Abstract: Advances in machine learning (ML) are making a large impact in many disciplines, including materials and computational chemistry. A particularly exciting application of ML is the prediction of quantum mechanical (QM) properties (e.g., formation energy, bandgap, etc.) using only the structure as input. Assuming sufficient accuracies in the ML models, these methods enable screening of a considerably large chemical space at orders of magnitude lower computational cost than available QM methods. Despite the promise of ML in chemistry, several key challenges remain in both applying and interpreting the results of ML algorithms. Here, we will discuss our efforts in addressing these issues, including our recent work on opening the black box of ML methods by identifying the domain of applicability, i.e., where a given model is reliable.

Bio: Chris Sutton is an Assistant Professor in the Department of Chemistry & Biochemistry at the University of South Carolina. Chris received his PhD at the Georgia Institute of Technology under the direction of Professor Jean-Luc Bredas, and then moved to Duke University for postdoctoral research with Professor Weitao Yang. Chris received the Alexander von Humboldt postdoctoral fellowship to work in the Theory Department at the Fritz Haber Institute in Berlin, Germany where Matthias Scheffler was the Director. Chris’ current research is focused on computational materials discovery through a combination of   electronic structure calculations, machine learning, and stochastic sampling techniques to speed up the traditional computational design of materials.

Michael Chabinyc

Materials Department

University of California Santa Barbara

Abstract: Polymers are essential for wearable electronic systems as active and passive materials.  We will discuss the role of molecular structure on the behavior of semiconducting polymers and dielectric elastomers. In both cases, the molecular architecture of polymers controls their ultimate functional behavior. First, we will discuss how relatively small changes in the design of the sidechains of semiconducting polymers can be used to modify donor-acceptor interactions with molecular dopants. These subtle changes control whether charge transfer is complete leading to an electrically conductive state, or partial leading to a poorly conducting charge-transfer state.  Second, we will discuss how polymers with a bottlebrush architecture can be used to form super-soft elastomers useful for pressure sensors. The low mechanical modulus of bottlebrush elastomers, which is comparable to that of hydrogels, allows for the simple formation of capacitive pressure sensors with sensitivity comparable to human touch. Recent results on 3D printing of super-soft materials will also be described.

Biography: Professor Michael Chabinyc is Chair of the Materials Department at the University of California Santa Barbara. He received his Ph.D. in chemistry from Stanford University and was an NIH postdoctoral fellow at Harvard University. He was a Member of Research Staff at (Xerox) PARC prior to joining UCSB in 2008. His research group studies fundamental properties of organic semiconducting materials and thin film inorganic semiconductors with a focus on materials useful for energy conversion. He has authored more than 200 papers across a range of topics and is inventor on more than 40 patents in the area of thin film electronics.  He is a fellow of the Materials Research Society (MRS), the American Physical Society (APS), the National Academy of Inventors (NAI), and the American Association for the Advancement of Science (AAAS).

Abstract:

Imparting supramolecular interactions on transition metal systems such as Iridium complexes (with various N^C ligands), can have a profound impact on their luminescence properties. These types of complexes are under intensive investigation due to their excellent performance when used as emitters in phosphorescent organic light emitting diodes (PhOLEDs).¹ The ideal interactions for holding supramolecular systems together are hydrogen bonds, as they combine relatively strong intermolecular attractions with excellent reversibility. In using DNA base-pair-like interactions in super strong hydrogen bonding arrays to drive assembly,² we can influence chromaticity efficiently.^3,4 Beyond molecular systems, we can also apply these principles in extended solid-state systems whose porosities are such that small molecule uptake can influence the inherent physical (and photophysical) properties of the host materials.⁵ In this lecture, a broad view of our research program will be presented, spanning molecular systems to solid-state materials, and how we can make use of inherent luminescence properties for chromaticity modulation, small molecule sensing, and diagnostics.^6,7

References:

1. A.F. Henwood, E. Zysman-Colman, Chem. Commun. 2017, 53, 807.
2. B.A. Blight, C.A. Hunter, D.A. Leigh, H. McNab, P.I.T. Thomson, Nature Chemistry, 2011, 3, 246.
3. B. Balónová, D.  Rota Martir, E.R. Clark, H.J. Shepherd, E. Zysman-Colman, B.A. Blight, Inorganic Chemistry, 2018, 57, 8581.
4. B. Balónová, H.J.  Shepherd, C.J. Serpell, B.A. Blight, Supramolecular Chemistry, 2019, DOI: 10.1080/10610278.2019.1649674
5. R.J. Marshall, Y. Kalinovskyy; S.L. Griffin, C. Wilson, B.A. Blight, R.S. Forgan, J. Am. Chem. Soc., 2017, 139, 6253.
6. S.J. Thomas, B. Balónová, J. Cinatl M.N. Wass, C.J. Serpell, B.A. Blight, M. Michaelis, ChemMedChem, 2020, 15(4), 349.
7. C.S. Jennings, J.S. Rossman, B.A. Hourihan, R.J. Marshall, R.S. Forgan, B.A. Blight, Soft Matter, 2021, In Press. DOI: 10.1039/D0SM02188A

Yu Seung Kim (yskim@lanl.gov)

Los Alamos National Laboratory

Abstract: A proper design of polymer electrolytes may result in significant performance and durability improvement in electrochemical devices. In this talk, I show some examples of how polymer electrolytes can bring remarkable performance improvement in low-temperature fuel cells, high-temperature fuel cells, alkaline anion-exchange membrane fuel cells, and alkaline water electrolyzers. Critical factors such as ionomer adsorption on the catalyst surface, the concentration of ionic functional groups, and polymer relaxation will be discussed to give insights to design high-performing electrochemical devices. 

Bio: Yu Seung Kim is a technical staff scientist at Los Alamos National Laboratory, USA. He received his B.S. degree from Korea University (1994) and his Ph.D. degree from Korea Advanced Institute of Science and Technology (1999) in the field of Chemical Engineering. He spent three years as a post-doctoral fellow at the Chemistry Department of Virginia Tech before joining the fuel cell group at Los Alamos (2003). He received the Outstanding Technical Contribution and Achievements Award from US DOE Hydrogen and Fuel Cell Program (2016). His current research interest is materials for fuel cells and electrolyzers. 

Abstract:  Conventionally physical chemistry is a field that mainly investigates physicochemical phenomena at atomic and molecular levels. Noticing the analogy between molecular (especially macromolecular) dynamics and cellular dynamics, in the past few years my lab has focused on introducing and generalizin

g the techniques and concepts of physical chemistry into cell biology studies. In this talk I will first discuss a long-standing Nobel-Prize winning puzzle on olfaction. Each olfactory sensory neuron stochastically expresses one and only one type of olfactory receptors, but the molecular mechanism remained unanswered for decades. I will show how simple physics taught in introductory physical chemistry textbook explains this seemingly complex problem, and briefly mention our ongoing efforts of investigating chromosome dynamics with a CRISPR-dCas9-based live cell imaging platform. 

In the second part of my talk, I will discuss our efforts on developing an emerging new field of single cell studies of the dynamics of cell phenotypic transition (CPT) processes, in parallel to single molecule studies in  chemistry. Mammalian cells assume different phenotypes that can have drastically different morphology and gene expression patterns, and can change between distinct phenotypes when subject to specific stimulation and microenvironment. Some examples include stem cell differentiation, induced reprogramming (e.g., iPSC) and others. In many aspects a CPT process is analogous to a chemical reaction. Using the epithelial-to-mesenchymal transition as a model system, I will present an integrated experimental-computational platform, and introduce concepts from chemical rate theories such as transition state, transition path, and reactive/nonreactive trajectories to quantitatively study the dynamcis of CPT processes.

Research: https://www.csb.pitt.edu/Faculty/xing/

Zirconium in the Spotlight: New Pathways to Photoluminescent Molecules

Carsten Milsmann

C. Eugene Bennett Department of Chemistry, West Virginia University

The efficient utilization of sunlight as a carbon-neutral, renewable energy source remains a challenge for scientists across many disciplines. The enormous scope of solar energy conversion on a global scale requires the development of photoactive materials from readily available and economically viable resources. Photoluminescent complexes based on earth-abundant early transition metals or main group elements present an attractive low-cost, low-toxicity alternative to precious metal photosensitizers commonly used in photochemical processes and solar energy conversion. However, the fundamentally different electronic structures of these elements requires the development of new approaches to light-induced charge separation and electron transfer.

This presentation will highlight the Milsmann group’s efforts to establish design principles for the generation of luminescent early transition metal complexes that can undergo photo-induced single electron transfer (SET) reactions upon irradiation with visible light. A particular focus will be on phosphorescent zirconium complexes that exhibit exceptionally long triplet excited state lifetimes. Our results show that these complexes can not only replace precious metal photosensitizers in photoredox catalytic reactions, but may exhibit optical properties that complement those of traditional late metal compounds. In addition, research towards the development of metal-free phosphorescent molecules based on silicon will be discussed.

Abstract:

The structure of graphene oxide (G-O) is still a challenging topic for developing useful and novel applications, where a compatibility, affinity or even covalent linkage is required at the interface. There is still a no consensus about the essential details, especially relating to the epoxy groups as main complexes in the basal plane, as well as the simultaneous presence of G-O sheets and oxidative debris (OD), with large difference in their oxygen content between both entities. The present seminar  deeps on this topic, through the characterization the base-washed G-O (bwGO) sheets, the OD and the humic fraction of the OD obtained by base digestion, when the parent G-O was previously dried or not, and previously sonicated or not. It was found that the presence of lactols at graphene edges as the dominant surface complexes agrees with all the characterization techniques, and also explains the high decrease of oxygen surface coverage in bwGO, where no carboxylic group removal was observed. These findings suggest that the Hummers-Offeman reaction produces a chemical scissor-effect during the water/hydrogen peroxide quenching step, yielding a broad size distribution of G-O sheets, with little in-plane oxidation, and the vast majority of edges being oxidized to form 7-ring lactol-type heterocyclic functionalities. Therefore, OD consists essentially of the very low sheet-size fractions, highly oxidized poly aromatic hydrocarbons, with a very high oxygen:carbon ratio due to the very high edge to weight ratio. 

Abstract:

Biological macromolecules function in dense, crowded cellular environments.

Early studies of crowding effects have emphasized volume exclusion effects, but it is becoming clear that frequent non-specific interactions between proteins, nucleic acids, and metabolites may be the more important factor in modulating the structure and dynamics of biomolecules. Computer simulation studies at different scales of a series of models ranging from concentrated homogeneous protein solutions to models of bacterial cytoplasms are presented to explore the effects of non-specific quinary protein-protein interactions on protein stability and dynamics.  One focus is on the formation of transient clusters that determine diffusive properties and lead to liquid-liquid phase transitions. The computational results are related to existing experimental data and the challenges and opportunities to expand the current studies to whole-cell modeling in molecular detail are discussed.

Abstract:

When an aqueous solution freezes at atmospheric conditions, essentially pure crystals of hexagonal ice are formed, and the solutes are threaded between the ice grains in ice boundary grooves or in puddles formed on the surface.

Certainly, there are several questions to ask about this process: What is the microstructure of ice with brine like? What is the chemical state and immediate environment of the solutes there? And, most importantly, how is the reactivity of the compounds influenced by freezing?

I would like to invite you to search for the answers with me, and I will be very pleased with your interest. So far, I have applied environmental scanning electron microscopy and optical spectroscopies in seeking indications of the aggregation, pH jumps, and electrical “freezing potential” formed at the interfaces of ice grains upon freezing. My goal is to explain the (photo) reactivity of compounds in environmental ices and during laboratory-based and industrial freezing procedures. I am currently a visiting scholar on sabbatical here at the University of Kentucky, and would appreciate any suggestions on facilities or methods available here.

Abstract:

Detailed understanding of how conformational dynamics orchestrates function in allosteric regulation of recognition and catalysis at atomic resolution remains ambiguous. The three dimensional structure of protein is not always adequate to provide a complete understanding of protein function. We use atomistic molecular dynamics simulations to complement experiments to understand how protein conformational dynamics are coupled to allosteric function. We analyze multi-dimensional simulation trajectories by mapping key dynamical features within individual macrostates as residue-residue contacts. In this talk, we will discuss computational studies on members of a ubiquitous family of enzymes that regulate many sub-cellular processes. The effects of distal mutations and substrate binding are observed at locations far beyond the mutation and binding sites, implying their importance in allostery. The results provide insights into the general interplay between enzyme conformational dynamics and catalysis from an atomistic perspective that have implications for structure based drug design and protein engineering.