Analia Iriel

Photophysics of supported dyes: phthalocyanine on silanized silica

Aluminum tetracarboxyphthalocyanine is adsorbed onto silanized silica particles at different dye to particle ratios. Diffuse reflectance spectra are measured and the equilibrium between dye monomers and aggregates is studied. Between 4.0 × 10−8 and 2.0 × 10−6 mol of dye g−1 of support, a simple dimerization equilibrium explains experimental results. Fluorescence spectra and quantum yields are calculated and corrected for light absorption by non-fluorescent dimers and reabsorption of emitted radiation. Once corrected, fluorescence quantum yields are of the same order of magnitude than in solution. Absorption spectra are also obtained for suspensions of the same materials in water. The hydrophilic environment enhances aggregation dramatically. Singlet oxygen quantum yields measured in suspension are lower than those found for the same phthalocyanine in solution of DMSO. Results are compared with those previously obtained for similar materials.

Is the flower fluorescence relevant in biocommunication

Flower fluorescence has been previously proposed as a potential visual signal to attract pollinators. In this work, this point was addressed by quantitatively measuring the fluorescence quantum yield (Φf) for flowers of Bellis perennis (white, yellow, pink, and purple), Ornithogalum thyrsoides (petals and ovaries), Limonium sinuatum (white and yellow), Lampranthus productus (yellow), Petunia nyctaginiflora (white), Bougainvillea spectabilis (white and yellow), Antirrhinum majus (white and yellow), Eustoma grandiflorum (white and blue), Citrus aurantium (petals and stigma), and Portulaca grandiflora (yellow). The highest values were obtained for the ovaries of O. thyrsoides (Φf = 0.030) and for Citrus aurantium petals (Φf = 0.014) and stigma (Φf = 0.013). Emitted photons as fluorescence were compared with reflected photons. It was concluded that the fluorescence emission is negligible compared to the reflected light, even for the most fluorescent samples, and it may not be considered as an optical signal in biocommunication. The work was complemented with the calculation of quantum catches for each studied flower species to describe the visual sensitization of eye photoreceptors.

Atrazine and Methyl Viologen Effects on Chlorophyll-a Fluorescence Revisited-Implications in Photosystems Emission and Ecotoxicity Assessment.

In this work, we use the effect of herbicides that affect the photosynthetic chain at defined sites in the photosynthetic reaction steps to derive information about the fluorescence emission of photosystems. The interpretation of spectral data from treated and control plants, after correction for light reabsorption processes, allowed us to elucidate current controversies in the subject. Results were compatible with the fact that a nonnegligible Photosystem I contribution to chlorophyll fluorescence in plants at room temperature does exist. In another aspect, variable and nonvariable chlorophyll fluorescence were comparatively tested as bioindicators for detection of both herbicides in aquatic environment. Both methodologies were appropriate tools for this purpose. However, they showed better sensitivity for pollutants disconnecting Photosystem II–Photosystem I by blocking the electron transport between them as Atrazine. Specifically, changes in the (experimental and corrected by light reabsorption) red to far red fluorescence ratio, in the maximum photochemical quantum yield and in the quantum efficiency of Photosytem II for increasing concentrations of herbicides have been measured and compared. The most sensitive bioindicator for both herbicides was the quantum efficiency of Photosystem II.

Effect of arsenic on reflectance spectra and chlorophyll fluorescence of aquatic plants

Arsenic pollution of groundwater is a serious problem in many regions of Latin America that causes severe risks to human health. As a consequence, non-destructive monitoring methodologies, sensitive to arsenic presence in the environment and able to perform a rapid screening of large polluted areas, are highly sought-after. Both chlorophyll - a fluorescence and reflectance of aquatic plants may be potential indicators to sense toxicity in water media. In this work, the effects of arsenic on the optical and photophysical properties of leaves of different aquatic plants (Vallisneria gigantea, Azolla filiculoides and Lemna minor) were evaluated. Reflectance spectra were recorded for the plant leaves from 300 to 2400 nm. The spectral distribution of the fluorescence was also studied and corrected for light re-absorption processes. Photosynthetic parameters (Fv/Fm and ΦPSII) were additionally calculated from the variable chlorophyll fluorescence recorded with a pulse amplitude modulated fluorometer. Fluorescence and reflectance properties for V. gigantea and A. filiculoides were sensitive to arsenic presence in contrast to the behaviour of L. minor. Observed changes in fluorescence spectra could be interpreted in terms of preferential damage in photosystem II. The quantum efficiency of photosystem II for the first two species was also affected, decreasing upon arsenic treatment. As a result of this research, V. gigantea and A. filiculoides were proposed as bioindicators of arsenic occurrence in aquatic media.

Biosorption of arsenic from groundwater using Vallisneria gigantea plants. Kinetics, equilibrium and photophysical considerations.

Arsenic (V) uptake from groundwater by using Vallisneria gigantea plants was studied using batch experiments. Reflectance and fluorescence of intact plants were investigated and changes in photophysical properties following arsenic absorption were reported. Good correlations have been found between arsenic concentration in groundwater and parameters derived from reflectance and fluorescence measurements. This system reached its equilibrium after seven days when the removal quantities were strongly dependent on the initial arsenic concentration. Interestingly, Vallisneria plants were able to accumulate from 100 to 600 mg As kg(-1) in roots and fronds although the translocation factors were low (0.6-1.6). Kinetic data for biosorption process followed a first-order law. At low arsenic concentrations the uptake in plants was governed by diffusion aspects. Langmuir, Freundlich and Dubinin-Radushkevich models were applied and results demonstrated that arsenic uptake was better described by the Langmuir model. As a final remark we concluded that a plant of this species should be able to remove 1mg As per week.

Energy transfer among dyes on particulate solids

Abstract Absorption and fluorescence properties of methylene blue (MB), a well-known singlet molecular oxygen photosensitizer, and its mixtures with pheophorbide-a (Pheo) sorbed on microgranular cellulose are studied, with emphasis on radiative and nonradiative energy transfer from Pheo to MB. Although pure MB builds up dimeric species on cellulose even at 2 × 10−8 mol g−1, addition of 2.05 × 10−7 mol g−1 Pheo largely inhibits aggregation up to nearly 10−6 mol g−1 MB. At the same time, the absorption spectrum of monomeric MB in the presence of Pheo differs from the spectrum in pure cellulose. Both effects reveal a strong influence of Pheo on the medium properties. A model relying entirely on experimental data is developed, through which energy transfer efficiencies can be calculated for thin and thick layers of dye-loaded cellulose. At the largest concentration of MB assuring no dye aggregation, nonradiative energy transfer efficiencies reach a maximum value of nearly 40%. This value is quite high, taking into account the low fluorescence quantum yield of Pheo, Φ = 0.21, and results from the existence of high local concentrations of the acceptor within the supporting material. These results show that large energy transfer rates can exist in a system devoid of any special molecular organization.

Spectroscopy, Microscopy and Fluorescence Imaging of Origanum vulgare L. Basis for Nondestructive Quality Assessment

The organs of Origanum vulgare L. plant were examined by optical microscopy, scanning electron microscopy and autofluorescence imaging. The different organs were also studied spectroscopically. Fluorescence emission spectra were recorded for intact inflorescences, leaves and stems. Several fluorescence ratios (Blue/Red, Blue/Far‐red, Green/Red and Green/Far‐red), which varied depending on the considered organ of the plant, were derived. For leaves, a dependence of fluorescence spectra with water content was obtained as well. The intact samples were also analyzed by Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy. These spectra were transformed to the Remission function depending on the wavenumber and two absorption bands (811 and 1740 cm−1), which displayed differences according to the plant organ sampled, were detected. These results were consistent with higher carvacrol content in inflorescences. The spectroscopic results were connected with the microscopic observation and with the presence of relevant nutraceutics contained in the plant. The optical indexes derived in this work may serve as potential indicators to be explored in the development of nondestructive methods for oregano quality assessment.

The removal of fluoride from aqueous solution by a lateritic soil adsorption : kinetic and equilibrium studies

The use of natural sorbents to remove fluoride from drinking water is a promising alternative because of its low-cost and easy implementation. In this article, fluoride adsorption on a latosol soil from Misiones province (Argentina) was studied regarding kinetic and equilibrium aspects. Experiments were conducted in batch at room temperature under controlled conditions of pH 4-8) and ionic strength (1-10mM KNO3). Experimental data indicated that adsorption processes followed a PSO kinetic where initial rates have showed to be influenced by pH solution. The necessary time to reach an equilibrium state had resulted approximately 30min. Equilibrium adsorption studies were performed at pH 8 which is similar to the natural groundwater. For that, fluoride adsorption data were successfully adjusted to Dubinin-Ataskhov model determining that the fluoride adsorption onto soil particles mainly followed a physical mechanism with a removal capacity of 0.48mgg-1. Finally, a natural groundwater was tested with laterite obtaining a reduction close to 30% from initial concentration and without changing significantly the physicochemical properties of the natural water. Therefore, it was concluded that the use of lateritic soils for fluoride removal is very promising on a domestic scale.

Sunlight and UVC-254 irradiation induced photodegradation of organophosphorus pesticide dichlorvos in aqueous matrices

Dichlorvos (DDVP) is an organophosphorus pesticide that has been classified as highly hazardous chemical by the World Health organization. In this study, the fate of the pesticide DDVP in natural water compartments was examined under simulated sunlight. Moreover, the effect of UV-254 irradiation on DDVP depletion was also studied. In deionized water, DDVP was photodegraded only in the presence of dissolved molecular oxygen. The photodegradation during the first 6 h of sunlight irradiation occurred with pseudo first-order kinetics, and the rate constants were 0.040 h-1 at pH 7 and 0.064 h-1 at pH 3. A reaction mechanism for the generation of reactive oxygen species (ROS) via DDVP photoabsorption was proposed. Humic acids (HA) played a double role as photosensitizer and inhibitor, observing an enhancement on DDVP photodegradation at low HA concentration (TOC = 2 mg L-1). The depletion of DDVP under 254 nm UV irradiation was ascribed to direct photodegradation and oxygen mediated photoinduced reactions. Direct photodegradation of DDVP decreased with 254 nm irradiation reduction, highlighting the importance of radical mediated mechanisms at low irradiation doses. Based on LC/MS data, the main photoproducts under simulated solar light and UV-C irradiation were identified and potential reaction pathways were postulated. The three main identified products were o-methyl 2,2-dichlorovinyl phosphate, dichloroacetaldehyde and dimethylphosphate. Moreover, the toxicity of samples was evaluated along the irradiation exposure time using Microtox® assays. This study brings new insights into the role of oxygen in the photodegradation of DDVP and the induced and inhibition mechanisms involved in the presence of the humic acids in natural waters.

Trace metals and oxidative status in soft tissues of caged mussels ( Aulacomya atra ) on the North Patagonian coastline

This study investigated metal accumulation and oxidative effects in mantle, gill and digestive gland of the ribbed mussel Aulacomya atra from the Argentinean North Patagonian coastline. Mussels were transplanted over an 18-month period from a site with low anthropogenic impact to a harbor site with higher seawater concentration of aluminum, chromium, copper, manganese, nickel and zinc. Total trace metal concentration in seawater did not change throughout the 18-month transplant in either site. A. atra bioaccumulated metals in digestive gland, gills and mantle at different levels. Digestive gland had the highest concentration of metals, especially towards the end of the transplant experiment in the harbor area. Mussels transplanted to the harbor site experienced an upregulation in their antioxidant system, which likely explains the lack of oxidative damage to lipids despite higher metal accumulation. These results demonstrate that A. atra selectively accumulates metals from the water column and their prooxidant effects depend on the tissue antioxidant defenses and the exposure time.