SERMACS

Seminar: Dr. Larry Que, Jr. (Minnesota) will present “The Amazing Nonheme High-Valent Iron-Oxo Landscape” to the department.

Dr. Janet McDonald (Vanderbilt University) will present “Nanostructures of Cu and Mo Sulfides: New chemistry from the surface to the core” to the department.

Abstract: Since our community began focusing on the “bottom-up” synthesis of nanoparticles and nanomaterials, our synthetic control has developed from control of the size of spherical, single component nanoparticles, to materials of increasing compositional complexity and structural design. These added design components lead to heightened functionality. In the Macdonald research laboratory, we allow a desired function, such as electrocatalytic reactivity or photocatalytic activity, to inspire new designs of nanoparticles. Our journey to achieve these goals leads to making fundamental discoveries about surface chemistry, crystalline order and reactivity. Our efforts have focused lately on a new binding mode of thiols on nanoparticle surfaces, that makes particles less prone to oxidation or ligand loss, and improves charge transfer in photocatalytic reactions. In a second project, we study the formation mechanism, the NIR luminescence and its origin in wurtzite CuInS2, a form only found in nanocrystals. Along the way we discovered an unreported type of crystalline order in mixed cation sulfides such as CuInS2 with sweeping implications for opto-electronic and thermo-electronic properties for these materials. In the last project presented here, we have developed petaled nanostructured cathodes of MoS2 that outperform Pt in Quantum Dot Sensitized Solar Cells.

Dr. Elizabeth Papish (University of Alabama) will present “New proton responsive ligands for metal complexes as catalysts and for pH activated anticancer properties” to the department.

Short Bio:
Elizabeth T. Papish was born and raised on Long Island in NY. She attended Cornell University, earning a BA degree in Chemistry in 1997, and thereafter she continued her education at Columbia University, earning a PhD degree in Chemistry in 2002. She has been a professor (teaching organic and inorganic chemistry) and has run a research group at Salisbury University, Drexel University, and since 2013 at the University of Alabama. Her research group studies bioinorganic and organometallic chemistry with an emphasis on designing new organic ligands for the use of transition metal complexes in energy related catalysis applications and for metal based therapies for health applications. She is the recipient of an NSF CAREER award and has been honored with the “Outstanding Research Mentor of the Year Award” at Salisbury University in 2007 and with the “College of Arts and Sciences Teaching Award” for excellence in teaching and mentorship from Drexel University in 2012. In 2013, Papish and her student received the “Division of Inorganic Chemistry Award for Undergraduate Research” from the American Chemical Society.

Abstract:
We aim to apply bioinorganic and organometallic chemistry to problems that relate to green chemistry and sustainability. In particular, we are interested in exploring how hydrogen-bonding groups impact catalysis. Within these broad goals, we have pursued reactivity inspired by the organometallic literature, specifically hydrogenation and water oxidation. Recently, we designed a new ligand (6,6’-dihydroxybipyridine) that places hydrogen bonding groups near the metal center on a bipyridine scaffold. This has allowed for formation of ruthenium and iridium complexes that perform catalytic hydrogenation in water and water oxidation. Hydrogenation and water oxidation are both of fundamental importance to the impending global energy crisis, as water oxidation is potentially a means of harnessing the sun’s energy, and hydrogenation chemistry can allow for energy storage. Furthermore, we have studied our hydroxyl substituted bipyridine ligands as a part of ruthenium based metallo-prodrugs. The ruthenium complexes are more labile with light under acidic conditions, which is similar to the conditions in cancer tumors. With collaborators Merino and Kim, we are studying the toxicity of these complexes towards cancer cells.

Dr. Christian Goldsmith (Auburn University) will present “The Development of Redox-Responsive MRI Contrast Agents – Steps Towards Detecting Oxidative Stress in Biological Systems” to the department.

Oxidative stress has been implicated in a wide variety of lethal and debilitating health conditions. The lack of sensors capable of imaging in vivo oxidative stress precludes us from fully understanding what roles reactive oxygen species play in disease progression. The Goldsmith laboratory has developed three Mn(II) complexes with redox-active ligands that are stable enough in water to serve as contrast agents for magnetic resonance imaging (MRI). These complexes react rapidly with H2O2 but do not display significant responses to O2. Installing quinol groups into the ligand framework allow turn-on responses to H2O2 in the T1-derived relaxivity. The sensor with the largest turn-on in relaxivity was used in ex vivo cardiac imaging. Preliminary results suggest that the probe can detect oxidative stress induced by the anti-cancer compound doxorubicin.

Biosketch: Prof. Goldsmith grew up in a suburb just outside of Boston, MA and attended Harvard University as an undergraduate, earning an A. B. in Chemistry in 1998 while performing research under the direction of Dick Holm. After this, Chris enrolled at Stanford University for his graduate work and obtained his Ph.D. in 2004 under the direction of Dan Stack. He was a postdoc for Steve Lippard at MIT until 2007, which is when he began his appointment at Auburn University. Dr. Goldsmith was promoted to Associate Professor in 2013. His independent research focuses on developing redox-active molecules capable of either catalyzing hydrocarbon oxidation reactions or serving as small molecule sensors for biologically relevant oxidants.

Dr. Konrad Patkowski (Auburn University) will present “Interactions of atoms, molecules, and surfaces – pushing the limits of accuracy” to the department.

Dr. Robert Cody (JEOL USA) will present “Inquiring Minds Want to Know! Fun and Games and Forensics with DART Mass Spectrometry” to the department.

Dr. Yu-Dong Zhou (Ole Miss) will present “Natural Products as Regulators of Oxygen Homeostasis” to the department.

Abstract: Transcription factor hypoxia-inducible factor-1 (HIF-1) dysregulation directly impacts cancer etiology and progression, while HIF-1 inhibition suppresses tumor growth and enhances the efficacy of radiation and chemotherapy. To discover novel HIF-1 inhibitors as potential drug leads for cancer, we took a natural product chemistry-based approach in combination with bioassays. A human breast tumor T47D cell-based reporter assay was established and validated. This assay was used to evaluate hundreds of purified natural products (small-molecule secondary metabolites), 15,000 natural product-rich marine invertebrate, and algae extracts, and 50,000 plant extracts from the U.S. National Cancer Institute’s Open Repository. Dozens of structurally novel and known compounds were isolated, identified, and their HIF-1 inhibitory activities characterized. These active compounds function through diverse pathways to inhibit HIF-1 activation, highlighting the potential of small-molecule HIF inhibitors as chemical probes for HIF biology and oxygen homeostasis. Employing mitochondrial complex I inhibitors as chemical probes, we uncovered that mitochondrial inhibitors trigger the endoplasmic reticulum (ER) stress response pathway to stall protein translation instead of through the more recognized AMPK pathway. This discovery revealed a new mechanism for mitochondrial inhibitors to regulate cellular signaling and paved the road for future research on the crosstalk between the ER and mitochondria. Meanwhile, a small scale screening campaign has led to the identification of natural product-based small-molecule HIF-1 activators. This research implicated that Golgi-mediated signaling pathway plays an important role in cellular oxygen homeostasis and HIF signaling.

Biography: After obtaining a Bachelor’s degree in Biochemistry at Fudan University (Shanghai, China), Dr. Yu-Dong Zhou moved to the US to pursue graduate education. She received her M.S. and Ph.D. degrees in Biochemistry and Molecular Biology at Emory University, Atlanta, Georgia, under the direction of Professor Kenneth E. Bernstein. Her subsequent postdoctoral research in the laboratory of Professor Steven L. McKnight at the University of Texas Southwestern Medical Center at Dallas (UTSW) led to the discovery and biological characterization of neuronal PAS domain protein 1 (NPAS1). Her natural product-focused research started after relocating to the University of Mississippi, first under the supervision of Dr. David S. Pasco and then as an independent scientist/research faculty (2000-present). Her UM research focuses on oxygen homeostasis, a fundamental principle of biology and medicine. Over the years, this UM molecular targeted anticancer natural product drug discovery effort has led to 40 research publications and two patents. Since joining Olemiss, Dr. Zhou has been a corresponding author or joint corresponding author on 33 original research publications. She has also served in the capacity of PI, co-PI, and investigator on a number of grants. Her research in natural product drug discovery, cancer biology, and cellular signaling has achieved significant recognition among her peers in the field, evidenced by invited presentations at national and international conferences, awards from the American Society of Pharmacognosy, and serving as a reviewer for high-impact scientific journals and funding agencies that include the NIH and Department of Defense.

Graduate Student Kimberly Poland will present “Bioimaging Mass Spectrometry of Trace Elements Using LA-ICPMS ” to the department.

Seminar: Dr. Kenneth Seddon (Queens University Belfast) will present “Applications of Ionic Liquids” to the department.

This paper covers two processes of industrial significance: if time permits, I will also describe work from Dr. Nimal Gunaratne, dealing with processes for personal care products.1 The first technology described is the first commercial application of ionic liquids for the removal of mercury from gas streams, and the first industrial application of solid-supported ionic liquids.2 Our novel technology is currently in
commercial practise in two reactors in Petronas facilities in Malaysia, treating natural gas streams within a gas processing plant for nearly four years of continuous operation. We describe here, to the extent possible at the moment, the process for mercury capture, comparing with extant technology, and the path to commercialisation in a record time for developments in this industry. In addition, we outline the salient features of a unique and special partnership between industry and academia that made this possible. The science, the fast track methodology and partnerships will be described. This commercial project draws on expertise and tools which were developed within QUILL, and described in “A Roadmap to Commercialisation with Ionic Liquids” (http://quill.qub.ac.uk/attachments/089_Q001.pdf). We will take the audience through parallel tracking of critical path activities including due diligence and risk assessment, and demonstrate how the technology was commercialised in less than three years with a high performance team. The second process described is carbon dioxide uptake from natural gas by binary ionic liquid-water mixture.3 Carbon dioxide solubility in a set of carboxylate ionic liquids formulated with near equimolar amounts of water is found to be significantly higher than for ionic liquids previously reported. This is due to synergistic chemical and physical absorption. The formulated ionic liquid/water mixtures show greatly enhanced carbon dioxide solubility relative to both anhydrous ionic liquids and aqueous ionic liquid solutions, and are competitive with commercial chemical absorbers, such as activated N-methyldiethanolamine or monoethanolamine.

1. H.Q.N. Gunaratne, P. Nockemann and K.R. Seddon, Chem. Commun., 2015, 51, 4455-4457.
2. M. Abai, M.P. Atkins, A. Hassan, J.D. Holbrey, Y. Kuah, P. Nockemann, A.A. Oliferenko, N.V. Plechkova, S. Rafeen, A.A. Rahman, R. Ramli, S.M. Shariff, K.R. Seddon, G. Srinivasan and Y. Zou, Dalton Trans., 2015, 44, 8617-24.
3. K. Anderson, M.P. Atkins, J. Estager, Y. Kuah, S. Ng, A.A. Oliferenko, N.V. Plechkova, A.V. Puga, K.R. Seddon and D.F. Wassell, Green Chem., 2015, 17, 4340-4354, 4500.