American cities have proliferated in the post-War era. More than 2,000 new cities were founded between 1950 and 2000. While the history of the local government boom has been documented, research into urban fragmentation has explored why there is no consolidation of metropolitan areas rather than exploring why Americans chose fragmentation initially. This dissertation proposes that individuals create new jurisdictions because individuals prefer to have governments which give them the services individuals desire, even if they could have similar (but not perfect) services cheaper in a larger jurisdiction. Individuals, however, must balance the benefit they get from better fitting cities with the price they must pay to live within the small cities. In the first part of the dissertation, I synthesize the literatures on urban governance and fragmentation with the literature on interest groups. This synthesis builds the argument for conceiving cities as interest groups and contributes a theory of urban behavior as the behavior of organized interest groups. I argue that urban fragmentation should exist anywhere there are urban areas –not only metropolises –and that fragmentation is produced by diversity in the population and constrained by the resources available for the formation of cities. In the second part of the dissertation, I analyze the fragmentation of both metropolitan and non-metropolitan areas to determine what drives fragmentation. I use Poisson regression on 2-period panel data from 1992 and 2002 collected from various public sources. I find that there are differences in the forms of fragmentation in the metropolis and the non-metropolis. In both types of urban settlement, fragmentation is driven by political and population diversity and available resources for forming cities. Legal authority and intergovernmental revenue are particularly important. Finally, I turn my attention to cities’ interactions with each other. I use a survey of Kentucky mayors, fielded with the Kentucky League of Cities, to determine why mayors of different cities to communicate with each other. Using specialized network methods I find that mayor-to-mayor contact is not based on goal and interest similarities as expected, but rather depends on sharing an organization which encourages communication –an Area Development District.

The aim of this work was to successfully prepare polymers of N-(2-hydroxypropyl)methacrylamide, (PHPMA) using controlled/"living" free-radical polymerisation technique. For this purpose, atom transfer radical polymerisation (ATRP) and reversible addition-fragmentation (chain) transfer (RAFT) polymerisation were used in preparation of a number of base polymers with the intention of quantitatively converting them into PHPMA. Both methods were applied under varying polymerisation conditions, and the kinetics of the systems investigated. Various rate constants were measured, while computer modelling of the experimental data allowed estimation of other kinetic parameters of interest. Investigations into solvent and ligand effects on the kinetics of ATRP of the activated ester methacryloyloxy succinimide (MAOS) and one of the archetypal methacrylate monomers, methyl methacrylate (MMA) were carried out. The method of RAFT was also employed in polymerisation of MAOS and a number of other monomers in the hope of finding the best synthetic precursor of PHPMA. Polymers of methacryloyl chloride (MAC) and p-nitrophenyl methacrylate (NPMA) were prepared, as well as the polymers of HPMA itself and N-isopropyl methacrylamide. Polymerisation of MMA by RAFT was also attempted in view of adding to current knowledge on the monomer's behaviour and the kinetic characteristics of its RAFT polymerisation. Preparation of PHPMA from PMAOS, PMAC and PNPMA was attempted. Successful preparation of PHPMA from the polymer of the acid chloride was achieved under mild reaction conditions, while displacement of N-hydroxysuccinimide groups of PMAOS resulted in unexpected modification of the polymer under the conditions used. Conversion of PNPMA into PHPMA was not achieved. At this stage these results suggest inadequacy of both PMAOS and PNPMA as reactive polymeric precursors.

Presented in this dissertation are FT-ICR H/D exchange and fragmentation studies of protonated peptides for the purpose of better understanding gas phase conformation and protonation motifs, and their affect on fragmentation patterns. In addition, a new ion activation method is developed to enhance the abundance of higher energy fragmentation pathways, thereby providing additional structural and/or mechanistic information.Studies to probe the relay mechanism of H/D exchange in small, model peptides found that residue position, proline configuration, and availability of the termini have a measurable effect on the H/D exchange behavior reflective of different conformation / protonation motifs.Charge remote cleavage C-terminal to aspartic acid was studied with the fixed charge derivative tris(2,4,6-trimethoxyphenyl) phosphonium (tTMP-P+). Ab initio calculations demonstrate that tTMP-P+ cannot activate the proposed aspartic acid nucleophile, the acidic side chain hydrogen initiates cleavage. Despite the absence of an ionizing proton, the derivatized peptide P+LDIFSDF (where P+ = tTMP-P+) exchanges three acidic hydrogens for deuterium. This supports the proposed aspartic acid cleavage mechanism that occurs without the direct involvement of an ionizing proton because acidic protons are able to participate in H/D exchange in the absence of an added proton. In addition, H/D exchange of P+LDIFSDF analogues provides insight into the sites and mechanisms of H/D exchange.H/D exchange to separate distinct peptide populations with differing rates and their subsequent fragmentation demonstrate that conformation / protonation motif affects the fragmentation spectrum observed. Studies of [P+LDIFSDF + H]2+, [RPPGFSPFR + 2H]2+ (bradykinin), and [RVYIFPF + 2H]2+ show that at least two distinct structures exist with different rates of H/D exchange and different fragmentation patterns. The overall MS/MS spectrum is a linear combination of all conformations and protonation motifs. In addition, fragmentation of labeled populations suggests that complementary bn+ / ym-n+ ion pairs are being formed from doubly-charged precursor by the same mechanism.SORI-RE CID is a new FT-ICR ion activation method based on the combination of sustained off-resonance irradiation (SORI) and on-resonant excitation (RE) with the purpose of enhancing higher energy fragmentation while maintaining low energy processes. The experiments presented serve to illustrate the usefulness of SORI-RE in diverse cases.

Mining of datasets obtained from proteomics experiments was performed to investigate the dissociation pathways of protonated peptides activated in the gas phase under low energy collision-induced dissociation (CID). Intensity patterns in ion trap tandem mass spectra were exploited and different statistical approaches were employed to elucidate the dissociation mechanisms.Chapter 2 describes a study of 506 doubly-protonated tryptic peptides that shows the presence of an internal basic residue can increase the preferential fragmentation C-terminal to aspartic acid (Asp-Xxx) significantly. The degree of enhancement varies with the identity of the basic residues. The result corroborates a previously published mechanism based on studies from model peptides, and was incorporated into an existing peptide sequencing algorithm. A preliminary test on a separate dataset of 119 spectra shows that implementing rules to predict enhanced cleavages at Asp-Xxx improves the ability of the algorithm to identify the correct sequence from a list of candidates.Chapters 3-4 describe much more elaborate analyses on 28,330 peptides of different sequences and charge states. Extensive sorting based on prior knowledge was first performed to probe the correlation of fragmentation patterns with structural features. Pair-wise fragmentation maps reveal that the difference in basicity between Arg and Lys results in different dissociation patterns among singly-protonated tryptic peptides. While one dominant protonation form (proton localized) exists for Arg-ending peptides, a heterogeneous population of two or more protonated forms (proton partially-mobile) exist for Lys-ending peptides. Asp/Glu-Xxx dominates spectra from peptides that have a localized proton(s) and Xxx-Pro dominates those that have a mobile or partially mobile proton(s). When Pro is absent from peptides that have a mobile or partially mobile proton(s), cleavage at each peptide bond becomes more prominent. A fundamental dependence of gas phase peptide fragmentation on conformational constraints was found.A knowledge mining scheme was proposed in Chapter 5 to bypass the prior knowledge constraints and cluster the dissociation behaviors of 28,330 peptides into four distinct categories. The most influential factors in the fragmentation process are: the mobility of the proton(s), the presence and the location of Pro and Arg. Structural motifs responsible for each dissociation behavior are also elucidated.

Exurbanization is occurring where large tracts of land are being sold to developers. Typically these are ranches that are then divided into 40-acre parcels and sold by developers, avoiding subdivision regulations requiring paved streets, utilities and other amenities. The result is an unplanned subdivision with no infrastructure, and tax revenues that cannot offset the cost of providing it. Interviews with professional planners suggested there may be independent variables capable of predicting the amount of human disturbance in an exurban area: parcel size, full cash value, tenure, distance to paved roads, site-built housing, mobile homes, and presence of biological or riparian areas. A total of 7,465 acres (3,022 ha) of parcel disturbance were digitized in exurban Arivaca, acreage values were converted to a binary dependent variable and used in logistic regression analysis to test independent variables' predictive value. Four were statistically significant: parcel size, full cash value, mobile homes and site-built housing. Landscape fragmentation was also tested using the presence of the variable scoring highest in probability - site-built housing. Zones of influence with a negative ecological influence surrounded the homes - up to 5,055 acres (2,046 ha) were impacted. Interviews with an exemplary sample of residents regarding their land use ethic found all had very strong opinions on how their properties should be treated as well as undesirable land uses such as overgrazing, over-use of groundwater for short-term economic gain and use of off-road vehicles. An explanation of the small sample size of both planners and residents is warranted. Planners were limited to those working in Pima County government who had professional experience with the study area of Arivaca and were familiar with its particular situation. The number of Arivaca residents interviewed was intended to discern an exemplary group's opinions based on how large a parcel they owned, the various sizes being a typical cross-section of acreage in the study area. What these findings illustrate is (1) the difficulty of predicting human-induced disturbance, (2) land fragmentation is more than the actual areas of physical disturbance and (3) some residents are aware of impacts related to their activities, mitigating damage wherever possible.

The phylo-geography and population genetics of three Crotalus species in Southern Arizona (C. atrox, C. cerastes, and C. scutulatus) were examined using mitochondrial DNA genes and nuclear microsatellite DNA markers. My focus was twofold: (1) the phylo-geography and population structure in Southern Arizona and (2) possible genetic signatures of population fragmentation by linear barriers on rattlesnakes populations at Picacho Peak. My results show genetic signatures of geneflow restrictions in one species (C. atrox) which coincide with Interstate 10. I did not observe similar genetic effects in C. cerastes or scutulatus, possibly caused by smaller sample sizes and marker numbers. I found limited phylo-geographic and population genetic structure for all three species in Southern Arizona indicating large interconnected populations. This study provides wildlife management with a powerful genetic toolset and provides important baseline data for future assessment and monitoring efforts of important predators and their populations in the Sonoran desert habitat.

Effective field theories can be used to describe measurements at e⁺e⁻ colliders over a wide kinematic range while allowing reliable error predictions and systematic extensions. We show this in two physical situations. First, we give a factorization formula for the e⁺e⁻ thrust distribution dσ/dτ with thrust T and τ = 1 − T based on soft collinear effective theory. The result is applicable for all τ, i.e. in the peak, tail, and far-tail regions. We present a global analysis of all available thrust distribution data measured at center-of-mass energies Q = 35 to 207 GeV in the tail region, where a two parameter fit to the strong coupling constant α(s)(m(Z)) and the leading power correction parameter Ω₁ suffices. We find α(s)(m(Z)) = 0.1135 ± (0.0002)expt ± (0.0005)hadr ± (0.0009)pert, with x²/dof = 0.91, where the displayed 1-sigma errors are the total experimental error, the hadronization uncertainty, and the perturbative theory uncertainty, respectively. In addition, we consider cumulants of the thrust distribution using predictions of the full spectrum for thrust. From a global fit to the first thrust moment we extract α(s)(m(Z)) and Ω₁. We obtain α(s)(m(Z)) = 0.1140 ± (0.0004)exp ± (0.0013)hadr ± (0.0007)pert which is compatible with the value from our tail region fit. The n-th thrust cumulants for n ≥ 2 are completely insensitive to Ω₁, and therefore a good instrument for extracting information on higher order power corrections, Ω'(n)/Qⁿ, from moment data. We find (˜Ω₂)^1/2 = 0.74 ± (0.11)exp ± (0.09)pert GeV. Second, we study the differential cross section dσ/dx of e⁺e⁻-collisions producing a heavy hadron with energy fraction x of the beam energy in the center-of-mass frame. Using a sequence of effective field theories we give a definition of the heavy quark fragmentation function in the endpoint region x → 1. From the perspective of our effective field theory approach we revisit the heavy quark fragmentation function away from the endpoint and outline how to develop a description of the heavy quark fragmentation function valid for all x. Our analysis is focused on Z-boson decays producing one B-meson. Finally, we will give a short outlook of how we want to apply our approach to determine the leading nonperturbative power corrections of the b-quark fragmentation function from LEP experiments.

The research presented in this dissertation consists of four topics. The first of these topics is an experimental study of rock fracturing due to rapid thermal cooling, and the other three topics are related to mine-to-optimization. This includes the development and testing of a site-specific model for blast fragmentation, the development of a technique for utilizing digital image processing and ground-based LIDAR for rock mass characterization, and an experimental study of the effects of ore blending on mineral recovery. All four topics are related through the subject of rock fracturing and rock fragmentation. The results from this research are important and can be used to improve engineering design associated with rock excavation and rock fragmentation. First of all, a successful set of laboratory experiments and 3D numerical modeling was conducted, looking at the effects of rapid thermal cooling on rock mechanical properties. The results gave the unexpected finding that depending on the rock type and the thermal conditions, rapid cooling can result in either overall crack growth or crack closing. Secondly, a site-specific model for predicting blast fragmentation was developed and tested at an open-pit copper mine in Arizona. The results provide a practical technique for developing a calibrated blasting model using digital images and digital image processing software to estimate in-situ block size, and a calibrated Schmidt hammer to estimate intact tensile strength. Thirdly, a new technique was developed to conduct cell mapping in open-pit mines using the new technologies of digital image processing and ground-based LIDAR. The results show that the use of these new technologies provide an increased accuracy and the ability for more sophisticated slope stability analyses with no increase in field time only a moderate increase in data processing time. Finally, a successful set of laboratory experiments was conducted looking at the effects of ore blending and grinding times on mineral recovery from a set of six ore from a copper mine in Arizona. The results gave the unexpected finding that for a fixed grinding time, the mineral recovery of the blended ores exceeded the average of the individual recoveries of the same ores unblended.

This dissertation examines the idea of constitutionalisation of international law in light of concerns of fragmentation. It focuses on the dynamic of fragmentation in the international legal system. It shows that arguments about constitutionalism do not represent a remedy to the phenomenon of fragmentation. Consequently, the dissertation advances arguments of integrity of international law. Further, the dissertation examines new developments in constitutionalisation practices that support a normative, teleological approach to constitutionalisation in the international legal system. The dissertation offers insights on both the autonomy of the concept of international constitutionalism and the idea of fragmentation as a universally recognised characteristic of modern international law. It offers recommendations on how to address charges of fragmentation in international law in light of the dominant conception of modern international law.

Dynamic memory management required by allocation-intensive (i.e., Object Oriented and linked data structured) applications has led to a large number of research trends. Memory performance due to the cache misses in these applications continues to lag in terms of execution cycles as ever increasing CPU-Memory speed gap continues to grow. Sophisticated prefetcing techniques, data relocations, and multithreaded architectures have tried to address memory latency. These techniques are not completely successful since they require either extra hardware/software in the system or special properties in the applications. Software needed for prefetching and data relocation strategies, aimed to improve cache performance, pollutes the cache so that the technique itself becomes counter-productive. On the other hand, extra hardware complexity needed in multithreaded architectures decelerates CPU's clock, since "Simpler is Faster." This dissertation, directed to seek the cause of poor locality behavior of allocation--intensive applications, studies allocators and their impact on the cache performance of these applications. Our study concludes that service functions, in general, and memory management functions, in particular, entangle with application's code and become the major cause of cache pollution. In this dissertation, we present a novel technique that transfers the allocation and de-allocation functions entirely to a separate processor residing in chip with DRAM (Intelligent Memory Manager). Our empirical results show that, on average, 60% of the cache misses caused by allocation and de-allocation service functions are eliminated using our technique.