A B S T R A C T Presented work focuses on experimental study of anion interaction with neutral particles at temperatures relevant for astrophysics. Anion H− , important for molecular hydrogen creation, and O− as a possible source of water are investigated. The temperature dependence of reac- tion rate coefficients from 10 to 150 K for reactions H− + H → H2 + e− and O− + H2 → H2O + e− has been determined. The energy distri- bution of electrons produced in the latter reaction at 300 K has also been acquired. These studies have been performed on two experimen- tal setups, which are presented together with the theory of operation, construction details, calibration, and supporting test measurements.

Melatonin is a neurohormone produced by the pineal gland in the brain. It functions as an antioxidant to scavenge free radicals. Free radicals are reactive species; they often oxidize the cells leading to oxidative stress which may lead to severe health complications. Reaction of melatonin with free radicals is known to be stepwise, as such the stability of the intermediates can be examined. Thus, the possibility of using melatonin as an in vivo spin trap can be determined. Spin traps allow characterization of unstable radical species using electron spin resonance spectroscopy. In this research, ab initio quantum chemistry techniques were used to calculate the energies of selected intermediates formed during the partial oxidation of melatonin by hydroxyl radical. Specifically, optimized geometries for melatonin, and selected intermediates with ·OH were obtained at the DFT/B3LYP/cc-pVXZ and HF/cc-pVXZ (X = D, T, Q) levels of theory. Extrapolations to the complete basis set limit were also performed.

The presence of excess free radicals in the body can result in severe health consequences because of oxidative damage to cells. Spin traps may be used as a probe to examine radical reactions in cells, but there is a need for less toxic and more lipid soluble examples. Melatonin is one of the numerous antioxidants used to scavenge free radicals in the body and reportedly one of the most efficient radical scavengers known. It is relatively nontoxic and easily crosses the lipid bilayer in cell membranes. Melatonin is thought to undergo a multistep oxidation process and this work investigates the potential for it to be used as a spin trap. The presence of electron withdrawing or donating groups added to melatonin may stabilize an intermediate and allow it to function as a spin trap. The essence of this study is to conduct a computational inquiry into the relative stability of melatonin, selected derivatives, and the partial oxidation products formed from the scavenging of hydroxyl radical. To determine this, geometries were optimized for each molecule at the DFT/B3LYP/6-31G(d) and HF/6-31G(d) levels of theory.

This report aimed to investigate how chlorophyll-concentrations (Chl-a) in the water column and varved sediments were affected by changes in air temperature and precipitation and consequently how climate change will affect the sedimentation and productivity in boreal aquatic ecosystems. VRS (visible-reflectance-spectroscopy) was used to asses Chl-a and its derivates in sediment trap samples between 2002-2021 and in a series of freeze cores (1979-2021) from lake Nylandssjön, with annually laminated sediments. In order to evaluate how weather and climate change affected the sedimentation and productivity in the lake the results were compared with meteorological data from SMHI (Swedish Meteorological and Hydrological Institute) and Chl-a data from seperate depths in the water column. The results indicate that the majority of the yearly sedimentation occur either in May or June, where a higher cumulative amount of precipitation in May lead to a higher sedimentation rate in May (r=0,49; p=0,03). The amount of precipitation in spring also had a significant impact on the primary production in spring and summer (r=0,59; p=0,01; r=0,73; p=0,002). Water column Chl-a and spectrally inferred Chl-a in sediments show similar trends in concentrations with deeper water sampling, however, water column Chl-a displayed significant differences in values between various depths (p=0,0004). Consequently, climate change will much likely increase the productivity of boreal aquatic ecosystems within years and the amount of sedimentation that occurs between years due to higher temperatures. An increased amount of precipitation will also enhance the primary productivity and the transportation of allochthonous- and minerogenic material to the lake.

京都大学 / 0048 / 新制・課程博士 / 博士(医学) / 甲第18857号 / 医博第3968号 / 新制||医||1008(附属図書館) / 31808 / 京都大学大学院医学研究科医学専攻 / (主査)教授 前川 平, 教授 江藤 浩之, 教授 河本 宏 / 学位規則第4条第1項該当 / Doctor of Medical Science / Kyoto University / DFAM

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Subterranean termites are ecologically and economically important insects that play major roles in organic matter decomposition and nutrient cycling. The Formosan subterranean termite, Coptotermes formosanus Shiraki, is an invasive species known to cause significant damage in urban areas through aggressive consumption of wooden structures and infestations of living trees. Little is known about the presence and impact of C. formosanus in forested ecosystems of the southeastern U.S. as the majority of studies have taken place in urban settings. This study investigates the prevalence of C. formosanus in localized forests, as well as the utilization of living trees by C. formosanus and native subterranean termite species (Reticulitermes spp.). Recently harvested timber stumps were inspected for subterranean termite presence on sites throughout Mississippi and Louisiana. Alate light traps were utilized for further C. formosanus detection. Three sites yielded C. formosanus alate catches, while 7,413 stump inspections produced 406 Reticulitermes spp. infestations.

Human disturbance is becoming an ever-bigger threat to biodiversity across the globe and should continue to be a field of conservation priority. Urbanisation, research and tourism put unavoidable pressure on the surrounding flora and fauna, therefore we need to gain knowledge on how to reduce future harm. Here we investigated the effects of human presence on medium-large terrestrial mammals in the south-eastern Peruvian Amazon, using camera traps to measure the number of human and mammal observations at varying distances from our research centre and the hiking trails. Species richness and the Shannon and Inverse Simpson diversity indices were also calculated during the four-month study period. Nineteen species were detected across fourteen camera sites. Distance from camp was positively correlated with species richness and the diversity indices, but showed no correlation with total mammal observations. Distance from nearest trail was negatively correlated with species richness, total mammal observations and the diversity indices. Total human observations was negatively correlated with species richness and the diversity indices, but had no impact on total mammal observations. Nevertheless, these results often had high p-values and low sample size and therefore should be interpreted with caution. Omnivores were the most sensitive trophic guild, showing a statistically significant negative correlation with total human observations, and a statistically significant positive correlation with distance from nearest trail. It is important then to assess these responses to human disturbance at the community and species level, as to truly understand the impact we are having.

The cyclic nitrone 5,5-dimethyl-1-pyrroline-N-oxide (DMPO), and the lesser known linear phenyl-N-tert-butylnitrone (PBN) and its phosphorylated analogues have been used as spin traps for the investigation of free radicals in biological systems. Theoretical work on these molecules suggests that there are important differences in their properties between biological systems and isolated molecules in the gas phase, most likely resulting from intra and intermolecular hydrogen bonding. Most dielectric solvation models such as the polarized continuum model and COSMO are incapable of direct determination of solvent-spin trap chemical interactions. To examine this, hybrid models incorporating COSMO for long range effects and discrete solvent molecules for short range effects, at the DFT/B3LYP/6-31G* level of theory, have been used to study the stabilization and alteration of the spin trap molecules properties in protic and aprotic polar solvents. The hybrid models have been successfully implemented to support the prominent role played by hydrogen bonding interactions in the stabilization of spin traps.

Melatonin (N-acetyl-5-methoxytryptamin, MLT) is a naturally occurring antioxidant which has shown some potential for use as a spin trap. Spin traps react with short lived hydroxyl radicals (HO·) to produce more stable products called spin adducts which may be characterized by electron paramagnetic resonance spectroscopy. However, the relative stability of hydroxyl spin adducts of melatonin derivatives (MLTD) compared to 2-hydroxymelatonin (HO-MLT) has not been examined computationally. Computational studies have been done on four selected MLTD; methylmelatonin (Me-MLT), chloromelatonin (Cl-MLT), cyanomelatonin (CN-MLT), and nitromelatonin (NO2-MLT). Geometry of the structures were optimized at the HF/6-31G(d), cc-pVXZ, (X=D and T) and DFT/B3LYP/6-31G(d), cc-pVDZ and cc-pVTZ levels of theory and extrapolated to the complete basis set limit using cc-pVXZ (X=D, T) basis sets. The lowest relative energy was found to be a mix of results for 2-OH-MLT-Me at HF and 2-OH-MLT-NO2 at DFT.