Oxana, Sam and Sandra take part in the 27th PhotoIUPAC conference in Dublin

PhotoIUPAC, the biennial global IUPAC conference for photochemistry, came to UCD this July (8th – 13th, 2018) and several TG members contributed throughout the week. Post-doctoral researchers Dr. Oxana Kotova and Dr. Sam Bradberry gave talks titled “Effect of Spacer Size in Chiral Luminescent Di-metallic Eu(III) Helicates” and “Supramolecular Scaffolds for Lanthanide Luminescence”, respectively, describing some of the research they have undertaken recently in the group.

PhD student Sandra Estalayo presented a poster on the Ru(II) complexes for singlet-oxygen generation work that she has been carrying out in her PhD in close collaboration with Prof. John Kelly (TCD). Working backstage, PhD students Jason Delente and Isabel Hegarty volunteered to help run the four parallel sessions throughout the week. The group were exposed to exciting and varied science from all corners of the globe, early career researchers and established names from every field of photochemistry, in what was an excellent and diverse programme of talks.

The conference, at its 27th edition, was organised by Dr. Susan Quinn of UCD and Prof. Miguel A. Garcia-Garibay from UCLA. It showcased world-class research in photochemistry with contributors from over 40 countries and was a very stimulating meeting. The 28th meeting will be held in Amsterdam in 2020. See you there, PhotoIUPAC!

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Fergus presented with the RIA Young Chemist Prize

Congratulations to Dr Fergus Poynton, who was formally presented with the RIA Young Chemist Prize today. The prize is awarded annually by the Royal Irish Academy for the most outstanding chemistry thesis in Ireland.

Fergus won the prize in March for his thesis “Spectroscopic Investigations into the Excited-State Processes and Reactivity of Ruthenium(II) Polypyridyl Complexes”, he has since won one of the five IUPAC-Solvay International Awards for Young Chemists, and will receive the prize at the 46th IUPAC World Chemistry Congress in São Paulo this July.

In a special ceremony in the Academy, the prize was presented by Prof. Pat Guiry, Vice-Chair of the Physical, Chemical & Mathematical Sciences of the RIA. The ceremony was also attended by Fergus’ family and friends, as well as collaborators Clive Williams, TCD and Susan Quinn from UCD, co-supervisor John Kelly and his colleagues from the Donnelly research group in the School of Medicine.

Well done!

New paper on DNA-targeting phototherapeutic drugs published in Chem. Eur. J.

Congratulations to Fergus and Bjørn on their recent paper in Chemistry a European Journal titled Inosine can increase DNA’s susceptibility to photo-oxidation by a Ru(II) complex due to structural change in the minor groove. Key to the development of DNA-targeting phototherapeutic drugs is determining the interplay between the photoactivity of the drug and its binding preference for a target sequence. In this work, the photoactivity of Λ-[Ru(TAP)2(dppz)]2+ and its binding to oligonucleotides was studied, showing enhanced photo-oxidation when guanine is substituted with inosine, in spite of inosine being less easily oxidised. The work has been performed in collaboration with Prof. Susan Quinn of University College Dublin, Páraic Keane and Prof. Christine Cardin of the University of Reading, Prof. John Kelly from Trinity College Dublin and groups at the Diamond Light Source and Rutherford Appleton Laboratories in England.

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Structural features of the interaction of the Ru(II) complex with two different DNA sequences.

Three new papers accepted for publication from the group

Many congratulations to Bjørn C. Poulsen, Sandra Estalayo-Adrián, Salvador Blasco and Sandra A. Bright, who in collaboration with Professors John Kelly and Clive Williams have had their manuscript “Luminescent ruthenium polypyridyl complexes with extended ‘dppz’ like ligands as DNA targeting binders and cellular agents”, accepted in the RSC journal Dalton Transactions. DOI: 10.1039/c6dt03792e. The work was mainly funded under the SFI PI scheme (2013), the IRC (Postgraduate fellowship to BCP) and via the Marie Curie Fellowship Programme (to SB).

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Six dppz-like ligands investigated as DNA targeting binders and cellular agents.

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Fluorescence Emission spectra in aqueous dispersions.

Many congratulations to Raju (Sankarasekaran Shanmugaraju) on the acceptance of his manuscript “Tröger’s base derived coordination zinc polymer for fluorescent sensing of phenolic-nitroaromatics explosives in water”. This work was funded in part though an IRC postdoctoral fellowship to Raju and comes out of a very fruitful collaboration between the TG research group and the Schmitt Group at TCD and the Kitchen Group at University of Southampton. The work is in part based on results obtained by a visiting student Charlyne Dabadie, who under Raju’s supervision spent 6 months in the TG laboratory in 2015, and is to be published in the RSC journal Chemical Science. DOI: 10.1039/C6SC04367D

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Ligand geometry, coordination environment and partially extended structure of a naphthalimide-based coordination polymer.

Many congratulations to Chris Hawes on his manuscript “Flexible porous coordination polymers from divergent photoluminescent 4-oxo-1,8-naphthalimide ligands”, that has been accepted for publication in the ACS journal Inorganic Chemistry. DOI: 10.1021/acs.inorgchem.6b02137. The work was made possible through a postdoctoral fellowship award to Chris from IRC and through the TCD Dean of Research Pathfinder Programme; the work being carried out in part in collaboration with the Schmitt research group in TCD.

Recently, Fergus and Sandra represented the Gunnlaugsson group at the 12th Nucleic Acids Forum in London, alongside Prof. John Kelly.

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Sandra and Fergus at the poster session

Fergus gave a talk entitled “Photochemically Active DNA-Intercalating Complexes – Insights by Combining Crystallography and Transient Spectroscopy”, where he presented some of our collaborative work into how time-resolved infrared spectroscopy, coupled with X-ray crystallography, enables us to study the interaction of the excited-states of intercalated ruthenium polypyridyl complexes with DNA and provides new insights into the nature of the binding sites of these complexes. Some of this work was recently published in

Sandra presented a poster entitled “New Ruthenium(II) Polypyridyl Complexes as Promising PDT Agents in HeLa Cells and Luminescent Probes for DNA”, showing the new classes of ruthenium polypyridyl complexes she designed and their potential biological applications.

Fergus, Thorri and John publish in Chemical Science

The article entitled “Direct Observation by Time-resolved Infrared Spectroscopy of the Bright and the Dark Excited States of the [Ru(phen)2(dppz)]2+ Light-switch Compound in Solution and when Bound to DNA” by Fergus Poynton, Thorfinnur Gunnlaugsson and John Kelly came out in Chemical Science at the start 0f 2016 and describes the “light-switch” effect of the highly topical [Ru(phen)2(dppz)]2+  compound as a DNA binding probe.

Graphical Abstract

Graphical Abstract

DOI: 10.1039/C5SC04514B

TG Group members published in Nature Chemistry

Research carried out by a team including TG Group member Fergus Poynton was published recently in Nature Chemistry. The group of scientists have developed a new technique for looking at the initial steps of DNA oxidation – a process which can lead to DNA damage, mutations and cancers. The breakthrough, which uses DNA in crystals, should help related research in the fields of cancer medicine and drug development.

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This work is a collaboration between teams in UCD (led by Dr Susan Quinn) and Trinity College Dublin (led by Professor John Kelly), the University of Reading (led by Professor Christine Cardin, whose BBSRC funded postdoctoral fellow Dr James Hall carried out the crystal growth, sample preparation and sample validation) and the Rutherford Appleton Laboratory (Professor Mike Towrie).

This paper presents the first study of the initial steps of DNA oxidation in crystals. Oxidation of DNA can lead to DNA damage, mutations and cancer and is therefore an extremely active area of research across many scientific disciplines. In this study a ruthenium complex, which has been shown to oxidise DNA when irradiated with light, was crystallised bound to DNA. We have previously demonstrated that when cancer cells are treated with this complex and irradiated with light, the cancer cells undergo cell death, showing the potential of this class of molecule in anti-cancer therapies.

The majority of studies of the interactions of small molecules with DNA are carried out in solution, where there are numerous ways by which these molecules can bind to DNA. This ambiguity complicates interpretation of results and poses a significant challenge to investigators. In this study however, the precise location of the complex bound to DNA is clearly defined in the crystal, therefore removing this uncertainty. This technique has the potential use in the study of other such systems looking at drug-DNA interactions and also looking at photo-damage of DNA associated with UV exposure.

Professor John Kelly from the School of Chemistry at Trinity College Dublin said: “This is an important step in our collaborative work to understand the action of DNA-targeting compounds when they are taken up by cancer cells. Professor Thorri Gunnlaugsson and Professor Clive Williams’ teams at Trinity have previously shown that related compounds can kill such cells when irradiated with visible light.”

The Irish teams have extensive experience in the ultrafast study of DNA, while the Reading group is a world-leader in the X-ray crystallographic analysis of DNA using the Diamond facility. The Rutherford group in the Central Laser Facility has developed extremely sensitive systems for the study of such ultra-fast chemical reactions (as low as a millionth-millionth of a second.).

The work has been supported by SFI/IRC (to Professor Gunnlaugsson) and the BBSRC and a key element of the funding for the collaboration has been provided by the Royal Irish Academy-Royal Society exchange programme.