DNA nanotechnology, the self-assembly of DNA into 2D and 3D nanoscale structures facilitated via Watson and Crick base pairing, provides alternative solutions for biomedical challenges, especially for therapeutic cargo delivery, because it is easily fabricated, exhibits low cytotoxicity, and high biocompatibility. However, the stability of these DNA nanostructures (DN) under cellular environment presents an issue due to their requirements for high salt conditions and susceptibility to nuclease degradation. Furthermore, DNs are typically trapped in endolysosomal compartments rather than the cytosol, where most of their cargo must be delivered. Many attempts to mitigate the stability issue have been made in recent years. Previously, our lab designed an endosomal escape peptide, Aurein 1.2 (denoted “EE, for endosomal escape)”, combined with a decalysine sequence (K10) proven to electrostatically adhere to and protect DNs under cell culture conditions. Unfortunately, this molecule, termed K10-EE, only resulted in endosomal escape in absence of serum due to formation of a protein corona on the surface of the coated DN.6 Therefore, we now propose to electrostatically coat the DN with a polymer composed of decalysine (K10), polyethylene glycol (PEG, which demonstrates antibiofouling properties), and peptide EE: K10- PEG1k-EE. Described herein are the attempted synthetic schemes of K10-PEG1k-EE, the successful synthesis of alternative products, K10-(EK)5 and K10-(PEG12)2-EE, and their resulting impacts on DN stability under biological conditions. Coating of the K10-(EK)5 with a DNA barrel origami demonstrated inefficient stabilizing capability in serum. Future studies include testing K10- (PEG12)2-EE protection for a variety of nucleic acid-based structures.

This thesis is about how Fe catalysts can be degraded using photocatalysis and how Fe catalysts can degrade small molecules in conjunction with light. The goal of this paper is to look further into more sustainable methods of organic chemistry. Many current organic chemistry practices involve the use of precious metals. Iron is a more sustainable catalyst because it is abundant and inexpensive which is important for preserving the earth and making the organic chemistry more accessible. Along the same lines, light is a renewable energy source and has demonstrated its ability to aid in reactions. Overall, the goal of this paper is to explore the more sustainable alternatives to harsh and toxic organic chemistry practices through the use of Iron and light.

Non-canonical amino acids (NCAAs) can be used in protein chemistry to determine their structures. A common method for imaging proteins is cryo-electron microscopy (cryo-EM) which is ideal for imaging proteins that cannot be obtained in large quantities. Proteins with indistinguishable features are difficult to image using this method due to the large size requirements, therefore antibodies designed specifically for binding these proteins have been utilized to better identify the proteins. By using an existing antibody that binds to stilbene, NCAAs containing this molecule can be used as a linker between proteins and an antibody. Stilbene containing amino acids can be integrated into proteins to make this process more access able. In this paper, synthesis methods for various NCAAs containing stilbene were proposed. The resulting successfully synthesized NCAAs were E)-N6-(5-oxo-5-((4-styrylphenyl) amino) pentanoyl) lysine, (R,E)-2-amino-3-(5-oxo-5-((4-styrylphenyl)amino)pentanamido)propanoic acid, (E)-2-amino-5-(5-oxo-5-((4-styrylphenyl) amino) pentanamido) pentanoic acid. A synthesis for three more shorter amino acids, (R,E)-2-amino-3-(3-oxo-3-((4-styrylphenyl) amino) propanamido) propanoic acid, (E)-2-amino-5-(3-oxo-3-((4-styrylphenyl) amino) propanamido) pentanoic acid, and (E)-N6-(3-oxo-3-((4-styrylphenyl) amino) propanoyl) lysine, is also proposed.