European Journal of Inorganic Chemistry

Cover image for Vol. 2015 Issue 24

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

Editor: Karen Hindson, Deputy Editor: Preeti Vashi

Impact Factor: 2.942

ISI Journal Citation Reports © Ranking: 2014: 8/44 (Chemistry Inorganic & Nuclear)

Online ISSN: 1099-0682

Associated Title(s): Angewandte Chemie International Edition, Chemistry - A European Journal, Chemistry – An Asian Journal, ChemistryOpen, ChemCatChem, Zeitschrift für anorganische und allgemeine Chemie

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  1. Full Papers

    1. Nanomedicine

      Monitoring the Hemolytic Effect of Mesoporous Silica Nanoparticles after Human Blood Protein Corona Formation

      Diego Stéfani T. Martinez, Amauri J. Paula, Leandro C. Fonseca, Luis Augusto V. Luna, Camila P. Silveira, Nelson Durán and Oswaldo L. Alves

      Article first published online: 26 AUG 2015 | DOI: 10.1002/ejic.201500573

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      The potential toxicity of protein-corona-coated nanoparticles is mitigated as a result of the steric and electrosteric barriers generated by adsorbed proteins, which largely prevents new interactions between the bare surface of the nanoparticles and red blood cell (RBC) membranes.

    2. POM-Containing Hybrid Films

      Covalent Attachment of Thiophene Groups to Polyoxomolybdates or Poly­oxotungstates for the Formation of Hybrid Films

      Ali Saad, Nargis Anwar, Guillaume Rousseau, Pierre Mialane, Jérôme Marrot, Mohamed Haouas, Francis Taulelle, Timothy Mc Cormac and Anne Dolbecq

      Article first published online: 26 AUG 2015 | DOI: 10.1002/ejic.201500660

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      A bisphosphonate ligand functionalized by a thiophene group has been covalently grafted to a polyoxomolybdate and Co- and Ni-containing polyoxotungstates. The hybrid polyoxometalates have been copolymerized with 3-methylthiophene.

    3. Ferrite Spinel Nanoparticles

      Synthesis, Structural Features, Cytotoxicity, and Magnetic Properties of Colloidal Ferrite Spinel Co1–xNixFe2O4 (0.1 ≤ x ≤ 0.9) Nanoparticles

      Robert Pązik, Aleksander Zięcina, Emilia Zachanowicz, Malgorzata Małecka, Blazej Poźniak, Julia Miller, Zbigniew Śniadecki, Natalia Pierunek, Bogdan Idzikowski, Lucyna Mrówczyńska, Anna Ekner-Grzyb and Rafal J. Wiglusz

      Article first published online: 26 AUG 2015 | DOI: 10.1002/ejic.201500668

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      Co1–xNixFe2O4 nanoparticles are produced by a modified Bradley synthesis. The ferrite particles exhibit superparamagnetic behavior, and Ni2+ substitution has no significant effect on the magnetic response. The cytotoxicity of the ferrites against murine macrophages, osteosarcoma cells, and red blood cells is dose-dependent. The particles do not induce hemolysis at concentrations of up to 0.1 mg/mL.

  2. Short Communications

    1. Post-Synthetically Modified MOFs

      Anchoring of Diphenylphosphinyl Groups to NH2-MIL-53 by Post-Synthetic Modification

      Sonia Castellanos, Karthick Babu Sai Sankar Gupta, Alexey Pustovarenko, Alla Dikhtiarenko, Maxim Nasalevich, Pedro Atienzar, Hermenegildo García, Jorge Gascon and Freek Kapteijn

      Article first published online: 25 AUG 2015 | DOI: 10.1002/ejic.201500678

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      Diphenylphosphinyl moieties were attached to NH2-MIL-53(Al) by means of post-synthetic modification. The resulting Ph2–NH–P=O– side group stabilizes the large-pore configuration of the metal–organic framework (MOF) and modifies the energetic levels and optical properties of the linker. This strategy can be useful for the preparation of new porous materials for electronics, sensing, or catalysis.

  3. Full Papers

    1. Thin Films

      Synthesis and Characterization of Fluorinated β-Ketoiminate Zinc Precursors and Their Utility in the AP-MOCVD Growth of ZnO:F

      Samuel D. Cosham, Gabriele Kociok-Köhn, Andrew L. Johnson, Jeff A. Hamilton, Michael S. Hill, Kieran C. Molloy and Rémi Castaing

      Article first published online: 24 AUG 2015 | DOI: 10.1002/ejic.201500536

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      A family of novel bis(β-ketoiminate) zinc precursors baring ether functionalized side arms, have been developed and evaluated for their use in the atmospheric pressure metal organic chemical vapor deposition growth of zinc oxide thin films. Fluorine doped ZnO thin films with a preferred orientation were grown on Si(100) and glass substrates.

    2. Water Oxidation

      Affecting the Catalytic Activity of the Known [Ru(tpy)(bpy)(OH2)]2+ Complex in Water Oxidation by Utilization of a Hangman Ligand

      Pierre Wrzolek and Matthias Schwalbe

      Article first published online: 21 AUG 2015 | DOI: 10.1002/ejic.201500632

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      A ruthenium-based hangman complex has been synthesized and tested in catalytic water oxidation. Experiments using cerium(IV) ammonium nitrate as oxidant in aqueous solution revealed that a mismatched pH retards oxygen evolution in comparison with the unfunctionalized parent compound.

  4. Consolidating Concepts

    1. Ligand Substitution

      New Insight into a Deceptively Simple Reaction: The Coordination of bpy to RuII–Carbonyl Precursors – The Central Role of the fac-[Ru(bpy)Cl(CO)3]+ Intermediate and the Chloride Rebound Mechanism

      Gabriele Balducci, Elisabetta Iengo, Nicola Demitri and Enzo Alessio

      Article first published online: 21 AUG 2015 | DOI: 10.1002/ejic.201500568

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      This manuscript reinvestigates the coordination of 2,2′-bipyridine (bpy) to RuII–chlorido–carbonyl precursors. A thorough review of the literature data is followed by our original results and a detailed discussion that wraps up old and new results in a comprehensive frame and shows that the coordination of diimines to RuII–carbonyl precursors has a more complex mechanism than anticipated.

  5. Short Communications

    1. Cooperative Catalysts

      Ruthenium(II) and Iridium(III) Complexes Bearing Phosphinepyridonate and Phosphinequinolinolate Chelates

      Fan Jiang, Mathieu Achard, Thierry Roisnel, Vincent Dorcet and Christian Bruneau

      Article first published online: 20 AUG 2015 | DOI: 10.1002/ejic.201500765

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      Well-defined ruthenium(II) and iridium(III) complexes featuring five-membered P,N and P,O chelates were synthesized. Owing to the hemilability as well as the reversible proton-responsive character of these chelates, the resulting ruthenium complexes exhibit interesting activities in hydrogenation.

  6. Microreviews

    1. Nanoparticle Toxicity

      Toxicity and Protective Effects of Cerium Oxide Nanoparticles (Nanoceria) Depending on Their Preparation Method, Particle Size, Cell Type, and Exposure Route

      Jacinthe Gagnon and Katharina M. Fromm

      Article first published online: 20 AUG 2015 | DOI: 10.1002/ejic.201500643

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      Nanoceria has attracted a lot of attention for biomedical applications thanks to its radiation-protecting, UV-protecting, and antioxidative properties. However, many studies report toxic effects for nanoceria. This microreview aims to compare the toxicity of nanoceria in terms of preparation method, particle size, concentration, host organism, and exposure method.

    2. Nanoparticles for Magnetic Hyperthermia

      Iron Oxide Based Nanoparticles for Magnetic Hyperthermia Strategies in Biological Applications

      Yolanda Piñeiro, Zulema Vargas, José Rivas and Manuel Arturo López-Quintela

      Article first published online: 20 AUG 2015 | DOI: 10.1002/ejic.201500598

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      Hierarchical core–shell architectures based on magnetic cores decorated with several agents (polymers, drugs, proteins, etc.) allow for multipurpose applications including magnetic hyperthermia, magnetic resonance imaging (MRI) or tissue engineering within a single design. The designed criteria emerge from the interaction of the nano–bio interface, and the planned therapeutic applications.

  7. Full Papers

    1. Zirconocene Polymerization Catalysts

      Controlling the Microstructure of Isotactic Polypropene by C2-Symmetric Zirconocene Polymerization Catalysts: Influence of Alkyl Substituents on Regio- and Stereocontrol

      Mikhail S. Kuklin, Ville Virkkunen, Pascal M. Castro, Luigi Resconi and Mikko Linnolahti

      Article first published online: 20 AUG 2015 | DOI: 10.1002/ejic.201500862

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      Microstructure of polypropene: A series of metallocene catalysts producing highly stereoregular isotactic polypropene is reported. A combined computational and experimental study reveals the dependence of catalytic behavior on ligand substitution pattern.

    2. Transfer Hydrogenations

      An Insight into Transfer Hydrogenation Reactions Catalysed by Iridium(III) Bis-N-heterocyclic Carbenes

      Nestor García, E. A. Jaseer, Julen Munarriz, Pablo J. Sanz Miguel, Victor Polo, Manuel Iglesias and Luis A. Oro

      Article first published online: 19 AUG 2015 | DOI: 10.1002/ejic.201500853

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      The study of a series of iridium(III) bis-NHC complexes in the transfer hydrogenation of imines and ketones shows how slight modifications of the ligand system significantly affect the activity of the active species. Moreover, a catalytic cycle based on DFT calculations and experimental observations has been proposed.

    3. Dimetallic Complexes

      A Pyrazolate-Bridged Bis(pentadentate) Ligand and Its Dinuclear Ruthenium Complex

      Anett C. Sander, Anne Schober, Sebastian Dechert and Franc Meyer

      Article first published online: 19 AUG 2015 | DOI: 10.1002/ejic.201500469

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      A new pyrazolate-bridged ligand has been developed that can bind two metal ions in two pentadentate compartments, leaving a single site per metal atom for binding of exogenous substrates within the dimetallic pocket. A dinuclear Ru complex illustrates the structural features, dynamics, and electronic coupling induced by the new ligand framework.

    4. Rhenium Carbonyl Complexes

      Rhenium Complexes of Ligands Based on Stilbene – Synthesis, Characterization, ­Reactivity, and Conformational Analysis

      Arantxa Pino-Cuevas, Rosa Carballo, Luis Muñoz and Ezequiel M. Vázquez-López

      Article first published online: 19 AUG 2015 | DOI: 10.1002/ejic.201500500

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      Rhenium(I) complexes of amine and imine ligands derived from stilbene are prepared. Configurational and conformational studies of the amine complex are performed through molecular modeling and experimental NMR spectroscopy data. The transformations of the amine complexes to the imine complexes are also monitored by UV/Vis and NMR spectroscopy.

    5. Recovery of Rare-Earths

      Dissolution of the Rare-Earth Mineral Bastnaesite by Acidic Amide Ionic Liquid for Recovery of Critical Materials

      John W. Freiderich, Joseph J. Stankovich, Huimin Luo, Sheng Dai and Bruce A. Moyer

      Article first published online: 19 AUG 2015 | DOI: 10.1002/ejic.201500509

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      A selective dissolution process has been developed to extract rare-earth metal ions through the use of protic ionic liquids.

    6. Iodoargentate Photocatalyst Polymers

      Syntheses, Crystal Structures, and Photocatalytic Properties of Polymeric Iodoargentates [TM(2,2-bipy)3]Ag3I5 (TM = Mn, Fe, Co, Ni, Zn)

      Xiao-Wu Lei, Cheng-Yang Yue, Jian-Qiang Zhao, Yong-Fang Han, Zhong-Ren Ba, Chen Wang, Xin-Ying Liu, Ya-Ping Gong and Xin-Yue Liu

      Article first published online: 19 AUG 2015 | DOI: 10.1002/ejic.201500684

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      A series of inorganic–organic hybrid iodoargentates – [TM(2,2-bipy)3]Ag3I5 (TM = Mn, Fe, Co, Ni, Zn) – have been solvothermally synthesized and structurally characterized. Their semiconductor nature leads to highly efficient heterogeneous photodegradation activities for crystal violet (CV) under visible light irradiation.

    7. Metal String Complexes

      A Very Stable Nickel Broken-Chain Complex with Isolated Ni–Ni Interactions

      Wen-Zhen Wang, Dan Zhao, Ting-Bin Tsao, Rayyat Ismayilov, Gene-Hsiang Lee and Shie-Ming Peng

      Article first published online: 19 AUG 2015 | DOI: 10.1002/ejic.201500674

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      The pentanickel-extended metal-atom chain [Ni55-dpznda)4Cl2] (H2dpznda = N2,N7-bis(pyrazin-2-yl)-1,8-naphthyridine-2,7-diamine) was synthesized, and its magnetism and conductance were studied. In its linear structure, which is partially delocalized, four ligands are wrapped around the metal string forming the core of the molecule.

    8. Controllable Drug Release

      Synthesis of CaTiO3 Nanofibers with Controllable Drug-Release Kinetics

      Qiuhong Zhang, Xiang Li, Zhaohui Ren, Gaorong Han and Chuanbin Mao

      Article first published online: 18 AUG 2015 | DOI: 10.1002/ejic.201500737

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      Calcium titanate (CaTiO3) nanofibers with controlled microstructure were fabricated by electrospinning. The nanofibers synthesized without F127 surfactant, which are of markedly increased surface area and pore volume, present the highest drug-loading capacity and the most sustained release kinetics.

    9. Colorimetric Sensors

      Colorimetric Detection of Spermine by the CuII Complex of Imine-Based Organic Nanoaggregates in Aqueous Medium

      Shweta Chopra, Jasminder Singh, Harpreet Kaur, Ajnesh Singh, Narinder Singh and Navneet Kaur

      Article first published online: 18 AUG 2015 | DOI: 10.1002/ejic.201500489

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      A sensor based on the copper complex of imine-based nanoaggregates can be used for nanomolar selective determination of spermine in aqueous samples without interference from any of the potential interferents. The distinct color change can be seen with the naked eye. The sensor can be used for real-time analysis of spermine in various samples.

    10. Chiral Ruthenium Complex

      Asymmetric Oxidation Synthesis of Modafinil Acid by Use of a Recyclable Chiral-at-Metal Complex

      Zheng-Zheng Li, Su-Yang Yao, A-Hao Wen and Bao-Hui Ye

      Article first published online: 18 AUG 2015 | DOI: 10.1002/ejic.201500617

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      Chiral modafinil acid and its analogues have been synthesized with high ee values by means of asymmetric coordination oxidation of a thioether complex in situ with a chiral-at-metal strategy.

    11. Iridium Selenohalogenides

      Mixed-Valent Selenium Ligands in the Uncharged Iridium Complexes [Ir4Se10Br16] and [Ir6Se8Cl30]

      Karoline Stolze, Bertold Rasche and Michael Ruck

      Article first published online: 17 AUG 2015 | DOI: 10.1002/ejic.201500659

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      The tetra- and hexanuclear ring-shaped iridium molecules [Ir4Se10Br16] and [Ir6Se8Cl30] are among the largest complexes in the category of halogen-rich chalcogen halides of the platinum-group metals. They feature unusual [SeBr] or [SeCl] ligands as well as diverse oxidation states of selenium in one molecule.

    12. Cerium(III) Electrochemistry

      Electrochemical, Thermodynamic and Spectroscopic Investigations of CeIII in a 1-Ethyl-3-methylimidazolium Ethyl Sulfate (EMIES) Ionic Liquid

      Ruma Gupta, Jayashree Gamare, Kavitha Jayachandran, Santosh K. Gupta, Kaiprath V. Lohithakshan and Jayashree V. Kamat

      Article first published online: 17 AUG 2015 | DOI: 10.1002/ejic.201500671

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      The electrochemical and thermodynamic behaviour of cerium was investigated in an ionic liquid using a glassy carbon electrode at different temperatures. The data obtained can be used to critically evaluate the ability to use electrochemical methods for controlled, potential-mediated separation of lanthanides and actinides by electroplating on electrode surfaces in ionic liquid media.

    13. Luminescent Lanthanide Compounds

      Europium Luminescence as a Structural Probe: Structure-Dependent Changes in Eu3+-Substituted Th(C2O4)2·xH2O (x = 6, 2, and 0)

      Santosh K. Gupta, B. Rajeshwari, S. N. Achary, S. J. Patwe, A. K. Tyagi, V. Natarajan and R. M. Kadam

      Article first published online: 17 AUG 2015 | DOI: 10.1002/ejic.201500623

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      The three different structures of Eu3+-doped hydrated thorium(IV) oxalate, Th(C2O4)2·xH2O (x = 6, 2, and 0), are prepared by controlled thermal treatment of the hydrous precipitate of thorium(IV) oxalate, and the structural distortions around the Th4+ ions are investigated through the variation of the luminescence properties of the Eu3+ ions.

    14. Si Hybrids for Fluorescence Imaging

      Multifunctional Hybrid Silica Nanoparticles with a Fluorescent Core and Active Targeting Shell for Fluorescence Imaging Biodiagnostic Applications

      Ana M. Santiago, Tânia Ribeiro, Ana S. Rodrigues, Bruno Ribeiro, Raquel F. M. Frade, Carlos Baleizão and José Paulo S. Farinha

      Article first published online: 14 AUG 2015 | DOI: 10.1002/ejic.201500580

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      We prepare hybrid nanoparticles with a brightly fluorescent silica core and a biocompatible thermoresponsive polymer shell containing a large amount of folic acid (FA) groups. The active cancer-targeting properties of the FA are evaluated against NCI-H460 tumor cells. The FA-loaded nanoparticles internalize faster and in larger amounts than control counterparts without FA.

    15. Group 4 Metal Reactions

      IR Spectra and DFT Calculations of ­M–η2-(NC)–CH3, CH3–MNC, and CH2=M(H)NC Prepared by Reactions of Laser-Ablated Hf and Ti Atoms with Aceto­nitrile

      Han-Gook Cho and Lester Andrews

      Article first published online: 14 AUG 2015 | DOI: 10.1002/ejic.201500624

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      The primary products from reactions of laser-ablated Hf and Ti atoms with acetonitrile. Both Hf and Ti form π complexes [M–η2-(NC)–CH3], which convert into the insertion and methylidene products. The weaker π and stronger m absorptions in the Hf spectra are in line with their relatively high and low energies, while the observed three products are the most stable steps in the proposed reaction path. The group 4 metal methylidenes are agostic.

    16. NLO-Active Sandwich Complexes

      Extended Threefold-Symmetric Second-Harmonic-Generation Chromophores Based on 1,3,5-Trisubstituted Benzene Complexes

      Elisabeth A. Ziemann, J. Benedikt Mietner, Michael Deffner, Nick Van Steerteghem, Koen Clays, Carmen Herrmann and Jürgen Heck

      Article first published online: 14 AUG 2015 | DOI: 10.1002/ejic.201500689

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      Synthetic strategies to protect C–C triple bonds from the electrophilic attack of the cationic organometallic complex CpRu+ (Cp = cyclopentadienyl) are examined. The achieved threefold-symmetric chromophores are characterized, and the concept of 3D nonlinear optically active chromophores is corroborated.

  8. Short Communications

    1. Ligand Deactivation

      Substrate-Mediated Deactivation of a Ru(PtBu2NBn2) Cooperative Complex

      John-Paul J. Bow, Paul D. Boyle and Johanna M. Blacquiere

      Article first published online: 14 AUG 2015 | DOI: 10.1002/ejic.201500798

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      Snapping Shut: The PR2NR′2 ligand family (R and R′ are removed for clarity in the graphic) open the door for easily tuned catalysts for cooperative organic transformations. However, the ligand swings toward the vinylidene, forming a stable (and catalytically inactive) Lewis acid–base adduct. (□ = open coordination site)

    2. Ferric Ammonium Citrate

      Ferric Ammonium Citrate – What's in It?

      Dana Tenne, Benny Bogoslavsky and Avi Bino

      Article first published online: 12 AUG 2015 | DOI: 10.1002/ejic.201500782

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      We eat it, we drink it, and patients swallow multigram quantities of this material, but its compositional and structural properties are unknown. Ferric ammonium citrate is a mixture of several species, and the dominant one is a trinuclear iron citrate complex, [Fe3(cit)4H]6–.

  9. Full Papers

    1. Cycloaddition to an Ru=C Bond

      Selective [2+2] Cycloaddition Reactions of Isocyanates and Thioisocyanates across the M=C Bond in a Ruthenium Carbene Complex

      Julia Weismann and Viktoria H. Gessner

      Article first published online: 12 AUG 2015 | DOI: 10.1002/ejic.201500719

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      Selective [2+2] cycloaddition reactions of heteroallenes across the M=C bond in a ruthenium carbene complex were achieved. The reactions occurred selectively according to the HSAB principle with the soft ruthenium center preferring the softer donor atom of the heteroallene.

    2. Magnetic Adsorbent Composites

      Hierarchical Fe3O4 Core–Shell Layered Double Hydroxide Composites as Magnetic Adsorbents for Anionic Dye Removal from Wastewater

      Qianjiang Yan, Zhang Zhang, Yili Zhang, Ahmad Umar, Zhanhu Guo, Dermot O'Hare and Qiang Wang

      Article first published online: 11 AUG 2015 | DOI: 10.1002/ejic.201500650

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      A hierarchical core-shell Fe3O4@layered double hydroxide composite consisting of a Fe3O4 core and a vertically aligned LDH shell was prepared as magnetic adsorbent for the removal of anionic dye. A record adsorption capacity of 1024 mg/g was achieved even during multi-cycles, suggesting that this novel adsorbent is promising for the treatment of wastewater contaminated by anionic dyes.

    3. Photocatalysis

      Doped Framework Iron Hydroxyl Phosphate as Photocatalyst for Hydrogen Production from Water/Methanol Mixtures

      Marco Serra, Herme G. Baldovi, Mercedes Alvaro and Hermenegildo Garcia

      Article first published online: 11 AUG 2015 | DOI: 10.1002/ejic.201500629

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      Open-framework iron hydroxyl phosphate can be easily doped and exhibits semiconductor behaviour under visible light leading to hydrogen generation

    4. Fluoride Matrices

      Chemical Aspects of the Generation, Trapping, and Decay of Atomic Hydrogen in AlF3 and CaF2

      Reinhard Stößer, Mike Ahrens and Gudrun Scholz

      Article first published online: 11 AUG 2015 | DOI: 10.1002/ejic.201500572

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      It is well known that hydrogen atoms can be generated in the matrices AlF3 and CaF2 at room temperature by ionizing radiation. To learn more about the nature of the hydrogen precursors and hydrogen traps, electron paramagnetic resonance spectroscopy studies regarding defined thermal and chemical influence, as well as mechanical impact on the fluoridic matrices before and after irradiation are performed.

    5. Gold Flavone Complexes

      Linking Flavonoids to Gold – A New Family of Gold Compounds for Potential Therapeutic Applications

      Nedaossadat Mirzadeh, Steven H. Privér, Amanda Abraham, Ravi Shukla, Vipul Bansal and Suresh K. Bhargava

      Article first published online: 11 AUG 2015 | DOI: 10.1002/ejic.201500514

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      The first examples of alkynyl phosphine gold compounds containing flavonoids have been synthesized. They exhibit cytotoxicity towards human prostate cancer cells.

    6. Os-Based Tamoxifen Derivatives

      Synthesis, Characterization, and Biological Properties of Osmium-Based Tamoxifen Derivatives – Comparison with Their Homologues in the Iron and Ruthenium Series

      Hui Zhi Shirley Lee, Olivier Buriez, François Chau, Eric Labbé, Rakesh Ganguly, Christian Amatore, Gérard Jaouen, Anne Vessières, Weng Kee Leong and Siden Top

      Article first published online: 11 AUG 2015 | DOI: 10.1002/ejic.201500770

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      The antiproliferative activities of newly synthesized osmium complexes are compared with those of their homologues in the iron and ruthenium series. All of the tamoxifen-like derivatives exhibit low IC50 values, whereas the Ru and Os diphenols are only slightly cytotoxic.

    7. Thin-Film Precursors

      Synergistic and Antagonistic Ligand Effects in the Transformation of Silver Compounds of Keto- and Cyano-Functionalised Oximates and Nitronates: A Systematic Study Using Thermal Analysis

      Rudolf C. Hoffmann and Jörg J. Schneider

      Article first published online: 10 AUG 2015 | DOI: 10.1002/ejic.201500704

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      The thermal decomposition of silver compounds with functionalised oximato and nitronato ligands proceeds by intra- and intermolecular redox reactions and can also involve unexpected rearrangements. The quest for suitable molecular precursors by variation of side groups within the ligands is a delicate matter, but can be facilitated by advanced thermal analysis. The correct combination of moieties can achieve decomposition at low temperatures.

    8. Anticancer Platinum(II) Complexes

      Cytotoxicity and Structural Analyses of 2,2′-Bipyridine-, 4,4′-Dimethyl-2,2′-bipyr­idine- and 2-(2′-Pyridyl)quinoxalineplatinum(II) Complexes

      Benjamin J. Pages, Yingjie Zhang, Feng Li, Jennette Sakoff, Jayne Gilbert and Janice R. Aldrich-Wright

      Article first published online: 7 AUG 2015 | DOI: 10.1002/ejic.201500754

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      Structurally distorted platinum complexes incorporating bpy, 44Me2bpy, and 2pq were synthesised. X-ray crystallography of five complexes showed unexpected coordination geometry that could impact biological activity and aggregation. PGSE NMR studies supplement these findings. Cytotoxicity was assessed against three cell lines, revealing unexpected trends between complexes and potent overall activity in the HT29 line.

    9. Contrast Agents

      Luminescence and Relaxometric Properties of Heteropolymetallic Metallostar Complexes with Selectively Incorporated Lanthanide(III) Ions

      Matthias Ceulemans, Elke Debroye, Luce Vander Elst, Wim De Borggraeve and Tatjana N. Parac-Vogt

      Article first published online: 7 AUG 2015 | DOI: 10.1002/ejic.201500648

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      The selective incorporation of gadolinium(III) and luminescent lanthanide ions into ditopic ligands results in highly paramagnetic and luminescent metallostar complexes with potential use as probes for bimodal contrast agents for magnet resonance imaging (MRI) and optical imaging.

    10. Bioinspired Hydrogenase Models

      Synthesis, Characterization, and Reactivity of Functionalized Trinuclear Iron–Sulfur Clusters – A New Class of Bioinspired Hydrogenase Models

      Manuel Kaiser and Günther Knör

      Article first published online: 7 AUG 2015 | DOI: 10.1002/ejic.201500574

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      Trinuclear bisphosphine-bridged iron carbonyl clusters are introduced as homogeneous catalysts for proton reduction. Hydrido species form in the presence of acids, and hydrogen is produced electrocatalytically at low overpotential. These electron-rich iron–sulfur clusters are discussed as a promising starting point for the development of photochemical model compounds of iron-based hydrogenases.

    11. Metal Oxide Nanoparticles

      Synthesis of Silica@Ni-Co Mixed Metal Oxide Core–Shell Nanorattles and Their Potential Use as Effective Adsorbents for Waste Water Treatment

      Syam Kandula and Pethaiyan Jeevanandam

      Article first published online: 7 AUG 2015 | DOI: 10.1002/ejic.201500444

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      SiO2@Ni-Co mixed metal oxide core–shell nanorattles are synthesized by the calcination of SiO2@Ni-Co layered double hydroxides at 500 °C. The nanorattles are explored as effective adsorbents for the removal of mixtures of rhodamine B and methylene blue from an aqueous solution. The nanorattles exhibit better adsorption capacity than the individual metal oxides.

    12. Photoluminescence

      Photoluminescence Modulation in Lan­thanide(III)/Pyrazine-2,5-dicarboxylato/Nitrato Frameworks

      Javier Cepeda, Sonia Pérez-Yáñez, Garikoitz Beobide, Oscar Castillo, Jose Ángel García and Antonio Luque

      Article first published online: 3 AUG 2015 | DOI: 10.1002/ejic.201500484

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      Four types of 3D LnIII/pyrazine-2,5-dicarboxylato/nitrato frameworks are synthesized through a solvent-free approach. Their structural diversity is rationalized according to the lanthanide contraction effect and the role played by the nitrate ion (ligand or counterion). The photoluminescence of the complexes can be tuned in response to thermal dehydration.

    13. Bio-Silica Nanocomposites

      Carrageenan–Silica Hybrid Nanoparticles Prepared by a Non-Emulsion Method

      Sofia F. Soares, Tito Trindade and Ana L. Daniel-da-Silva

      Article first published online: 3 AUG 2015 | DOI: 10.1002/ejic.201500450

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      Nanoparticles of κ-carrageenan–silica hybrids with narrow size distribution were prepared by using a sol–gel non-emulsion method. Unlike silica particles, these hybrids display thermal sensitivity, which is of great relevance for biomedical applications such as drug encapsulation and thermally controlled drug-delivery systems.

    14. Borosulfates

      Borosulfates Cs2B2S3O13, Rb4B2S4O17, and A3HB4S2O14 (A = Rb, Cs) – Crystalline Approximants for Vitreous B2O3?

      Michael Daub and Harald Hillebrecht

      Article first published online: 30 JUL 2015 | DOI: 10.1002/ejic.201500603

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      Cs2B2S3O13 and Rb4B2S4O17 are the first examples of borosulfates with directly connected BO4 tetrahedra. Similar motifs are known for borates and borosulfates. In A3HB4S2O14 (A = Rb, Cs) there are planar layers of B2O3 with trigonal BO3 units and boroxol rings B3O3. These are the characteristic features of vitreous B2O3.

    15. Nanoparticle-Modified Ferritins

      Orthogonal Functionalization of Ferritin via Supramolecular Re-Assembly

      Silvia J. Spa, Anton Bunschoten, Marcus T. M. Rood, Ruud J. B. Peters, Abraham J. Koster and Fijs W. B. van Leeuwen

      Article first published online: 24 JUL 2015 | DOI: 10.1002/ejic.201500386

      Thumbnail image of graphical abstract

      To investigate the control on ferritin functionalization by supramolecular re-assembly, ferritin with modular functionality and still capable of iron mineralization was created. The ratio in which Cy3-, Cy5-, and non-functionalized subunits were mixed, was indicative for the ratio in which the variable subunits were observed in the re-assembled capsids.

    16. Fluorescent Quantum-Dot Bioconjugates

      Cytocompatible Fluorescent Quantum Dot/PEG-Chitosan Bioconjugates for Nanomedicine Applications

      Alexandra A. P. Mansur, Camila G. de Almeida, Sandhra M. de Carvalho, Lucas V. de Faria, Mauro V. de Almeida and Herman S. Mansur

      Article first published online: 23 JUL 2015 | DOI: 10.1002/ejic.201500441

      Thumbnail image of graphical abstract

      Novel nanobioconjugates based on Cd-based quantum dots and a PEGylated chitosan derivative as capping ligand have been designed and synthesised by a single-step aqueous route at room temperature. These nanohybrids are luminescent and cytocompatible towards two cell lines tested in vitro, therefore showing potential as biomarkers in nanomedicine applications.

  10. Correspondence

    1. Sensors for Iron Ions

      Key Considerations for Sensing FeII and FeIII in Aqueous Media

      Shawn C. Burdette

      Article first published online: 17 JUL 2015 | DOI: 10.1002/ejic.201500566

      Thumbnail image of graphical abstract

      Recently, Ghosh et al. reported on the fluorescent response of N-(2-aminoethyl)naphthalen-1-amine toward FeII, FeIII, and HgII (K. Ghosh, S. Rathi, P. Gupta, P. Vashisth, V. Pruthi, Eur. J. Inorg. Chem. 2015, 311), concluding that metal binding to the diamine chelator leads to chelation-induced quenching; however, the experimental protocols are incompatible with the aqueous chemistry of FeIII.

  11. Short Communications

    1. Terminal Phosphinidenes

      The Reaction of Terminal Phosphinidene Complexes [RP–W(CO)5] with Vinylbor­onic Acids: Cycloaddition vs. P–C Bond Formation

      Yong Xiang Ng and François Mathey

      Article first published online: 14 JUL 2015 | DOI: 10.1002/ejic.201500594

      Thumbnail image of graphical abstract

      Terminal phosphinidene complexes react with vinylboronic acid to give the expected phosphirane complexes, but the addition of K3PO4 changes the course of the reaction, and secondary vinylphosphine complexes are obtained instead.

  12. Full Papers

    1. Phosphacyclobutadiene Complexes

      Cobalt(I) and Nickel(II) Complexes of Bis(1,3-diphosphacyclobutadiene) Sandwich Anions

      Christian Rödl and Robert Wolf

      Article first published online: 14 JUL 2015 | DOI: 10.1002/ejic.201500583

      Thumbnail image of graphical abstract

      Dinuclear diphosphacyclobutadiene complexes have been synthesized by transmetalating the thallium(I) salt [Tl(thf)2{Co(P2C2tBu2)2}] with organometallic cobalt(I) and nickel(II) halides. The structural, spectroscopic, and redox properties of two new bimetallic complexes are presented, and their electronic structures are analyzed by DFT calculations.

  13. Microreviews

    1. Bioinorganic Interfaces

      Understanding and Tuning Bioinorganic Interfaces for the Design of Bionanocomposites

      Hugo Voisin, Carole Aimé and Thibaud Coradin

      Article first published online: 14 JUL 2015 | DOI: 10.1002/ejic.201500403

      Thumbnail image of graphical abstract

      Understanding and controlling interfacial interactions between biological molecules – from lipids to proteins – and inorganic nano-objects, polyoxometallates and colloids allows the synthesis of bionanocomposites with applications in biotechnology and biomedicine.

  14. Full Papers

    1. Upconversion Nanomaterials

      The Effects of Morphology and Linker Length on the Properties of Peptide–Lanthanide Upconversion Nanomaterials as G2 Phase Cell Cycle Inhibitors

      Chi-Fai Chan, Chen Xie, Ming-Kiu Tsang, Sam Lear, Lixiong Dai, Yan Zhou, Jakub Cicho, Miroslaw Karbowiak, Dariusz Hreniak, Rongfeng Lan, Steve L. Cobb, Michael Hon-Wah Lam, Jianhua Hao and Ka-Leung Wong

      Article first published online: 8 JUL 2015 | DOI: 10.1002/ejic.201500321

      Thumbnail image of graphical abstract

      Plk1-specific peptides are bioconjugated onto spherical and cubic NaGdF4@SiO2 nanoparticles, and the inhibitory effects of the hybrid materials towards normal cells and cancer cells are investigated.

  15. Short Communications

    1. Glycerodendrimers

      Platinum Nanoparticles Stabilized by Glycerodendrimers: Synthesis and Application to the Hydrogenation of α,β-Unsaturated Ketones under Mild Conditions

      Bérengère Menot, Lionel Salmon and Sandrine Bouquillon

      Article first published online: 24 JUN 2015 | DOI: 10.1002/ejic.201500530

      Thumbnail image of graphical abstract

      Pt nanoparticles are stabilized by glycerodendrimers (GD) and used (and recycled) for the reduction of α,β-unsaturated ketones to saturated ketones at room temperature in water under H2 (101.3 kPa).

  16. Full Papers

    1. Bimodal MRI Agents

      Magnetofluorescent Nanoaggregates Incorporating Terbium(III) Complexes as Potential Bimodal Agents for Magnetic Resonance and Optical Imaging

      Michael Harris, Sophie Carron, Luce Vander Elst, Sophie Laurent and Tatjana N. Parac-Vogt

      Article first published online: 23 JUN 2015 | DOI: 10.1002/ejic.201500310

      Thumbnail image of graphical abstract

      Magnetofluorescent nanoaggregates incorporating amphiphilic terbium(III) complexes are created and their potential as bimodal agents for magnetic resonance and optical imaging are examined.

    2. Nanophosphors

      Uniform Poly(acrylic acid)-Functionalized Lanthanide-Doped LaVO4 Nanophosphors with High Colloidal Stability and Biocompatibility

      Nuria O. Nuñez, Paola Zambrano, Jorge García-Sevillano, Eugenio Cantelar, Sara Rivera-Fernández, Jesús M. de la Fuente and Manuel Ocaña

      Article first published online: 22 JUN 2015 | DOI: 10.1002/ejic.201500265

      Thumbnail image of graphical abstract

      Uniform lanthanide-doped LaVO4 nanospheres functionalized with poly(acrylic acid) are synthesized with a controllable size by a one-pot procedure. As these nanoparticles present strong red (Eu) or near-infrared (Nd) luminescence, are nontoxic for cells, and show high colloidal stability in physiological buffer, they are good candidates as optical biomarkers for in vitro applications.

    3. Multimodal Imaging

      Patent Blue Derivatized Dendronized Iron Oxide Nanoparticles for Multimodal Imaging

      Lai Truong-Phuoc, Marie Kueny-Stotz, Julien Jouhannaud, Antonio Garofalo, François-Xavier Blé, Hervé Simon, Franklin Tellier, Patrick Poulet, Piero Chirco, Sylvie Begin-Colin, Geneviève Pourroy and Delphine Felder-Flesch

      Article first published online: 2 JUN 2015 | DOI: 10.1002/ejic.201500289

      Thumbnail image of graphical abstract

      Iron oxide particles of 10 and 20 nm diameter, dendronized and derivatized with Patent Blue VF dye, survived subcutaneous injection for bimodal lymph node detection with a hand-held probe during surgery.

    4. Magnetic Colloids

      Long-Term Stability and Reproducibility of Magnetic Colloids are Key Issues for Steady Values of Specific Power Absorption Over Time

      Beatriz Sanz, M. Pilar Calatayud, Nicolás Cassinelli, M. Ricardo Ibarra and Gerardo F. Goya

      Article first published online: 2 JUN 2015 | DOI: 10.1002/ejic.201500303

      Thumbnail image of graphical abstract

      The poly(ethyleneimine)-coated magnetic nanoparticles (PEI-MNPs) prepared in this work by oxidative hydrolysis show good reproducibility of size and size distribution. In addition, these PEI-MNPs show only a moderate decrease in the specific power absorption when they aggregate over time. These results render these particles suitable for applications in magnetic hyperthermia.

  17. Microreviews

    1. Bio-Inspired Si Coatings

      Bio-Inspired Formation of Silica Thin Films: From Solid Substrates to Cellular Interfaces

      Woo Kyung Cho and Sung Ho Yang

      Article first published online: 19 MAY 2015 | DOI: 10.1002/ejic.201500308

      Thumbnail image of graphical abstract

      The bio-inspired formation of silica thin films on the surfaces of flat solids, microparticles, nanoparticles, and living cells is reviewed.

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