ChemPhysChem

Cover image for Vol. 18 Issue 14

Early View (Online Version of Record published before inclusion in an issue)

Editor: Greta Heydenrych; Editorial Board Chairs: Christian Amatore, Michael Grätzel, Michel Orrit

Impact Factor: 3.075

ISI Journal Citation Reports © Ranking: 2016: 8/35 (Physics Atomic Molecular & Chemical); 54/145 (Chemistry Physical)

Online ISSN: 1439-7641

Associated Title(s): Advanced Materials, ChemBioChem, ChemCatChem, ChemElectroChem, ChemPhotoChem, ChemSusChem, Small

  1. Articles

    1. NMR Study of the Reductive Decomposition of [BMIm][NTf2] at Gold Electrodes and Indirect Electrochemical Conversion of CO2

      Roman Michez, Prof. Thomas Doneux, Prof. Claudine Buess-Herman and Prof. Michel Luhmer

      Version of Record online: 20 JUN 2017 | DOI: 10.1002/cphc.201700421

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      Controlled-potential electrolyses are performed at Au electrodes in [BMIm][NTf2] under nitrogen-saturated conditions. After electrolyses, the formation of carbene, hydrogenated monomers, and neutral dimers are highlighted by NMR spectroscopy. It is found that CO2 is indirectly converted by these electro-generated products to form imidazolium-2-carboxylate.

  2. Communications

    1. You have full text access to this OnlineOpen article
      The Effect of Temperature on Selectivity in the Oscillatory Mode of the Phenylacetylene Oxidative Carbonylation Reaction

      Dr. Julie Parker and Dr. Katarina Novakovic

      Version of Record online: 19 JUN 2017 | DOI: 10.1002/cphc.201700359

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      Temperature effects: Under mild conditions (0–40 °C, 1 atm) and in oscillatory pH mode, the selectivity of products formed in the phenylacetylene oxidative carbonylation reaction changes with temperature. By conducting experiments in a reaction calorimeter, oscillations in pH are related to pulsatile heat released by the reaction. A section of a single pH oscillation linked with each heat pulse is identified and a plausible reaction pathway is given.

  3. Articles

    1. Does Confinement Always Lead to Thermodynamically and/or Kinetically Favorable Reactions? A Case Study using Diels–Alder Reactions within ExBox+4 and CB[7]

      Debdutta Chakraborty, Ranjita Das and Prof. Pratim Kumar Chattaraj

      Version of Record online: 19 JUN 2017 | DOI: 10.1002/cphc.201700308

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      Forced to react: The cycloaddition reaction of 1,3-butadiene and ethylene becomes thermodynamically and kinetically more favorable inside cucurbit[7]uril as compared with that inside ExBox+4 as well as in the unconfined state.

    2. The Role of Water in the Catalyst-Free Aldol Reaction of Water-Insoluble N-Methyl-2,4-thiazolidinedione with N-Methylisatin from QM/MM Monte Carlo Simulations

      Jianming Zhao, Fen He, Fan Zhang, Dr. Xin Yang, Zhiyue Tian and Prof. Ying Xue

      Version of Record online: 19 JUN 2017 | DOI: 10.1002/cphc.201700423

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      How does your aldol go? Mixed quantum mechanics and molecular mechanics (QM/MM) Monte Carlo simulations with free energy perturbation theory are performed to investigate the effects of solvents on the uncatalyzed aldol reaction of N-methyl-2,4-thiazolidinedione with N-methylisatin “on-water” and in DMSO (see figure). Rate acceleration on-water is attributed to enhanced hydrogen-bond interactions between water molecules and the reaction system as the reaction proceeds.

    3. Influence of Divalent Counterions on the Dynamics in DNA as Probed by Using a Minor-Groove Binder

      Sneha Paul, Tasnim Ahmed and Prof. Anunay Samanta

      Version of Record online: 14 JUN 2017 | DOI: 10.1002/cphc.201700251

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      DNA dynamics in the presence of divalent (Mg2+ and Ca2+) and monovalent (Na+) ions is determined from the time-resolved Stokes shifts of 4′,6-diamidino-2-phenylindole (a minor-groove binder) over subpicosecond-to-nanosecond timescales. Similar dynamics in the presence of higher-valence ions and monovalent ions is observed, and is explained by the strong hydration shell that screens the electric field and the preferential binding sites of these divalent ions.

    4. Single-Molecule and Ensemble Diffusivities in Individual Nanopores with Spatially Dependent Mobility

      Julia Rybka, Prof. Dr. Jörg Kärger and Prof. Dr. Ulrich Tallarek

      Version of Record online: 14 JUN 2017 | DOI: 10.1002/cphc.201700231

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      Test of ergodicity for pore diffusion: Ergodicity is proven for single-molecule and ensemble diffusivities of solvent and solute molecules in a silica nanopore with a hydrophobic surface modification. Molecular dynamics simulations allow quantification of the effects of spatially dependent mobility near the surface (which stems from the microheterogeneity induced by the nonpolar bonded phase) on the effective pore-diffusion coefficient (Dpore).

    5. Computational Insights into the CH3Cl+OH Chemical Reaction Dynamics at the Air–Water Interface

      Dr. Marilia T. C. Martins-Costa, Dr. Josep M. Anglada and Dr. Manuel F. Ruiz-López

      Version of Record online: 14 JUN 2017 | DOI: 10.1002/cphc.201700437

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      Unknown waters: Quantum/classical molecular dynamics simulations combined with high-level ab initio calculations have been carried out to study the H-abstraction from methyl chloride by the OH radical in gas phase and at the air–water interface. The reaction dynamics and time scales are discussed.

    6. Slicing Diamond for More sp3 Group 14 Allotropes Ranging from Direct Bandgaps to Poor Metals

      Laura-Alice Jantke, Prof. Dr. Antti J. Karttunen and Prof. Dr. Thomas F. Fässler

      Version of Record online: 13 JUN 2017 | DOI: 10.1002/cphc.201700290

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      Chemi-inspired networks: Tetrahedral frameworks, adapted from known binary and ternary intermetallic compounds, serve as the basis for novel tetrel allotropes. An easy but effective construction kit shows that they also derive from the simple cubic diamond structure.

  4. Communications

    1. Toward Hyperpolarized 19F Molecular Imaging via Reversible Exchange with Parahydrogen

      Prof. Roman V. Shchepin, Prof. Boyd M. Goodson, Prof. Thomas Theis, Prof. Warren S. Warren and Prof. Eduard Y. Chekmenev

      Version of Record online: 13 JUN 2017 | DOI: 10.1002/cphc.201700594

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      NMR signals of 3-fluoropyridine are enhanced by ≈100-fold, corresponding to 0.3 % nuclear spin polarization (at 9.4 T), using 50 % parahydrogen. While future optimization efforts can further increase the efficiency of 19F hyperpolarization (i.e. in excess of 20 % using the presented approach), the authors demonstrate the potential of this technology on pioneering examples of high-resolution hyperpolarized 19F imaging and hyperpolarized 19F pH sensing.

  5. Articles

    1. Modulation of Wetting Gradients by Tuning the Interplay between Surface Structuration and Anisotropic Molecular Layers with Bipolar Electrochemistry

      Dr. Laurent Bouffier, Dr. Stéphane Reculusa, Prof. Dr. Valérie Ravaine and Prof. Dr. Alexander Kuhn

      Version of Record online: 13 JUN 2017 | DOI: 10.1002/cphc.201700398

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      Slippery slope: The combination of surface structuration and molecular layers allows the preparation of tunable surface gradients. Wetting is modulated by reductive desorption of layers by means of bipolar electrochemistry (see figure).

    2. Selection of a Single Isotope of Multiply Charged Xenon (AXez+, A=128–136, z=1–6) by Using a Bradbury–Nielsen Ion Gate

      Akihiro Kitashoji, Taiki Yoshikawa, Dr. Akimasa Fujihara, Takaaki Kamamori, Dr. Shigeki Nashima and Prof. Dr. Tomoyuki Yatsuhashi

      Version of Record online: 12 JUN 2017 | DOI: 10.1002/cphc.201700381

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      Isolating isotopes: A single isotope of Xe6+ was successfully selected by using a time-of-flight mass spectrometer equipped with a curved-field reflectron and the newly constructed Bradbury–Nielsen ion gate (BNG). The actual ion selection ability, i.e. the gate function, by BNG was evaluated to be 36.5±0.5 ns (fwhm) in width, which is sufficient to analyze not only multiply charged small organic molecules but also large molecules such as proteins and peptides.

    3. Odd-Electron Bonds

      Prof. Dr. Timothy Clark

      Version of Record online: 12 JUN 2017 | DOI: 10.1002/cphc.201700417

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      Odd bonding: One- and three-electron bonds are reviewed and discussed. The graphic shows the singly occupied orbital of the PH3-OH2+. three-electron bonded radical cation.

    4. Unconventional Behavior of Friction at the Nanoscale beyond Amontons’ Law

      Prof. Jingrun Chen and Prof. Wang Gao

      Version of Record online: 9 JUN 2017 | DOI: 10.1002/cphc.201700378

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      Tip sliding away: Atomic-scale friction of an Si tip/graphene substrate system is studied by a DFT approach corrected for many-body van der Waals (vdW) interactions. Tip–substrate distance plays an essential role in nanofriction by determining the competition between vdW and electronic contributions, which results in a transition from attraction to repulsion and from negative to positive friction coefficient (see figure).

  6. Communications

    1. Predicting the Solvent Effect on Esterification Kinetics

      Max Lemberg and Prof. Dr. Gabriele Sadowski

      Version of Record online: 9 JUN 2017 | DOI: 10.1002/cphc.201700507

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      A thermodynamic model is applied to account for solvent/reactant interactions during the esterification of acetic acid and propionic acid with ethanol in different solvents. Using only one intrinsic kinetic constant for all the solvent systems, the new activity-based kinetic modeling approach predicts the solvent effects on reaction kinetics in very good agreement with experimental data.

    2. A Free-Radical Pathway to Hydrogenated Phenanthrene in Molecular Clouds—Low Temperature Growth of Polycyclic Aromatic Hydrocarbons

      Aaron M. Thomas, Dr. Michael Lucas, Dr. Tao Yang, Prof. Dr. Ralf I. Kaiser, Luis Fuentes, Daniel Belisario-Lara and Prof. Dr. Alexander M. Mebel

      Version of Record online: 8 JUN 2017 | DOI: 10.1002/cphc.201700515

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      A low-temperature pathway accounting for the barrierless formation of the polycyclic aromatic hydrocarbon (PAH) 1,4-dihydrophenanthrene, via the elementary bimolecular gas-phase reaction of the 1-naphthyl radical with 1,3-butadiene, is revealed. This type of reaction defies conventional wisdom that PAH growth is predominantly a high-temperature phenomenon and may represent an overlooked path to complex PAHs in cold regions of the interstellar medium (TMC image credit: European Southern Observatory, eso1209eb, Creative Commons Attribution 4.0 International License).

  7. Articles

    1. Enabling Fast Pseudo-2D NMR Spectral Acquisition for Broadband Homonuclear Decoupling: The EXACT NMR Approach

      Dr. Ikenna E. Ndukwe, Dr. Alexandra Shchukina, Dr. Vadim Zorin, Dr. Carlos Cobas, Dr. Krzysztof Kazimierczuk and Dr. Craig P. Butts

      Version of Record online: 8 JUN 2017 | DOI: 10.1002/cphc.201700474

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      Bringing NMR up to speed: Pseudo-2D NMR spectroscopy provides a means of acquiring broadband homonuclear decoupled spectra useful for structural characterization of complex molecules. In this work, the concept of EXACT NMR (“burst” non-uniform sampling of data points) is explored in pseudo-2D experiments enabling the significantly accelerated acquisition of spectral data with no loss in spectral quality or signal intensity.

    2. Ca2+-Cl Association in Water Revisited: the Role of Cation Hydration

      Prof. Mathieu Salanne, Dr. Sami Tazi, Prof. Rodolphe Vuilleumier and Dr. Benjamin Rotenberg

      Version of Record online: 8 JUN 2017 | DOI: 10.1002/cphc.201700286

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      What goes around: The dissociation of a calcium-chloride ion pair in water (see Figure) involves rearrangements of the solvation shell of both ions. Using molecular simulations, we show that the coordination number of calcium by water molecules should be considered in addition to the interionic distance to investigate this process, in particular when computing the potential of mean force.

    3. Noncovalent Interactions between Dopamine and Regular and Defective Graphene

      Ana C. Rossi Fernández and Prof. Dr. Norberto J. Castellani

      Version of Record online: 8 JUN 2017 | DOI: 10.1002/cphc.201700252

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      Perfectly noncovalent! The adsorption of dopamine on perfect graphene involves noncovalent interactions of π–π and CH⋅⋅⋅π character, according to the adsorption mode, as well as electron drift from substrate to adsorbate. On graphene with monovacancies, a hydrogen bond is formed involving a hydroxy group of dopamine and a carbon atom of the vacancy in the AB stacking mode.

    4. Self-Assembly and Local Manipulation of Au-Pyridyl Coordination Networks on Metal Surfaces

      Yang Song, Yuxu Wang, Qiao Jin, Kun Zhou, Dr. Ziliang Shi, Prof. Pei-Nian Liu and Prof. Yu-qiang Ma

      Version of Record online: 7 JUN 2017 | DOI: 10.1002/cphc.201700439

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      Control at both the micro- and nanoscale: Scanning tunnelling microscopy is employed to demonstrate that Au-pyridyl coordination can be used to globally control and locally manipulate the polymorphism of a two-dimensional coordination network on metal surfaces. Using the STM tip, α-network domains were locally created within the homogeneous β-network domain areas on Au(111).

    5. Electroluminescent and Optoelectronic Properties of OLEDs with Bay-Extended, Distorted Perylene Esters as Emitter Materials

      Dr. Joachim Vollbrecht, Simon Blazy, Philipp Dierks, Samuel Peurifoy, Dr. Harald Bock and Prof. Heinz Kitzerow

      Version of Record online: 6 JUN 2017 | DOI: 10.1002/cphc.201700502

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      Different perylene derivatives are tested as emitter materials in organic light-emitting diodes. After thermal treatment, the emission can be altered due to the formation of a denser packed nanofilm. This behavior can be explained by the formation of excited dimers and is in agreement with prior studies.

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