The Other Side of Entropy

Abstract: Following its inception in the mid-19th century, our understanding of thermodynamic entropy has undergone many revisions, most notably through the development of microscopic descriptions by Boltzmann and Gibbs, which led to a deep understanding of equilibrium thermodynamics.

Tandem Insertion/Sigmatropic Rearrangements by Insertion of Rhodium Carbenes into Sulfur Bonds

Abstract:

This dissertation will focus on four main areas: The first aspect to be discussed will be reaction of allyl 2-diazo-2-phenylacetates with trimethylsilyl thioethers in the presence of rhodium(II) catalysts. These conditions generate α-allyl-α-thio silyl esters which undergo a spontaneous Ireland–Claisen rearrangement. Competing side-reactions, substrate scope and application will be explored.

New Synthetic Tools for Peptide Medicinal Chemistry

Abstract: While the use of small organic molecules as therapeutic agents (drugs) goes back to antiquity, the therapeutic use of peptide drugs is a very recent phenomenon. Approximately 60 peptides have been introduced for clinical use in the past 25 years. 85% of these peptides contain at least one non-proteinogenic amino acid—those outside of the naturally encoded and translated amino acids—to confer metabolic stability, receptor potency and/or receptor selectivity to the peptide.

Analysis of allostery in a transcription factor using molecular simulations and machine learning

Abstract: While allostery has been a topic of intense interest for the past several decades, our understanding of the underlying mechanism at the molecular level continues to be challenged by new experimental observations. Specifically, a recent deep mutational scanning study of a bacterial transcription factor TetR found that allostery hotspot residues are broadly distributed over a major portion of the protein structure, rather than being clustered near the ligand-binding and DNA-binding domain interfaces as often discussed in structure-based studies.

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