ORCID Profile
0000-0002-6634-4717
Current Organisation
University of Southampton
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Publisher: Royal Society of Chemistry (RSC)
Date: 2013
DOI: 10.1039/C3CE41538D
Publisher: MDPI AG
Date: 25-08-2023
Abstract: Purpose: Triple-negative breast cancer (TNBC) is a molecularly complex and heterogeneous breast cancer subtype with distinct biological features and clinical behavior. Although TNBC is associated with an increased risk of metastasis and recurrence, the molecular mechanisms underlying TNBC metastasis remain unclear. We performed whole-exome sequencing (WES) analysis of primary TNBC and paired recurrent tumors to investigate the genetic profile of TNBC. Methods: Genomic DNA extracted from 35 formalin-fixed paraffin-embedded tissue s les from 26 TNBC patients was subjected to WES. Of these, 15 were primary tumors that did not have recurrence, and 11 were primary tumors that had recurrence (nine paired primary and recurrent tumors). Tumors were analyzed for single-nucleotide variants and insertions/deletions. Results: The tumor mutational burden (TMB) was 7.6 variants/megabase in primary tumors that recurred (n = 9) 8.2 variants/megabase in corresponding recurrent tumors (n = 9) and 7.3 variants/megabase in primary tumors that did not recur (n = 15). MUC3A was the most frequently mutated gene in all groups. Mutations in MAP3K1 and MUC16 were more common in our dataset. No alterations in PI3KCA were detected in our dataset. Conclusions: We found similar mutational profiles between primary and paired recurrent tumors, suggesting that genomic features may be retained during local recurrence.
Publisher: Wiley
Date: 07-06-2021
Abstract: Industrial purification of propylene and ethylene requires cryogenic distillation and selective hydrogenation over palladium catalysts to remove propane, ethane and/or trace amounts of acetylene. Here, we report the excellent separation of equimolar mixtures of propylene ropane and ethylene/ethane, and of a 1/100 mixture of acetylene/ethylene by a highly robust microporous material, MFM‐520, under dynamic conditions. In situ synchrotron single crystal X‐ray diffraction, inelastic neutron scattering and analysis of adsorption thermodynamic parameters reveal that a series of synergistic host–guest interactions involving hydrogen bonding and π⋅⋅⋅π stacking interactions underpin the cooperative binding of alkenes within the pore. Notably, the optimal pore geometry of the material enables selective accommodation of acetylene. The practical potential of this porous material has been demonstrated by fabricating mixed‐matrix membranes comprising MFM‐520, Matrimid and PIM‐1, and these exhibit not only a high permeability for propylene (≈1984 Barrer), but also a separation factor of 7.8 for an equimolar mixture of propylene ropane at 298 K.
Publisher: Royal Society of Chemistry (RSC)
Date: 2012
DOI: 10.1039/C2CC34687G
Abstract: Crystalline (PMePh(3))(2)[Cd(2)(dhbq)(3)], (dhbq(2-) = deprotonated 2,5-dihydroxybenzoquinone, H(2)dhbq), attached to electrode surfaces, survives repeated cycles of reduction followed by re-oxidation when placed in contact with aqueous electrolyte media. The results afford encouragement that a range of coordination networks containing redox active connecting ligands and/or redox active metal centres may be reducible or oxidisable in the solid state.
Publisher: Royal Society of Chemistry (RSC)
Date: 2010
DOI: 10.1039/C001505A
Publisher: Elsevier BV
Date: 03-2016
Publisher: Elsevier BV
Date: 10-2016
Publisher: American Chemical Society (ACS)
Date: 30-07-2014
DOI: 10.1021/CM502189C
Publisher: World Scientific Pub Co Pte Lt
Date: 07-2018
DOI: 10.1142/S1088424618500815
Abstract: X-ray structures of gold corroles, which are still rather uncommon, afford significant insights into intermolecular interactions involving Au(III), a subject that has been much less studied than aurophilic and metallophilic interactions involving Au(I). The X-ray structure of gold [Formula: see text]-octabromo-meso-tris(para-pentafluorosulfanylphenyl)corrole, reported herein, has revealed two Au···Br interactions (∼4.2 Å) per Au atom. We suggest that analogous but somewhat stronger Au···Br interactions are a key factor underlying the remarkable insolubility of gold octabromocorrole derivatives.
Publisher: American Chemical Society (ACS)
Date: 11-12-2017
Abstract: Two sets of complexes of Co-triarylcorrole-bispyridine complexes, Co[TpXPC](py)
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C7TA05910H
Abstract: Physisorption drives structural change leading to thermally stable CO chemisorption.
Publisher: MDPI AG
Date: 18-12-2017
DOI: 10.3390/CRYST7120382
Publisher: American Chemical Society (ACS)
Date: 12-04-2019
Publisher: Royal Society of Chemistry (RSC)
Date: 2023
DOI: 10.1039/D3SC04191C
Publisher: Springer Science and Business Media LLC
Date: 12-11-2020
DOI: 10.1038/S41598-020-76308-7
Abstract: As part of our efforts to develop rhenium-oxo corroles as photosensitizers for oxygen sensing and photodynamic therapy, we investigated the potential β -perhalogenation of five ReO meso -tris( para -X-phenyl)corroles, Re[T p XPC](O) (X = CF 3 , H, F, CH 3 , and OCH 3 ), with elemental chlorine and bromine. With Cl 2 , β -octachlorinated products Re[Cl 8 T p XPC](O) were rapidly obtained for X = CF 3 , H, and CH 3 , but X = OCH 3 resulted in overchlorination on the meso -aryl groups. Full β -octabromination proved slower relative to Cu and Ir corroles, but the desired Re[Br 8 T p XPC](O) products were finally obtained for X = H and F after a week at room temperature. For X = CH 3 and OCH 3 , these conditions led to undecabrominated products Re[Br 11 T p XPC](O). Compared to the β -unsubstituted starting materials, the β -octahalogenated products were found to exhibit sharp 1 H NMR signals at room temperature, indicating that the aryl groups are locked in place by the β -halogens, and substantially redshifted Soret and Q bands. Single-crystal X-ray structures of Re[Cl 8 T p CF 3 PC](O), Re[Cl 8 T p CH 3 PC](O), and Re[Br 8 T p FPC](O) revealed mild saddling for one Cl 8 structure and the Br 8 structure. These structural variations, however, appear too insignificant to explain the slowness of the β -octabromination protocols, which seems best attributed to the deactivating influence of the high-valent Re center.
Publisher: American Chemical Society (ACS)
Date: 06-06-2018
DOI: 10.1021/ACS.INORGCHEM.8B00537
Abstract: Presented herein is a detailed multitechnique investigation of ligand noninnocence in S =
Publisher: American Chemical Society (ACS)
Date: 18-07-2018
Publisher: American Chemical Society (ACS)
Date: 23-04-2018
Publisher: American Chemical Society (ACS)
Date: 02-04-2018
DOI: 10.1021/ACS.INORGCHEM.7B02767
Abstract: Halterman corroles have been synthesized for the first time from pyrrole and Halterman's aldehyde via Gryko's "water-methanol method". These were derivatized to the corresponding copper complexes and subsequently to the β-octabromo complexes. Electronic circular dichroism spectra were recorded for the enantiopure copper complexes, affording the first such measurements for the inherently chiral Cu corrole chromophore. Interestingly, for a given configuration of the Halterman substituents, X-ray crystallographic studies revealed both P and M conformations of the Cu-corrole core, proving that the substituents, even in conjunction with β-octabromination, are unable to lock the Cu-corrole core into a given chirality. The overall body of evidence strongly indicates a dynamic equilibrium between the P and M conformations. Such an interconversion, which presumably proceeds via saddling inversion, provides a rationale for our failure so far to resolve sterically hindered Cu corroles into their constituent enantiomers by means of chiral HPLC.
Publisher: Springer Science and Business Media LLC
Date: 22-11-2019
DOI: 10.1038/S41557-019-0356-0
Abstract: Air pollution by nitrogen oxides, NO
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C5DT02924D
Abstract: Four different coordination polymers were prepared by reaction of Zn(OAc) 2 and 5-methoxy isophthalic acid using various aqueous/aqueous alcohol solvent systems.
Publisher: Royal Society of Chemistry (RSC)
Date: 2014
DOI: 10.1039/C3DT52579A
Abstract: A single-crystal to single-crystal transformable coordination polymer compound was hydrothermally synthesized. The structural rearrangement is induced by selecting a ligand that contains both strong and weaker coordinating groups. Both hydrated and dehydrated structures were determined by single crystal X-ray analysis.
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C9OB00168A
Abstract: Free-base meso -triarylcorroles and pyrrole undergo oxidative coupling in dichloromethane in the presence of DDQ affording 35–60% yields of 5/10-pyrrole-appended isocorroles in a matter of seconds.
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C5CE02091C
Publisher: American Chemical Society (ACS)
Date: 09-05-2018
Publisher: Springer Science and Business Media LLC
Date: 05-05-2020
DOI: 10.1038/S41598-020-64389-3
Abstract: Six-coordinate iridium(III) triarylcorrole derivatives, Ir[T p XPC)]L 2 , where T p XPC = tris( para -X-phenyl)corrole (X = CF 3 , H, Me, and OCH 3 ) and L = pyridine (py), trimethylamine (tma), isoquinoline (isoq), 4-dimethylaminopyridine (dmap), and 4-picolinic acid (4pa), have been examined, with a view to identifying axial ligands most conducive to near-infrared phosphorescence. Disappointingly, the phosphorescence quantum yield invariably turned out to be very low, about 0.02 – 0.04% at ambient temperature, with about a two-fold increase at 77 K. Phosphorescence decay times were found to be around ~5 µs at 295 K and ~10 µs at 77 K. Fortunately, two of the Ir[T p CF 3 PC)]L 2 derivatives, which were tested for their ability to sensitize singlet oxygen formation, were found to do so efficiently with quantum yields Φ( 1 O 2 ) = 0.71 and 0.38 for L = py and 4pa, respectively. Iridium corroles thus may hold promise as photosensitizers in photodynamic therapy (PDT). The possibility of varying the axial ligand and of attaching biotargeting groups at the axial positions makes iridium corroles particularly exciting as PDT drug candidates.
Publisher: Springer Science and Business Media LLC
Date: 14-10-2019
DOI: 10.1038/S41563-019-0495-0
Abstract: Emissions of SO
Publisher: American Chemical Society (ACS)
Date: 17-08-2018
Publisher: American Chemical Society (ACS)
Date: 17-08-2017
DOI: 10.1021/ACS.INORGCHEM.7B01740
Abstract: One-pot reactions between the [Mn
Publisher: Royal Society of Chemistry (RSC)
Date: 2022
DOI: 10.1039/D1CC06889J
Abstract: Facile synthetic alteration of the calix[4]arene methylene bridges provides access to a range of new molecules whilst preserving the characteristics of this extremely versatile host framework.
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C7DT04233G
Abstract: Bis-calix[4]arene is a highly versatile ligand that is capable of forming a range of polymetallic clusters. Use of an N , O -chelating co-ligand affords a very high nuclearity mixed-valence Mn cluster (shown here) that displays coordination modes relative to each ligand type.
Publisher: Wiley
Date: 06-2011
Abstract: The combination of Cu(NO(3))(2), potassium hydrogen saccharate (KC(6)H(9)O(8)) and 1,10-phenanthroline (phen) yields a pair of chiral cluster compounds, each with composition Cu(21)(C(6)H(5)O(8))(6)(phen)(12)(NO(3))(12) ⋅solvate. One of the compounds forms as orthorhombic crystals, while the other forms cubic crystals. Each of the clusters has D(3) or approximate D(3) symmetry, but the arrangement of the saccharate ion in the clusters is quite different in the two cases. The clusters in the cubic form interact with neighbouring clusters through face-to-face π interactions involving the phen ligands, an association that leads to the generation of very large solvent-filled spaces in the crystal structure. In contrast the clusters in the orthorhombic form are much more densely packed. At the centre of each cluster that crystallises in the orthorhombic form is a nitrate anion that binds to six Cu(II) centres. ESI mass spectral studies indicate that the Cu(21) clusters exist in solution. Solid-state magnetic studies of the cubic form of Cu(21) show that antiferromagnetic coupling occurs to leave a non-zero-spin ground state, and comparisons are made to the magnetic data for other large Cu(II) clusters.
Publisher: American Chemical Society (ACS)
Date: 16-06-2011
DOI: 10.1021/CG2005908
Publisher: Wiley
Date: 29-03-2017
Abstract: Single-crystal X-ray analysis of the β-heptakis(trifluoromethyl)-meso-tetrakis(p-fluorophenyl)porphyrin, H
Publisher: American Chemical Society (ACS)
Date: 22-01-2014
DOI: 10.1021/IC402860R
Abstract: The trianion Z(3-) obtained from 9-phenyl 2,3,7-trihydroxyfluor-6-one, ZH3, affords dioxomolybdenum and dioxotungsten derivatives which contain [4 + 4] metallocycles of composition [(MO2)4Z4](4-) (M = Mo, W) in combination with a variety of counter cations. The syntheses, structures and ESMS of the following compounds are presented: compound 1, (MePPh3)3(NBu4)[(MoO2)4Z4] compound 2, (MePPh3)3(NBu4)[(WO2)4Z4] compound 3, (MePPh3)4[(WO2)4Z4] compound 4, (PPh4)2(NBu4)2[(MoO2)4Z4] compound 5, (AsPh4)3(NBu4)[(MoO2)4Z4] compound 6, (AsPh4)2(NBu4)2[(WO2)4Z4] compound 7, (Ph3PNPPh3)(NBu4)3[(MoO2)4Z4] compound 8, (Ph3PNPPh3)(NBu4)3[(WO2)4Z4] compound 9, (NEt4)(NBu4)3[(MoO2)4Z4]. The metallocycles in all of these compounds have similar structures, with the four metal centers located at the corners of a square slightly distorted, to varying degrees, toward a rhombus and also toward a tetrahedron. Various cations are bound inside the anionic metallocycles. ESI mass spectrometry shows that the metallocycles remain intact in the gas phase, forming [(MO2)4Z4](4-), {X-[(MO2)4Z4]}(3-) and in some cases {X2-[(MO2)4Z4]}(2-) where X(+) is an organic cation.
Publisher: Royal Society of Chemistry (RSC)
Date: 2022
DOI: 10.1039/D2DT01477G
Abstract: An [Fe III 8 ] hexagonal bipyramid displays antiferromagnetic exchange between the two capping tetrahedral ions and the six ring octahedral ions resulting in a spin ground state, S = 10.
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C8CC01561A
Abstract: A novel Fe( ii ) MOF is reported to show an unprecedented 1D chain with a perfect linearity. Moreover, this structure expands to a third dimension to form a very robust MOF. The structure displays an amazing resemblance to a 14th century mosaic found in the Alhambra Palace in Granada.
Publisher: MDPI AG
Date: 24-12-2017
DOI: 10.3390/CRYST8010006
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C5DT04095G
Abstract: 1D coordination polymers undergo transformations upon desolvation to yield sorbent materials.
Publisher: American Chemical Society (ACS)
Date: 07-09-2016
Publisher: Wiley
Date: 17-06-2011
Publisher: American Chemical Society (ACS)
Date: 19-02-2021
DOI: 10.1021/JACS.0C11930
Publisher: American Chemical Society (ACS)
Date: 17-05-2021
Publisher: Royal Society of Chemistry (RSC)
Date: 17-09-2014
DOI: 10.1039/C4CP03298E
Abstract: An experimental study of Xe and Kr adsorption in metal-organic frameworks CPO-27-Ni, CPO-27-Mg, and ZIF-8 was carried out. In situ synchrotron X-ray powder diffraction experiments allowed precise determination of the adsorption sites and sequence of their filling with increasing of gas pressure at different temperatures. Structural investigations were used for interpretation of gas adsorption measurements.
Publisher: American Chemical Society (ACS)
Date: 06-12-2017
DOI: 10.1021/ACS.INORGCHEM.7B01828
Abstract: A reinvestigation of cobalt-corrole-triphenylphosphine complexes has yielded an unexpectedly subtle picture of their electronic structures. UV-vis absorption spectroscopy, skeletal bond length alternations observed in X-ray structures, and broken-symmetry DFT (B3LYP) calculations suggest partial Co
Publisher: Wiley
Date: 24-01-2019
Publisher: Springer Science and Business Media LLC
Date: 13-08-2018
DOI: 10.1038/S41557-018-0104-X
Abstract: Highly porous metal-organic frameworks (MOFs), which have undergone exciting developments over the past few decades, show promise for a wide range of applications. However, many studies indicate that they suffer from significant stability issues, especially with respect to their interactions with water, which severely limits their practical potential. Here we demonstrate how the presence of 'sacrificial' bonds in the coordination environment of its metal centres (referred to as hemilability) endows a dehydrated copper-based MOF with good hydrolytic stability. On exposure to water, in contrast to the indiscriminate breaking of coordination bonds that typically results in structure degradation, it is non-structural weak interactions between the MOF's copper paddlewheel clusters that are broken and the framework recovers its as-synthesized, hydrated structure. This MOF retained its structural integrity even after contact with water for one year, whereas HKUST-1, a compositionally similar material that lacks these sacrificial bonds, loses its crystallinity in less than a day under the same conditions.
Publisher: American Chemical Society (ACS)
Date: 12-07-2023
Publisher: Elsevier BV
Date: 09-2019
DOI: 10.1016/J.SSNMR.2019.05.005
Abstract: NMR spectroscopy of paramagnetic materials (pNMR) has the potential to provide great structural insight, but many challenges remain in interpreting the spectra in detail. This work presents a study of a series of structurally analogous metal-organic frameworks (MOFs) based on 5-substituted isophthalate linkers and Cu(II) paddlewheel dimers, of interest owing to their "crumple zone" structural rearrangement on dehydration/rehydration.
Publisher: MDPI AG
Date: 16-05-2022
Abstract: Background: Although triple-negative breast cancer (TNBC) is associated with an increased risk of recurrence and metastasis, the molecular mechanisms underlying metastasis in TNBC remain unknown. To identify transcriptional changes and genes regulating metastatic progression in TNBC, we compared the transcriptomic profiles of primary and matched metastatic tumors using massively parallel RNA sequencing. Methods: We performed gene expression profiling using formalin-fixed paraffin-embedded (FFPE) TNBC tissues of patients from two cohorts: the Zurich cohort (n = 31) and the Stavanger cohort (n = 5). Among the 31 patients in the Zurich cohort, 18 had primary TNBC tumors that did not metastasize, and 13 had primary tumors that metastasized (11 paired primary and locoregional recurrences). The Stavanger cohort included five matched primary and metastatic TNBC tumors. Significantly differentially expressed genes (DEGs absolute fold change ≥2, p 0.05) were identified and subjected to functional analyses. We investigated if there was any overlap between DEGs from both the cohorts with epithelial-to-mesenchymal-to-amoeboid transition (EMAT) gene signature. xCell was used to estimate relative fractions of 64 immune and stromal cell types in each RNA-seq s le. Results: In the Zurich cohort, we identified 1624 DEGs between primary TNBC tumors and matched metastatic lesions. xCell analysis revealed a significantly higher immune scores for metastatic lesions compared to paired primary tumors in the Zurich cohort. We also found significant upregulation of three MammaPrint signature genes (HRASLS, TGFB3 and RASSF7) in primary tumors that metastasized compared to primary tumors that remained metastasis-free. In the Stavanger cohort, we identified 818 DEGs between primary tumors and matched metastatic lesions. No significant differences in xCell immune scores were observed. We found that 21 and 14 DEGs from Zurich and Stavanger cohort, respectively, overlapped with the EMAT gene signature. In both cohorts, genes belonging to the MMP, FGF, and PDGFR families were upregulated in primary tumors compared to matched metastatic lesions. Conclusions: Our results suggest that distinct gene expression patterns exist between primary TNBCs and matched metastatic tumors. Further studies are warranted to explore whether these discrete expression profiles underlie or result from disease status.
Publisher: Elsevier BV
Date: 11-2015
Publisher: American Chemical Society (ACS)
Date: 07-02-2019
DOI: 10.1021/ACS.INORGCHEM.8B03391
Abstract: A series of metal-metal bonded osmium corrole dimers, {Os[T pXPC]}
Publisher: American Chemical Society (ACS)
Date: 30-10-2020
DOI: 10.1021/JACS.0C08794
Publisher: Elsevier BV
Date: 02-2009
Publisher: Wiley
Date: 25-07-2014
Abstract: Effective separation of mixtures of enantiomers is of continuing interest in analytical and preparative chromatography, with new materials frequently designed and tested. We report two new enantiomerically pure 2D→3D interpenetrated materials used as stationary liquid chromatographic (LC) phases that are shown to resolve selected racemic mixtures with enantiomeric and chemical selectivity. Dicarboxylate ligands derived from amino acids on naphthalene and perylene cores form 2D frameworks that interpenetrate to give 3D structures. Selectivity is initially tested by uptake from solution subsequent LC methods show that the materials exhibit resolution of racemic analytes in 'micro-columns' and that the two closely related materials show markedly different selectivity for different analytes with much greater activity than the ligands alone. Comparison with a close-packed analogue suggests that the separation activity is largely due to surface effects.
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C7CC01549F
Abstract: The homoleptic sandwich compounds – Mo and W biscorroles – showcase strong relativistic effects on redox potentials and optical spectra.
Publisher: Wiley
Date: 24-01-2019
Abstract: Engineering high-recognition host-guest materials is a burgeoning area in basic and applied research. The challenge of exploring novel porous materials with advanced functionalities prompted us to develop dynamic crystalline structures promoted by soft interactions. The first ex le of a pure molecular dynamic crystalline framework is demonstrated, which is held together by means of weak "sticky fingers" van der Waals interactions. The presented organic-fullerene-based material exhibits a non-porous dynamic crystalline structure capable of undergoing single-crystal-to-single-crystal reactions. Exposure to hydrazine vapors induces structural and chemical changes that manifest as toposelective hydrogenation of alternating rings on the surface of the [60]fullerene. Control experiments confirm that the same reaction does not occur when performed in solution. Easy-to-detect changes in the macroscopic properties of the s le suggest utility as molecular sensors or energy-storage materials.
Publisher: Informa UK Limited
Date: 02-2018
Publisher: Wiley
Date: 08-08-2013
Abstract: A series of urea-derived heterocycles, 5N-substituted hexahydro-1,3,5-triazin-2-ones, has been prepared and their structures have been determined for the first time. This family of compounds only differ in their substituent at the 5-position (which is derived from the corresponding primary amine), that is, methyl (1), ethyl (2), isopropyl (3), tert-butyl (4), benzyl (5), N,N-(diethyl)ethylamine (6), and 2-hydroxyethyl (7). The common heterocyclic core of these molecules is a cyclic urea, which has the potential to form a hydrogen-bonding tape motif that consists of self-associative R₂²(8) dimers. The results from X-ray crystallography and, where possible, Laue neutron crystallography show that the hydrogen-bonding motifs that are observed and the planarity of the hydrogen bonds appear to depend on the steric hindrance at the α-carbon atom of the N substituent. With the less-hindered substituents, methyl and ethyl, the anticipated tape motif is observed. When additional methyl groups are added onto the α-carbon atom, as in the isopropyl and tert-butyl derivatives, a different 2D hydrogen-bonding motif is observed. Despite the bulkiness of the substituents, the benzyl and N,N-(diethyl)ethylamine derivatives have methylene units at the α-carbon atom and, therefore, display the tape motif. The introduction of a competing hydrogen-bond donor/acceptor in the 2-hydroxyethyl derivative disrupts the tape motif, with a hydroxy group interrupting the N-H···O=C interactions. The geometry around the hydrogen-bearing nitrogen atoms, whether planar or non-planar, has been confirmed for compounds 2 and 5 by using Laue neutron diffraction and rationalized by using computational methods, thus demonstrating that distortion of O-C-N-H torsion angles occurs to maintain almost-linear hydrogen-bonding interactions.
Location: United States of America
Location: United Kingdom of Great Britain and Northern Ireland
Location: United Kingdom of Great Britain and Northern Ireland
No related grants have been discovered for Laura McCormick McPherson.