In the theoretical part of this study, the thermodynamics of ionic hydration was considered. Hydration functions were assumed to consist of neutral and electrostatic terms. Neutral contributions were evaluated from noble gas solubility data. Mean Spherical Approximation equations, combined with the Stillinger ST-2 off-centered water dipole model, supplied values for the electrostatic functions. Calculated Gibbs free energies of hydration for several ions agreed with experiment. Discrepancies between the calculated and absolute values of entropies of hydration can be correlated with the structure breaking tendency of monovalent ions. / A tracer level solvent extraction technique was used to investigate ionic interactions in aqueous electrolytes. Am(III) was chosen as a test metal ion and a cation exchanger HDEHP as the extractant. From the activity coefficients, calculated by Pitzer's theory, and measured distribution ratios it was deduced that the ion pairing of Am(III) in single electrolytes with anion X('-) (X('-) is ClO(,4)('-), NO(,3)('-) and Cl('-)) first increases with the concentration of X('-), then decreases and finally rises again. The salting out phenomenon at intermediate concentrations was attributed to the energetically unfavored co-sphere overlap between Am(III) and X('-). / The extraction of Am(III) from constant ionic strength (1.00, 2.50 and 5.00 M) electrolyte mixtures was analyzed by the stability constant technique. Stoichiometric first stability constants for AmNO(,3)('2+) and AmClO(,3)('2+) were determined. Problems with the evaluation method were also discussed. As an alternative treatment of the data, an empirical equation of the form DELTA = i(,2)(1 - i(,2)) (u + (1 - 2i(,2))v was introduced, where DELTA is proportional to the reciprocal of the distribution ratio. Variation of the interaction parameters u and v can be interpreted in terms of the thermodynamic properties of the medium ions. Except when DELTA varies about zero, u and v vary consistently with the ionic stength, which allows for predictions of distribution ratios at untested ionic strengths and composition. / Source: Dissertation Abstracts International, Volume: 48-03, Section: B, page: 0776. / Thesis (Ph.D.)--The Florida State University, 1987.

The ground state properties and excited-state dynamics of two complex molecules of biological significance have been investigated experimentally by steady-state and picosecond transient absorption spectroscopy, and theoretically by molecular orbital calculations. Lumichrome (7,8-dimethylalloxazine), has been found to form a ground-state anion in p-dioxane and certain alcohol solvents. Picosecond transient absorption studies of lumichrome in acetic acid, pyridine, p-dioxane, methanol, and water at pH 9.8, as well as 1,3-dimethyllumichrome and lumiflavin in methanol solvents are reported. The picosecond transient absorption measurements of lumichrome in p-dioxane solvent revealed the presence of a ground-state and possibly excited-state anion, as well as a rapid risetime of $\rm T\sb{\rm n}\gets\rm T\sb1$ absorption of the normal molecule. Studies of lumichrome in methanol solvent indicate the occurrence of excited-state proton-ejection. Picosecond transient absorption experiments of lumichrome in acetic acid and in pyridine solvents suggested that excited-state proton transfer may be preceded by excited-state proton ejection. The absence of observed $\rm T\sb{\rm n}\gets\rm T\sb1$ absorption of the tautomer form of lumichrome in these solvents suggested that the triplet population of the isoalloxazine form may be rapidly depleted by semiquinone radical formation. / Possible radiationless deactivation pathways of the non-fluorescent molecule, 5-hydroxyflavone, have been investigated by steady-state and picosecond transient absorption spectroscopy, as well as by molecular orbital calculations. The specific solvent dependence of the steady-state absorption spectra of 5-hydroxyflavone reflects the previously-proposed strength of the intramolecular H-bond and suggests a strong vibronic coupling. A weakly-absorbing transient was observed beginning at ca. 50 ps in methanol solvent. Ab initio SCF molecular orbital calculations were performed on both the normal and tautomer forms of 5-hydroxyflavone. Ab initio SCF and geometry optimization, and semi-empirical INDO/S-CI calculations were performed on the small analog, 5-hydroxychromone. Results of these calculations, in conjunction with experimental results, suggest that two plausible mechanisms for radiationless pathways in 5-hydroxyflavone are a pseudo-Jahn-Teller effect, and a rapid intersystem crossing, both in the tautomer form of the molecule which is presumed to form via excited-state proton transfer. / Source: Dissertation Abstracts International, Volume: 48-09, Section: B, page: 2659. / Thesis (Ph.D.)--The Florida State University, 1987.

Excited-state proton transfer reactions are investigated for three different molecular species, 3-hydroxyflavone, 7-azaindole, and lumichrome. Both steady-state and picosecond spectroscopic techniques are used to establish the dominant role of solvent structure and dynamics in the tautomerization mechanisms of these systems. The explicit consideration of a ground-state hydrogen-bonding equilibrium together with the subsequent excited-state solvent/solute relaxation dynamics allows for a precise interpretation of the processes which occur in these molecules following electronic excitation. / Proton transfer in 3-hydroxyflavone is formally an intramolecular process. The tautomerization process in this molecule, however, is found to depend sensitively on interactions with the surrounding solvent molecules. Distinct ground-state species which give rise to different excited-state luminescence behavior are identified and characterized. In the absence of hydrogen-bonding perturbations the tautomerization in 3-hydroxyflavone is rapid, efficient, and effectively independent of both temperature and viscosity. / The isolated 7-azaindole molecule possesses no direct pathway for tautomerization. If proton transfer is to occur it must do so through a molecular bridge of some sort. This class of excited-state reactions is refered to as pseudointramolecular proton transfer to distinguish it from the purely intramolecular case. In alcoholic solvents the proton transfer in 7-azaindole takes place in cyclically hydrogen-bonded complexes. Although the physical mechanisms differ, the dynamical aspects of the tautomerization process in 7-azaindole are strikingly similar to those of 3-hydroxyflavone. The tautomerism is intimately coupled to the structure and dynamics of the surrounding solvent cage. / Lumichrome provides a particularly interesting case of pseudo-intramolecular proton transfer. Tautomerization takes place in the solvents pyridine, glacial acetic acid, and in the various derivatives of these. The roles of solvent structure and dynamics on the proton transfer process in these systems are investigated. / Source: Dissertation Abstracts International, Volume: 46-04, Section: B, page: 1188. / Thesis (Ph.D.)--The Florida State University, 1985.

The theory of coastally trapped waves has been developed for the bottom topography of two opposite continental shelves that meet along a common trough. The double shelf topography supports two sets of waves propagating in opposite directions. For this topography, the Kelvin waves are an important mode of motion; therefore the inclusion of the horizontal divergence effect is crucial. Other modes of motion are made up by the continental shelf waves. The double shelf model of straight coasts and constant cross-shore slope is applied to the Yellow Sea for the period of January 10 to April 12, 1986, during which direct observations in the trough of currents and bottom pressure were made. There is good agreement between the model results and the observations. The fluctuations of bottom pressure are chiefly accounted for by the Kelvin wave mode and those of the currents by the continental shelf wave modes. / Source: Dissertation Abstracts International, Volume: 48-07, Section: B, page: 1924. / Thesis (Ph.D.)--The Florida State University, 1987.

The purpose of this study was to investigate the effect of an eight-week mastery learning approach teacher training program on achieving mastery of two physical education teaching styles: the practice style and the reciprocal style. Forty male undergraduate physical education majors enrolled at Yarmouk University, Irbid, Jordan, served as subjects. The subjects were divided into two groups of 20. One group was assigned to the practice style and the other group was assigned to the reciprocal style. Knowledge tests and performance tests were administered in a pretest, training treatment sequence, posttest format. / In order to examine the effect of the training program, the results of the two knowledge tests and the two performance tests were analyzed using the t-test. A descriptive analysis was also used to determine the mastery level reached by the subjects. To record the data from the performance tests, an event-recording behavior observation system was used to code the teacher's behaviors. The results indicated that significant increases in knowledge posttest scores, for both the practice and the reciprocal groups, were achieved as a result of the mastery learning approach teacher training program. Data tabulated from posttest scores revealed that 92.5 percent of the 40 subjects obtained a mastery level. A significant increase in the amount of appropriate teaching behaviors, for both the practice and the reciprocal style groups, was also witnessed as a result of the training program. Data seemed to suggest that mastery learning approach teacher training programs can be effectively applied in a physical education environment. / Source: Dissertation Abstracts International, Volume: 46-09, Section: A, page: 2614. / Thesis (Ph.D.)--The Florida State University, 1985.

The prospect of rising sulfur dioxide emissions from increased coal combustion presents risks, not only of acid rain, but also to health by inhalation of the SO(,2) and of sulfate aerosols which may enhance transport of dissolved SO(,2) and acid to the lung. This study was undertaken to determine the effects of ambient air, acidic sulfate aerosol, sulfur dioxide, and the combination of sulfur dioxide and aerosol on selected pulmonary function measurements after 20 minutes of exercise at 75%-80% maximal heart rate in a hot (36-19 degrees C) and humid (70%-90% RH) environment. Six male subjects between the ages 26 and 33 years with no pre-existing pulmonary or cardiovascular problems rode a stationary bicycle for 20 minutes during each exposure condition at a workload pre-set to assure that each subject would attain an average minute ventilation of 50-60 1/min (BTPS). Exposure to 2.5 p.p.m. sulfur dioxide alone led to a significant lowering of FVC, FEV1, and FEF50. Exposure to sulfur dioxide plus aerosol led to a significant decrease of FVC. Baseline comparisons reflected a significant decline in FVC, FEV1, FEF25, FEF50, FEF75, and FEF25-75 between the pre-ambient and post-exposure. This decline suggests a residual effect of the air pollutant exposures. Significant differences were also observed between the pre-aerosol and pre-sulfur dioxide exposures for FVC, FEV1, FEF50, and FEF25-75. / Source: Dissertation Abstracts International, Volume: 46-09, Section: A, page: 2617. / Thesis (Ph.D.)--The Florida State University, 1985.

The steady state and pre-steady state kinetics of hydrolysis of the fluorescent peptide substrate, Leu-Gly-NHNH-Dns, by porcine kidney leucine aminopeptidase (LAP) have been studied by stopped flow cryoenzymology. Experiments have been carried out with LAP species containing Zn(II) in the catalytic site and various other divalent metal ions in the regulatory site. These species are denoted ((LAP)Zn$\sb6$Me$\sb6$), where Me(II) = Zn(II), Ni(II), Cu(II), Mg(II), Mn(II) and empty. The stopped flow fluorescence traces obtained with direct substrate excitation for these reactions carried out at ambient temperatures are consistent with formation of a single intermediate, (E$\cdot$S), and have been used to determine the steady-state kinetic parameters. When the metal ion in the regulatory site is changed, k$\sb{\rm cat}$ and K$\sb{\rm M}$ are altered in the same direction to approximately the same extent, leaving the values of k$\sb{\rm cat}$/K$\sb{\rm M}$ almost unchanged. / The effect of methanol on the hydrolysis of Leu-Gly-NHNH-Dns by ((LAP)Zn$\sb6$Me$\sb6$) has also been investigated. Increasing percentages of methanol lower k$\sb{\rm cat}$ markedly and decrease K$\sb{\rm M}$ slightly, causing a net decrease in k$\sb{\rm cat}$/K$\sb{\rm M}$. Low-temperature stopped-flow experiments for the reaction of Leu-Gly-NHNH-Dns with ((LAP)Zn$\sb6$Me$\sb6$) have been carried out in 50% methanol, 0.1 M KCl, 10 mM Tris, pH$\sp*$ 9.0 under non-turnover conditions. For several ((LAP)Zn$\sb6$Me$\sb6$) a new relaxation is observed at $-40\sp\circ$C that has been shown to correspond to the interconversion of a new intermediate, (E$\cdot$S) $\sp\prime$, with (E$\cdot$S). The pre-steady state kinetic parameters, K$\sb{\rm s}$, k$\sb2$ and k$\sb{-2}$, for the hydrolysis of Leu-Gly-NHNH-Dns by ((LAP)Zn$\sb6$Ni$\sb6$) at $-40\sp\circ$C are 0.28 mM, 54 sec$\sp{-1}$ and 4.4 sec$\sp{-1}$, respectively. / Source: Dissertation Abstracts International, Volume: 48-09, Section: B, page: 2658. / Thesis (Ph.D.)--The Florida State University, 1987.

The purpose of this study was to investigate the differences in job satisfaction and leadership behavior of athletic directors in the NCAA and NAIA athletic organizations. Forty eight percent from the original sample (n = 400) returned usable instruments and participated in the study. Fifty three percent had tenure status and averaged 47 years of age and 22 years of working experience. The data collection was accomplished by the use of a Personal Data Form developed by the author, the Job Description Index and the Leadership Behavior Description Questionnaire Ideal. The job satisfaction scales and the dimensions of leadership behavior were analyzed by ANOVA, Pearson Product-Moment Correlation and the Newman-Keuls Range Test at the Education Computer Center of Florida State University. It was found in the study that athletic directors from the NCAA were more satisfied than dissatisfied with their jobs and that their job attitudes did not influence their leadership behavior. / Source: Dissertation Abstracts International, Volume: 43-07, Section: A, page: 2278. / Thesis (Ph.D.)--The Florida State University, 1982.

Using Geosecs Atlantic, Pacific, and Indian Ocean hydrographic data, a set of ocean-specific models have been constructed to estimate the concentrations of inorganic, PO(,4)('-3) ((mu)gram-atoms/kg) in the upper water column, based upon the concentration of dissolved O(,2) (ml/l), and temperature ((DEGREES)C), assuming that the Redfield {O:P} ratio maintains. Substitution of foraminiferally-derived values of (delta)('13)C and (delta)('18)O into these ocean-specific models, as functions of dissolved O(,2) and temperature, yields a set of paleophosphate models which can be used down-core. / Calculated PO(,4)('-3) profiles for the upper water column, using observed temperature and (delta)('13)C(,(SIGMA)CO(,2)) data in the paleophosphate expressions, faithfully replicates the observed PO(,4)('-3) profiles at selected sites in all major ocean basins, between 50(DEGREES) north and 50(DEGREES) south latitude. Average PO(,4)('-3) concentrations approximated from the (delta)('13)C and (delta)('18)O of recent planktic foraminifera in the Indian Ocean, were similar to observed PO(,4)('-3) concentrations at those levels in the water column at which the organisms presumably secreted their tests. / Down-core data covering the last 18,000 years in the northern Indian Ocean suggests that at 9,000 kyBP, the upper water column in the northern Indian Ocean was more productive than at present or at 18 kyBP due presumably to a rapid overturn of old water closely following the last glacial readvance and the onset of a major warming trend. / Source: Dissertation Abstracts International, Volume: 43-12, Section: B, page: 3901. / Thesis (Ph.D.)--The Florida State University, 1982.

Source: Dissertation Abstracts International, Volume: 29-02, Section: B, page: 0563. / Thesis (Ph.D.)--The Florida State University, 1968.