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PubMed1998

Effect of hydration and dehydration on initiation and dynamics of some physiological reactions in desiccation tolerant cyanobacterium Scytonema geitleri.

The effect of hydration and dehydration has been studied on extent and recovery of some metabolic reactions in desiccation tolerant terrestrial cyanobacterium Scytonema geitleri. The results show that the energy transducing reactions like photochemical reactions of photosynthesis recover first, followed by increase in ATP pool size. During later phase of hydration, appearance of energy consuming processes such as CO2 fixation and nitrogen fixation have been observed. Sensitivity of reactions during dehydration followed the pattern reverse to recovery processes.

Adenosine Triphosphate↗
PubMed2003

The effect of humic acids on nitrobenzene oxidation by ozonation and O3/UV processes.

Three types of commercially available humic acids from different sources were used to simulate natural organic matter in water for the investigation of nitrobenzene oxidation by ozonation and O(3)/UV. Despite the structural differences among the Fluka, Aldrich and Suwanee River humic acids as reflected by the UV absorptivity, their effects on nitrobenzene removal rate was observed to be similar for the two processes. Removal rate of nitrobenzene was hindered by the addition of humic acids in ozonation as well as in O(3)/UV processes. However, the hindrance by the humic acids was more pronounced in O(3)/UV as compared to the ozonation process. The effect of humic acid in O(3)/UV was primarily a UV light screening. Addition of humic acids above a certain concentration did not cause any further retardation on nitrobenzene removal rate by ozonation and O(3)/UV. Accumulation of hydrogen peroxide as well as probable formation of peroxy radicals in the solutions might induce chain promoting reactions to produce hydroxyl radical during the nitrobenzene oxidation. For waters containing high levels of humic acid, ozonation alone might be as effective as O(3)/UV process for the removal of nitrobenzene.

Humic Substances↗
PubMed2003

Effect of initial microbial density on inactivation of Giardia muris by ozone.

Inactivation of microorganisms by disinfectants frequently shows non-linear behavior on a semilogarithmic plot of log survival ratio versus time. A number of models have been developed to depict these deviations from Chick's Law. Some of the models predict that the log survival ratio (at a particular disinfectant dose and contact time, even in absence of demand) would be a function of the initial concentration of microorganisms (N(0)), while other models do not predict such an effect. The effect of N(0) on the survival ratio has not been deliberately tested. This work examined the inactivation of Giardia muris by ozone in batch systems, deliberately varying the disinfectant dose and N(0). It was found that the models predicting a dependency of survival on N(0) gave a better description to the data than models that did not predict such a dependency. Hence there is an apparent decrease in disinfection efficiency of ozone against Giardia muris (at pH 8 and 15 degrees C) as the initial microorganism concentration decreases. This phenomena should be taken into account by both disinfection researchers and by process design engineers.

Animals↗
PubMed2003

Ozone and natural systems: understanding exposure, response, and risk.

Research aimed at understanding the response of plants to ozone has been conducted for over four decades but little of it has addressed intact natural systems. Even so, there is sufficient scientific information at this time to support air quality standards that will protect natural terrestrial ecosystems from ozone. What is unknown is the risk associated with continued exposure of natural systems, including both above- and below-ground components, in combination with other stresses including changing temperature and precipitation, elevated carbon dioxide, pests and pathogens, invasive species, and other activities that may fragment the landscape. Research to support an assessment of the ecological risk associated with ozone as it exists, in a milieu of stresses, must include endpoints beyond those addressed in the past, primarily productivity and species composition. To estimate the risk to society of ozone impacts on natural systems, endpoints such as the integrity of soil food webs, the quantity and quality of water supplied from terrestrial ecosystems, wildlife and recreational values, and the transfer and fate of carbon, nutrients, and water within the systems must be quantified. Not only will this research provide the basis for a sound estimate of risk, but also it will improve our understanding of fundamental ecosystem processes.

Air Pollutants↗
PubMed1991

3D grating optics of human vision.

The approximately 6-7 layers of closestpacked photoreceptor cell bodies in the outer nuclear layer of the human retina are interpreted as hexagonal multilayer phase or three-dimensional gratings with refractive index differences between the cell nucleus and the cytoplasm. A multilayer 3D grating of this type allows incident light to be processed by Fresnel interference in the plane of focus of the geometrical-optical system of the human eye, forming triplets of chromatic interference maxima made available, at discrete concentric locations, to the outer segments of the cones and rods for further processing. Transformation of the 3D grating spacing (in the sense of a stimulus-adaptive optic) into the dimensional periodicity of the spectral stimulus which is processed with maximum amplitude in the 111 color channel gives three chromatic signals at 559/537/447 nm in the visible 'spectral window', i.e. at spectral locations which match the 3 wavelengths of (photochemically determined) maximum spectral sensitivity in photopic vision. Variation of the cell geometry in the 3D grating gives rise to the Purkinje shift with fusion of the RED-GREEN diffraction orders at 512 nm. Color proves mathematically to be the product (varied by the diffraction order triplets) of the speed of light and the three-dimensional geometry. The chemistry of the photoreceptors, i.e. the programming of the visual pigments, would consequently be based on 3D grating optics. The human eye would process trichromatic Fourier signals, not geometrical-optical images. The first stage of color vision would be based on 3D grating optics, without the involvement of neuronal networks. New interpretations ensue for color constancy, color adaptation, color visual field, inter alia. The eye, as a trichromatic Fresneloptical modulator of the information present in the amplitude, phase and frequency of the processed light, receives considerably more information on perceived objects than it passes on to the brain. Cellular 3D gratings may also be models for the interference of acoustic, chemical and other waves in cortical processing centers.

Color Perception↗
PubMed2005

Acceleration and quenching of the photolysis of PCB in the presence of surfactant and humic materials.

The photodecay of a polychlorobiphenyl (PCB) congener, 2,3,4,5-tetrachlorobiphenyl (TeCB), in a surfactant-aided soil-washing process was investigated. The surfactant was found to be a useful hydrogen source in improving the TeCB photodecay via photoreduction process, while the light attenuation effect resulted from the nontarget compounds in the solution, and the impact of humic materials that co-extracted from the soil played important roles in the process of photolytic destruction of TeCB. A well-defined sediment, EPA-11, was used as the source of humic materials in examining the acceleration and quenching effects in the photolysis process. Experimental results indicated that the low dose of humic materials mainly acted as a supplementary hydrogen source to improve the photodegradation rate, while at a higher dose its amphoteric property of being a photochemical quencher become perceptible gradually, thus retarding the reaction. These effects were inspected and the dominant rate constants were quantified through the examination of possible sub-reactions in the assistant of proposed linear models in this study. The models under three different conditions at zero, low, and high humic levels associated with a light attenuation model were successfully developed to solve the dominant rate constants of the process. The good correlations between the experimental data and the models verify that the proposed reaction mechanisms of rate acceleration (resulting from the hydrogen source characteristics of the surfactant and humic material) and rate retardation (high levels of humic materials) coexist in the process.

Humic Substances↗
PubMed1975

Energetics of abiogenic chemical systems.

After recalling the energy consumption necessary to produce the main categories of biochemicals from the equilibrium state of an hydrogenated atmosphere, the primary processes by which energy can be absorbed in a mixture of methane and ammonia in the presence of aqueous solutions are defined. From the very first excitations, unsaturated products are formed. In fact, this formation of atmospheric precursors is the primordial state of a photochemically induced redox dismutation. The evolution of solutions obtained from the dissolution of these atmospheric precursors in aqueous media is described from experimental data and analysed on energetic grounds. The relaxation of energy accumulated in such solutions involves non enzymic archetypes of the main categories of metabolic processes; in particular some unsaturated atmospheric precursors must be looked upon as primordial representatives of biochemical dehydrating agents. Absorption of light energy in the solutions obtained from the evolution of precursors happens near the visible range and should govern their further evolution. In fact, biochemicals which were previously detected as products of model experiments are not present in these solutions. They were probably obtained during analytical procedures from products of the evolution of atmospheric precursors which are unstable against decreases of pH. Cyclic autocatalytic effects must be involved in the further evolution of the models of the first aqueous solutions. Their possible role in the appearance of optical dissymmetry is emphasized on theoretical grounds.

Amino Acids↗
PubMed2004

High-throughput laser-mediated in situ cell purification with high purity and yield.

BACKGROUND: Technologies for purification of living cells have significantly advanced basic and applied research in many settings. Nevertheless, certain challenges remain, including the robust and efficient purification (e.g., high purity, yield, and sterility) of adherent and/or fragile cells and small cell samples, efficient cell cloning, and safe purification of biohazardous cells. In addition, existing purification methods are generally open loop and exhibit an inverse relation between cell purity and yield. METHODS: An automated closed-loop (i.e., employing feedback control) cell purification technology was developed by building upon medical laser applications and laser-based semiconductor manufacturing equipment. Laser-enabled analysis and processing has combined high-throughput in situ cell imaging with laser-mediated cell manipulation via large field-of-view optics and galvanometer steering. Laser parameters were determined for cell purification using three mechanisms (photothermal, photochemical, and photomechanical), followed by demonstration of system performance and utility. RESULTS: Photothermal purification required approximately 10(8) W/cm(2) at 523 nm in the presence of Allura Red, resulting in immediate protein coagulation and cell necrosis. Photochemical purification required approximately 10(9) W/cm(2) at 355 nm, resulting in apoptosis induction over 4 to 24 h. Photomechanical purification required more than 10(10) W/cm(2) independent of wavelength, resulting in immediate cell lysis. Each approach resulted in high efficiency purification (>99%) after a single operation, as demonstrated with eight cell types. An automated closed-loop process to re-image and irradiate remaining targets in situ was implemented, resulting in improved purification (99.5-100%) without decreasing cell yield or affecting sterility in this closed system. Efficient purification was demonstrated with B- and T-cell mixtures over a wide range of contaminating cell percentages (0.1-99%) and cell densities (10(4)-10(6)/cm(2)). Efficient cloning of 293T cells based on fluorescence with green fluorescent protein after plasmid transfection was also demonstrated. CONCLUSIONS: In situ laser-mediated purification was achieved with nonadherent and adherent cells on the automated laser-enabled analysis and processing platform. Closed-loop processing routinely enabled greater than 99.5% purity with a greater than 90% cell yield in sample sizes ranging from 10(1) to 10(8) cells. Throughput ranged from approximately 10(3) to 10(5) total cells/s for contaminating percentages ranging from 99% to 0.1%, respectively.

Automation↗
PubMed2006

Evaluation of biodegradability and oxidation degree of hospital wastewater using photo-Fenton process as the pretreatment method.

In this work, the photo-Fenton process was used for the pretreatment of hospital wastewater with the objective of improving its overall biodegradability and determining the degree of increased oxidation. The chemical oxygen demand (COD), 5-day biochemical oxygen demand (BOD5), total organic carbon (TOC) and toxicity towards the gram negative marine bioluminescent bacteria of the species V. fischeri were selected as the environmental sum parameters to follow the performance of this process. The enhancement of biodegradability, evaluated in terms of the BOD5/COD ratio, increased from 0.3 to 0.52 and the oxidation degree, calculated in terms of AOS, leveled up from -1.14 to +1.58 at the optimum conditions; a dosage ratio of COD:H2O2:Fe(II) at 1:4:0.1, and a reaction pH of 3. The reduction in the inhibition percentage from the toxicity test indicated the safe levels for micro-organisms in degrading the residual organic substance in this method. Almost total removal percentages of COD, BOD5, and TOC were found by a sequential activated sludge process for the pre-treated wastewater. Results obtained from this work indicated that the photo-Fenton process could be a suitable pretreatment method in reducing toxicity of pollutants and enhancing biodegradability of hospital wastewaters treated in a coupled photochemical-biological system.

Aerobiosis↗
PubMed2006

8-hydroxyquinoline derivatives as fluorescent sensors for magnesium in living cells.

Despite the key role of magnesium in many fundamental biological processes, knowledge about its intracellular regulation is still scarce, due to the lack of appropriate detection methods. Here, we report the spectroscopic and photochemical characterization of two diaza-18-crown-6 hydroxyquinoline derivatives (DCHQ) and we propose their application in total Mg(2+) assessment and in confocal imaging as effective Mg(2+) indicators. DCHQ derivatives 1 and 2 bind Mg(2+) with much higher affinity than other available probes (K(d) = 44 and 73 microM, respectively) and show a strong fluorescence increase upon binding. Remarkably, fluorescence output is not significantly affected by other divalent cations, most importantly Ca(2+), or by pH changes within the physiological range. Evidence is provided on the use of fluorometric data to derive total cellular Mg(2+) content, which is consistent with atomic absorption data. Furthermore, we show that DCHQ compounds can be effectively employed to map intracellular ion distribution and movements in live cells by confocal microscopy. A clear staining pattern consistent with known affinities of Mg(2+) for biological ligands is shown; moreover, changes in the fluorescence signal could be tracked following stimuli known to modify intracellular Mg(2+) concentration. These findings suggest that DCHQ derivatives may serve as new tools for the study of Mg(2+) regulation, allowing sensitive and straightforward detection of both static and dynamic signals.

Biosensing Techniques↗
PubMed2006

Transients in the oxidative and H-atom-induced degradation of 1,3,5-trithiane. Time-resolved studies in aqueous solution.

The (*)OH-induced oxidation of 1,3,5-trithiacyclohexane (1) in aqueous solution was studied by means of pulse radiolysis with optical and conductivity detection. This oxidation leads, via a short-lived (*)OH radical adduct (<1 micros), to the radical cation 1(*+) showing a broad absorption with lambda(max) equal to 610 nm. A defined pathway of the decay of 1(*+) is proton elimination. It occurs with k = (2.2 +/- 0.2) x 10(4) s(-1) and yields the cyclic C-centered radical 1(-H)(*). The latter radical decays via ring opening (beta-scission) with an estimated rate constant of about 10(5) s(-1). A distinct, immediate product (formed with the same rate constant) is characterized by a narrow absorption band with lambda(max) = 310 nm and is attributed to the presence of a dithioester function. The formation of the 310 nm absorption can be suppressed in the presence of oxygen, the rationale for this being a reaction of the C-centered cyclic radical 1(-H)(*) with O(2). The disappearance of the 310 nm band (with a rate constant of 900 s(-1)) is associated with the hydrolysis of the dithioester functionality. A further aspect of this study deals with the reaction of H(*) atoms with 1 which yields a strongly absorbing, three-electron-bonded 2sigma/1sigma* radical cation [1(S therefore S)-H](+) (lambda(max) = 400 nm). Its formation is based on an addition of H(*) to one of the sulfur atoms, followed by beta-scission, intramolecular sulfur-sulfur coupling (constituting a ring contraction), and further stabilization of the S therefore S bond thus formed by protonation. [1(S therefore S)-H](+) decays with a first-order rate constant of about 10(4) s(-1). Its formation can be suppressed by the addition of oxygen which scavenges the H(*) atoms prior to their reaction with 1. Complementary time-resolved conductivity experiments have provided information on the quantification of the 1(*+) radical cation yield, the cationic longer-lived follow-up species, extinction coefficients, and kinetics concerning deprotonation processes as well as further reaction steps after hydrolysis of the transient dithioesters. The results are also discussed in the light of previous photochemical studies.

Journal Article↗
PubMed1998

Photophysical properties of porphyrin planar aggregates in liposomes.

This paper describes studies of some photophysical properties of non-covalent planar aggregates of hematoporphyrin and protoporphyrin. This porphyrin species has been recently discovered and can be generated in lipid bilayers such as liposomes and inner mitochondrial membranes. The relative weight of this species in different media, as compared to porphyrin monomers and stacked aggregates, has been deduced by fluorescence decay studies. In contrast with what is observed for stacked aggregates, promotion of planar suprastructures can occur both in aqueous and lipid environments. The spectroscopic properties are very similar to those of the corresponding monomers, in particular as regards the shape of the absorption and emission spectra. The fluorescence decay times are generally higher than those of the monomers, and depend on the medium in which the planar aggregates are formed. The photooxidation properties of porphyrin planar aggregates, as revealed by oxygen consumption and histidine photodegradation upon irradiation at 365 nm, were compared to those of the monomers. The extent of the photooxidation process is nearly 20-30% higher in planar aggregates than in the monomers. In contrast, it is well known that cofacial aggregates are photochemically inert and only monomeric species of porphyrin are efficient photosensitizers. The biological relevance of these findings is discussed.

1,2-Dipalmitoylphosphatidylcholine↗
PubMed2006

Ecophysiological traits associated with drought in Mediterranean tree seedlings: individual responses versus interspecific trends in eleven species.

Species differ regarding their drought tolerance and individuals of a given species can modify their morphology and physiology in response to drought. However, since evolutionary and ecological selective pressures differ, individual and interspecific responses to drought might not match. We determined summer survival and a number of ecophysiological variables in two factorial experiments with seedlings of eleven tree species present in Mediterranean ecosystems, grown under slowly imposed water stress and control conditions. Plants experiencing drought exhibited reduced growth, low specific leaf area, chlorophyll content, and photosynthetic rate when compared to the controls, and species-specific drought tolerance was associated with an analogous set of trait values. However, while species with high leaf area ratio and shoot-root ratio exhibited greater drought tolerance, drought induced the reversed response within species. Contrary to expectations, water use efficiency was lower in drought-tolerant species and decreased in water-stressed individuals compared to the control plants. There was a distinctive phylogenetic signal in the functional grouping of species, with oaks, pines, and other genera being clearly different from each other in their drought tolerance and in their functional responses to drought. However, all relationships between ecophysiological variables and drought tolerance were significant after accounting for phylogenetic effects, with the exception of the relationship between drought tolerance and photochemical efficiency. Our results show that drought tolerance is not achieved by a single combination of trait values, and that even though evolutionary processes and individual responses tend to render similar results in terms of functional traits associated with drought, they do not necessarily match.

Ecosystem↗
PubMed2004

Photocatalytic activity of gold nanocrystals and its role in determining the stability of surface thiol monolayers.

Colloidal gold nanocrystals were found to be efficient photocatalysts for the oxidation of thiols to the corresponding disulfide in aqueous solution under UV radiation, although no noticeable catalytic effect of gold nanocrystals was observed under dark conditions for the same process. The turnover number per particle increased with the size of the nanocrystals and reached 1200 molecules/s for 45-nm gold nanocrystals. The photochemical instability of colloidal gold nanocrystals coated by thiol ligands was found to be determined by the photocatalytic oxidation of the thiol ligands.

Catalysis↗
PubMed1984

Photolytic changes in lens proteins.

Many of the age related and cataractous changes that occur in the human lens may be due to some photolytic process. These include either the direct photolysis of lens protein or photosensitized reactions involving 3-OH Kyn glucoside. The extent to which these photochemical reactions play a role is determined by the level of lens oxygen and the presence of quenchers endogenous to the lens.

Adolescent↗
PubMed1988

Inhibition of the mitochondrial F1-ATPase by rose bengal mediated photooxidation. Interaction of the Fe2+ chelate of bathophenanthroline with the sensitizer.

Rose Bengal mediated photooxidation of mitochondrial F1-ATPase and its beta-subunit resulted in inactivation and loss of about 50 and 60% of their histidine residues, respectively. The beta-subunit was not cleaved upon photooxidation. Photooxidation of histidine probably results in changes in the conformational stability of F1-ATPase leading to its inactivation. The participation of singlet molecular oxygen during the photooxidation process is suggested by the selective loss of histidine residues, while other amino acids, also sensitive to singlet oxygen attack, were not affected. Photochemical damage of F1-ATPase was prevented by various phenanthroline compounds, the order of efficiency being bathophenanthroline-Fe chelate greater than bathophenanthroline greater than orthophenanthroline-Fe chelate greater than bathophenanthroline-sulfonate-Fe chelate. The prevention by bathophenanthroline-Fe chelate of photochemical damage is interpreted on the basis of its interaction with the photosensitizer, Rose Bengal, probably implying a chemical reaction which decreases the actual concentration of the sensitizer and, thereby, the extent of photoinactivation.

Amino Acids↗
PubMed1990

Mechanism of photoinhibition in vivo. A reversible light-induced conformational change of reaction center II is related to an irreversible modification of the D1 protein.

The light-induced inactivation of the photochemical reaction center II (RCII) of oxygenic chloroplasts (photoinhibition) was investigated in cells and isolated thylakoids of the green alga Chlamydomonas reinhardtii. The process is resolved into a reversible conformational change followed by an irreversible modification of RCII D1 protein. The light-induced changes in vivo persisted in isolated thylakoids. The first step is characterized by (i) destabilization of the secondary acceptor semiquinone anion, Q-B, bound to the D1 protein. This is demonstrated by a reduction in the activation energy of S2,3Q-B charge recombination as measured by the thermoluminescence technique; and (ii) a rise in the intrinsic fluorescence and a decrease of the maximal fluorescence. Unoccupancy of the QB site by plastoquinone partially protected RCII against the light-induced destabilization of Q-B. The extent of charge separation (P+680Q-A) was not affected. However, the slow phase (microsecond) of P+680 dark reduction increased, and the amplitude of signal II was reduced by 20-30%, indicating that in a fraction of RCII, electron donation from Z to P+680 was impaired without losing primary photochemistry. This modification correlates with the irreversible change in D1 protein resulting in the formation of a trypsin-resistant fragment of 16 kDa detected in D1 isolated from light-exposed cells. The change in the Q-B stability could allow charge equilibration with QA and thus explain the rise in the intrinsic fluorescence level and reduction of electron flow to plastoquinone. The change in the lifetime of P+680 can account for further reduction in electron flow (photo-inhibition). The irreversible light-dependent modification of D1 may serve as the signal for its degradation and replacement by a newly synthesized molecule (turnover).

Chlamydomonas↗