ChemPhysChem

Cover image for Vol. 9 Issue 16

November 10, 2008

Volume 9, Issue 16

Pages 2277–2422

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Minireview
    6. Communications
    7. Articles
    8. Preview
    1. Cover Picture: Progress in Hyperpolarized Ultrafast 2D NMR Spectroscopy (ChemPhysChem 16/2008) (page 2277)

      Mor Mishkovsky and Lucio Frydman

      Version of Record online: 31 OCT 2008 | DOI: 10.1002/cphc.200890064

      Thumbnail image of graphical abstract

      The cover picture illustrates the benefits that result from combining ex situ dynamic nuclear polarization (DNP) with "ultrafast" 2D NMR. In their article on page 2340, M. Mishkovsky and L. Frydman show that the single-scan nature of the latter approach makes good use of the sensitivity enhancement afforded by the hyperpolarization procedure, which in the case of small molecules often exceeds 1,000. 2D heteronuclear correlation spectra correlating the non-protonated 13C sites with nearby protons—methyls for the indicated molecules—can thus be collected in negligible amounts of spectrometer time (1 scan vs 2048 scans) and at considerably lower final concentrations (0.2 mm vs 20 mm) than upon using conventional counterparts.

  2. Graphical Abstract

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

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

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Minireview
    6. Communications
    7. Articles
    8. Preview
    1. Chemical Imaging of Monolayers on Metal Surfaces: Applications in Corrosion, Catalysis, and Self-Assembled Monolayers (pages 2291–2298)

      Steven Baldelli

      Version of Record online: 16 OCT 2008 | DOI: 10.1002/cphc.200800501

      Thumbnail image of graphical abstract

      Scratching the surface: Nearly all surfaces have spatial heterogeneities. Recent developments in spectroscopic techniques, photo-electron microscopy, infrared and Raman imaging, and nonlinear optical imaging vibrational spectroscopy (see picture) can provide spatial, spectroscopic, and in situ information. These techniques are applied to corrosion, catalysis and self-assembled monolayers.

  5. Communications

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Minireview
    6. Communications
    7. Articles
    8. Preview
    1. An Aqueous Electrochemical Energy Storage System Based on Doping and Intercalation: Ppy//LiMn2O4 (pages 2299–2301)

      Gaojun Wang, Qunting Qu, Bin Wang, Yi Shi, Shu Tian and Yuping Wu

      Version of Record online: 10 OCT 2008 | DOI: 10.1002/cphc.200800424

      Thumbnail image of graphical abstract

      Green energy: An aqueous rechargeable lithium battery (ARLB) based on a doping and intercalation mechanism is presented. This battery is safe, environmentally friendly, and cheap, and could therefore have important applications in new energy storage systems. The new ARLB is composed of polypyrrole and LiMn2O4 electrodes, which are stable and allow a good performance (see voltammograms).

    2. Self-propelled Oil Droplets on Metal Surfaces during Electrodeposition (pages 2302–2304)

      Shuji Nakanishi, Tomoyuki Nagai, Daisuke Ihara and Yoshihiro Nakato

      Version of Record online: 22 SEP 2008 | DOI: 10.1002/cphc.200800438

      Thumbnail image of graphical abstract

      Self-propelled droplet: During electrodeposition of Sn, droplets on electrode surfaces show self-propelled motions driven by the imbalance of the interfacial free energy between the front and the rear sides of the droplet (see graphic). This also occurs for other metal–solvent combinations, depending on the properties of the solution/metal interface.

    3. An NMR Investigation of Fast Proton Transfer along the Surface of Cationic Micelles (pages 2305–2308)

      Laurence Dupont-Leclercq, Jean-Jacques Delpuech and Bernard Henry

      Version of Record online: 26 SEP 2008 | DOI: 10.1002/cphc.200800493

      Thumbnail image of graphical abstract

      CMCs and proton exchange rates of cationic micelles are shown to increase linearly with 1/[H+]. Enhanced proton transfers in micelles (see picture) are assigned to two major factors: a pH elevation of ca. 2 units around the micellar surface and a diffusion-like proton switch from polar head to polar head. Rate enhancements are larger when the number of methylenic carbons in the surfactants used is increased from 8 to 10.

    4. New Insight into the Properties of Proton-Conducting Oxides from Neutron Total Scattering (pages 2309–2312)

      Lorenzo Malavasi, Hyunjeong Kim and Thomas Proffen

      Version of Record online: 22 SEP 2008 | DOI: 10.1002/cphc.200800514

      Thumbnail image of graphical abstract

      Promising oxides: Cerates, which are important proton-conducting oxides with promising applications in solid oxide fuel cells, are investigated by means of pair distribution function (PDF) analysis of the total neutron scattering data (see figure). The results are important for understanding the functional properties of these materials.

    5. Beyond Isotropic Tumbling Models: Nuclear Spin Relaxation in Liquids from First Principles (pages 2313–2316)

      Jochen Schmidt, Jürg Hutter, Hans-Wolfgang Spiess and Daniel Sebastiani

      Version of Record online: 9 OCT 2008 | DOI: 10.1002/cphc.200800435

      Thumbnail image of graphical abstract

      Relaxed rolling: First-principles MD simulations are used to compute the longitudinal quadrupolar relaxation of the 17O and 2H nuclei of liquid water at ambient conditions. The limits of the commonly assumed simple exponential decay of the EFG autocorrelation functions is elucidated (see graph) and their relation to the physics of the system is demonstrated.

    6. Fabrication of Highly Ordered Gold Nanoparticle Arrays Templated by Crystalline Lattices of Bacterial S-Layer Protein (pages 2317–2320)

      Jilin Tang, Helga Badelt-Lichtblau, Andreas Ebner, Johannes Preiner, Bernhard Kraxberger, Hermann J. Gruber, Uwe B. Sleytr, Nicola Ilk and Peter Hinterdorfer

      Version of Record online: 20 OCT 2008 | DOI: 10.1002/cphc.200800507

      Thumbnail image of graphical abstract

      Biotemplating: The square lattice of S-layer protein rSbpA–Cys is used as a biotemplate for directing self-assembly of gold nanoparticle (NP) arrays with controlled distance (see graphic). The gold NPs are specifically bound to the exposed cysteines on the S-layer protein lattice and assembled into square symmetry nanoarrays, which show the same periodicity as the S-layer template.

    7. Lipid Thermodynamics: Melting is Molecular (pages 2321–2324)

      Sailaja Krishnamurty, Milen Stefanov, Tzonka Mineva, Sylvie Bégu, Jean Marie Devoisselle, Annick Goursot, Rui Zhu and Dennis R. Salahub

      Version of Record online: 16 OCT 2008 | DOI: 10.1002/cphc.200800511

      Thumbnail image of graphical abstract

      Heads or tails? The distance-fluctuation criterion for melting, ΔB, shows that a dimyristoyl phosphatidylcholine (DMPC) molecule undergoes a gel-to-liquid-crystal phase transition (Tm) at 297–301 K (see graph). Alkyl chains transform from trans to gauche at 297 K and interchain disorder sets in at 301 K. These temperatures are close to the Tm of a DMPC bilayer, which implies that the Tm is driven by intramolecular dynamical properties.

  6. Articles

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Minireview
    6. Communications
    7. Articles
    8. Preview
    1. Two Photon-Induced Electron Injection From a Nanotrigger in Native Endothelial NO-Synthase (pages 2325–2331)

      Edward Beaumont, Jean-Christophe Lambry, Anne-Claire Robin, Pavel Martasek, Mireille Blanchard-Desce and Anny Slama-Schwok

      Version of Record online: 10 OCT 2008 | DOI: 10.1002/cphc.200800411

      Thumbnail image of graphical abstract

      Photoactive nanotrigger: Ultrafast kinetics demonstrate that electron injection can be photoinduced from a designed NADPH-substitute (that acts as a nanotrigger) into an electron-accepting enzyme (see figure). Activation of the NO-synthase is feasible via two-photon excitation of the nanotrigger which provides temporal and spatial control of the catalysis for future experimental studies in cellular systems.

    2. Multiple-Replica Exchange with Information Retrieval (pages 2332–2339)

      Manuel Athènes and Florent Calvo

      Version of Record online: 16 OCT 2008 | DOI: 10.1002/cphc.200800427

      Thumbnail image of graphical abstract

      Information retrieval: The Landau free energy of the 20×20 ferromagnetic Ising model as a function of magnetization (see picture) is obtained from multiple-replica-exchange Monte Carlo and replica-exchange Monte Carlo methods with or without virtual-move averaging. The curves are the average of 200 independent simulations.

    3. Progress in Hyperpolarized Ultrafast 2D NMR Spectroscopy (pages 2340–2348)

      Mor Mishkovsky and Lucio Frydman

      Version of Record online: 10 OCT 2008 | DOI: 10.1002/cphc.200800461

      Thumbnail image of graphical abstract

      Sensitive multidimensional NMR: The combination of ex situ dynamic nuclear polarization (DNP) and single-scan 2D NMR methodologies opens new vistas in the collection of multidimensional data with high sensitivity. Experimental results show the benefits expected for optimized spectroscopic acquisitions implemented on small- and medium-sized organic molecules (see figure).

    4. A DFT-Based Investigation of Hydrogen Abstraction Reactions from Methylated Polycyclic Aromatic Hydrocarbons (pages 2349–2358)

      Karen Hemelsoet, Veronique Van Speybroeck and Michel Waroquier

      Version of Record online: 16 OCT 2008 | DOI: 10.1002/cphc.200800475

      Thumbnail image of graphical abstract

      Does size matter? The influence of the size and local environment of polycyclic aromatic hydrocarbons on the thermodynamic and kinetic properties of methyl-assisted hydrogen abstraction reactions is investigated (see picture). Reliable DFT results add insight into the radical characteristics of these large species, for which no experimental data are available.

    5. Spontaneous Emergence of Homochirality via Coherently Coupled Antagonistic and Reversible Reaction Cycles (pages 2359–2371)

      Michael Mauksch and Svetlana B. Tsogoeva

      Version of Record online: 21 OCT 2008 | DOI: 10.1002/cphc.200800226

      Thumbnail image of graphical abstract

      Homochiral states: Spontaneous mirror-symmetry breaking in stereoselective reactions is possible under nominally achiral conditions and in reversible closed autocatalytic reaction networks. The curves for production of enantiomers L and D practically coincide and only racemic product is formed until a critical time is reached, where a bifurcation occurs and the system rapidly evolves into a fully homochiral state with near 100 % ee and pure D (see picture).

    6. CO Blocking of D2 Dissociative Adsorption on Ru(0001) (pages 2372–2378)

      Hirokazu Ueta, Irene M. N. Groot , Michael A. Gleeson, Steven Stolte , George C. McBane, Ludo B. F. Juurlink and Aart W. Kleyn 

      Version of Record online: 26 SEP 2008 | DOI: 10.1002/cphc.200800294

      Thumbnail image of graphical abstract

      CO poisons surface reactivity: Dissociative adsorption of D2 on Ru(0001) is blocked by pre-adsorption of CO molecules. The dependence of CO blocking radius on D2 kinetic energy (see picture) shows a behaviour that differs markedly from that of a simple steric model. The results suggest that a CO-induced barrier for D2 dissociation exists in the vicinity of CO molecules, and at high CO coverage all D2 dissociation occurs via this barrier.

    7. Insight into Markovnikov Reactions of Alkenes in Terms of Ab Initio and Molecular Face Theory (pages 2379–2389)

      Zhong-Zhi Yang, Yan-Li Ding and Dong-Xia Zhao

      Version of Record online: 20 OCT 2008 | DOI: 10.1002/cphc.200800364

      Thumbnail image of graphical abstract

      Which way to go? The electrophilic addition of hydrogen halides to alkenes is systematically investigated with high-level ab initio calculations. The authors demonstrate the correlation between the properties of Markovnikov addition reactions and the electron density encoded on the molecular face, which provides an image of a molecule's shape and charge distribution (see figure of HCl approaching ethylene).

    8. Structural Characteristics of Hydrogenated Carbon and Boron Nitride Nanotubes: Impact of H[BOND]H Interactions (pages 2390–2396)

      Jukka T. Tanskanen, Mikko Linnolahti, Antti J. Karttunen and Tapani A. Pakkanen

      Version of Record online: 1 OCT 2008 | DOI: 10.1002/cphc.200800389

      Thumbnail image of graphical abstract

      Significantly different: Fully hydrogenated carbon and boron nitride nanotubes prefer distinctly different structures due to H[BOND]H interactions. A systematic study of nanotubes up to 5 nm in diameter is performed by using quantum chemical calculations (see picture). Electrostatic H[BOND]H interactions are beneficial for hydrogenated boron nitride nanotubes, which prefer multilayering.

    9. Hydrophobic N-Diazeniumdiolates and the Aqueous Interface of Sodium Dodecyl Sulfate (SDS) Micelles (pages 2397–2405)

      Andreas Mohr, Tommy Pozo Vila, Hans-Gert Korth, Heinz Rehage and Reiner Sustmann

      Version of Record online: 27 OCT 2008 | DOI: 10.1002/cphc.200800399

      Thumbnail image of graphical abstract

      Kinetics as magnifying glass: The decomposition of zwitterionic N-diazeniumdiolates is accelerated by SDS micelles in dependence on surfactant concentration and length of the alkyl side chains (see graphs). These N-diazeniumdiolates are not only promising NO-releasing agents, but are also useful probes for the determination of the interfacial pH value in the Stern region of negatively charged micellar systems.

    10. Spectroscopic and Electrochemical Evaluation of Salt Effects on Electron-Transfer Equilibria between Donor/Acceptor and Ion-Radical Pairs in Organic Solvents (pages 2406–2413)

      Sergiy V. Rosokha, Duoli Sun, Jeffrey Fisher and Jay K. Kochi

      Version of Record online: 10 OCT 2008 | DOI: 10.1002/cphc.200800470

      Thumbnail image of graphical abstract

      Donor/acceptor electron transfer in organic solvents is drastically affected by the “inert” salt tetrabutylammonium hexafluorophosphate (Bu4NPF6) (see figure). The resulting ion-radical concentrations are related to ion pairing and activity variations.

    11. Measurement of Slow Diffusion Coefficients of Molecules with Arbitrary Scalar Couplings via Long-Lived Spin States (pages 2414–2419)

      Riddhiman Sarkar, Puneet Ahuja, Paul R. Vasos and Geoffrey Bodenhausen

      Version of Record online: 27 OCT 2008 | DOI: 10.1002/cphc.200800476

      Thumbnail image of graphical abstract

      Slowly does it: New experiments, suitable for molecules or conformations featuring a wide range of J-couplings, are described for the determination of very slow diffusion constants by means of NMR using long-lived (singlet) states. The new method is used to determine the diffusion coefficients of 2,3,6-trichlorobenzaldehyde and 2-chloroacrylonitrile simultaneously (see graphs).

  7. Preview

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Minireview
    6. Communications
    7. Articles
    8. Preview
    1. You have free access to this content
      Preview: ChemPhysChem 17/2008 (page 2422)

      Version of Record online: 31 OCT 2008 | DOI: 10.1002/cphc.200890067

SEARCH

SEARCH BY CITATION