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Electronic Theses and Dissertations

Theses/Dissertations

1995

Chemistry

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The Structure And Spectroscopic Properties Of Langmuir-Blodgett Films Of Perylene Tetracarboxylic Derivatives., Eric G. Johnson Jan 1995

The Structure And Spectroscopic Properties Of Langmuir-Blodgett Films Of Perylene Tetracarboxylic Derivatives., Eric G. Johnson

Electronic Theses and Dissertations

A series of perylene tetracarboxylic diimides and monoimides have been fabricated into Langmuir and Langmuir-Blodgett films. These films have been spectroscopically characterized through UV-visible absorption, steady-state fluorescence, infrared and Raman techniques. Molecular exciton and excimer formation have been observed for these films. The average molecular orientation of the chromophore was deduced through infrared transmission and reflection/absorption techniques. Electronic spectroscopy revealed the nature of the packing of the materials. The role of subphase/molecule and molecule/molecule interactions in the structure of the film were discussed, as well as the role of the imide substitution. These materials were successfully incorporated, as donors, into …


A Study Of Thin Solid Organic Films By Fourier Transform Surface-Enhanced Raman Scattering And Atomic Force Microscopy., Carol Ann. Jennings Jan 1995

A Study Of Thin Solid Organic Films By Fourier Transform Surface-Enhanced Raman Scattering And Atomic Force Microscopy., Carol Ann. Jennings

Electronic Theses and Dissertations

Fourier transform surface-enhanced Raman scattering (FT-SERS) in the near-infrared and atomic force microscopy (AFM) have been used to characterize thin solid organic films. The pigments studied were phthalocyanines and perylenes which have applications as charge generation materials in organic photoreceptors. Techniques for film preparation such as Langmuir-Blodgett (LB) deposition and vacuum evaporation are discussed. The literature was reviewed for FT-Raman spectroscopy, surface-enhanced Raman spectroscopy and atomic force microscopy. A model according to Gersten and Nitzan was applied and SERS enhancement factors in the near-IR were calculated for various metal hemi-spheroids. FT-Raman spectra were presented for thin vacuum evaporated films of …


Cobalt Stabilized Gamma-Chloroalkynones And Alkynoates As Gamma-Carbonyl Cation Synthons., Charles Stephen. Vizniowski Jan 1995

Cobalt Stabilized Gamma-Chloroalkynones And Alkynoates As Gamma-Carbonyl Cation Synthons., Charles Stephen. Vizniowski

Electronic Theses and Dissertations

$\gamma$-Cationic-$\alpha,\beta$-unsaturated carbonyl synthons have been prepared via hexacarbonyldicobalt complexed $\gamma$-chloroalkynoates and alkynones (100). Treatment of 100 with silver salts in the presence of silyl enol ethers (102-104) generated 2-alkynyl-1,6-dicarbonyl compounds (134-149) in poor to good yields. Products of 101, with a non hydrogen substituent at the propargyl site, with 102 and 103 generated syn and anti diastereomers. The ratios of syn:anti diastereomers range from 1.3: 1 to 2.1: 1 for 102 to 6.9: 1 to 15: 1 for 103. These ratios are similar to literature compounds. Decomplexation to the alkyne effected in good to excellent yields. A dimer 151 was …


Induction Of Aryl Hydrocarbon Hydroxylase And Ethoxyresorufin O-Deethylase In Human And Murine Cells By 2,3,7,8-Tetrachlorodibenzo-P-Dioxin (Tcdd) And Polycholrinated Biphenyls (Pcbs)., Andreas. Vamvakas Jan 1995

Induction Of Aryl Hydrocarbon Hydroxylase And Ethoxyresorufin O-Deethylase In Human And Murine Cells By 2,3,7,8-Tetrachlorodibenzo-P-Dioxin (Tcdd) And Polycholrinated Biphenyls (Pcbs)., Andreas. Vamvakas

Electronic Theses and Dissertations

To assess the relevance of H4IIE for human populations, we examined levels of aryl hydrocarbon hydroxylase (AHH) and ethoxyresorufin O-deethylase (EROD) activities H4IIE rat liver, HepG2 human liver and MCF-7 human breast cells after exposure to a variety of HAHs. These included TCDD, and three coplanar non-ortho substituted polychlorinated biphenyl (PCB) congeners: 3,3$\sp\prime$,4,4$\sp\prime$-tetrachlorobiphenyl (PCB 77), 3,3$\sp\prime$,4,4$\sp\prime$5-pentachlorobiphenyl (PCB 126), and 3,3$\sp\prime$,4,4$\sp\prime$,5,5$\sp\prime$-hexachlorobiphenyl (PCB 169), either alone or in combination. AHH and EROD activities were also examined after treatment with muscle tissue extracts of Lake Ontario rainbow trout (Oncorhynchus mykiss). H4IIE was generally more sensitive to all HAH treatments. AHH and EROD activities …


Two-Dimensional Nuclear Magnetic Resonance Studies Of Thymosin-Alpha(1) (A Myosin Light Chain Kinase Activating Peptide), And Ribonuclease A In The Presence Of Uridine Vanadate., Timothy Daniel. Veenstra Jan 1995

Two-Dimensional Nuclear Magnetic Resonance Studies Of Thymosin-Alpha(1) (A Myosin Light Chain Kinase Activating Peptide), And Ribonuclease A In The Presence Of Uridine Vanadate., Timothy Daniel. Veenstra

Electronic Theses and Dissertations

1. The structure of the peptide thymosin $\alpha\sb1$ has been investigated by circular dichroism and one- and two-dimensional nuclear magnetic resonance spectroscopy. Thymosin $\alpha\sb1$ is a highly acidic peptide composed of 28 amino acid residues. Through the use of circular dichroism and two-dimensional nuclear magnetic resonance techniques, the structure of thymosin $\alpha\sb1$ in 30% (v/v) deuterated 2,2,2-trifluoroethanol has been solved. Thymosin $\alpha\sb1$ contains an $\alpha$-helix extending from residue 16 to 26 and a turn between residues 5 and 8. Thymosin $\alpha\sb1$ has been shown to be a potent activator of skeletal muscle myosin light chain kinase, a well known calmodulin-dependent …


Purification, Characterization, And Functional Investigations Of Novel Platelet Proteins., Jeffrey Stephen. Baldwin Jan 1995

Purification, Characterization, And Functional Investigations Of Novel Platelet Proteins., Jeffrey Stephen. Baldwin

Electronic Theses and Dissertations

Recently, a novel Kunitz inhibitor of trypsin-like enzymes has been discovered in bovine platelets that has a higher degree of association for plasmin than trypsin, and thereby has been termed bovine platelet plasmin inhibitor (BPPI). Basic problems in the purification, resulting in protein that was essentially insoluble, has hampered structural determinations by x-ray or NMR analysis. An investigation into the cause of the protein insolubility has revealed that an excessively high concentration of acetonitrile, used to elute the protein from a C18 reversed-phase cartridge, was most probably the cause of the insolubility. Concentrated BPPI solutions permitted the preparation of a …


Metalated Macrocyclic Receptors., James Edward. Kickham Jan 1995

Metalated Macrocyclic Receptors., James Edward. Kickham

Electronic Theses and Dissertations

The dissertation describes the incorporation of a stable organopalladium fragment into several macrocyclic structures, in which three of four palladium coordination sites are permanently occupied by an S$\sb2$C ligand "bracket". The remaining metal site is filled by a more labile donor, and is used for binding ancillary ligands (substrates) such as phosphines, o-aminopyridine, DNA nucleobases and hydrazine derivatives. Chapter 2 describes the synthesis, oxidative addition, and coordination chemistry of (Pt(TT(11) MC)) (BF$\sb4\rbrack$ (4), (PD(TT(11) MC)) (BF$\sb4\rbrack$, (8) and (Pd(pr-TOMB-1)) (BF$\sb4\rbrack$ (14), in which one donor (E = S,O) is displaced by stronger ancillary ligands, as confirmed by X-ray structural data …


Some Aspects Of Glutathione And L-Arginine/Nitric Oxide Metabolism In The Maintenance Of Platelet Function., Daniel Joseph. Sexton Jan 1995

Some Aspects Of Glutathione And L-Arginine/Nitric Oxide Metabolism In The Maintenance Of Platelet Function., Daniel Joseph. Sexton

Electronic Theses and Dissertations

Evidence is presented here for the regulation of platelet activation by intra-platelet levels of glutathione (GSH) and L-arginine. Our data is consistent with the intra-platelet GSH ((GSH) $\sb{\rm ip}$) modulation through the regulation of the thromboxane A$\sb2$ (TxA$\sb2$) biosynthesis. The reduction of (GSH) $\sb{\rm ip}$ by 100 $\mu$M 1-chloro-2,4-dinitrobenzene (CDNB) enhanced thrombin-induced platelet aggregation and ADP-induced platelet aggregation was inhibited by the elevation of (GSH) $\sb{\rm ip}$ through a facilitative GSH-specific transport system. Platelet facilitative GSH uptake was subsequently characterized as being Na$\sp+$-independent, concentration dependent (K$\sb{\rm M}$ and V$\sb{\rm max}$ for GSH uptake in platelet plasma membrane vesicles (PPMV) is …


In Vitro Short-Term Human Bioassays In Environmental Cytotoxicity And Genotoxicity Assessments., Masumeh. Abdolalipour Jan 1995

In Vitro Short-Term Human Bioassays In Environmental Cytotoxicity And Genotoxicity Assessments., Masumeh. Abdolalipour

Electronic Theses and Dissertations

In this study, an in vitro human cell culture, the HepG2 cell line, has been adapted and calibrated to be used as a surrogate human model system in environmental toxicology studies. To evaluate both cellular and genetic effects of test chemicals, a cytotoxicity test and a genotoxicity test were developed in the HepG2 cell line. A Neutral Red (NR) dye-uptake assay was used to assess cytotoxicity, and an alkaline unwinding, DNA break assay (AU) was developed to detect genotoxicity of both known toxicants as well as unknown environmental samples. The response of the NR and AU bioassays was calibrated by …