The total synthesis of a highly potent cytotoxic marine natural product, phorboxazole A, is described. Both a palladium(II)-mediated and a palladium(II)-catalyzed intramolecular alkoxycarbonylation were used as key steps for the preparation of the two cis-2,6-disubstituted tetrahydropyran rings (C22-C26 and C11-C15) of phorboxazole A.
The synthesis used a convergent approach involving...
Three approaches toward the core of halichlorine and pinnaic acid are described. The first approach entails a racemic transannular nitrone-olefin [3+2] cycloaddition from nitrone 238. Construction of the nitrone 238 began with aldehyde 241. Another key feature in this route involved a ring-closing metathesis for the formation of a 14-membered...
Studies towards the total synthesis of (−)-kendomycin (1), a bacterial metabolite with
a unique molecular architecture and pronounced biological activity, are described. These
studies resulted in the synthesis of advanced intermediate 208, containing all of the
carbon atoms of 1.
A Dötz annulation between alkyne 122 and novel chromium carbenoid...
Studies toward the total syntheses of highly potent cytotoxic alkaloids
including the bromopyrrole alkaloids and indole alkaloids were conducted and are
described. Studies carried out in the course of this dissertation consist of five total syntheses of natural products that include bromopyrrole alkaloids nagelamide A, D and agelastatin D as...
The central purpose of this dissertation was to explore and expand the use of
an uniform electric field for orientation and for subsequent spectroscopic investigation of asymmetric polar molecules in the gas phase. The systems of study were nitrobenzene (NB) and the nitrotoluene (NT) isomers. We were able to quantitatively...
SOCs volatility and persistence properties cause many SOCs to become ubiquitous in the environment as well as accumulate in areas with lower temperatures such as polar or orographic regions. Many anthropogenic SOCs pose a serious risk to human and ecosystem health because of their persistent, bioaccumulative, and toxic properties in...
Current studies suggest that perfluorinated organic compounds, such as fluorotelomer alcohols (FtOHs) in the troposphere, may be precursors of perfluorocarboxylic acids and perfluorosulfonates in remote regions. Fluorinated organic compounds were investigated in archived extracts collected from remote locations in Okinawa, Japan (HSO) and Mount Bachelor, Oregon (MBO) during the springs...
Many pesticides, polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers
(PBDEs), and polycyclic aromatic hydrocarbons are persistent, bio-accumulative, and
toxic. These semi-volatile organic compounds (SOCs) can undergo atmospheric
transport and deposition in cold, remote ecosystems. A better understanding of their
accumulation in the fish of these ecosystems is important to better predict...
While fluorochemicals have been detected all over the world and in wastewater
treatment plants, the effect of wastewater effluent on the receiving waters has not been
evaluated. In the first study, the mass flow of fluorochemicals emanating from
wastewater treatment plants along the Glatt River in Switzerland was evaluated. The...
The oxidation of sorbitol by soluble extracts of A. suboxydans proceeds by two pathways depending upon which pyridine nucleotide is present. In the presence of TPN, sorbose is formed. In the presence of DPN fructose is
produced. Both products of the oxidation of sorbitol have been identified by paper chromatography,...
The thermodynamic properties of 39 PBDEs have been calculated using Gaussian 03
on the B3LYP/6-31G(d)//B3LYP/6-31G(d) level. The PBDE congeners' enthalpies of
formation increase with increasing number of bromines and show a strong dependence on
the bromine substitution pattern. The effects of bromine substitution pattern have been
quantitatively studied by GAM...
The general emphasis of this work has been synthesis, characterization, and applications of n- and p-type inorganic oxide thin films that are deposited from solutions. In particular, a study of n-type transparent semiconductor films of tin (IV) oxide and zinc-doped tin (IV) oxide has been performed by spin coating. Solution...
Dielectrophoresis (DEP) is a separation method in which a non-uniform electric
field is used to induce a dipole moment in a suspended particle. If the polarization
of the particle is greater than that of the suspending medium, the particle will move
towards the region of higher field strength (positive DEP);...
The atmospheric transport of anthropogenic semivolatile organic compounds (SOCs) from Asian sources to the Western U.S. was investigated. In addition, the SOC extraction method was optimized. Hansen solubility parameter plots were used to aid in the pressurized liquid extraction (PLE) solvent selection of air sampling media in order to minimize...
The purpose of this investigation was to determine the nature of the extractives from red alder bark in an effort to discover the materials which cause the red stain in red alder wood. Samples of bark and wood were obtained and successively extracted with hexane, benzene, ether, ethanol, and hot...
New chemical synthesis strategies have been investigated for the preparation of acceptor-type graphite intercalation compounds (GIC's) with fluoroanions in order to obtain new materials and to develop a better understanding of the synthetic approaches and properties of the products. New GIC's containing borate chelate anion such as bis(oxalato)borate, CxB[OC(O)C(O)O]₂•δF, are...
The fusion reaction ²⁰⁸Pb (⁵⁰Ti, xn) ²⁵⁸⁻x Rf (x = 1-3) was studied to determine PCN (probability that the mononucleus system evolves to form a compound nucleus inside the fission saddle point) and to establish the value of Wsur (survival probability) for the given reaction experimentally. The fission excitation function...
In this dissertation, I present the work of developing more efficient and economical techniques for fragmenting large bio-molecules, and ultimately making mass spectrometry a more powerful tool in proteomics, DNA sequencing, and other areas of biomolecular analysis.
Aiming at lowering the installation and operating cost, and delivering electron capture dissociation...
Myosins are actin-based molecular motors that may have specialized trafficking and contractile functions in cytoskeletal compartments that lack microtubules. The postsynaptic excitatory synapse is one such specialization, yet little is known about the spatial organization of myosin motor proteins in the mature brain. We used a proteomics approach to determine...
The fragmentation characteristics of protonated peptides have been investigated using
tandem mass spectrometry (MS/MS) under various fragmentation regimes and detailed
density functional theory (DFT) reaction pathway calculations. The DFT calculations
predict novel salt-bridge stabilized transition structures as well as consecutive reactions
occurring in proton-bound dimers for some of the ions...