Sulfoxides as an intramolecular sulfenylating agent for indoles and diverse applications of the sulfide-sulfoxide redox cycle in organic chemistry

This dissertation involves study of various aspects of sulfoxide chemistry. Specifically designed t-butyl and propanenitrile sulfoxides tethered to indole-2-carboxamide were used as a source of intramolecular sulfenylating agents to synthesize novel indolo[3,2-b]-1-5-benzothiazepinones which are structurally analogous to the other biologically active benzothiazepinones. This study reveals that the intramolecular cyclization of sulfoxide follows an electrophilic sulfenylation (Sulfoxide Electrophilic Sulfenylation, SES) reaction pathway. Evidence of the absence of sulfenic acid as a transient reactive intermediate in such intramolecular cyclization is also provided. In another study, sulfoxide was used as a “protecting group” of thioether to synthesize 8-membered, indole substituted, thiazocine-2-acetic acid derivative via Ring Closing Metathesis (RCM). Protection (oxidation) of inert (to RCM) sulfide to sulfoxide followed by RCM produced cyclized product in good yields. Deprotection (reduction) of sulfoxide was achieved using Lawessons Reagent (L.R.). Application of the sulfide-sulfoxide redox cycle to solve the existing difficulties in using RCM methodology to thioethers is illustrated. A new design of a “molecular brake”, based on the sulfide-sulfoxide redox cycle is described. N-Ar rotation in simple isoindolines is controlled by the oxidation state of the proximate sulfur atom. Sulfide [S(II)] shows “free” [brake OFF] N-Ar rotation whereas sulfoxide displayed hindered [brake ON] N-Ar rotation. The semi-empirical molecular orbital (PM3) calculations revealed concerted pyramidalization of amidic nitrogen with N-Ar rotation.

Boron nitride nanotubes : synthesis, characterization, functionalization, and potential applications

Boron nitride nanotubes (BNNTs) are structurally similar to carbon nanotubes (CNTs), but exhibit completely different physical and chemical properties. Thus, BNNTs with various interesting properties may be complementary to CNTs and provide an alternative perspective to be useful in different applications. However, synthesis of high quality of BNNTs is still challenging. Hence, the major goals of this research work focus on the fundamental study of synthesis, characterizations, functionalization, and explorations of potential applications. In this work, we have established a new growth vapor trapping (GVT) approach to produce high quality and quantity BNNTs on a Si substrate, by using a conventional tube furnace. This chemical vapor deposition (CVD) approach was conducted at a growth temperature of 1200 °C. As compared to other known approaches, our GVT technique is much simpler in experimental setup and requires relatively lower growth temperatures. The as-grown BNNTs are fully characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), electron energy loss spectroscopy (EELS), Energy Filtered Mapping, Raman spectroscopy, Fourier Transform Infra Red spectroscopy (FTIR), UV-Visible (UV-vis) absorption spectroscopy, etc. Following this success, the growth of BNNTs is now as convenient as growing CNTs and ZnO nanowires. Some important parameters have been identified to produce high-quality BNNTs on Si substrates. Furthermore, we have identified a series of effective catalysts for patterned growth of BNNTs at desirable or pre-defined locations. This catalytic CVD technique is achieved based on our finding that MgO, Ni or Fe are the good catalysts for the growth of BNNTs. The success of patterned growth not only explains the role of catalysts in the formation of BNNTs, this technique will also become technologically important for future device fabrication of BNNTs. Following our success in controlled growth of BNNTs on substrates, we have discovered the superhydrophobic behavior of these partially vertically aligned BNNTs. Since BNNTs are chemically inert, resistive to oxidation up to ~1000°C, and transparent to UV-visible light, our discovery suggests that BNNTs could be useful as self-cleaning, insulating and protective coatings under rigorous chemical and thermal conditions. We have also established various approaches to functionalize BNNTs with polymeric molecules and carbon coatings. First, we showed that BNNTs can be functionalized by mPEG-DSPE (Polyethylene glycol-1,2-distearoyl-sn-glycero-3-phosphoethanolamine), a bio-compatible polymer that helps disperse and dissolve BNNTs in water solution. Furthermore, well-dispersed BNNTs in water can be cut from its original length of >10µm to(>20hrs). This success is an essential step to implement BNNTs in biomedical applications. On the other hand, we have also succeeded to functionalize BNNTs with various conjugated polymers. This success enables the dispersion of BNNTs in organic solvents instead of water. Our approaches are useful for applications of BNNTs in high-strength composites. In addition, we have also functionalized BNNTs with carbon decoration. This was performed by introducing methane (CH4) gas into the growth process of BNNT. Graphitic carbon coatings can be deposited on the side wall of BNNTs with thicknesses ranging from 2 to 5 nm. This success can modulate the conductivity of pure BNNTs from insulating to weakly electrically conductive. Finally, efforts were devoted to explore the application of the wide bandgap BNNTs in solar-blind deep UV (DUV) photo-detectors. We found that photoelectric current generated by the DUV light was dominated in the microelectrodes of our devices. The contribution of photocurrent from BNNTs is not significant if there is any. Implication from these preliminary experiments and potential future work are discussed.

VERIFYING SUCCESS OF ARTIFICIAL REEFS IN THE HURON-ERIE CORRIDOR FOR LAKE STURGEON

Lake sturgeon (Acipenser fulvescens) were historically abundant in the Huron-Erie Corridor (HEC), a 160 km river/channel network composed of the St. Clair River, Lake St. Clair, and the Detroit River that connects Lake Huron to Lake Erie. In the HEC, most natural lake sturgeon spawning substrates have been eliminated or degraded as a result of channelization and dredging. To address significant habitat loss in HEC, multi-agency restoration efforts are underway to restore spawning substrate by constructing artificial spawning reefs. The main objective of this study was to conduct post-construction monitoring of lake sturgeon egg deposition and larval emergence near two of these artificial reef projects; Fighting Island Reef in the Detroit River, and Middle Channel Spawning Reef in the lower St. Clair River. We also investigated seasonal and nightly timing of larval emergence, growth, and vertical distribution in the water column at these sites, and an additional site in the St. Clair River where lake sturgeon are known to spawn on a bed of ~100 year old coal clinkers. From 2010-12, we collected viable eggs and larvae at all three sites indicating that these artificial reefs are creating conditions suitable for egg deposition, fertilization, incubation, and larval emergence. The construction methods and materials, and physical site conditions present in HEC artificial reef projects can be used to inform future spawning habitat restoration or enhancement efforts. The results from this study have also identified the likelihood of additional uncharacterized natural spawning sites in the St. Clair River. In addition to the field study, we conducted a laboratory experiment involving actual substrate materials that have been used in artificial reef construction in this system. Although coal clinkers are chemically inert, some trace elements can be reincorporated with the clinker material during the combustion process. Since lake sturgeon eggs and larvae are developing in close proximity to this material, it is important to measure the concentration of potentially toxic trace elements. This study focused on arsenic, which occurs naturally in coal and can be toxic to fishes. Total arsenic concentration was measured in samples taken from four substrate treatments submerged in distilled water; limestone cobble, rinsed limestone cobble, coal clinker, and rinsed coal clinker. Samples were taken at three time intervals: 24 hours, 11 days, and 21 days. ICP-MS analysis showed that concentrations of total arsenic were below the EPA drinking water standard (10 ppb) for all samples. However, at the 24 hour sampling interval, a two way repeated measures ANOVA with a Holm-Sidak post hoc analysis (α= 0.05) showed that the mean arsenic concentration was significantly higher in the coal clinker substrate treatment then in the rinsed coal clinker treatment (p=0.006), the limestone cobble treatment (p