Competition between collisions and optical pumping in unimolecular reactions induced by monochromatic infrared radiation

The optical pumping process in infrared multiphoton induced unimolecular reactions is studied by measuring the pressure dependence of the reaction yield as a function of the laser energy fluence and pulse shape. The dissociation of sulphur hexafluoride is taken as a model reaction. Rate constants for optical pumping near the reaction threshold were found to be directly proportional to the laser intensity for the range of conditions applied.     

N-acetyl-L-cysteine prevents DNA damage induced by UVA, UVB and visible radiation in human fibroblasts

The thiol N-acetyl-L-cysteine (NAC) is a source of cysteine for the synthesis of the endogenous antioxidant glutathione (GSH) which is depleted by ultraviolet radiation. It is also associated with the scavenging of reactive oxygen species (ROS). In this study the effects of NAC were examined in cultured human fibroblasts during prolonged exposure to ultraviolet B (UVB), ultraviolet A (UVA) and visible irradiation (280-700 nm), delivered by a 150 W xenon-arc lamp. The alkaline comet assay was used to assess the DNA damage in individual cells. It was found that incubating skin and lung fibroblasts at 37 degrees C for 1 h with an optimal 6 mM NAC supplement prior to light exposure, significantly reduced the level of DNA damage in both cell types, however, the skin fibroblasts were less sensitive to xenon-arc lamp irradiation than lung fibroblasts. NAC incubation resulted in an initial delay in DNA damage when the cells were irradiated. There was also a significant reduction in the overall levels of DNA damage observed with continued irradiation. NAC significantly reduced the DNA damage produced in lung fibroblasts depleted of normal GSH protection by the glutamylcysteinyl synthetase inhibitor, L-buthionine-[S,R]-sulfoximine. Although the specific mechanism of NAC protection has not yet been elucidated, these results support the hypothesis that NAC may protect the cells directly, by scavenging ROS induced by UVA and visible radiation, and indirectly by donating cysteine for GSH synthesis.     

Changes in the composition and properties of graphene oxide films under monochromatic vacuum UV radiation

The photolysis of a graphene oxide film by monochromatic vacuum UV radiation with a wavelength of 123.6 nm has been studied. It has been shown that photoreduction as a result of the detachment of the C?O polar groups is also accompanied by an increase in the conductivity, wettability, and surface energy of the graphene oxide film.     

Nonlinear intensity dependence of the rate coefficient in unimolecular reactions induced by monochromatic infrared radiation

It is shown that essentially incoherent, stepwise one-photon transitions arising in dense multilevel structures of polyatomic molecules irradiated with monochromatic coherent infrared radiation can give rise (under specified conditions) to a more than proportional intensity dependence of the steady-state rate coefficient in unimolecular reactions induced by monochromatic infrared radiation.     

Bystander effects in cell death induced by photodynamic treatment UVA radiation and inhibitors of ATP synthesis

Confluent layers of MDCK II cells were treated with four different photosensitizers (a purified version of hematoporphyrin derivative [Photofrin], tetra(3-hydroxyphenyl)porphine [3-THPP], meso-tetra(4-sulphonatophenyl)porphine [TPPS4] and ALA-induced Protoporphyrin IX) and irradiated with blue light, with UVA without exogenous photosensitizers, or incubated with the metabolic inhibitors carbonyl cyanide m-chlorophenylhydrazone and 2-deoxy-D-glucose. Necrotic and apoptotic cells were detected about 4 h later by fluorescence microscopy. Dead cells appeared in distinct clusters in the confluent layers. The number of dead cells in these clusters was determined by manual counting and image analysis. Forty-one of the 43 experimental distributions of dead cells in clusters were found to be significantly different from a Monte Carlo simulation of the distribution of independently inactivated cells. However, a Monte Carlo simulation model, assuming that each dead cell increased the probability of inactivation of adjacent cells, fitted 34 of the 43 observed distributions of dead cells in clusters, indicating a significant bystander effect for all the investigated treatments. The bystander-effect model parameter, defined as a cell's increase in probability of dying when it has dead neighbors, was significantly lower for 3-THPP-PDT and TPPS4-PDT than for Photofrin-PDT, ALA-PDT and treatment with metabolic inhibitors.     

Protection from inflammation, immunosuppression and carcinogenesis induced by UV radiation in mice by topical Pycnogenol

Pycnogenol is a standardized extract of the bark of the French maritime pine, Pinus pinaster Ait., that has multiple biological effects, including antioxidant, anti-inflammatory and anticarcinogenic properties. This study describes the effect of topical application of lotions containing Pycnogenol to Skh:hr hairless mice undergoing minimally inflammatory daily exposures to solar-simulated UV radiation (SSUV). We report that concentrations of Pycnogenol of 0.05-0.2% applied to the irradiated dorsal skin immediately after exposure resulted in dose-dependent reduction of the inflammatory sunburn reaction, measured as its edema component. When mice received three consecutive daily exposures of minimally edematous SSUV, their ability to raise a contact hypersensitivity (CHS) reaction was suppressed by 54%. Pycnogenol lotions applied postirradiation reduced this immunosuppression to 22% (0.05% Pycnogenol) and 13% (0.1% Pycnogenol). Furthermore, when CHS was suppressed by 71% with exogenous treatment with cis-urocanic acid, the putative epidermal mediator of photoimmunosuppression, 0.2% Pycnogenol lotion reduced the immunosuppression to 18%. Chronic exposure to SSUV on 5 days/week for 10 weeks induced skin tumors from 11 weeks in both control mice and in mice receiving daily applications of 0.05% Pycnogenol, but tumor appearance was significantly delayed until 20 weeks in mice receiving 0.2% Pycnogenol. Furthermore, whereas 100% of control mice had at least one tumor by 30 weeks, and mice treated with 0.05% Pycnogenol by 33 weeks, the maximum tumor prevalence in mice treated with 0.2% Pycnogenol was significantly reduced to 85%, with some mice remaining tumor free. Average tumor multiplicity was also significantly reduced by 0.2% Pycnogenol, from 5.2 in control mice to 3.5 at 35 weeks. Thus, topical Pycnogenol offered significant and dose-dependent protection from SSUV-induced acute inflammation, immunosuppression and carcinogenesis, when applied to the skin after daily irradiation. Pycnogenol, therefore, in addition to its recognized health benefits in other organs, appears to have potential in providing photoprotection for humans in a complementary role with sunscreens, having demonstrable activity when applied to the skin after, rather than before, UV exposure.     

Base pairing enhances fluorescence and favors cyclobutane dimer formation induced upon absorption of UVA radiation by DNA

The photochemical properties of the DNA duplex (dA)(20)·(dT)(20) are compared with those of the parent single strands. It is shown that base pairing increases the probability of absorbing UVA photons, probably due to the formation of charge-transfer states. UVA excitation induces fluorescence peaking at ～420 nm and decaying on the nanosecond time scale. The fluorescence quantum yield, the fluorescence lifetime, and the quantum yield for cyclobutane dimer formation increase upon base pairing. Such behavior contrasts with that of the UVC-induced processes.     

Redox processes induced in methemoglobin solution by mercury lamp UV light and spark-discharge plasma radiation

The buildup of–SH groups in methemoglobin by irradiation with emission of spark discharge plasma in air and UV light from a low-pressure mercury lamp (λ = 253.7 nm) has been studied. The concentration of–SH groups increases the during spark discharge treatment, with the methionine amino acid residue in the methemoglobin molecule being reduced by nitrous and peroxynitrous acids; the bonds in the methemoglobin molecule are destroyed within 20 minutes of the spark treatment. By the action of UV radiation, methionine is reduced through chromophores (tryptophan, tyrosine) and methemoglobin is reduced by O₂^.- radical ions to oxy- and deoxyhemoglobin.     

Elastic light scattering from nanoparticles by monochromatic vacuum-ultraviolet radiation

Elastic light scattering is reported using monochromatic vacuum-ultraviolet radiation to study free, spherical silica nanoparticles prepared by approaches from colloidal chemistry, with diameters between 100 and 240 nm. The colloidal nanoparticles of defined size are transferred from an aqueous solution into the gas phase using a particle beam experiment. After focusing of the particle beam by an aerodynamic lens, the scattered light from monochromatic synchrotron radiation is measured. Angle-resolved elastically scattered light is detected, showing a strong forward-scattering component. Additional evidence for the detection of elastically scattered light comes from plotting the scattered light intensity as a function of the dimensionless parameter qR, where q is the magnitude of the scattering wave vector and R is the particle radius. This yields different power-law regimes that are assigned to scattering from the surface and the bulk of the nanoparticles. Furthermore, there is evidence for modulations in the scattered light intensity as a function of scattering angle, which is clearly distinguished from the forward-scattering component. The experimental results are compared to Mie scattering simulations for isolated particles, yielding general agreement with the experimental results. Deviations from Mie simulations are observed for samples consisting of significant amounts of aggregates. The present results indicate that the optical properties of free nanoparticles are sensitively probed by vacuum-ultraviolet radiation.     

Exacerbating effect of vitamin E supplementation on DNA damage induced in cultured human normal fibroblasts by UVA radiation

The effects of vitamin E supplementation were evaluated in cultured human normal fibroblasts exposed to ultraviolet A radiation (320-380 nm) (UVA). Cells were incubated in medium containing alpha-tocopherol, alpha-tocopherol acetate or the synthetic analog Trolox for 24 h prior to UVA exposure. DNA damage in the form of frank breaks and alkali-labile sites, collectively termed single-strand breaks (SSB), was assayed by the technique of single cell gel electrophoresis (comet assay), immediately following irradiation or after different repair periods. The generation of hydrogen peroxide (H2O2) and superoxide ion (O2.-) was measured by flow cytometry through the oxidation of indicators into fluorescent dyes. It was observed that pretreatment of cells with any form of vitamin E resulted in an increased susceptibility to the photoinduction of DNA SSB and in a longer persistence of damage, whereas no significant change was observed in the production of H2O2 and O2.- reactive oxygen species, compared to untreated controls. These findings indicate that in human normal fibroblasts, exogenously added vitamin E exerts a promoting activity on DNA damage upon UVA irradiation and might lead to increased cytotoxic and mutagenic risks.     

UV radiation curing of epoxidized palm oil-cycloaliphatic diepoxide system induced by cationic photoinitiators for surface coatings

Epoxidized palm oil (EPO) can be cured with ultraviolet (UV) radiation using either radical, cationic or hybrid initiation. Cationic curing system has been chosen in this study due to the fact that epoxy groups present in EPO can be utilized directly to form cross links. Curing was carried out in a 20 cm wide UV IST machine. Triaryl sulphonium salts and ferrocenium salt were used as cationic photo initiators. Formulations were developed based on selected grades of EPO. Other materials employed included different types and concentrations of photo initiators, monomers and photo-sensitizer. The effect of post-cure conditions was also studied. The properties of the cured film, namely, pendulum hardness, percentage of gel content and tensile strength were determined. It was found that triarylsulphonium hexafluorophosphate exhibited low solubility in EPO. Addition of a vinyl ether monomer to the formulation did not enhance pendulum hardness and gel content of the cured films. Post-cure temperature had no significant effect on the properties of the cured film. The FTIR studies showed evidence of the ring opening of the epoxide groups present in the formulation.     

UV radiation and skin cancer in Norway

A distinct increase in skin cancer incidences is observed since the registration started in Norway in the 1950s. As UV radiation is assumed to be the main risk factor for skin cancer, hourly values of the UV irradiance were reconstructed for the period 1957–2005 for 17 of the Norwegian counties (58–70°N). For reconstruction, a radiation transfer model is run with total ozone amount and cloud information as meteorological input. Reconstructed hourly erythemally weighted UV irradiances for about 5 years are compared to measurements at four stations, two stations representing the north–south extension of Norway, and two stations at about 60°N representing the eastern inland – Western coastal contrasts. The agreement between reconstructed and measured UV varies between 0% for the northernmost site to 10–15% overestimation for the other locations. For clear sky, a reasonable agreement between reconstructed and measured data was found for all stations, while for overcast, an overestimation of 10–20% was found for all but the northernmost station. Both the cancer incidences and the reconstructed UV values have a distinct north–south increase. The UV increase towards south is mostly due to increasing solar elevation. The west to east increase is much smaller, and differences in UV are due to differences in both cloud optical thickness and total cloud amount. One additional outcome from this work is that long-term UV-data are reconstructed for Norway, data that can be used in further biological and medical studies related to UV effects.     

Reductive DNA cleavage induced by UVA photoirradiation of NADH without oxygen

UVA irradiation of dihydronicotinamide coenzyme (NADH), which plays a key role in a number of biological redox processes, results in effective DNA cleavage without oxygen via photoionization of NADH and the subsequent reaction of hydrated electron with DNA as well as photoinduced electron transfer from NADH to DNA.     

Purification and crystallization of aldolase from Drosophila melanogaster

A method for the preparation of pure crystalline aldolase (type A) from pupae of Drosophila melanogaster is described.     

Isoflavonoid compounds from red clover (Trifolium pratense) protect from inflammation and immune suppression induced by UV radiation

Isoflavones derived from many edible plants have been reported to possess significant antioxidant, estrogenic and tyrosine kinase inhibitory activity. Genistein has been found previously to provide protection from oxidative damage induced by UV radiation both in vitro and following dietary administration. We have therefore examined the potential of a number of isoflavones from red clover (Trifolium pratense) and some metabolically related compounds to offer protection from UV irradiation in hairless mice by topical application after UV exposure. We show that whereas the primary isoflavones, daidzein, biochanin A and formononetin, were inactive, 20 microM lotions of genistein and the metabolites equol, isoequol and the related derivative dehydroequol had powerful potential to reduce the inflammatory edema reaction and the suppression of contact hypersensitivity induced by moderate doses of solar-simulated UV radiation. For equol the protection was concentration dependent and 5 microM equol markedly reduced the UV-induced inflammation but abrogated the UV-induced immunosuppression. Equol protected similarly from immunosuppression induced by the putative epidermal mediator, cis-urocanic acid (UCA), indicating a potential mechanism of action involving inactivation of this UV-photoproduct. Since immunosuppression induced by both UV radiation and by cis-UCA appears to be an oxidant-dependent response our observations support the actions of these topically applied isoflavones and their metabolites as antioxidants. They also indicate that lotions containing equol, unlike topical UV sunscreens, more readily protect the immune system from photosuppression than from the inflammation of the sunburn reaction, even when applied after exposure, and thus such compounds may have a future role as sun-protective cosmetic ingredients.     

Photo-degradation of PADC by UV radiation at various wavelengths

The effects of ultraviolet (UV) photons at different wavelengths (namely UVA, UVA + B and UVC) on PADC (polyallyl diglycol carbonate) were investigated in this study. The chemical modifications were studied by Fourier Transform Infrared (FTIR) spectrometry and the corresponding nano-mechanical properties were also determined. The scission process could be revealed by the decreasing net absorbance at particular wavelengths in the infrared (IR) spectra. On the other hand, the cross-linking was indicated by the increased hardness and reduced modulus determined with a nanoindenter. UVA caused no chemical modifications as most of the UV photons in this range were not absorbed by PADC. Both UVA + B and UVC irradiation caused scission of the chemical bonds, which was also manifested by the faster chemical etching rates. The bulk etch rate increased from 1.37 to 5.73 μm/h for 60 h of UVA + B exposure for 3 h of chemical etching, and increased to 5.13 μm/h for 60 h of UVC exposure. For 3 h of etching, the bulk etch rate remained unchanged for UVC exposures longer than 20 h. The saturation of the bulk etch rate was due to formation of cross-linked structures on the surface of the PADC samples. It was also observed that a UVC exposure caused a comparatively higher bulk etch rate at the beginning of etching. However, the bulk etch rate decreased with the depth of the PADC sample due to the lower rate of oxygen diffusion into deeper regions.     

Photoimmunology: the mechanisms involved in immune modulation by UV radiation

Ultraviolet radiation (UVR) may be the most prevalent agent that man encounters in his environment. As a result, certain biological adaptations take advantage of the beneficial effects of UVR exposure, e.g. the photoactivation steps involved in vitamin D metabolism. In this regard, UVR plays an important role in maintaining our good health; however, it must be noted that UVR is potentially the most harmful naturally occurring agent in our environment. Thus, it appears that several mechanisms have evolved to protect us against the detrimental effects of UVR overexposure. Although epidermal melaninization or "tanning" may be the most obvious example of these processes, we would argue that adoptive mechanisms within the immune system also provide protection against UVR-induced skin damage. It is now known that UVR affects the distribution and functional activities of various immunocompetent cells within the skin, as well as modifying the production of inflammatory and hematopoietically active cytokines. This review will focus on the known mechanisms involved in the immune modulatory effects of UVR and how adoptive immune responses to UVR-induced skin damage contribute to specific pathological processes.     

Hydroxyl radical quenching agents protect against DNA breakage caused by both 365-nm UVA and by gamma radiation

The ability of hydroxyl radical (.OH) scavengers to reduce DNA breakage in isolated DNA from Bacillus subtilis by either gamma radiation or monochromatic radiation in the UVA region (365 nm) was examined by comparing dose reduction factors (the ratio of dose required to induce n DNA breaks in the absence to the presence of quencher). Previous data have demonstrated that acetate, formate, azide, and mannitol protect supercoiled DNA against gamma-radiation-induced ssb (single-strand breaks-relaxation of supercoil by first nick) in close agreement with the rate at which their solutions quench .OH. Here we show that these quenchers also protect against 365-nm-induced ssb. The ratios for protection against 365-nm induced DNA ssb in isolated B. subtilis DNA by the four quenchers are also in proportion to their ability to quench .OH. In view of the diverse chemical nature of the quenchers and the wide range of concentrations involved, these findings are evidence that both these radiations may induce ssb in DNA via a common step that might involve .OH.     

Induction and repair of cyclobuta-dithymidine photoproducts in hamster skin by solar-simulated UV radiation

The induction and repair of cyclobuta-dithymidine (T less than greater than T) photoproducts in hamster skin was measured following exposure to artificial solar radiation. DNA extracted from irradiated hamster epidermis was analyzed by enzyme-linked immunosorbent assay (ELISA) using a monoclonal antibody specific for T less than greater than T photoproducts. Between 49% and 58% of T less than greater than T antibody binding sites were eliminated from DNA by 24 h after radiation exposures comparable with approximately 60 - 120 min of midday sunlight, whereas all detectable T less than greater than T binding sites were eliminated by 24 h after a radiation exposure comparable with 30 min of sunlight.