UV radiation can cause harmful effects to human skin, including premature skin ageing and skin cancer. Historically, sunscreens were developed to filter out UVB (290 nm-320 nm), but now the importance of UVA (320 nm-400 nm) sunscreens is realised. The most common UVA sunscreens are based on dibenzoylmethane (1,3-diphenyl propan-l,3-dione, DBM), of which the most common is Parsol 1789 (4'- methoxy 4'-tertiarybutyl DBM). The photochemistry of these materials has, however, been poorly understood. In this work the photophysics and photochemistry of DBM, Parsol 1789, Parsol DAM and ditertiarybutyl DBM have been studied, along with the respective 0-methylated and C-methylated compounds of DBM and Parsol 1789.DBMs exist primarily as an intra-molecularly bonded enol, which absorbs strongly at λ≈340 nm due to a π,π* transition. The absorption spectra of DBMs also exhibit a smaller peak at λ≈250 nm, due to an n,π* transition of the diketone content. At low temperature the main absorption band of DBMs shifts to longer wavelengths and vibrational structure can be observed. The enol form of DBMs fluorescence at low temperature, (v(_0)’→v’’(_0) at λ≈385 nm), and phosphorescence can be observed from both the diketone (λ(_em)≈495 nm,) and enol forms (λ(_em)≈425 nm). Thus the triplet energies of the diketones and enols of the DBMs studied have been measured. 0-methylated DBMs do not possess an intra-molecular H-bond, and the π,π* absorption band falls to lower wavelengths than for chelated DBMs. C-methylated DBMs exist as a diketone structure, and display photophysics typical of an aromatic ketone. It has been suggested that the main process on irradiation of DBM is the formation of a short-lived non-chelated enol, however no direct evidence as to the structure of this species is reported in the literature. Formation of the diketone form of DBM on prolonged irradiation in acetonitrile solution has also been reported, and in this work the quantum yield of this process has been measured; ɸ≈0.01 ± 0.004. In this work, direct (low temperature) IR spectroscopic evidence is presented to prove that the short-lived species produced on irradiation is indeed a non-chelated enol. The infra-red studies also suggest that the non-chelated enol form of DBM form complexes with polar solvents, as has been proposed in the literature. Quantum yields of non-chelated enol formation in cyclohexane at room temperature have been measured to be approximately ɸ=0.5 + 0.07. This work indicates that the rate of transient decay is enhanced by the interaction of the transient molecules with chelated enol molecules or other transient molecules. IR studies of low temperature transient formation confirm the interaction of transient molecules by the observation of inter-molecular hydrogen-bonding. By comparison with the E and Z isomers of 0-methylated DBM it is suggested that at low temperature DBM initially forms a Z-cis non-hydrogen bonded enol, which then converts to an E-trans non-hydrogen bonded enol with further irradiation. The kinetics and the temperature variation of the enol recovery support the theory that there is more than one species formed. The photochemistry of DBM in emulsions has also been studied in this work. It has been shown that the photochemistry occurring on irradiation is similar to that observed in solutions. This indicates that simple solutions are a good model for actual sunscreen formulations. Singlet oxygen is a highly reactive species capable of causing serious biological damage, however this work shows that DBM sunscreens generate singlet oxygen by photosensitisation, with quantum yields ɸ∆≈0.005-0.01. It has also been shown that the lifetime of the excited state of DBM involved in singlet oxygen production is very short, approximately τ <1 µs.

Thesis (Ph. D.)--University of Hong Kong, 2000. / Includes bibliographical references.

Thesis (Ph. D.)--State University of New York at Binghamton, Chemistry Department, 2005. / Includes bibliographical references.

abstract: Americans spend upwards of 90% of their time indoors, hence indoor air quality (IAQ) and the impact of IAQ on human health is a major public health concern. IAQ can be negatively impacted by outdoor pollution infiltrating indoors, the emission of indoor pollutants, indoor atmospheric chemistry and poor ventilation. Energy saving measures like retrofits to seal the building envelope to prevent the leakage of heated or cooled air will impact IAQ. However, existing studies have been inconclusive as to whether increased energy efficiency is leading to detrimental IAQ. In this work, field campaigns were conducted in apartment homes in Phoenix, Arizona to evaluate IAQ as it relates to particulate matter (PM), carbonyls, and tobacco specific nitrosamines (TSNA). To investigate the impacts of an energy efficiency retrofit on IAQ, indoor and outdoor air quality sampling was carried out at Sunnyslope Manor, a city-subsidized senior living apartment complex. Measured indoor formaldehyde levels before the building retrofit exceeded reference exposure limits, but in the long term follow-up sampling, indoor formaldehyde decreased for the entire study population by a statistically significant margin. Indoor PM levels were dominated by fine particles and showed a statistically significant decrease in the long term follow-up sampling within certain resident subpopulations (i.e. residents who reported smoking and residents who had lived longer at the apartment complex). Additionally, indoor glyoxal and methylglyoxal exceeded outdoor concentrations, with methylglyoxal being more prevalent pre-retrofit than glyoxal, suggesting different chemical pathways are involved. Indoor concentrations reported are larger than previous studies. TSNAs, specifically N'-nitrosonornicotine (NNN), 4-(methyl-nitrosamino)-4-(3-pyridyl)-butanal (NNA) and 4-(methylnitrosoamino)-1-(3-pyridyl)-1-butanone (NNK) were evaluated post-retrofit at Sunnyslope Manor. Of the units tested, 86% of the smoking units and 46% of the non-smoking units had traces of at least one of the nitrosamines. / Dissertation/Thesis / Doctoral Dissertation Chemistry 2014

Made available in DSpace on 2014-10-09T12:53:04Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:58:24Z (GMT). No. of bitstreams: 0 / Dissertação (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Made available in DSpace on 2014-10-09T12:53:04Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:58:24Z (GMT). No. of bitstreams: 0 / Análogos da timidina têm sido marcados com diferentes radioisótopos devido ao seu potencial em monitorar a proliferação incontrolável de células. Considerando que o radioisótopo tecnécio-99m mantém ainda uma posição privilegiada devido às suas propriedades químicas e nucleares, este trabalho constituiu-se do desenvolvimento de uma nova técnica de marcação da timidina com o 99mTc, mediante o emprego de complexos organometálicos. Os objetivos do trabalho foram: a síntese do complexo organometálico carbonil-tecnécio-99m; marcação da timidina com este complexo precursor; avaliação da estabilidade; e avaliações radioquímicas e biológicas com animais sadios e portadores de tumor. A preparação do complexo precursor, utilizando o gás CO foi de fácil execução, assim como a marcação da timidina com este precursor, obtendo-se uma pureza radioquímica &ge; 97% e &ge; 94%, respectivamente. Sistemas cromatográficos com bons níveis de confiabilidade foram utilizados, podendo qualificar e quantificar as espécies radioquímicas. O resultado do estudo in vitro da lipofilicidade revelou que o a timidina radiomarcada é hidrofílica, com um coeficiente de partição (log P) de -1,48. O complexo precursor e a timidina radiomarcada apresentaram boa estabilidade radioquímica em até 6 h em temperatura ambiente. A estabilidade com soluções de cisteína e histidina apresentaram perdas entre oito e onze pontos percentuais para concentrações de até 300 mM. Os ensaios de biodistribuição em camundongos sadios indicaram que a timidina radiomarcada apresentou uma rápida depuração sangüínea e baixa captação nos demais órgãos, com predominância de excreção da droga pelo sistema urinário e hepatobiliar. A captação tumoral foi baixa, apresentando valores de 0,28 e 0,18 %DI/g para tumor de pulmão e mama, respectivamente. Os resultados obtidos sugerem mais investigações em outros modelos tumorais ou a modificação da estrutura da molécula orgânica que atua como ligante. / Dissertação (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Many organometallic reactions are solvent-dependent, suggesting solvent molecules interact with reaction intermediates. Studies of the solvent exchange reaction of group 6 transition metal carbonyls with moderately binding ligands have provided insight into these interactions, however, studies of the mechanism for this reaction with weakly binding ligands have not been performed. Experiments were conducted on the nanosecond time scale in methylcyclohexane over the temperature range of 4 to 44 °C using Step Scan FTIR (SS FTIR) spectroscopy with weakly binding ligands benzene and mesitylene. Upon photolysis of the metal hexacarbonyls, the kinetically favored product (M(CO)5(solv)), decays following pseudo-first-order kinetics to the thermodynamical favored product, M(CO)5(L). The decay is fit using a single exponential decay with a single exponential instrument response function, time zero and an offset. An Arrhenius plot yielded activation energies of 23.7 kJ/mol (M = Mo, L = benzene), 35.1 kJ/mol (M = W, L = benzene) and 29.8 kJ/mol (M = Mo, L = mesitylene). DFT calculations using NWCHEM gave binding energies of 45.8 and 54.3 kJ mol-1 for Mo(CO)5C6H12 and W(CO)5C6H12. The experimental and computational results suggest the exchange mechanism proceeds through an associative pathway, were slightly negative values of the entropy of reaction denote that the transition state has greater metal solvent bond breaking character then the more moderately binding ligands in the literature. Density Functional theory was used to calculate C-O vibrational frequencies of metal carbonyl complexes measured in our work and other complexes from the literature, with density functionals B3LYP, M06 and M06-L. Measured and computational frequencies were compared to obtain both an overall vibrational shift and a scaling factor. Scaling factors were found to be 0.9519±0.0095 for B3LYP, 0.9429 ± 0.0087 for M06 and 0.9565 ± 0.0095 for M06-L with overall shifts of 102 ± 16, 121 ± 15, 93 ± 17 cm-1, respectively. The molybdenum mediated Pauson-Khand reaction, a [2+2+1] cyclo-addition begins very similarly to the solvent exchange reaction on molybdenum. The initial product, the solvated complex, decays away with pseudo-first-order kinetics as the solvent is replaced by the C-C triple bond in 2-(2-propen-1-yl)-2-(2-propyn-1-yl)-,1,3-diethyl ester. An Arrhenius plot over the temperature range of -8 to 20° C yielded an energy of activation of 15.6 kJ/mol.

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