In young coho salmon (Oncorhynchus kisutch), UVR is known to elicit exposure avoidance behavior and suppress aggressiveness. The latter observation has been attributed to the indirect effect of fish seeking shade from solar UVR under rocks consequently losing sight of prospective rivals. The present study quantified the direct impacts of UVR on agonistic (Strikes, Chases, Approaches) and feeding behaviors in juvenile coho salmon by furnishing outdoor aquaria with structural elements (i.e., inverted funnels) that provided habitat complexity without generating shade during midday experimental trials. Frequencies and durations of behaviors were compared between conditions that excluded or included natural solar UVR. Results indicated that hostile pursuits (Chases) persisted significantly longer under UVR illumination. Likewise, the frequencies of more belligerent interactions (Strikes, Chases) tended to increase under UVR, while milder territorial assertions (Approaches) and foraging (Feeding Efforts) tended to decline. However, none of the latter four outcomes tested as significant.

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.

No description available.

No description available.

Some physicochemical properties of several series of transition metal chalcocarbonyls such as ((eta)('6)-C(,6)H(,6))Cr(CO)(,2)(CX) and Cr(CO)(,5)(CX) (X = O, S, Se) have been investigated. In particular, the infrared, ('13)C and ('17)O nuclear magnetic resonance and ultraviolet spectra have been examined. The results show that the order of (sigma)-donor and (pi)-acceptor capabilities of the ligands is CO CS. The M((pi)) (--->) CX((pi)*) ultraviolet charge-transfer bands are shown to correlate with the respective (mu)'(,MCX) and ('13)C NMR data. Also, the ('13)C NMR chemical shifts and GQVFF force constants are found to be highly correlated. The ('17)O NMR spectra of the metal chalcocarbonyl complexes display chemical shifts in the opposite direction to the corresponding ('13)C ones. No correlation is found between the ('17)O shieldings and the other spectroscopic data. Reaction of Cr(CO)(,5)(CX) (X = S, Se) with halide ions (Y('-)) afforded mixtures of {Cr(CO)(,5)Y}('-) and trans-{Cr(CO)(,4)(CX)Y}('-) while Cr(CO)(,5)(CS) reacted with cyclohexylamine to give Cr(CO)(,5)(CNC(,6)H(,11)). The similarities and differences in the physicochemical behaviour of the metal chalcocarbonyls compared to related systems are discussed in the light of the different bonding patterns.

This project was designed to investigate the impact of natural levels of ultraviolet-B radiation on the genomic mutation rate in Arabidopsis thaliana. UV-B radiation is a known mutagen, but plants may have evolved mechanisms to cope with any genomic damage induced by routine exposure to this radiation. In an attempt to determine whether the genomic mutation rate in a plant species is elevated in the presence of UV-B, two eleven generation mutation accumulation studies were preformed. One study incorporated levels of UV-B similar to that encountered on a clear mid-summer's day, while the other was performed in the absence of this mutagen. Mutation rate estimates, obtained primarily from maximum likelihood analysis of phenotypic data, were not significantly greater than zero, both in the presence and absence of UV-B. No evidence was found to support the notion that the genomic mutation rate is increased by exposure to natural levels of UV-B.

Shallow-dwelling scleractinian corals live in high irradiance environments where they are exposed to large fluxes of ultraviolet radiation (UVR, 280 - 400 nm). A suite of UV-aborbing compounds, know as mycosporine-like amino acids, is found within the tissues of coral-algal symbioses and may perform a sun-screening role. The seasonal variation in MAA concentration was investigated for two corals in Kaneohe Bay, Hawai'i, Porites compressa and Montipora verrucosa. Regressions of MAA concentration and the amount of UVR measured prior to collection date were not significant for total MAA concentration of either species. However, individual MAAs, shinorine in P. compressa and palythene in M. verrucosa, did show significant correlation with UVR. The effects of UVR and water motion on Porites compressa were investigated in a flume and in the field. Exposure to ambient UVR was the most important factor tested in determining the concentration of MAAs in the tissues of P. compressa. Water motion also positively affected the concentration of MAAs, but only in the presence of UVR. When UVR was screened from the corals' environment, the tissue concentration of MAAs slowly decreased over time (approximately 2.5 to 5% per week) regardless of water motion. The effect of UVR on coral planulae was investigated in field experiments with Pocillopora damicornis. Larvae were taken from four different source adults: those from <0.5 m, those from 3 m, those incubated in the absence of UVR for two months, and those incubated in ambient UVR for two months. Deep larvae and larvae from adults incubated in the absence of UVR had roughly half the amount ofMAAs found in the shallow larvae and the larvae from adults in ambient UVR. Origin of larvae was not a significant factor in determining larval survival or recruitment success. UVR, however, was important in determining recruitment rate. Larvae were less likely to recruit to the settlement tile in the presence of ambient UVR than in treatments where the UVR was screened out. / Thesis (Ph. D.)--University of Hawaii at Manoa, 1999. Includes bibliographical references (leaves 151-164).

Mast cells (MCs) play a central role in inflammation by releasing mediators following activation. S100A8 and S100A9 are abundantly expressed in inflammatory sites such as asthmatic lung, sunburnt skin and atherosclerosis where MCs are involved in pathogenesis; roles of S100A8 in MC function are undetermined. The aims of this thesis were to determine effects of S100A8 on MC activation, particularly provoked by IgE and UVB. Initially, effects of UVB on MC activation were investigated as detailed functions were unclear. Cord blood-derived human mast cells (CBMCs) were treated in vitro with varying doses of UVB and production of multiple cytokines and viability investigated. UVB exposure selectively increased levels of IL-8 (CXCL8), and to a less extent IL-1β, but not eight other cytokines tested. New protein synthesis partially contributed and IL-8 production was p38 MAPK-dependent. UVB dose-dependently induced MC apoptosis indicating a potential regulatory mechanism of MC function. The ability of recombinant S100A8, S100A9 or S100A8/9 heterodimer to modulate IgE/antigen (DNP/anti-DNP)-mediated activation of a murine MC line, and of bone marrow-derived (mBM) MC activation was determined. The S100s did not directly induce degranulation or induce IL-6. S100A8 significantly inhibited DNP/anti-DNP-provoked degranulation, and IL-6 and TNF mRNA and protein induction. S100A8 did not alter FcεRIα expression. S100A9 was less effective; and the S100A8/9 complex was also suppressive. S100A8 only weakly suppressed non-specific MC degranulation. Mutation of Cys41 in S100A8 negated its suppressive activity. Because S100A8 scavenges oxidants via this reactive Cys residue, we propose that this may mediate its ability to downmodulate IgE-dependent MC responses. Similar to the thiol scavenger N-acetyl-L-cysteine, S100A8 but not the Ala41 mutant, attenuated DNP/anti-DNP-provoked LAT phosphorylation. However, the disulfide-bonded S100A8 dimer and S100A8 containing a sulfinamide bond between Cys41 and Lys34/35 also reduced MC activation, indicating an additional pathway(s). S100A8 did not suppress antigen/IgE-induced responses of CBMC possibly because these may not truly reflect fullymature human tissue MCs. S100A8 did not alter UVB-induced IL-8 release by CBMCs, or affect apoptosis. Murine S100A8 may have anti-inflammatory properties by regulating MC activation in an activator-specific manner, at least partially by scavenging ROS to suppress intracellular signalling.

Bibliography: leaves [250]-268 / 268, ca. 130 leaves : ill. ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, Dept. of Physics, 1983

Thesis (Ph.D.) -- McMaster University, 1998. / Includes bibliographical references (leaves 167-182). Also available via World Wide Web.