating the COSMO-RS Method for Modeling Hydrogen Bonding in Solution (pages 1909–1919)

      Sofja Tshepelevitsh, Merit Oss, Astrid Pung and Prof. Ivo Leito

      Article first published online: 29 APR 2013 | DOI: 10.1002/cphc.201300186

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      Bond, hydrogen bond: The hydrogen bond modeling ability of the COSMO-RS method is evaluated using a range of acceptors and donors in different solvents.

    14. In Situ Direct Measurement of Vapor Pressures and Thermodynamic Parameters of Volatile Organic Materials in the Vapor Phase: Benzoic Acid, Ferrocene, and Naphthalene (pages 1920–1925)

      Dr. Walid M. Hikal and Dr. Brandon L. Weeks

      Article first published online: 19 APR 2013 | DOI: 10.1002/cphc.201300182

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      Reflections on vapor: A commercially available UV-spectrometer is used to determine absorption cross-sections, vapor densities, vapor pressures, and sublimation enthalpies of three reference materials in the vapor phase. The optical and thermodynamic properties are in agreement with the ICTAC recommended values with uncertainties of ∼5 and ∼1 % for vapor pressures and sublimation enthalpies.

    15. Nanoparticle Size and Concentration Dependence of the Electroactive Phase Content and Electrical and Optical Properties of Ag/Poly(vinylidene fluoride) Composites (pages 1926–1933)

      Ana Catarina Lopes, Dr. Sonia A. C. Carabineiro, Prof. Manuel Fernando R. Pereira, Prof. Gabriela Botelho and Prof. Senentxu Lanceros-Mendez

      Article first published online: 22 APR 2013 | DOI: 10.1002/cphc.201300174

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      In phase: Silver nanoparticles incorporated into poly(vinylidene fluoride) induce the nucleation of the electroactive γ phase of the polymer. Surface plasmon resonance absorption in the composites increases with the concentration and size of the nanoparticles. This behavior is correlated to an electrical response and is related to the extra bands and electrons provided by the nanoparticles in the large energy band gap of the polymer.

    16. Experimental and First-Principles Characterization of Functionalized Magnetic Nanoparticles (pages 1934–1942)

      Dr. Georgios S. E. Antipas, Eleftherios Statharas, Philippos Tserotas, Dr. Nikolaos Papadopoulos and Prof. Dr. E. Hristoforou

      Article first published online: 6 MAY 2013 | DOI: 10.1002/cphc.201300161

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      An iron constitution: Magnetic iron oxide nanoparticles (NPs) synthesized by coprecipitation and thermal decomposition methods are magnetite-rich and maghemite-rich, respectively (see images). IR spectroscopy reveals that the NPs are coated with layers of oleic acid (OA) surfactant. The inner layer is chemically adsorbed on the NP surface whereas the rest of the OA is physically adsorbed.

    17. Fluorine Substitution Effects on Flexibility and Tunneling Pathways: The Rotational Spectrum of 2-Fluorobenzylamine (pages 1943–1950)

      Dr. Camilla Calabrese, Dr. Assimo Maris, Dr. Luca Evangelisti, Prof. Walther Caminati and Prof. Sonia Melandri

      Article first published online: 18 APR 2013 | DOI: 10.1002/cphc.201300121

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      Bringing on a substitute: High-resolution spectral data in the gas phase coupled to theoretical calculations for 2-fluorobenzylamine (see picture) show that substitution of a single hydrogen atom with fluorine produces a change of structural and dynamical properties of the fluorine-substituted molecule relative to the unsubstituted form.

    18. Coherent Anti-Stokes Emission from Gold Nanorods and its Potential for Imaging Applications (pages 1951–1955)

      Li Jiang, Dr. Iwan W. Schie, Prof. Dr. Jun Qian, Prof. Dr. Sailing He and Prof. Dr. Thomas Huser

      Article first published online: 6 MAY 2013 | DOI: 10.1002/cphc.201300091

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      Scattered in all directions: Coherent anti-Stokes scattering (CAS) is used to characterize individual gold nanorods (GNRs) and GNR aggregates. The CAS signal is also examined as a function of the excitation polarization. Irregularly oriented GNRs exhibit a different scattering pattern to that observed for regularly oriented GNRs. The polarization-dependent scattering from oriented GNRs shows cos6 (θ) behavior (see picture).

    19. Viscosity Mixing Rules for Binary Systems Containing One Ionic Liquid (pages 1956–1968)

      Dr. Mohammed Tariq, Dr. Tausif Altamash, Dr. Daniel Salavera, Prof. Alberto Coronas, Prof. Luis P. N. Rebelo and Prof. Jose N. Canongia Lopes

      Article first published online: 6 MAY 2013 | DOI: 10.1002/cphc.201300086

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      A good mix: The applicability to [ionic liquid (IL)+molecular solvent (MS)] systems of four of the most commonly used viscosity mixing rules is assessed. More than 100 systems subdivided into different IL of MS series are analyzed and the corresponding trends discussed in terms of the average deviations produced by the use of each type of mixing rule.

    20. Adsorption of Water on an MgSO4(100) Surface: A First-Principles Investigation (pages 1969–1976)

      Jin-Hua Luo, Prof. Yun-Hong Zhang and Prof. Ze-Sheng Li

      Article first published online: 29 APR 2013 | DOI: 10.1002/cphc.201300077

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      Surface factors: The adsorption properties of water molecules on an MgSO4(100) surface are studied by using density functional theory (see picture). The configurations of water molecules adsorbed on atoms of the second and third atomic layers of MgSO4(100) are quite stable. In addition, water molecules preferentially adsorb onto a defective surface.

    21. Characterizing the Role of Iodine Doping in Improving Photovoltaic Performance of Dye-Sensitized Hierarchically Structured ZnO Solar Cells (pages 1977–1984)

      Jia-Xing Zhao, Dr. Yan-Zhen Zheng, Xin-Hong Lu, Prof. Jian-Feng Chen, Prof. Xia Tao and Prof. Weilie Zhou

      Article first published online: 18 APR 2013 | DOI: 10.1002/cphc.201300066

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      I for increasing efficency: Inherent drawbacks of ZnO solar cells related to a poor light-harvesting capability and easy recombination of photogenerated electron-hole pairs are progressively circumvented by doping iodine into the hierarchically structured ZnO lattice. This is demonstrated by microscopic characterization, spectroscopic analysis, and electrochemical/photoelectrochemical measurement results.

    22. The Factors Influencing Nonlinear Characteristics of the Short-Circuit Current in Dye-Sensitized Solar Cells Investigated by a Numerical Model (pages 1985–1992)

      Yushuai Shi  and Xiandui Dong

      Article first published online: 25 APR 2013 | DOI: 10.1002/cphc.201300061

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      Super- and sublinear character of the short-circuit current jsc in dye-sensitized solar cells (see picture) should be attributed to low electron-collection efficiency and low dye-regeneration efficiency, respectively, according to a numerical model developed on the basis of the continuity equation.

    23. Intermolecular Interactions in Li+-glyme and Li+-glyme–TFSA Complexes: Relationship with Physicochemical Properties of [Li(glyme)][TFSA] Ionic Liquids (pages 1993–2001)

      Dr. Seiji Tsuzuki, Wataru Shinoda, Dr. Shiro Seki, Prof. Yasuhiro Umebayashi, Dr. Kazuki Yoshida, Prof. Kaoru Dokko and Prof. Masayoshi Watanabe

      Article first published online: 17 APR 2013 | DOI: 10.1002/cphc.201200843

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      The interactions in Li+-glymes-TFSA complexes: The interactions of Li+ with glymes (tri- and tetra-glyme) are strong (−96 and −108 kcal mol−1), while the interactions of the [Li(glyme)]+ complexes with TFSA (−82 and −70 kcal mol−1) are weaker than that between Li+ and TFSA (−137 kcal mol−1).

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