ChemPhysChem

Cover image for Vol. 13 Issue 9

June 18, 2012

Volume 13, Issue 9

Pages 2221–2419

  1. Cover Picture

    1. Top of page
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    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Review
    7. Minireview
    8. Concept
    9. Highlight
    10. Communications
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    1. Cover Picture: Quantum-Chemical Validation of the Local Assumption of Chemomechanics for a Unimolecular Reaction (ChemPhysChem 9/2012) (page 2221)

      Dr. Yancong Tian and Prof. Roman Boulatov

      Version of Record online: 12 JUN 2012 | DOI: 10.1002/cphc.201290041

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      DFT calculations reveal a large effect of “inert” polymer linkers on how much the reactivity of a functional group (trans-3,4-substituted cyclobutene) embedded in a macromolecular chain changes when the polymer is stretched. The results, presented on p. 2277 ff. by R. Boulatov and Y. Tian, illustrate the significance of conformational entropy in governing kinetic stabilities of reactive sites in stretched polymers and suggest that extrapolating such stabilities from calculations on a single conformer, as is often done, may be unreliable.

  2. Inside Cover

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    1. Inside Cover: Spiral Intramolecular Charge Transfer and Large First Hyperpolarizability in Möbius Cyclacenes: New Insight into the Localized π Electrons (ChemPhysChem 9/2012) (page 2222)

      Rong-Lin Zhong, Dr. Hong-Liang Xu, Prof. Zhong-Min Su, Prof. Zhi-Ru Li, Dr. Shi-Ling Sun and Prof. Yong-Qing Qiu

      Version of Record online: 12 JUN 2012 | DOI: 10.1002/cphc.201290042

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      [8] Möbius cyclacene is used as a one-sided π-conjugated bridge in a donor–π-acceptor framework to induce a large intramolecular electron transfer through a spiral conjugated region, as shown on p. 2349 by H.-L. Xu, Z.-M. Su, Z.-R. Li et al.

  3. Graphical Abstract

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  4. News

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    1. A Big Event for Chemists (page 2237)

      Version of Record online: 12 JUN 2012 | DOI: 10.1002/cphc.201200418

  5. Review

    1. Top of page
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    1. Feeling Inter- or Intramolecular Interactions with the Polymer Chain as Probe: Recent Progress in SMFS Studies on Macromolecular Interactions (pages 2238–2256)

      Dr. Ningning Liu and Prof. Wenke Zhang

      Version of Record online: 23 APR 2012 | DOI: 10.1002/cphc.201200154

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      Feel the force! Recent advances in single-molecule force spectroscopic studies on inter- and intrapolymer interactions, mechanochemistry of covalent bonds, force-induced acceleration/inhibition of enzymatic reactions, polymer–interface interactions, and polymer interactions in the condensed state, by using the polymer chain as probe, are reviewed. Future opportunities and challenges are discussed.

  6. Minireview

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    1. Firefly Chemiluminescence and Bioluminescence: Efficient Generation of Excited States (pages 2257–2262)

      Dr. Luís Pinto da Silva and Prof. Dr. Joaquim C. G. Esteves da Silva

      Version of Record online: 24 APR 2012 | DOI: 10.1002/cphc.201200195

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      Efficient bio- and chemiluminescence of firefly oxyluciferin are reviewed. The thermal decomposition of firefly dioxetanones and 1,2-dioxetanes is discussed (see picture), as are their chemiexcitation mechanisms.

  7. Concept

    1. Top of page
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    1. Formation of Chiral Environments by a Mechanical Induced Vortex Flow (pages 2263–2271)

      Dr. Kunihiko Okano and Prof.Dr. Takashi Yamashita

      Version of Record online: 19 APR 2012 | DOI: 10.1002/cphc.201200003

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      Stir to chirality: Several types of supramolecular structures formed by achiral molecules exhibit chirality in a vortex flow used as a source of physical chirality. This article describes which chemical structures show chirality in stirred solutions and how they affect this phenomenon with reviewing the related studies.

  8. Highlight

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    1. Beyond Carbon Nanopeapods (pages 2273–2276)

      Dr. Humberto Terrones

      Version of Record online: 4 MAY 2012 | DOI: 10.1002/cphc.201200321

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      Fullerene peapods have opened the possibility of studying reactions in a confined space that might lead to materials which under other conditions would be impossible to synthesize. Progress has been made, but there are more challenges ahead.

  9. Communications

    1. Top of page
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    4. Graphical Abstract
    5. News
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    7. Minireview
    8. Concept
    9. Highlight
    10. Communications
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    1. Quantum-Chemical Validation of the Local Assumption of Chemomechanics for a Unimolecular Reaction (pages 2277–2281)

      Dr. Yancong Tian and Prof. Roman Boulatov

      Version of Record online: 18 APR 2012 | DOI: 10.1002/cphc.201200207

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      Localized reactions: Computations of complete conformational ensembles of cyclobutene derivatives coupled to an external constraint validate the key assumption of chemomechanics and show that while the correlation between the constraining force and reaction kinetics depends on multiple factors, including substituents and the size of the molecular moiety, coupling between local restoring force and reactivity does not.

    2. Does Water Affect the Acidity of Surfaces? The Proton-Donating Ability of Silanol and Carboxylic Acid Groups at Mesoporous Silica (pages 2282–2285)

      Andrey A. Gurinov, Dr. Daniel Mauder, Dr. Dilek Akcakayiran, Prof. Gerhard H. Findenegg and Dr. Ilya G. Shenderovich

      Version of Record online: 19 APR 2012 | DOI: 10.1002/cphc.201200204

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      Solvation at the interphase: A study of the influence of water on the effective acidity of silanol and carboxylic acid groups of propionic acid functionalized SBA-15 reveals that to affect the proton-donating ability of an acidic group at the surface, water should be able to form a solvation shell around that group. As a result, water does not affect the acidity of native SBA-15 but dramatically enhances that of SBA-15 functionalized with propionic acid moieties.

    3. Stabilizing H3: Or Are We Stabilizing a Proton? (pages 2286–2288)

      Prof. Sławomir J. Grabowski and Prof. Roald Hoffmann

      Version of Record online: 19 APR 2012 | DOI: 10.1002/cphc.201200182

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      Gestalt: The (LiHHHLi)+ cation can be looked at in two ways - as a stabilized linear H3 anion. Or as two LiH molecules stabilizing a proton. It is not certain if this interesting pentatomic cation can be detected, for it is computed to have only marginal stability with respect to decomposition to its only likely escape channel, to a complex of H2 and the LiHLi+ ion.

    4. Photocurrent Response of Surface-Functionalized Metal Oxides with Well-Matched Energy Levels: From Nothing to Something (pages 2289–2292)

      Shengxue Yang, Huiyan Ma, Yunqing Luo and Prof. Jian Gong

      Version of Record online: 8 MAY 2012 | DOI: 10.1002/cphc.201101053

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      No longer silent: A surface-functionalization method with well-matched energy levels is presented to induce UV or Vis photoresponse in semiconducting materials (see picture) that provide only weak photoresponse prior to the treatment or are completely silent. UV and Vis photoresponses of the metal oxides, Bi2O3 and V2O5, have been realized for the first time through the functionalization of their surfaces with polyaniline.

    5. Rapid Lithium Insertion and Location of Mobile Lithium in the Defect Perovskite Li0.18Sr0.66Ti0.5Nb0.5O3 (pages 2293–2296)

      William R. Brant, Dr. Siegbert Schmid, Dr. Alois Kuhn, Dr. James Hester, Dr. Maxim Avdeev, Matthew Sale and Dr. Qinfen Gu

      Version of Record online: 9 MAY 2012 | DOI: 10.1002/cphc.201200017

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      Fast and fancy: Lithium that was originally disordered within the structure of the perovskite Li0.18Sr0.66Ti0.5Nb0.5O3 can be induced into ordering within the yellow region of the unit cell by low temperatures and treatment with n-butyl-lithium. The fast kinetics of lithium insertion, in connection with a color change, make this nontoxic, air-stable material a suitable candidate for use in electrochromic systems or lithium-storage batteries.

  10. Articles

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Review
    7. Minireview
    8. Concept
    9. Highlight
    10. Communications
    11. Articles
    12. Preview
    1. The Nature of Chemical Bonds from PNOF5 Calculations (pages 2297–2303)

      Dr. Jon M. Matxain, Dr. Mario Piris , Dr. Jon Uranga, Dr. Xabier Lopez, Prof. Dr. Gabriel Merino  and Prof. Dr. Jesus M. Ugalde

      Version of Record online: 21 MAY 2012 | DOI: 10.1002/cphc.201200205

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      A localized orbital picture which agrees with chemical intuition is provided by Piris natural orbital functional in its fifth implementation (PNOF5). As an example, PNOF5 valence orbitals of ethane, ethylene, and acetylene, along with their corresponding diagonal Lagrange multipliers in Hartrees and occupation numbers in parenthesis, are shown in the picture.

    2. The Role of Effective Mass of Carrier in the Photocatalytic Behavior of Silver Halide-Based Ag@AgX (X=Cl, Br, I): A Theoretical Study (pages 2304–2309)

      Xiangchao Ma, Prof. Dr. Ying Dai, Meng Guo and Prof. Dr. Baibiao Huang

      Version of Record online: 19 APR 2012 | DOI: 10.1002/cphc.201200159

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      What′s your weight? The electronic structures and effective masses of electrons and holes in silver halides are studied. The effective mass of holes differs along different directions and with the anion of the silver halide (see picture). The effective mass characteristics of the holes can be used to understand the experimental observed morphology and anion effects on the photocatalytic activities of silver halide-based Ag@AgX (X=Cl, Br, I).

    3. Conformational Distributions of N-Acetyl-L-cysteine in Aqueous Solutions: A Combined Implicit and Explicit Solvation Treatment of VA and VCD Spectra (pages 2310–2321)

      Mohammad Reza Poopari, Zahra Dezhahang, Prof. Dr. Guochun Yang and Prof. Dr. Yunjie Xu

      Version of Record online: 27 APR 2012 | DOI: 10.1002/cphc.201200152

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      Role models: N-Acetylcysteine is investigated in aqueous solutions of different pH values using vibrational absorption and vibrational circular dichroism spectroscopy in combination with ab initio and molecular dynamics calculations. Implicit and explicit solvation models, the latter based on small water-solvated clusters (see picture), are systematically evaluated to derive detailed conformational distributions.

    4. On the Electrochemistry and Spectroelectrochemistry of Small Model Star-Shaped Compounds: 1,3,5-Triaryl-1-Methoxybenzenes and 2,4,6-Triaryl-1,3,5-Trimethoxybenzenes (pages 2322–2330)

      Dr. Peter Rapta , Dr. Vladimír Lukeš , Dr. Krzysztof R. Idzik , Prof. Rainer Beckert and Prof. Lothar Dunsch

      Version of Record online: 13 MAY 2012 | DOI: 10.1002/cphc.201200127

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      Redox-active, cross-linked, hyperbranched polymers: On oxidative polymerization of various 1,3,5-trithienylbenzenes with methoxy-substituted benzene cores, C[BOND]C coupling of the thienyl substituents leads to a variety of oligomeric structures, as revealed inter alia by cyclic voltammetry (see picture; C green, H gray, O red, S yellow).

    5. You have full text access to this OnlineOpen article
      An ATR-FTIR Study on the Effect of Molecular Structural Variations on the CO2 Absorption Characteristics of Heterocyclic Amines, Part II (pages 2331–2341)

      Kelly Robinson , Prof. Adam McCluskey and Dr. Moetaz I. Attalla

      Version of Record online: 19 APR 2012 | DOI: 10.1002/cphc.201200066

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      Carbon dioxide fixation by absorption in aqueous solutions of heterocyclic diamines (hexahydropyrimidine, 2-methyl- and 2,2-dimethylhexahydropyrimidine, hexahydropyridazine, piperazine and 2,5- and 2,6-dimethylpiperazine) is studied by ATR-FTIR spectroscopy (see picture).

    6. CuO/ZnO Nanocomposite Gas Sensors Developed by a Plasma-Assisted Route (pages 2342–2348)

      Dr. Quentin Simon, Dr. Davide Barreca, Dr. Alberto Gasparotto, Dr. Chiara Maccato, Prof. Eugenio Tondello, Dr. Cinzia Sada, Dr. Elisabetta Comini, Prof. Giorgio Sberveglieri, Dr. Manish Banerjee, Dr. Ke Xu, Prof. Anjana Devi and Prof. Roland A. Fischer

      Version of Record online: 24 APR 2012 | DOI: 10.1002/cphc.201101062

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      Trapped in the array: High-purity p-type CuO/n-type ZnO nanocomposites were prepared by Cu sputtering on columnar ZnO arrays obtained by plasma-enhanced chemical vapor deposition, followed by annealing in air. Preliminary gas-sensing tests revealed very attractive responses, along with the possibility of discriminating between oxidizing and reducing species.

    7. Spiral Intramolecular Charge Transfer and Large First Hyperpolarizability in Möbius Cyclacenes: New Insight into the Localized π Electrons (pages 2349–2353)

      Rong-Lin Zhong, Dr. Hong-Liang Xu, Prof. Zhong-Min Su, Prof. Zhi-Ru Li, Dr. Shi-Ling Sun and Prof. Yong-Qing Qiu

      Version of Record online: 21 MAY 2012 | DOI: 10.1002/cphc.201200213

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      Spiral π bridge: [8]Möbius cyclacene is used as a one-sided π-conjugated bridge in a donor–π–acceptor framework to induce large intramolecular electron transfer. For example, NH2-6-[8]MC-10-NO2 (see picture) shows dramatic enhancement of the first hyperpolarizability β0, because the difference in dipole moments Δμ between the ground and the crucial excited states is significantly increased.

    8. Surface Defects Activating New Reaction Paths: Formation of Formate during Methanol Oxidation on Ru(0001) (pages 2354–2360)

      Dr. Irene Palacio, Prof. Juan M. Rojo and Dr. Oscar Rodríguez de la Fuente

      Version of Record online: 19 APR 2012 | DOI: 10.1002/cphc.201200190

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      The discreet charm of imperfections: A new reaction path emerges during methanol oxidation on Ru(0001) when the surface has a high concentration of surface defects, namely the formation of formate (see graphic).

    9. Structural Characteristics of Graphane-Type C and BN Nanostructures by Periodic Local MP2 Approach (pages 2361–2367)

      Dr. Jukka T. Tanskanen, Dr. Lorenzo Maschio, Dr. Antti J. Karttunen, Dr. Mikko Linnolahti and Prof. Tapani A. Pakkanen

      Version of Record online: 21 MAY 2012 | DOI: 10.1002/cphc.201200189

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      Layer-up: Quantum chemical methods are used to investigate the structural characteristics of fully-hydrogenated monolayers and nanotubes of both C and BN, placing particular emphasis on the potential of the nanostructures to form multilayered structures analogous to graphite and h-BN. The energetic preference of the nanostructures for existing as multilayered structures (see picture) is demonstrated.

    10. Calixarene-Based Surfactants: Conformational-Dependent Solvation Shells for the Alkyl Chains (pages 2368–2376)

      Dr. Nuno Basílio and Prof. Dr. Luis Garcia-Rio

      Version of Record online: 21 MAY 2012 | DOI: 10.1002/cphc.201200175

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      Stand out from the crowd: A microcalorimetric study on the aggregation of amphiphilic calix[n]arenes provided detailed information about the hydration of the hydrophobic alkyl chain in this special class of surfactants and supported previous observations of preorganization effects contributing to the free energy of micellization in these amphiphiles (see picture).

    11. An MO-Based Identification of Charge-Shift Bonds (pages 2377–2381)

      Renana Gershoni-Poranne and Prof. Amnon Stanger

      Version of Record online: 4 JUN 2012 | DOI: 10.1002/cphc.201200147

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      A shift in bond: The difference between Hartree–Fock and CI energies of isodesmic reactions serves as a tool for identifying charge-shift bonds.

    12. Ion-Specific Aggregation of Hydrophobic Particles (pages 2382–2391)

      Dr. Teresa López-León, Dr. Juan Luis Ortega-Vinuesa and Dr. Delfina Bastos-González

      Version of Record online: 3 MAY 2012 | DOI: 10.1002/cphc.201200120

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      Aggregation kinetics of a polystyrene latex is detected by means of changes in the intensity of light scattered at 5°. The salt concentration was always constant, set at 600 mM (see picture), but the nature of the anions was changed: NaCl (blue triangles), NaNO3 (cyan circles), NaSCN (green squares), and Na2SO4 (red stars).

    13. Mechanisms of Silicon Alkoxide Hydrolysis–Oligomerization Reactions: A DFT Investigation (pages 2392–2404)

      Xueli Cheng, Prof. Dr. Dairong Chen and Prof. Dr. Yongjun Liu

      Version of Record online: 23 APR 2012 | DOI: 10.1002/cphc.201200115

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      Overcoming barriers: The hydrolysis–oligomerization mechanisms of silicon alkoxides in neutral, acidic (see picture), and alkaline solutions were revealed with density functional theory calculations.

    14. Combination of DQ and ZQ Coherences for Sensitive Through-Bond NMR Correlation Experiments in Biosolids under Ultra-Fast MAS (pages 2405–2411)

      Dr. Amy L. Webber, Dr. Andrew J. Pell, Emeline Barbet-Massin, Dr. Michael J. Knight, Prof. Ivano Bertini, Prof. Isabella C. Felli, Prof. Roberta Pierattelli, Prof. Lyndon Emsley, Dr. Anne Lesage and Dr. Guido Pintacuda

      Version of Record online: 23 APR 2012 | DOI: 10.1002/cphc.201200099

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      Multitasking: The implementation of a new scheme for through-bond correlations in solids is presented, which provides remarkable transfer efficiencies, by simultaneous detection of multiple-quantum coherences, and improved resolution, by integrating a virtual J-decoupling block (see picture). The application to a microcrystalline protein sample is presented.

    15. Low-Temperature Route to Crystalline Titania Network Structures in Thin Films (pages 2412–2417)

      Monika Rawolle, Erik V. Braden, Martin A. Niedermeier, David Magerl, Kuhu Sarkar, Thomas Fröschl, Prof. Nicola Hüsing, Dr. Jan Perlich and Prof. Peter Müller-Buschbaum

      Version of Record online: 21 MAY 2012 | DOI: 10.1002/cphc.201200056

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      Less is more: A low temperature route to crystalline titania nanostructures is presented. Deliberate tailoring of the nanostructures obtained from an ethylene glycol-modified titanate precursor on large sample areas is achieved by combining sol-gel chemistry with a block-copolymer template. Annealing at 90 °C only leads to a well-defined crystalline titania network structure, as probed with scanning electron microscopy (see picture).

  11. Preview

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Review
    7. Minireview
    8. Concept
    9. Highlight
    10. Communications
    11. Articles
    12. Preview
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      Preview: ChemPhysChem 10/2012 (page 2419)

      Version of Record online: 12 JUN 2012 | DOI: 10.1002/cphc.201290045

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