ChemPlusChem

Cover image for Vol. 79 Issue 4

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

Editor: Neville Compton, Deputy Editor: Marisa Spiniello

Online ISSN: 2192-6506

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

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  1. 1 - 36
  1. Interviews

    1. You have free access to this content
      Lucio Isa

      Article first published online: 17 APR 2014 | DOI: 10.1002/cplu.201400036

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      Guaranteed to make me laugh is a good joke about geeks! Not taking ourselves too seriously is one of the privileges of being a scientist. My most exciting discovery to date has been new methodology to measure the wetting properties of individual nanoparticles at fluid interfaces. This technique has opened up a whole range of unprecedented possibilities to look at the details of adsorption and assembly of nanoscale objects at interfaces that form the basis many fundamental phenomena and applications.

  2. Full Papers

    1. Heterojunction Ag–TiO2 Nanopillars for Visible-Light-Driven Photocatalytic H2 Production

      Dr. Yang Qu, Dr. Wei Zhou, Dr. Zhiyu Ren, Dr. Chungui Tian, Dr. Jialin Li and Prof. Honggang Fu

      Article first published online: 16 APR 2014 | DOI: 10.1002/cplu.201402012

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      Under the sun: Heterojunction Ag–TiO2 nanopillars have been fabricated by a one-pot method. They exhibit high photocatalytic H2 production efficiency under visible-light irradiation owing to the contacted junctions and surface plasmon resonance effect, which result in effective charge separation and solar energy utilization (see figure).

    2. Receptor with an Active Methylene Group as Binding Site for Extraction of Inorganic Fluoride Ions from Seawater

      Madhuprasad and Dr. Darshak R. Trivedi

      Article first published online: 16 APR 2014 | DOI: 10.1002/cplu.201402018

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      Watercolors: A receptor based on a triphenylphosphonium salt that contains an active methylene group has been designed and synthesized for the colorimetric detection and extraction of F ions from seawater with 99 % efficiency. The process results in an instantaneous color change (see figure).

    3. Surface Functionalization for Synergistic Catalysis: Silica–Alumina-Supported Cationic Indium and Organic Base for Cyanoethoxycarbonylation

      Dr. Ken Motokura, Yasuhiro Ito, Hiroto Noda, Dr. Akimitsu Miyaji, Dr. Sho Yamaguchi and Prof. Dr. Toshihide Baba

      Article first published online: 15 APR 2014 | DOI: 10.1002/cplu.201402004

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      Close relationship: A silica–alumina (SiO2–Al2O3) surface possessing both In3+ cations and an amine base is described. These two functions on same solid surface act as acidic and basic units in the catalytic cyanoethoxycarbonylation of aldehyde (see picture).

  3. Communications

    1. 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.

  4. Cover Pictures

    1. In Situ Growth of Noble-Metal Nanoparticles on Cu2O Nanocubes for Surface-Enhanced Raman Scattering Detection

      Jie Wang, Fangling Cui, Sibin Chu, Xiaoquan Jin, Jun Pu and Prof. Dr. Zhenghua Wang

      Article first published online: 15 APR 2014 | DOI: 10.1002/cplu.201400039

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      The cover picture shows the growth mechanism of Cu2O/noble-metal nanocomposites and the application of these nanocomposites as surface-enhanced Raman scattering (SERS) substrates, as reported by Z. H. Wang and co-workers in their Full Paper (DOI: 10.1002/cplu.201400028). They aim to synthesize SERS substrates with high sensitivity and good reproducibility for the detection of food contaminants.

  5. Cover Profiles

    1. You have free access to this content
      In Situ Growth of Noble-Metal Nanoparticles on Cu2O Nanocubes for Surface-Enhanced Raman Scattering Detection

      Jie Wang, Fangling Cui, Sibin Chu, Xiaoquan Jin, Jun Pu and Prof. Dr. Zhenghua Wang

      Article first published online: 15 APR 2014 | DOI: 10.1002/cplu.201400037

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      by carefully controlling the particle sizes and distributions of noble-metal nanoparticles on semiconductor substrates, we aimed to obtain SERS-active substrates with high sensitivity and good reproducibility.” This and more about the story behind the cover in the Cover Profile and about the research itself on page (DOI: 10.1002/cplu.201400028).

  6. 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.

    2. From Molecular Structures of Ionic Liquids to Predicted Retention of Fatty Acid Methyl Esters in Comprehensive Two-Dimensional Gas Chromatography

      Chadin Kulsing, Yada Nolvachai, Annie Xu Zeng, Dr. Sung-Tong Chin, Dr. Blagoj Mitrevski and Prof. Philip J. Marriott

      Article first published online: 11 APR 2014 | DOI: 10.1002/cplu.201300410

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      Forecasting a result: Prediction of the separation performance of fatty acid methyl ester (FAME) analytes on capillary columns coated with ionic liquid phases by knowledge of their molecular structures is possible (see figure; LSER=linear solvation energy relationship). Whilst providing deeper insight into separation mechanisms, trial-and-error experimentation related to method development in multidimensional gas chromatography can also be reduced.

    3. Durable Superhydrophobic/Superoleophilic Polyurethane Sponges Inspired by Mussel and Lotus Leaf for the Selective Removal of Organic Pollutants from Water

      Bucheng Li, Lingxiao Li, Lei Wu, Junping Zhang and Aiqin Wang

      Article first published online: 10 APR 2014 | DOI: 10.1002/cplu.201300403

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      Sponges for separation: A versatile approach for the preparation of durable superhydrophobic polyurethane (PU) sponges is developed through in-turn covalent modification with polydopamine, silver nanoparticles, and dodecyl mercaptan. The superhydrophobic PU sponges feature a high water contact angle, low water shedding angle, good durability, and high oil/water separation efficiency (see figure).

    4. Syntheses, Structures, and Luminescence Properties of Lanthanide Coordination Polymers with a Polycarboxylic Terpyridyl Derivative Ligand

      Juan Xie, Hui-Ming Shu, Prof. Dr. Huai-Ming Hu, Zhong-Xi Han, Sa-Sa Shen, Fei Yuan, Meng-Lin Yang, Fa-Xin Dong and Prof. Gang-Lin Xue

      Article first published online: 9 APR 2014 | DOI: 10.1002/cplu.201402030

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      Made to fit: A new H3L ligand, 4′-(3-carboxylpyridyl)-2,2′:6′,2“-terpyridine- 6,6”-dicarboxylic acid, is described for the formation of seven lanthanide–organic frameworks (see picture). The seven complexes crystallized in three structural types owing to the lanthanide contraction effect, which is reflected in the differences in the coordination number and geometry of lanthanide ions.

    5. Silver Coordination Polymers Based on p-Cyanophenylsilanes as Ligands

      Bianca Blankschein, Prof. Dr. Axel Schulz, Dr. Alexander Villinger and Dr. Ronald Wustrack

      Article first published online: 8 APR 2014 | DOI: 10.1002/cplu.201402026

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      Cross my polymer with silver: A general synthesis for different p-cyanophenylsilanes and their application as bi-, tri and tetradentate ligands in the coordination chemistry of AgIX (X=O3SCF3, CO2CF3) is presented. Treatment of AgO2CCF3 with the tetradentate ligand Si(C6H4CN)4 leads to the formation of a diamond-like 3D network with two interpenetrating nets linked by bridging Ag2(CF3CO2)2 dimers. (see picture).

    6. Graphene Oxides: Transformations in Natural Waters over a Period of Three Months

      Wei Zhe Teo and Prof. Martin Pumera

      Article first published online: 7 APR 2014 | DOI: 10.1002/cplu.201400033

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      Natural waters: Graphene oxide nanomaterials prepared from different oxidative treatments of graphite underwent different and even opposing transformations in natural waters (lake water, rainwater, and seawater) over a period of three months (see figure).

    7. Diagnosis of the Redox Levels of TCNQF4 Compounds Using Vibrational Spectroscopy

      Dr. Naomi L. Haworth, Dr. Jinzhen Lu, Nguyen Vo, Dr. Thanh Hai Le, Dr. Christopher D. Thompson, Prof. Alan M. Bond and Assoc. Prof. Lisandra L. Martin

      Article first published online: 6 APR 2014 | DOI: 10.1002/cplu.201402013

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      Righting wrongs: The vibrational spectroscopy of TCNQF4 is reassessed, revealing many bands have been mis-assigned in recent studies. The revised data have allowed the development of a series of diagnostics for characterisation of TCNQF4 redox levels (see figure). The previous primary diagnostic tool, the ν(C≡N) modes, is sensitive to metal-ion coordination. Recognition of this sensitivity is essential for interpreting spectra of organic molecular species.

    8. A Metal-Free, Carbon-Based Catalytic System for the Oxidation of Lignin Model Compounds and Lignin

      Dr. Yongjun Gao, Jiaguang Zhang, Xi Chen, Prof. Ding Ma and Prof. Ning Yan

      Article first published online: 1 APR 2014 | DOI: 10.1002/cplu.201300439

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      Low mass, high conversion: Nitrogen-containing graphene-based carbon material has been used to establish a metal-free catalytic system for the oxidation of α-O-4 and β-O-4 types of lignin model compounds in the presence of tert-butyl hydroperoxide (see figure). In the oxidative depolymerization of organosolv lignin, a significant portion of liquefied, low-molecular-mass product is produced.

    9. Effect of Aluminum Doping on the Growth and Optical and Electrical Properties of ZnO Nanorods

      Ruiqiang Chen, Dr. Pengli Zhu, Libo Deng, Tao Zhao, Prof. Rong Sun and Prof. Chingping Wong

      Article first published online: 26 MAR 2014 | DOI: 10.1002/cplu.201300398

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      Desirable defects: Zinc oxide and aluminum-doped zinc oxide (AZO) nanorods have been synthesized by a solvothermal route. The growth and optoelectronic properties of the nanorods have been studied systematically, and provide insights into the role of defects in AZO materials (see graphic).

  7. Reviews

    1. 1,8-Cineole: Chemical and Biological Oxidation Reactions and Products

      Dr. Robert Azerad

      Article first published online: 26 MAR 2014 | DOI: 10.1002/cplu.201300422

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      Turn over a new leaf: The products of chemical and biological oxidation (hydroxy, oxo, and acid derivatives) of 1,8-cineole (see figure) are reviewed with a focus on the diverse regio- and stereoselectivities obtained from this meso monoterpenic compound abundantly present in eucalyptus leaves.

  8. Communications

    1. Derivatization and Multidimensional Gas-Chromatographic Resolution of α-Alkyl and α-Dialkyl Amino Acid Enantiomers

      Dr. Cornelia Meinert and Prof. Dr. Uwe J. Meierhenrich

      Article first published online: 26 MAR 2014 | DOI: 10.1002/cplu.201300328

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      Touching base: Baseline separation of enantiomers of α-dialkyl amino acids is achieved by employing a novel derivatization method in combination with comprehensive two-dimensional GC coupled to time-of-flight mass spectrometry (see figure for d,l-2,3-diaminopropanoic acid (DAP)). The data are important for analyses of samples relevant for D-amino acid related sciences and the origin of homochirality on Earth.

    2. Synthesis and Contact Angle Measurements of Janus Particles

      Dr. Alla Synytska, M. Sc.Alina Kirillova and Prof. Dr. Lucio Isa

      Article first published online: 25 MAR 2014 | DOI: 10.1002/cplu.201400020

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      Two-faced: Janus microparticles are a promising alternative to molecular surfactants for emulsion stabilisation. The synthesis of diverse Janus microparticles (figure, top) with a defined Janus ratio is reported and their position in situ at a water/oil interface using freeze-fracture, shadow-casting cryo-SEM is measured (figure, bottom).

  9. Full Papers

    1. Self-Assembly of Nanocellulose and Indomethacin into Hierarchically Ordered Structures with High Encapsulation Efficiency for Sustained Release Applications

      Jiali Gao, Qing Li, Wenshuai Chen, Yixing Liu and Prof. Haipeng Yu

      Article first published online: 19 MAR 2014 | DOI: 10.1002/cplu.201300434

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      Long-lasting effects: A hierarchical structure of cellulose nanofibers and indomethacin has been fabricated through self-assembly and recrystallization under the combined effects of solvent and processing method (see figure). Such hybrid films possess a high loading capacity and encapsulation efficiency, and show a sustained drug release period over 30 days.

    2. Facile Synthesis of N-doped TiO2 and Its Enhanced Photocatalytic Activity for Degrading Colorless Pollutants

      Mingzheng Xie, Yujie Feng, Yunbo Luan, Xuedong Fu and Liqiang Jing

      Article first published online: 19 MAR 2014 | DOI: 10.1002/cplu.201400021

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      Visible photocatalysis: N-doped TiO2, synthesized through a simple ammonia-modified hydrolysis-solvothermal process, exhibits high visible photocatalytic activities for the degradation of acetaldehyde and phenol. The photocatalytic activity is further enhanced upon increasing the O2 adsorption through phosphate modification (see figure).

    3. Helical Carbon Segment in Carbon–Boron–Nitride Heteronanotubes: Structure and Nonlinear Optical Properties

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

      Article first published online: 19 MAR 2014 | DOI: 10.1002/cplu.201300381

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      Helix topological effect: The helix C segment in HA-9 leads to fascinating long-range charge-transfer character. As a result, the β0 value of HA-9 is 1.80×104 a.u., which is clearly larger than that of PA-9 (4.99×103 a.u.). Further investigations show that the larger β0 value of HA-9 is essentially induced by the helix topological effect of the C-segment (see figure).

    4. Flexible Janus Nanofibers: Facile Electrospinning Construction and Enhanced Luminescent–Electrical–Magnetic Trifunctionality

      Dr. Nan Lv, Qianli Ma, Prof. Xiangting Dong, Assoc. Prof. Jinxian Wang, Dr. Wensheng Yu and Guixia Liu

      Article first published online: 18 MAR 2014 | DOI: 10.1002/cplu.201300404

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      Two-faced fibers: Flexible Janus nanofibers with enhanced luminescent–electrical–magnetic trifunctionality have been successfully fabricated (see picture). The unique structure allows the isolation of Fe3O4 nanoparticles (NPs) and polyaniline (PANI) from [Tb(ba)3(phen)] (ba=benzoic acid, phen=1,10-phenanthroline), resulting in weaker light absorption of Fe3O4 NPs and PANI, and strong luminescence of the nanofibers.

    5. Enhanced Aerobic Epoxidation of Styrene with Copper(II), Cobalt(II), Iron(III), or Oxovanadium(IV) Salen Complexes Immobilized onto Carbon-Coated Fe3O4 Nanoparticles Hybridized with Graphene Sheets

      Dr. Zhifang Li, Shujie Wu, Dafang Zheng, Hong Ding, Xiufang Wang, Xiaoyuan Yang, Prof. Qisheng Huo, Prof. Jingqi Guan and Prof. Qiubin Kan

      Article first published online: 18 MAR 2014 | DOI: 10.1002/cplu.201300424

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      Extra support: Core–shell-structured magnetic nanocatalysts have been prepared and used as efficient heterogeneous catalysts for the aerobic oxidation of styrene. Mildly reduced graphene oxide (MRGO; see picture)/Fe3O4@C–salen–Co showed over 91 % conversion of styrene and over 52 % selectivity to the styrene oxide. The materials can be easily recovered through simple magnetic separation.

    6. Photocatalytic Carboxylation of Organic Substrates with Carbon Dioxide at Zinc Sulfide with Deposited Ruthenium Nanoparticles

      Tomasz Baran, Prof. Angela Dibenedetto, Prof. Michele Aresta, Dr. Krzysztof Kruczała and Prof. Wojciech Macyk

      Article first published online: 18 MAR 2014 | DOI: 10.1002/cplu.201300438

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      Dropping acid: Zinc sulfide with deposited ruthenium(0) nanoparticles photocatalyzes the carboxylation of acetylacetone with carbon dioxide as a substrate (see picture). The reaction proceeds through coupling of photogenerated R. and CO2.− radicals.

    7. In Situ Growth of Noble-Metal Nanoparticles on Cu2O Nanocubes for Surface-Enhanced Raman Scattering Detection

      Jie Wang, Fangling Cui, Sibin Chu, Xiaoquan Jin, Jun Pu and Prof. Dr. Zhenghua Wang

      Article first published online: 18 MAR 2014 | DOI: 10.1002/cplu.201400028

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      The cube root: Cu2O[BOND]Au and Cu2O[BOND]Ag nanocomposites have been synthesized through an in situ wet-chemical reduction route with Cu2O nanocubes as both substrate and reducing agent. The composites serve as effective surface-enhanced Raman scattering substrates (see figure).

    8. One-Dimensional [Ni(O2CR)2(N[BOND]N)x] Polymers: Structural, Magnetic, and Density Functional Theory Studies

      Miguel Cortijo, Dr. Santiago Herrero, Belén Jerez, Prof. Reyes Jiménez-Aparicio, Dr. Josefina Perles, Dr. José L. Priego, Dr. Javier Torroba and Dr. José Tortajada

      Article first published online: 18 MAR 2014 | DOI: 10.1002/cplu.201402005

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      Explaining antiferromagnetism: Five 1 D Ni2+ complexes are prepared and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, X-ray diffraction, and magnetic studies. Three different arrangements are found. The magnetic behavior of the compounds indicates the presence of antiferromagnetic interactions that vary from very strong to very weak. Density functional calculations using the broken-symmetry approach are performed to gain insights into this magnetic behavior.

    9. Synthesis and Electron-Transfer Processes in a New Family of Ligands for Coupled Ru−Mn2 Complexes

      Dr. Erik A. Karlsson, Dr. Bao-Lin Lee, Dr. Rong-Zhen Liao, Dr. Torbjörn Åkermark, Dr. Markus D. Kärkäs, Valeria Saavedra Becerril, Prof. Per E. M. Siegbahn, Prof. Xiaodong Zou, Prof. Maria Abrahamsson and Prof. Björn Åkermark

      Article first published online: 12 MAR 2014 | DOI: 10.1002/cplu.201402006

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      Power of two: Three new ruthenium-containing ligands have been developed with the aim of preparing coupled Ru[BOND]Mn2 complexes such as 1 (see picture). Although dyad 1 is capable of catalyzing chemical water oxidation, photochemical water oxidation in the presence of an external electron acceptor fails. The photophysical behavior can be explained by the presence of an intricate excited-state manifold.

  10. Communications

    1. Influencing the Orientation of Jahn–Teller Axes in Butterfly-Like MnIII4 Clusters

      Dr. Ross McLellan, Dr. Maria A. Palacios, Prof. Euan K. Brechin and Dr. Scott J. Dalgarno

      Article first published online: 11 MAR 2014 | DOI: 10.1002/cplu.201400031

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      In the wings: A bis-phenolate with calixarene character influences the orientation of Jahn–Teller axes (shown by arrows in the figure) in a tetranuclear MnIII cluster. Structural changes and prevailing magnetic properties are presented.

    2. Titanium(IV)-Immobilized Hydrophilic Hierarchically Ordered Macro-/Mesoporous Silica for Fast Enrichment of Phosphopeptides

      Dr. Yinghua Yan, Zhifang Zheng, Yan Li, Prof. Chunhui Deng and Prof. Xiangmin Zhang

      Article first published online: 11 MAR 2014 | DOI: 10.1002/cplu.201300411

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      Signal enhancement: Nanocomposites with a polydopamine coating on hierarchically ordered macro-/mesoporous silica and functionalized with titanium ions (HOMMS-PD-Ti4+) were prepared through a facile reaction (see picture). By taking advantage of the pure phosphate–Ti4+ interface and high loading amount of Ti4+, the composites present remarkable selectivity for phosphopeptides with a rapid enrichment speed.

    3. Understanding the Photochemical Pathway of In Vitro Target Delivery of Aluminium Phthalocyanine: A Mechanistic Approach Using Radical Reaction Chemistry

      Victor Akpe, Dr. Erik Vernet, Dr. Christian Madu, Dr. Joseph C. Obirai and Prof. Dr. Hjalmar Brismar

      Article first published online: 11 MAR 2014 | DOI: 10.1002/cplu.201300402

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      Stain removal: The photochemistry of aluminium phthalocyanine (AlPc) and its use in chromophore-assisted laser inactivation has been studied in cell-free and cell-based systems. In the former system, the photosensitiser recovers its fluorescence signal through a reversible photobleaching–phosphorescence process (see figure). In the cell-based system, photoactivation of antibody-conjugated AlPc results in irreversible loss of fluorescence signal.

    4. Direct Synthesis of Phenol from Benzene by Pd[BOND]VOx Nanoparticles Using Molecular Oxygen

      Sensen Shang, Dr. Hua Yang, Dr. Jun Li, Bo Chen, Ying Lv and Prof. Shuang Gao

      Article first published online: 11 MAR 2014 | DOI: 10.1002/cplu.201400007

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      Bimetallic nanoparticles: Pd[BOND]VOx nanoparticles (NPs) have been prepared by a one-pot hydrogenation method and used as the catalyst for direct hydroxylation of benzene to phenol with O2 as the oxygen source in aqueous acetic acid medium (see figure). NPs of different diameters display different catalytic activities.

  11. Full Papers

    1. Chirality Transfer in Magnetic Coordination Complexes Monitored by Vibrational and Electronic Circular Dichroism

      Dr. Tao Wu, Xiao-Peng Zhang, Prof. Xiao-Zeng You, Prof. Yi-Zhi Li and Prof. Petr Bouř

      Article first published online: 24 FEB 2014 | DOI: 10.1002/cplu.201300429

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      Good vibrations: Chirality transfer in magnetic 1D iron(III) Schiff base complexes has been recorded by circular dichroism (CD) spectroscopy. Vibrational CD characterization of coordination polymers in solution has been demonstrated for monitoring the polymerization process (see figure).

    2. Experimental and Theoretical Characterization of 5,10-Diminoporphodimethenes: Dearomatized Porphyrinoids from Palladium-Catalyzed Hydrazinations of 5,10-Diarylporphyrins

      Dr. Bruno Bašić, Dr. Oliver B. Locos, Dr. Llew Rintoul, Jinglan Kan, Prof. Jianzhuang Jiang and Assoc. Prof. Dennis P. Arnold

      Article first published online: 20 FEB 2014 | DOI: 10.1002/cplu.201300433

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      A new dearomatized porphyrinoid, 5,10-diiminoporphodimethene, has been prepared and characterized spectroscopically and by theoretical calculations (see figure). The strongly redshifted HOMO–LUMO absorption band has the character of a charge transfer from the unique pyrrole ring to the tripyrrole fragment.

  12. Communications

    1. Quantification of 3-Monochloropropane-1,2-diol Esters in Edible Oils by Large-Volume Injection Coupled to Comprehensive Gas Chromatography–Time-of-Flight Mass Spectrometry

      Dr. Sjaak de Koning

      Article first published online: 29 JAN 2014 | DOI: 10.1002/cplu.201300351

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      Food contaminants: A method for the determination of 3-monochloropropane-1,2-diol (3-MCPD) esters in edible oils and fats is presented. The simplified sample preparation consists of alkaline hydrolysis followed by extraction of 3-MCPD from the lipid matrix and derivatization with phenylboronic acid. The limit of detection is 0.8 μg kg−1. The highlighted peak in the graphic shows the clear separation of 3-MCPD ester.

  13. Call for Papers

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