Quinine is a naturally occurring alkaloid found in the bark of the cinchona tree.1 Its medicinal relevance cannot be overstated as it is one of the most widely used anti-malarial drugs in the world.1 While the synthetic pathway to derive quinine is of limited relevance due to its abundance and ease of extraction, the puzzle of engineering reactions to isolate a stereochemically pure product of quinine captivated chemists for generations. The purpose of this study was to prove the conceptual route proposed by Stotter, Friedman, and Minter2 for the stereochemically pure total synthesis of quinine via a non-nitrogenous analog where the two nitrogen atoms of quinine are substituted with carbon atoms. The product of the analogous route is 1,1’-Dideaza-Quinine. Quinine is stereochemically complex, containing four separate stereocenters, thus the synthesis of quinine opens up the possibility of generating sixteen different isomeric structures.3 While the total synthesis of quinine with the correct stereochemistry was accomplished in 2001,3 the proposed route simplifies the process by relying on a stereospecific aldol condensation to eliminate potential isomerization.2 The results of the study validate the proposed route and add to the field of Organic Synthesis by illustrating an example of a stereoselective aldol condensation. Additionally, due to the analogous nature of the synthetic route utilized, many novel compounds were generated adding to the body of knowledge available to the Chemistry community.

Hard-soft acid base theory is often used to explain the selectivity of chemical reactions, under the assumption that hard (soft) nucleophiles prefer to react with hard (soft) electrophiles. Computationally, quantifying the relative hardness and softness of different sites in a molecule remains challenging. Our "orbital overlap distance function" allows us to quantify which regions in a molecule contain compact vs. diffuse molecular orbitals. Here we explore the idea that compact molecular orbitals correspond to chemically hard regions, and that diffuse and polarizable orbitals correspond to chemically soft regions. We combine the orbital overlap distance with electrostatic potentials to quantify the hardness and electrophilicity of different sites in heterocyclic aromatic compounds. Results are compared to known experimental trends in aromatic reactivity

Peptide nucleic acids (PNA) are artificially synthesized monomers or polymers that mimic DNA or RNA sequences. Due to their stability in biological conditions and their ability to bind complementary to DNA or RNA, PNAs have potential medicinal value since they can be used to block processes like replication or protein synthesis. Though most PNAs are commercially synthesized, the goal of this project was to begin the synthesis with propargyl bromide. This would allow the final monomer to have a propargyl group which allows functional groups (like a polyamine tail, fluorescent tag, or alkylating group) to be added at the end or any time throughout the synthesis. The PNA monomer will be made with all four DNA bases (thymine, cytosine, adenine, and guanidine) attached. Another importance of this PNA monomer is its ability to undergo click reactions to create a PNA oligomer. Click chemistry is a chemical reaction that uses copper-catalyzed coupling to combine an azide with an alkyne. The ability to use click chemistry is vital since it can be done in biological conditions, has an excellent yield with few byproducts, and is relatively quick to perform. In conclusion, this project is useful since these PNA sequences can be used to modulate processes and treat a variety of diseases while having the ability to add functional groups to track the PNA oligomer.

A library of novel pyridinophane tetra-aza macrocyclic molecules derived from 1,4,7,10-tetraaza-2,6-pyridinophane (pyclen) capable of chelating biologically relevant metal ions have been synthesized. Applications of these types of molecules currently being pursued are 1) therapeutic, focusing on radical scavenging and metal chelation and 2) diagnostic, focusing on magnetic resonance imaging (MRI) contrast agents when complexed with specific metal ions. Despite wide interest in these molecules, a full study of the electronic effects imparted by substitution to the pyridyl moiety and the subsequent impact on the metal center has not yet been conducted. The objective of the present study is to characterize metal complexes of four, new tetra-aza macrocyclic metal chelating molecules. The pyridyl functional groups studied include: A) unmodified pyridyl (L1), B) 14-hydroxyl (L2), C) 14-nitrile (L3), and D) 14--nitro (L4) modified pyclen structures. Procedures for metal ion chelation with copper (II) ion, followed by characterization and analysis of the electronic environments of each are presented.

The dye-sensitized solar cells (DSSCs) are a possible alternative tool to harvest solar energy instead of the traditional silicon-based solar cells. DSSCs offer various advantages, such as good energy conversion efficiencies in low-light condition, simple fabrication, low cost, and the ability to modify key properties of the solar cell such as the absorbance wavelengths. We are interested in developing new types of semiconductor supports for use in DSSCs based on tin(IV) oxide nanoparticles (NPs). Tin(IV) oxide offers a wide band gap and higher electron mobility as compared with the more widely used titanium dioxide. In this study, two morphologies of tin(IV) oxide, spherical and flower-like NPs, are synthesized. These two types of tin(IV) oxide NPs and mixtures of both at various ratios are used to fabricate DSSCs. We find that nanoflowers usually give the cells higher open circuit voltages but with lower photocurrent. Nanospheres give much higher photocurrent but with lower open circuit voltage. A mixture that has a 1:2 molar ratio of nanoflowers and nanospheres gave the best performance in terms of photocurrent and voltage. Furthermore, we are investigating the effect of a deposited layer of titanium(IV) oxide on top of the tin(IV) oxide to further enhance the photoperformace of the solar cells.