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Peroxynitrite Mediated Oxidations: Spin Trap Studies; Nitration And Hydroxylation Of Phenol Result From Different Intermediates; Co(2) Catalyzes The Decomposition Of Peroxynitrite., Jean-Noel Lemercier
Peroxynitrite Mediated Oxidations: Spin Trap Studies; Nitration And Hydroxylation Of Phenol Result From Different Intermediates; Co(2) Catalyzes The Decomposition Of Peroxynitrite., Jean-Noel Lemercier
LSU Historical Dissertations and Theses
In the first project the spin trap DMPO was used to probe for the production of hydroxyl radicals from peroxynitrite. Peroxynitrite reacts with DMPO to give $\sp\cdot$DMPO-OH, suggesting that $\sp\cdot$DMPO-OH results from a reaction between DMPO and HOONO or between DMPO and an activated intermediate of HOONO. Thiols produce a large increase in the $\sp\cdot$DMPO-OH signal intensity. Experiments employing SOD suggest that this increase results from the decomposition of $\sp\cdot$DMPO-OOH. These results are incompatible with the decomposition of peroxynitrite to form $\sp\cdot$OH but suggest that an intermediate of HOONO is produced that is less reactive and more selective than the …
Preparation Of Strained Nitrogen Heterocycles For Spin Trapping Applications., Anna Patrice Shanklin
Preparation Of Strained Nitrogen Heterocycles For Spin Trapping Applications., Anna Patrice Shanklin
LSU Historical Dissertations and Theses
This work discusses the synthesis of bicyclic nitrogen heteorocycles with the emphasis placed on the design and evaluation of a bicyclic nitrone for spin trapping applications. Camphorolactams, 1,7,7-trimethyl-2-aza-bicyclo(2.2.1) heptan-3-one and 1,7,7-trimethyl-3-azabicyclo (2.2.1) heptan-2-one were prepared from camphoric anhydride under Curtius conditions with sodium azide and dimethylformamide. 2-azabicyclo(2.2.1) heptan-3-one was also prepared under Curtius conditions from cis-1,3-cyclopentane-dicarboxylic acid anhydride. N-benzyl-2-azabicyclo (2.2.1) -heptane and N-benzyl-2-azabicyclo (2.2.2) octane were prepared from their aliphatic amine derivatives under Hofmann-Loeffler conditions in low yields. 1,3,3-trimethyl-6-azabicyclo (3.2.1) octane, N-oxide was prepared from its parent amine under sodium tungstate catalyzed oxidation with hydrogen peroxide. The bicyclic nitrone was …
Synthesis Of Novel Cyclopentadienyl And Pyrrole Compounds., Alfonso Davila
Synthesis Of Novel Cyclopentadienyl And Pyrrole Compounds., Alfonso Davila
LSU Historical Dissertations and Theses
This dissertation describes the preparation of two classes of compounds: cyclopentadienes and pyrroles. These compounds are key elements in the synthesis of conducting materials. A general novel methodology for the cyclopentadienylannulation of strained cycloalkynes has been developed. Bromination of 1,5-cycloctadiene produces 1,2,5,6-tetrabromocyclooctane, which under further treatment with DBU eliminates two moles of HBr to produce a mixture of 2 diastereomeric bisvinylbromides. These isomers eliminate one mol of HBr when treated with t-BuOK under phase transfer conditions producing a cyclooctene-yne. This bromoalkyne reacts in situ with dimethylfulvene in a sealed tube at 100$\sp\circ$C to produce a Diels-Alder adduct. Treatment of this …
The Synthesis Of Novel Phosphine-Modified Ligands For Use In Bimetallic Hydroformylation., Howard Frederick Koch Iii
The Synthesis Of Novel Phosphine-Modified Ligands For Use In Bimetallic Hydroformylation., Howard Frederick Koch Iii
LSU Historical Dissertations and Theses
The tetraphosphine ligand, Et$\sb2$P(CH$\sb2)\sb2$P(Ph)CH$\sb2$P(Ph)(CH$\sb2)\sb2$PEt$\sb2 ,$ et,ph-P4, was designed to be a binucleating ligand for use in bimetallic hydroformylation catalysis. This ligand can be tailored for both electronic and steric factors at the internal and external phosphorus atoms. It is hoped that through careful tuning of this ligand, the rate and selectivity of our bimetallic catalyst can be optimized for various substrates. Modification of the original ligand may also lead us to a better understanding of the mechanism involved in the catalytic cycle. My goal has been to replace the phenyl substituents on the internal phosphorus atoms with various alkyl groups. …
Synthesis Of Monodisperse Poly(Gamma-Benzyl-Alpha,L-Glutamate) Oligomers And Their Star-Shaped Derivatives., Xiaolan Wang
Synthesis Of Monodisperse Poly(Gamma-Benzyl-Alpha,L-Glutamate) Oligomers And Their Star-Shaped Derivatives., Xiaolan Wang
LSU Historical Dissertations and Theses
Poly($\gamma$-benzyl-$\alpha$,L-glutamate), PBLG, is a widely studied example of polypeptides. The preparation of monodisperse samples of PBLG and PBLG oligomer is difficult to achieve. In this work we probe the possibility of preparation of PBLG oligomers by polymerization of L-glutamic acid N-carboxyanhydride (NCA) with different initiators such as primary amine, sterically hindered secondary amine, tertiary amine, and strong base. Information regarding molecular weight distribution of these oligomers was obtained by applying MALDI-TOF mass spectrometry and reversed phase HPLC. While some researchers reported that application of primary amine initiators or polar solvents such as DMF could improve the molecular weight distributions of …