Hippadine and pratosine are lycorine-type pharmacologically active Amaryllidaceae alkaloids. Various total syntheses of these natural products have been developed. However, most of these synthetic routes require prohibitively expensive materials and/or achieve yields that are subpar, making these schemes unlikely to be used in an industrial setting. Current research involves developing better synthetic methods for these two alkaloids starting with a 6,7-disubstituted isoquinoline. These syntheses are appealing since they utilize readily available starting materials and avoid expensive catalysts. The key step in the synthetic scheme centers around an intramolecular de Mayo photocyclization which involves a reaction between an alkene moiety in the isocarbostyril system and a 1,3-diketone (a functionalized tether on nitrogen), which forms a third ring in the structure of the molecule. When the photochemical reaction was attempted, an unexpected cyclic photoproduct was obtained; fortunately, this product is a cyclic hemiketal of the expected 1,5-dicarbonyl compound. A base-catalyzed aldol addition affords the final ring in the system; dehydration of this product affords a β-enone that can be transformed to a diene. Oxidation of the diene with DDQ affords the target natural products after simple chromatographic purification. This new synthetic pathway circumvents the need for catalysts that are either expensive or contain metals such as palladium or iridium; moreover, our method allows for the synthesis of various natural and unnatural alkaloids in high yields by modification of the N-tether.

Molecules previously developed by the Green Research Group (L2 and L3) have been shown to reduce reactive oxygen species (ROS) through multiple pathways of activity. Although unclear if ROS is the only source, Alzheimer’s disease and other neurodegenerative disorders are known to be initiated from the formation of these ROS. For these molecules to appropriately execute their antioxidant and radical scavenging ability, they must enter into the brain where the damaging ROS are located. The blood brain barrier (BBB) is a natural obstacle that prevents toxins and infections from reaching the brain. The L2 and L3 ligands must penetrate this barrier to be in the desired site of action to reduce the number of ROS. Addition of a glucose moiety to other therapeutic molecules has been shown to increase permeability across the BBB. The target of this project is to enhance these synthetic pathways of glycosylation and increase product yield. Initially, direct addition of the glucose moiety to the L2 and L3 molecules was achieved. However, challenges with purification techniques suggested a different route to purification or design should be considered and one new route is presented here. With L2 and L3 being inherently hydrophilic, addition of an aliphatic chain to the hydroxyl group of L2 or L3 should increase the hydrophobicity of the molecule allowing for different purification techniques, which can ultimately be glycosylated to give purified desired compounds.

A recent and promising development in solar energy involves a class of materials known as organometal halide perovskites, capable of efficiencies (>20%) comparable to the current industry standard of silicon. These materials also demonstrate strong light emission, a key property associated with energy-efficient sources of lighting, suggesting potential applications in light-emitting devices such as light-emitting diodes (LED). The goal of this project was to investigate the fundamental photoluminescence (PL) properties of perovskites housed in a nanoporous material known as semiconducting porous silicon (pSi).

pSi provides a nanoscale template to control the growth of the light-emitting perovskite structure and is an electrically-responsive host matrix, ideally regulating the flow of charge to/from the perovskite. Samples were prepared within the pores of surface oxidized pSi and hydride-terminated pSi, each with a mesoporous width in the 5 – 50 nm range. The perovskite-loaded pSi was fabricated through solution-loading of perovskite precursors into warmed pSi (60ºC), removal of excess reactant solution, and drying. While perovskites can feature a wide range of halide compositions (including mixed halides), this research thus far has focused on methylammonium lead iodide (MAPbI3) perovskite.

These perovskite nanostructures formed within pSi were characterized using a variety of techniques. Following synthesis, the stability of each prepared sample was monitored for 3 weeks through tracking its relative photoluminescence intensity at its maximum value. Perovskite morphology was evaluated by SEM (scanning electron microscope) and TEM (transmission electron microscope) imaging, crystalline structure was evaluated by XRD (x-ray powder diffraction), and elemental analysis was evaluated by EDX (energy-dispersive x-ray spectroscopy).

In this study, SEM imaging showed consistent perovskite particle size and ununiformed perovskite infiltration. It is found that the emission intensity for MAPbI3 formed within hydride-terminated pSi (at ~730nm) and oxidized pSi (at ~740nm) were relatively stable over a 3 week period, but the emission intensity for perovskite microrods formed in the absence of any pSi template actually decreased over time. More detailed measurements of the long term stability of these new nanoscale materials are currently under evaluation.

Significant increases in average life expectancy in the last century have brought a growth in human illnesses related to aging: chronic wounds, bone diseases, eye diseases and cancer. In this work, we demonstrate fabrication of biodegradable polymer scaffolds that can be used for drug delivery and tissue engineering to treat the above-mentioned ailments. Tissue engineering can be defined as the use of a combination of engineering and materials methods and appropriate biochemical factors to improve or replace biological tissues.
This project includes fabrication of solid and porous fibers from the biocompatible PCL polymer. This polymer is currently used for surgical sutures, nerve guides and three-dimensional scaffolds for use in tissue engineering. The drug release rate is faster when it is loaded into porous PCL fibers compared to solid PCL fibers, creating an advantage for porous fiber fabrication. Use of a technique known as electrospinning of a solution of PCL and chloroform results in solid fibers that are 4 (± 2.0) micrometers (μm) in diameter. The porous fiber scaffolds are fabricated using a 50% weight of PCL compared to volume of solvent (w/v) solution prepared in a mixture of solvents 9:1 dichloromethane (DCM):dimethyl sulfoxide (DMSO) and 60% w/v PCL in 8:2 DCM:DMSO. The porous fibers are collected at 0-5 oC with a pore size of 50.0 (± 10.0) nanmoeters (nm) and fiber diameter of 3.0 (± 1.0) μm. The porosity for 50% w/v PCL and 60% w/v PCL fibers ranges from 40-50%.
Fiber surface morphology is characterized using field emission scanning electron microscopy (FESEM). In addition, the melting temperature and percent crystallinity are determined via differential scanning calorimetry (DSC). The melting temperature was collected of PCL bulk, 30%w/w PCL solid fibers, 50% w/v PCL and 60% w/v PCL. The crystallinity of PCL in solid fiber and porous fiber forms ranges from 52-55%, compared to the 60% crystallinity of PCL bulk. Solid PCL fibers showed to be more crystalline compared to porous PCL fibers, which in turn can effect the degradation time.
In order for these composites to be identified as a major technological advancement, the aging and degradation of the polymer scaffold must also be understood. The degradation of a given polymer matrix impacts the potential drug delivery behavior when testing in vitro. Degradation studies of the above mentioned materials are currently ongoing.

While cis/Z-substituted alkenes are usually less stable than their trans/E-substituted counterparts, the cis-2-butenyl anion shows a higher preference over the trans-isomer. Calculations suggest that the discrepancy is due to two cooperating effects: electrostatic interactions between the anionic center (C1) to the methyl group (C4) and coupling between the C=C pi* antibonding orbital and both the CH2 pz and CH3 C-H sigma bonds. Supporting the charge transfer is the fact that substitution on C1 with EDG stabilizes the cis more while substitution on C4 with EWG stabilizes the cis more. For the coupling interaction the C=C bond was stretched which increased the cis stabilization by lowering the pi* orbital energy and increasing the coupling between the lone pair on C1 and pi*.