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Instruments / Technical Area	Publication Details	Published	Actions
I14-Hard X-ray Nanoprobe	A photodynamic and photochemotherapeutic platinum-iridium charge-transfer conjugate for anticancer therapy Huayun Shi , Oliver W. L. Carter , Fortuna Ponte , Cinzia Imberti , Miguel A. Gomez-Gonzalez , Fernando Cacho-Nerin , Paul D. Quinn , Julia E. Parker , Emilia Sicilia , Huaiyi Huang , Peter J. Sadler Angewandte Chemie International Edition 12 DOI: 10.1002/anie.202400476 Diamond Proposal Number(s): [27852] Open Access Show Abstract ▼ Abstract: The novel hetero-dinuclear complex trans,trans,trans-[PtIV(py)2(N3)2(OH)(μ-OOCCH2CH2CONHCH2-bpyMe)IrIII(ppy)2]Cl (Pt-Ir), exhibits charge transfer between the acceptor photochemotherapeutic Pt(IV) (Pt-OH) and donor photodynamic Ir(III) (Ir-NH2) fragments. It is stable in the dark, but undergoes photodecomposition more rapidly than the Pt(IV) parent complex (Pt-OH) to generate Pt(II) species, an azidyl radical and 1O2. The Ir(III)* excited state, formed after irradiation, can oxidise NADH to NAD⋅ radicals and NAD+. Pt-Ir is highly photocytotoxic towards cancer cells with a high photocytotoxicity index upon irradiation with blue light (465 nm, 4.8 mW/cm2), even with short light-exposure times (10–60 min). In contrast, the mononuclear Pt-OH and Ir-NH2 subunits and their simple mixture are much less potent. Cellular Pt accumulation was higher for Pt-Ir compared to Pt-OH. Irradiation of Pt-Ir in cancer cells damages nuclei and releases chromosomes. Synchrotron-XRF revealed ca. 4× higher levels of intracellular platinum compared to iridium in Pt-Ir treated cells under dark conditions. Luminescent Pt-Ir distributes over the whole cell and generates ROS and 1O2 within 1 h of irradiation. Iridium localises strongly in small compartments, suggestive of complex cleavage and excretion via recycling vesicles (e.g. lysosomes). The combination of PDT and PACT motifs in one molecule, provides Pt-Ir with a novel strategy for multimodal phototherapy.	Apr 2024
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

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