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A number of nitroxide adducts and N-acyloxytrialkylammonium salts were prepared, isolated, characterized and evaluated as initiators for the controlled and living free radical polymerization of methacrylate and dimethacrylate monomers under mildly thermal and photochemical conditions. The initiators and polymerization methods that were developed could potentially be used for improving resins employed in dental applications. Using very easy synthesis strategies, the following nitroxide initiators were prepared in high purity, isolated and characterized: 1-Benzoylperoxy-2,2,6,6-tetramethyl-piperidine (BPO/TEMPO), 1-(2'-Cyano-2'-propoxy)-2,2,6,6-tetramethylpiperidine (AIBN/TEMPO), 1,1-ditertbutyl-1-(1-methyl-1-cyanoethoxy)-amine (AIBN/DBN), 1,1-ditertbutyl-1-(benzoylperoxy)-amine (BPO/DBN) and 2,2,6,6,-tetramethyl-4-oxo-1-(1-methyl-1-cyanoethoxy)-piperidine (AIBN/4-OXO-TEMPO). Using H2SO4 additive and an improved unimolecular initiation in nitroxide mediated polymerization, living and controlled polymerization of methyl methacrylate (MMA), tri-ethylene glycol dimethacrylate (TEGDMA) and ethoxylated bisphenol A dimethacrylate (EBPADMA) were accomplished, for the first time ever for most of the initiators. Linear polymers (PMMA) were produced in high yield (93 %) under mildly thermal conditions (T = 70 oC) and with excellent attributes: (PDI = 1.04-1.26), Mn (87000), Tg (122-128 oC), Td (290-410 oC). Highly crosslinked polymers, poly(TEGDMA) and poly(EBPADMA), were produced in high yield (100 %) with Td (350-400 oC). The initiators were stable for a year and half at 0 oC. Two routes were investigated for the preparation of N-acyloxytrialkylammonium salts. The more efficient of these routes was used to make several novel analogs of the salts. The salts were evaluated for the free radical polymerization of MMA, TEGDMA and EBPADMA under mildly thermal (T = 60 oC) conditions with and without H2SO4 additive. Polymerization rate, yield and polymer attributes all improved upon application of H2SO4 additive. PMMA was produced with excellent attributes (PDI = 1.01-1.06), Mn (96,000-122000), Td (330-385) and Tg (127-134). Highly crosslinked poly(TEGDMA) and poly(EBPADMA) were produced with Td ranges of 300-374 oC and 375-411 oC respectively. / Chemistry

Environmental monitoring is becoming increasingly important, primarily in urban areas due to the concentrated levels of human activities. The air sampling device presented is a novel method to sample air which harnesses the power of paper spray ionization paired with the intrinsic advantages of mass spectrometry such as high sensitivity, high selectivity, high throughput, and the ability to monitor multiple compounds at once.

Master of Science / Department of Chemistry / Christopher T. Culbertson / Mixing is an essential process to many areas of science for example it is important in studying chemical reaction kinetics, chemical synthesis, DNA hybridization and PCR amplification. Mixing on the macroscale level is readily achieved through convection. Rapid mixing on microchips however, is problematic as the low Reynolds numbers and high Peclet numbers indicate that fluid flow is in the laminar regime and limits mixing on microchips to diffusion. Because of these limitations mixing on microchips is often relegated to diffusional mixing which requires long channels and long time periods. Several methods have been developed to increase the speed and efficiency of mixing on microfluidic devices. A variety of techniques have been employed to overcome these obstacles including for example 1) 3 dimensional channel designs to split up and recombine flows 2) employing sophisticated lithographic techniques to make grooves within a channel to generate transverse flows and 3) using lateral flow created by using spiral channels. Other groups have used outside energy sources to achieve mixing by changing of the zeta potential within the channel, using induced charge electroosmosis, and also by modifying the electrokinetic flow. We propose using dielectric elastomers (DEs) to modulate flow as a means to achieve rapid and active mixing on the microchip format. Electroactive polymers such as poly(dimethylsiloxane) function as DEs and are capable of converting electrical energy into mechanical energy. The application of an electrical potential across the PDMS results in a change in the dimensions of the PDMS dielectric layer between the two actuating electrodes creating an actuator. When employed in microfluidic devices this actuator can be used to change the volumes of the microfluidic channels on the PDMS. If the actuators are placed near a T-intersection where two components are entering the intersection the actuators can serve to improve mixing on microfluidic devices. Studies were conducted on how on the magnitude of the actuation, the frequency of actuation, the field strength, the electrode design and position relative to the T intersection, the channel dimensions and the overall channel design impacted mixing efficiency. Mixing results showed promise but further development of technology is necessary to achieve adequate mixing in microfluidic channels using DEs.

Thallium based superconductors have the highest, reproducible transition temperatures to date, $\rm Tl\sb2Ba\sb2Ca\sb2Cu\sb3O\sb{x},$ at 122 K. Difficulty arises in preparing these materials using the common "shake and bake" procedure. The high temperature stability of BaCO$\sb3$ and the volatility of the $\rm Tl\sb2O\sb3$ pose additional problems which appear to be insurmountable. Thus, it is necessary to investigate alternative routes. / The use of a single phase precursor is an attractive option. One could pre-react the Ba-Ca-Cu starting materials and, in the final step, add an appropriate amount of $\rm Tl\sb2O\sb3$. The mixture would then be fired for a short period of time, preferably at temperatures below the volatility of $\rm Tl\sb2O\sb3$. / In order to successfully use a precursor route, the chemistry of the precursor material must be understood. The ternary BaO-CaO-CuO system is not well characterized. A methodical investigation of this system will provide a better understanding of the chemistry involved. / Presented in this paper is an investigation of selected regions of the ternary phase system. Two alternative preparative methods will be compared the common "shake and bake" method. Effects of time and heating temperature of these materials are examined and presented. / Source: Dissertation Abstracts International, Volume: 55-04, Section: B, page: 1412. / Director: Ronald J. Clark. / Thesis (Ph.D.)--The Florida State University, 1994.

<p> Nanomaterials are the focus of intense research efforts in a variety of fields because of dramatic differences in properties when compared to the corresponding bulk materials. Catalysis is one material property that can become more pronounced at the nanoscale. By lowering energy requirements for chemical reactions, catalysts reduce production costs in diverse sectors of the economy, including medicine, transportation, environmental protection, oil and gas, food, and synthetic materials. Transition metals are an important class of catalysts capable of facilitating reduction and oxidation of molecular species. Since the discovery of transition metal catalysts nearly 200 years ago, certain metals were considered more active as catalysts (i.e., Pt, Pd, and Ru), while others (Au) appeared to have negligible catalytic activity as bulk materials. In recent years, gold nanoparticles (AuNPs) have become a fast-growing field of research owing to their unexpected catalytic properties not present in the bulk material. However, unsupported AuNPs are highly prone to flocculation and subsequent reduced catalytic activity. The choice of an appropriate aggregation-resistant stabilizing ligand for these nanoparticles is an important part of maintaining nanoscale catalytic properties. Additional stability is provided by anchoring AuNPs to support materials, allowing for dramatic improvements in catalyst lifetimes. This work discusses the development of novel diamond support materials for improving the stability of catalytically active AuNPs. Synthetic nanodiamond is a widely available, inexpensive, and robust material that has found applications in a wide range of commercial abrasives, lubricants, and composite materials. By exploiting the rich surface chemistry of nanodiamond, we have developed versatile catalyst support materials that offer unrivaled chemical and mechanical stability. Various nanodiamond surface modifications are readily prepared using a combination of chemical vapor deposition, photo-active polymer chemistry, and synthetic organic chemistry techniques. Control over the surface chemistry and properties of the resulting nanodiamond allow for increased stability of AuNPs via surface anchored thiol and amine moieties. The use of diamond as a support material should allow a wide variety of noble and nonprecious metal composite materials to be used as catalysts in harsh chemical environments not suitable for existing support materials.</p><p>

acase@tulane.edu