Exposure of the skin to ultraviolet radiation (UVR) results clinically in the formation of deep wrinkles and mottled pigmentation and histologically, in a vast remodelling of the dermal extracellular matrix (ECM), in particular the elastic fibre network. Fibrillin microfibrils and fibulin-5 are early biomarkers of photoageing, where a loss of these fibres from the dermal epidermal junction is apparent. A study by our group showed that isolated fibrillin microfibrils and fibronectin which are rich in amino acids which absorb energy from UVR (UV-chromophores) are susceptible to UVR-induced damage, whilst UV-chromophore poor collagen type I is not. This research, with other earlier studies, indicates that acellular mechanism may work in tandem with cell-mediated up-regulation of matrix metalloproteinases (MMPs) in the progression of photoageing. This thesis aims to: i) test whether acellular mechanisms of photoageing are a result of direct photon absorption and/or the photodynamic production of reactive oxygen species (ROS); ii) assess the functional consequences of UVB degradation on the susceptibility of fibrillin microfibrils to MMPs and; iii) assay whether ECM proteins are differentially susceptible to solar simulated radiation (SSR) or UVA (315-400nm) alone using physiologically relevant doses of irradiation. Isolated proteins were exposed to UVB (280-315nm) in depleted-O2 conditions and in the presence of deuterium oxide. Depleted-O2 conditions decreased and deuterium oxide conditions increased UVR-induced degradation. Isolated proteins also show a similar pattern of degradation when exposed to H2O2 as an exogenous source of ROS. These results indicate that ROS play an important role in the differential degradation of dermal proteins. MMPs-3 and -9 are both upregulated in the skin after exposure to UVR and have the ability to degrade elastic fibre components. After exposure to UVB, damaged fibrillin microfibrils become more susceptible to degradation by both MMPs-3 and -9. Chromophore-rich fibrillin microfibrils and fibronectin are susceptible to degradation by both SSR and UVA alone, whereas chromophore-poor collagens type I and VI and tropoelastin are not. These results support our previous findings that amino acid composition of proteins is a good indicator of their relative susceptibility to UV-induced damage with a physiologically relevant irradiation system. In conclusion this work shows that ROS are an important mediator of acellular mechanisms of photoageing and that amino acid composition is a good indication of relative susceptibility of proteins to both ROS and UVR. The ability to predict ROS-susceptible proteins also has wider implications for human ageing as a whole.

Please read the abstract in the section, 00front, of this document / Dissertation (MEng)--University of Pretoria, 2008. / Chemical Engineering / unrestricted

Underwater wireless optical communication (UWOC) has attracted increasing interest for data transfer in various underwater activities. However, the complexity of the water environment poses considerable challenges to establish aligned and reliable UWOC links. Therefore, solutions that are capable of relieving the requirements on positioning, acquisition and tracking (PAT) are highly demanded. Different from the conventional blue-green light band utilized in UWOC, ultraviolet (UV) light is featured with low solar background noise, non-line-of-sight (NLOS) and good secrecy. The proposed work is directed towards the demonstration and evaluating the feasibility of high- speed NLOS UWOC for easing the strict requirement on alignment, and thus circumvent the issues of scintillation, deep-fading, and complete signal blockage presented in conventional LOS UWOC. This work was first started with the investigation of proper NLOS configurations. Path loss (PL) was chosen as a figure-of-merit for link performance. With the understanding of favorable NLOS UWOC configurations, we established a 377-nm laser-based, the first-of-its-kind NLOS UWOC link. The practicality of such NLOS UWOC links has been further tested in a field trial. Besides the underwater communication links, UV-based NLOS is also appealing to be the link for direct communication across the wavy water-air interface. Investigations for such a direct communication link have been carried out to study data rate, coverage and robustness to the dynamic wave movement, based on the performance of different modulation schemes, including non-return-to-zero (NRZ)-OOK and quadrature amplitude modulation (QAM)-orthogonal frequency division multiplexing (OFDM). Further this study, an in-Red Sea canal field in-situ test has been conducted, showing strong robustness of the system. In addition, an in-diving pool drone-aided real-application deployment has been carried on. The trial results indicate link stability, which alleviates the issues brought about by the misalignment and mobility in harsh environments, paving the way towards real applications. Our studies pave the way foreventual applications of UWOC byrelieving the strict requirements on PAT using UV-based NLOS. Such modality is much sought-after for implementing robust, secure, and high-speed UWOC links in harsh oceanic environments.

We provide an in-depth analysis of the He II and H I absorption in the intergalactic medium (IGM) at redshifts z = 2.3-2.9 toward HE 2347-4342, using spectra from the Far Ultraviolet Spectroscopic Explorer and the Ultraviolet-Visual Echelle Spectrograph on the Very Large Telescope. Following up on our earlier study, we focus here on two major topics: (1) small-scale variability (Δz ≈ 10-3) in the ratio η = N(He II)/N(H I) and (2) an observed correlation of high-η absorbers (soft radiation fields) with voids in the (H I) Lyα distribution. These effects may reflect fluctuations in the ionizing sources on scales of 1 Mpc, together with radiative transfer through a filamentary IGM whose opacity variations control the penetration of 1-5 ryd radiation over 30-40 Mpc distances. Given the photon statistics and backgrounds, we can measure optical depths over the ranges 0.1 < τHe II < 2.3 and 0.02 < τH I < 3.9 and reliably determine values of η ≈ 4τHe II/τH I over the range 0.1-460. Values η = 20-200 are consistent with models of photoionization by quasars with observed spectral indices α s = 0-3. Values η > 200 may require additional contributions from starburst galaxies, heavily filtered quasar radiation, or density variations. Regions with η < 30 may indicate the presence of local hard sources. We find that η is higher in "void" regions, where H I is weak or undetected and ∼80% of the path length has η > 100. These voids may be ionized by local soft sources (dwarf starbursts) or by QSO radiation softened by escape from the active galactic nucleus cores or transfer through the "cosmic web." The apparent differences in ionizing spectra may help to explain the 1.45 Gyr lag between the reionization epochs of H I (zH I ∼ 6.2 ± 0.2) and He II (zHe II ∼ 2.8 ± 0.2).

The problem was to study several hydrocarbons when they were subjected to ultraviolet light of 2536 Å in the presence of mercury vapor. It would be expected from the work of Stallings that the rupture of any tertiary hydrogen bond in the molecule would be the predominant effect. However, secondary and primary bond splitting would occur as well as some C-C bond rupturing, but these could be expected to a lesser degree than the first, since the t-hydrogen has the greatest reactivity.

<p> In Part I of this thesis, the design, construction, and calibration of a twenty-one foot off-plane Eagle vacuum spectrograph, a Lyman source, and predispersion unit are described.</p> <p> In Part II, the results of an investigation of the electronic absorption spectra of the cyanogen halides, obtained with the apparatus described in Part I, are given. Several electronic absorption systems have been observed for each of the cyanogen halides. These have been correlated and assigned to electronic transitions. Vibrational analyses have been made and the excited state dimensions have been determined by a quantitative application of the Franck-Condon principle for two absorption systems of each of the cyanogen halides.</p> / Thesis / Doctor of Philosophy (PhD)

This thesis describes an experiment in the ultraviolet absorption of hydrocarbons.

La viabilidad de los tratamientos con radiación ultravioleta (UV-C) a 254 nm como proceso no térmico para la conservación de ovoproductos líquidos fue evaluada desde el punto de vista de la eficiencia en la descontaminación y sus efectos en los atributos de calidad. Los estudios cinéticos sobre la inactivación de microorganismos inoculados y de los principales grupos de microorganismos alterantes sirvieron para discriminar los parámetros más relevantes del tratamiento con UV-C. Los estudios de vida útil sirvieron para evaluar las ventajas aportadas por esta tecnología frente a tratamientos térmicos tradicionales. Las fracciones de huevo (clara, yema y huevo entero) tratadas con UV-C fueron analizadas en cuanto a los cambios de pH, color, estabilidad de lípidos (TBARS, colesterol y valor de peróxidos), efectos en las proteínas (oxidación proteica, DSC, SDS-PAGE), propiedades reológicas (viscosidad dinámica, comportamiento de flujo, viscosidad en función de la temperatura), propiedades funcionales (emulsionantes y espumantes), composición nutricional (vitaminas y minerales), composición de componentes saludables (carotenoides), y cito-genotoxicologia. Finalmente, la aceptación sensorial de los ovoproductos líquidos tratados por UV-C y de productos preparados con ovoproductos líquidos tratados por UV-C (mayonesa, bizcocho y pudin) fueron evaluadas por medio de pruebas triangulares y afectivas. El tratamiento con UV-C demostró ser una excelente alternativa a la pasteurización térmica. En microorganismos inoculados, se demostró una reducción de 5 Log tanto para Gram(+) como para Gram(-) en un equipo comercial para tratamientos en régimen continuo (UVivatec�). En tandas, los resultados también mostraron decrecimientos importantes en el recuento de microorganismos inoculados, aunque serían necesarios tiempos largos de tratamiento para producir una descontaminación comparable a la pasteurización térmica. Los ovoproductos líquidos tratados con UV-C fueron estables durante 8 / Mendes De Souza, P. (2012). Study of short-wave ultraviolet treatments (UV-C) as a non-thermal preservation process for liquid egg products [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/16696

Plusieurs types de granules ARN sont observables dans toutes les cellules. Certains correspondent à des structures où la régulation post-transcriptionnelle est effectuée; parmi ceux-ci on retrouve les granules de stress (GS) et les "processing bodies" (PB). Les GS sont des structures ribonucléoprotéiques cytoplasmiques formées suite à un stress cellulaire et dans lesquels les ARNm sont remisés pour y être transitoirement réprimés et protégés en attendant de meilleures conditions physiologiques. Les PB sont aussi des granules cytoplasmiques ribonucléoprotéiques formés entre autre des composants de la machinerie de dégradation et de la surveillance de l'ARN. De nombreuses études citent l'apparition des GS suite à l'irradiation aux UV. Cependant, cette observation n'a pas été validée. Nous avons donc cherché à caractériser les granules induits par les UV en suivant le comportement de FMRP, une protéine de liaison à l'ARN présente dans les GS. Dans cette étude, nous avons montré que les UV induisent la formation de granules cytoplasmiques qui n'ont ni la même taille, ni la même cinétique d'apparition et de disparition, ni la même composition des GS. Nous avons aussi noté l'absence des protéines de la petite sous-unité ribosomale normalement présentes dans les GS. Nous avons montré également que les cellules irradiées peuvent reprendre certaines fonctions physiologiques. Nous proposons donc l'hypothèse qu'il existerait une nouvelle classe de granules ARN induits par les UV dans lesquels seront accumulés les ARN potentiellement endommagés, ceci serait un nouveau mécanisme de régulation post-tanscriptionnelle.

The development and application of photoredox methodologies in organic synthesis is a powerful paradigm in the synthesis of value-added products. While conventional methods of photoredox catalysis employ ultraviolet (UV) or blue light (i.e. visible light), the associated high energies can lead to deleterious off-cycle pathways and the formation of undesired byproducts. Transitioning to a low-energy (i.e. red/orange) light manifold can mitigate some of these challenges and promote batch-scale reactivity. We first show standardized syntheses and photophysical/electrochemical characterizations of a library of Os(II) polypyridyl complexes activatable by red light and demonstrate their application in metallaphotoredox-assisted aryl etherification. Thereafter, we leverage the advantages of spin-forbidden excitation (SFE) in the activation of novel Irⁱⁱⁱ photocatalysts, showing the first known examples of C(sp²)–C(sp³) bond formation with low-energy light. Finally, we utilize the low triplet energy and high redox versatility of an orange light photocatalyst to enable unified oxidative/reductive pathways in decarboxylative arylation, the first such photoredox system to effect dual catalytic manifolds in this paradigm with broadly similar reaction conditions.