Industrialization and urbanization have brought about localized demand and regional competition for water resources in parts of the eastern United States. Thus, some states have faced critical decisions concerning how to best manage their available water supplies. As fundamental public values have changed over time, public opinion concerning the way in which water supplies should be managed has changed as well, especially in recent years. Consequently, many eastern states have restructured the institutional mechanisms governing water supply management to reflect those changing values and opinions. Massachusetts is a prime example of a state where changes in publicly held values have caused a thorough restructuring of the institutional mechanisms governing water supply management. A case study examines developments that led to the current institutional mechanisms in Massachusetts. Special attention is given to the issues and values that shaped the State’s water supply policy, legislation, and regulatory programs. / Master of Science

Isoquinoline alkaloids have long been known for their biological activity. Many of the isoquinoline alkaloids have been made as racemic mixtures. The present investigation was aimed at developing methodology for the asymmetric synthesis of some isoquinoline alkaloids through Reissert compound chemistry. The stereochemistry of lepidine and isoquinoline Reissert compounds has not been reported. To better understand the stereochemistry of these compounds, selected Reissert compounds were synthesized and subsequently studied by proton NMR. The two types of isomerism studied were amide isomerism and aryl / carbonyl rotation. In at least some cases, both amide isomers and restricted aryl / carbonyl rotamers were observed. For other cases only the restricted aryl / carbonyl rotamers were observed. The presence of ortho substituents on the aroyl moiety was found to greatly increase the chance amide isomerism on the NMR time scale. (-)-Menthy] chloroformate, (+)-menthy] chloroformate, and (-)-menthoxyacety] chloride have been utilized as chiral acyl auxiliaries to induce the stereochemistry at C,, resulting in diastereomeric isoquinoline Reissert compounds. By reaction of a mixture of the diastereomeric Reissert anions of 2-(1)-(mentho1 ,x2-ydichyadrroisboqouinnayldolni)tr-il e (110) with pivaldehyde we were able to form the resulting diastereomeric carbonates of 1-isoquinolyl-t-butyl carbinyl menthyl carbonate (120) in a 77:23 ratio by NMR [82 : 18 ratio by HPLC). After obtaining the major diastereomer of the carbonate in pure form, hydrolysis yielded the enantiomerically pure (S)-(-)-1-isoquinoy] t-buty] carbinol (121). The proton NMR spectra of the diastereomeric Reissert compounds led to elucidation of the stereochemistry. The diastereomeric ratios were determined for both 110 and 2-(1)-methoxyacetyl- 1 ,2-dihydroisoquinaldonitrile (125). Amide isomerism was observable in the case of 110 but not in the case of 125. Aromatic solvent induced shift (ASIS) studies of the compound 125 showed the s-trans amide to be predominant. The reaction of the diastereomeric Reissert anion of 110 with CS, and partial conversion with pivaldehyde allowed us to determine that the Reissert anion equilibrates. Reaction of the anion of 125 with pivaldehyde gave 1-isoquinolyl t-butyl carbinyl menthyl acetate (127) in quantitative yield and 0 % de. However, the diastereomers are easily separated using simple silica gel column chromatography. / Master of Science

In this paper we investigate several aspects of computing control system radii for finite element approximations of control systems governed by partial differential equations. Finite element approximations of the heat equation (parabolic), the wave equation (hyperbolic) and the equations of thermoelasticity (mixed) are used as test cases. Balanced realizations, reduced order models and other transformed models are also studied. / Master of Science

A preliminary fireplace design to reduce particulate, carbon monoxide, and unburned hydrocarbon emissions has been fabricated and tested. Using a damper and glass pane, the design solves the problem of uncontrolled air entering the firebox. The pane reduces the inlet area and directs the flow of air towards the charcoal bed. The damper aids in slowing down the inlet air flow and decreasing the amount of excess air in the combustion region. Limiting the supply of inlet air produces a slower flow through the combustion zone resulting in higher temperatures and longer residence times. The aesthetic appearance of the fire has nonetheless been maintained. The preliminary design was tested using two methods which varied in fuel type, test length, and fuel reloading. Each method followed dilution tunnel particulate sampling EPA method 5G. Carbon monoxide emissions were continuously monitored with an infrared gas analyzer. The average preliminary design particulate emission factor was reduced from baseline testing by 84 percent with method 1 and 86 percent with method 2 testing. The average preliminary design carbon monoxide emission factors for method 1 and 2 testing, were decreased by 57 and 59 percent respectively. A baseline test was defined as the operation of the fireplace as it would arrive from the factory. Safety issues were not addressed in this thesis. Improvements in safety will likely be required and may cause an increase in emissions from the preliminary design. A two dimensional variable property cartesian coordinate computer model has been written which determines the temperature and velocity distributions in the firebox. Properties of air were used to represent the fluid. The model determined stack flow rates and temperatures in the flue for the preliminary design. These values were then compared to experimental data. Four calculations were run under various conditions of inlet air, heat source, and baffie temperatures. The heat source temperature ranged from 1000 to 1300 K. The temperatures predicted by the computer model were within 1 to 28 percent of measured values. Stack flow rates determined by the model were 66 to 78 percent less than measured. The model also predicted a recirculation area. / Master of Science

Rural development in Africa’s arid rangelands has been exceptionally difficult. Conventional approaches to range and livestock development have consistently failed to meet desired goals, including increased productivity and improved living standards for pastoralists. Perspectives on constraints to successful development can be divided into two major viewpoints. The dominant view, which has guided these failed attempts, blames pastoralist for traditionalism and clinging to economically irrational and environmentally destructive herding strategies. From this conventional perspective, project planners have sought radical changes from current indigenous practice towards "modern" beef ranching and sedentary agriculture. The other major perspective views pastoral systems as basically economically and environmentally sound, though they are increasingly becoming less so due largely to pressures for such modernization. From this view, development projects should instead include the participation of herder populations and be based upon indigenous livestock and range management practices. Thus far there have been few projects which encourage herders to build upon elements of traditional pastoralism, though such an approach is seen as having a better chance for success than the conventional approach. Several examples of failed projects are presented. Two of these failed partly because they denied genuine herder participation and were based on an inadequate understanding of indigenous pastoral systems. A third project faltered due to the unwillingness of the government in question to follow through on its appropriate, herder-oriented design. Two successful, NGO-sponsored projects are offered as evidence that the participatory/indigenous knowledge approach can serve as a viable strategy in donor-sponsored projects. / Master of Science

When oven drying Douglas fir to determine moisture content, volatile organics evolving from the wood cause error in the moisture measurement. An apparatus was constructed to measure the carbon contained in the evolved organics and to measure the chemical energy content of the organics which evolved at temperatures up to 103°C. Data were collected and used to estimate errors in moisture content measurement. The data were also used to provide insight into differences that exist in fuelwood and how these differences might affect wood heater test results. For the wood examined, the lower heating value of the evolved organics averaged 283 MJ/kmol carbon. This value indicates that the volatile material had a high oxygen content. Using the average heating value, the mass fraction of oxygen contained in the evolved organics was estimated to be near 0.47. Using the estimated oxygen mass fraction combined with the carbon loss data, errors in moisture content measurement resulting from volatile loss were estimated to range from 0.1% to 2.0% of measured values. The larger of these errors would cause less than a 0.1% error (percent of measured value) in the calculated efficiency of a typical woodstove. The amount of highly volatile organics was found to vary greatly between different pieces of Douglas fir. For the wood tested, carbon loss ranged from 0.02% to 0.35% of the carbon initially contained in the wood. These differences in fuelwood volatility may affect wood heater performance and possibly cause some of the scatter observed in wood heater test data. Conventional proximate analyses were performed on two wood samples, one exhibiting high volatility at 103°C, the other exhibiting low volatility at 103°C. These proximate analyses did not show significant differences between the two samples. Bomb calorimetry was used to measure the heating value of the Douglas fir samples both before and after oven drying. The bomb calorimetry, however, proved to not have the sensitivity to accurately measure the small differences in heating value caused by volatile emissions during oven drying. / Master of Science

In this study, a slider-crank mechanism driven by an induction motor was studied for the purpose of deriving simulation data for the identification of the important operating parameters in the machine. First, a modification of a motor simulation program emphasizing losses is presented. The program is used to generate dynamic motor data for an analysis of a reciprocating mechanism. By analyzing the dynamic motor data, the operating parameters in the mechanism can be identified. The purpose of the reciprocating mechanism analysis was to define an algorithm for the identification of the parameters of mass, damping, spring stiffness, and preload force of the mechanism. The time domain data (e.g. the motor net input torque, the mechanism load torque, the angular velocity, and angular acceleration, etc.) of the mechanism from a simulation can be related through the use of Newton’s dynamic motion equation. By transforming the time domain data into frequency domain spectra and using a least squares algorithm, the mechanism parameters can be estimated. The results show that the calculated mass and stiffness can be accurately solved to within 1%. While the damping and preload force may be solved within 2% and 4% respectively. The results also confirm that the separation of the load torque signal can be used in the solution technique. That is, the load torque signal of the mechanism is an arithmetic sum of the contribution of mass, damping, spring stiffness, and preload force. The identification method of the above parameters could lead to an advancement in machine diagnosis in the future, since the operating parameters in a reciprocating machine are greatly related to an impending machine failure. / Master of Science

The importance of taxol as an anticancer drug lies not only in its activity in antitumor assays but also in its unique mechanism of action. Unfortunately, taxol is not water-soluble and therefore must be given in conjunction with emulsifying agents. Modifications of taxol were carried out in order to prepare water-soluble taxol derivatives. The C-2’ hydroxyl group of taxol was substituted with various groups to increase water solubility. The synthesized taxol derivatives, 2’-((3-sulfo-1-oxopropyl)oxy)taxol sodium salt, 2’-((4-((2-sulfoethyl)amino)-1,4-dioxobutyl)oxy)taxol sodium salt, and 2’-((4-((3-sulfopropyl)amino)-1,4-dioxobutyl)oxy)taxol sodium salt were more water-soluble than taxol. The synthetic pathways to these compounds are compared and discussed. / Master of Science

The cyclic allylamine I-methyl-4-phenyl-l ,2,3,6-tetrahydropyridine (MPTP) is a potent and specific neurotoxin that causes a parkinsonian like syndrome in humans and subhuman primates. Research has revealed that MPTP is bioactivated in a reaction catalyzed by flavin containing monoamine oxidase B (MAO B) to yield the dihydropyridinium species MPDP+ which undergoes further oxidation to the ultimate toxin, the I-methyl-4-phenylpyridinium species MPP+. The research summarized in this thesis describes a potential model reaction for the MAO catalyzed conversion of MPTP to MPDP+ and the synthesis and biological evaluation of MPTP analogs bearing a heteroatom at C-4 of the tetrahydropyridine ring. The model for the enzyme catalyzed oxidation of MPTP to MPDP+ is based on the anhydride mediated conversion of MPTP Noxide to MPDP+. This reaction pathway was visualized to mimic a reaction sequence in which an FAD-MPTP adduct cleaves to yield MPDP+ and FADH2. Attempts were made to assess the isotope effect associated with this reaction and to compare that value with the corresponding values for the MAO-B catalyzed reaction [D(V max/Km) = 7-9], the cytochrome P-450 catalyzed reaction [D(V max/Km) = 1.04] and the electrochemical oxidation (D k = 1.35). Unfortunately experimental difficulties prevented a complete analysis of the problem. Specialized equipment will be required to obtain accurate isotope effect measurements. The second study concerns the preparation of the MPTP analogs 4-chloro-, 4-cyano-, and 4-( 4-fluorophenoxy)-1,2,3,6-tetrahydropyridine as potential MAO B substrates that could generate neurotoxic pyridinium metabolites. Results obtained with MAO B have revealed that the dihydropyridinium intermediate formed from 4-( 4-fluorophenoxy)-1 ,2,3, 6-tetrahydropyridine undergoes spontaneous hydrolysis to generate 4-fluorophenol and 1- methyl-4-pyridone. The significance of this finding with respect to neurotoxic mechanisms and design are discussed. / Master of Science

This study investigated the effects of dietary tyrosine or tryptophan supplementation on immunity and brain neurotransmitter levels after antigen challenge. Chickens were given 0.1%, 0.5% or 1% supplemental dietary L-tyrosine or L-tryptophan prior to the injection of sheep red blood cells (SRBC). The 0.1% tyrosine supplementation increased primary IgM and secondary IgG titers at some time periods in Leghorns and decreased secondary IgM titers at Day 5 in broilers, while 0.1% tryptophan addition decreased Leghorn secondary IgM titers and increased secondary IgG titers at Day 9 and broiler secondary IgM titers at Day 9. The phytohemagglutinin (PHA) wattle response in Leghorns and broilers and resistance of Leghorns to E. coli challenge were not affected with the 0.1% supplemental level. With higher levels, 0.5% tyrosine supplementation increased Leghorn primary IgM titers at Day 11. In broilers, 0.5 and 1% tryptophan supplementation decreased secondary total antibody titers at Day 2, while the secondary IgM titers at Day 6 with the 0.5% tyrosine supplementation were higher than those with 1% tyrosine or tryptophan supplementation. The 0.5% or 1% tryptophan supplementation also lowered stressed broiler primary IgM titers at Day 3. After pooling the titer results within two dietary supplemental levels (0.5% and 1%) of a given amino acid, the tyrosine treatment appeared to suppress antibody response in unstressed broilers, but not stressed ones, while tryptophan displayed a suppressive trend in broilers under both situations. Supplementation with 0.5% or 1% dietary tyrosine did not alter brain catecholamine or serotonin (5-HT) levels in Leghorns. In contrast, 0.5% or 1% dietary tryptophan supplementation generally increased 5-HT, and its metabolite 5-HIIAA, and S-HIAA/5-HT ratios in the diencephalon, telecephalon, and brain stem in Leghorns. Tryptophan supplementation caused a dose-response increase in S-IIT and S-IHIAA levels of the brain stem. The results demonstrated that 0.5-1% dietary tryptophan supplementation suppressed broiler, but not Leghorn, antibody response, and the mechanism was probably via enhancing 5-IIT synthesis and release. The results also suggested that lower levels (0.1-0.5%) of dietary tyrosine supplementation may enhance immune response in Leghorns and stressed broilers, but ingesting large quantity of tyrosine, occurred in broilers, suppresses the response. / Master of Science