Monday, Sept. 21, 2020, 4 p.m. through Monday, Sept. 21, 2020, 5 p.m.
Professor Annia Galano
Department of Chemistry
Metropolitan University of Mexico
Mexico City, Mexico
Host: Professor Ilja Siepmann
QM-ORSA: An accurate computational protocol to explore the tip of the antioxidant iceberg
Chemical antioxidants are potential candidates to ameliorate the deleterious effects of oxidative stress-related diseases. However, both oxidative damage and antioxidant protection are complex and interrelated processes. That is why investigations on this field frequently focus on specific aspects of the whole phenomenon. Probably, the most widely explored aspect of chemical antioxidants is their ability to deactivate free radicals. The Quantum Mechanics-based Test for Overall Free Radical Scavenging Activity (QM-ORSA) is a computational protocol designed to be a reliable tool in the study of radical-molecule reactions in solution. It can be used to provide a universal and quantitative way of evaluating the free radical scavenging activity of chemical compounds. It provides a separated quantification of such activity in polar (aqueous) and non-polar (lipid) media. It includes two different scales for quantification: (i) absolute, based on overall rate coefficients; and (ii) relative, using Trolox as a reference antioxidant. QM-ORSA also allows identifying the main mechanisms of reaction involved in the free radical scavenging activity of chemical antioxidants and establishing the influence of pH on such an activity. The QM-ORSA protocol has been validated versus experimental results, and its uncertainties were proven to be no larger than those arising from experiments.
- Annia Galano, Juan Raúl Alvarez-Idaboy “A Computational Methodology for Accurate Predictions of Rate Constants in Solution: Application to the Assessment of Primary Antioxidant Activity” J. Comput. Chem. 2013, 34 (28), 2430–2445.
- Annia Galano, Gloria Mazzone, Ruslán Alvarez-Diduk, Tiziana Marino, J. Raúl Alvarez-Idaboy, Nino Russo. “Food Antioxidants: Chemical Insights at the Molecular Level” Annu. Rev. Food Sci. Technol. 2016, 7, 335–352.
- Annia Galano, Juan Raúl Alvarez-Idaboy “Computational strategies for predicting free radical scavengers’ protection against oxidative stress: Where are we and what might follow?” Int. J. Quantum Chem. 2019, 119, e25665 (23 páginas).
Professor Annia Galano’s research group applies computational chemistry to the investigation of physicochemical insights directly related to atmospheric pollution, carbon-based nanomaterials, oxidative stress, and antioxidant activity. The current central themes of her group are:
- The elucidation of the chemical behavior of antioxidants and the relative efficiency for that purpose of a large variety of chemical compounds.
- The systematic design of new antioxidants with multifunctional behavior and possible neuro-protective effects.
Her group is involved in interdisciplinary research that mixes theoretical chemistry, organic synthesis, analytical chemistry, chemical biology, and medicinal chemistry.
Professor Galano received her bachelor’s degree and her doctorate at Havana University, Cuba. She performed postdoctoral studies at the Mexican Institute of Petroleum and at the Metropolitan Autonomous University (UAM, according to its Spanish acronym). She had research stays at Uppsala University and Calabria University and joined the faculty at the UAM in 2008.
Tuesday, Sept. 22, 2020, 9:45 a.m. through Tuesday, Sept. 22, 2020, 11 a.m.
Reactivity-property relationships in photocontrolled polymer networks
In polymer networks based on dynamic covalent bonds, changes in reactivity can be translated into macroscopic responses. Light offers precise, tunable, and noninvasive spatiotemporal control over molecular reactivity. The Kalow lab has designed crosslinks that allow us to tune the thermodynamics and kinetics of dynamic covalent bonds with light, including visible light, based on the conformation of an adjacent photoswitch. When incorporated into polymer networks, the mechanics can be tuned reversibly with light. I will discuss the molecular mechanism underlying these macroscopic changes, and their applications in biomaterials.
Professor Julia Kalow engages in research at the interface of organic synthesis, polymer chemistry, and materials science through two distinct approaches: materials-inspired reaction discovery and reactivity-driven materials discovery. In the first, researchers develop new synthetic transformations that provide control over the molecular structure of 1- and 2-dimensional organic polymers. In the second, they use knowledge of organic reactivity to tune the properties and functions of soft materials. These efforts enable the study of structure-property relationships and materials optimization for targeted applications, including optoelectronics and magnetooptics, catalysis, sensing, and biomaterials.
Professor Kalow obtained her Bachelor of Arts degree at Columbia University, where she studied chemistry and creative writing. Following an internship in the medicinal chemistry department at Merck, she pursued graduate studies at Princeton University as a National Science Foundation predoctoral fellow. She developed asymmetric catalytic fluorinations using a latent source of HF and studied their mechanisms in detail; her work was recognized by an American Chemical Society Division of Organic Chemistry Graduate Fellowship Award. After completing her doctorate, she joined the Massachusetts Institute of Technology as a Ruth L. Kirschstein National Institutes of Health National Research Service Award postdoctoral fellow, studying the synthesis and self-assembly of novel architectures of conjugated block copolymers as well as responsive surfactant design for sensing applications. She started her independent career at Northwestern’s Department of Chemistry in July 2016.
Thursday, Sept. 24, 2020, 9:45 a.m. through Thursday, Sept. 24, 2020, 11 a.m.
Polymethine fluorophores for in vivo shortwave infrared imaging
Fluorescence imaging is a central tool for visualizing complex biological systems, yet the contrast and resolution attainable in vivo is limited by diffuse light originating from background and scattering at visible and near-infrared (NIR) wavelengths. Recently, the shortwave infrared region of the electromagnetic spectrum (SWIR, 1000 – 2000 nm) has emerged as an optimal region for in vivofluorescence imaging due to its minimal light scattering and low tissue autofluorescence compared to the NIR. While the SWIR demonstrates great promise, suitable materials are needed with emission at these low energies for the development of optical contrast agents. Our group develops biocompatible polymethine fluorophores for the shortwave infrared region. In 2017, we discovered a bright shortwave infrared emitter containing flavylium heterocycles that we deemed Flav7. Since that time, we have systematically investigated Flav7 using physical organic chemistry approaches and can now predictably tune the absorption and emission properties. These insights have lead to new SWIR fluorophores that enable multiplexed in vivo imaging and the fastest SWIR imaging to date.
Professor Ellen Sletten's research group applies the fundamental principles of physical organic chemistry to create enhanced nanotherapeutics and diagnostics, new chemical tools to study living systems, and novel light-harvesting materials. The central theme of her group is the element fluorine, which imparts unique, orthogonal behavior to molecules and materials. Research within the group involves an interdisciplinary mix of organic synthesis, fluorous chemistry, chemical biology, self-assembly, polymer synthesis, photophysics, nanomedicine, and pharmacology.
Professor Sletten received her bachelor's degree from Stonehill College, and her doctorate at the University of California, Berkeley. Her thesis work involved the optimization and development of bioorthogonal chemistries and their subsequent applications in labeling living systems. She performed her post-doctoral studies at the Massachusetts Institute of Technology. She joined the faculty at UCLA in 2015.
Monday, Sept. 28, 2020, 4 p.m. through Monday, Sept. 28, 2020, 5 p.m.
Kevin Cole, Ph.D.
Senior Research Scientist
Eli Lilly and Company
Junliang Hao, Ph.D.
Research Adviser, Discovery Chemistry
Eli Lilly and Company
Host: Nicholas Race
Discovery and development of mevidalen, a first-in-class positive allosteric modulator of the dopamine D1 receptor
Kevin Cole was born in St. Paul, MN, and received his Bachelor of Science in chemistry from the University of Minnesota in 1999. He stayed at Minnesota for graduate studies, earning a doctorate in 2005, working with Professor Richard Hsung developing novel methodologies to apply to natural product total synthesis. He then moved to The Scripps Research Institute in San Diego to work with Professor K.C. Nicolaou investigating complex natural product synthesis. In 2007, Cole joined the process development group at Eli Lilly in Indianapolis, IN. As a principal research scientist, Cole has primarily worked to develop new production routes for early–mid phase clinical assets and has utilized continuous processing to support the supply for a number of clinical assets.
Junliang Hao received his doctorate from University of Minnesota in 2002, and did his post-doctoral researches at The Scripps Research Institute and Harvard University. He started at Eli Lilly at Indianapolis in 2006, and has worked primarily on small molecule drug discovery. More recently, he has worked on RNA therapeutics. He currently holds the title of Research Adviser, and his research has contributed to several clinical candidates that have reached phase two clinical studies, one of which is the first-in-class D1PAM he will share in this seminar.
Tuesday, Sept. 29, 2020, 9:30 a.m. through Tuesday, Sept. 29, 2020, 11 a.m.
Claire E. Dingwell at 9:30 a.m.
Adviser: Professor Marc Hillmyer
Processable and Photocurable Epoxy-functional Polyolefin Prepolymers from Ring-Opening Metathesis Polymerization
Brendan J. Graziano at 10 a.m.
Adviser: Professor Connie Lu
Organometallic Reactivity of Nickel Complexes Bearing PAlP Pincer-Type Ligands
Rishad J. Dalal at 10:30 a.m.
Adviser: Professor Theresa Reineke
Cationic Bottlebrush Polymers for Nucleic Acid Delivery
Thursday, Oct. 1, 2020, 9:30 a.m. through Thursday, Oct. 1, 2020, 11 a.m.
Mengyuan Jin at 9:30 a.m.
Adviser: Professor Thomas Hoye
Untethered/Intermolecular” Hexadehydro-Diels–Alder (HDDA) Reaction of Alkynyl Borane Esters Mediated by Lewis-Pair Interactio
Stephanie R. Liffland at 10 a.m.
Adviser: Professor Marc Hillmyer
Mechanical Properties of Linear and Star Block Aliphatic Polyester Thermoplastic Elastomers
Ethan A. Gormong at 10:30 a.m.
Advisers: Professor Theresa M. Reineke & Professor Thomas R. Hoye
Adapting the Glaser-Hay Coupling toward Sugar-derived Poly(propargyl ether diynes)
Monday, Oct. 5, 2020, 4 p.m. through Monday, Oct. 5, 2020, 5 p.m.
Nano-diving into the clouds: Uncovering molecular mechanisms of heterogeneous ice nucleation
The presence of particles such as dust and pollen affect cloud microphysics significantly through their effect on the state of water. These particles can hinder or accelerate the liquid-to-solid transition of water, and also affect the ice polymorph formed in the clouds. This indirectly cloud reflectivity, cloud lifetime, and precipitation rates. While a predominant phenomenon, the understanding of the surface factors that affect ice nucleation is minimal. In our research, we use molecular simulations to illuminate the pathways through which surface properties influence ice nucleation. Experiments cannot probe the length and time scales relevant to nucleation. While molecular simulations, in principle, can probe the length and time scales of nucleation, in practice nucleation is challenging to sample. Nucleation is often associated with large free energy barriers and thus, is difficult to sample in straightforward simulations. Advanced sampling techniques and other creative approaches are needed. In this talk, I will discuss the insights we have obtained on heterogeneous ice nucleation through studies of three surfaces – silver iodide, kaolinite and mica. I will also highlight the synergistic combination of experiments and simulations in understanding heterogeneous ice nucleation. I will introduce a recently developed method in our group facilitate computational studies of heterogeneous nucleation. I will conclude by providing a perspective on the broader implications of our studies on interfacial phenomena and surface design.
Sapna Sarupria is an associate professor in Chemical and Biomolecular Engineering at Clemson University. She received her Master's degree from Texas A & M University where her thesis focused on thermodynamic modeling of clathrate hydrates of gas mixtures formed in the presence of electrolyte solutions. She obtained her doctorate from Rensselaer Polytechnic Institute, where she studied pressure effects on water-mediated interactions and proteins. She was a postdoctoral researcher in Princeton University and studied hydrate and ice nucleation using advanced path sampling techniques. She received the NSF CAREER award, ACS COMP Outstanding Junior Faculty Award and Clemson’s Board of Trustees Award of Excellence. She is an active member of Women in Chemical Engineering (WIC) and Computational and Molecular Science and Engineering Forum (CoMSEF) in AIChE.
Professor Sarupria's research focuses on surface-driven phenomena. Current projects include heterogeneous ice nucleation, protein adsorption on surfaces and fouling on water purification membranes. The central theme in Sarupria group involves developing cutting-edge sampling techniques in molecular simulations and applying them in understand long standing problems in condensed matter. We recently developed novel transition path sampling methods and software to enable their large-scale implementation in HPC infrastructure. These methods will be used to study ice nucleation, and reactions in condensed phases including enzymatic reactions.
Tuesday, Oct. 6, 2020, 9:30 a.m. through Tuesday, Oct. 6, 2020, 11 a.m.
Michael Dorante at 9:30 a.m.
Adviser: Professor Connie Lu
Catalytic N2 to NH3 conversion by a tin-supported Iron complex
Yukun Cheng at 10 a.m.
Adviser: Professor Ian Tonks
Synthesis of Pentasubstituted 2-Aryl Pyrroles from Boryl and Stannyl Alkynes via One-Pot Sequential Ti-Catalyzed [2+2+1] Pyrrole Synthesis/Cross Coupling Reaction
Chase S. Abelson at 10:30 a.m.
Adviser: Professor Lawrence Que Jr.
A Highly Reactive High-Valent Iron-Oxo Oxidant Generated upon the Addition of Strong Acids to a FeIII-OOH Complex
Thursday, Oct. 8, 2020, 9:30 a.m. through Thursday, Oct. 8, 2020, 11 a.m.
Casey Carpenter at 9:30 a.m.
Adviser: Professor Christopher Douglas
Studies Towards Azacyclacene
Steven Prinslow at 10 a.m.
Adviser: Professor Connie C. Lu
Exploring Alkane Oxidation at Isolated Fe(II) Sites in the Metal-Organic Framework PCN-250s
Daniel Blechschmidt at 10:30 a.m.
Adviser: Professor Steven Kass
Earth-Abundant Metal Incorporation into Charge-Enhanced Brønsted Acid Catalysis
Monday, Oct. 12, 2020, 4 p.m. through Monday, Oct. 12, 2020, 5 p.m.
Varinia Bernales, Ph.D.
Senior Chemist, Research & Development
Dow Chemical Company
Host: Professor Ilja Siepmann
Insights from quantum chemistry toward a sustainable future
In this talk, I will cover the catalytic activity of transition metals supported on different scaffolds in the context of multireference wavefunction theory and density functional theory. Specifically, I will focus on earth-abundant metals that have the potential to provide more affordable and sustainable alternatives to current technologies. First, I will present a series of bimetallic complexes with promising catalytic activity for nitrogen fixation. Their peculiarity lies in a unique interplay between the two metals and the ligand hemilability. In the second part, I will discuss transition-metal atoms supported on metal–organic frameworks nodes with promising catalytic activity for alkane/alkene conversion into valuable chemicals. These are great examples where quantum chemical calculations provide fundamental understanding of the electronic structure and catalytic behavior of supported metals. Computational results demonstrate that the catalytic activity of these species is influenced by the direct coordination sphere of the active site. These insights can guide future theoretical and experimental catalyst design.
- V. Bernales, M. A. Ortuño, D. G. Truhlar, C. J. Cramer, L. Gagliardi. Computational Design of Functionalized Metal–Organic Framework Nodes for Catalysis. ACS Cent. Sci., 2018, 4, 5–19.
- Z. Li, A. W. Peters, V. Bernales, M. A. Ortuño, N. M. Schweitzer, M. R. DeStefano, L. C. Gallington, A. E. Platero-Prats, K. W. Chapman, C. J. Cramer, L. Gagliardi, J. T. Hupp, O. K. Farha. Metal–Organic Framework Supported Cobalt Catalysts for the Oxidative Dehydrogenation of Propane at Low Temperature. ACS Cent. Sci., 2017, 3, 31–38.
- V. Bernales, A. B. League, Z. Li, N. M. Schweitzer, A. W. Peters, J. T. Hupp, O. K. Farha, C. J. Cramer, L. Gagliardi. Computationally Guided Discovery of a Catalytic Cobalt-Decorated Metal–Organic Framework for Ethylene Dimerization. J. Phys. Chem. C, 2016, 120, 23576–23583.
- R. B. Siedschlag, V. Bernales, K. D. Vogiatzis, N. Planas, L. J. Clouston, E. Bill, L. Gagliardi, and C. C. Lu. Catalytic Silylation of Dinitrogen with a Dicobalt Complex. J. Am. Chem. Soc., 2015, 137, 4638–4641.
Varinia Bernales, Ph.D., received her bachelor’s degree and doctorate in chemistry from the University of Chile. Her thesis involved the experimental and theoretical study of solvation effects in ionic liquids, including the generation of a solvation database to validate implicit and explicit solvation models.
She performed her postdoctoral studies at the University of Minnesota under the supervision of Professor Laura Gagliardi. There, she participated in a variety of energy-related projects involving actinide materials, small molecule activation by transition metal-based homogeneous and heterogeneous systems, and development of multireference and quantum chemical methods. In 2017, she received the Wiley Computers in Chemistry Outstanding Postdoc Award.
In 2018, she joined The Dow Chemical Company as a Senior Chemist, where she continues her career as a quantum chemist in the Chemical Science group within Core Research & Development. Since 2012, she has authored 30 peer-reviewed publications and filed two patent applications, currently under provisional status.