Alistair C McKinlay

University of St Andrews, Saint Andrews, Scotland, United Kingdom

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Publications (12)70.92 Total impact

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    ABSTRACT: The room temperature sorption properties of the biological gas nitric oxide (NO) have been investigated on the highly porous and rigid iron or chromium carboxylate based metal-organic frameworks Material Institut Lavoisier (MIL)-100(Fe or Cr) and MIL-127(Fe). In all cases, a significant amount of NO is chemisorbed at 298 K with a loading capacity that depends both on the nature of the metal cation, the structure and the presence of additional iron(II) Lewis acid sites. In a second step, the release of NO triggered by wet nitrogen gas has been studied by chemiluminescence and indicates that only a partial release of NO occurs as well as a prolonged delivery at the biological level. Finally, an in situ infrared spectroscopy study confirms not only the coordination of NO over the Lewis acid sites and the stronger binding of NO on the additional iron(II) sites, providing further insights over the partial release of NO only in the presence of water at room temperature.
    APL Materials 12/2014; 2(12):124112. DOI:10.1063/1.4904069 · 2.79 Impact Factor
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    ABSTRACT: Adsorption and release of the biologically active nitric oxide (NO) was evaluated over a series of highly flexible iron(III) dicarboxylate MOFs of the MIL-88 structure type, bearing fumaric or terephthalic spacer functionalized or not by polar groups (NO2, 2OH). As evidenced by ex situ X-ray powder diffraction and in situ IR spectroscopy, it appears that if the contracted dried forms of MIL-88 do not expand their structures in the presence of NO, the combination of very narrow pores and trimers of iron polyhedra leads to the adsorption of significant amounts of NO either physisorbed (very narrow pores) and/or chemisorbed [iron(II) or iron(III) coordinatively unsaturated metal sites (CUS)]. The delivery of NO under vapor of water or in simulated body fluid does not exceed 20% range of the total adsorbed amount probably due to a partial release that occurs between the adsorption/desorption setup and the chemiluminescence release tests. Some of these solids nevertheless exhibit a significant release at the biological levels over a long period of time (>16 h) that make these biocompatible and biodegradable MOFs of interest for the controlled release of NO.
    Chemistry of Materials 04/2013; 25(9):1592–1599. DOI:10.1021/cm304037x · 8.54 Impact Factor
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    ABSTRACT: Solid-state (13)C magic-angle spinning (MAS) NMR spectroscopy is used to investigate the structure of the Cu(ii)-based metal-organic frameworks (MOFs), HKUST-1 and STAM-1, and the structural changes occurring within these MOFs upon activation (dehydration). NMR spectroscopy is an attractive technique for the investigation of these materials, owing to its high sensitivity to local structure, without any requirement for longer-range order. However, interactions between nuclei and unpaired electrons in paramagnetic systems (e.g., Cu(ii)-based MOFs) pose a considerable challenge, not only for spectral acquisition, but also in the assignment and interpretation of the spectral resonances. Here, we exploit the rapid T(1) relaxation of these materials to obtain (13)C NMR spectra using a spin-echo pulse sequence at natural abundance levels, and employ frequency-stepped acquisition to ensure uniform excitation of resonances over a wide frequency range. We then utilise selective (13)C isotopic labelling of the organic linker molecules to enable an unambiguous assignment of NMR spectra of both MOFs for the first time. We show that the monomethylated linker can be recovered from STAM-1 intact, demonstrating not only the interesting use of this MOF as a protecting group, but also the ability (for both STAM-1 and HKUST-1) to recover isotopically-enriched linkers, thereby reducing significantly the overall cost of the approach.
    Physical Chemistry Chemical Physics 11/2012; 15(3). DOI:10.1039/c2cp43445h · 4.20 Impact Factor
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    ABSTRACT: The magnetic interaction between dinuclear copper (II) in a new copper carboxylate compound, STAM-1, has been investigated by means of EPR and SQUID measurements. The powder EPR spectra, measured at 9.80 and 34.5 GHz and at different temperatures, show the typical lines of the triplet state (S = 1), attributed to Cu2+–Cu2+ dimers, in addition of a temperature dependent central lines. The zero field splitting parameters obtained are |Dobs| = 0.337 cm−1 and E ∼ 0. Magnetic susceptibility data, performed in the range 1.8–300 K, shows a strong antiferromagnetic exchange coupling between the Cu2+ centers in the paddle-wheel units with the exchange coupling constant 2J = −334 ± 4 cm−1.
    Chemical Physics Letters 08/2012; 544:17–21. DOI:10.1016/j.cplett.2012.06.012 · 1.99 Impact Factor
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    ABSTRACT: A new flexible ultramicroporous solid, La(H(5)DTMP)·7H(2)O (1), has been crystallized at room temperature using the tetraphosphonic acid H(8)DTMP, hexamethylenediamine-N,N,N',N'-tetrakis(methylenephosphonic acid). Its crystal structure, solved by synchrotron powder X-ray diffraction, is characterised by a 3D pillared open-framework containing 1D channels filled with water. Upon dehydration, a new related crystalline phase, La(H(5)DTMP) (2) is formed. Partial rehydration of 2 led to La(H(5)DTMP)·2H(2)O (3). These new phases contain highly corrugated layers showing different degrees of conformational flexibility of the long organic chain. The combination of the structural study and the gas adsorption characterization (N(2) and CO(2)) suggests an ultramicroporous flexible framework. NO isotherms are indicative of a strong irreversible adsorption of NO within the pores. Impedance data indicates that 1 is a proton-conductor with a conductivity of 8 × 10(-3) S cm(-1) at 297 K and 98% of relative humidity, and an activation energy of 0.25 eV.
    Dalton Transactions 01/2012; 41(14):4045-51. DOI:10.1039/c2dt11992g · 4.20 Impact Factor
  • Patricia Horcajada · Christian Serre · Alistair C. McKinlay · Russell E. Morris
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    ABSTRACT: IntroductionMOFs for BioapplicationsTherapeuticsDiagnosticsFrom Synthesis of Nanoparticles to Surface Modification and ShapingDiscussion and Conclusion References
    Metal-Organic Frameworks, 07/2011: pages 213-250; , ISBN: 9783527328703
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    ABSTRACT: Formed by linking metals or metal clusters through organic linkers, metal-organic frameworks are a class of solids with structural and chemical properties that mark them out as candidates for many emerging gas storage, separation, catalysis and biomedical applications. Important features of these materials include their high porosity and their flexibility in response to chemical or physical stimuli. Here, a copper-based metal-organic framework has been prepared in which the starting linker (benzene-1,3,5-tricarboxylic acid) undergoes selective monoesterification during synthesis to produce a solid with two different channel systems, lined by hydrophilic and hydrophobic surfaces, respectively. The material reacts differently to gases or vapours of dissimilar chemistry, some stimulating subtle framework flexibility or showing kinetic adsorption effects. Adsorption can be switched between the two channels by judicious choice of the conditions. The monoesterified linker is recoverable in quantitative yield, demonstrating possible uses of metal-organic frameworks in molecular synthetic chemistry as 'protecting groups' to accomplish selective transformations that are difficult using standard chemistry techniques.
    Nature Chemistry 04/2011; 3(4):304-10. DOI:10.1038/nchem.1003 · 23.30 Impact Factor
  • ChemInform 01/2011; 42(3). DOI:10.1002/chin.201103263
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    ABSTRACT: The class of highly porous materials called metal-organic frameworks offer many opportunities for applications across biology and medicine. Their wide range of chemical composition makes toxicologically acceptable formulation possible, and their high level of functionality enables possible applications as imaging agents and as delivery vehicles for therapeutic agents. The challenges in the area encompass not only the development of new solids but also improvements in the formulation and processing of the materials, including tailoring the morphology and surface chemistry of the frameworks to fit the proposed applications.
    Angewandte Chemie International Edition 08/2010; 49(36):6260-6. DOI:10.1002/anie.201000048 · 11.26 Impact Factor
  • Angewandte Chemie 08/2010; 122(36):6400 - 6406. DOI:10.1002/ange.201000048
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    Nathan J. Hinks · Alistair C. McKinlay · Bo Xiao · Paul S. Wheatley · Russell E. Morris
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    ABSTRACT: Metal organic frameworks (MOFs) are highly porous materials that can store significant amounts of gas, including nitric oxide. The chemical composition and toxicology of many (but not all) of these materials makes them potentially suitable for medical applications. In this paper, we will describe how triggered release methods can be used to deliver biologically relevant amounts of NO and then show how Ni, Co and Cu-containing MOFs are biologically active materials with potential applications in several different areas (anti-thrombosis, dermatology and wound healing, anti-bacterial, vasodilation etc.). We will also discuss the pros and cons of MOFs, including their chemical and biological stability and the toxicology of MOFs in general.
    Microporous and Mesoporous Materials 04/2010; 129(3):330–334. DOI:10.1016/j.micromeso.2009.04.031 · 3.21 Impact Factor
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    ABSTRACT: Two porous metal organic frameworks (MOFs), [M2(C8H2O6)(H2O)2] x 8 H2O (M = Co, Ni), perform exceptionally well for the adsorption, storage, and water-triggered delivery of the biologically important gas nitric oxide. Adsorption and powder X-ray diffraction studies indicate that each coordinatively unsaturated metal atom in the structure coordinates to one NO molecule. All of the stored gas is available for delivery even after the material has been stored for several months. The combination of extremely high adsorption capacity (approximately 7 mmol of NO/g of MOF) and good storage stability is ideal for the preparation of NO storage solids. However, most important is that the entire reservoir of stored gas is recoverable on contact with a simple trigger (moisture). The activity of the NO storage materials is proved in myography experiments showing that the NO-releasing MOFs cause relaxation of porcine arterial tissue.
    Journal of the American Chemical Society 08/2008; 130(31):10440-4. DOI:10.1021/ja801997r · 11.44 Impact Factor