ChemPhysChem

Cover image for Vol. 10 Issue 14

October 5, 2009

Volume 10, Issue 14

Pages 2357–2547

  1. Cover Picture

    1. Top of page
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    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
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    10. Communications
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    1. Cover Picture: Effect of PCBM Concentration on Photoluminescence Properties of Composite MEH-PPV/PCBM Nanoparticles Investigated by a Franck–Condon Analysis of Single-Particle Emission Spectra (ChemPhysChem 14/2009) (page 2357)

      Daeri Tenery and Andre J. Gesquiere

      Version of Record online: 28 SEP 2009 | DOI: 10.1002/cphc.200990055

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      The cover picture illustrates the use of composite organic nanoparticles to investigate structure-property relationships of blended functional organic material systems at the molecular and nanoscale. The cartoon in the center shows the type of nanoparticles that were fabricated and studied. In the background, a TEM image of these nanoparticles can be seen in which the dark spots represent the location of individual nanoparticles. Clockwise from the bottom left corner, a photograph of nanoparticle suspensions under UV illumination, a single-particle confocal fluorescence image, single-particle spectral data fitted with a Franck-Condon model, and a cartoon illustrating the concept of using nanoparticles as model systems to study the complex nanostructured active layer in bulk heterojunction organic photovoltaic devices are shown. On page 2449, D. Tenery and A. J. Gesquiere discuss the effects of material morphology and phase separation on exciton delocalization and collapse (trapping) in composite conjugated polymer/fullerene nanoparticles based on a detailed Franck-Condon analysis of single-particle emission spectra.

  2. Inside Cover

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    1. Inside Cover: Measuring the Friction of Nanoparticles: A New Route towards a Better Understanding of Nanoscale Friction (ChemPhysChem 14/2009) (page 2358)

      André Schirmeisen and Udo D. Schwarz

      Version of Record online: 28 SEP 2009 | DOI: 10.1002/cphc.200990056

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      The inside cover illustrates the novel approach to studying atomic-scale friction that is reviewed by A. Schirmeisen and U. D. Schwarz on page 2373 of this issue. The tip of an atomic force microscope is used as a tool for pushing nanoparticles with taylored physical and chemical properties while simultaneously measuring the interfacial particle-substrate friction.

  3. Graphical Abstract

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  4. Corrigendum

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      The Effect of Platinum on Diffusion Kinetics in β-NiAl: Implications for Thermal Barrier Coating Lifetimes (page 2367)

      Kristen A. Marino and Emily A. Carter

      Version of Record online: 28 SEP 2009 | DOI: 10.1002/cphc.200990058

      This article corrects:
  5. News

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  6. Minireview

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    1. Measuring the Friction of Nanoparticles: A New Route towards a Better Understanding of Nanoscale Friction (pages 2373–2382)

      André Schirmeisen and Udo D. Schwarz

      Version of Record online: 22 AUG 2009 | DOI: 10.1002/cphc.200900378

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      Rubbing it in: Investigation of nanoscale friction by the manipulation of nanoparticles with an atomic force microscope (AFM) is reviewed. Experiments and theories on the phenomenon of frictional duality are highlighted. The picture (left) shows how a nanoparticle is moved by placing an AFM tip on top of the object. On the right, an antimony particle is moved on a flat graphite surface while the friction force is measured.

  7. Highlight

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    1. Steady Light from Quantum Dots, at Last. But How? (pages 2383–2385)

      Michel Orrit and Thomas Basché

      Version of Record online: 11 SEP 2009 | DOI: 10.1002/cphc.200900602

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      Leaving the lights on: Because of its prevalence under widely different conditions, the phenomenon of fluorescence intermittence, or blinking, is sometimes considered as nearly universal (see picture for a typical trace). Therefore, the announcement of the synthesis of non-blinking dots has stunned—and thrilled—the scientific community and is highlighted herein.

  8. Concept

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    1. Electron Transport and Redox Reactions in Molecular Electronic Junctions (pages 2387–2391)

      Richard L. McCreery

      Version of Record online: 7 AUG 2009 | DOI: 10.1002/cphc.200900416

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      Molecular electronics: Electron transport through molecules occurs by several mechanisms, including coherent tunneling, activated transfer between potential wells and hopping modes. Redox events in molecular junctions are amenable to spectroscopic monitoring in working devices (see figure), and can have major effects on the electronic behavior of the junction.

  9. Communications

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    1. A Simple Approach to the Solution of the Diffusion Equation at the Microcylinder Electrode—an Inspiration from the Film Projector (pages 2393–2396)

      Yi-Min Fang, Jian-Jun Sun and Guo-Nan Chen

      Version of Record online: 18 AUG 2009 | DOI: 10.1002/cphc.200900404

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      16 frames per second: A new and simple route for the solution of diffusion equation at three types of electrode (see picture) is based on a time-dependent diffusion layer approximation and time-dependent boundary conditions, without employing the traditional Laplace transform.

    2. A Caveat for Single-Molecule Magnetism: Non-linear Arrhenius Plots (pages 2397–2400)

      Christos Lampropoulos, Stephen Hill and George Christou

      Version of Record online: 7 AUG 2009 | DOI: 10.1002/cphc.200900420

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      Around the bend: The magnetization relaxation of Mn12 single-molecule magnets (SMMs) does not follow a simple Arrhenius law (see picture), even for data collected at low frequencies, due to contributions from relaxation pathways via excited S states with a larger thermal barrier but faster spin reversal rates. A modified Arrhenius equation is proposed.

    3. Nitroxyl Radical Self-Assembled Monolayers on Gold: Versatile Electroactive Centers in Aqueous and Organic Media (pages 2401–2404)

      Olivier Alévêque, Fawzia Seladji, Christelle Gautier, Marylène Dias, Tony Breton and Eric Levillain

      Version of Record online: 28 JUL 2009 | DOI: 10.1002/cphc.200900448

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      Nitroxyl radical SAMs on gold afford a noteworthy electrochemical stability in both aqueous and organic media (see figure). The control of the redox center accessibility using mixed SAMs is illustrated by the electrocatalytic activities towards benzyl-alcohol oxidation in CH2Cl2 and H2O.

    4. A Novel Thermo-Induced Self-Bursting Microcapsule with Magnetic-Targeting Property (pages 2405–2409)

      Wei Wang, Li Liu, Xiao-Jie Ju, Djamal Zerrouki, Rui Xie, Lihua Yang and Liang-Yin Chu

      Version of Record online: 24 AUG 2009 | DOI: 10.1002/cphc.200900450

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      A novel thermo-induced self-bursting microcapsule with magnetic-targeting property is developed (see figure). The Fe3O4 nanoparticles-embedded PNIPAM shell enables magnetic-targeting and thermo-induced self-bursting of the microcapsules. Lipophilic chemicals dissolved in the oil core are completely released with the burst release of the encapsulated oil.

    5. The [(Al2O3)2] Anion Cluster: Electron Localization–Delocalization Isomerism (pages 2410–2413)

      Marek Sierka, Jens Döbler, Joachim Sauer, Hua-Jin Zhai and Lai-Sheng Wang

      Version of Record online: 17 JUL 2009 | DOI: 10.1002/cphc.200900460

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      Structural diversity: The [(Al2O3)2] cluster anion shows energetically close lying but structurally distinct cage and sheet-like isomers (see figure) which differ by delocalization/localization of the extra electron. The isomers co-exist experimentally and their relative energies are modeled computationally.

    6. Defect-Enhanced Dispersion of Carbon Nanotubes in DNA Solutions (pages 2414–2417)

      Jin Hee Kim, Masakazu Kataoka, Daisuke Shimamoto, Hiroyuki Muramatsu, Yong Chae Jung, Tomohiro Tojo, Takuya Hayashi, Yoong Ahm Kim, Morinobu Endo, Mauricio Terrones and Mildred S. Dresselhaus

      Version of Record online: 28 JUL 2009 | DOI: 10.1002/cphc.200900362

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      Nanotubes wrapped up: In nanotube–DNA hybrid structures (see figure), defects on the sidewall of carbon nanotubes effects the dispersibility. DNA is helically wrapped around the nanotubes in an irregular pattern and structural defects on the sidewall of the nanotubes provide additional sites for binding with DNA.

  10. Articles

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
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    7. Minireview
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    9. Concept
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    1. Imidazoline-N-oxyl: A DFT Study of Its Protonation Reaction (pages 2419–2428)

      Sandrine Chenesseau, Nicolas Ferré, Sylvain R. A. Marque and Didier Siri

      Version of Record online: 28 SEP 2009 | DOI: 10.1002/cphc.200900206

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      Imidazoline-based nitroxides have pKa values that vary from 1 to 11 depending on the ring substituents. Analysis of Mulliken charges (picture, left) and calculated Gibbs energies of protonation ΔrGg (right) are used to elucidate the effects governing these striking changes in pKa.

    2. Intracrystalline Transport Resistances in Nanoporous Zeolite X (pages 2429–2433)

      Armin Feldhoff, Jürgen Caro, Hervé Jobic, Jacques Ollivier, Cordula B. Krause, Petrik Galvosas and Jörg Kärger

      Version of Record online: 25 AUG 2009 | DOI: 10.1002/cphc.200900279

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      Real nature of zeolite disclosed: Herein pulsed-field gradient nuclear magnetic resonance and quasi-elastic neutron scattering are applied to measure the diffusion of n-octane on different length scales. The real structure of zeolite X (see picture) is defined by transmission electron microscopy, revealing the presence of intracrystalline transport resistances due to mirror-twin symmetry.

    3. Investigation of (1R,2S)-(−)-Ephedrine by Cryogenic Terahertz Spectroscopy and Solid-State Density Functional Theory (pages 2434–2444)

      Patrick M. Hakey, Damian G. Allis, Matthew R. Hudson, Wayne Ouellette and Timothy M. Korter

      Version of Record online: 7 AUG 2009 | DOI: 10.1002/cphc.200900293

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      Solid performance: The terahertz vibrational spectrum of ephedrine recorded at liquid-nitrogen temperature is assigned by solid-state DFT calculations. By accounting for the influence of crystal packing and strong intermolecular forces on changes to molecular geometry (see figure), solid-state calculations perform better than isolated-molecule calculations in predicting the geometries of molecules.

    4. Supramolecular Assembly of a 2D Binary Network of Pentacene and Phthalocyanine on Cu(100) (pages 2445–2448)

      Tobias N. Krauss, Esther Barrena, Helmut Dosch and Yutaka Wakayama

      Version of Record online: 7 AUG 2009 | DOI: 10.1002/cphc.200900408

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      Order please! A crystalline nanoporous molecular network is tailored by supramolecular assembly of pentacene and F16CuPc on Cu(100) [see picture]. A model of the epitaxial relationship on Cu(100) is given which suggests C[BOND]F⋅⋅⋅H bonding as a possible driving force for the bimolecular self-assembly in addition to the still strong interaction between substrate and organic bilayer.

    5. Effect of PCBM Concentration on Photoluminescence Properties of Composite MEH-PPV/PCBM Nanoparticles Investigated by a Franck–Condon Analysis of Single-Particle Emission Spectra (pages 2449–2457)

      Daeri Tenery and Andre J. Gesquiere

      Version of Record online: 28 SEP 2009 | DOI: 10.1002/cphc.200900413

      Thumbnail image of graphical abstract

      Insights into the structure–property relationships of bulk conjugated polymer/fullerene blended materials are obtained with single-particle spectroscopic studies on composite nanoparticle systems (see figure). Blending conjugated polymers with fullerenes at various doping levels induces changes in interchain interactions and aggregate site density even at length scales below a few tens of nanometers.

    6. Real-Time Nanomicroscopy via Three-Dimensional Single-Particle Tracking (pages 2458–2464)

      Yoshihiko Katayama, Ondrej Burkacky, Martin Meyer, Christoph Bräuchle, Enrico Gratton and Don C. Lamb

      Version of Record online: 16 SEP 2009 | DOI: 10.1002/cphc.200900436

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      Life in 3D: A novel tracking microscope is presented using a feedback control system to follow individual particles in 3D in real time (see figure). The system is synchronized to a wide-field setup allowing individual particles and their direct environment and interactions to be imaged simultaneously.

    7. Oligothiophene Self-Assembly on the Surface of ZnO Nanorods: Toward Coaxial p–n Hybrid Heterojunctions (pages 2465–2470)

      Cyril Martini, Guillaume Poize, Daniel Ferry, Daiki Kanehira, Noriyuki Yoshimoto, Jörg Ackermann and Frédéric Fages

      Version of Record online: 10 SEP 2009 | DOI: 10.1002/cphc.200900552

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      Structured nanorods: Hybrid 1D nanostructures are prepared by supramolecular self-assembly of oligothiophene molecules on the surface of zinc-oxide nanorods in solution at room temperature (see graphic). These nanostructures form ambipolar semiconducting nanostructured layers in field-effect transistors.

    8. Physical–Chemical Properties and Transfection Activity of Cationic Lipid/DNA Complexes (pages 2471–2479)

      Maria N. Antipina, Ingo Schulze, Martin Heinze, Bodo Dobner, Andreas Langner and Gerald Brezesinski

      Version of Record online: 3 SEP 2009 | DOI: 10.1002/cphc.200900069

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      Gene delivery systems: Two new core structures are synthesized for application as DNA delivery vectors. Both compounds show good transfection efficacy and low toxicity in the in vitro experiments. The capacity of the new compounds to bind DNA (see picture) was found to depend on the structure of the lipid head group.

    9. Modelling the Two-Dimensional Polymerization of 1,4-Benzene Diboronic Acid on a Ag Surface (pages 2480–2485)

      Michel Sassi, Vincent Oison, Jean-Marc Debierre and Stéphane Humbel

      Version of Record online: 25 AUG 2009 | DOI: 10.1002/cphc.200900168

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      Silver service: The 2D polymerization of 1,4-benzene diboronic acid on the Ag(111) surface leads to the formation of a covalent organic framework (see picture). The thermodynamic functions are obtained from DFT calculations. The entropic effect of the surface plays an important role in the polymerization free energy.

    10. Analysis of Single-Molecule Fluorescence Spectroscopic Data with a Markov-Modulated Poisson Process (pages 2486–2495)

      Mark Jäger, Alexander Kiel, Dirk-Peter Herten and Fred A. Hamprecht

      Version of Record online: 30 JUL 2009 | DOI: 10.1002/cphc.200900331

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      Experiment and theory together: The process of association and dissociation of Cu2+ ions is monitored with single-molecule fluorescence spectroscopy. An analysis based on a Markov-modulated Poisson process (see figure) characterizes the dynamics of the complex formation and dissociation of Cu2+ ions with bidentate ligand acids in water.

    11. Magnetic Anisotropy in a Family of Experimentally Synthesized and Theoretically Modeled M′6M8(CN24) Systems (pages 2496–2502)

      Yi-Quan Zhang and Cheng-Lin Luo

      Version of Record online: 27 AUG 2009 | DOI: 10.1002/cphc.200900339

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      Magnetic attraction: A density functional study of the magnetic coupling interactions and magnetic anisotropy in M′6M8(CN24) (M′=CuII, NiII or CoII; M=FeIII or CrIII) is presented (see figure). The interactions are all ferromagnetic and the near cubic symmetry of Cu6Fe8 results in its negative magnetic anisotropy parameter (D).

    12. Rotational Spectrum of the Mixed van der Waals Triad Pyridine–Ar–Ne (pages 2503–2507)

      Sonia Melandri, Barbara M. Giuliano, Assimo Maris, Luca Evangelisti, Biagio Velino and Walther Caminati

      Version of Record online: 31 JUL 2009 | DOI: 10.1002/cphc.200900366

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      Kept apart: The measured rotational spectrum of the heterotriad pyridine–Ar–Ne belongs to the [1,1] conformer, in which the Ne and Ar atoms are located on either side of the ring plane, while the [2,0] species, with the two noble gas atoms on the same side of the ring, is not observed (see picture).

    13. Amplification of Chirality and Enantioselectivity in the Asymmetric Autocatalytic Soai Reaction (pages 2508–2515)

      Luca Schiaffino and Gianfranco Ercolani

      Version of Record online: 25 AUG 2009 | DOI: 10.1002/cphc.200900369

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      Heterochiral 2:2 tetramers (see picture) that are more stable than their homochiral and 3:1 heterochiral counterparts are the likely cause of the amplification of enantiomeric excess by six orders of magnitude observed in the addition of diisopropylzinc to pyrimidine carbaldehydes (Soai reaction) at 0 °C, which cannot be explained by the dimer model, according to a kinetic analysis, including the formation of tetramers, and DFT calculations.

      Corrected by:

      Corrigendum: Corrigendum: Amplification of Chirality and Enantioselectivity in the Asymmetric Autocatalytic Soai Reaction

      Vol. 11, Issue 10, 2060, Version of Record online: 7 JUL 2010

    14. Ionic Association of the Ionic Liquids [C4mim][BF4], [C4mim][PF6], and [Cnmim]Br in Molecular Solvents (pages 2516–2523)

      Huiyong Wang, Jianji Wang, Sheli Zhang, Yuanchao Pei and Kelei Zhuo

      Version of Record online: 10 SEP 2009 | DOI: 10.1002/cphc.200900438

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      Opposites attract: The ionic association of ionic liquids in solution (see picture) is modulated by the alkyl chain length of the cation, the type of anion, and the physical properties of the molecular solvent—and it is expected to have an important influence on the applications of ionic liquids.

    15. Single-Molecule Spectroscopy on a Ladder-Type Conjugated Polymer: Electron–Phonon Coupling and Spectral Diffusion (pages 2524–2534)

      Richard Hildner, Laura Winterling, Ulrich Lemmer, Ullrich Scherf and Jürgen Köhler

      Version of Record online: 25 AUG 2009 | DOI: 10.1002/cphc.200900445

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      Polymer dynamics: The electron–phonon coupling strength and the character of low-energy vibrational modes that couple to the electronic transitions of a ladder-type π-conjugated polymer (see figure) is revealed by low-temperature single-molecule spectroscopy. In addition the origin of the spectral diffusion processes of the optical transitions is investigated.

    16. Strong CH⋅⋅⋅Halide Hydrogen Bonds from 1,2,3-Triazoles Quantified Using Pre-Organized and Shape-Persistent Triazolophanes (pages 2535–2540)

      Indrajit Bandyopadhyay, Krishnan Raghavachari and Amar H. Flood

      Version of Record online: 2 SEP 2009 | DOI: 10.1002/cphc.200900476

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      Accurate calculations of triazolophanes show them to be free from conformation changes and polarization effects upon anion binding (see figure). These features provide an unprecedented chance to cleanly decompose the CH hydrogen-bond strengths of the receptor into its components with the aid of electronic-structure calculations.

  11. Preview

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Minireview
    8. Highlight
    9. Concept
    10. Communications
    11. Articles
    12. Preview
    1. You have free access to this content
      Preview: ChemPhysChem 15/2009 (page 2547)

      Version of Record online: 28 SEP 2009 | DOI: 10.1002/cphc.200990060

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