Metal nanoparticle-decorated titanium dioxide (M@TiO₂) materials are an increasingly popular class of heterogeneous catalyst, useful in both photochemical and thermal systems. Heterogenous catalysts offer the advantage of reusability and ease of catalyst separation, when compared to similar homogeneous systems. M@TiO₂ catalysts also have the benefit of water/air environment stability, strong photoactivity for oxidation and reduction reactions, as well as easy and low cost synthesis of the catalyst. Other heterogeneous catalysts can offer better activity for certain reactions; however, M@TiO₂ materials are extremely versatile in a variety of different reactions and applications, and often are cheaper than other alternatives. In this dissertation, M@TiO₂ catalysts will be evaluated in hydrogen generation, solvent radical chemistry, and organic synthesis utilizing calcium carbide. Firstly, M@TiO₂ were evaluated for photocatalytic hydrogen generation from pure water splitting, and with the presence of sacrificial electron donors (SEDs) such as methanol. Efficient pure water splitting is of great interest for fuel production as it offers a perfect cycle with hydrogen gas burning to reform water as the only product. However, quite often SEDs are utilized to boost hydrogen gas generation due to poor conversion from pure water. It is often assumed that a photocatalyst effective with a SED will also be effective with water splitting. This assumption was tested, by comparing a variety of different M@TiO₂ photocatalysts for both water splitting, and SED-based hydrogen generation. Interestingly, it was found that the trends of hydrogen generation between photocatalysts are not the same in pure water splitting, as when SEDs are present. For example, Pd@TiO₂ shows great activity with a 1% methanol solution; however, no considerable H₂ generation for pure water splitting. This shows that the mechanisms of hydrogen generation with water splitting, and when SEDs are present, are very different and not directly comparable. It was also found that M@TiO₂ materials offer decent hydrogen generation rates, especially when considering the overall cost of the material. M@TiO₂ materials were then tested for their ability to photocatalytically form usable free-radicals from ethers. This was evaluated with scavenging of generated radicals by TEMPO, as well as monitoring the resulting H₂ production during the reduction portion of the system. Overall, it was found that M@TiO₂ photocatalysts are exceptional at forming radicals from ethers. All the ethers tested are able to undergo proton-coupled electron transfer (PCET) with the hole of TiO₂, as seen by the H₂ generation observed. The main considerations are instead for the ether-radical, and if the radical will fragment or primarily undergo other reactions. This led to only some of the ethers being able to form TEMPO-ether adducts. The photogenerated hole of TiO₂ is also strong enough to form benzylic radicals from toluene, highlighting the further versatility of the catalyst. To further explore TiO₂-generated radicals, heterogeneous laser flash photolysis techniques were then developed. Laser flash photolysis of TiO₂ suspensions is an uncommon, and underdeveloped technique in the research field. It was considered if low concentration suspensions of TiO₂ could allow for lowered impact from the absorbance and scattering from the TiO₂ particles. This allowed for monitoring the transient absorbance of a benzylic radical from the reaction between 1,1-diphenylethylene and 1,3-dioxolane solvent radicals formed by the photogenerated hole of TiO₂. The strength of this transient signal also showed dependence on the solvent, with 1,4-dioxane showing lower signal as expected from it's reactivity. This technique, with further development, should prove useful in expanding the kinetic evaluation of radicals generated by TiO₂ suspensions. Finally, Pd@TiO₂ was evaluated as a thermal catalyst for a Sonogashira-like reaction between calcium carbide and bromobenzene in DMSO under low water conditions. This palladium catalyst was effective in catalyzing the reaction; however, the more interesting aspect was in the chemistry of the calcium carbide itself. Calcium carbide is typically used for the in-situ formation of acetylene gas through the addition of water. However, it was found that in DMSO with low amounts of water, the formation of a soluble ethynyl calcium hydroxide intermediate could be selected for. This allowed for a more controlled and effective coupling with bromobenzene in solution. Further expansion on the use of this intermediate may be invaluable in expanding calcium carbide chemistry beyond the formation of acetylene gas.

<p> There is only one unambiguous report in the literature of anchimeric assistance by the π-bond in a free radical reaction. It was the purpose of this work to investigate the possibility of such acceleration in the thermal homolysis of 7-norbornene peresters. Two such t-butyl peresters, the isomeric syn- and anti-7-norbornene percarboxylates as well as t-butyl 7-norbornane percarboxylate, were prepared and their decomposition was studied by kinetic methods and product analysis.</p> <p> The homolysis of 7-norbornene peresters is shown to occur with rate-determining perester O-O bond rupture, the transition state of which may be a hybrid of radical and polar structures. A low order of anchimeric acceleration may also assist the decomposition of the syn compound.</p> <p> The pKa values for syn- and anti- 7-norbornene- and 7-norbornane- carboxylic acid are reported.</p> / Thesis / Doctor of Philosophy (PhD)

A series of studies were conducted to examine the antioxidant status, drought and disease tolerance, and growth response to foliar application of soluble seaweed (Ascophyllum nodosum) extracts (SE) and humic acid (HA; 25% active HA or 2.9% active HA) in tall fescue (Festuca arundinacea Schreb), Kentucky bluegrass (Poa pratensis L.) and creeping bentgrass (Agrostis palusttis Huds.) grown under low (-0.5 MPa) and high (-0.03 MPa) soil moisture environments. Foliar application of humic acid (2.9 % active HA) at 23.7 and 47.4 l/ha improved leaf water status, shoot and root development in tall fescue, Kentucky bluegrass and creeping bentgrass grown under drought. Humic acid (2.9% active HA) at 15.5 l/ha or SE at 326 g/ha significantly reduced dollarspot incidence and improved turf quality in creeping bentgrass. Drought stress induced an increase of antioxidants alpha-tocopherol and ascorbic acid concentrations in the three turfgrass species. In the experiment with Kentucky bluegrass, drought stress increased beta-carotene concentration, but did not significantly influence superoxide dismutase (SOD) activity. Foliar application of humic acid (25% active HA) at 5 l/ha and/or SE at 326 g/ha consistently enhanced alpha-tocopherol and ascorbic acid concentrations, leaf water status, and growth in the three cool-season turfgrass species grown under low and high soil moisture environments. In the experiment with Kentucky bluegrass, application of HA at 5 l/ha plus SE at 326 g/ha also increased beta-carotene content and SOD activity under low and high soil moisture environments. There were close positive correlations between the antioxidant status and shoot or root growth in the three turfgrass species regardless of soil moisture levels. The antioxidant SOD activity, photosynthetic capacity in terms of Fvm690, and chlorophyll content in terms of Fm730/Fm690 exhibited a seasonal fluctuation in endophyte [Neotiphodium coenophialum (Morgan Jones and Gams) Glenn, Bacon, Price and Hanlin] -free and endophyte-infected tall fescue. Application of SE enhanced SOD activity, photosynthetic capacity, and chlorophyll content in tall fescue, especially at 4 weeks after SE treatment. The SOD activity, photosynthetic capacity and chlorophyll content were not significantly influenced by the endophyte infection. A close positive correlation between SOD and photosynthetic capacity during the summer was found in endophyte-free and endophyte-infected tall fescue. / Ph. D.

Thesis (Ph. D.)--University of Texas at Austin, 2008. / Vita. Includes bibliographical references.

Thesis (doctoral)--Lund University, 1994.

The extent to which endogenous free radical-scavenging defense mechanisms are involved in experimental and human diabetes was investigated in various tissues of animals with chemically-induced or spontaneous diabetes (BB Wistar rats) and in erythrocytes of patients with either Type I or Type II diabetes. Diabetes was induced in female Wistar rats using alloxan (ALX) or streptozotocin (STZ), each administered in a dose of 50 mg/kg body wt., intravenously. The present study also included a group -of animals in which body wt. loss was induced by food-deprivation for 72 h. The effects of pharmacological interventions (insulin or allopurinol (ALP)), on these processes were also investigated in chemically-induced diabetes., The activities of catalase (CAT), CuZn-superoxide dismutase (CuZn-SOD), glutathione peroxidase (GSH-PX) and glutathione reductase (GSSG-RD) as well as levels of reduced glutathione (GSH) were examined in heart, pancreas, liver and kidney as well as in erythrocytes. Erythrocytes were also examined for their susceptibility to in vitro oxidative stress induced by hydrogen peroxide (H₂0₂). Criteria studied in this regard were GSH-depletion and malondi-aldehyde (MDA) production (an index of lipid peroxidation). The results obtained showed that tissue antioxidant systems are altered in experimental diabetes and that the magnitude of the alterations increased with the degree of body weight loss. Furthermore, the duration of hypoinsulinemia might contribute to the nature of alterations in antioxidant mechanisms. The complex patterns of the alterations observed varied from one tissue to another and may be the result of compensatory increases, usually involving enzymes whose activity in the particular tissue may be limiting, and direct inhibitory effects of endogenous oxidants on the enzymatic components of tissue antioxidant systems. The ability of insulin (9-12 U/kg body wt., subcutaneously) to reverse the many similar alterations of tissue antioxidant enzymes in diabetes induced by either STZ or ALX suggests that these changes are more likely attributable to hypoinsulinemia rather than to direct effects of either diabetogenic drug. The above-mentioned effects indicate that insulin can markedly influence tissue antioxidant status. However, the reason for the persistence of decreased CuZn-SOD activity in both liver and kidney of ALX-diabetic rats after 12 wk of treatment with insulin is not clear at present, and requires further investigation to determine whether this reflects the presence of a residual deficit in tissue antioxidant processes in liver and kidney despite insulin treatment, or whether it is the result of a direct effect exerted by ALX. Acute ALP administration (50 mg/kg body wt., intraperitoneally) was associated with reductions in ketonuria and early mortality among ALX-diabetic rats, and long-term ALP treatment (1.9 mg/day in drinking water) resulted in a normalization of renal CuZn-SOD activity in these animals. Comparable (although not identical) changes in tissue antioxidant status are present in insulin-dependent spontaneously diabetic BB (ISDBB) rats and in animals made diabetic by STZ or ALX administration. Our data also demonstate that the alterations in tissue GSH levels characterizing ALX-diabetes more closely paralleled changes seen in the ISDBB rat than did those in the diabetic state induced by STZ. If the alterations in antioxidant status in uncontrolled chemically-induced diabetes are attributable to a lack of insulin, the observed changes in ISDBB rats are suggestive of sub-optimal insulin therapy in these animals. The results obtained from BB rats demonstrate two types of alterations in antioxidant status: strain-related differences (increased CAT activity in pancreas and decreased GSH levels in pancreas and liver of both ISDBB and their non-diabetic littermates (NDLM)) and diabetes-related changes (mani- fested by an increase in cardiac GSH content and increases in activities of cardiac CAT and GSSG-RD, pancreatic CuZn-SOD and GSSG-RD, and renal GSH-PX). Whether or not these "strain-related" alterations in antioxidant status increase the susceptibility of these animals to developing diabetes remains unknown. Certain alterations were observed in red cells from diabetic patients and from animals with experimental diabetes suggesting that these alterations are more likely to be diabetes-related than species-dependent. Red cells in chemically-induced and clinical diabetes showed an increased resistance to peroxide-induced depletion of GSH, an effect attributed to hyperglycemia, which results in an increased supply of NADPH through the hexose monophosphate shunt for regeneration of GSH from GSSG via the GSSG-RD system. However, the susceptibility of red cells from diabetic patients and animals to lipid peroxidative damage was increased as reflected in augmented MDA production. In addition, insulin treatment did not normalize MDA production in red cells subjected to oxidative challenge and vigorous insulin treatment in both ALX- and STZ-diabetic rats resulted in a markedly decreased MDA production in response to H₂0₂. Moreover, GSSG-RD activity of red cells was increased in both uncontrolled and insulin-treated diabetic animals as well as in diabetic patients. However, some differences in erythrocyte antioxidant enzymes were also observed in erythrocytes from diabetic subjects and animals. For example, diabetic patients showed an increased activity of CuZn-SOD, while erythrocytes from diabetic animals showed no alterations in the activity of this enzyme. Erythrocyte membrane NADH-dehydrogenase activity was increased only in diabetic patients with Type I diabetes, but not in Type II diabetes or in diabetic animals. Erythrocytes from ALX- and STZ-diabetic animals showed an increase in the activity of GSH-PX and those from NDLM BB rats showed a decrease in CAT activity, alterations that were not observed in human diabetes. Finally, as far as antioxidant defense mechanisms are concerned, our results suggest that diabetes is associated with some common alterations in these mechanisms regardless of the model (chemically-induced versus the spontaneous type of diabetes) or the species used (animal versus human diabetes). Some of these alterations seem to be influenced by the degree of diabetic control, while others are apparently independent of it. Future studies will focus on the extent to which alterations in red cells of human diabetics can be used to predict the development of long-term sequelae of the disease. / Medicine, Faculty of / Anesthesiology, Pharmacology and Therapeutics, Department of / Graduate

The gaseous free radicals, alkaline-earth metal monoalkylamides, monoacetylides, monoformamidates and monopyrrolidates, consisting of a metal atom (Ca or Sr) bonded to a single ligand, were synthesized in a Broida oven. The electronic and vibrational structures of these molecules were studied by low-resolution laser spectroscopy techniques. These inorganic molecules are ionic, well represented by the structure M⁺L⁻ (M = Ca, Sr: L = ligand). Three electronic transitions were identified for the metal monoalkylamides and the metal monoformamidates. The formamidate anion bonds to the metal in a bidentate fashion through the oxygen and nitrogen atoms. Two electronic transitions were observed for the metal monopyrrolidates. The pyrrolide anion ring bonds to the metal to provide these "open-faced sandwich" type molecules with pseudo-C₅ᵥ symmetry. For the metal monoacetylide molecules, only one electronic transition (Ā²Π-Ẋ²Σ⁺) was observed. Several vibrational frequencies were determined for these inorganic molecules from the low-resolution spectra. The Ā²Π-Ẋ²Σ⁺ transition of the calcium monoacetylide molecule was rotationally analyzed at high-resolution using the filtered laser excitation spectoscopy technique. The rotational line positions were fitted to a ²Π-²Σ⁺ Hamiltonian to obtain several rotational constants. The calcium-carbon bond length in CaCCH was calculated for the ground (2.248 Å) and excited (2.200 Å) electronic states. The vibration-rotation spectra of the gaseous bismuth hydride and bismuth deuteride molecules were recorded, using a diode laser system. The 1-0 fundamental band and several hot bands with Δv-1 were rotationally analyzed. The rotational line positions were fitted first, to a Dunham energy expression and then to a ³Σ⁻ Hamiltonian, to obtain ground state rotational constants. The bismuth-hydrogen (deuterium) bond distance was calculated to be 1.809 Å (1.807 Å).

No description available.

Antioxidant properties of green tea (GT) have been widely reported. The antioxidant capacity (AOC) of green tea was investigated to include the effect of infusion time over 24 hours. The AOC was measured by the FRAP, DPPH, TEAC, and CBA assays. It was proven according that after 2 hours of brewing, tea has higher AOC and Total phenolic content (TPC), these significantly decreases after 4 hours. GT has a high amount of polyphenols with potent AOC. However, interactions between polyphenols and food matrix may decrease their potential benefit. The objective of this experiment was to test the hypothesis that the addition of milk (full fat, semi-skimmed, and skimmed) may affect the phenolic content and AOC was measured. The results indicated the plain GT had highest activity; then tea with FFM had a significantly higher amount of AO than others. Plant extracts possess health promoting properties. The objective of this study was to determine the TPC and AOA of different concentrations of spice extracts (fennel, clove, cardamom, cinnamon, ginger, anise, and black pepper) with DPPH, TEAC and Rancimat methods. At low concentration, black pepper had a highest activity but at high concentration, ginger showed the highest activity among the extracts. The TPC for spice extract was greater for anise. Results provided evidence that the studied spices may be used as a natural AO. In recent decades, saliva has emerged as a new way to diagnose and investigate basic health problems. In this study, salivary TPC and AOC were measured after consumption a single cup of green tea with and without of milk. In a healthy adult crossover design. The salivary AOC and TPC were measured before and after consumption up to 3 hours. Results indicated that milk decreased AOC of GT when compared with the control water. The activity reached peak 1 hour after ingestion and then decreased returning to the baseline. Results confirmed that saliva could be used as an easier and safer alternative to blood to assess AOA in humans.

The addition of benzyltrimethylsilane to maleic anhydride mediated by TiO2 photocatalysis was initially investigated. The affect of changing the catalyst, the radical trap loading and the substitution of the benzyltrimethylsilane molecule was assessed. Cyclisation precursors based on benzyltrimethylsilane were prepared, but were found not to cyclise via TiO2 photocatalysis. A number of other systems were assessed for their ability to cyclise under TiO2 photocatalysis; tertiary amines, aminomethyltrimethylsilanes, phenoxymethyltrimethylsilanes and phenoxyacetic acids. Phenoxymethyltrimethylsilane and phenoxyacetic acid were found to add effectively to maleic anhydride under TiO2 photocatalysis conditions, however they were unreactive with regards to cyclisation. EPR spectroscopy has been employed to characterise further the reaction of benzylsilanes with maleic anhydride under TiO2 photocatalytic conditions. A number of EPR active species were observed; trapped holes and electrons, which reside within the TiO2 catalyst. In addition, methyl and benzyl radicals were observed and were found to originate from the oxidation of the benzylsilanes by trapped holes in the TiO2 catalyst. However, no radical species were observed from the maleic anhydride. These observations had the following consequences for the currently proposed reaction mechanism for the addition of benzyltrimethylsilane with maleic anhydride under TiO2 photocatalysis.  The observation of the benzyl radical definitely proved that the reactive intermediate was indeed the proposed benzyl radical  The absence of any maleic anhydride EPR active species cast doubt on the role of maleic anhydride as an electron trap. Moreover when maleic anhydride is removed from the reaction system, interstitial Ti3+ species is absent from the EPR spectra, indicating that maleic anhydride is in fact acting as a hole trap.