ChemPlusChem

Cover image for Vol. 79 Issue 8

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

Editor: Neville Compton, Deputy Editor: Marisa Spiniello

Impact Factor: 3.242

ISI Journal Citation Reports © Ranking: 2013: 38/148 (Chemistry Multidisciplinary)

Online ISSN: 2192-6506

Associated Title(s): Angewandte Chemie International Edition, Chemistry - A European Journal

VIEW

  1. 1 - 65
  1. Full Papers

    1. Functionalized Tri- and Tetraphosphine Ligands as a General Approach for Controlled Implantation of PhosphorusDonors with a High Local Density in Immobilized Molecular Catalysts

      Dr. Matthieu Beaupérin, Dr. Radomyr Smaliy, Dr. Hélène Cattey, Prof. Dr. Philippe Meunier, Dr. Jun Ou, Prof. Dr. Patrick H. Toy and Prof. Dr. Jean-Cyrille Hierso

      Article first published online: 26 AUG 2014 | DOI: 10.1002/cplu.201402195

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      Lean on Me: Modular formation of functionalized polyphosphines is a general solution for generating localized high-density phosphorus donors on supports. The conformational arrangement of P donors in the immobilized catalysts is evidenced by 31P NMR spectroscopic “through-space” coupling. Pd-catalyzed direct C[BOND]H arylation of heteroaromatics with chloroarenes illustrates the performance of these polydentate catalytic materials.

  2. Interviews

    1. You have free access to this content
      Rie Makiura

      Article first published online: 22 AUG 2014 | DOI: 10.1002/cplu.201402168

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      My favorite time of day is when I sit in my desk in the early morning and begin to check calmly the new results from my research group. Young people should study chemistry because understanding chemistry makes our life richer as we are surrounded by materials created from chemical reactions.

  3. Full Papers

    1. Well-Aligned Quaternary Cu2CoSnS4 Single-Crystalline Nanowires as a Potential Low-Cost Solar Cell Material

      Prof. Liang Shi, Yanan Li, Haojun Zhu and Prof. Quan Li

      Article first published online: 21 AUG 2014 | DOI: 10.1002/cplu.201402172

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      Down to the wire: Ordered single-crystalline Cu2CoSnS4 nanowires with a [112] growth direction are described. An optimal solvent of diethylenetriamine is critical for the formation of single-crystalline Cu2CoSnS4 nanowires (see figure). A thin film prepared from Cu2CoSnS4 single-crystalline nanowires displays a clear photoelectric response, which suggests potential applications in photovoltaic devices.

  4. Communications

    1. Light-Accelerated Biocatalytic Oxidation Reactions

      Dr. Svenja Kochius, Dr. Yan Ni, Dr. Selin Kara, Serena Gargiulo, Prof. Dr. Jens Schrader, Dr. Dirk Holtmann and Dr. Frank Hollmann

      Article first published online: 21 AUG 2014 | DOI: 10.1002/cplu.201402152

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      Let the sunshine in: Simple illumination with visible light can significantly accelerate the activity of laccase mediator systems (LMSs). Illumination can have a dramatic effect on LMS-mediated regeneration of oxidized nicotinamide adenine dinucleotide (phosphate) (NAD(P)+) cofactors (see scheme).

    2. Enhanced Penetration of Silver Nanocomposite Assemblies into Dentine Using Iontophoresis: Toward the Treatment of Dental Caries

      Dr. Donald R. Schwass and Dr. Carla J. Meledandri

      Article first published online: 19 AUG 2014 | DOI: 10.1002/cplu.201402132

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      A silver bullet? A simple but effective electrophoretic method has been developed for the enhanced delivery and retention of antibacterial silver nanoparticle-based materials to dentine tubules (see figure). This innovative approach may lead to more successful management of tooth decay, without the corresponding staining effects caused through the use of silver compounds.

  5. Full Papers

    1. Very Important Paper

      5-(1H-Tetrazolyl)-2-Hydroxy-Tetrazole: A Selective 2N-Monoxidation of Bis(1H-Tetrazole)

      Prof. Dr. Thomas M. Klapötke, Matthias Q. Kurz, Regina Scharf, Philipp C. Schmid, Jörg Stierstorfer and Dr. Muhamed Sućeska

      Article first published online: 19 AUG 2014 | DOI: 10.1002/cplu.201402124

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      Energetic materials: Following the recent trend in the synthesis of new energetic materials with high densities and stabilities, the first bistetrazole 2N-monoxide was prepared (see figure). 5-(1H-Tetrazolyl)-2-hydroxy-tetrazole and several energetic salts were synthesized, characterized, and compared with RDX and other energetic tetrazole-N-oxides.

    2. Nanoparticles

      Surface-Enhanced Raman Scattering (SERS) Substrate Based on Large-Area Well-Defined Gold Nanoparticle Arrays with High SERS Uniformity and Stability

      Yan Zheng, Wenxin Wang, Dr. Qun Fu, Dr. Minghong Wu, Kamran Shayan, Dr. Kin Mun Wong, Dr. Sukhdeep Singh, Prof. Andreas Schober, Prof. Peter Schaaf and Prof. Yong Lei

      Article first published online: 19 AUG 2014 | DOI: 10.1002/cplu.201402154

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      Insane for the membrane: Surface-enhanced Raman scattering (SERS) substrates with high uniformity and stability have been achieved based on large-area well-defined gold nanoparticle arrays, which can be obtained by a fabrication process that combines an ultrathin alumina membrane surface nanopatterning technique and physical vapor deposition (see figure). An advantageous feature of such a SERS substrate is its long-term stability.

    3. Development and Potential Theranostic Applications of a Self-Assembled Hybrid of Magnetic Nanoparticle Clusters with Polysaccharide Nanogels

      Prof. Kiyofumi Katagiri , Keiko Ohta, Kaori Sako, Prof. Kei Inumaru, Dr. Koichiro Hayashi , Prof. Yoshihiro Sasaki and Prof. Kazunari Akiyoshi 

      Article first published online: 19 AUG 2014 | DOI: 10.1002/cplu.201402159

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      Inside job: Self-assembled hybrids were prepared by incorporating Fe3O4 nanoparticle clusters in a polysaccharide nanogel (see scheme). The hybrid showed high colloidal stability and dispersibility in aqueous media, and displayed theranostic potential as a magnetic resonance imaging (MRI) contrast agent and in magnetic hyperthermia therapy.

    4. Photocatalytic Generation of Hydrogen from Water under Aerobic Conditions

      Robert Staehle, Dr. Sebastian Losse, Dr. Milos R. Filipovic, Prof. Dr. Ivana Ivanović-Burmazović, Prof. Dr. Johannes G. Vos and Prof. Dr. Sven Rau

      Article first published online: 14 AUG 2014 | DOI: 10.1002/cplu.201402174

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      Water reduction: A detailed investigation of a photocatalytic system capable of producing hydrogen under aerobic conditions (see figure) is reported. This system consists of a nitrile-functionalized chromophore, [Co(dmgH)2] (dmgH=dimethylglyoximato) as the reduction catalyst and triethylamine as the electron donor. Surprisingly, the system shows a higher catalytic activity under aerobic than under inert conditions.

  6. Cover Pictures

    1. Major Influence of the Substituent Size and Position of 3,4-Propylenedioxythiophene on the Formation of Highly Hydrophobic Nanofibers

      Claudio Mortier, Dr. Thierry Darmanin and Prof. Frédéric Guittard

      Article first published online: 14 AUG 2014 | DOI: 10.1002/cplu.201402250

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      The back cover picture shows the huge influence of substituent position and size on the formation of surface structures, in this case nanofibers, and the resulting surface hydrophobicity by electrodeposition of substituted poly(3,4-propylenedioxythiophene). Details are given in the Full Paper (DOI: 10.1002/cplu.201402187) by Frédéric Guittard and co-workers.

  7. Full Papers

    1. Synthesis of Cross-Linked Glycopeptides and Ureas by a Mechanochemical, Solvent-Free Reaction and Determination of Their Structural Properties by TEM and X-ray Crystallography

      Vajinder Kumar, Santosh Kumar Giri, Prof. Dr. Paloth Venugopalan and Prof. Dr. K. P. Ravindranathan Kartha

      Article first published online: 12 AUG 2014 | DOI: 10.1002/cplu.201402185

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      Just milling around! A highly efficient, cost-effective, green method for the synthesis of complex glycopeptides and ureas mediated by N,N′-carbonyldiimidazole under solvent-free conditions is reported (see picture). The reactions are performed by dry grinding and isolation of the sugar derivatives is efficiently achieved by size exclusion chromatography with environmentally benign substances.

    2. Light-Triggered Green Fluorescent Protein Silencing in Human Keratinocytes in Culture Using Antisense Oligonucleotides Coupled to a Photoreactive Ruthenium(II) Complex

      Dr. Lionel Marcélis, Dr. Nancy Van Overstraeten-Schlögel, Javiera Lambermont, Dr. Sébastien Bontems, Dr. Nicolas Spinelli, Prof. Eric Defrancq, Prof. Cécile Moucheron, Prof. Andrée Kirsch-De Mesmaeker and Prof. Martine Raes

      Article first published online: 8 AUG 2014 | DOI: 10.1002/cplu.201402212

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      Silence, please: The specific ruthenium(1,4,5,8-tetraazaphenanthrene)–antisense oligodeoxyribonucleotide (Ru(TAP)–ASO) conjugate is able to significantly reduce green fluorescent protein (GFP) expression after Ru–ASO visible excitation in treated cells (see figure).

    3. A Vanadium–Cerium Redox Flow Battery with an Anion-Exchange Membrane Separator

      Sukhwan Yun, Dr. Javier Parrondo and Prof. Vijay Ramani

      Article first published online: 8 AUG 2014 | DOI: 10.1002/cplu.201402096

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      Membranes in charge: Quaternized cardo-poly(etherketone) (QPEK-C) anion-exchange membranes (AEMs) have been prepared and employed as a separator in a redox flow battery [carbon felt|V3+, V2+ (0.5 M)||carbon felt|Ce4+, Ce3+ (0.5 M)]. The low cation permeability of the AEM together with its good mechanical and chemical stability give this material improved coulombic efficiency (CE) and energy efficiency (EE) during cycling (see figure).

    4. Interplay between Resonance-Assisted Hydrogen Bonding and Coordination in Sulfo-Functionalized Arylhydrazones of Active Methylene Compounds

      Dr. Kamran T. Mahmudov, Dr. Maximilian N. Kopylovich, Prof. M. Fátima C. Guedes da Silva and Prof. Armando J. L. Pombeiro

      Article first published online: 8 AUG 2014 | DOI: 10.1002/cplu.201402088

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      E/Z resolution: Hydrogen bonding and coordination can interact towards isomeric resolution and preparation of different types of coordination compounds (see scheme).

  8. Communications

    1. Highly Twisted 1,2:8,9-Dibenzozethrenes: Synthesis, Ground State, and Physical Properties

      Dr. Zhe Sun, Dr. Bin Zheng, Pan Hu, Prof. Kuo-Wei Huang and Prof. Jishan Wu

      Article first published online: 8 AUG 2014 | DOI: 10.1002/cplu.201402127

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      Twisted zethrene! Highly twisted 1,2:8,9-dibenzozethrenes are synthesized and isolated in crystalline form (see figure). They are found to have a small biradical character with a small energy gap, showing NIR emission and amphoteric redox behavior.

  9. Cover Pictures

    1. Diethyl Tartrate Linked Chiral Macrocyclic Manganese(III)–Salen Complex for Enantioselective Epoxidation of Olefins and Oxidative Kinetic Resolution of Racemic Secondary Alcohols

      Nabin Ch. Maity, Prasanta Kumar Bera, S. Saravanan , Dr. Sayed H. R. Abdi , Dr. Rukhsana I. Kureshy , Dr. Noor-ul H. Khan  and Dr. Hari C. Bajaj 

      Article first published online: 6 AUG 2014 | DOI: 10.1002/cplu.201402207

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      The front cover picture shows a single metal complex that can catalyse asymmetric epoxidation of non-functionalised olefins as well as the oxidative kinetic resolution of racemic alcohols with great ease. In this way the use of expensive homogeneous catalyst can be maximised by carrying out two asymmetric organic transformations. Details are given in the Full Paper (DOI: 10.1002/cplu.201402131) by Sayed H. R. Abdi and co-workers.

  10. Cover Profiles

    1. You have free access to this content
      Diethyl Tartrate Linked Chiral Macrocyclic Manganese(III)–Salen Complex for Enantioselective Epoxidation of Olefins and Oxidative Kinetic Resolution of Racemic Secondary Alcohols

      Nabin Ch. Maity, Prasanta Kumar Bera, S. Saravanan , Dr. Sayed H. R. Abdi , Dr. Rukhsana I. Kureshy , Dr. Noor-ul H. Khan  and Dr. Hari C. Bajaj 

      Article first published online: 6 AUG 2014 | DOI: 10.1002/cplu.201402205

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      we strive to understand the mechanism involved in catalytic cycles in order to further modify the catalytic processes” This and more about the story behind the cover in the Cover Profile and about the research itself on page (DOI: 10.1002/cplu.201402131).

  11. Full Papers

    1. Ionic-Liquid-Functionalized Polyoxometalates for Heterogeneously Catalyzing the Aerobic Oxidation of Benzene to Phenol: Raising Efficacy through Specific Design

      Zhouyang Long, Dr. Yu Zhou, Weilin Ge, Guojian Chen, Jingyan Xie, Qian Wang and Prof. Jun Wang

      Article first published online: 6 AUG 2014 | DOI: 10.1002/cplu.201402186

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      Reuse and recycle: Tuning functional groups on cations of ionic liquid–molybdovanadophosphoric acid (IL-PMoV2) hybrids leads to a reusable heterogeneous catalyst for the aerobic oxidation of benzene to phenol. The phenol yield was 13.0 % under optimized reaction conditions with catalyst derived from 1,1′-(butane-1,4-diyl)-bis(3-cyanopyridine) ([D-3-CNPy]2; see figure).

    2. Shape-Controlled Synthesis of Monodispersed Ultrasmall CaGd3F11 Nanocrystals for Potential Dual-Modal Probes

      Prof. Yang Tian, Hong-Yu Yang, Shanshan Yu and Prof. Xia Li

      Article first published online: 6 AUG 2014 | DOI: 10.1002/cplu.201402085

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      Small wonder: High-quality CaGd3F11 nanoparticles and nanorods were synthesized by means of a solvothermal method for the first time. The nanocrystals were monodispersed and an ultrasmall size. Moreover, shape-dependent upconversion luminescence and magnetic resonance imaging properties of dual-modal nanoprobes for the nanocrystals were studied for their performance enhancement (see figure).

    3. Function of Metals and Supports on the Hydrodeoxygenation of Phenolic Compounds

      Ayillath K. Deepa and Dr. Paresh L. Dhepe

      Article first published online: 6 AUG 2014 | DOI: 10.1002/cplu.201402145

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      Hydrodeoxygenation of bio-oils: The influence of supports (acidic, neutral, and basic) and the catalytic performances of noble metals (Pd, Pt, and Ru) are studied in terms of their hydrodeoxygenation (HDO) activity on lignin-derived phenolic monomers such as phenol, guaiacol, and eugenol at 523 K and 3 MPa H2 pressure (see figure).

    4. Tuning the Mechanical and Adsorption Properties of Silica with Graphene Oxide

      Dr. Vivek K. Singh, M. Erkin Cura, Dr. Xuwen Liu, Dr. Leena-Sisko Johansson, Dr. Yanling Ge and Prof. Dr. Simo-Pekka Hannula

      Article first published online: 30 JUL 2014 | DOI: 10.1002/cplu.201402138

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      Get set, GO! Silica/graphene oxide (GO) composite powders of various compositions have been synthesized and compacted by spark plasma sintering. The optical and mechanical properties of silica were tuned by varying the GO content (see figure). Improved fracture toughness occurred with increasing amount of GO. Powders were also applied to Cu removal from water; the adsorption properties of silica were improved with a high concentration of GO.

    5. The Oxygen Reduction Reaction in Ferrofluids: Towards Membrane-less and Spill-less Gas Sensors

      Dr. Janjira Panchompoo, Mengchen Ge, Dr. Chuan Zhao, Dr. May Lim and Dr. Leigh Aldous

      Article first published online: 30 JUL 2014 | DOI: 10.1002/cplu.201402105

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      Spill-less droplets: An aqueous ferrofluid based upon poly(diallyldimethyl ammonium chloride)-coated maghemite (γ-Fe2O3) iron oxide nanoparticles can be used on disposable screen-printed electrodes to create simple membrane-less and spill-less gas sensors (see figure). Apparent electrocatalysis towards the oxygen reduction reaction is observed owing to the polymer; an applied magnetic field strength both immobilises the electrolyte and enhances the oxygen reduction current.

  12. Communications

    1. Mechanical Model of Globular Transition in Polymers

      Dr. Simon Tricard, Dr. Robert F. Shepherd, Dr. Claudiu A. Stan, Dr. Phillip W. Snyder, Dr. Rebecca Cademartiri, Danny Zhu, Dr. Igor S. Aranson, Prof. Eugene I. Shakhnovich and Prof. George M. Whitesides

      Article first published online: 30 JUL 2014 | DOI: 10.1002/cplu.201402203

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      Different phases: A millimeter-scale granular model of coil-to-globule transitions: one “polymer” chain—a cylinders-on-a-string “pearl necklace”—and many spheres, all shaken on a horizontal surface, is described by using formalisms generally applied in statistical physics of polymers, namely, first- and second-order coil-to-globule transitions, to give insight into molecular behavior through granular experiments (see picture).

    2. You have full text access to this OnlineOpen article
      Stratified Dipole-Arrays Model Accounting for Bulk Properties Specific to Perfluoroalkyl Compounds

      Prof. Takeshi Hasegawa, Dr. Takafumi Shimoaka, Nobutaka Shioya, Kohei Morita, Prof. Masashi Sonoyama, Dr. Toshiyuki Takagi and Dr. Toshiyuki Kanamori

      Article first published online: 30 JUL 2014 | DOI: 10.1002/cplu.201402156

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      Chain effects: A perfluoroalkyl (Rf) group with (CF2)9 or longer spontaneously aggregates in a hexagonal manner through the stratified dipole-arrays aggregation mechanism, which explains Rf-specific bulk properties (see picture).

  13. Full Papers

    1. Electrochemical Characterization of Gel Electrolytes for Aqueous Lithium-Ion Batteries

      Dr. Jelena Stojadinović, Anastasiya Dushina, Dr. Rafael Trócoli and Dr. Fabio La Mantia

      Article first published online: 30 JUL 2014 | DOI: 10.1002/cplu.201402143

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      Opening the window: Gelation of 2 M Li2SO4 with carboxymethyl cellulose (CMC) and agar results in the augmentation of the electrochemical stability window ΔE (see figure) relative to that of the liquid electrolyte, and in the reduction of the electrolyte ionic conductivity.

    2. Au–Co3O4/C as an Efficient Electrocatalyst for the Oxygen Evolution Reaction

      Zhuo-ying Li, Kai-hang Ye, Qi-sui Zhong, Chan-juan Zhang, Shu-ting Shi and Dr. Chang-wei Xu

      Article first published online: 28 JUL 2014 | DOI: 10.1002/cplu.201402136

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      What a bind! The electron binding energy of Co 2p shows a positive shift of about 0.89 eV after loading with Au (see figure). Such a big shift in binding energy promotes the formation of CoIV and increases the population of active centers on the catalyst surface. Gold, a highly electronegative metal, acts as an electron adsorbate, which facilitates the deprotonation of the OOH species by an electron inductive effect.

    3. Lithium–Air Oxygen Shuttle Battery with a ZrO2-Based Ion-Conducting Oxide Electrolyte

      Dr. Atsushi Inoishi, Maki Matsuka, Prof. Takaaki Sakai, Dr. Young-Wan Ju, Prof. Shintaro Ida and Prof. Tatsumi Ishihara

      Article first published online: 28 JUL 2014 | DOI: 10.1002/cplu.201402041

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      Full of hot air! A lithium–air cell based on the concept of an “oxygen shuttle” in a calcium-stabilized ZrO2 (CSZ) electrolyte is described. The observed open-circuit voltage and discharge capacity are 1.81 V and 2179 mAh per gram of Li, respectively, at 1073 K (see picture). The observed overpotential in the anode is similar to that in a Mg–air cell reported previously, and much smaller than that of a H2–air fuel cell.

  14. Communications

    1. PEG600-Carboxylates as Efficient Reusable Reaction Media and Acylating Agents for the Resolution of sec-Alcohols

      Dr. Carlos M. Monteiro, Dr. Nuno M. T. Lourenço, Dr. Frederico C. Ferreira and Prof. Dr. Carlos A. M. Afonso

      Article first published online: 28 JUL 2014 | DOI: 10.1002/cplu.201402049

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      Simple and common: We describe a simple, attractive, and reusable methodology for one-pot resolution/separation of free sec-alcohols by the combination of sustainable acylating agents/solvents (polyethylene glycol derivatives) and a common biocatalyst (Candida antarctica lipase B) under irreversible conditions, and a separation process by extraction or distillation (see figure).

  15. Minireviews

    1. Next-Generation, High-Energy-Density Redox Flow Batteries

      Qizhao Huang and Dr. Qing Wang

      Article first published online: 25 JUL 2014 | DOI: 10.1002/cplu.201402099

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      Go with the flow: The latest advances in redox flow battery (RFB) related technologies are highlighted in the context of a few decades of development. The technology has mainly advanced through a process of enlarging the electrochemical window by using organic solvents and replacing liquid electrolytes with solid or semisolid materials (see picture).

  16. Full Papers

    1. Synthesis of Bright Alkenyl-1H-1,2,4-triazoles: A Theoretical and Photophysical Study

      Dr. Cristina Cebrián, Dr. Juan de Mata Muñoz, Dr. Cristian Alejandro Strassert, Dr. Pilar Prieto, Prof. Ángel Díaz-Ortiz, Prof. Luisa De Cola and Prof. Antonio de la Hoz

      Article first published online: 23 JUL 2014 | DOI: 10.1002/cplu.201402153

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      Bright 1H-1,2,4-triazoles: A series of alkenyl-1H-1,2,4-triazoles has been synthesized by the eco-friendly Hiyama coupling under microwave irradiation (see figure). The compounds are good blue emitters, with their photophysical properties dependent on the substituent pattern. The emission was modeled computationally, which resulted in a predictive method that could be used for the a priori evaluation of the emissive properties from new related compounds.

  17. Cover Profiles

    1. You have free access to this content
      Dithienopyrrole-/Benzodithiophene-Based Donor–Acceptor Polymers for Memristor

      Cheng Wang, Prof. Dr. Gang Liu, Prof. Dr. Yu Chen, Shanshan Liu, Prof. Dr. Qibin Chen, Prof. Dr. Runwei Li and Dr. Bin Zhang

      Article first published online: 22 JUL 2014 | DOI: 10.1002/cplu.201402204

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      we are proceeding to develop biocompatible and implantable memristive polymers, which show the possibility of repairing or replacing human nerve cells ” This and more about the story behind the cover in the Cover Profile and about the research itself on page (DOI: 10.1002/cplu.201402133).

  18. Full Papers

    1. A New Class of Phase-Selective Synthetic β-Amino Acid Based Peptide Gelator: From Mechanistic Aspects to Oil Spill Recovery

      Maruthi Konda, Indrajit Maity, Dnyaneshwar B. Rasale and Dr. Apurba K. Das

      Article first published online: 22 JUL 2014 | DOI: 10.1002/cplu.201402120

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      Pick and choose: The mechanistic aspects of supramolecular ordering of a nanoscale β-amino acid based phase-selective peptide gelator are reported. Furthermore, the phase-selective gelation process is efficiently used for oil spill recovery.

  19. Cover Pictures

    1. B12-TiO2 Hybrid Catalyst for Light-Driven Hydrogen Production and Hydrogenation of C[BOND]C Multiple Bonds

      Prof. Dr. Hisashi Shimakoshi and Prof. Dr. Yoshio Hisaeda

      Article first published online: 18 JUL 2014 | DOI: 10.1002/cplu.201402216

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      The back cover picture shows a schematic image of the hybrid catalyst composed of titanium oxide and metal complex derived from naturally occurring B12 (cobalamin). This hybrid catalyst shows catalysis for hydrogen evolution and alkene reduction under UV irradiation under mild conditions of room temperature, ordinary pressure, and with water or alcohol as solvent. In their Communication (DOI: 10.1002/cplu.201402081), Hisashi Shimakoshi and Yoshio Hisaeda show the synergistic effect of the naturally occurring cobalamin derivative and inorganic TiO2 in unique catalysis of the metal complex–semiconductor hybrid system.

  20. Full Papers

    1. You have full text access to this OnlineOpen article
      Towards Rational Modulation of In-Plane Molecular Arrangements in Metal–Organic Framework Nanosheets

      Dr. Rie Makiura, Ryo Usui, Yuta Sakai, Dr. Akihiro Nomoto, Prof. Akiya Ogawa, Prof. Osami Sakata and Dr. Akihiko Fujiwara

      Article first published online: 18 JUL 2014 | DOI: 10.1002/cplu.201402150

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      Nanosheets at the interface: Modulation of the in-plane molecular arrangement in highly crystalline metal–organic framework (MOF) nanosheets assembled by two-dimensional interfacial reactions of porphyrins and metal linkers at the air/liquid interface was demonstrated (see picture).

  21. Cover Pictures

    1. Dithienopyrrole-/Benzodithiophene-Based Donor–Acceptor Polymers for Memristor

      Cheng Wang, Prof. Dr. Gang Liu, Prof. Dr. Yu Chen, Shanshan Liu, Prof. Dr. Qibin Chen, Prof. Dr. Runwei Li and Dr. Bin Zhang

      Article first published online: 18 JUL 2014 | DOI: 10.1002/cplu.201402206

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      The cover picture shows fundamental passive circuit elements of resistor, capacitor, inductor and memristor and the correlations between the circuit variables. Memristor has been considered capable of mimicking the function of a mammalian synapse with the ability to learn and memorize new information, and to allow powerful and energy-efficient processing capability for complex open-ended computing tasks. Details are given in the Full Paper (DOI: 10.1002/cplu.201402133) by Y. Chen and co-workers.

  22. Communications

    1. Structure-Dependent Selective Hydrogenation of α,β-Unsaturated Aldehydes over Platinum Nanocrystals Decorated with Nickel

      Zhi Jiang, Dr. Yonghui Zhao, Dr. Lingzhao Kong, Dr. Ziyu Liu, Prof. Yan Zhu and Prof. Yuhan Sun

      Article first published online: 17 JUL 2014 | DOI: 10.1002/cplu.201402109

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      Taking sides: Pt3Ni cubes with six (100) surfaces enhanced the selectivity of C[DOUBLE BOND]O bond hydrogenation and suppressed the selectivity of C[DOUBLE BOND]C bond hydrogenation, whereas an octahedron with closely packed (111) surfaces (see figure), regardless of whether it is Pt, Pt3Ni, or PtNi, is an unfavorable structure for C[DOUBLE BOND]O hydrogenation.

  23. Full Papers

    1. One-Step Approach to 2,5-Diformylfuran from Fructose by Using a Bifunctional and Recyclable Acidic Polyoxometalate Catalyst

      Ruliang Liu, Prof. Dr. Jinzhu Chen, Dr. Limin Chen, Yuanyuan Guo and Jiawei Zhong

      Article first published online: 17 JUL 2014 | DOI: 10.1002/cplu.201402147

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      Balance of sites: A one-step approach to 2,5-diformylfuran from fructose is achieved with Cs3HPMo11VO40 as a bifunctional, recyclable catalyst with molecular oxygen as oxidant under environmentally benign conditions (see picture). Cs3HPMo11VO40 behaves as a heterogeneous catalyst and can be easily reused.

  24. Minireviews

    1. Implications of the Unpaired Spins in Li–O2 Battery Chemistry and Electrochemistry: A Minireview

      Dr. Kah Chun Lau, Dr. Jun Lu, Xiangyi Luo, Dr. Larry A. Curtiss and Dr. Khalil Amine

      Article first published online: 17 JUL 2014 | DOI: 10.1002/cplu.201402053

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      Battery design: An overview is given of unpaired electron spins related to the chemical species in a Li–O2 cell environment and their possible impact on the design and development of a practical Li–O2 cell. The discharge products consist of composite structures of Li/O2 compounds, such as Li2O2, O-rich Li2O2, LiO2-like superoxide, and Li2O (see figure).

  25. Full Papers

    1. Chain Length Effect of the Multidentate Block Copolymer Strategy to Stabilize Ultrasmall Fe3O4 Nanoparticles

      Dr. Nicky Chan, Puzhen Li and Prof. Dr. Jung Kwon Oh

      Article first published online: 16 JUL 2014 | DOI: 10.1002/cplu.201402112

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      On the starting blocks: A multidentate block copolymer strategy has been used to stabilize ultrasmall superparamagnetic iron oxide nanoparticles exhibiting excellent colloidal stability under biologically relevant conditions. The materials provide effective T1-weighted contrast enhancement for magnetic resonance imaging (see figure).

    2. 2-Phenylquinoline-Based Cyclometalated Platinum(II) Complexes: Synthesis and Structure–Photoelectric Properties Relationship in Oxygen Sensing

      Dr. Chun Liu, Xinlong Song, Zhonggang Wang and Jieshan Qiu

      Article first published online: 16 JUL 2014 | DOI: 10.1002/cplu.201402125

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      Phosphorescence: A series of novel 2-phenylquinoline-based cyclometalated PtII complexes are synthesized and fully characterized. The results of the O2-sensing sensitivity analyses of the PtII complexes show that the complex with a triphenylamine group on the quinoline exhibits the highest sensitivity (see figure). The present work provides the first example of a series of 2-phenylquinoline-based cyclometalated PtII complexes for efficient O2 sensing.

    3. Design and Characterization of Two Bifunctional Cryptophane A-Based Host Molecules for Xenon Magnetic Resonance Imaging Applications

      Federica Rossella, Dr. Honor May Rose, Dr. Christopher Witte, Dr. Jabadurai Jayapaul and Dr. Leif Schröder

      Article first published online: 16 JUL 2014 | DOI: 10.1002/cplu.201402179

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      Label mates: Bifunctional biosensors for optical imaging and xenon magnetic resonance imaging (MRI) have been designed. Compounds that contain a cryptophane molecule and bear a fluorophore were compared. Both displayed good cellular uptake suitable for cell-labeling studies. These compounds are also flexible building blocks for the synthesis of more complex xenon-MRI biosensors (see figure).

    4. Bottom-Up Hybridization: A Strategy for the Preparation of a Thermostable Polyoxometalate–Polymer Hybrid with Hierarchical Hybrid Structures

      Jing Tang, Dr. Wei Yu, Dr. Min-Biao Hu, Yu Xiao, Xiao-Gang Wang, Li-Jun Ren, Ping Zheng, Dr. Wen Zhu, Prof. Dr. Yongming Chen and Prof. Dr. Wei Wang

      Article first published online: 15 JUL 2014 | DOI: 10.1002/cplu.201402092

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      Back to basics: A hybrid molecule of a polyoxometalate (POM) cluster and a polymer chain linked with a covalent bond produces hierarchical structures: hybrid lamellae and hybrid superstructures (see picture). The strong electrostatic interactions of the POM cluster are retained, and thus, add thermostability to the mechanical properties of the hybrid materials through the structural hierarchy.

    5. Tin Nanoparticles in Carbon/Silica Hybrid Materials by the Use of Twin Polymerization

      Christian Leonhardt, Susann Brumm, Dr. Andreas Seifert, Dr. Arno Lange, Dr. Szilard Csihony and Prof. Dr. Michael Mehring

      Article first published online: 10 JUL 2014 | DOI: 10.1002/cplu.201402137

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      Twin-(em)bedded: Uniformly distributed tin nanoparticles embedded in a carbon/silica matrix have been obtained from tin and silica precursors by the use of the twin polymerization process followed by reduction with Ar/H2 (see figure). The final Sn@C/SiO2 hybrid materials have high BET surface areas up to 352 m2 g−1 and tin particle sizes in the range of 20–100 nm.

  26. Communications

    1. B12-TiO2 Hybrid Catalyst for Light-Driven Hydrogen Production and Hydrogenation of C[BOND]C Multiple Bonds

      Prof. Dr. Hisashi Shimakoshi and Prof. Dr. Yoshio Hisaeda

      Article first published online: 10 JUL 2014 | DOI: 10.1002/cplu.201402081

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      Hybrid catalyst: TiO2 modified with the B12 complex (cobyrinic acid), B12-TiO2, mediates hydrogen evolution under UV irradiation (see figure). B12-TiO2 also efficiently catalyzes the hydrogenation of a variety of alkenes under mild conditions (room temperature, ordinary pressure, and water or alcohol solvent), and the turnover number of the B12 complex is a maximum of 100 per hour.

  27. Full Papers

    1. A Ratiometric Tetrazolylpyridine-Based “Turn-On” Fluorescent Chemosensor for Zinc(II) Ion in Aqueous Media

      Palanichamy Kaleeswaran, Dr. Ismail Abulkalam Azath, Dr. Vairaperumal Tharmaraj and Prof. Kasi Pitchumani

      Article first published online: 10 JUL 2014 | DOI: 10.1002/cplu.201402126

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      A rapid turn-on: 2-(1H-Tetrazole-5-yl)pyridine (2PT) is a simple chemosensor for Zn2+ ion, based on an excited-state intramolecular proton transfer mechanism at the micromolar level in aqueous medium, such as potable water. The ligand forms a 1:1 complex with Zn2+ and shows high selectivity in the presence of other metal ions (see figure).

    2. Water-Soluble Reduced Graphene Oxide–Carboxymethylcellulose Hybrid Nanomaterial for Electrochemical Biosensor Design

      Elena Araque, Dr. Reynaldo Villalonga, Dr. María Gamella, Prof. Paloma Martínez-Ruiz, Dr. Alfredo Sánchez, Prof. Valentín García-Baonza and Prof. José M. Pingarrón

      Article first published online: 8 JUL 2014 | DOI: 10.1002/cplu.201402017

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      Construction site: A novel water-soluble graphene derivative prepared by covalent grafting with carboxymethylcellulose and its use as a nanostructured scaffold for tyrosinase biosensor construction is described (see figure).

  28. Interviews

    1. You have free access to this content
      Zaozao Qiu

      Article first published online: 3 JUL 2014 | DOI: 10.1002/cplu.201402167

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      My favorite molecule is carborane because this 12-vertex cage has many reaction sites. My most exciting discovery to date has been the discovery of transition metal-catalyzed B[BOND]H bond activation for carborane fluorination.

  29. Full Papers

    1. Characterization of Silver and Fluorescent Dyes Incorporated in Self-Assembling Peptides and Their Potential Applications in Biology

      Dr. Chivukula Subbalakshmi and Dr. Ramakrishnan Nagaraj

      Article first published online: 2 JUL 2014 | DOI: 10.1002/cplu.201402077

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      Silver lining: Silver nanoparticles (AgNPs) and charged fluorescent dyes have been incorporated into nanostructures comprising di- and tripeptides and their physical and chemical properties have been described. The antibacterial activity of the resultant AgNP-incorporated peptide aggregates is demonstrated (see figure).

  30. Communications

    1. Ultraviolet-Induced Fluorescence of Polydopamine-Coated Emulsion Droplets

      Dr. Sandrine Quignard, Prof. Marco d'Ischia, Prof. Yong Chen and Dr. Jacques Fattaccioli

      Article first published online: 2 JUL 2014 | DOI: 10.1002/cplu.201402157

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      Fluorescent droplets: We disclose the first polydopamine-based system that can develop fluorescence without chemical manipulation. The polymerization of dopamine in the presence of oil microdroplets results in the formation of smooth PDA-coated core–shell droplets, which develop a bright and persistent fluorescence upon UVA illumination (see figure).

  31. Full Papers

    1. Hierarchical Graphene-Rich Carbon Materials with Trace Nonprecious Metals for High-Performance Li–O2 Batteries

      Jing Li , Prof. Yining Zhang, Wei Zhou , Hongjiao Nie , Baoshan Wu and Prof. Huamin Zhang

      Article first published online: 1 JUL 2014 | DOI: 10.1002/cplu.201402044

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      Improving cathodes: Added transition-metal components, as assisting templates and graphitization catalysts, have a great effect on the pore optimization and graphene-rich structure formation in carbon frameworks (see figure). The obtained hierarchical carbon materials doped with trace metals exhibit enhanced discharge capacities, electrocatalytic activities, and stabilities for use in Li–O2 batteries.

    2. Diethyl Tartrate Linked Chiral Macrocyclic Manganese(III)–Salen Complex for Enantioselective Epoxidation of Olefins and Oxidative Kinetic Resolution of Racemic Secondary Alcohols

      Nabin Ch. Maity, Prasanta Kumar Bera, S. Saravanan , Dr. Sayed H. R. Abdi , Dr. Rukhsana I. Kureshy , Dr. Noor-ul H. Khan  and Dr. Hari C. Bajaj 

      Article first published online: 30 JUN 2014 | DOI: 10.1002/cplu.201402131

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      Proceed with determination: A diethyl tartrate linked chiral macrocyclic MnIII–salen (salen=N,N′-ethylenebis(salicylimine); see picture) complex has been used for the enantioselective epoxidation of nonfunctionalized alkenes and for the oxidative kinetic resolution of racemic alcohols.

    3. Chemical Hydrogen Storage: Ammonia Borane Dehydrogenation Catalyzed by NP3 Ruthenium Hydrides (NP3=N(CH2CH2PPh2)3)

      Dr. Andrea Rossin, Andrea Rossi, Dr. Maurizio Peruzzini and Fabrizio Zanobini

      Article first published online: 30 JUN 2014 | DOI: 10.1002/cplu.201402108

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      H2 from AB and RuII hydrides: The RuII hydrides (κ4-NP3)Ru(H)2 and [(κ4-NP3)Ru(H)(η2-H2)]BArCl4 (ArCl=3,5-dichlorophenyl) have been exploited as homogeneous catalysts in the ammonia borane (AB) dehydrogenation reaction (see figure). Both compounds generate two H2 equivalents per AB equivalent, with a good reaction rate at temperatures between 298 and 330 K. Two activation pathways are made possible by the hemilabile coordination hapticity of the NP3 ligand.

    4. Synthesis and Characterization of a Stable Copper(I) Complex for Radiopharmaceutical Applications

      Dr. Ewen Bodio, Dr. Mohammed Boujtita, Dr. Karine Julienne, Patricia Le Saec, Dr. Sébastien G. Gouin, Jonathan Hamon, Dr. Eric Renault and Dr. David Deniaud

      Article first published online: 24 JUN 2014 | DOI: 10.1002/cplu.201402031

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      N4Cu complexes: A series of ligands has been synthesized and their complexation with copper(II) precursors studied. The combination of several analytical techniques and density functional calculations shows that N4 copper(I) complexes are formed from a copper(II) salt (see figure). Preliminary tests of complexation show the ability of these ligands to chelate 64Cu in very diluted medium, which is of interest for developing new positron emission tomography imaging agents.

    5. Photocatalytic Application of 4f–5f Inorganic–Organic Frameworks: Influence of Lanthanide Contraction on the Structure and Functional Properties of a Series of Uranyl–Lanthanide Complexes

      Ya-Nan Hou, Xue-Ting Xu, Na Xing, Prof. Feng-Ying Bai, Shi-Bo Duan, Dr. Qiao Sun, Si-Yue Wei, Prof. Zhan Shi, Dr. Huan-Zhi Zhang and Prof. Yong-Heng Xing

      Article first published online: 24 JUN 2014 | DOI: 10.1002/cplu.201402121

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      Switching the atom: A series of 4f–5f inorganic–organic frameworks has been synthesized and the influence of lanthanide contraction on the surface photoelectronic and photocatalytic properties has been studied (see scheme). It was found that the introduction of different lanthanide atoms led to different photocatalytic effects.

    6. Toward Tunable Immobilized Molecular Catalysts: Functionalizing the Methylene Bridge of Bis(N-heterocyclic carbene) Ligands

      Rui Zhong, Dr. Alexander Pöthig, Stefan Haslinger, Benjamin Hofmann, Dr. Gabriele Raudaschl-Sieber, Dr. Eberhardt Herdtweck, Prof. Dr. Wolfgang A. Herrmann and Prof. Dr. Fritz E. Kühn

      Article first published online: 24 JUN 2014 | DOI: 10.1002/cplu.201402135

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      Bridge work: The hydroxymethyl-functionalized methylene-bridged bis(NHC) (NHC=N-heterocyclic carbene) ligand system allows immobilization of the bis(NHC) motif while preserving the possibility of different wingtip substituents (see figure). Thus, fine-tuning of the steric and electronic properties of the immobilized complex is feasible. The obtained catalysts have been utilized for Suzuki–Miyaura cross-coupling reactions.

    7. Dithienopyrrole-/Benzodithiophene-Based Donor–Acceptor Polymers for Memristor

      Cheng Wang, Prof. Dr. Gang Liu, Prof. Dr. Yu Chen, Shanshan Liu, Prof. Dr. Qibin Chen, Prof. Dr. Runwei Li and Dr. Bin Zhang

      Article first published online: 20 JUN 2014 | DOI: 10.1002/cplu.201402133

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      Superior memory: Two new donor–acceptor copolymers, P1 and P2, are described. In contrast with the P2-based device with almost negligible memristive behavior, the P1-based memristor (see left-hand part of the figure) exhibits a smoother tuning of the sample conductance during the voltage sweeping processes, with a maximum ILRS/IHRS ratio of approximately 10 at ±2.0 V.

    8. Enhanced Photocatalytic Activity of P25 TiO2 after Modification with Phosphate-Treated Porous SiO2

      Dr. Yunbo Luan, Prof. Yujie Feng, Dr. Haiqin Cui, Yue Cao and Prof. Liqiang Jing

      Article first published online: 11 JUN 2014 | DOI: 10.1002/cplu.201402063

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      TiO2 photocatalysis: The increase in the amount of .OH produced on TiO2 is attributed to the promoted adsorption of O2 after modification of the TiO2 photocatalyst with phosphate-treated porous SiO2. The strong fluorescence signal in the .OH-related fluorescence spectra corresponds to high photogenerated charge separation, which leads to the enhanced photocatalytic activity of TiO2 for the degradation of colorless pollutants (see figure).

    9. Characterization of Layered LiMO2 Oxides for the Oxygen Evolution Reaction of Metal–Air Batteries (M=Mn, Co, Ni)

      Dr. Veronica Augustyn and Prof. Arumugam Manthiram

      Article first published online: 11 JUN 2014 | DOI: 10.1002/cplu.201402107

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      Evolutionary behavior: The behavior of layered LiMO2 (M=Mn, Co, Ni) has been systematically characterized for the oxygen evolution reaction. Nickel-rich compositions exhibit the highest activities, whereas the substitution of manganese in LiM1−xMnxO2 (M=Co and Ni) decreases the activity (see figure). Electrochemical evidence suggests that the LiMO2 surface is transformed in situ into a highly active catalyst.

    10. Palladium Nanoparticles Supported on Poly(N-vinyl- imidazole-co-N-vinylcaprolactam) as an Effective Recyclable Catalyst for the Suzuki Reaction

      Alexandra V. Selivanova, Dr. Vladimir S. Tyurin and Prof. Irina P. Beletskaya

      Article first published online: 11 JUN 2014 | DOI: 10.1002/cplu.201402111

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      Fast or slow? Palladium nanoparticles immobilized on poly(N-vinylimidazole-co-N-vinylcaprolactam) reveal unusual kinetic behavior in the Suzuki reaction. This can be explained on the basis of the observation of changes to the sizes of the particles during recycling, and is in accordance with the concept of leaching during the process.

    11. Cyclic Performance Analysis of Hydrogen/Bromine Flow Batteries for Grid-Scale Energy Storage

      Dr. Kyu Taek Cho, Dr. Michael C. Tucker, Markus Ding, Paul Ridgway, Dr. Vincent S. Battaglia, Dr. Venkat Srinivasan and Dr. Adam Z. Weber

      Article first published online: 3 JUN 2014 | DOI: 10.1002/cplu.201402043

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      Reversible energy storage: Hydrogen/bromine flow batteries are analyzed in terms of their efficiency, self-discharge, side reactions, and anode Pt dissolution over a wide range of operating conditions. A single cell cycled more than 600 times shows good stability and an energy efficiency of around 75 % (see figure). The system shows promise for grid-scale energy storage.

    12. Impact of Proton Concentration on Equilibrium Potential and Polarization of Vanadium Flow Batteries

      Xiaoli Xi, Prof. Xianfeng Li, Chenhui Wang, Prof. Qinzhi Lai, Yuanhui Cheng, Wei Zhou, Cong Ding and Prof. Huamin Zhang

      Article first published online: 21 MAY 2014 | DOI: 10.1002/cplu.201402040

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      Maximizing potential: The impact of proton concentration in an electrolyte on the equilibrium potential and polarization of a vanadium flow battery (VFB) are investigated systematically with the aim of utilizing VFB electrolyte effectively. (see picture).

    13. Surfactant for Enhanced Rheological, Electrical, and Electrochemical Performance of Suspensions for Semisolid Redox Flow Batteries and Supercapacitors

      Lénaïc Madec, Mohamed Youssry, Manuella Cerbelaud, Patrick Soudan, Dominique Guyomard and Bernard Lestriez

      Article first published online: 20 MAY 2014 | DOI: 10.1002/cplu.201402042

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      Anolyte performance: A non-ionic surfactant is used to improve the rheological, electrical, and electrochemical properties of a suspension used as the anolyte for nonaqueous lithium-based redox flow batteries (see figure).

  32. Communications

    1. Reversibility of Lithium-Ion–Air Batteries Using Lithium Intercalation Compounds as Anodes

      Jinyoung Chun, Hyojin Kim, Changshin Jo, Eunho Lim, Prof. Jinwoo Lee and Prof. Youngsik Kim

      Article first published online: 6 MAY 2014 | DOI: 10.1002/cplu.201402035

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      Out of thin air: A lithium (ion)–air battery was designed, in which 0.1 M LiOH(aq) was used as the catholyte with oxygen from the air and lithium intercalation compounds such as graphite (C6) and Li4Ti5O12 (LTO) were used as the anodes (see figure). In this system, reversible utilization of Li harvested from the cathode was investigated.

    2. An Aqueous Lithium–Iodine Battery with Solid Polymer Electrolyte-Coated Metallic Lithium Anode

      Dr. Yu Zhao, Nadège Bonnet Mercier and Dr. Hye Ryung Byon

      Article first published online: 15 APR 2014 | DOI: 10.1002/cplu.201402038

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      On solid ground: Aqueous lithium–iodine (Li–I2) cells with solid polymer electrolyte-passivated metallic lithium have been demonstrated (see figure). The solid-state polymer electrolyte protects the metallic Li and the aqueous Li–I2 cells deliver a capacity of approximately 190 mA h g−1 with ideal Coulombic efficiency and a discharge potential of 3.4 V versus Li+/Li.

  33. Full Papers

    1. Simulation Analysis of Regional Temperature Effects and Battery Management Schedules for a Residential-Scale Vanadium Redox Flow Battery System

      Dr. Ao Tang and Prof. Maria Skyllas-Kazacos

      Article first published online: 11 APR 2014 | DOI: 10.1002/cplu.201400034

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      Battery management: For all-vanadium redox flow batteries (see figure), prevention of vanadium-component precipitation and restoration of capacity loss are two critical concerns. Dynamic modelling and simulation analysis were thus performed to explore electrolyte temperature variations associated with different regional temperature effects and provide deeper insights into scheduling necessary battery operation management.

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