Energetic Wavelengths Research Articles

Understanding the Internal Conversion Efficiency of BiVO4/SnO2 Photoanodes for Solar Water Splitting: An Experimental and Computational Analysis.

This work aims to understand the spin-coating growth process of BiVO4 photoanodes from a photon absorption and conversion perspective. BiVO4 layers with thicknesses ranging from 7 to 48 nm and the role of a thin (<5 nm) SnO2 hole-blocking layer have been studied. The internal absorbed photon-to-current efficiency (APCE) is found to be nonconstant, following a specific dependence of the internal charge separation and extraction on the increasing thickness. This APCE variation with BiVO4 thickness is key for precise computational simulation of light propagation in BiVO4 based on the transfer matrix method. Results are used for accurate incident photon-to-current efficiency (IPCE) prediction and will help in computational modeling of BiVO4 and other metal oxide photoanodes. This establishes a method to obtain the sample's thickness by knowing its IPCE, accounting for the change in the internal APCE conversion. Moreover, an improvement in fill factor and photogenerated voltage is attributed to the intermediate SnO2 hole-blocking layer, which was shown to have a negligible optical effect but to enhance charge separation and extraction for the lower energetic wavelengths. A Mott-Schottky analysis was used to confirm a photovoltage shift of 90 mV of the flat-band potential.

Green synthesis silver nanoparticles Bougainvillea glabra Choisy/LED light with high catalytic activity in the removal of methylene blue aqueous solution.

In this study, we evaluated, in a pioneering way, the influence of wavelengths from the decomposition of white light on the production and physicochemical properties of silver nanoparticles (AgNPs). Bearing in mind a process of green synthesis, an extract of the bracts of Bougainvillea glabra Choisy (BgC) was used, a species native to tropical and subtropical regions and frequently used in ornamentation, possessing in its photochemical composition, biomolecules capable of acting as reducing agents for convert Ag+ to Ag0. We used light-emitting diodes (LED) to obtain the desired wavelengths (violet, blue, green, yellow, orange, and red) in the test called rainbow, and we evaluated the obtaining of AgNPs compared to white LED light, nature, and absence of light. In the rainbow assay, we obtained a gradual increase in the intensity of the plasmonic band resonance from the red wavelength (0.124 ± 0.067 a.u.) to violet (0.680 ± 0.199 a.u.), indicating a higher reaction yield in obtaining AgNPs. Smaller hydrodynamic sizes (approximately 150nm) at more energetic wavelengths (violet, blue, and green) about less energetic wavelengths (yellow, orange, and red) (approximately 400nm) were obtained. Analysis by SEM microscopy, FTIR spectroscopy, and X-ray diffraction indicates the presence of silver nanoparticles in all LED colors used together with white LED light and Laboratory light (natural light). Due to the high environmental demand to remove pollutants from water sources, including textile dyes, we applied AgNPs/BgC to remove methylene blue (MB) dye from an aqueous solution. A minimum removal percentage greater than 65%, with emphasis on formulations synthesized by the colors of violet LED (84.27 ± 2.65%) and orange LED (85.91 ± 1.95%), was obtained.

Synthesis of Catechol Derived Rosamine Dyes and Their Reactivity toward Biogenic Amines.

Functional organic dyes play a key role in many fields, namely in biotechnology and medical diagnosis. Herein, we report two novel 2,3- and 3,4-dihydroxyphenyl substituted rosamines (3 and 4, respectively) that were successfully synthesized through a microwave-assisted protocol. The best reaction yields were obtained for rosamine 4, which also showed the most interesting photophysical properties, specially toward biogenic amines (BAs). Several amines including n- and t-butylamine, cadaverine, and putrescine cause spectral changes of 4, in UV–Vis and fluorescence spectra, which are indicative of their potential application as an effective tool to detect amines in acetonitrile solutions. In the gas phase, the probe response is more expressive for spermine and putrescine. Additionally, we found that methanolic solutions of rosamine 4 and n-butylamine undergo a pink to yellow color change over time, which has been attributed to the formation of a new compound. The latter was isolated and identified as 5 (9−aminopyronin), whose solutions exhibit a remarkable increase in fluorescence intensity together with a shift toward more energetic wavelengths. Other 9-aminopyronins 6a, 6b, 7a, and 7b were obtained from methanolic solutions of 4 with putrescine and cadaverine, demonstrating the potential of this new xanthene entity to react with primary amines.

Ultraviolet Spectroscopy and Photochemistry of SO2/H2O Ices

The presence of sulfur dioxide on the trailing hemisphere of Europa’s surface is well-established, and both its presence and its chemistry are influenced by sulfur ion implantation. Particle irradiation is known to be a significant radiolysis source, particularly on the trailing surface, which is subject to particles in Jupiter’s plasma torus. Photochemistry driven by solar ultraviolet (UV) photons is also significant. To date, most studies have investigated the effects of vacuum UV radiation, while photochemistry at longer wavelengths is less well-studied. This work investigates chemical changes in thin, cryogenic films of SO2/H2O at temperatures and pressures relevant to Europa’s surface when subjected to temperature changes and UV radiation at 147, 206, 254, and 284 nm. Spectra were collected in both the mid-infrared range and the UV range, which elucidates electronic transitions that are less diagnostic but perhaps more applicable to reflectance spectra of solar system bodies. These experiments show irreversible red shifting of the B̃ ← X̃ absorption peak upon heating likely as a result of crystallization and/or thermal chemical reactions. Further, photons with wavelengths up to 284 nm are shown to induce significant chemistry in SO2/H2O mixtures. This in conjunction with the increased solar flux compared to more energetic wavelengths and the strong C̃ ← X̃ and B̃ ← X̃ absorption bands in SO2 suggests that far-UV radiation plays a significant role in the sulfur cycle on Europa.

Synthesis of novel ZnO/carbon xerogel composites: Effect of carbon content and calcination temperature on their structural and photocatalytic properties

This paper reports the development of new ZnO/carbon xerogel composites (XZn w) for photocatalytic applications. The use of black wattle tannin as a precursor to the carbon xerogel aimed at reducing costs and environmental impacts. The composites were characterized by diffuse reflectance spectroscopy (DRS), BET surface area, scanning electron microscopy (FEG-SEM), X-ray photoelectron spectroscopy (XPS), energy dispersive spectroscopy (EDS), infrared spectroscopy (IR), and X-ray diffraction (XRD). The photocatalytic performance of the materials was evaluated in the decomposition process of methylene blue, a known toxic pollutant. The impacts of the catalyst dosage and calcination temperature on the photocatalytic process were also examined systematically. The X-ray profiles of the XZn w evidenced the existence of the hexagonal structure of the zinc oxide (wurtzite) in the composites. The XPS and XRD analyses confirmed the incorporation of carbon in the zinc oxide crystalline structure. The higher carbon content resulted in a larger surface area. All composites presented the ability to absorb radiation in less energetic wavelengths, contrary to pure zinc oxide that only absorbs radiation of wavelengths below 420 nm. The optimal dosage and calcination temperature were found to be 0.2 g L−1 and 300 °C. All the developed composites displayed significant photocatalytic activities in the decomposition of methylene blue under both visible and solar light. The composites had superior photocatalytic efficiency under visible light when compared to pure zinc oxide. The XZn 0.5 presented the best degradation efficiency under visible radiation. All materials presented similar photocatalytic responses under solar light, evidencing the synergy between the carbon xerogel and the zinc oxide. The photocatalytic mechanism was evaluated by trapping experiments to be mainly controlled by the electron vacancies that are generated during the photoexcitation of the composites.

Photochemical release of sediment bound brevetoxin (PbTx-2) from resuspended sediments

Marine sediments from coastal Florida, USA impacted by Karenia brevis blooms were resuspended in seawater and irradiated in a solar simulator to determine if sedimentary bound PbTx-2 is photolytically released into the aqueous phase. All bulk and size-fractionated (<10–20μm) sediments exhibited photorelease of PbTx-2 after a six-hour full spectrum irradiation. The magnitude of photorelease of a size-fractionated sediment (250±20pmolg−1) was greater on a per gram basis compared to an analogous bulk sediment (1.66±0.89pmolg−1). Experiments conducted with photosynthetically active radiation (λ=400–700nm) indicated that these less energetic wavelengths are also capable of releasing toxin from sediments. Two of three sediments autoclaved prior to irradiation with full spectrum sunlight exhibited a statistically significant photorelease of PbTx-2 into the aqueous phase suggesting abiotic processes are important in photoproduction of the toxin. The importance of PbTx-2 production from exposure of resuspended sediments to sunlight was estimated using photorelease data from the current study and previously reported total suspended solid concentrations for this region. The PbTx-2 produced from this process could account for 0.5–13% of extracellular brevetoxin concentration previously reported during a low level Karenia brevis bloom. Results of this study have significant implications for water quality management because they suggest a potentially important vector of toxin to overlying waters and ecosystems even in the absence of a Karenia brevis bloom.

Photocontrolled release using one-photon absorption of visible or NIR light

Light is an excellent means to externally control the properties of materials and small molecules for many applications. Light's ability to initiate chemistries largely independent of a material's local environment makes it particularly useful as a bio-orthogonal and on-demand trigger in living systems. Materials responsive to UV light are widely reported in the literature; however, UV light has substantial limitations for in vitro and in vivo applications. Many biological molecules absorb these energetic wavelengths directly, not only preventing substantial tissue penetration but also causing detrimental photochemical reactions. The more innocuous nature of long-wavelength light (>400nm) and its ability at longer wavelengths (600–950nm) to effectively penetrate tissues is ideal for biological applications. Multi-photon processes (e.g. two-photon excitation and upconversion) using longer wavelength light, often in the near-infrared (NIR) range, have been proposed as a means of avoiding the negative characteristics of UV light. However, high-power focused laser light and long irradiation times are often required to initiate photorelease using these inefficient non-linear optical methods, limiting their in vivo use in mammalian tissues where NIR light is readily scattered. The development of materials that efficiently convert a single photon of long-wavelength light to chemical change is a viable solution to achieve in vivo photorelease. However, to date only a few such materials have been reported. Here we review current technologies for photo-regulated release using photoactive organic materials that directly absorb visible and NIR light.

Cutaneous hypothalamic-pituitary-adrenal axis homolog: regulation by ultraviolet radiation

The hypothalamic-pituitary-adrenal (HPA) axis maintains basal and stress-related homeostasis in vertebrates. Skin expresses all elements of the HPA axis including corticotropin-releasing hormone (CRH), proopiomelanocortin (POMC), ACTH, β-endorphin (β-END) with corresponding receptors, the glucocorticoidogenic pathway, and the glucocorticoid receptor (GR). To test the hypothesis that cutaneous responses to environmental stressors follow the organizational structure of the central response to stress, the activity of the "cutaneous HPA" axis homolog was investigated after exposure to ultraviolet radiation (UVR) wavelengths of UVA (320-400 nm), UVB (280-320 nm), and UVC (100-280 nm) in human skin organ culture and in co-cultured keratinocytes/melanocytes. The level of stimulation of CRH, POMC, MC1R, MC2R, CYP11A1, and CYP11B1 genes was dependent on UV wavelengths and doses, with the highest effects observed for highly energetic UVC and UVB. ELISA and Western assays showed significant production of CRH, POMC, ACTH, and CYP11A1 proteins and of cortisol, with a decrease in GR expression only after UVB and UVC. However, β-END expression was also stimulated by UVA. Immunocytochemistry localized the deposition of the aforesaid antigens predominantly to the epidermis with additional accumulation of CRH, β-END, and ACTH in the dermis. UVR-stimulated CYP11A1 expression was seen in the basal layer of the epidermis and cells of adjacent dermis. Thus, the capacity to activate or change the spatial distribution of the cutaneous HPA axis elements is dependent on highly energetic wavelengths (UVC and UVB), implying a dependence of a local stress response on their noxious activity with overlapping or alternative mechanisms activated by UVA.

Surface checking of wood is increased by photodegradation caused by ultraviolet and visible light

The aim of this research was to test the hypothesis that exposure to solar radiation increases the checking of wood exposed to the weather, and to examine the causes and spectral dependency of such an effect. Lodgepole pine decking samples were exposed outdoors under filters, which blocked selected regions of the solar spectrum while allowing other weathering factors to act on samples. Surface checking in samples was quantified after 12, 24 and 36 weeks of exposure, and the chemical and micro-structural changes occurring at weathered wood surfaces were examined. Check numbers and dimensions were greater in samples exposed under a filter to the full solar spectrum than in samples exposed under filters that blocked the transmission of UV, visible or infrared radiation. Samples that were shielded from more energetic wavelengths developed less checking and also showed less delignification at the exposed wood surfaces. Checks developed at the margins of rays and propagated at the interface between adjacent tracheids, close to the middle lamella. We conclude that exposure to UV and visible light increases the tendency of wood to check during exterior exposure. Our findings point to a link between changes in cell micro-structure as a result of photodegradation of lignin and the development of visible checks in wood exposed outdoors.

Evaluating UV-B effects and EDU protection in cucumber leaves using fluorescence images and fluorescence emission spectra

A newly developed laboratory fluorescence imaging system was used to obtain fluorescence images (FImage) of freshly excised cucumber ( Cucumis sativus L.) leaves in spectral bands centered in the blue (F450), green (F550), red (F680), and far-red (F730) spectral regions that resulted from a broad-band (300-400 nm) excitation source centered at 360 nm. Means of relative fluorescence intensities (RFI) from these spectral fluorescence images were compared with spectral fluorescence emission data obtained from excitation wavelengths at 280 nm (280EX, 300-550 nm) and 380 nm (380EX, 400-800 nm) of dimethyl sulfoxide (DMSO) extracts from these leaves. All three fluorescence data types (FImage, 280EX, 380EX) were used to assess ultraviolet-B (UV-B, 280-320 nm) induced physiological changes and the possible use of N-[2-(2-oxo-1-imidazolidinyl) ethyl]-N′-phenylurea (EDU or ethylenediurea) as a chemical protectant against UV-B damage. Plants exhibited well known foliar growth and pigment responses to UV-B exposure (e.g., increased UV-B absorbing compounds and decreased leaf area, chlorophyll a content; and and lower chlorophyll a/b and chlorophyll/carotenoid pigment ratios). Since EDU alone had no effect on foliar variables, there was no evidence that EDU afforded protection against UV-B. Instead, EDU augmented some UV-B effects when provided in conjunction with UV-B irradiation (e.g., reductions in the chlorophyll/carotenoid ratio, total photosynthetic pigments, and chlorophyll b content).Relative fluorescence intensities (RFI) in the longer visible wavelengths (green, red, and far-red) were uncorrelated for comparisons between the FImage and 380EX data sets. However, blue and green RFI were significantly correlated (0.8≫r≫0.6; P ≤0.002) for comparisons between FImage and 280EX data sets. UV-B treatment caused an increase in blue RFI (e.g., F450) in both images and 280EX measurements. One explanation is that the UV-B excitation of both 280EX and FImage stimulates processes that produce excess blue fluorescence. The molecules that produce the excess blue fluorescence in both the 280EX and the Fimage data are different electron transfer agents that operate in parallel. For FImage, the UV excitation penetrates leaf surface layers to stimulate fluorescence from compounds in mesophyll and epidermal tissues (as occurs for the extracts of leaf discs), whereas emissions captured at longer, less energetic wavelengths, were primarily from the epidermal layer. UV-B irradiated leaves showed much greater heteorgeneity of RFI in both the green (F550 FImag ) and the red (F680 FImag ) bands than unirradiated leaves; this was true irrespective of EDU treatment.Although qualitative responses in individual bands differed between FImage and 380EX data, similar results were obtained in the detection of UV-B induced effects when the red/green and blue/far-red fluorescence ratios of these data were compared. The red/green ratio (either F680/F550 FImage or F675/F525 380EX ) was lower for UV-B exposed plants in both images and 380EX data. UV-B exposure also significantly enhanced the blue/far-red ratio of images (F450/F740 FImage ) and the comparable 380EX ratio (F450/F730 380EX ) for the combined UV-B/EDU group. The far-red/red ratios were not useful in separating treatment effects in images or 380EX. Although comparable ratios were not available in 280EX data, the UV/blue ratio (F315/F420 280EX ) was substantially reduced by UV-B exposure and was inversely related to total photosynthetic pigment content. These findings suggest that the red/green ratio (FImage, 380EX) and the UV/blue ratio (280EX) may be as useful as the blue/far-red ratio (380EX) reported previously in detection of UV-B stress. Furthermore, the results support the validity of the imaging technique as a non-destructive diagnostic tool for assessing UV-B stress damage in plants.

Abiotic persistence of atrazine and simazine in water

Hydrolysis and photolysis experiments have been undertaken to investigate the abiotic persistence of atrazine and simazine in a variety of waters. Hydrolysis only occurs to a significant extent at pH values at the lower limit of those found in the natural aquatic environment (pH 4.0 or less). Photolysis was initiated by a wide range of wavelengths in waters at pH 4.0, but only by more energetic wavelengths of less than 300 nm at higher pH values (pH 6 to 8). Based on these data, the aquatic half-life of atrazine and simazine in well-lit acidic upland waters will be typically six days. In lowland rivers with higher pH (7 to 8.5), these triazines are likely to exhibit half-lives of months rather than days. In groundwaters, atrazine and simazine will have half-lives in the order of years, due to the exceedingly slow rate of hydrolysis. © 1999 Society of Chemical Industry

Long Afterglows Reveal the Secrets of Distant Fireballs

GAMMA-RAY BURSTSHUNTSVILLE, ALABAMA-- The mysterious cosmic blasts that were the focus of the Fourth Huntsville Gamma-Ray Burst Symposium held here last week are followed by in progressively longer, less energetic wavelengths: x-rays, visible light, and radio waves. In the last few months, clues ranging from the rate at which the afterglows fade to the twinkling of the radio signal have supported the idea that GRBs emerge from shocks within gigantic fireballs billions of light-years from Earth.

Ultraviolet Radiation and Plants: Burning Questions.

Plants use sunlight for photosynthesis and, as a consequence, are exposed to the ultraviolet (UV) radiation that is present in sunlight. UV radiation is generally divided into three classes: UV-C, UV-6, and UV-A. The UV-C region of the UV spectrum includes wavelengths below 280 nm; these highly energetic wavelengths are effectively absorbed by ozone in the stratosphere and, thus, are not present in sunlight at the earth’s surface. UV-C wavelengths will be removed from the light reaching the earth’s surface’so long as there is any ozone present (Caldwell et al., 1989). In contrast, UV radiation in the UV-B region, from 280 to 320 nm, does reach ground level. The UV-B portion of sunlight has received much attention in recent years because irradiation from this spectral region (especially 297 to 310 nm) will increase as the stratospheric ozone concentration decreases (Caldwell et al., 1989). Currently, ozone decreases result from chlorofluorocarbon contamination of the stratosphere (McFarland and Kaye, 1992). UV wavelengths from 320 to 390 nm, which make up the UV-A region of the spectrum, are not attenuated by ozone, so their fluence will be unaffected by ozone layer reduction. Like all living organisms, plants sense and respond to UV radiation, both the wavelengths present in sunlight (UV-A and UV-B) and the wavelengths below 280 nm (UV-C). AI1 types of UV radiation are known to damage various plant processes. Such damage can be classified into two categories: damage to DNA (which can cause heritable mutations) and damage to physiological processes. There has been much speculation about how increased UV radiation exposure will affect plants, but as yet, there are no definitive answers. In this review, I will discuss the kinds of damage that UV radiation can inflict on plants, the mechanisms plants use to perceive and respond to UV radiation, and the ecological relevance of UV light wavelengths that have been used in the experimental analysis of plant responses to UV radiation.

Distribution and accumulation of ultraviolet-radiation-absorbing compounds in leaves of tropical mangroves

Ultraviolet (UV)-absorbing phenolic compounds that have been shown to be protective against the damaging: effects of UV-B radiation (Tevini et al., 1991, Photochem. Photobiol. 53, 329-333) were found in the leaf epidermis of tropical mangrove tree species. These UV-absorbing phenolic compounds and leaf succulence function as selective filters, removing short and energetic wavelengths. A field survey showed that the concentration of UV-absorbing compounds varied between species, between sites that would be experiencing similar levels of UV radiation, and between sun and shade leaves. Sun leaves have greater contents of phenolic compounds than shade leaves, and more saline sites have plants with greater levels in their leaves than less saline sites. In addition, increases in leaf nitrogen contents and quantum yields did not correlate with increasing levels of UV-absorbing compounds. It was concluded from these results that although UV-absorbing compounds form a UV-screen in the epidermis of mangrove leaves, UV radiation may not be the only factor influencing the accumulation of phenolic compounds, thus an experiment which altered the level of UV radiation incident on mangrove species was done. Near ambient levels of UVA and UV-B radiation resulted in a greater content of UV-absorbing compounds in Bruguiera parviflora (Roxb.) Wight and Arn. ex Griff., but did not result in increases in B. gymnorrhiza (L.) Lamk or Rhizophora apiculata Blume. Total chlorophyll contents were lower in R. apiculata when it was grown under near-ambient levels of UV radiation than when it was grown under conditions of UV-A and UV-B depletion, but no differences were observed between the UV radiation treatments in the other two species. There was no difference in leaf morphology, carotenoid/chlorophyll ratios, or chlorophyll a/b ratios between UV treatments, although these varied among species; B. parviflora had the highest carotenoid/chlorophyll ratio and R. apiculata had the lowest. Thus it is proposed that differences in species response tu UV radiation may be influenced by their ability to dissipate excess visible solar radiation.