<p>The study introduces and puts forward Sector Policing as a model to expand community Policing and to broaden the scope of crime prevention. It also demonstrates how Sector Policing can be utilised to decentralise policing and deepen community participation.</p>

Thèse numérisée par la Division de la gestion de documents et des archives de l'Université de Montréal

Divalent thulium has been doped into CsCaI₃, CsCaBr₃, CsCaCl₃ and RbCaI₃- a series of AMX₃ salts. Using previously published optical spectra, a series of parameterised energy level calculations have been performed. The calculated energy levels, optimised crystal field parameters and simulated optical absorption spectra are presented. Theoretical predictions yield excellent approximation to the experimental data. Temperature dependent fluorescent lifetimes from the (³F₄,t₂g) and (³H₆,t₂g) excited (emitting) states have been measured using a pulsed dye laser. For CsCaBr₃ and RbCaI₃ doped with Tm²⁺, visible emission for the (³F₄,t₂g) state yields 10 K and 28 K lifetimes of 1.7 μs and 0.40 μs respectively. In both cases no emission is observed at room temperature. Considering direct multiphonon relaxation to the lower lying (³H₆,t₂g) levels, a simple energy gap law well accounts for the measured data with effective phonon energies in the range 100-200 cm⁻¹ - consistent with the phonon density of states in these low phonon energy hosts. Monitoring infrared emission from the (³H₆,t₂g) states, 14 K and 10 K lifetimes of 301 μs and 250 μs are found for CsCaBr₃ and CsCaCl₃ respectively. For CsCaBr₃ this value reduces to 270 μs at 200 K and is not quenched until 300 K, whilst for CsCaCl₃ emission is quenched by 170 K. This temperature dependent behavior is interpreted in terms of internal conversion via configurational crossing between the excited and ground state potential energy surfaces. Fitting the fluorescence lifetime data to a modified Mott equation, it is inferred that the potential barrier for non-radiative relaxation is five times larger in CsCaBr₃ compared to CsCaCl₃. This explains the fact that emission is still observable in the bromide host at room temperature.

The spectroscopy of wide-bandgap fluoride materials doped with divalent ytterbium is presented. The structure of impurity-trapped excitons is explored, vacuum ultraviolet excitation is used to investigate the transfer processes between excitations, and the effect of confinement on self-trapped excitons is studied. The excited-state structure of impurity-trapped excitons is measured in the multisite system NaMgF₃:Yb²⁺. A two-colour ultraviolet-infrared pulsed photoluminescence enhancement technique is employed to probe the interlevel transitions and dynamics of impurity-trapped excitons in doped insulating phosphor materials. NaMgF₃:Yb²⁺ exhibits emission from two charge-compensation centres with peaks at 22 300 cm⁻¹ (448 nm) and 24 000 cm⁻¹ (417 nm). The observed photoluminescence enhancement is caused by a combination of intra-excitonic excitation and electron trap liberation. The electron traps are inferred to have a depth of approximately 800 cm⁻¹. Time-resolved VUV spectroscopic studies of emission and excitation spectra of CaF₂:Yb, NaMgF₃Yb and MgF₂:Yb are presented to investigate excitation and relaxation mechanisms of both impurity-trapped excitons and intrinsic excitons in each fluoride host. Host-to-impurity energy transfer mechanisms leading to formation of impurity-trapped excitons are discussed. The 4f¹⁴ → 4f¹³5d CaF₂:Yb²⁺ absorption bands are successfully modeled with a semi-empirical effective Hamiltonian calculation for NaMgF₃:Yb²⁺ and MgF₂:Yb²⁺. The excitation and emission spectra of all studied materials are compared. Results on VUV spectroscopy of 3 and 5 monolayer CdF₂–CaF₂ superlattices show the change in optical behaviour of the self-trapped exciton in CdF₂ when it is confined and give an indication of the radius of the exciton. The decay of the emission is modeled with three components, corresponding to three self-trapped exciton states. Results on the VUV spectroscopy of CdF₂–CaF₂ superlattices show that the confinement effect seems to equally influence the energy of excitonic and bandgap absorption in 3 and 5 monolayer superlattices. At the same time, as the self-trapped exciton is more confined, the emission is blue-shifted by 1600 cm⁻¹ indicating that the effective excitonic radius is about three monolayers.

Lanthanide (III) complexes are used extensively in solar conversion devices, such as Luminescent Solar Concentrators (LSCs) and Luminescent Down-Shifting (LDS) for their peculiar characteristics of narrow band emission, avoidance of re-absorption losses due to large Stokes shift and possibility of high photoluminescence quantum yield (PLQY). The study has looked into the synthesis of Ln (III) complexes of the general formula: [Ln(hfac)3DPEPO], where DPEPO = bis(2-(diphenylphosphino)phenyl)ether oxide, and hfac = hexafluoroacetylacetonate. The work presented in this thesis focuses on the synthesis, and subsequent photophysical characterisation of these Ln(III) complexes, plus characterisation and spectroscopic study of [Tb(pobz)3(hacim)2], (where Hpobz = phenoxybenzoic acid, and Hacim = acetylacetone imine), yielding results that open new design of functional Ln(III) systems. Spectroscopic study of Chromium dioxalate and analogous compounds has revealed that with the appropriate design, Cr(III)Ln(III) energy transfer can be achieved, while study of polyaromatic hydrocarbons (PAH) such as coronene, enable to explore a ligand with better absorption in the whole UV region. These results open attractive perspectives for light-conversion systems, such as LSC devices.

A variety of highly hydrated ions were generated and studied using electrospray ionization mass spectrometry (ESI-MS) including proton, a series of triply charged lanthanide ions, the doubly charged lead ion and various methylated guanidinium ions. In each case large hydrated water clusters were mass selected and fragmented through collision induced dissociation (CID) to investigate their properties. The fragmentation of protonated water clusters highlighted the stability of the “magic” water cluster [H(H2O)21]+. Typically unstable triply charge lanthanide water clusters and the previously unobserved doubly charged lead water clusters were generated. Fragmentation studies indicated that both the charge density and the geometry of the clusters affect their stability. The charge reduction of triply charged lanthanide clusters led to the direct observation of ion evaporation. Finally, the dehydration of various methylated guanidinium ions indicated a structural basis for differences in their ability to hydrogen bond.

Pharmaceutical and personal care products (PPCPs) triclosan and nonylphenol, were investigated throughout wastewater treatment in a publicly owned treatment works (POTW). Both compounds react quickly upon chlorination under laboratory conditions, transforming into mono and dichlorinated species. A novel quantitative analytical method employing mass spectrometry was demonstrated on Delaware POTW wastewater samples. Specific transformation products were not detected and the concentration of precursor analytes was not found to be statistically different after treatment. Under tertiary chlorination conditions, transformation products are not produced. ESI-MS was used to explore triply charged, highly hydrated lanthanide ions and charge reduction was directly observed in the MS collision cell. This process proceeded via proton transfer, proved by a strong correlation between the minimum number of water molecules required to stabilize the Ln3+ and the first hydrolysis constant (R2=0.92). The effect of different solvents on the surface activity of ions under electrospray ionization (ESI) was investigated using dilute ionic liquids and the relative surface activity of a given pair of ions could be reversed by moving from a relatively polar solvent to a relatively non-polar one. / Graduate

A new class of polymer coated lanthanide fluoride nanoparticle aggregates (NPAs) was developed as potential MRI contrast agents. The NPA synthesis has been perfected to control the size distribution and optimize relaxivities. Polyacrylic acid was used as a stabilizing polymer, and was conjugated to folic acid to improve targeting to SK-BR-3 breast cancer cells. Terbium was incorporated in the synthesis to study the passive and active targeting properties of NPAs. Through a series of microscopy experiments, a significant difference in uptake between NPAs with and without targeting moieties occurs after 48 hours of incubation. The relaxivity of the optimized nanoparticles was measured to be 56 s-1(mg/ml)-1 using a 1.5 T scanner, which may be compared to that of the commercially available Gd3+-DTPA [R1 = 7 s-1(mg/ml)-1]. Abdominal perfusion studies in rats also demonstrated that the NPAs provide better contrast of the vasculature than Gd3+-DTPA does at the same mass concentration.

Dreiwertige Actinide (An(III)) und Lanthanide (Ln(III)) stellen im Falle ihrer Inkorporation eine ernste Gefahr für die Gesundheit des Menschen dar. An(III) sind künstlich erzeugte, stark radioaktive Elemente, die insbesondere bei der nuklearen Energiegewinnung in Kernkraftwerken entstehen. Durch Störfälle oder nicht fachgerechte Lagerung radioaktiven Abfalls können sie in die Umwelt und die Nahrungskette des Menschen gelangen. Ln(III) sind hingegen nicht radioaktive Elemente, die natürlicherweise vorkommen und für vielfältige Anwendungen in Technik und Medizin abgebaut werden. Folglich kann der Mensch sowohl mit An(III) als auch Ln(III) in Kontakt kommen bzw. sie inkorporieren. Es ist daher von enormer Wichtigkeit, das Verhalten dieser Elemente im menschlichen Körper aufzuklären. Während makroskopische Vorgänge wie Verteilung, Anreicherung und Ausscheidung bereits sehr gut untersucht sind, ist das Wissen hinsichtlich der chemischen Bindungsform (Speziation) von An(III) und Ln(III) in Körperflüssigkeiten noch sehr lückenhaft. In der vorliegenden Arbeit wurde daher erstmals die chemische Bindungsform von Cm(III) und Eu(III) in natürlichem menschlichem Urin (in vitro) spektroskopisch aufgeklärt und die gebildeten Komplexe identifiziert. Hierzu wurden auch grundlegende Untersuchungen zur Komplexierung von Cm(III) und Eu(III) in synthetischem Modellurin sowie mit den urinrelevanten organischen Modellliganden Harnstoff, Alanin, Phenylalanin, Threonin und Citrat durchgeführt und die noch unbekannten Komplexbildungskonstanten bestimmt. Abschließend wurden alle experimentellen Ergebnisse mit Literaturdaten und Vorherberechnungen mittels thermodynamischer Modellierung verglichen. Auf Grund der hervorragenden Lumineszenzeigenschaften von Cm(III) und Eu(III) konnte insbesondere auch die Eignung der zeitaufgelösten laserinduzierten Fluoreszenzspektroskopie (TRLFS) als Methode zur Untersuchung dieser Metallionen in unbehandelten, komplexen biologischen Flüssigkeiten demonstriert werden. Die Ergebnisse dieser Arbeit liefern damit neue Erkenntnisse zu den biochemischen Reaktionen von An(III) und Ln(III) in Körperflüssigkeiten auf molekularer Ebene und tragen zu einem besseren Verständnis der bekannten, makroskopischen Effekte dieser Elemente bei. Darüber hinaus sind sie die Grundlage weiterführender in-vivo-Untersuchungen.

The common ringtail possum (Pseudocheirus peregrinus), a member of the family Pseudocheiridae, is an arboreal folivorous marsupial that feeds predominantly on Eucalyptus foliage. Contrary to the expectation that small body size would inhibit utilisation of a diet containing such high levels of lignified fibre because of relatively low gut volume to body mass ratios and relatively high mass-specific metabolic rates and nutrient requirements (Hume 1999), the ringtail possum is able to survive solely on a diet of Eucalyptus foliage. The rabbit (Oryctolagus cuniculus) is a terrestrial herbivore and is a member of the family Leporidae that feeds predominantly on grasses. The rabbit was proposed as a digesta flow model for the ringtail possum since both are caecotrophic (periodically re-ingest caecal contents) and both are proposed to exhibit a colonic separation mechanism (CSM) where fluids and small, easily digested particles are preferentially returned to the caecum. The rabbit is of value for the modelling process since it is more accessible for experimental manipulation than the ringtail possum. This study investigated a proposal to use digesta passage through the gastrointestinal tract (GIT) of the rabbit as a model of digesta passage for the ringtail possum on the basis that both are caecotrophic caecum fermenters. A number of potential problems were identified with this proposal and investigation of these problems formed the basis for the research described in this thesis. Two main areas were identified as being potentially problematic: 1) fundamental flaws with the particulate markers used in digesta rate of passage studies; and 2) differences in animal behaviour and natural diet between the two subject species which suggested different digestive strategies and hence different patterns of digesta flow through the GIT. The proposed digesta passage markers were lanthanide metals (Dy, Tm, Eu and Yb) attached to either fibrous particles (1200 - 600�m) or formalin-fixed rumen bacteria (20 � 0.2�m). These markers were shown to not be of the assumed size classes and the extent of lanthanide metal binding differed between the four metals used. An effect due to method of dosing was also observed. The findings of marker inconsistencies caused major limitation to model development and further research is necessary to clarify these markers. The proposal to use digesta flow in the rabbit GIT as a model for digesta flow in the ringtail possum was shown to be idealistic due to the differences in anatomy and behaviour observed between the two herbivores. Laboratory observations, time series analysis and compartmental modelling confirmed the differences between the animals. This study showed: 1) the GIT of the rabbit was more complex both anatomically and functionally than that of the ringtail possum; 2) behaviour affecting digesta passage of the rabbit and ringtail were different and; 3) compartmental models confirmed the anatomical and behavioural findings. Digesta passage in the rabbit could not be modelled mathematically using data on digesta passage due to complexities of the system. In contrast, a basic model was constructed for digesta passage in the ringtail possum. On the basis of these findings, the research hypothesis "that digesta passage in rabbits is similar to that in ringtail possums" was rejected.