For biomass derived molecules to serve as precursors for biofuel and other related energy sources, more stable and efficient catalysts are needed. Drawing inspiration from enzymes, our group has recently shown that a bifunctional acid–base metal–organic framework (MOF) with co-localized acid and base sites outperforms a MOF with randomly dispersed acid and base sites as a catalyst for the aldol condensation of biomass-derived carbonyls. These active acid–base sites are composed of a primary amine and carboxylic acid. However, to further improve catalytic activity a templated framework with secondary amine and carboxylic acid active sites can be developed. Relative to primary amines, secondary amines should favor the formation of the key enamine intermediate and increase catalytic rates. Framework synthesis and characterization show success of incorporation of the secondary amine, and preliminary catalysis results indicate how successful this secondary amine has been. Overall, this work expands on the previous introduction of metal-organic framework catalysts as an alternative to common industrial catalysts in the biomass upcycling process by exploring the utility of a new templated secondary amine acid–base MOF. 

Rising atmospheric carbon dioxide levels have driven research into efficient gas separation materials. Polymers of intrinsic microporosity (PIMs) is one promising solution due to their rigid, porous structures and processability, allowing them to be turned into thin films for membrane-based gas separations. My research focuses on enhancing the carbon dioxide selectivity of helicene-based PIMs through post-synthetic modification of these polymers. I have synthesized a small molecule model of the PIM to screen for amine substitution conditions and ensure the viability of post-synthetic modification on the larger helicene-based PIM. Characterization techniques, multinuclear NMR and mass spectrometry, have verified the synthesis and amination of my model system. By incorporating nucleophilic amines into PIMs, these polymers can feature enhanced binding to electrophilic carbon dioxide, thereby increasing the interactions with carbon dioxide over other mixed gases, leading to separation. In my future studies, I will extend these modifications to the helicene-base PIM, fabricate films and evaluate their properties. Surface area measurements using N₂ gas sorption methods and CO₂ absorption isotherms will quantify gas-binding affinity and separation performance.

Malaria is one of the most prevalent diseases worldwide, with nearly half of the world residing in regions at risk of transmission. It is commonly spread to humans through the bite of a female Anopheles mosquito infected with Plasmodium spp. parasites. When feeding, mosquitoes ingest biogenic amines at concentrations found in the blood of the host. Adult patients with severe malaria have altered concentrations of serotonin and histamine in their blood compared to healthy individuals. Previous work showed the ingestion of serotonin and/or histamine concentrations associated with adult patients with severe malaria influenced key mosquito behaviors, such as the tendency to take a second blood meal, flight behavior, and visual object inspection—traits that are related to the transmission of malaria. However, the mechanisms by which serotonin and histamine modulate mosquito behavior remain unclear. Given the known involvement of these biogenic amines in physiological processes, we hypothesize that the ingestion of varying serotonin and histamine concentrations in Anopheles stephensi mosquitoes will alter their distribution across tissues. Mosquitoes are fed with deuterated serotonin and histamine at levels associated with patients with severe malaria versus healthy individuals. These deuterated compounds serve as tracers to distinguish endogenous (natural) from exogenous (ingested) serotonin and histamine in the tissue. The mosquitoes are dissected to retrieve the head as a proxy for the brain, the midgut, and sensory appendages including maxillary palps, antennae, legs, and proboscis. All tissue samples are extracted and analyzed via liquid chromatography-mass spectrometry (LC-MS) to distinguish and quantify deuterated and non-deuterated serotonin and histamine. By viewing all aforementioned tissue regions and comparing endogenous versus exogenous biogenic amine levels in the samples, we hope to understand the modulation of biogenic amine distribution in An. stephensi tissue and offer insights into possible connections between neuromodulators and behavior in the mosquitoes.