Thesis (M.S.)--University of Wisconsin--Madison, 1981. / Typescript. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 92-103).

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The following study examined the effectiveness and administrative implications of Virginia Tech football's two-a-day practice schedule changes. More specifically, the research examined the relationship between weight loss and hydration as associated with two-a-day practices and studied the deviation with relations to practice patterns. Participants included members of the Virginia Tech Football team for the years 2001, 2002, 2003, and 2004. All participants were examined by the team physician and declared fit to participate in Division IA NCAA collegiate football. Measures included the amount of weight loss and the number of heat related incidences (i.e. heat illness and IV fluid administration) from 2001 through 2004 seasons to determine if a change in practice patterns could reduce or minimize heat related illnesses. There were numerous findings from the study to suggest that the changes in NCAA and Virginia Tech two-a-day practice policies were successful in the prevention of heat related incidences and improving the overall safety for the participants. This study concluded that the overall weight loss among players decreased in accordance with the mandated practice changes. In addition, the number of heat related illnesses decreased from 2001 to 2004. Upon examination of these factors, it can be concluded that the practice schedule changes have in fact, been effective at decreasing weight loss/hydration among players and preventing heat related illness. These findings can be used by athletic administrators to further develop athletic policies that will ensure the safety of student athletes involved in collegiate football during extreme environmental conditions. In addition, this study displays the cost effectiveness of both medical personnel and hydration supplies in the reduction of heat related illnesses during two a day practice sessions. / Ed. D.

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Thesis (Ph. D.)--Columbia University, 1936. / Vita. Bibliography: p. [40].

This thesis work resulted from an on-going project in this laboratory focusing on the hydration of olefins, using transition metal complexes as catalysts, with the ultimate aim of achieving catalytic asymmetric hydration, for example: (HO₂C)CH=CH(CO₂H) → (HO₂C)CH₂-CH(OH)(CO₂H) (C = chiral carbon atom). Initially, the hydration of maleic to malic acid, catalyzed by Cr(H₂O)₆³⁺ at 100°C in aqueous solution was studied, including the kinetic dependences on Cr³⁺, maleic acid and pH. A proposed mechanism involving 1:1 complexes of Cr³⁺ with the maleato and malato monoanions is consistent qualitatively with the kinetic data. This Cr system was, however, ineffective for hydration of prochiral olefins, and the work became a minor component of the thesis and is described in the last chapter. Emphasis was switched to the study of water-soluble phosphine systems based on Pd and Pt. The major part of this thesis describes the synthesis and characterization, principally by ¹H, ³¹P{¹H} and ¹⁹⁵Pt{¹H} NMR spectroscopies, of: square-planar complexes of the type MX₂(PPh₃₋npyn)₂ (M = Pd, Pt; X = halides; n = 1, 2, 3); the binuclear species M₂X₂(µ-PPh₃₋npyn)₂ (head-to-tail, HT) and Pt₂I₂ (µ-PPh₃₋pyn)₂ (head-to-head, HH; n = 1,10a, n = 2, 10b and n = 3, 10c); and the Pt(PPh₂py)₃,27a, and Pt(Ppy₃)₃, 26c, complexes. The reactivities of the binuclear complexes toward acetylenes, and the Pt(0) species toward O₂, olefins, HCl and MeI, are also described. With use of PPhpy₂ within the binuclear phosphine-bridged species, the P atom incidentally becomes chiral. The diastereomers of 10b were isolated and characterized by ³¹P{¹H} NMR spectral data. All the isolated binuclear complexes react in CH₂Cl₂ with dimethylacetylene-dicarboxylate, DMAD, to form an A-frame insertion product. The HH or HT configuration of the precursor is maintained in every case except for 10b and 10c which form initially an HH-DMAD adduct that slowly isomerizes to the corresponding HT-DMAD adduct. Detailed ³¹P{¹H} NMR spectroscopic studies show that the presence of a properly positioned pyridyl group promotes the isomerization by forming a detectable chelated P-N intermediate, and that insertion of DMAD precedes chelation. The reactions of Pt₂l₂ (u-PPh₃₋npyn) ₂ (HH) (n = 1, 2, 3) with DMAD in CH₂CI₂ are kinetically first-order in both [Pt₂] and [DMAD] for the insertion step, and first-order in [Pt₂] and zero-order in [DMAD] for the isomerization step. The activation parameters for the insertion step are consistent with oxidative addition to a binuclear system. A proposed mechanism is fully supported by ³¹P{¹H) and ¹⁹⁵Pt{¹H] NMR spectral data. Complex 26c, reacts in CH₂CI₂ or CDCI₃ with limited oxygen to give Pt(Ppy₃)₃(O₂), which may contain an end-on superoxo structure as judged by an IR band at 1114 cm⁻¹. Complex 26c, under 1 atm O2, forms the 'expected' peroxo species Pt(Ppy₃)₂O₂. Complexes 26c and 27a, react with the olefins (maleic anhydride, acrylonitrile, methacrylonitrile and crotonitrile) to give the square-planar species Pt(PPh₃₋npyn) ₂(ɳ²-olefin). The square-planar geometry infers strong Π-back donation from metal to olefin, a state which is probably undesirable for the purpose of olefin activation toward hydration. Indeed, complex Pt(PPh₂py) ₂(Π²-maleic anhydride), 47a, shows no olefin hydration product when heated at 80°C in aqueous NaOH solution. Trans-Pt(H)Cl(PPh₂py) ₂, 50a, was prepared from 27a and gaseous HCl in THF; 50a in acetone-d6, reacts with acrylonitrile to give cis-PtCl(CH₂CH₂CN)(PPh₂py)₂, but in the presence of aqueous NaOH at 80°C, 50a was inactive for hydration of acrylonitrile to either β-cyanoethanol or acrylamide. / Science, Faculty of / Chemistry, Department of / Graduate

This describes a study of some unusual features of the hydrated electron, [symbol omitted] in particular the kinetics of its decay during a period of non-homogeneity lasting tens of nanoseconds, the formation and photodissociation of a hydrated dielectron species [symbol omitted], and the photoexcitation of [symbol omitted]. Nanosecond pulse radiolysis (p.r.) studies on the kinetic behaviour of [symbol omitted](> 10⁻⁴ M) in pure deaerated water revealed a complicated interplay of mechanisms for the first half life ∼110 nsec. This is partly attributable to an initial non-homogeneity in the distribution of reacting species within the system, because the spurs are essentially isolated for tens of nanoseconds. Calculations based on a qualitative model revealed that the times necessary for spur-overlap through diffusion (during which > 40% [symbol omitted] were lost to reaction) were in agreement with experimental observations. However the anomalous trends in κ, a rate parameter describing [formula omitted] within this period, led to the subsequent discovery of a process by which [symbol omitted] were formed after the electron pulse. The use of selective ion and radical scavengers strongly implied that the increase in [symbol omitted] occurred via another radiolytic product, XB. Three plausible mechanisms have been outlined in which XB is (e_ ) [formulae omitted]. XB undoubtedly affects the values of κ but it is not possible at this time to discard the notion of microscopic non-homogeneity within the spur itself as the trends in κ might suggest. Four conclusions are drawn; (i) in some p.r. studies we may not calculate meaningful second order rate constants with concentrations evaluated from optical density data, (ii) the "instantaneous" yield of [symbol omitted] seen through nsec p.r. is higher than that established through μsec p.r. or steady-state techniques because of the rapid initial loss of [symbol omitted] (iii) but the total [symbol omitted] yield will be less since the latter techniques cannot distinguish the source of [symbol omitted]. (iv) there is a critical need for a nanosecond p.r. yield of [symbol omitted] to establish the true primary yield, [symbol omitted]. Some microsecond flash photolysis (f.p.) experiments were performed on hydrogen saturated alkaline solutions. Hydrated electrons were produced following the ultra-violet photolysis of OH⁻ and reacted bimolecularly to give a species which on subsequent infra-red flash photolysis regenerated [symbol omitted]. This species is postulated to be a hydrated electron dimer [formula omitted] the spin state of which is unspecified The remaining purpose of this work was to photoexcite [symbol omitted]. The nature of the excited state of [symbol omitted] and the origin of the optical absorption band is still open to speculation although Jortner and others have performed calculations in which the transition at λmax is assigned to a 2p + 1s excitation. The photolysis of [symbol omitted] was attempted through both p.r. and f.p. techniques, neither of which yielded any conclusive information because of the presence of XB or [symbol omitted] in the system. / Science, Faculty of / Chemistry, Department of / Graduate

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