Coded metrics that compare representations of structures within the human body to evaluate their similarity are considered useful for planning radiation therapy on cancer targets. However, existing metrics fail to take into account the dose of radiation that will be received by both the target, and surrounding non-target tissue, during...
The development of analytical methods for emerging contaminants creates many unique challenges for analytical chemists. By their nature, emerging contaminants have inherent data gaps related to their environmental occurrence, fate, and impact. This dissertation is a compilation of three studies related to method development for the structural identification of emerging...
Fungi have long been a prolific source of clinically approved drugs. The antibiotic penicillin, the cholesterol lowering statins, and the immunosuppressant cyclosporine have changed the treatment of human diseases in the last century. Recently, genome analysis of filamentous fungi has revealed that the biosynthetic potential for natural product expression is...
Solid-state amorphous materials show amazing promise in thin-film electronics. The interface-to-bulk ratio of thin films makes interfacial chemistries of these systems of utmost importance. Thin films of amorphous metals, dielectrics and semiconductors have novel chemistries that are not only based upon their elemental constituent makeup, but also based upon the...
Lycopodium alkaloids have generated enormous amounts of interest from the scientific community, both as synthetic targets and for their medicinal properties. Herein is described work towards a unifying approach to large segments of the Lycopodium family. An organocatalyzed intramolecular heteroatom Michael reaction method, for the construction of piperidine and piperizine...
Lycopodium alkaloids have shown widespread and noteworthy biological activity, consisting of over 250 known natural products. Moreover, their structural complexity and diversity have attracted considerable attention from numerous laboratories including our own. Recently, we have developed a unified approach that would provides access to numerous, previously unprepared C₁₀-functionalized lycopodium alkaloids....
A convergent synthesis of epothilone B that generates all seven of its
asymmetric centers in a completely stereoselective fashion has been
completed. Key reactions include an anti-Felkin aldol condensation to
set the C6 and C7 stereochemistry, a directed α-hydroxylation to install
the C15 (S)-hydroxyl substituent, and a Wittig condensation to...
7,7'-Dihydroxy-8,8'-biquinolyl (azaBINOL) was prepared from 7-hydroxyquinoline via N,N-dimethyl O-quinol-7-yl carbamate by directed ortho-metallation followed by FeCl₃-mediated oxidative coupling of the 8-lithioquinoline intermediate. Saponification of the resulting dicarbamate provided crystalline (±)-azaBINOL in 56% overall yield. 6,6'-Bis(dimethylaminocarbonyl)-7,7'-dihydroxy-8,8´-biquinolyl was prepared from the same dicarbamate by a double anionic-Fries rearrangement in 43% yield. 7,7'-Bis(diethylamino-carbonyloxy)-6,6'-diiodo-8,8´-biquinolyl...
The variegated aqueous chemistries of metal cations are applied to the design and synthesis of non-toxic solution precursors suitable for additive printing of large-area oxide electronics. Polycondensation behaviors of aqueous Al+3 and PO4 +3 are manipulated in the deposition of atomically smooth amorphous aluminum oxide phosphate (AlPO) dielectric films. AlPO...
Sulfoxide-ligand exchange (SLE) and asymmetric halogen-metal exchange (AHME) processes were separately examined for the enantioselective synthesis of functionalized alpha-haloalkylmetal (carbenoid) reagents. Carbenoids derived from SLE were used to effect stereospecific reagent-controlled homologation (StReCH) of boronic esters and those generated via AHME were engaged in Darzens-type chemistry with aldehydes.
Abstract for...