Studies toward the total synthesis of (+)-providencin (1), a highly oxygenated cembranoid dipterpene with a unique bicyclo[12.2.0]hexadecane skeleton and pronounced biological activity, are described. These studies resulted in the synthesis of advanced intermediates 320 and 332 which contain all of the carbon atoms of 1. In a first generation approach...
Femtosecond stimulated Raman spectroscopy (FSRS) is an ultrafast vibrational technique which allows rapid collection of Raman spectra with simultaneously high temporal and spectral resolution. With the recent development of FSRS methodology, three FSRS techniques (conventional, tunable, and anti-Stokes) have been implemented in our laboratory to dissect the excited state structural...
Iron oxide materials including ferrihydrite and magnetite play essential roles in contaminant transport, pH control of surface and groundwater, and microbial activity. They have various applications ranging from data storage to cancer therapy. Recent studies showed that the NPs growth does not involve atom by atom nucleation but starts by...
Polyoxometalates are a rapidly growing class of discrete metal oxide clusters with a wide range of applications including functional materials. These anionic clusters of the group V and VI transition metals are inexpensive and non-toxic. Within group V polyoxometalates, niobium and tantalum chemistry has been underdeveloped owing to their unique...
One post-transcriptional mechanism that regulates the progression of cancer and other diseases involves small 22-23 nucleotide sequences called microRNA (miR). Early detection of small changes in concentration of these biomarkers holds potential to diagnose diseases at their earliest stages. Use of current nucleic-acid based biosensors, like molecular beacons, for in...
This thesis is separated into three distinct projects. First, synthetic studies towards the furanosteroid viridin shown in part I. Second, synthetic studies towards the diperene obtusanal shown in part II. Third, the analysis, characterization, and synthesis of coronene derivatives towards their application in organic batteries shown in part III. Significant...
Metabolomics has recently gained momentum in biomolecule research and complements the genomics and proteomics research space. Metabolomics strives to detect, identify, and quantify all metabolites present in biological samples. In particular, biomolecular analysis using ultra-performance liquid chromatography combined with mass spectrometry (UPLC-MS) has become increasingly important for metabolomic analyses. Similarly,...
Aromatic heterocycles are core structural motifs in natural products, pharmaceuticals and biological polymers. Indoles, in particular, represent a significant subclass of aromatic heterocycles, both in terms of sheer numbers, but also in biological and pharmaceutical relevance. As such, new methodologies for the synthesis of indoles represent an important and continually...
Studies toward synthesis of subunits of sanglifehrin A, an immunosuppressant featuring a highly substituted [5,5]-spirolactam moiety as well as a 22-membered macrocycle are described. The macrolactone contains a peptidic backbone characterized by an unusual [beta]-substituted (S)-piperazic acid and (S)-m-hydroxyphenylalanine units. These studies resulted in the synthesis of advanced intermediate 358...
Studies towards the total synthesis of (+)-Phomactin A (1), D (6), and G (9), fungal metabolites with unique molecular architecture and pronounced biological activity, are described. These studies resulted in the synthesis of advanced intermediates 354 and 356, which contain all of the carbon atoms of 1, 6 and 9....