UVA and UVB Photoprotective Capabilities of Topical Formulations Containing Mycosporine-like Amino Acids (MAAs) through Different Biological Effective Protection Factors (BEPFs).

The safety and stability of synthetic UV-filters and the procedures for evaluating the photoprotective capability of commercial sunscreens are under continuous review. The influence of pH and temperature stressors on the stability of certain Mycosporine-like amino acids (MAAs) isolated at high purity levels was examined. MAAs were highly stable at room temperature during 24 h at pH 4.5⁻8.5. At 50 °C, MAAs showed instability at pH 10.5 while at 85 °C, progressive disappearances were observed for MAAs through the studied pH range. In alkaline conditions, their degradation was much faster. Mycosporine-serinol and porphyra-334 (+shinorine) were the most stable MAAs under the conditions tested. They were included in four cosmetically stable topical sunscreens, of which the Sun Protection Factor (SPF) and other Biological Effective Protection Factors (BEPFs) were calculated. The formulation containing these MAAs showed similar SPF and UVB-BEPFs values as those of the reference sunscreen, composed of synthetic UV absorbing filters in similar percentages, while UVA-BEPFs values were slightly lower. Current in vitro data strongly suggest that MAAs, as natural and safe UV-absorbing and antioxidant compounds, have high potential for protection against the diverse harmful effects of solar UV radiation. In addition, novel complementary in vitro tests for evaluation of commercial sunscreens efficacy are proposed.

Solar urticaria in 145 patients: Assessment of action spectra and impact on quality of life in adults and children.

BACKGROUND: Solar urticaria (SU) is a rare chronic inducible urticaria triggered via uncharacterized chromophores. We detail responses of a large patient series to monochromator phototesting and broadband ultraviolet radiation (UVR); relationship to life quality is explored. METHODS: Retrospective review of all SU patients undergoing standardized diagnostic photoinvestigation at a specialist centre during 2000-2016. From 2011, patients completed dermatology life quality index (DLQI) questionnaires for the past week and year. RESULTS: In 145 patients (mean: 35.8, range: 3-69 years; 18 aged <18 years; 100 female), combined phototesting with broadband UVR and monochromator sources successfully provoked 74.5% patients, with 65.6% provoked by broadband UVR alone and 57.9% by monochromated radiation alone. The narrow wavebands most frequently eliciting wheal and flare response were between 370 and 400 nm, with 25% patients at 300 ± 5 nm, 53.6% at 320 ± 10 nm, 66.7% at 330 ± 10 nm, 77.4% at 350 ± 20 nm, 83.3% at 370 ± 20 nm, 86.9% at 400 ± 20 nm, 44% at 500 ± 20 nm and 17.8% at 600 ± 20 nm. In 62 patients, the DLQI revealed 56.1% had very to extremely large impact in the past week (all patients: mean score: 11.1, range: 0-29) rising to 69.8% for the past year (12.5, 0-30); adults and children were similarly affected. Patients with positive photoprovocation had higher DLQI score than those who were negative (DLQI for past week: mean: 12.6 ± SEM 1.1 vs 4.6 ± 1.4, P < .01). CONCLUSION: SU is predominantly provoked by longer UVA-shorter visible radiation, which penetrates window-glass and where sunscreens are less effective; impact on life quality is considerable. Photoprotective agents effective against this spectrum are needed.

Wavelength-dependent photooxidation and photoreduction of protochlorophyllide and protochlorophyll in the innermost leaves of cabbage (Brassica oleracea var. capitata L.).

The photoreduction and photooxidation processes of different protochlorophyll(ide) forms were studied in the innermost leaves of cabbage (Brassica oleracea var. capitata L.) under monochromatic irradiations. Room-temperature fluorescence emission spectra were measured from the same leaf spots before and after illumination to follow the wavelength dependence of the photochemical reactions. Short-wavelength light of 7 µmol photons m(-2) s(-1) (625-630 nm) provoked mainly bleaching, and longer wavelengths (630-640 nm) caused both bleaching and photoreduction, while above 640 nm resulted in basically photoreduction. When bleached leaves were kept in darkness at room temperature, all protochlorophyll(ide) forms regenerated during 72 h. Oxygen-reduced environment decreased the extent of bleaching suggesting the involvement of reactive oxygen species. These results confirm that the short-wavelength, 628 nm absorbing, and 633 nm emitting protochlorophyll(ide) form in etiolated cabbage leaves sensibilizes photooxidation. However, the 628 nm light at low intensities stimulates the photoreduction of the longer wavelength protochlorophyllide forms. Kinetic measurements showed that photoreduction saturates at a low PFD (photon flux density) compared to bleaching, suggesting that the quantum yield of photoreduction is higher than that of bleaching.

Method for correction of experimental action spectrum using actual overlapping spectra of radiation sources.

Experimental dependency of the photosystem's response on the wavelength of exciting radiation, also known as action spectrum, may be substantially affected by the spectrum shape of this radiation. This is especially important in the case, when different radiation sources are used for the investigation of action spectrum. For instance, too wide emission peaks of radiation sources can blur the scopes of actual action spectrum and distort information about the properties of photosystem at certain wavelength regions. Here, we propose a method for the correction of experimental action spectrum by the recalculation of experimental data of photoresponse according to actual spectra of exciting radiation. In the case of overlapping radiation spectra from different radiation sources, this method results in much better correlation of experimental action spectrum to actual action spectrum or absorption spectrum of photosystem. The data on photoactivity of several photocatalysts are presented to illustrate and validate the proposed method.•Activity of photosystem depends on the actual spectrum of the radiation source•Single-peak optical radiation sources with the same basic wavelength may cause a different photoactivity•Effect of actual spectrum of the light source on the photoactivity is to be considered.

Wavelengths and temporal effects on the response of mammalian cells to UV radiation: Limitations of action spectra illustrated by genotoxicity.

All photobiological events depend on the wavelength of the incident radiation. In real-life situations and in the vast majority of laboratory experiments, exposure always involves sources with various emission spectra spreading over a wide wavelength range. Action spectra are often used to describe the efficiency of a process at different wavelengths and to predict the effects of a given light source by summation of the individual effects at each wavelength. However, a full understanding of the biological effects of complex sources requires more than considering these concomitant events at each specific wavelength. Indeed, photons of different energies may not have additive but synergistic or inhibitory effects on photochemical processes and cellular responses. The evolution of a photobiological response with post-irradiation time must also be considered. These two aspects may represent some limitations to the use of action spectra. The present review, focused on mammalian cells, illustrates the concept of action spectrum and discusses its drawbacks using theoretical considerations and examples taken from the literature. Emphasis is placed on genotoxicity for which wavelength effects have been extensively studied. Other effects of UV exposure are also mentioned.

Functional Characterization of Pseudoidium neolycopersici Photolyase Reveals Mechanisms Behind the Efficacy of Nighttime UV on Powdery Mildew Suppression.

Powdery mildews can be controlled by brief exposure to ultraviolet (UV) radiation with devastating effect on their developmental stages including conidia germination. The treatment effect can be impaired by subsequent exposure to UV-A/blue light. UV-A/blue light-activated photolyase may be responsible for this and therefore we tested the function of three cryptochrome/photolyase family (CPF)-like genes (OINE01015670_T110144, OINE01000912_T103440, and OINE01005061_T102555) identified in the obligate biotrophic fungus Pseudoidium neolycopersici, the cause of tomato powdery mildew. A photolyase-deficient mutant of Escherichia coli transformed with coding sequence of OINE01000912_T103440 and exposed to brief (UV)-C treatment (peak emission at 254 nm) showed photoreactivation and cell survival when exposed to subsequent blue light, indicating complementation of photolyase activity. In contrast, the same photolyase-deficient E. coli transformed with the coding sequences of other two CPF-like genes did not survive this treatment, even though their expression were confirmed at protein level. This confirmed that OINE01000912_T103440 is a gene encoding photolyase, here named PnPHR1, with functionality similar to the native photolyase in E. coli, and classified as a class I cyclobutane pyrimidine dimer (CPD) photolyase. Modeling of the 634-amino acid sequence of PnPHR1 suggested that it is capable of binding flavin adenine dinucleotide (FAD) and methenyltetrahydrofolate (MTHF). However, spectroscopic data of the protein produced in an E. coli expression system could only reveal the presence of a reduced form of FAD, i.e., FADH- as an intrinsic chromophore. Within the tested wavelength range of 365-525 nm, the survival of photolyase-deficient mutant E. coli transformed with PnPHR1 showed a broad action spectrum from 365 to 454 nm. This was very similar to the previously characterized action spectrum for survival of P. neolycopersici conidia that had been treated with UV-C. Quantitative RT-PCR revealed that the expression of PnPHR1 in P. neolycopersici conidia was induced by UV-C, and peak expression occurred 4 h after brief UV-C treatment. The expression of PnPHR1 was repressed when incubated in red light after the UV-C treatment, but not when incubated in UV-A/blue light. The results may explain why the disease-reducing effect of short wavelength UV is impaired by exposure to UV-A and blue light.

Wavelength-Specific Behavior of the Western Flower Thrips (Frankliniella occidentalis): Evidence for a Blue-Green Chromatic Mechanism.

The western flower thrips (Frankliniella occidentalis) is a serious pest in horticulture, feeding on leaf tissue and floral resources. Blue and yellow sticky traps are commonly used for monitoring and control in greenhouses. The mechanisms underlying the color preferences are largely unknown. The use of light-emitting diodes (LEDs) is a promising approach to increase the attractiveness of visual traps and to study the color choice behavior in insects. The color preferences of F. occidentalis were systematically investigated in a series of choice experiments with several LEDs from the ultraviolet (UV) and visible spectral range. Blue LEDs were most attractive, followed by green, while only a moderate attractiveness of UV was observed. Blue and green were identified as two separate attractive ranges. When light from blue and green LEDs was mixed, the attractiveness decreased compared to its single components. In conclusion, F. occidentalis exhibits two different wavelength specific behaviors towards blue and green. Compelling indications are provided that these behaviors are controlled by two photoreceptors maximally sensitive in the blue and green range with an inhibitory chromatic interaction between both. Since the known UV sensitive photoreceptor could be confirmed, a trichromatic photoreceptor setup is suggested for F. occidentalis. For advanced plant protection strategies, the results offer several opportunities to optimize monitoring or even develop mass trapping devices.

Wavelength dependent recovery of UV-mediated damage: Tying up the loose ends of optical based powdery mildew management.

Controlled environment chamber experiments at Petri dish level were conducted to examine the wavelength and dose dependent efficacy of ultraviolet (UV) radiation, the recovery action potential of optical radiation applied concomitantly/subsequently to effective UV treatment, and the lapse time between UV treatment and subsequent exposure to recovery wavelength on germination efficiency of Oidium neolycopersici conidia. Conidia of eight- to nine-day-old colonies were dusted on water agar surface in Petri dishes and exposed to UV treatments (without lid). Immediately after UV treatments, Petri dishes were sealed and incubated in darkness or differing optical environments generated using seven different radiation sources (range 290nm to 780nm). Twenty-four hours after UV treatment, fifty conidia from each sample were assessed for germination. Compared to non-UV controls, <10% of the conidia germinated after 30s of exposure to 254nm or 283nm UV and subsequent dark incubation. Conidia germination was almost negligible if the exposure duration increased to 4min. Germination was about 60% with broad spectrum UV after 1min of exposure, and about 35% after 2 to 4min of exposure. There was no reduction of conidia germination with the exposure of ≤4min with 310nm. With the tested wavelength and dose ranges, germination recovery was effective in the 350nm to 500nm range. Germination efficiency of conidia treated with effective UV was significantly higher (>73%) if incubated subsequently in the 350nm to 500nm range (germination recovery). Furthermore, germination recovery depends on the characteristics of UV treatment (wavelength, and duration of exposure) and the lapse time between UV treatment and subsequent exposure to optical radiation in the recovery range. The findings of this study provide key criteria for wavelength selection, combination and application time in the optical radiation range, enabling improved design of optical based management strategies against powdery mildews.

Partitioning of absorbed light energy within photosystem II in barley can be affected by chloroplast movement.

Plants have developed many ways to protect reaction centres of photosystems against overexcitation. One of the mechanisms involves reduction of the leaf absorption cross-section by light-induced chloroplast avoidance reaction. Decrease in the probability of photon absorption by the pigments bound within photosystem II (PSII) complexes leads to the increase in quantum yield of PSII photochemistry (ΦPSII). On the other hand, the decrease of PSII excitation probability causes reduction of chlorophyll a fluorescence intensity which is manifested as the apparent increase of determined quantum yield of regulated light-induced non-photochemical quenching (ΦNPQ). Absorption of different light intensity by phototropins led to the different chloroplast distribution within barley leaves, estimated by measurement of the leaf transmittance. Due to a weak blue light used for transmittance measurements, leaves exposed to actinic light with wavelengths longer than 520 nm undergo chloroplast accumulation reaction, in contrast with leaves exposed to light with shorter wavelengths, that showed a different extent of chloroplast avoidance reaction. Based on the ΦNPQ action spectra measured simultaneously with the transmittance, the influence of different chloroplast distribution on ΦNPQ was assessed. The analysis of results showed that decrease in the leaf absorption cross-section due to increasing part of chloroplasts reaching profile position significantly affected the partitioning of excitation energy within PSII and such rearrangement also distorted measured ΦNPQ and cannot be neglected in its interpretation. When the majority of chloroplasts reached profile position, the photoprotective effect appeared to be the most prominent for strong blue light that has the highest absorption in the upper leaf layers in comparison with green or red ones.

Determination of UV action spectra affecting the infection process of Oidium neolycopersici, the cause of tomato powdery mildew.

Oidium neolycopersici, the cause of powdery mildew in tomato, was exposed to UV radiation from 250 to 400 nm for 1, 12, or 24 min. Radiation ≤ 280 nm strongly reduced conidial germination, hyphal expansion, penetration attempt and infection of O. neolycopersici. From 290 to 310 nm the effect depended on duration of exposure, while there was no effect ≥ 310 nm. There were no significant differences within the effective UV range (250-280 nm). Conidial germination on a water agar surface was <20% or around 40%, respectively, if samples were exposed for 1 min within the effective UV range followed by 24h or 48 h incubation. Twelve or 24 min exposure reduced germination to close to nil. A similar trend occurred for germination of conidia on leaf disks on water agar in Petri dishes. The effective UV range significantly reduced all subsequent developmental stages of O. neolycopersici. There was no cytoplasmic mitochondrial streaming in conidia exposed to the effective UV range, indicating that there may be a direct effect via cell cycle arrest. There was no indication of reactive oxygen species involvement in UV mediated inhibition of O. neolycopersici. Optical properties of O. neolycopersici indicated that the relative absorption of UV was high within the range of 250 to 320 nm, and very low within the range of 340 to 400 nm. Identification of UV wavelengths effective against O. neolycopersici provides a future basis for precise disease control.

Two wavelength-dependent mechanisms of sensitisation of light-induced quenching in the isolated light-harvesting complex II.

The efficiency of visible light in inducing fluorescence quenching in the isolated light-harvesting complex II (LHCII) of higher plants is investigated by action spectroscopy in the visible portion of photosynthetic active radiation. The efficiency spectrum displays a relatively homogenous quenching yield across the most intense electronic transitions of the chlorophyll a and carotenoid pigments, indicating that quenching proceeds from the equilibrated state of the complex. Larger yields are observed in the 510-640-nm window, where weak transitions of LHCII-bound chromophores occur. This observation is interpreted in terms of an additional quenching sensitisation process mediated by these electronic transitions.

Aerobic photoreactivity of synthetic eumelanins and pheomelanins: generation of singlet oxygen and superoxide anion.

In this work, we examined photoreactivity of synthetic eumelanins, formed by autooxidation of DOPA, or enzymatic oxidation of 5,6-dihydroxyindole-2-carboxylic acid and synthetic pheomelanins obtained by enzymatic oxidation of 5-S-cysteinyldopa or 1:1 mixture of DOPA and cysteine. Electron paramagnetic resonance oximetry and spin trapping were used to measure oxygen consumption and formation of superoxide anion induced by irradiation of melanin with blue light, and time-resolved near-infrared luminescence was employed to determine the photoformation of singlet oxygen between 300 and 600 nm. Both superoxide anion and singlet oxygen were photogenerated by the synthetic melanins albeit with different efficiency. At 450-nm, quantum yield of singlet oxygen was very low (~10-4 ) but it strongly increased in the UV region. The melanins quenched singlet oxygen efficiently, indicating that photogeneration and quenching of singlet oxygen may play an important role in aerobic photochemistry of melanin pigments and could contribute to their photodegradation and photoaging.

Effect of Substrates on the Photoelectrochemical Reduction of Water over Cathodically Electrodeposited p-Type Cu2O Thin Films.

In this study, we demonstrate development of p-Cu2O thin films through cathodic electrodeposition technique at constant current of 0.1 mA/cm(2) on Cu, Al, and indium tin oxide (ITO) substrates from basic CuSO4 solution containing Triton X-100 as the surfactant at 30-35 °C. The optical and morphological characterizations of the semiconductors have been carried out using UV-vis spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), and Raman spectroscopy. The band gap energy of ∼2.1 eV is recorded, whereas SEM reveals that the surface morphology is covered with Cu2O semiconductors. XRD analyses confirm that with change in substrate, the size of Cu2O "cubic" crystallites decreases from ITO to Al to Cu substrates. Photoelectrochemical characterizations under dark and illuminated conditions have been carried out through linear sweep voltammetry, chronoamperometry and electrochemical impedance spectroscopic analysis. The photoelectrochemical reduction of water (H2O → H2) in pH 4.9 aqueous solutions over the different substrates vary in the order of Cu > Al > ITO. The highest current of 4.6 mA/cm(2) has been recorded over the Cu substrate even at a low illumination of 35 mW/cm(2), which is significantly higher than the values (2.4 mA/cm(2) on Au coated FTO or 4.07 mA/cm(2) on Cu foil substrate at an illumination of 100 mW/cm(2)) reported in literature.

Soret Band of the Gas-Phase Ferri-Cytochrome c.

We report the first visible spectrum of a heme-protein in the gas phase. The aim of this work was to provide a reference for the optical absorption of an isolated heme-protein to better understand the influence of protein conformation and fluctuation and of solvent on its optical properties. After laser irradiation of gas-phase cytochrome c (cyt c), electron emission is observed. Electron photodetachment yield of cyt c 6- was recorded in the region of the Soret band of the porphyrin group, showing a maximum at 410 nm. Our results are compared with optical spectra of gas-phase heme and of cyt c in solution. We discuss the influence of the polypeptide chain and of the solvent on both the position and the broadening of the Soret band. Action spectrum of gas-phase cyt c is close to the absorption of native cyt c in solution, suggesting an efficient protection of the heme group from solvent accessibility by the polypeptide chain and similar interactions between the two moieties in solution and the gas phase.