Celebratory Symposium A – Catalysis and the Periodic Table Hybrid Ligands for Metal Complexes, Catalysts and Nanomaterials

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Reactivity of Metal (Co, Ni, Cu) Bound Peptides with Organometallic Fragments and Small Molecules

abstract: Understanding the mechanisms of metalloproteins at the level necessary to engineer new functionalities is complicated by the need to parse the complex overlapping functions played by each amino acid without negatively impacting the host organism. Artificial or designed metallopeptides offer a convenient and simpler platform to explore metal-ligand interactions in an aqueous, biologically relevant coordination context. In this dissertation, the peptide SODA (ACDLPCG), a synthetic derivative of the nickel-binding pocket of nickel superoxide dismutase, is used as a scaffold to construct a variety of novel metallopeptides and explore their reactivity. In Chapter 2, I show that SODA binds Co(II) and the resulting peptide, CoSODA, reacts with oxygen in an unexpected two step process that models the biosynthesis of Co nitrile hydratase. First, the thiolate sulfur is oxidized and then the metallocenter is oxidized to Co(III). In Chapter 3, I show that both CoSODA and CuSODA form CN- adducts. Spectroscopic investigations of these metallopeptides are compared with data from NiSODA and Ni(CN)SODA to show the remarkable geometric versatility of SODA with respect to interactions with metallocenters. In Chapter 4, exploiting the propensity of sulfur ligands to form bridging structures, NiSODA is used as a metallosynthon to direct synthesis of hetero bi- and tri-metallic peptides as models for [NiFe]-hydrogenases and the A cluster of acetyl-CoA synthase carbon monoxide dehydrogenase. Building on this synthetic strategy, in Chapter 5, I demonstrate synthesis of NiRu complexes including a Ru(bipyridine)2 moiety and characterize their photochemistry.Dissertation/ThesisPh.D. Chemistry 201

Photodynamic Therapy of Inorganic Complexes for the Treatment of Cancer

Photodynamic therapy (PDT) is a medicinal tool that uses a photosensitiser and a light source to treat several conditions, including cancer. PDT uses reactive oxygen species (ROS) such as cytotoxic singlet oxygen 1O2 to induce cell death in cancer cells. Chemotherapy has historically utilized the cytotoxic effects of many metals, especially transition-metal complexes. However, chemotherapy is a systemic treatment so all cells in a patient\u27s body are exposed to the same cytotoxic effects. Transition metal complexes have also shown high cytotoxicity as PDT agents. PDT is a potential localized method for treating several cancer types by using inorganic complexes as photosensitizing agents. This review covers several in vitro and in vivo studies, as well as clinical trials that reported on the anti-cancer properties of inorganic pharmaceuticals used in PDT against different types of cancer

Synthesis and reactivity of metal acetylide complexes

Concerted research is being carried out to synthèses various types of metal acetylides. Acetylides give excellent reaction versatility towards metal counterpart. Flexibility in the molecular conformation also increases. In this project two metal acetylides of iron and tungsten have been prepared. [LM(CO)nC≡CR] [{L=5-C5H5, M = W, R = (5-C5H4)Fe(5-C5H5), n = 3},{L=5-C5Me5, M = Fe, R = Ph, n = 2}] . Then CS2 has been incorporated in the metal acetylides prepared. Insertion of CS2 has been observed into metal –carbon acetylide bond when exposed to mild sunlight to obtain a variety of transition metal dithiolato complexes. The tungsten complex containing ferrocenyldithiolato ligand has been very interesting due to the presence of two types of metal species bridged by a S2C3 unit. The resulting compound was characterised by UV-visible spectroscopy, IR, NMR. The electrochemical studies was carried out

In honour of the 70th birthday of Professor Luis A. Oro

EssayWhen Professor Luis Oro turns over the middle of June, he will be 70 years old, and he will be completing a cycle of almost half a century (48 years) dedicated to chemical research in the field of organometallics and homogeneous catalysis, and in general to the development of chemistry. In this aim, he has assumed different and complementary responsibilities, from leading innovative research projects, to the formation of professional scientists for academia or the chemical industry, from the direction of the Spanish Royal Society of Chemistry, to that of diverse editorial management consortia or even having taken the responsibility of guiding the overall Spanish scientific policy. It has been a long trek done with tons of enthusiasm, excellent companions and plenty of generosity. It is our pleasure and privilege to walk around the main steps of Professor Oro’s life; a life dedicated to investigate and to work to situate chemical research, and science in general, in the proper place it should be in our modern society.Peer Reviewe