ChemPhysChem

Cover image for Vol. 15 Issue 9

June 23, 2014

Volume 15, Issue 9

Pages 1713–1898

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Concepts
    6. Communication
    7. Articles
    1. You have free access to this content
      Cover Picture: Long-Lasting Oscillations in the Electro-Oxidation of Formic Acid on PtSn Intermetallic Surfaces (ChemPhysChem 9/2014) (page 1713)

      Nickson Perini, Dr. Bruno C. Batista, Prof. Antonio C. D. Angelo, Prof. Irving R. Epstein and Prof. Hamilton Varela

      Article first published online: 20 JUN 2014 | DOI: 10.1002/cphc.201490040

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      The cover image shows a schematic view of the long-lasting oscillations observed during the electro-oxidation of formic acid on PtSn ordered intermetallic phases. Within the long road perspective that remits to infinity, oscillations on PtSn are very stable when compared to that on platinum. The higher stability of the oscillations on ordered PtSn surfaces is caused by its tolerance towards surface poisoning, which prevents surface deactivation and slows down the natural drift of the system. This is presented on p. 1753 by H. Varela et al.

    2. You have free access to this content
      Inside Cover: Thermodynamics of Micellization from Heat-Capacity Measurements (ChemPhysChem 9/2014) (page 1714)

      Dr. Bojan Šarac, Prof. Dr. Marija Bešter-Rogač and Prof. Dr. Jurij Lah

      Article first published online: 20 JUN 2014 | DOI: 10.1002/cphc.201490041

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      In the picture blue lines represent heat capacity vs temperature curves accompanying micellization/demicellization at different surfactant concentrations, as presented on p. 1827 by B. Šarac, M. Bešter-Rogač and J. Lah. The dark green area between the peaks represents the region where micelles and surfactant monomers coexist.

  2. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Concepts
    6. Communication
    7. Articles
    1. Graphical Abstract: ChemPhysChem 9/2014 (pages 1715–1721)

      Article first published online: 20 JUN 2014 | DOI: 10.1002/cphc.201490042

  3. News

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Concepts
    6. Communication
    7. Articles
    1. Editors' Selection: ChemPhysChem 9/2014 (page 1723)

      Article first published online: 20 JUN 2014 | DOI: 10.1002/cphc.201490043

  4. Concepts

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Concepts
    6. Communication
    7. Articles
    1. Magnetic Resonance Imaging of Electrochemical Cells Containing Bulk Metal (pages 1731–1736)

      Dr. Melanie M. Britton

      Article first published online: 30 APR 2014 | DOI: 10.1002/cphc.201400083

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      Caught on film: Magnetic resonance imaging (MRI) is common in medical research and, more recently, is being applied to visualize chemical composition, molecular transport, and physical environment in engineering and materials research. Researchers are now starting to use these techniques to investigate electrochemical devices.

    2. Coherent Magnetic Resonance of Nanocrystal Quantum-Dot Luminescence as a Window to Blinking Mechanisms (pages 1737–1746)

      Dr. Kipp J. van Schooten, Prof. Christoph Boehme and Prof. John M. Lupton

      Article first published online: 23 APR 2014 | DOI: 10.1002/cphc.201400081

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      Quantum dot sub-ensembles: Auger recombination and charge trapping are identified as underlying mechanisms of quantum dot (QD) blinking but are difficult to address as isolated effects. By using coherent magnetic resonance to define QD sub-ensembles, spin-dependent photoluminescence-quenching mechanisms are addressed individually with pulses of microwaves. This technique reveals spin-dependent transitions consistent with blinking mechanisms, complementing information from single QD microscopy.

  5. Communication

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Concepts
    6. Communication
    7. Articles
    1. Electrically Controlled Eight-Spin-Qubit Entangled-State Generation in a Molecular Break Junction (pages 1747–1751)

      Dr. Mausumi Chattopadhyaya, Md. Mehboob Alam, Dr. Debasis Sarkar and Dr. Swapan Chakrabarti

      Article first published online: 24 APR 2014 | DOI: 10.1002/cphc.201400029

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      Tale of entanglement: An eight-spin-qubit quantum entangled state can be realized in a dinuclear Fe(II) complex which (under a specific set of quantum-logic-gate operations) can act as a source of multi-qubit generation. The large decoherence time with high quantum fidelity factor makes the system an efficient quantum-computing object.

  6. Articles

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Concepts
    6. Communication
    7. Articles
    1. Long-Lasting Oscillations in the Electro-Oxidation of Formic Acid on PtSn Intermetallic Surfaces (pages 1753–1760)

      Nickson Perini, Dr. Bruno C. Batista, Prof. Antonio C. D. Angelo, Prof. Irving R. Epstein and Prof. Hamilton Varela

      Article first published online: 30 APR 2014 | DOI: 10.1002/cphc.201301186

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      Can′t stop: Most electrocatalytic reactions under oscillatory conditions oscillate for only a few dozen stable cycles. We found unprecedented long-lasting oscillations in the electro-oxidation of formic acid on an ordered intermetallic PtSn phase. The introduction of Sn substantially increases the catalytic activity and retards the irreversible surface oxidation, which results in a 30–40-fold stabilization of the oscillation with respect to the behavior of pure Pt surfaces.

    2. Study of Carbamate-Modified Disiloxane in Porous PVDF-HFP Membranes: New Electrolytes/Separators for Lithium-Ion Batteries (pages 1761–1771)

      Steffen Jeschke, Dr. Monika Mutke, Dr. Zhongxiang Jiang, Dr. Burkhard Alt and Prof. Hans-Dieter Wiemhöfer

      Article first published online: 15 APR 2014 | DOI: 10.1002/cphc.201400065

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      Soaked through: A porous poly(vinylidene fluoride–hexafluoropropylene) (PVDF-HFP) membrane soaked in a liquid electrolyte containing a carbamate-modified disiloxane and lithium bis(trifluoromethane)sulfonimide (LiTFSI, see picture) results in gel electrolyte membranes, which can be analyzed by using a broad variety of experimental methods.

    3. From Molecules to Materials: Computational Design of N-Containing Porous Aromatic Frameworks for CO2 Capture (pages 1772–1778)

      Dr. Wenliang Li, Haijie Shi and Prof. Jingping Zhang

      Article first published online: 20 JUN 2014 | DOI: 10.1002/cphc.201400064

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      Pores for thought: N-containing porous aromatic frameworks (PAFs) for CO2 capture are investigated by using computational design. The interaction energies (Eint) between CO2 and the six-membered rings are calculated at the B2PLYP/def2-TZVPP level. Six-membered rings with high CO2-binding affinity are selected for use in the PAFs. Selectivity of CO2 over CH4, H2, and N2 and the Eint of CO2 in PAFs are investigated.

    4. Does Tautomerization of FapyG Influence Its Mutagenicity? (pages 1779–1784)

      Dr. Nihar R. Jena, Prof. Alan E. Mark and Prof. Phool C. Mishra

      Article first published online: 14 MAY 2014 | DOI: 10.1002/cphc.201400045

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      New mutation for FapyG: It is revealed that the enol tautomer of FapyG might lead to a guanine-to-adenine mutation, whereas its keto tautomer might induce a guanine-to-thymine mutation. The conformational flexibility of the N-glycosidic bond of FapyG might also play an important role in these mutations.

    5. Swelling Kinetics of Microgels Embedded in a Polyacrylamide Hydrogel Matrix (pages 1785–1792)

      Na Huang, Prof. Dr. Ying Guan, Prof. Dr. X. X. Zhu and Prof. Dr. Yongjun Zhang

      Article first published online: 23 MAY 2014 | DOI: 10.1002/cphc.201400027

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      Having a swell time: A kinetic study confirms that composite hydrogels—macroscopic hydrogels with embedded microgel particles—are capable of responding quickly to external stimuli.

    6. Does Excited-State Proton-Transfer Reaction Contribute to the Emission Behaviour of 4-Aminophthalimide in Aqueous Media? (pages 1793–1798)

      Dr. Dinesh Chandra Khara, Sanghamitra Banerjee and Prof. Anunay Samanta

      Article first published online: 17 APR 2014 | DOI: 10.1002/cphc.201400078

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      Insight into photophysics: The time-resolved and time-integrated fluorescence response of 4-aminophthalimide and its derivative does not indicate photoinduced solvent-mediated intramolecular proton transfer in protic media. Two distinct types of hydrogen-bonded complex of the molecule with the solvent are identified and a new explanation for the solvent isotope effect is suggested.

    7. Characteristic Spectral Patterns in the Carbon-13 Nuclear Magnetic Resonance Spectra of Hexagonal and Crenellated Graphene Fragments (pages 1799–1808)

      Nergiz Özcan, Jarkko Vähäkangas, Dr. Perttu Lantto and Prof. Dr. Juha Vaara

      Article first published online: 7 MAY 2014 | DOI: 10.1002/cphc.201301184

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      Flake fingerprints: Characteristic spectral profiles as well as their system-size-dependence are predicted for finite graphene and graphane/fluorographene quantum dots. The differences result from different coupling to the magnetically allowed excited states and the different boundary regions (see figure).

    8. Advances in Modeling Sorption and Diffusion of Moisture in Porous Reactive Materials (pages 1809–1820)

      Dr. Stephen J. Harley, Dr. Elizabeth A. Glascoe, Dr. James P. Lewicki and Dr. Robert S. Maxwell

      Article first published online: 12 MAY 2014 | DOI: 10.1002/cphc.201301097

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      Suck it up! Moisture-vapor-uptake experiments were performed on a silica-filled poly(dimethylsiloxane) network and modeled by using two different approaches (see figure). The data was modeled by using established methods and the model parameters were used to predict moisture uptake in a sample. A high-fidelity modeling approach is derived here and used to improve the modeling of moisture uptake and diffusion.

    9. Photochemical Behavior of Single-Walled Carbon Nanotubes in the Presence of Propylamine (pages 1821–1826)

      Prof. Yutaka Maeda, Yuhei Hasuike, Prof. Kei Ohkubo, Atsushi Tashiro, Shinya Kaneko, Masayuki Kikuta, Dr. Michio Yamada, Prof. Tadashi Hasegawa, Prof. Takeshi Akasaka , Dr. Jing Zhou, Prof. Jing Lu, Prof. Shigeru Nagase and Prof. Shunichi Fukuzumi 

      Article first published online: 2 APR 2014 | DOI: 10.1002/cphc.201301045

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      In a new light: The photochemistry of single-walled carbon nanotubes (SWNTs) in the presence of propylamine is investigated. Spectral changes due to photoirradiation indicate that reactions occur predominantly with metallic and small-diameter SWNTs. After photoreduction of the SWNTs, subsequent selective sidewall functionalization of the small-diameter SWNTs occurs (see picture).

    10. Thermodynamics of Micellization from Heat-Capacity Measurements (pages 1827–1833)

      Dr. Bojan Šarac, Prof. Dr. Marija Bešter-Rogač and Prof. Dr. Jurij Lah

      Article first published online: 23 APR 2014 | DOI: 10.1002/cphc.201400096

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      Dissection of micellization: The importance of a proper understanding and analysis of differential scanning calorimetry thermograms for thermodynamic characterization of micellization of different surfactant types is shown. The fraction of micelles (and thus heat capacity) changes upon heating a 10 mM surfactant (sodium lauroyl sarcosinate) solution (see picture). The heat-capacity peaks coincide with the critical micelle concentration values at the indicated temperatures (arrows).

    11. Operations and Thermodynamics of an Artificial Rotary Molecular Motor in Solution (pages 1834–1840)

      Dr. Lorenzo Moro, Dr. Matteo di Giosia, Dr. Matteo Calvaresi, Dr. Evangelos Bakalis and Prof. Francesco Zerbetto

      Article first published online: 21 MAY 2014 | DOI: 10.1002/cphc.201400061

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      To the end of the walk: The time-dependent properties of a stochastic system moving far from equilibrium are estimated by a theoretical approach. The process is investigated in terms of nonequilibrium thermodynamics of a molecular rotary motor (see figure). The energy path that the motor walks is obtained from atomistic calculations. The simple approach can be used to gain insight into the dynamics of any molecular-level machine.

    12. Structural Control of Hierarchically-Ordered TiO2 Films by Water for Dye-Sensitized Solar Cells (pages 1841–1848)

      Sung Hoon Ahn, Dong Jun Kim, Dr. Dong Kyu Roh, Won Seok Chi and Prof. Jong Hak Kim

      Article first published online: 9 MAY 2014 | DOI: 10.1002/cphc.201400053

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      Dye-sensitized solar cells: Crack-free, hierarchically-ordered TiO2 films with bimodal pores, high porosity, good interconnectivity, and excellent light scattering properties result in high efficiency dye-sensitized solar cells if combined with solid polymerized ionic liquids (7.7 % at 100 mW cm−2).

    13. Kinetic Modeling of α-Hydrogen Abstractions from Unsaturated and Saturated Oxygenate Compounds by Carbon-Centered Radicals (pages 1849–1866)

      Paschalis D. Paraskevas, Dr. Maarten K. Sabbe, Prof. Marie-Françoise Reyniers, Prof. Dr. Nikos Papayannakos and Prof. Dr. Guy B. Marin

      Article first published online: 14 MAY 2014 | DOI: 10.1002/cphc.201400039

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      Predicting kinetic parameters: Kinetic modeling of gas-phase hydrogen-abstraction reactions from oxygenates by carbon-centered radicals at temperatures ranging from 300 to 1500 K is examined. On the basis of high-level CBS-QB3 quantum chemical calculations and by using group additivity, an accurate set of values and corrections that account for resonance and/or hyperconjugative interactions around the forming/breaking bond is provided.

    14. Characterizing the B[BOND]P Stretching Vibration in Phosphorus-Substituted Phosphine Boranes (pages 1867–1871)

      Dana N. Reinemann, Prof. Gregory S. Tschumper and Prof. Nathan I. Hammer

      Article first published online: 25 MAR 2014 | DOI: 10.1002/cphc.201400036

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      Size does matter: The B[BOND]P stretching frequencies of phosphine boranes with bulky hydrocarbon substituents are accurately reproduced by calculations at the M06-2X/6-311G(2df, 2pd) level of theory.

    15. Spatially Selective Heteronuclear Multiple-Quantum Coherence Spectroscopy for Biomolecular NMR Studies (pages 1872–1879)

      Dr. Bharathwaj Sathyamoorthy, Dr. David M. Parish, Prof. Gaetano T. Montelione, Dr. Rong Xiao and Prof. Thomas Szyperski

      Article first published online: 30 APR 2014 | DOI: 10.1002/cphc.201301232

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      Expect longer delays: Spatially selective (SS) HMQC NMR spectroscopy is presented for solution studies of proteins. Using SS HMQC allows one to employ long delays for longitudinal nuclear spin relaxation at high repetition rates for acquisition of free induction decays. This technique is applied to uniformly 13C,15N-labeled and uniformly 2H,13C,15N-labeled (but methyl group protonated) proteins with molecular weights of 7.5 and 43 kDa.

    16. Quantum Chemical Studies on Solvents for Post-Combustion Carbon Dioxide Capture: Calculation of pKa and Carbamate Stability of Disubstituted Piperazines (pages 1880–1886)

      Satesh Gangarapu, Gerben J. Wierda, Dr. Antonius T. M. Marcelis and Prof. Han Zuilhof

      Article first published online: 29 APR 2014 | DOI: 10.1002/cphc.201301217

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      Capture if you can: Substituted piperazines with [BOND]CH2NH2 and [BOND]CH2OH at the 2- and 5-positions are better solvents for CO2 capture than the industrial solvent monoethanolamine (see picture).

    17. Mechanistic Investigation into the Cleavage of a Phosphomonoester Mediated by a Symmetrical Oxyimine-Based Macrocyclic Zinc(II) Complex (pages 1887–1898)

      Xuepeng Zhang, Xianyan Xu, Huiying Xu, Xiting Zhang, Prof. Dr. David Lee Phillips and Prof. Dr. Cunyuan Zhao

      Article first published online: 1 APR 2014 | DOI: 10.1002/cphc.201301216

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      Where does your phosphate cleave? A concentration-dependent mechanism is proposed for the cleavage of phosphomonoester NPP (4-nitrophenyl phosphate) catalyzed by a symmetrical oxyimine-based macrocyclic dinuclear zinc(II) complex. Eight individual mechanisms are provided.

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