ChemPhysChem

Cover image for Vol. 12 Issue 9

June 20, 2011

Volume 12, Issue 9

Pages 1601–1771

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Review
    8. Highlights
    9. Communications
    10. Articles
    11. Correspondence
    12. Book Review
    13. Preview
    1. Cover Picture: Long-Term Stable Silver Subsurface Ion-Exchanged Glasses for SERS Applications (ChemPhysChem 9/2011) (page 1601)

      Anne Simo, Virginia Joseph, Robert Fenger, Prof. Dr. Janina Kneipp and Prof. Dr. Klaus Rademann

      Article first published online: 10 JUN 2011 | DOI: 10.1002/cphc.201190044

      Thumbnail image of graphical abstract

      A novel method for fabricating silver-based SERS-active substrates is reported by K. Rademann et al. on p. 1683. Long-term stable (more than two years) silver ion-exchanged metal-oxide glasses conserve silver nanoparticles in the subsurface region. Etching the protective glass surface activates the substrate. When exposed to analyte molecules, a strong Raman enhancement can be recorded as a SERS spectrum. The picture shows adenine as a test molecule.

  2. Inside Cover

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Review
    8. Highlights
    9. Communications
    10. Articles
    11. Correspondence
    12. Book Review
    13. Preview
    1. Inside Cover: Kinetic Magnetic-Field Effect Involving the Small Biologically Relevant Inorganic Radicals NO and O2.− (ChemPhysChem 9/2011) (page 1602)

      Tatiana Y. Karogodina, Igor G. Dranov, Dr. Svetlana V. Sergeeva, Dr. Dmitry V. Stass and Prof. Dr. Ulrich E. Steiner

      Article first published online: 10 JUN 2011 | DOI: 10.1002/cphc.201190045

      Thumbnail image of graphical abstract

      The recombination kinetics of the biochemically prominent radicals NO and O2− to form ONOO (“peroxynitrite”) is sensitive to high magnetic fields, as shown by U. E. Steiner, D. V. Stass et al. on on p. 1714.

  3. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Review
    8. Highlights
    9. Communications
    10. Articles
    11. Correspondence
    12. Book Review
    13. Preview
    1. Graphical Abstract: ChemPhysChem 9/2011 (pages 1603–1612)

      Article first published online: 10 JUN 2011 | DOI: 10.1002/cphc.201190046

  4. Corrigendum

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Review
    8. Highlights
    9. Communications
    10. Articles
    11. Correspondence
    12. Book Review
    13. Preview
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      Corrigendum: Nanoporous Glass as a Model System for a Consistency Check of the Different Techniques of Diffusion Measurement (page 1612)

      Dr. Christian Chmelik, Prof. Dr. Dirk Enke, Dr. Petrik Galvosas, Oliver Gobin, Dr. Andreas Jentys, Dr. Hervé Jobic, Prof. Dr. Jörg Kärger, Cordula B. Krause, Jens Kullmann, Prof. Dr. Johannes Lercher, Dr. Sergej Naumov, Prof. Dr. Douglas M. Ruthven and Tobias Titze

      Article first published online: 10 JUN 2011 | DOI: 10.1002/cphc.201100390

      This article corrects:

      Nanoporous Glass as a Model System for a Consistency Check of the Different Techniques of Diffusion Measurement

      Vol. 12, Issue 6, 1130–1134, Article first published online: 22 MAR 2011

  5. News

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Review
    8. Highlights
    9. Communications
    10. Articles
    11. Correspondence
    12. Book Review
    13. Preview
  6. Review

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Review
    8. Highlights
    9. Communications
    10. Articles
    11. Correspondence
    12. Book Review
    13. Preview
    1. Brønsted Acidity and the Medium: Fundamentals with a Focus on Ionic Liquids (pages 1622–1632)

      Prof. Lynn M. Mihichuk, Prof. Gordon W. Driver  and Prof. Keith E. Johnson

      Article first published online: 1 JUN 2011 | DOI: 10.1002/cphc.201100087

      Thumbnail image of graphical abstract

      When is an acid not an acid? Brønsted acidity is discussed for protic molecules in the sequence gas, liquid, liquid salt and liquid in solution. The individuality of the medium is paramount—acidic species can be cationic or anionic. Acidity in water cannot be used as a measure of acidity in ionic liquids; methods of measuring acidity are required for each system.

  7. Highlights

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Review
    8. Highlights
    9. Communications
    10. Articles
    11. Correspondence
    12. Book Review
    13. Preview
    1. Dilemmas of Dye-Sensitized Solar Cells (pages 1633–1636)

      Prof. Juan Bisquert

      Article first published online: 3 MAY 2011 | DOI: 10.1002/cphc.201100248

      Thumbnail image of graphical abstract

      Ferrocene to the rescue: The dye-sensitized solar cell allows changes in the energetics of electron transport, molecular absorbers, and hole transport materials to better harvest the energy of solar photons (see picture). A recent paper describing a new dye with a high excited state in combination with ferrocene redox mediator shows progress in this direction.

    2. Wrapping Bacteria in Graphene (pages 1637–1639)

      Prof. Dr. Florian Banhart

      Article first published online: 2 MAY 2011 | DOI: 10.1002/cphc.201100255

      Thumbnail image of graphical abstract

      Good graphene: Wrapping bacteria in graphene protects them from damage during inspection in an electron microscope. A recent study shows that the ultrastrong and impermeable graphene shell prevents outgassing, overheating, and radiation damage of bacteria (see picture).

  8. Communications

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Review
    8. Highlights
    9. Communications
    10. Articles
    11. Correspondence
    12. Book Review
    13. Preview
    1. Adsorption of Formate and Its Role as Intermediate in Formic Acid Oxidation on Platinum Electrodes (pages 1641–1644)

      Vitali Grozovski, Dr. Francisco J. Vidal-Iglesias, Prof. Dr. Enrique Herrero and Prof. Dr. Juan M. Feliu

      Article first published online: 6 MAY 2011 | DOI: 10.1002/cphc.201100257

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      Formate adsorption: Fast electrochemical techniques allow the detection of formate as the adsorbed species from formic acid on platinum single-crystal electrodes (see picture). Additionally, the oxidation current for formic acid oxidation is directly proportional to the formate coverage, which indicates that adsorbed formate is the active intermediate.

    2. The Aggregation of Silver Nanoparticles in Aqueous Solution Investigated via Anodic Particle Coulometry (pages 1645–1647)

      Dr. Neil V. Rees, Yi-Ge Zhou and Prof. Dr. Richard G. Compton

      Article first published online: 10 MAY 2011 | DOI: 10.1002/cphc.201100207

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      Informative collisions: The use of quantitative oxidative collisions between silver nanoparticles (AgNPs) and an electrode surface to monitor the aggregation of single AgNPs into larger clusters is reported (see graph).

    3. Dip-Coating-Induced Fiber Growth of a Soluble Heterotriangulene (pages 1648–1651)

      Suhao Wang, Dr. Milan Kivala, Dr. Ingo Lieberwirth, Katrin Kirchhoff, Dr. Xinliang Feng, Dr. Wojciech Pisula and Prof. Dr. Klaus Müllen

      Article first published online: 20 MAY 2011 | DOI: 10.1002/cphc.201100199

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      Long-range well-aligned fibers are fabricated from a soluble heterotriangulene derivative via simple dip coating by controlling the concentration of the compound. This procedure is an alternative route for the generation of unique microstructures of organic semiconductors—both for both fundamental studies and for practical device applications.

    4. Dissociation Termination of Methane–Ethane Hydrates in Temperature-Ramping Tests at Atmospheric Pressure below the Melting Point of Ice (pages 1652–1656)

      Dr. Tsutomu Uchida, Dr. Masato Kida and Dr. Jiro Nagao

      Article first published online: 19 APR 2011 | DOI: 10.1002/cphc.201100116

      Thumbnail image of graphical abstract

      Dissociated gas ratios of pure methane hydrate, pure ethane hydrate, and methane–ethane mixed-gas hydrates in temperature-ramping tests indicate that ethane-containing hydrates also exhibit a self-preservation effect (see graph).

    5. Improved Photon Yield from a Green Dye with a Reducing and Oxidizing System (pages 1657–1660)

      Antoine Le Gall , Dr. David Dulin , Dr. Gilles Clavier, Dr. Rachel Méallet-Renault, Dr. Philippe Bouyer, Dr. Karen Perronet and Prof. Dr. Nathalie Westbrook

      Article first published online: 31 MAY 2011 | DOI: 10.1002/cphc.201100085

      Thumbnail image of graphical abstract

      An optimized chemistry turns a small green dye into a useful label for single-molecule experiments where steric hindrance is an issue. Thanks to a reducing and oxidizing system combined to oxygen depletion, a single Bodipy (boron-dipyrromethene) FL fluorophore emits, on average, 20 times more photons around 510 nm (see picture) and its lifetime before photobleaching is increased by the same amount, reaching several seconds.

    6. Morphological and Compositional Characterization of Self-Preserved Gas Hydrates by Low-Vacuum Scanning Electron Microscopy (pages 1661–1665)

      Dr. Hiroshi Ohno , Dr. Okio Nishimura , Dr. Kiyofumi Suzuki , Dr. Hideo Narita and Dr. Jiro Nagao 

      Article first published online: 20 APR 2011 | DOI: 10.1002/cphc.201100079

      Thumbnail image of graphical abstract

      Unequal interactions: A backscattering electron microscopy study reveals that some Kr hydrates can be trapped in ice products during dissociation (see image) whereas no clear evidence of such a phenomenon is found for Ar samples. Also, the texture of ice from Ar-hydrate decomposition is more cohesive than that observed for Kr samples. The different dissociation behavior between the two systems may be attributed to differences in the interaction between gas and water molecules.

    7. Do Metal⋅⋅⋅Water Hydrogen Bonds Hold in Solution? Insight from Ab Initio Molecular Dynamics Simulations (pages 1666–1668)

      Dr. Pietro Vidossich, Manuel Á. Ortuño, Dr. Gregori Ujaque and Prof. Agustí Lledós

      Article first published online: 9 MAY 2011 | DOI: 10.1002/cphc.201100234

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      Hydration pattern: The involvement of transition metal atoms as proton acceptors in hydrogen bonding interactions has been revealed recently by neutron diffraction studies. Here, by a realistic model system we show computationally that indeed such interaction hold in solution, although the picture of the solvation shell arising from simulations is more complex than what may be inferred from crystal data and quantum chemical calculations based on small size models (see picture).

    8. Effects of a Self-Assembled Molecular Capsule on the Ultrafast Photodynamics of a Photochromic Salicylideneaniline Guest (pages 1669–1672)

      Dr. Michel Sliwa, Prof. Panče Naumov, Prof. Heung-Jin Choi, Dr. Quoc-Thiet Nguyen, Bruno Debus, Prof. Stéphanie Delbaere and Dr. Cyril Ruckebusch

      Article first published online: 19 MAY 2011 | DOI: 10.1002/cphc.201100232

      Thumbnail image of graphical abstract

      Selective and slow: The effects on the photophysics of a single salicylideneaniline molecule, induced by confinement in an all-organic, weakly interacting molecular capsule of a matching size, are studied by time-resolved spectroscopy. The capsule acts efficiently to select only one deactivation pathway after photoexcitation and keeps the photochromism in the solid state with a 300-fold retardation—relative to the solution state—in the decay time of the photochromic product (see picture).

    9. Natural Orbital Functional Theory and Reactivity Studies of Diradical Rearrangements: Ethylene Torsion as a Case Study (pages 1673–1676)

      Prof. Xabier Lopez, Prof. Mario Piris, Dr. Jon M. Matxain, Dr. Fernando Ruipérez and Prof. Jesus M. Ugalde

      Article first published online: 27 MAY 2011 | DOI: 10.1002/cphc.201100190

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      Radical rearrangements: Natural orbital functional theory (NOFT) is used to investigate the potential energy surface of ethylene torsion. The study shows that NOFT correctly describes degeneracy effects in diradical rearrangements (see picture).

    10. Influence of the Anchor Group on Charge Transport through Single-Molecule Junctions (pages 1677–1682)

      Dr. Emanuel Lörtscher, Clara J. Cho, Prof. Dr. Marcel Mayor, Meinrad Tschudy, Charles Rettner and Dr. Heike Riel

      Article first published online: 1 JUN 2011 | DOI: 10.1002/cphc.201000960

      Thumbnail image of graphical abstract

      The molecule–metal coupling in molecular junctions is investigated at the single-molecule level by anchoring a phenyl ring, using either thiol (Figure, A) or isocyanide (Figure, B) linkers, to two gold electrodes of a mechanically controllable break-junction. The transport properties of the single-molecule junctions are recorded while repeatedly forming and breaking the molecular junction. Thiol linkage results in a 50 % larger molecular-level broadening compared to isocyano linkage.

  9. Articles

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Review
    8. Highlights
    9. Communications
    10. Articles
    11. Correspondence
    12. Book Review
    13. Preview
    1. Long-Term Stable Silver Subsurface Ion-Exchanged Glasses for SERS Applications (pages 1683–1688)

      Anne Simo, Virginia Joseph, Robert Fenger, Prof. Dr. Janina Kneipp and Prof. Dr. Klaus Rademann

      Article first published online: 27 MAY 2011 | DOI: 10.1002/cphc.201100098

      Thumbnail image of graphical abstract

      Undercover: Long-term stable silver nanoparticles can be embedded into a glassy matrix (see picture). The particles can be easily uncovered before each Raman experiment. The solid substrates show constant enhancement by a factor of greater than 107.

    2. Channels to Singlet and Triplet Phenylcarbenes in Phenyldiazomethane: A CASSCF and MRCI Study (pages 1689–1696)

      Dr. Ganglong Cui and Prof. Dr. Weihai Fang

      Article first published online: 19 APR 2011 | DOI: 10.1002/cphc.201100025

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      Photolytic channels: The photodissociation dynamics of phenyldiazomethane to singlet and triplet phenylcarbene (C6H5CH) and molecular N2 are studied with multi-reference configuration interaction (MRCI) and complete active space self-consistent field (CASSCF) computational methods. Based on equilibrium structures, transition states, and minimum-energy crossing points of C6H5C(H)N2 (see picture) possible reaction pathways are discussed.

    3. Open-Shell Characters and Second Hyperpolarizabilities of One-Dimensional Graphene Nanoflakes Composed of Trigonal Graphene Units (pages 1697–1707)

      Kyohei Yoneda, Prof. Masayoshi Nakano, Hitoshi Fukui, Takuya Minami, Dr. Yasuteru Shigeta, Prof. Dr. Takashi Kubo, Dr. Edith Botek and Prof. Dr. Benoît Champagne

      Article first published online: 17 MAY 2011 | DOI: 10.1002/cphc.201001089

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      Topology matters: The open-shell characters and second hyperpolarizabilities (γ) of 1D graphene nanoflakes composed of trigonal graphene units are investigated using long-range corrected spin-unrestricted density functional theory. It is found that the open-shell characters strongly depend on the topology, that is, the way the trigonal units are linked to each others, leading to substantial variations of the longitudinal γ values in the singlet state (see picture).

    4. The Kinetics of Ferrocene Volatilisation from an Ionic Liquid (pages 1708–1713)

      Chaopeng Fu, Dr. Leigh Aldous, Edmund J. F. Dickinson, Dr. Ninie S. A. Manan and Prof. Richard G. Compton

      Article first published online: 23 MAY 2011 | DOI: 10.1002/cphc.201100204

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      Volatile solutes in non-volatile liquids: The volatilization of ferrocene is studied in detail in the room-temperature ionic liquid N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, [C4mpyrr][NTf2] in a specially designed T-cell (see picture). Ferrocene is removed by evaporation under a flow of either dry or wet nitrogen gas in a kinetically limited process with an activation energy of 85 (±2) kJ mol−1.

    5. Kinetic Magnetic-Field Effect Involving the Small Biologically Relevant Inorganic Radicals NO and O2.− (pages 1714–1728)

      Tatiana Y. Karogodina, Igor G. Dranov, Dr. Svetlana V. Sergeeva, Dr. Dmitry V. Stass and Prof. Dr. Ulrich E. Steiner

      Article first published online: 20 MAY 2011 | DOI: 10.1002/cphc.201100178

      Thumbnail image of graphical abstract

      Magnetic-field-dependent yield of substrate oxidation by ONOO, generated in a biomimetic system by recombination of NO and O2.−, is revealed by carrying out reactions between 0 and 18 T. This magnetic-field effect can be theoretically accounted for in terms of the spin chemistry of the NO/O2.− radical pair (see picture). Spin chemistry thus allows magnetic effects of these radicals to be detected under conditions where they cannot be observed by conventional magnetic resonance techniques.

    6. Surface-State-Mediated Charge-Transfer Dynamics in CdTe/CdSe Core–Shell Quantum Dots (pages 1729–1735)

      Sachin Rawalekar, Sreejith Kaniyankandy, Sandeep Verma and Dr. Hirendra N. Ghosh

      Article first published online: 12 MAY 2011 | DOI: 10.1002/cphc.201100105

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      Trapping the charge carriers: The influence of surface states on the charge-transfer dynamics of CdTe and CdTe/CdSe core–shell quantum dots (QDs) is demonstrated by means of ultrafast transient absorption spectroscopy (see picture). Carrier quenchers are used to qualitatively identify the charge-carrier traps.

    7. Probing the Functionalization of Gold Surfaces and Protein Adsorption by PM-IRRAS (pages 1736–1740)

      Dr. Rodrigo Marques de Oliveira, Prof. Dr. Jacqueline Ferreira, Prof. Dr. Marcos J. L. Santos, Prof. Dr. Roberto M. Faria and Prof. Dr. Osvaldo N. Oliveira Jr.

      Article first published online: 28 APR 2011 | DOI: 10.1002/cphc.201100080

      Thumbnail image of graphical abstract

      Molecular architecture: The versatility and sensitivity of polarization-modulated infrared reflection–absorption spectroscopy was used to monitor film growth and organization on a gold surface. The complete blocking of the gold surface was verified by cyclic voltammograms, as the charge transfer through a packed layer of an alcanothiol is minimized (see picture).

    8. Activation/Inhibition Effects during the Coelectrodeposition of PtAg Nanoparticles: Application for ORR in Alkaline Media (pages 1741–1746)

      Stefanie Schwamborn, Dr. Leonard Stoica and Prof. Dr. Wolfgang Schuhmann

      Article first published online: 27 MAY 2011 | DOI: 10.1002/cphc.201100029

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      Two is better than one: PtAg bimetallic nanoparticles for oxygen reduction reaction in alkaline media were prepared by pulse electrodeposition. The mechanism for the co-deposition was elucidated by potential pulse experiments. Nuclei of Pt are predominantly formed onto which a nonhomogenous Ag shell grows. The PtAg nanoparticles exhibit an enhanced oxygen reduction reaction (ORR) activity as compared to pure Ag nanoparticles (see picture).

    9. Aggregation of 2-Aminobenzimidazole—A Combined Experimental and Theoretical Investigation (pages 1747–1755)

      Dr. Silvia E. Angelova, Dr. Milena I. Spassova, Vera V. Deneva, Dr. Marin I. Rogojerov and Dr. Liudmil M. Antonov

      Article first published online: 12 MAY 2011 | DOI: 10.1002/cphc.201100002

      Thumbnail image of graphical abstract

      Dynamic equilibria: The tautomerism and the intermolecular interactions (hydrogen bonding) of 2-aminobenzimidazole, leading to the formation of molecular aggregates has been studied. Theory and experiment complement each other in the recognition of the individual components of the studied samples in solution and conclusions about the hydrogen bonding and cooperative effects can be drawn (see picture).

    10. Wet-Chemical Synthesis of Nanoscale Iron Boride, XAFS Analysis and Crystallisation to α-FeB (pages 1756–1760)

      Steffi Rades, Andreas Kornowski, Prof. Dr. Horst Weller and Prof. Dr. Barbara Albert

      Article first published online: 12 MAY 2011 | DOI: 10.1002/cphc.201001072

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      At the atomic length scale: A one-step wet-chemical synthesis with lithium tetrahydridoborate and iron bromide as educts leads to an ultrafine X-ray amorphous precipitate. X-ray absorption spectroscopy (XAFS) provides structural information despite the lack of long-range order in the product. In combination with TEM, XAFS is the ultimate means to identify the precipitate as nanoscaled iron boride (see picture).

  10. Correspondence

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Review
    8. Highlights
    9. Communications
    10. Articles
    11. Correspondence
    12. Book Review
    13. Preview
    1. Note on “The Electrochemical Promotion of Ethylene Oxidation at a Pt/YSZ Catalyst” (pages 1761–1763)

      Prof. Dr. Constantinos G. Vayenas and Dr. Philippe Vernoux

      Article first published online: 30 MAY 2011 | DOI: 10.1002/cphc.201000904

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      One or two? Can a single oxygen spillover species on Pt explain the effect of electrochemical promotion of catalysis (EPOC) with O2− conductors such as yttria-stabilized ZrO2 (YSZ), as suggested in a paper published recently by Toghan et al. (ChemPhysChem, 2010, 11, 1452)? Or is it necessary to use the long-tested sacrificial promoter mechanism, which involves two oxygen species (see picture)?

    2. Comment on the Note by Vayenas and Vernoux on “The Electrochemical Promotion of Ethylene Oxidation at a Pt/YSZ Catalyst” (pages 1764–1766)

      Prof. Dr. Ronald Imbihl and Arafat Toghan

      Article first published online: 30 MAY 2011 | DOI: 10.1002/cphc.201100262

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      Sacrificial promoter versus ignition: The Correspondence by Vayenas and Vernoux defends the “sacrificial promoter” mechanism, which involves two oxygen species, against the ignition mechanism suggested recently by Toghan et al. (ChemPhysChem, 2010, 11, 1452, see picture, YSZ=yttrium-stabilized zirconia). But is a special spillover species really required to explain the large non-Faradaic effects found in many electrochemical promotion of catalysis (EPOC) experiments?

  11. Book Review

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Review
    8. Highlights
    9. Communications
    10. Articles
    11. Correspondence
    12. Book Review
    13. Preview
    1. Electrocatalysis of Direct Methanol Fuel Cells: From Fundamentals to Applications. Edited by Hansan Liu and Jiujun Zhang (page 1767)

      Dr. Julia Kunze and Dr. Odysseas Paschos

      Article first published online: 20 APR 2011 | DOI: 10.1002/cphc.201000649

      Wiley-VCH 2009, XXII+584 pp., hardcover, € 139.00—ISBN 978-527-32377-7

  12. Preview

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Review
    8. Highlights
    9. Communications
    10. Articles
    11. Correspondence
    12. Book Review
    13. Preview
    1. You have free access to this content
      Preview: ChemPhysChem 10/2011 (page 1771)

      Article first published online: 10 JUN 2011 | DOI: 10.1002/cphc.201190048

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