The increasing food demand as well as the need to predict the impact of warming climate on vegetation makes it critical to find the best tools to assess crop production and carbon dioxide (CO₂) exchange between the land and atmosphere. Photosynthesis is a good indicator of crop production and CO₂ exchange. Chlorophyll fluorescence (ChF) is directly related to photosynthesis. ChF can be measured at leaf-scale using active techniques and at field-scales using passive techniques. The measurement principles of both techniques are different. In this study, three overarching questions about ChF were addressed: Q1) How water, nutrient and ambient light conditions determine the relationships between photosynthesis and ChF? Which is the optimum irradiance level for detecting water and nutrient deficit conditions with ChF?; Q2) which are the limits within which active and passive techniques are comparable?; and Q3) What is the seasonal relationship between photosynthesis and ChF when nitrogen is the limiting factor? To address these questions, two main experiments were conducted: Exp1) Concurrent photosynthesis and ChF light-response curves were measured in camelina and wheat plants growing under (i) intermediate-light and (ii) high-light conditions respectively. Plant stress was induced by (i) withdrawing water, and (ii) applying different nitrogen levels; and Exp2) coincident active and passive ChF measurements were made in a wheat field under different nitrogen treatments. The results indicated ChF has a direct relationship with photosynthesis when water or nitrogen drives the relationship. This study demonstrates that the light level at which plants were grown was optimum for detecting water and nutrient deficit with ChF. Also, the results showed that for leaf-average-values, active measurements can be used to better understand the daily and seasonal behavior of passive ChF. Further, the seasonal relation between photosynthesis and ChF with nitrogen stress was not a simple linear function. Our study showed that at times in the season when nitrogen was sufficient and photosynthesis was highest, ChF decreased because these two processes compete for available energy. These results demonstrated that ChF is a reliable indicator of crop stress and has great potential for better understand the CO₂ exchange between the land and atmosphere.

The response of low energy nuclear recoil in NaI(Tl) is investigated in the following experiment. Such detectors have been used recently to search for evidence of dark matter in the form of weakly interacting massive particles (WIMPs). NaI(Tl) crystal response to nuclear recoil energy deposition is a key element in these searches. I discuss the cosmological and experimental motivations for these experiments, followed by an overview of the physics of direct detection and current relevant WIMP search experiments. With the experiment motivations covered, the details of NaI(Tl) detectors are reviewed. The specifics of our experiment are laid out including the neutron production, neutron beam calibration, shielding optimization, experimental design and setup. Then the crystal response calibration studies and Geant4 simulations are discussed followed by the final quenching factor values and uncertainties. This experiment measured quenching factors for sodium recoils in the energy range of (9 keV-40 keV) of 19%-27% QF. These results are similar to current published measurements. Interesting features of the QF measurements include an increase at low energies and a dip in the values at 30 keV, the iodine K-shell absorption edge. The goal of this experiment was to add valuable measurements of nuclear recoils at low energies that are relevant to low-mass WIMP experiments. Future plans will improve and expand on these measurements in order to better understand the response of NaI(Tl) at low energies.

The ability of six types of granular activated carbon (GAC) to quench H2O2 was evaluated by bench-scale H2O2 decomposition kinetics tests and pilot-scale H2O2 breakthrough tests. Bench-scale studies showed that carbon ageing significantly reduced the performance of H2O2 quenching by the GAC, but that the greatest impacts occurred within the first 25 000 bed volumes of water treated, with performance tending to stabilize afterwards. Pilot-scale studies suggested that both H2O2 exposure and exposure to natural organic matter were important factors in GAC ageing, with exposure to oxygen also suspected of being important. A continuously stirred tank reactor (CSTR)-in-series model was proposed for the prediction of H2O2 breakthrough in a GAC column.

The ability of six types of granular activated carbon (GAC) to quench H2O2 was evaluated by bench-scale H2O2 decomposition kinetics tests and pilot-scale H2O2 breakthrough tests. Bench-scale studies showed that carbon ageing significantly reduced the performance of H2O2 quenching by the GAC, but that the greatest impacts occurred within the first 25 000 bed volumes of water treated, with performance tending to stabilize afterwards. Pilot-scale studies suggested that both H2O2 exposure and exposure to natural organic matter were important factors in GAC ageing, with exposure to oxygen also suspected of being important. A continuously stirred tank reactor (CSTR)-in-series model was proposed for the prediction of H2O2 breakthrough in a GAC column.

Hot forming of boron steels is becoming increasingly popular in the automotive industry due to the demands for weight reduction and increased safety requirements for new vehicles. Hot formed components offer a significant increase in strength over conventional cold-formed steels, which has allowed for reductions in material thickness (and thus weight) while maintaining the same strength. Hot formed components are typically used in structural applications to improve the integrity of the vehicle’s cabin in the event of a collision. It has been suggested, however, that the crash performance of certain hot formed parts may be increased by locally tailoring their mechanical properties to improve their energy absorption. The final microstructure of a hot formed part is driven by the rate at which it is cooled within the tooling during the forming and quenching process. By controlling the cooling rate of the part, it is possible to control the final microstructure, and thus the final mechanical properties. This thesis outlines the experimental and numerical studies that were performed for the hot forming of a lab-scale B-pillar. A hot forming die set was developed which has both heating and cooling capabilities to control the local cooling rate of the blank as it is formed and quenched. The first aspect of this research is to produce a hot formed part which is representative of an industrial component, and then to numerically model the process to predict the final mechanical properties. The second aspect is to produce a hot formed part with tailored mechanical properties, such that there are regions of the part with very high strength (very hard) and other regions with increased ductility (softer). By tailoring the microstructure to meet the performance requirement of a hot formed part, it may be possible to optimize its crash behavior and also reduce the overall weight. Cartridge heaters were installed into sections of the tooling allowing it to reach a maximum temperature of 400°C. Cooling channels are used in other sections to maintain it at approximately room temperature. Experiments were performed on 1.2 mm Usibor® 1500P steel at heated die temperatures ranging from 25°C to 400°C. In the fully cooled region, the Vickers hardness of the blank was measured to be 450 – 475 HV, on average. As the temperature of the heated region was increased, a significant softening trend was observed in the areas of the blank that were in contact with the heated tool. The greatest levels of softening occurred in the 400°C heated die trial. Hardness measurements as low as 234 HV were recorded, which represents a reduction in hardness of 49% compared to the fully cooled trials. Numerical models of the experiments were developed using LS-DYNA and use of its advanced hot forming material model which allows for microstructure and hardness prediction within the final part. The numerical models have shown promising results in terms of predicting the hardness trends as the temperature of the die increases. Thermal expansion of the tooling resulted in local changes in the geometry of the tooling which proved to be problematic during the forming and quenching stages of the process. The expansion caused unexpected changes in the part-die contact, and the resulting microstructures were altered. These thermal expansion issues were addressed in the current work by shimming the tooling; however, in future work the tooling should be designed to account for this expansion at the desired operating temperature.

This thesis presents a joint experimental and theoretical study of vector correlations in the electronically, vibrationally, and rotationally inelastic collisions of simple molecules with rare-gas atoms. In the first instance, empirical and calculated data are presented for rotationally inelastic scattering in the NO(X)+Ar and ND₃(X̃)+Ar systems at collision energies in the range 405-2210 cm^-1. These experiments - the first to be conducted on a newly commissioned crossed-molecular beam machine - measured the k-k' correlation, i.e. that between the vectors describing the relative velocities before and after collision, respectively. The empirical data were subjected to rigorous comparison with both quantum-mechanical and quasi-classical trajectory (QCT) calculations. For both the NO(X)+Ar and ND₃(X̃)+Ar systems, there is generally good agreement between experiment and theory at all four collision energies investigated. Two chapters of this thesis focus on the development of trajectory surface-hopping (TSH) QCT models of the OH(A, v = 0)+Kr and OH(A, v = 0)+Xe systems. Experimental data relating to scalar quantities (rotational energy transfer (RET) and electronic quenching) and to the j-j' correlation (which quantifies the depolarisation of the angular momentum of the OH(A) radical) are compared to variable-collision-energy TSH QCT calculations in which the length of the OH bond is fixed. The algorithms involve all three PESs of the OH(A/X)+Kr system, and the full range of electrostatic and roto-electronic mechanisms that couple them, for the first time. The most complete model succeeded in accounting for 93% of experimentally observed quenching. For the OH(A/X)+Xe system, coupling matrix elements were estimated from those of OH(A/X)+Kr, and the most complete model recovered 63% of experimentally observed quenching. This thesis also presents a novel theoretical study of rotationally inelastic dynamics in the OH(A, v = 1)+Kr system. Provisional results from adiabatic calculations in which the OH bond length is allowed to vary over the course of a trajectory are presented alongside experimental data that were reported previously. To date, these calculations continue to underestimate the extent of empirical RET data. Reasons for the observed discrepancy, and suggestions to resolve it, are outlined in detail.

Nonphotochemical quenching is an important protective mechanism of photosynthetic proteins against excessive irradiation. In this work, isolation of native light harvesting antennae from alga Chromera velia was optimized using methods of sucrose density centrifugation, isoelectric focusing, ion exchange chromatography and gel electrophoresis. Moreover, the ability of light harvesting antennae to trigger nonphotochemical quenching was studied in vivo and in vitro.

Orientadora: Profa. Dra. Paula Homem de Mello / Tese (doutorado) - Universidade Federal do ABC. Programa de Pós-Graduação em Ciência e Tecnologia/Química, 2016. / The interaction between molecules and solids is the subject of study of various areas and has a plethora of technological applications. In this work, we have studied experimentally and computationally two systems: (i) the interaction between fluorophores and platinum nanoparticles and (ii) diclofenac oxidation process using a diamond electrode. From the computational simulation point of view, both systems are challenging because the proposed models have to include minima requirements to explain the behavior observed experimentally. For the first system, it was possible to establish computational and experimental protocols to study the effect of platinum nanoparticles in the absorption and emission spectra of polycyclic aromatic hydrocarbons (PAHs). Absorption and emission spectra of pyrene are suppressed by the nanoparticle presence. On the other hand, anthracene spectra is enhanced. The interaction between nanoparticles and pyrene molecules occurs more rapidly and intensely than with anthracene, what favors the quenching in pyrene spectra, and, in contrast, the enhancement of anthracene bands. For pyrene-nanoparticle system, all transitions are shifted to the metal system, while the anthracene-nanoparticle, there is a charge transfer from nanoparticles towards anthracene during electronic excitation. Regarding the second system, the electrooxidation of diclofenac, there were experimental evidences that the process involves the loss of two electrons and two protons, as well as the formation of dimers. Our study, based on Monte Carlo method and on the density functional theory, was fundamental in establishing important intermediate species in the oxidation process, as well as indicate the relative abundance of dimers obtained.

abstract: Non-photochemical quenching (NPQ) is a photoprotective regulatory mechanism essential to the robustness of the photosynthetic apparatus of green plants. Energy flow within the low-light adapted reaction centers is dynamically optimized to match the continuously fluctuating light conditions found in nature. Activated by compartmentalized decreases in pH resulting from photosynthetic activity during periods of elevated photon flux, NPQ induces rapid thermal dissipation of excess excitation energy that would otherwise overwhelm the apparatus’s ability to consume it. Consequently, the frequency of charge separation decreases and the formation of potentially deleterious, high-energy intermediates slows, thereby reducing the threat of photodamage by disallowing their accumulation. Herein is described the synthesis and photophysical analysis of a molecular triad that mimics the effects of NPQ on charge separation within the photosynthetic reaction centers. Steady-state absorption and emission, time-resolved fluorescence, and transient absorption spectroscopies were used to demonstrate reversible quenching of the first singlet excited state affecting the quantum yield of charge separation by approximately one order of magnitude. As in the natural system, the populations of unquenched and quenched states and, therefore, the overall yields of charge separation were found to be dependent upon acid concentration. / Dissertation/Thesis / Doctoral Dissertation Chemistry 2015

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