ChemPhysChem

Cover image for Vol. 10 Issue 6

April 14, 2009

Volume 10, Issue 6

Pages 861–987

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Highlight
    6. Concept
    7. Communications
    8. Articles
    9. Retraction
    10. Articles
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    1. Cover Picture: On the Origin of the “Giant” Electroclinic Effect in a “De Vries”-Type Ferroelectric Liquid Crystal Material for Chirality Sensing Applications (ChemPhysChem 6/2009) (page 861)

      Nadia Kapernaum, David M. Walba, Eva Korblova, Chenhui Zhu, Chris Jones, Yongqian Shen, Noel A. Clark and Frank Giesselmann

      Version of Record online: 3 APR 2009 | DOI: 10.1002/cphc.200990020

      Thumbnail image of graphical abstract

      The cover picture shows characteristics of a new ‘de Vries’-type ferroelectric liquid crystal in which the ferroelectric transition is an order–disorder transition where the directions of molecular tilt inside a smectic layer order into a certain direction. Since the rod-like molecules (drawn as cylinders) are tilted in the paraelectric SmA* (with random tilt directions) as well as in the ferroelectric SmC* phase, the ferroelectric transition is connected with a rather weak contraction of the smectic layer thickness (even though the optical tilt θ reaches values of about 25°). On page 890, F. Giesselmann et al. show that this new ferroelectric material exhibits a remarkably weak temperature dependence of its giant electroclinic effect (the coupling between tilt and elelctric field) in the SmA* phase. The origin of this striking electroclinic effect is the co-occurrence of a ‘de Vries’-type ordering with a weak first-order tilting transition.

  2. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Highlight
    6. Concept
    7. Communications
    8. Articles
    9. Retraction
    10. Articles
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  3. News

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Highlight
    6. Concept
    7. Communications
    8. Articles
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  4. Highlight

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Highlight
    6. Concept
    7. Communications
    8. Articles
    9. Retraction
    10. Articles
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    1. Attosecond Quantum Stroboscope (pages 875–877)

      Gerhard G. Paulus and Gernot Stania

      Version of Record online: 17 MAR 2009 | DOI: 10.1002/cphc.200800673

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      Electron disco: A “quantum stroboscope” for capturing the electron motion on a subfemtosecond timescale for a particular class of problems is highlighted. The picture shows a diffraction pattern caused by wave packets obtained by synchronizing attosecond UV pulses to a near-IR field and ionizing rare-gas atoms.

  5. Concept

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    4. News
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    7. Communications
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    1. Non-Blinking Semiconductor Colloidal Quantum Dots for Biology, Optoelectronics and Quantum Optics (pages 879–882)

      Piernicola Spinicelli, Benoit Mahler, Stéphanie Buil, Xavier Quélin, Benoit Dubertret and Jean-Pierre Hermier 

      Version of Record online: 17 MAR 2009 | DOI: 10.1002/cphc.200800827

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      Twinkle, twinkle: The blinking of semiconductor colloidal nanocrystals is the main inconvenience of these bright nanoemitters. There are various approaches for obtaining non-blinking nanocrystals, one of which is to grow a thick coat of CdS on the CdSe core (see picture). Applications of this method in the fields of optoelectronic devices, biologic labelling and quantum information processing are discussed.

  6. Communications

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    7. Communications
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    1. Infrared Spectroscopy of Fragments from Doubly Protonated Tryptic Peptides (pages 883–885)

      Benjamin J. Bythell, Undine Erlekam, Béla Paizs and Philippe Maître

      Version of Record online: 2 MAR 2009 | DOI: 10.1002/cphc.200800804

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      Most proteins in proteomics are identified from tandem mass spectra of doubly protonated tryptic peptides. Statistical studies indicate that these spectra fall into two distinct classes. IR spectroscopy experiments and DFT calculations performed on model b2 ions show that peptides producing Class I spectra form protonated oxazolone ions (see figure) and not protonated diketopiperazines as proposed elsewhere.

    2. Dispersed Fluorescence and Delayed Ionization of Jet-Cooled 2-Aminopurine: Relaxation to a Dark State Causes Weak Fluorescence (pages 886–889)

      Ke Feng, Gernot Engler, Kai Seefeld and Karl Kleinermanns

      Version of Record online: 23 MAR 2009 | DOI: 10.1002/cphc.200800816

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      Dark state: The photophysics of 9H-2AP (see figure) depends strongly on the solvent and the temperature. In polar, aprotic solvents the fluorescence quantum yield is lower compared to protic ones. Analysis of the diffuse fluorescence spectra point to the existence of a dark singlet n,pi* state which is long-lived (1 microsecond).

    3. On the Origin of the “Giant” Electroclinic Effect in a “De Vries”-Type Ferroelectric Liquid Crystal Material for Chirality Sensing Applications (pages 890–892)

      Nadia Kapernaum, David M. Walba, Eva Korblova, Chenhui Zhu, Chris Jones, Yongqian Shen, Noel A. Clark and Frank Giesselmann

      Version of Record online: 5 MAR 2009 | DOI: 10.1002/cphc.200900065

      Thumbnail image of graphical abstract

      W415 is a chiral smectic compound with a remarkably weak temperature dependence of its giant electroclinic effect in the liquid crystalline smectic A* phase. Furthermore it possesses a high spontaneous polarization in the smectic C* phase. The origin of this striking electroclinic effect is the co-occurrence of a de Vries-type ordering with a weak first-order tilting transition (see the synchroton X-ray scattering profiles).

    4. Adiabatic Low-Pass J Filters for Artifact Suppression in Heteronuclear NMR (pages 893–895)

      Sebastian Meier, Andrew J. Benie, Jens Ø. Duus and Ole W. Sørensen

      Version of Record online: 13 MAR 2009 | DOI: 10.1002/cphc.200900072

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      NMR artifact purging: Modern NMR experiments depend on efficient coherence transfer pathways for their sensitivity and on suppression of undesired pathways leading to artifacts for their spectral clarity. A novel robust adiabatic element suppresses hard-to-get-at artifacts (see picture).

    5. Non-Covalent Interactions in Supramolecular Assemblies Investigated with Electron Spectroscopies (pages 896–900)

      Miguel Ruiz-Osés, Dimas G. de Oteyza, Isabel Fernández-Torrente, Nora Gonzalez-Lakunza, Phillipp M. Schmidt-Weber, Thorsten Kampen, Karsten Horn, André Gourdon, Andrés Arnau and J. Enrique Ortega

      Version of Record online: 26 FEB 2009 | DOI: 10.1002/cphc.200800828

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      A new view: A picture of the different non-covalent interactions relevant for the self-assembly of organic layers and their spectroscopic fingerprints is provided (see figure). In particular, state-of-the-art spectroscopic measurements are performed for supramolecular assemblies, comparing the electronic structure of single-component layers with that of binary organic layers.

  7. Articles

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Highlight
    6. Concept
    7. Communications
    8. Articles
    9. Retraction
    10. Articles
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    1. Infrared Absorption Spectra of t-HNOH Radicals Generated on VUV Irradiation of NO in Solid Hydrogen (pages 901–904)

      Yu-Jong Wu, Meng-Yeh Lin, Sheng-Chuan Hsu and Bing-Ming Cheng

      Version of Record online: 12 MAR 2009 | DOI: 10.1002/cphc.200800775

      Thumbnail image of graphical abstract

      Photoproduct signature: Irradiation of solid hydrogen near 3 K containing NO with vacuum-UV light from synchrotron radiation yields new infrared absorption lines at 1241.7, 1063.6 and 726.2 cm−1 (see figure). These new lines are assigned to vibrational modes of t-HNOH. This photoproduct is formed from electronically excited NO reacting with neighboring hydrogen in the solid sample.

    2. Selective Enhancement of Carbon Nanotube Photoluminescence by Resonant Energy Transfer (pages 905–909)

      Ashraf Ahmad, Klaus Kern and Kannan Balasubramanian

      Version of Record online: 23 MAR 2009 | DOI: 10.1002/cphc.200800796

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      Highly selective: Enhancement of the photoluminescence (PL) emission efficiency of selected chiral forms of semiconducting single-walled carbon nanotubes (SWCNTs) is presented (see figure). Excitation of Nile blue A in the presence of SWCNTs results in the quenching of its fluorescence. The energy is resonantly transferred to the (7,5) SWCNT whereas the (8,7) tube is not in resonance; hence, its PL remains unaffected.

    3. Spectroscopic Investigation of the Ultrafast Photoinduced Dynamics in π-Conjugated Terpyridines (pages 910–919)

      Ronald Siebert, Denis Akimov, Michael Schmitt, Andreas Winter, Ulrich S. Schubert, Benjamin Dietzek and Jürgen Popp

      Version of Record online: 19 MAR 2009 | DOI: 10.1002/cphc.200800847

      Thumbnail image of graphical abstract

      Ultrafast light-induced processes in a series of π-conjugated mono-, bis-, tris- and tetrakis(terpyridine) derivatives are investigated by femtosecond time-resolved spectroscopy. Non-exponential excited-state dynamics involving singlet–triplet intersystem crossing are observed which span from picoseconds to nanoseconds (see figure).

    4. Spectroscopy and Defect Identification for Fluorinated Carbon Nanotubes (pages 920–925)

      Carla Bittencourt, Gregory Van Lier, Xiaoxing Ke, Irene Suarez-Martinez, Alexandre Felten, Jacques Ghijsen, Gustaaf Van Tendeloo and Christopher P. Ewels

      Version of Record online: 5 MAR 2009 | DOI: 10.1002/cphc.200800851

      Thumbnail image of graphical abstract

      Finely tuned: Carbon nanotubes are exposed to a CF4 radio-frequency plasma (see picture). High-resolution photoelectron spectroscopy shows that the treatment effectively grafts fluorine atoms onto the MWCNTs, altering the valence electronic states. Fluorine surface concentration can be tuned by varying the exposure time.

    5. Tuning of Electronic Properties of Single-Walled Carbon Nanotubes under Homogenous Conditions (pages 926–930)

      Yutaka Maeda, Akiko Sagara, Masahiro Hashimoto, Yuya Hirashima, Katsuya Sode, Tadashi Hasegawa, Makoto Kanda, Midori O. Ishitsuka, Takahiro Tsuchiya, Takeshi Akasaka, Toshiya Okazaki, Hiromichi Kataura, Jing Lu, Shigeru Nagase and Seiji Takeuchi

      Version of Record online: 5 MAR 2009 | DOI: 10.1002/cphc.200800651

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      Reversible and non-bonding interaction between SWNTs and ODCB is observed from the analyses of visible near-infrared absorption data and Raman spectroscopies (see spectra). The solvent effect on SWNTs effectively controls the electronic structure of SWNTs under homogeneous conditions.

    6. Host-Assisted Guest Self-Assembly: Enhancement of the Dimerization of Pyronines Y and B by γ-Cyclodextrin (pages 931–939)

      Jorge Bordello, Belén Reija, Wajih Al-Soufi and Mercedes Novo

      Version of Record online: 17 MAR 2009 | DOI: 10.1002/cphc.200800776

      Thumbnail image of graphical abstract

      Buckle up! The dimerization of small fluorescent guests is strongly enhanced in presence of a cyclodextrin host. The host cavity acts like a belt to assist the self-assembly of guests (see picture). Small variations in the guest structure have significant influence on the stability and geometry of the aggregates.

    7. Mechanism of the Catalytic Activity of Nucleophiles in the Stepwise Hydrolysis and Condensation Reactions of Tetramethoxysilane (pages 940–945)

      Igor S. Ignatyev, Manuel Montejo and Juan Jesús López González

      Version of Record online: 5 MAR 2009 | DOI: 10.1002/cphc.200800784

      Thumbnail image of graphical abstract

      Active ingredients: A model for the simplest hydrolysis reaction is applied to all stages of stepwise hydrolysis and condensation taking place during a sol–gel process. The picture shows the molecular structures of the transition states of the ammonia- (left) and OH-promoted (right) condensation reactions of two Si(OH)4 molecules, including an additional water molecule.

  8. Retraction

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    3. Graphical Abstract
    4. News
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    6. Concept
    7. Communications
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    1. ONIOM Study of Isomerization Reactions of Aromatic Hydrocarbons in Acidic Mordenite Zeolite (pages 946–953)

      Jing Yang

      Version of Record online: 19 FEB 2009 | DOI: 10.1002/cphc.200800785

      Thumbnail image of graphical abstract

      Two different mechanisms: Shift 1,2-isomerization and isomerization via the disproportionation reaction are investigated for aromatic hydrocarbons over acidic mordenite zeolite by using our own n-layered integrated molecular orbital and molecular mechanics (ONIOM) scheme. The picture shows a schematic energy profile for the isomerization of toluene catalyzed by acidic mordenite.

      Corrected by:

      Corrigendum: ONIOM Study of Isomerization Reactions of Aromatic Hydrocarbons in Acidic Mordenite Zeolite

      Vol. 10, Issue 8, 1158, Version of Record online: 26 MAY 2009

  9. Articles

    1. Top of page
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    6. Concept
    7. Communications
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    1. Chiral Induction, Memory, and Amplification in Porphyrin Homoaggregates Based on Electrostatic Interactions (pages 954–962)

      LiXi Zeng, Yujian He, Zhifeng Dai, Jian Wang, Qian Cao and Yuliang Zhang

      Version of Record online: 4 MAR 2009 | DOI: 10.1002/cphc.200800810

      Thumbnail image of graphical abstract

      Supramolecular chirality in two configurational homoaggregates of anionic meso-tetrakis(4-sulfonatophenyl)porphyrin (TPPS) can be induced by D- and L-alanine in acidic water (see picture). The chirality can be further memorized and enforced through strong electrostatic interactions between TPPS aggregates and achiral poly(allylamine) [PAA].

    2. Ferrocene and Porphyrin Monolayers on Si(100) Surfaces: Preparation and Effect of Linker Length on Electron Transfer (pages 963–971)

      Kai Huang, Florence Duclairoir, Tiziana Pro, Julien Buckley, Gilles Marchand, Eugénie Martinez, Jean-Claude Marchon, Barbara De Salvo, Guillaume Delapierre and Françoise Vinet

      Version of Record online: 4 MAR 2009 | DOI: 10.1002/cphc.200800818

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      The missing link: Ferrocene and porphyrin monolayers are tethered on silicon surfaces with short (see picture, left) or long (right) linkers. Electron transfer to the silicon substrate is faster for monolayers with a short linker.

    3. Ab Initio Kinetics for Decomposition/Isomerization Reactions of C2H5O Radicals (pages 972–982)

      Zhen Feng Xu, Kun Xu and Ming Chang Lin

      Version of Record online: 27 MAR 2009 | DOI: 10.1002/cphc.200800719

      Thumbnail image of graphical abstract

      Radical reactions: The ground-state potential energy surface of the C2H5O system is investigated by ab initio methods using optimized geometries. The rate constants for the unimolecular isomerization and decomposition reactions of the three isomeric radicals (see picture) are calculated by microcanonical transition-state theory at 200–3000 K, varying the pressures of the diluents.

  10. Preview

    1. Top of page
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    3. Graphical Abstract
    4. News
    5. Highlight
    6. Concept
    7. Communications
    8. Articles
    9. Retraction
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    1. Preview: ChemPhysChem 7/2009 (page 987)

      Version of Record online: 3 APR 2009 | DOI: 10.1002/cphc.200990023

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