Research in Prof. Funk’s lab continued to focus on two main projects: synthesis and catalytic applications of (cyclopentadienone)iron carbonyl compounds, and the development of a library of cyanuric chloride-based lipids for use in vaccine development and drug delivery—a collaboration with University of Kentucky School of Pharmacy professor Vince Venditto (’03 Chem).
Even with the campus being “de-densified” during the 2020-2021 academic year, multiple students were able to stay on campus and participate in socially distanced research. Bryn Werley (’23 CHEM and Music) took over Evan Bertonazzi’s (’20 Chem) project studying a trimethylamine-bound iron cyclopentadienone compound. She grew x-ray-quality crystals that Prof. Anthony Chianese at Colgate University was able to get a structure of. Bryn did a great deal of NMR spectroscopy work to show that this trimethylamine compound is an important intermediate in the catalytic cycle of transfer hydrogenations and dehydrogenations with this class of catalysts. She continued working over the summer of 2021 and throughout the 2021-2022 academic year and collected a great deal of mechanistic information about these catalysts.
Auden Cameron-Lampariello (’22 Chem) also worked on the iron project. Over the summer of 2021 and throughout the 2021-2022 academic year, he developed new catalysts that selectively oxidized primary over secondary alcohols. Danielle Kleinberg (’23 Chem and ES) took over Melanie Hempel’s (’20 BMB) project during the summer of 2021 exploring the reactivity of alcohols in transfer dehydrogenations with our iron catalysts using sustainable furfural as a hydrogen acceptor. She discovered that with some alcohols, the reactions could be run in water. Katy Wnuk-Fink (’22 Chem and Bio) worked on the same project during the spring of 2021 and throughout the 2021-2022 academic year, focusing on how substrate electronics and functional groups other than alcohols affect the process. Nicolle Elahian López (’24 Chem) joined the lab in the spring of 2022, and during the summer she worked on the selective oxidation of secondary over primary alcohols. Cole Springer (’25 Chem and German Studies) started in the summer of 2022 and optimized the work-up for the furfural-mediated, iron-catalyzed oxidations.
We began lab work on the lipid synthesis project in the fall of 2020, later than hoped due to the pandemic. Peter Zhang (’21 BMB) started by working on a way to connect cholesterol to cyanuric chloride. We took the project in a different direction in the summer of 2022 when Emily Howe (’23 BMB) attached fatty esters via an amine linker to cyanuric chloride. After some hard work and meaningful progress, she hit a wall late in the spring of 2022 that forced us to take a different approach. Emily Sullivan (’24 BMB) and Tommy Megna (’25 BMB) worked on the new approach during the summer of 2022 and made excellent progress, showing that these lipids can be prepared. Now the goal is to start preparing a library of them with different hydrophobic tail lengths and sending them to Prof. Vince Venditto’s lab for biophysical studies.
In addition to these two projects, Chloe May (’21 Chem) worked on our old dental polymer project through the 2020-2021 academic year. She showed that we can make polyacrylates bearing photocleavable triazene groups, they survive the radical polymerization conditions, and they can be cleaved using near-UV light.
Prof. Funk gave a few presentations over the last two years. He presented a virtual poster titled “Alcohol oxidations using air-stable (cyclopentadienone)iron catalysts and sustainable hydrogen acceptors” at the ACS Green Chemistry & Engineering Conference in June 2021. He also gave two talks during the spring of 2022: one at the ACS National Meeting in San Diego, CA in March 2022 titled “Sustainable transfer dehydrogenations with (cyclopentadienone)iron carbonyl catalysts”, and an invited talk at the Mid-Atlantic Regional Meeting (MARM) of the ACS at The College of New Jersey in June 2022 titled “(Cyclopentadienone)iron carbonyl compounds: Sustainable catalysts and sustainable undergraduate research projects.”
Four students in the Funk lab presented posters at the San Diego ACS Meeting in March 2022. Bryn Werley’s was titled “Isolation, characterization, and reactivity of a trimethylamine-ligated (cyclopentadienone)iron carbonyl compound”, Katy Wnuk-Fink’s was called “Improving the sustainability of (cyclopentadienone)iron-catalyzed alcohol oxidations”, Auden Cameron Lampariello’s was titled “Ligand steric effects on the selectivity of primary alcohol oxidations using (cyclopentadienone)iron tricarbonyl catalysts”, and Emily Howe presented “Toward the synthesis of a library of modular, functionalizable lipids”.
