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126 items found (0 items not approved), displaying 1 to 10.[First/Prev] 1, 2, 3, 4, 5, 6, 7, 8 [Next/Last]

Instruments / Technical Area	Publication Details	Published
B24-Cryo Soft X-ray Tomography	X-ray tomography of cryopreserved human prostate cancer cells: mitochondrial targeting by an organoiridium photosensitiser Elizabeth M. Bolitho , Carlos Sanchez-cano , Huaiyi Huang , Ian Hands-portman , Matthew Spink , Paul D. Quinn , Maria Harkiolaki , Peter J. Sadler Jbic Journal Of Biological Inorganic Chemistry 56 DOI: 10.1007/s00775-020-01761-8 Diamond Proposal Number(s): [18339, 19615] Open Access Show Abstract ▼ Abstract: The organoiridium complex Ir[(C,N)2(O,O)] (1) where C, N = 1-phenylisoquinoline and O,O = 2,2,6,6-tetramethyl-3,5-heptanedionate is a promising photosensitiser for Photo-Dynamic Therapy (PDT). 1 is not toxic to cells in the dark. However, irradiation of the compound with one-photon blue or two-photon red light generates high levels of singlet oxygen (1O2) (in Zhang et al. Angew Chem Int Ed Engl 56 (47):14898-14902 https://doi.org/10.1002/anie.201709082,2017), both within cell monolayers and in tumour models. Moreover, photo-excited 1 oxidises key proteins, causing metabolic alterations in cancer cells with potent antiproliferative activity. Here, the tomograms obtained by cryo-Soft X-ray Tomography (cryo-SXT) of human PC3 prostate cancer cells treated with 1, irradiated with blue light, and cryopreserved to maintain them in their native state, reveal that irradiation causes extensive and specific alterations to mitochondria, but not other cellular components. Such new insights into the effect of 1O2 generation during PDT using iridium photosensitisers on cells contribute to a detailed understanding of their cellular mode of action.	Mar 2020
I19-Small Molecule Single Crystal Diffraction	Entropy-driven incommensurability: Chemical pressure-guided polymorphism in PdBi and the origins of lock-in phenomena in modulated systems Laura C. Folkers , Hillary E. Mitchell Warden , Daniel C. Fredrickson , Sven Lidin Inorganic Chemistry DOI: 10.1021/acs.inorgchem.0c00197 Show Abstract ▼ Abstract: Incommensurate order, in which two or more mismatched periodic patterns combine to make a long-range ordered yet aperiodic structure, is emerging as a general phenomenon impacting the crystal structures of compounds ranging from alloys and nominally simple salts to organic molecules and proteins. The origins of incommensurability in these systems are often unclear, but it is commonly associated with relatively weak interactions that become apparent only at low temperatures. In this article, we elucidate an incommensurate modulation in the intermetallic compound PdBi that arises from a different mechanism: the controlled increase of entropy at higher temperatures. Following the synthesis of PdBi, we structurally characterize two low-temperature polymorphs of the TlI-type structure with single crystal synchrotron X-ray diffraction. At room temperature, we find a simple commensurate superstructure of the TlI-type structure (comm-PdBi), in which the Pd sublattice distorts to form a 2D pattern of short and long Pd–Pd contacts. Upon heating, the structure converts to an incommensurate variant (incomm-PdBi) corresponding to the insertion of thin slabs of the original TlI type into the superstructure. Theoretical bonding analysis suggests that comm-PdBi is driven by the formation of isolobal Pd–Pd bonds along shortened contacts in the distorted Pd network, which is qualitatively in accord with the 18-n rule but partially frustrated by the population of competing Bi–Bi bonding states. The emergence of incomm-PdBi upon heating is rationalized with the DFT-Cemical Pressure (CP) method: the insertion of TlI-type slabs result in regions of higher vibrational freedom that are entropically favored at higher temperatures. High-temperature incommensurability may be encountered in other materials when bond formation is weakened by competing electronic states, and there is a path for accommodating defects in the CP scheme.	Mar 2020
I11-High Resolution Powder Diffraction	Evidence of paracrystalline cation order in the ruddlesden–popper phase LaSr3NiRuO8 through neutron total scattering techniques Margaret Lea Robinson , Ernestine Whitaker , Lun Jin , Michael A. Hayward , Geneva Laurita Inorganic Chemistry DOI: 10.1021/acs.inorgchem.9b03382 Diamond Proposal Number(s): [13284] Show Abstract ▼ Abstract: Cation ordering in perovskite-derived phases can lead to a wealth of tunable physical properties. Ordering is typically driven by a large difference between the cation size and charge, but many Ruddlesden–Popper phases An+1BnO3n+1 appear to lack such B-site ordering, even when these differences are present. One such example is the “double” Ruddlesden–Popper n = 1 composition LaSr3NiRuO8. In this material, a lack of B-site ordering is observed through traditional crystallographic techniques, but antiferromagnetic ordering in the magnetism data suggests that B-site cation ordering is indeed present. Neutron total scattering, particularly analysis of the neutron pair distribution function, reveals that the structure is locally B-site-ordered below 6 Å but becomes slightly disordered in the midrange structure around 12 Å. This provides evidence for paracrystalline order in this material: cation ordering within a single perovskite sheet that lacks perfect registry within the three-dimensional stack of sheets. This work highlights the importance of employing a structural technique that can probe both the local and midrange order in addition to the crystallographic structure and provides a structural origin to the observed magnetic properties of LaSr3NiRuO8. Further, it is proposed that paracrystalline order is likely to be common among these layered-type oxides.	Feb 2020
I11-High Resolution Powder Diffraction	Sn6SiO8, a tin(II) silicate with a zinc blende related structure and high thermal stability Daniel S. Parsons , Savvaki N. Savva , Wai Chi Tang , Andrew Ingram , Joseph A. Hriljac Inorganic Chemistry DOI: 10.1021/acs.inorgchem.9b02615 Diamond Proposal Number(s): [12092] Show Abstract ▼ Abstract: The crystal structure of a novel cubic tin(II) silicate, Sn6SiO8 (space group F4̅3m, a = 10.40708(2) Å, and Z = 4), synthesized by microwave-assisted hydrothermal synthesis has been solved by Rietveld refinement of the powder X-ray diffraction (PXRD) data. The structure, analogous to zinc blende, comprises a face-centered-cubic array of [Sn6O8]4– anions, with Si4+ occupying half of the tetrahedral holes. The tin(II) silicate has been further characterized by variable-temperature PXRD, demonstrating stability of the structure and resistance to SnII oxidation up to ∼600 °C, when the compound begins to thermally decompose.	Dec 2019
I11-High Resolution Powder Diffraction	Average and local structure of apatite-type germanates and implications for oxide ion conductivity Mathew S. Chambers , Philip A. Chater , Ivana Radosavljevic Evans , John S. O. Evans Inorganic Chemistry DOI: 10.1021/acs.inorgchem.9b02544 Diamond Proposal Number(s): [14188] Show Abstract ▼ Abstract: Materials with the apatite structure have a range of important applications in which their function is influenced by details of their local structure. Here, we describe an average and local structural study to probe the origins of high-temperature oxide ion mobility in La10(GeO4)6O3 and La8Bi2(GeO4)6O3 oxygen-excess materials, using the low-conductivity interstitial oxide-free La8Sr2(GeO4)6O2 as a benchmark. For La10 and La8Bi2, we locate the interstitial oxygen, Oint, responsible for conductivity by Rietveld refinement and relate the P63/m to P1̅ phase transitions on cooling to oxygen ordering. Local structural studies using neutron total scattering reveal that well-ordered GeO5 square pyramidal groups form in the structure at low temperature, but that Oint becomes significantly more disordered in the high-conductivity, high-temperature structures, with a transition to more trigonal-bipyramid-like average geometry. We relate the higher conductivity of Bi materials to the presence of several Oint sites of similar energy in the structure, which correlates with its less-distorted low-temperature average structure.	Oct 2019
I11-High Resolution Powder Diffraction	Exsolution of SrO during the topochemical conversion of LaSr3CoRuO8 to the oxyhydride LaSr3CoRuO4H4 Lun Jin , Maria Batuk , Franziska K. K. Kirschner , Franz Lang , Stephen J. Blundell , Joke Hadermann , Michael A. Hayward Inorganic Chemistry DOI: 10.1021/acs.inorgchem.9b02552 Diamond Proposal Number(s): [13284] Show Abstract ▼ Abstract: Reaction of the n = 1 Ruddlesden–Popper oxide LaSr3CoRuO8 with CaH2 yields the oxyhydride phase LaSr3CoRuO4H4 via a topochemical anion exchange. Close inspection of the X-ray and neutron powder diffraction data in combination with HAADF-STEM images reveals that the nanoparticles of SrO are exsolved from the system during the reaction, with the change in cation stoichiometry accommodated by the inclusion of n > 1 (Co/Ru)nOn+1H2n “perovskite” layers into the Ruddlesden–Popper stacking sequence. This novel pseudotopochemical process offers a new route for the formation of n > 1 Ruddlesden–Popper structured materials. Magnetization data are consistent with a LaSr3Co+Ru2+O4H4 (Co+, d8, S = 1; Ru2+, d6, S = 0) oxidation/spin state combination. Neutron diffraction and μ+SR data show no evidence for long-range magnetic order down to 2 K, suggesting the diamagnetic Ru2+ centers impede the Co–Co magnetic-exchange interactions.	Oct 2019
I19-Small Molecule Single Crystal Diffraction	Macropolyhedral nickelaboranes from the metal-assisted fusion of KB9H14 Michael G. S. Londesborough , Ramón Macías , John D. Kennedy , William Clegg , Jonathan Bould Inorganic Chemistry 58, 13258-13267 DOI: 10.1021/acs.inorgchem.9b02116 Diamond Proposal Number(s): [16117] Show Abstract ▼ Abstract: The reaction of K[arachno-B9H14] with [NiCl2(dppe)] produces four new 19-vertex macropolyhedral metallaboranes that result from borane cluster fusion: [9′-(dppe)-9′-Ni-anti-B18H20] (1) and isomeric [11′-(dppe)-11′-Ni-syn-B18H20] (2), together with the chlorine-substituted derivative of 1, [5′-Cl-9′-(dppe)-9′-Ni-anti-B18H19] (3), and the 18-vertex cluster compound [7′-(dppe)-7′-anti-NiB17H21] (4). Two closo 10-vertex single-cluster species, [1-(dppe)-1-closo-NiB9H7Cl2] (5) and [1-(dppe)-1-closo-NiB9H7Cl(OH)] (6), were also isolated from the reaction. The production of the metalated syn-octadecaborane isomer 2 from the fusion of two arachno-nonaborate clusters is the first such case to be observed; in all other reported cases fusion has resulted in products with the anti-octadecaboranyl bis-nido configuration.	Sep 2019
I11-High Resolution Powder Diffraction	Iodine adsorption in a redox-active metal–organic framework: electrical conductivity induced by host−guest charge-transfer Xinran Zhang , Ivan Da Silva , Rodrigo Fazzi , Alena M. Sheveleva , Xue Han , Ben F. Spencer , Sergey A. Sapchenko , Floriana Tuna , Eric J. L. Mcinnes , Ming Li , Sihai Yang , Martin Schroder Inorganic Chemistry DOI: 10.1021/acs.inorgchem.9b02176 Diamond Proposal Number(s): [21079] Show Abstract ▼ Abstract: We report a comparative study of the binding of I2 (iodine) in a pair of redox-active metal–organic framework (MOF) materials, MFM-300(VIII) and its oxidized, deprotonated analogue, MFM-300(VIV). Adsorption of I2 in MFM-300(VIII) triggers a host-to-guest charge-transfer, accompanied by a partial (∼30%) oxidation of the VIII centers in the host framework and formation of I3– species residing in the MOF channels. Importantly, this charge-transfer induces a significant enhancement in the electrical conductivity (Δσ = 700000) of I2@MFM-300(VIII/IV) in comparison to MFM-300(VIII). In contrast, no host–guest charge-transfer or apparent change in the conductivity was observed upon adsorption of I2 in MFM-300(VIV). High-resolution synchrotron X-ray diffraction of I2@MFM-300(VIII/IV) confirms the first example of self-aggregation of adsorbed iodine species (I2 and I3–) into infinite helical chains within a MOF.	Sep 2019
I11-High Resolution Powder Diffraction	Increasing alkyl chain length in a series of layered metal–organic frameworks aids ultrasonic exfoliation to form nanosheets David J. Ashworth , Thomas M. Roseveare , Andreas Schneemann , Max Flint , Irene Dominguez Bernáldes , Pia Vervoorts , Roland A. Fischer , Lee Brammer , Jonathan A. Foster Inorganic Chemistry DOI: 10.1021/acs.inorgchem.9b01128 Show Abstract ▼ Abstract: Metal–organic framework nanosheets (MONs) are attracting increasing attention as a diverse class of two-dimensional materials derived from metal–organic frameworks (MOFs). The principles behind the design of layered MOFs that can readily be exfoliated to form nanosheets, however, remain poorly understood. Here we systematically investigate an isoreticular series of layered MOFs functionalized with alkoxy substituents in order to understand the effect of substituent alkyl chain length on the structure and properties of the resulting nanosheets. A series of 2,5-alkoxybenzene-1,4-dicarboxylate ligands (O2CC6H2(OR)2CO2, R = methyl–pentyl, 1–5, respectively) was used to synthesize copper paddle-wheel MOFs. Rietveld and Pawley fitting of powder diffraction patterns for compounds Cu(3–5)(DMF) showed they adopt an isoreticular series with two-dimensional connectivity in which the interlayer distance increases from 8.68 Å (R = propyl) to 10.03 Å (R = pentyl). Adsorption of CO2 by the MOFs was found to increase from 27.2 to 40.2 cm3 g–1 with increasing chain length, which we attribute to the increasing accessible volume associated with increasing unit-cell volume. Ultrasound was used to exfoliate the layered MOFs to form MONs, with shorter alkyl chains resulting in higher concentrations of exfoliated material in suspension. The average height of MONs was investigated by AFM and found to decrease from 35 ± 26 to 20 ± 12 nm with increasing chain length, with the thinnest MONs observed being only 5 nm, corresponding to five framework layers. These results indicate that careful choice of ligand functionalities can be used to tune nanosheet structure and properties, enabling optimization for a variety of applications.	Aug 2019
I18-Microfocus Spectroscopy	Synchrotron radiation X-ray fluorescence elemental mapping in healthy versus malignant prostate tissues provides new insights into the glucose-stimulated zinc trafficking in the prostate as discovered by MRI Veronica Clavijo Jordan , Alia Al-ebraheem , Kalotina Geraki , Eric Dao , Andre F. Martins , Sara Chirayil , Michael Farquharson , A. Dean Sherry Inorganic Chemistry DOI: 10.1021/acs.inorgchem.9b01132 Diamond Proposal Number(s): [14747] Show Abstract ▼ Abstract: Prostatic zinc content is a known biomarker for discriminating normal healthy tissue from benign prostatic hyperplasia (BPH) and prostate cancer (PCa). Given that zinc content is not readily measured without a tissue biopsy, we have been exploring noninvasive imaging methods to detect these diagnostic differences using a zinc-responsive MRI contrast agent. During imaging studies in mice, we observed that a bolus of glucose stimulates secretion of zinc from the prostate of fasted mice. This discovery allowed the use of a Gd-based zinc sensor to detect differential zinc secretion in regions of healthy versus malignant prostate tissue in a transgenic adenocarcinoma mouse model of PCa. Here, we used a zinc-responsive MRI agent to detect zinc release across the prostate during development of malignancy and confirm the loss of total tissue zinc by synchrotron radiation X-ray fluorescence (μSR-XRF). Quantitative μSR-XRF results show that the lateral lobe of the mouse prostate uniquely accumulates high concentrations of zinc, 1.06 ± 0.08 mM, and that the known loss of zinc content in the prostate is only observed in the lateral lobe during development of PCa. Additionally, we confirm that lesions identified by a loss of zinc secretion indeed represent malignant neoplasia and that the relative zinc concentration in the lesion is reduced to 0.370 ± 0.001 mM. The μSR-XRF data also provided insights into the mechanism of zinc secretion by showing that glucose promotes movement of zinc pools (∼1 mM) from the glandular lumen of the lateral lobe of the mouse prostate into the stromal/smooth muscle surrounding the glands. Co-localization of zinc and gadolinium in the stromal/smooth muscle areas as detected by μSR-XRF confirm that glucose initiates secretion of zinc from intracellular compartments into the extracellular spaces of the gland where it binds to the Gd-based agent and albumin promoting MR image enhancement.	Jul 2019

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