Matthew J. Rosseinsky

University of Liverpool, Liverpool, England, United Kingdom

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Publications (438)2666.72 Total impact

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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 · 4.56 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 · 8.54 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 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    Advanced Materials 03/2015; 27(18). DOI:10.1002/adma.201405452 · 15.41 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 · 31.48 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 International Edition 12/2014; 53(52). DOI:10.1002/anie.201407179 · 11.34 Impact Factor
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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: 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 · 1.68 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 · 8.60 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 · 2.20 Impact Factor
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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 · 1.25 Impact Factor
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    ABSTRACT: Heteroepitaxial growth of BaSnO3 and Ba1−xLaxSnO3 (x = 7%) lanthanum doped barium stannate thin films on different perovskite single crystal (SrTiO3 (001) and SmScO3 (110)) substrates has been achieved by pulsed laser deposition under optimized deposition conditions. X-ray diffraction measurements indicate that the films on either of these substrates are relaxed due to the large mismatch and present a high degree of crystallinity with narrow rocking curves and smooth surface morphology while analytical quantification by proton induced X-ray emission confirms the stoichiometric La transfer from a polyphasic target, producing films with measured La contents above the bulk solubility limit. The films show degenerate semiconducting behavior on both substrates, with the observed room temperature resistivities, Hall mobilities, and carrier concentrations of 4.4 mΩ cm, 10.11 cm2 V−1 s−1, and 1.38 × 1020 cm−3 on SmScO3 and 7.8 mΩ cm, 5.8 cm2 V−1 s−1, and 1.36 × 1020 cm−3 on SrTiO3 ruling out any extrinsic contribution from the substrate. The superior electrical properties observed on the SmScO3 substrate are attributed to reduction in dislocation density from the lower lattice mismatch.
    Applied Physics Letters 08/2014; 105(025104). DOI:10.1063/1.4891816 · 3.52 Impact Factor
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    ABSTRACT: Oligodendrocyte precursor cells (OPCs) have shown high promise as a transplant population to promote regeneration in the central nervous system, specifically, for the production of myelin – the protective sheath around nerve fibers. While clinical trials for these cells have commenced in some areas, there are currently key barriers to the translation of neural cell therapies. These include the ability to (a) image transplant populations in vivo; (b) genetically engineer transplant cells to augment their repair potential; and (c) safely target cells to sites of pathology. Here, we review the evidence that magnetic nanoparticles (MNPs) are a 'multifunctional nanoplatform' that can aid in safely addressing these translational challenges in neural cell/OPC therapy: by facilitating real-time and post-mortem assessment of transplant cell biodistribution, and biomolecule delivery to transplant cells, as well as non-invasive 'magnetic cell targeting' to injury sites by application of high gradient fields. We identify key issues relating to the standardization and reporting of physicochemical and biological data in the field; we consider that it will be essential to systematically address these issues in order to fully evaluate the utility of the MNP platform for neural cell transplantation, and to develop efficacious neurocompatible particles for translational applications.
    07/2014; 2:23. DOI:10.1186/2052-8426-2-23
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    ABSTRACT: A solution chemistry synthetic route yields Cs3C60 with the face-centred cubic structure. The described method uses well-established Schlenk techniques and THF as a solvent. The controlled addition of an organo-metallic salt reducing agent prevents the formation of C604- salts. The final product can be precipitated from the solution using hexane as an anti-solvent.
    Faraday Discussions 07/2014; DOI:10.1039/C4FD00085D
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    ABSTRACT: We have investigated the low-temperature magnetic state of face-centered-cubic (fcc) ${\mathrm{Cs}}_{3}{\mathrm{C}}_{60}$, a Mott insulator and the first molecular analog of a geometrically frustrated Heisenberg fcc antiferromagnet with $S=1/2$ spins. Specific heat studies reveal the presence of both long-range antiferromagnetic ordering and a magnetically disordered state below ${T}_{N}=2.2$ K, which is in agreement with local probe experiments. These results together with the strongly suppressed ${T}_{N}$ are unexpected for conventional atom-based fcc antiferromagnets, implying that the fulleride molecular degrees of freedom give rise to the unique magnetic ground state.
    Physical Review B 07/2014; 90(1). DOI:10.1103/PhysRevB.90.014413 · 3.66 Impact Factor
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    ABSTRACT: The Extended Module Materials Assembly computational method for structure solution and prediction has been implemented for close-packed lattices. Exploring the family of B-site deficient materials in hexagonal perovskite barium cobalt niobates, it is found that the EMMA procedure returns the experimental structures as the most stable for the known compositions of Ba3CoNb2O9, Ba5Nb4O15 and Ba8CoNb6O24. The unknown compositions Ba11Co2Nb8O33 and Ba13CoNb10O39, having longer stacking sequences, are predicted to form as intergrowths of Ba3CoNb2O9 and Ba5Nb4O15, and are found to have similar stability to pure Ba3CoNb2O9 and Ba5Nb4O15, indicating that it is likely they can be synthesised.
    Physical Chemistry Chemical Physics 05/2014; 16(39). DOI:10.1039/c4cp01542h · 4.20 Impact Factor
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    ABSTRACT: Heteroepitaxial growth of BaSnO$_3$ (BSO) and Ba$_{1-x}$La$_x$SnO$_3$ (x = 7 %) (LBSO) thin films on different perovskite single crystal (SrTiO$_3$ (001) and SmScO$_3$ (110)) substrates has been achieved by Pulsed Laser Deposition (PLD) under optimized deposition conditions. X-ray diffraction measurements indicate that the films on either of these substrates are relaxed due to the large mismatch and present a high degree of crystallinity with narrow rocking curves and smooth surface morphology while analytical quantification by proton induced x-ray emission (PIXE) confirms the stoichiometric La transfer from a polyphasic target, producing films with La contents above the bulk solubility limit. The films show degenerate semiconducting behavior on both substrates, with the observed room temperature resistivities, Hall mobilities and carrier concentrations of 4.4 $m \Omega cm$, 10.11 $cm^2 V^{-1} s^{-1}$, and 1.38 $\cdot 10^{20} cm^{-3}$ on SmScO$_3$ and 7.8 $m \Omega cm$, 5.8 $cm^2 V^{-1} s^{-1}$, and 1.36 $\cdot 10^{20} cm^{-3}$ on SrTiO$_3$ ruling out any extrinsic contribution from the substrate. The superior electrical properties observed on the SmScO3 substrate are attributed to reduction in dislocation density from the lower lattice mismatch.

Publication Stats

15k Citations
2,666.72 Total Impact Points

Institutions

  • 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
    • 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
  • 2006–2007
    • 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
  • 1991–1992
    • University of Sussex
      Brighton, England, United Kingdom
  • 1989–1992
    • Institut Laue-Langevin
      Grenoble, Rhône-Alpes, France