Matthew J. Rosseinsky

University of Liverpool, Liverpool, England, United Kingdom

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Publications (453)2882.24 Total impact

  • [Show abstract] [Hide abstract]
    ABSTRACT: We report two isoreticular 3D peptide-based porous frameworks formed by coordination of the tripeptides Gly-L-His-Gly and Gly-L-His-L-Lys to Cu(II) which display sponge-like behaviour. These porous materials undergo structural collapse upon evacuation that can be reversed by exposure to water vapour, which permits recovery of the original open channel structure. This is further confirmed by sorption studies that reveal that both solids exhibit selective sorption of H2 O while CO2 adsorption does not result in recovery of the original structures. We also show how the pendant aliphatic amine chains, present in the framework from the introduction of the lysine amino acid in the peptidic backbone, can be post-synthetically modified to produce urea-functionalised networks by following methodologies typically used for metal-organic frameworks built from more rigid "classical" linkers.
    Chemistry - A European Journal 09/2015; DOI:10.1002/chem.201502098 · 5.73 Impact Factor
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    ABSTRACT: Ferroelectric and ferromagnetic materials exhibit long-range order of atomic-scale electric or magnetic dipoles that can be switched by applying an appropriate electric or magnetic field, respectively. Both switching phenomena form the basis of non-volatile random access memory, but in the ferroelectric case, this involves destructive electrical reading and in the magnetic case, a high writing energy is required. In principle, low-power and high-density information storage that combines fast electrical writing and magnetic reading can be realized with magnetoelectric multiferroic materials. These materials not only simultaneously display ferroelectricity and ferromagnetism, but also enable magnetic moments to be induced by an external electric field, or electric polarization by a magnetic field. However, synthesizing bulk materials with both long-range orders at room temperature in a single crystalline structure is challenging because conventional ferroelectricity requires closed-shell d(0) or s(2) cations, whereas ferromagnetic order requires open-shell d(n) configurations with unpaired electrons. These opposing requirements pose considerable difficulties for atomic-scale design strategies such as magnetic ion substitution into ferroelectrics. One material that exhibits both ferroelectric and magnetic order is BiFeO3, but its cycloidal magnetic structure precludes bulk magnetization and linear magnetoelectric coupling. A solid solution of a ferroelectric and a spin-glass perovskite combines switchable polarization with glassy magnetization, although it lacks long-range magnetic order. Crystal engineering of a layered perovskite has recently resulted in room-temperature polar ferromagnets, but the electrical polarization has not been switchable. Here we combine ferroelectricity and ferromagnetism at room temperature in a bulk perovskite oxide, by constructing a percolating network of magnetic ions with strong superexchange interactions within a structural scaffold exhibiting polar lattice symmetries at a morphotropic phase boundary (the compositional boundary between two polar phases with different polarization directions, exemplified by the PbZrO3-PbTiO3 system) that both enhances polarization switching and permits canting of the ordered magnetic moments. We expect this strategy to allow the generation of a range of tunable multiferroic materials.
    Nature 09/2015; 525:363 - 366. DOI:10.1038/nature14881 · 41.46 Impact Factor
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    ABSTRACT: A porphyrin-based metal-organic framework is shown to be structurally stable towards acid loading using either hydrochloric or formic acid. The capacity of this material as an ammonia sorbent was analysed using micro-breakthrough experiments in both dry and humid ammonia flows. The acid loaded material exhibited excellent uptake in comparison with the parent MOF.
    Chemical Communications 08/2015; DOI:10.1039/c5cc06209h · 6.83 Impact Factor
  • Hripsime Gasparyan · John Bleddyn Claridge · Matthew J Rosseinsky
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    ABSTRACT: The oxygen permeation performance of Ba0.5Sr0.5Co0.8-xFe0.2-yMox+yO3-δ (x+y=0; 0.025; 0.05; 0.25; 0.375 for Co/Fe=4 and x+y=0.125 for Co/Fe=2) ceramic perovskite materials was studied. The effects of the composition, structure, morphology and membrane thickness on permeation flux were investigated. We demonstrate how Mo substitution significantly improves the stability of BSCF membranes not only under static but also dynamic conditions by depressing the degradation rates at 750 oC. The highest permeation flux among the studied membranes was measured for a 1 mm thick Ba0.5Sr0.5Co0.78Fe0.195Mo0.025O3-δ as 1.55 ml min-1 cm-2 at 950 oC which is very close to the flux measured for BSCF (1.65 ml min-1 cm-2) under the same conditions.
    07/2015; DOI:10.1039/C5TA04046A
  • Michael Barrow · Arthur Taylor · Patricia Murray · Matthew J Rosseinsky · Dave J Adams
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    ABSTRACT: Iron oxide nanoparticles (IONPs, sometimes called superparamagnetic iron oxide nanoparticles or SPIONs) have already shown promising results for in vivo cell tracking using magnetic resonance imaging (MRI). To fully exploit the potential of these materials as contrast agents, there is still a need for a greater understanding of how they react to physiological conditions. A key aspect is the specific nature of the surface coating, which can affect important properties of the IONPs such as colloidal stability, toxicity, magnetism and labelling efficiency. Polymers are widely used as coatings for IONPs as they can increase colloidal stability in hydrophilic conditions, as well as protect the iron oxide core from degradation. In this tutorial review, we will examine the design and synthesis approaches currently being employed to produce polymer coated IONPs as cell tracking agents, and what considerations must be made. We will also give some perspective on the challenges and limitations that remain for polymer coated IONPs as MRI contrast agents for stem cell tracking.
    Chemical Society Reviews 07/2015; DOI:10.1039/c5cs00331h · 33.38 Impact Factor
  • Pancreatology 06/2015; 15(3):S22. DOI:10.1016/j.pan.2015.05.111 · 2.84 Impact Factor
  • Matthew J Rosseinsky · Martin W Smith · Christopher M Timperley
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    ABSTRACT: News & Views article discussing the Nature Materials paper by J Mondloch and colleagues describing the accelerated destruction of organophosphorus nerve agents by metal-organic frameworks.
    Nature Material 04/2015; 14:469-470. DOI:10.1038/nmat4272 · 36.50 Impact Factor
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    ABSTRACT: Reaction of iron (IIII) with the free base tetrakis(4-carboxyphenyl)porphyrin (H2TCPP) in presence of different bases leads to the formation of a series of iron/porphyrin metal organic frameworks. Such crystal engineering approach led to the obtaining of four structures presenting three different topologies and inorganic secondary building units (SBU). Depending on the synthesis conditions: isolated FeIII octahedra, diiron(II) paddle wheel dimers or extended [FeIII(OH)O4]n chains could be obtained in a controlled manner. The influence of the synthetic conditions on the final structure and the oxidation state of iron is discussed. Stability of the porous solids towards air and water is studied and their intrinsic porosity is assessed.
    Crystal Growth & Design 04/2015; 15(4):1819-1826. DOI:10.1021/cg501855k · 4.89 Impact Factor
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    ABSTRACT: Calculation of the energetics of aliovalent substitution into the olivine LiMgPO4 suggests that replacement of Mg2+ by In3+ is the most effective way to introduce lithium vacancies and thus generate lithium ion conductivity. Experimental synthesis accesses materials with up to 17% Li vacancy content. An order of magnitude increase in the high temperature hopping rates probed by 7Li NMR spin lattice relaxation, and over two orders of magnitude increase in the room temperature Li+ ion conductivity measured by impedance spectroscopy is observed on introduction of In3+ ions and Li vacancies. NMR spectroscopy and calculations reveal that the energy barrier to site-to-site hopping is 0.3 eV - 0.5 eV, comparable with best-in-class non-oxide systems such as argyrodite, but NMR derived hopping rates, and impedance spectroscopy shows that longer range transport is less facile with activation energies in the range of 0.7 - 1 eV. Calculations suggest that this is because the Li vacancies are strongly bound to the In3+ dopants, suggesting that high lithium mobilities in oxides are accessible but high conductivities require strategies to separate defect from dopant.
    Chemistry of Materials 03/2015; 27(6):2074-2091. DOI:10.1021/cm504518q · 8.35 Impact Factor
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    ABSTRACT: Lead-free bismuth-based perovskite oxides with polarization directed along the [001]p primitive perovskite unit cell edge, analogous to tetragonal PbTiO3, are synthesized at ambient pressure. Enhanced piezoelectric properties, large polarizations, and high depolarization temperatures are observed in the wide morphotropic phase boundary region formed with a rhombohedral phase, with up to 92.5% Bi on the perovskite A site. © 2015 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    Advanced Materials 03/2015; 27(18). DOI:10.1002/adma.201405452 · 17.49 Impact Factor
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    ABSTRACT: Tracking stem cells in vivo using non-invasive techniques is critical to evaluate the efficacy and safety of stem cell therapies. Superparamagnetic iron oxide nanoparticles (SPIONs) enable cells to be tracked using magnetic resonance imaging (MRI), but to obtain detectable signal cells need to be labelled with a sufficient amount of iron oxide. For the majority of SPIONs, this can only be obtained with the use of transfection agents, which can adversely affect cell health. Here, we have synthesised a library of dextran-based polymer coated SPIONs with varying surface charge from −1.5 mV to +18.2 mV via a co-precipitation approach and investigated their ability to be directly internalised by stem cells without the need for transfection agents. The SPIONs were colloidally stable in physiological solutions. The crystalline phase of the particles was confirmed with powder X-ray diffraction and their magnetic properties were characterised using SQUID magnetometry and magnetic resonance. Increased surface charge led to six-fold increase in uptake of particles into stem cells and higher MRI contrast, with negligible change in cell viability. Cell tracking velocimetry was shown to be a more accurate method for predicting MRI contrast of stem cells compared to measuring iron oxide uptake through conventional bulk iron quantification.
    02/2015; 3(4). DOI:10.1039/C5BM00011D
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    ABSTRACT: Crystalline materials that combine electrical polarization and magnetization could be advantageous in applications such as information storage, but these properties are usually considered to have incompatible chemical bonding and electronic requirements. Recent theoretical work on perovskite materials suggested a route for combining both properties. We used crystal chemistry to engineer specific atomic displacements in a layered perovskite, (Ca(y)Sr(1- y))(1.15)Tb(1.85)Fe2O7, that change its symmetry and simultaneously generate electrical polarization and magnetization above room temperature. The two resulting properties are magnetoelectrically coupled as they arise from the same displacements. Copyright © 2015, American Association for the Advancement of Science.
    Science 01/2015; 347(6220-6220):420-424. DOI:10.1126/science.1262118 · 33.61 Impact Factor
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    ABSTRACT: The synthesis of metal–organic frameworks with large three-dimensional channels that are permanently porous and chemically stable offers new opportunities in areas such as catalysis and separation. Two linkers (L1=4,4′,4′′,4′′′-([1,1′-biphenyl]-3,3′,5,5′-tetrayltetrakis(ethyne-2,1-diyl)) tetrabenzoic acid, L2=4,4′,4′′,4′′′-(pyrene-1,3,6,8-tetrayltetrakis(ethyne-2,1-diyl))tetrabenzoic acid) were used that have equivalent connectivity and dimensions but quite distinct torsional flexibility. With these, a solid solution material, [Zr6O4(OH)4(L1)2.6(L2)0.4]⋅(solvent)x, was formed that has three-dimensional crystalline permanent porosity with a surface area of over 4000 m2 g−1 that persists after immersion in water. These properties are not accessible for the isostructural phases made from the separate single linkers.
    Angewandte Chemie 01/2015; 127(1). DOI:10.1002/ange.201406501
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    ABSTRACT: A stable visible-light-driven photocatalyst (λ≥450 nm) for water oxidation is reported. Rhodium substitution into the pyrochlore Y2Ti2O7 is demonstrated by monitoring Vegard′s law evolution of the unit-cell parameters with changing rhodium content, to a maximum content of 3 % dopant. Substitution renders the solid solutions visible-light active. The overall rate of oxygen evolution is comparable to WO3 but with superior light-harvesting and surface-area-normalized turnover rates, making Y2Ti1.94Rh0.06O7 an excellent candidate for use in a Z-scheme water-splitting system.
    Angewandte Chemie 12/2014; 126(52). DOI:10.1002/ange.201407179
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    ABSTRACT: A stable visible-light-driven photocatalyst (λ≥450 nm) for water oxidation is reported. Rhodium substitution into the pyrochlore Y2Ti2O7 is demonstrated by monitoring Vegard′s law evolution of the unit-cell parameters with changing rhodium content, to a maximum content of 3 % dopant. Substitution renders the solid solutions visible-light active. The overall rate of oxygen evolution is comparable to WO3 but with superior light-harvesting and surface-area-normalized turnover rates, making Y2Ti1.94Rh0.06O7 an excellent candidate for use in a Z-scheme water-splitting system.
    Angewandte Chemie International Edition 12/2014; 53(52). DOI:10.1002/anie.201407179 · 11.26 Impact Factor
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    ABSTRACT: The electrochemical performance of the layered perovskite YSr2Cu3-xCoxO7+δ, a potential solid oxide fuel cell (SOFC) cathode, is improved by increasing the Co content from x = 1.00 to a maximum of x = 1.30. Single phase samples with x > 1.00 are obtained by tuning the Y/Sr ratio, yielding the composition Y1-ySr2+yCu3-xCoxO7+δ (where y ≤ 0.05). The high temperature structure of Y0.95Sr2.05Cu1.7Co1.3O7+δ at 740 °C is characterised by powder neutron diffraction and the potential of this Co-enriched material as a SOFC cathode is investigated by combining AC impedance spectroscopy, four-probe DC conductivity and powder XRD measurements to determine its electrochemical properties along with its thermal stability and compatibility with a range of commercially available electrolytes. The material is shown to be compatible with doped ceria electrolytes at 900 °C.
    Solid State Sciences 11/2014; 37. DOI:10.1016/j.solidstatesciences.2014.07.013 · 1.84 Impact Factor
  • Christophe Didier · John Claridge · Matthew Rosseinsky
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    ABSTRACT: The title compound is prepared by solid state reaction of stoichiometric mixtures of BaCO3, Ga2O3, and In2O3 (alumina boat, 12 h at either 1100, 1200, or 1300 °C under ambient air) and characterized by powder XRD, time-of-flight neutron diffraction, and impedance measurements.
    ChemInform 10/2014; 45(41). DOI:10.1002/chin.201441003
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    ABSTRACT: Development of heterogeneous catalysts for complex reactions such as Fischer-Tropsch synthesis of fuels is hampered by difficult reaction conditions, slow characterisation techniques such as chemisorption and temperature-programmed reduction and the need for long term stability. High-throughput (HT) methods may help, but their use has until now focussed on bespoke micro-reactors for direct measurements of activity and selectivity. These are specific to individual reactions and do not provide more fundamental information on the materials. Here we report using simpler HT characterisation techniques (XRD and TGA) along with ageing under Fischer-Tropsch reaction conditions to provide information analogous to metal surface area, degree of reduction and thousands of hours of stability testing time for hundreds of samples per month. The use of this method allowed the identification of a series of highly stable, high surface area catalysts promoted by Mg and Ru. In an advance over traditional multichannel HT reactors, the chemical and structural information we obtain on the materials allows us to identify the structural effects of the promoters and their effects on the modes of deactivation observed.
    Chemical Science 10/2014; 6(2). DOI:10.1039/C4SC02116A · 9.21 Impact Factor
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    Christophe Didier · John Claridge · Matthew Rosseinsky
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    ABSTRACT: Ba2InGaO5 was prepared by high-temperature solid-state reaction. This compound adopts a brownmillerite structure below 1200 degrees C, which was not found in past studies of Ba-2(In1-xGax)(2)O-5. Combined structure refinements against neutron and X-ray powder diffraction data show that this material adopts a layered ordering of In and Ga. This is one of a few examples of such an ordering in the brownmillerite structure solely due to size difference between the B cations. This ordering further stabilizes the brownmillerite crystal structure compared to other compositions at smaller Ga contents (x < 0.5), for which the transition to a disordered cubic perovskite occurs at a much lower temperature. As could be expected, such stronger ordering is detrimental to ionic conductivity. Crown Copyright (C) 2014 Published by Elsevier Inc.
    Journal of Solid State Chemistry 10/2014; 218:38–43. DOI:10.1016/j.jssc.2014.06.011 · 2.13 Impact Factor
  • Kyriakos C. Stylianou · John Bacsa · Darren Bradshaw · Matthew J. Rosseinsky
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    ABSTRACT: The reaction of NiII with a tetra-benzoate pyrene ligand produces a 3D porous framework based on infinite 1D NiII chains. The NiII–O connectivity and the formation of a hydroxo-bridge (μ3-OH) responsible for the connection of the central NiII atoms within the 1D NiII–(μ3-OH)2–NiII chains can be straightforwardly compared with the TiIV–O–TiIV connectivity seen in TiO2. The arrangement of the TBAPy ligand around the 1D rutile-based chains leads in the generation of a porous framework with two distinct types of pores; based on the chemistries of these two types of pores, one can be labelled as hydrophobic and the other as hydrophilic. The use of different activation methods results in the generation of either a porous framework free of guest molecules or a completely solvent-free material, in which the terminal H2O molecules bound to NiII were removed, leading thus to a framework with open NiII sites. CO2 isotherms collected on both frameworks at 195 K and one barshowed type I isotherms characteristic of microporous materials (BET surface areas for: guest-free framework: 257(3) m2·g–1; solvent-free framework: 362(2) m2·g–1). The affinity of both networks at zero coverage for both CO2 and CH4 was found to be greater when the unsaturated NiII sites are available within the void space.
    Zeitschrift für anorganische Chemie 09/2014; 640(11). DOI:10.1002/zaac.201400136 · 1.16 Impact Factor

Publication Stats

16k Citations
2,882.24 Total Impact Points


  • 2000–2015
    • University of Liverpool
      • Department of Chemistry
      Liverpool, England, United Kingdom
  • 2014
    • University of Oslo
      • Department of Chemistry
      Kristiania (historical), Oslo County, Norway
  • 2012
    • Hungarian Academy of Sciences
      • Institute for Solid State Physics and Optics
      Budapest, Budapest fovaros, Hungary
  • 2011–2012
    • Sun Yat-Sen University
      • Department of Chemical Engineering
      Shengcheng, Guangdong, China
  • 2010
    • University of Exeter
      Exeter, England, United Kingdom
  • 1989–2010
    • University of Oxford
      • • Inorganic Chemistry Laboratory
      • • Department of Chemistry
      Oxford, England, United Kingdom
  • 2007
    • Beverly Hospital, Boston MA
      Beverly, Massachusetts, United States
  • 2006
    • Durham University
      • Department of Chemistry
      Durham, England, United Kingdom
    • Boston College, USA
      Boston, Massachusetts, United States
  • 2004
    • AGH University of Science and Technology in Kraków
      • Department of Solid State Physics
      Cracovia, Lesser Poland Voivodeship, Poland
    • The University of Sheffield
      • Department of Materials Science and Engineering
      Sheffield, England, United Kingdom
  • 2003
    • Okayama University
      • Department of Chemistry
      Okayama, Okayama, Japan
  • 1993
    • University of Cambridge
      Cambridge, England, United Kingdom
  • 1989–1992
    • Institut Laue-Langevin
      Grenoble, Rhône-Alpes, France
  • 1991
    • University of Sussex
      Brighton, England, United Kingdom