Carotenoid-induced non-photochemical quenching in the cyanobacterial chlorophyll synthase-HliC/D complex

Czech Academy of Sciences Publication Activity Database

Niedzwiedzki, D.M.; Tronina, T.; Liu, H.; Staleva, H.; Komenda, Josef; Sobotka, Roman; Blankenship, R.E.; Polívka, T.

2016-01-01

Roč. 1857, č. 9 (2016), s. 1430-1439 ISSN 0005-2728 R&D Projects: GA ČR GBP501/12/G055 Institutional support: RVO:61388971 Keywords : Carotenoids * Non-photochemical quenching * Energy transfer Subject RIV: CE - Biochemistry Impact factor: 4.932, year: 2016

Laser induced photochemical and photophysical processes in fuel reprocessing: present scenario and future prospects

International Nuclear Information System (INIS)

Bhowmick, G.K.; Sarkar, S.K.; Ramanujam, A.

2001-01-01

State-of-art lasers can meet the very stringent requirements of nuclear technology and hence find application in varied areas of nuclear fuel cycle. Here, we discuss two specific applications in nuclear fuel reprocessing namely (a) add-on photochemical modifications of PUREX process where photochemical reactors replace the chemical reactors, and (b) fast, matrix independent sensitive laser analytical techniques. The photochemical modifications based on laser induced valency adjustment offers efficient separation, easy maintenance and over all reduction in the volume of radioactive waste. The analytical technique of time resolved laser induced fluorescence (TRLIF) has several attractive features like excellent sensitivity, element selective, and capability of on line remote process monitoring. For optically opaque solutions, optical excitation is detected by its conversion into thermal energy by non-radiative relaxation processes using the photo-thermal spectroscopic techniques. (author)

Photochemical modelling of photo-oxidant levels over the Swiss plateau and emission reduction scenarios

International Nuclear Information System (INIS)

Rosselet, C.M.; Kerr, J.A.

1993-05-01

During summertime high pressure conditions, high photo-oxidant (O 3 , H 2 O 2 , PAN and others) levels are frequently observed in the planetary boundary layer in central Europe. It is well known that close to the earth's surface ozone is formed by complex reactions involving VOC, NO x , and sunlight. Substantial reductions of both precursors are needed to reduce photo-oxidant levels. In this context the reductions of the abundance of the precursors and the variation of their ratios is of great importance. Here we report model calculations from the Harwell Photochemical Trajectory Model of the levels of O 3 , H 2 O 2 and PAN along a trajectory over the Swiss Plateau from Lake Constance to Lake Geneva. These calculations are in satisfactory agreement with measurements made during the intensive observation period of the research program POLLUMET (Pollution and Meteorology in Switzerland). Sensitivity calculations of emission reduction scenarios indicate that on the Swiss Plateau the ozone production may be mainly NO x -limited; under conditions where the CO levels are closer to the upper limit within the range (120-600 ppbv). The calculated peak ozone level reduction caused by an exclusive NO x -emission reduction is about three times larger than that caused by an exclusive VOC reduction. The combined reduction of all precursor compounds is the most efficient strategy, although it is only marginally more efficient than the NO x -reduction scenario alone. (author) figs., tabs., 75 refs

Vegetation Function and Physiology: Photosynthesis, Fluorescence and Non-photochemical Quenching (NPQ)

Science.gov (United States)

Zhang, Q.; Yao, T.

2017-12-01

Photosynthesis is a basic physiological function of vegetation that relies on PAR provided through photosynthetic pigments (mainly chlorophyll) for plant growth and biomass accumulation. Vegetation chlorophyll (chl) content and non-chlorophyll (non-chl) components vary with plant functional types (PFTs) and growing stages. The PAR absorbed by canopy chlorophyll (APARchl) is associated with photosynthesis (i.e., gross primary production, GPP) while the PAR absorbed by canopy non-chl components (APARnon-chl) is not associated with photosynthesis. Under non-optimal environmental conditions, vegetation is "stressed" and both photosynthesis (GPP) and light use efficiency are reduced, therefore, excess portions of APARchl are discarded as fluorescence or non-photochemical quenching (NPQ). The photochemical reflectance index (PRI) is a measurement related to NPQ. Both PRI and yield of solar induced chlorophyll fluorescence (SIFyield = SIF/APARchl) have been proposed as possible bio-indicators of LUEchl. We have successfully developed an algorithm to distinguish between chlorophyll and non-chl components of vegetation, and to retrieve fractional absorptions of PAR by chlorophyll (fAPARchl) and by non-chl components (fAPARnon-chl) with surface reflectance of MODIS bands 1 - 7. A method originally pioneered by Hanan et al. (2002) has been used to retrieve fAPAR for vegetation photosynthesis (fAPARPSN) at flux tower sites based on the light response curve of tower net ecosystem exchange (NEE) and incident PAR at low light intensity. We have also retrieved the PRI from MODIS data (bands 11 and 1) and have derived SIFyield with the Global Ozone Monitoring Experiment - 2 (GOME-2) SIF data. We find that fAPARPSN at flux tower sites matches well with site fAPARchl, and ratio fAPARnon-chl/fAPARchl varies largely. APARchl can explain >=78% variation in seasonal GPP . We disentangle the possible impact of fAPARchl on PRI from physiological stress response, disentangle the possible

Arbuscular mycorrhizal symbiosis ameliorates the optimum quantum yield of photosystem II and reduces non-photochemical quenching in rice plants subjected to salt stress.

Science.gov (United States)

Porcel, Rosa; Redondo-Gómez, Susana; Mateos-Naranjo, Enrique; Aroca, Ricardo; Garcia, Rosalva; Ruiz-Lozano, Juan Manuel

2015-08-01

Rice is the most important food crop in the world and is a primary source of food for more than half of the world population. However, salinity is considered the most common abiotic stress reducing its productivity. Soil salinity inhibits photosynthetic processes, which can induce an over-reduction of the reaction centres in photosystem II (PSII), damaging the photosynthetic machinery. The arbuscular mycorrhizal (AM) symbiosis may improve host plant tolerance to salinity, but it is not clear how the AM symbiosis affects the plant photosynthetic capacity, particularly the efficiency of PSII. This study aimed at determining the influence of the AM symbiosis on the performance of PSII in rice plants subjected to salinity. Photosynthetic activity, plant gas-exchange parameters, accumulation of photosynthetic pigments and rubisco activity and gene expression were also measured in order to analyse comprehensively the response of the photosynthetic processes to AM symbiosis and salinity. Results showed that the AM symbiosis enhanced the actual quantum yield of PSII photochemistry and reduced the quantum yield of non-photochemical quenching in rice plants subjected to salinity. AM rice plants maintained higher net photosynthetic rate, stomatal conductance and transpiration rate than nonAM plants. Thus, we propose that AM rice plants had a higher photochemical efficiency for CO2 fixation and solar energy utilization and this increases plant salt tolerance by preventing the injury to the photosystems reaction centres and by allowing a better utilization of light energy in photochemical processes. All these processes translated into higher photosynthetic and rubisco activities in AM rice plants and improved plant biomass production under salinity. Copyright © 2015 Elsevier GmbH. All rights reserved.

Research opportunities in photochemical sciences

Energy Technology Data Exchange (ETDEWEB)

NONE

1996-07-01

The workshop entitled {open_quotes}Research Opportunities in Photochemical Sciences{close_quotes} was initiated by the U.S. Department of Energy (DOE), Office of Energy Research (ER), Office of Basic Energy Sciences (BES), Division of Chemical Sciences. The National Renewable Energy Laboratory (NREL) in Golden, Colorado was requested by ER to host the workshop. It was held February 5-8, 1996 at the Estes Park Conference Center, Estes Park, CO, and attended by about 115 leading scientists and engineers from the U.S., Japan, and Europe; program managers for the DOE ER and Energy Efficiency and Renewable Energy (EERE) programs also attended. The purpose of the workshop was to bridge the communication gap between the practioneers and supporters of basic research in photochemical science and the practioneers and supporters of applied research and development in technologies related to photochemical science. For the purposes of the workshop the definition of the term {open_quotes}photochemical science{close_quotes} was broadened to include homogeneous photochemistry, heterogeneous photochemistry, photoelectrochemistry, photocatalysis, photobiology (for example, the light-driven processes of biological photosynthesis and proton pumping), artificial photosynthesis, solid state photochemistry, and solar photochemistry. The technologies under development through DOE support that are most closely related to photochemical science, as defined above, are the renewable energy technologies of photovoltaics, biofuels, hydrogen energy, carbon dioxide reduction and utilization, and photocatalysis for environmental cleanup of water and air. Individual papers were processed separately for the United states Department of Energy databases.

Seasonal photochemical transformations of nitrogen species in a forest stream and lake.

Directory of Open Access Journals (Sweden)

Petr Porcal

Full Text Available The photochemical release of inorganic nitrogen from dissolved organic matter is an important source of bio-available nitrogen (N in N-limited aquatic ecosystems. We conducted photochemical experiments and used mathematical models based on pseudo-first-order reaction kinetics to quantify the photochemical transformations of individual N species and their seasonal effects on N cycling in a mountain forest stream and lake (Plešné Lake, Czech Republic. Results from laboratory experiments on photochemical changes in N speciation were compared to measured lake N budgets. Concentrations of organic nitrogen (Norg; 40-58 µmol L-1 decreased from 3 to 26% during 48-hour laboratory irradiation (an equivalent of 4-5 days of natural solar insolation due to photochemical mineralization to ammonium (NH4+ and other N forms (Nx; possibly N oxides and N2. In addition to Norg mineralization, Nx also originated from photochemical nitrate (NO3- reduction. Laboratory exposure of a first-order forest stream water samples showed a high amount of seasonality, with the maximum rates of Norg mineralization and NH4+ production in winter and spring, and the maximum NO3- reduction occurring in summer. These photochemical changes could have an ecologically significant effect on NH4+ concentrations in streams (doubling their terrestrial fluxes from soils and on concentrations of dissolved Norg in the lake. In contrast, photochemical reactions reduced NO3- fluxes by a negligible (<1% amount and had a negligible effect on the aquatic cycle of this N form.

Photochemical reactions of actinide ions

International Nuclear Information System (INIS)

Tomiyasu, Hiroshi

1995-01-01

This paper reviews the results of photochemical studies of actinide ions, which have been performed in our research group for past several years as follows: I) behavior of the excited uranyl(VI) ion; II) photo-reductions of the uranyl ion with organic and inorganic compounds; III) photo-oxidations of uranium(IV) and plutonium(III) in nitric acid solutions. (author)

The interrelationship between the lower oxygen limit, chlorophyll fluorescence and the xanthophyll cycle in plants.

Science.gov (United States)

Wright, A Harrison; DeLong, John M; Gunawardena, Arunika H L A N; Prange, Robert K

2011-03-01

The lower oxygen limit (LOL) in plants may be identified through the measure of respiratory gases [i.e. the anaerobic compensation point (ACP) or the respiratory quotient breakpoint (RQB)], but recent work shows it may also be identified by a sudden rise in dark minimum fluorescence (F(o)). The interrelationship between aerobic respiration and fermentative metabolism, which occur in the mitochondria and cytosol, respectively, and fluorescence, which emanates from the chloroplasts, is not well documented in the literature. Using spinach (Spinacia oleracea), this study showed that F(o) and photochemical quenching (q(P)) remained relatively unchanged until O(2) levels dropped below the LOL. An over-reduction of the plastoquinone (PQ) pool is believed to increase F(o) under dark + anoxic conditions. It is proposed that excess cytosolic reductant due to inhibition of the mitochondria's cytochrome oxidase under low-O(2), may be the primary reductant source. The maximum fluorescence (F(m)) is largely unaffected by low-O(2) in the dark, but was severely quenched, mirroring changes to the xanthophyll de-epoxidation state (DEPS), under even low-intensity light (≈4 μmol m(-2) s(-1)). In low light, the low-O(2)-induced increase in F(o) was also quenched, likely by non-photochemical and photochemical means. The degree of quenching in the light was negatively correlated with the level of ethanol fermentation in the dark. A discussion detailing the possible roles of cyclic electron flow, the xanthophyll cycle, chlororespiration and a pathway we termed 'chlorofermentation' were used to interpret fluorescence phenomena of both spinach and apple (Malus domestica) over a range of atmospheric conditions under both dark and low-light.

Trace organic removal by photochemical oxidation

International Nuclear Information System (INIS)

Gupta, S.K. Sen; Peori, R.G.; Wickware, S.L.

1995-02-01

Photochemical oxidation methods can be used for the destruction of dissolved organic contaminants in most process effluent streams, including those originating from the nuclear power sector. Evaporators can be used to separate organic contaminants from the aqueous phase if they are non volatile, but a large volume of secondary waste (concentrate) is produced, and the technology is capital-intensive. This paper describes two different types of photochemical oxidation technologies used to destroy trace organics in wastewater containing oil and grease. (author). 9 refs., 4 figs

Synthesis of fluorescent metal nanoparticles in aqueous solution by photochemical reduction

KAUST Repository

Kshirsagar, Prakash; Sangaru, Shiv; Brunetti, Virgilio; Malvindi, Maria Ada Da; Pompa, Pier Paolo

2014-01-01

A facile green chemistry approach for the synthesis of sub-5 nm silver and gold nanoparticles is reported. The synthesis was achieved by a photochemical method using tyrosine as the photoreducing agent. The size of the gold and silver nanoparticles

Non-animal photosafety assessment approaches for cosmetics based on the photochemical and photobiochemical properties.

Science.gov (United States)

Onoue, Satomi; Suzuki, Gen; Kato, Masashi; Hirota, Morihiko; Nishida, Hayato; Kitagaki, Masato; Kouzuki, Hirokazu; Yamada, Shizuo

2013-12-01

The main purpose of the present study was to establish a non-animal photosafety assessment approach for cosmetics using in vitro photochemical and photobiochemical screening systems. Fifty-one cosmetics, pharmaceutics and other chemicals were selected as model chemicals on the basis of animal and/or clinical photosafety information. The model chemicals were assessed in terms of photochemical properties by UV/VIS spectral analysis, reactive oxygen species (ROS) assay and 3T3 neutral red uptake phototoxicity testing (3T3 NRU PT). Most phototoxins exhibited potent UV/VIS absorption with molar extinction coefficients of over 1000M(-1)cm(-1), although false-negative prediction occurred for 2 cosmetic phototoxins owing to weak UV/VIS absorption. Among all the cosmetic ingredients, ca. 42% of tested chemicals were non-testable in the ROS assay because of low water solubility; thereby, micellar ROS (mROS) assay using a solubilizing surfactant was employed for follow-up screening. Upon combination use of ROS and mROS assays, the individual specificity was 88.2%, and the positive and negative predictivities were estimated to be 94.4% and 100%, respectively. In the 3T3 NRU PT, 3 cosmetics and 4 drugs were incorrectly predicted not to be phototoxic, although some of them were typical photoallergens. Thus, these in vitro screening systems individually provide false predictions; however, a systematic tiered approach using these assays could provide reliable photosafety assessment without any false-negatives. The combined use of in vitro assays might enable simple and fast non-animal photosafety evaluation of cosmetic ingredients. Copyright © 2013 Elsevier Ltd. All rights reserved.

Photochemical technique for reduction of uranium and subsequently plutonium in the Purex process

International Nuclear Information System (INIS)

Goldstein, M.; Barker, J.J.; Gangwer, T.

1976-09-01

A photochemical modification of the Purex process is described in which a purified side stream of UO 2 ++ ion is reduced to U +4 outside the radioactive area of the reprocessing plant. The U +4 is then cycled back to step 2 of the Purex process to reduce the plutonium and effect separation within the partitioning column. This process is shown to be very energy efficient and compatible with existing conventional lamp technology. Preliminary cost estimates of the energy requirements for photon production are essentially negligible. Conceptual systems and photochemical reactor designs are presented. Potential benefits of this system are discussed

Maize w3 disrupts homogentisate solanesyl transferase (ZmHst) and reveals a plastoquinone-9 independent path for phytoene desaturation and tocopherol accumulation in kernels

Science.gov (United States)

Maize white seedling 3 (w3) has been used to study carotenoid deficiency for almost 100 years, although its genetic basis remained unknown. We show here that w3 phenotype is caused by disruption of homogentisate solanesyl transferase (HST), which catalyzes the first committed step in plastoquinone-9...

Non-animal photosafety screening for complex cosmetic ingredients with photochemical and photobiochemical assessment tools.

Science.gov (United States)

Nishida, Hayato; Hirota, Morihiko; Seto, Yoshiki; Suzuki, Gen; Kato, Masashi; Kitagaki, Masato; Sugiyama, Mariko; Kouzuki, Hirokazu; Onoue, Satomi

2015-08-01

Previously, a non-animal screening approach was proposed for evaluating photosafety of cosmetic ingredients by means of in vitro photochemical and photobiochemical assays; however, complex cosmetic ingredients, such as plant extracts and polymers, could not be evaluated because their molecular weight is often poorly defined and so their molar concentration cannot be calculated. The aim of the present investigation was to establish a photosafety screen for complex cosmetic ingredients by using appropriately modified in vitro photosafety assays. Twenty plant extracts were selected as model materials on the basis of photosafety information, and their phototoxic potentials were assessed by means of ultraviolet (UV)/visible light (VIS) spectral analysis, reactive oxygen species (ROS)/micellar ROS (mROS) assays, and 3T3 neutral red uptake phototoxicity testing (3T3 NRU PT). The maximum UV/VIS absorption value was employed as a judgment factor for evaluating photoexcitability of samples, and the value of 1.0 was adopted as a tentative criterion for photosafety identification. The ROS/mROS assays were conducted at 50 μg/mL, and no false negative prediction was obtained. Furthermore, the ROS/mROS assays at 50 μg/mL had a similar predictive capacity to the ROS/mROS assays in the previous study. A systematic tiered approach for simple and rapid non-animal photosafety evaluation of complex cosmetic ingredients can be constructed using these modified in vitro photochemical assays. Copyright © 2015 Elsevier Inc. All rights reserved.

Photochemical air pollution

International Nuclear Information System (INIS)

Te Winkel, B.H.

1992-01-01

During periods of severe photochemical air pollution (smog) the industry in the Netherlands is recommended by the Dutch government to strongly reduce the emissions of air pollutants. For the electric power generating companies it is important to investigate the adequacy of this policy. The purpose of this investigation is to determine the contribution of electric power plants to photochemical air pollution and to assess the efficacy of emission reducing measures. A literature survey on the development of photochemical air pollution was carried out and modelled calculations concerning the share of the electric power plants to the photochemical air pollution were executed

Bipyridine based metallogels: an unprecedented difference in photochemical and chemical reduction in the in situ nanoparticle formation.

Science.gov (United States)

Tatikonda, Rajendhraprasad; Bertula, Kia; Nonappa; Hietala, Sami; Rissanen, Kari; Haukka, Matti

2017-02-28

Metal co-ordination induced supramolecular gelation of low molecular weight organic ligands is a rapidly expanding area of research due to the potential in creating hierarchically self-assembled multi-stimuli responsive materials. In this context, structurally simple O-methylpyridine derivatives of 4,4'-dihydroxy-2,2'-bipyridine ligands are reported. Upon complexation with Ag(i) ions in aqueous dimethyl sulfoxide (DMSO) solutions the ligands spontaneously form metallosupramolecular gels at concentrations as low as 0.6 w/v%. The metal ions induce the self-assembly of three dimensional (3D) fibrillar networks followed by the spontaneous in situ reduction of the Ag-centers to silver nanoparticles (AgNPs) when exposed to daylight. Significant size and morphological differences of the AgNP's was observed between the standard chemical and photochemical reduction of the metallogels. The gelation ability, the nanoparticle formation and rheological properties were found to be depend on the ligand structure, while the strength of the gels is affected by the water content of the gels.

The influence of aerosols on photochemical smog in Mexico City

Energy Technology Data Exchange (ETDEWEB)

Castro, T.; Mar, B. [UNAM, Mexico, Centro de Ciencias de la Atmosfera (Mexico); Madronich, S.; Rivale, S. [National Center for Atmospheric Research, Boulder, CO (United States); Muhlia, A. [UNAM, Mexico, Inst. de Geofysica (Mexico)

2001-04-01

Aerosols in the Mexico City atmosphere can have a non-negligible effect on the ultraviolet radiation field and hence on the formation of photochemical smog. We used estimates of aerosol optical depths from sun photometer observations in a detailed radiative transfer model, to calculate photolysis rate coefficients (J{sub NO2}) for the key reaction NO{sub 2}+h{nu}{yields}NO+O ({lambda}<430nm). The calculated values are in good agreement with previously published measurements of J{sub NO2} at two sites in Mexico City: Palacio de Mineria (19 degrees 25'59''N, 99 degrees 07'58''W, 2233masl), and IMP (19 degrees 28'48''N, 99 degrees 11'07''W, 2277masl) and in Tres Marias, a town near Mexico City (19 degrees 03'N, 99 degrees 14'W, 2810masl). In particular, the model reproduces very well the contrast between the two urban sites and the evidently much cleaner Tres Marias site. For the measurement days, reductions in surface J{sub NO2} by 10-30% could be attributed to the presence of aerosols, with considerable uncertainty due largely to lack of detailed data on aerosol optical properties at ultraviolet wavelengths (esp. the single scattering albedo). The potential impact of such large reductions in photolysis rates on surface ozone concentrations is illustrated with a simple zero-dimensional photochemical model. (Author)

Photochemical Copper Coating on 3D Printed Thermoplastics

Science.gov (United States)

Yung, Winco K. C.; Sun, Bo; Huang, Junfeng; Jin, Yingdi; Meng, Zhengong; Choy, Hang Shan; Cai, Zhixiang; Li, Guijun; Ho, Cheuk Lam; Yang, Jinlong; Wong, Wai Yeung

2016-08-01

3D printing using thermoplastics has become very popular in recent years, however, it is challenging to provide a metal coating on 3D objects without using specialized and expensive tools. Herein, a novel acrylic paint containing malachite for coating on 3D printed objects is introduced, which can be transformed to copper via one-step laser treatment. The malachite containing pigment can be used as a commercial acrylic paint, which can be brushed onto 3D printed objects. The material properties and photochemical transformation processes have been comprehensively studied. The underlying physics of the photochemical synthesis of copper was characterized using density functional theory calculations. After laser treatment, the surface coating of the 3D printed objects was transformed to copper, which was experimentally characterized by XRD. 3D printed prototypes, including model of the Statue of Liberty covered with a copper surface coating and a robotic hand with copper interconnections, are demonstrated using this painting method. This composite material can provide a novel solution for coating metals on 3D printed objects. The photochemical reduction analysis indicates that the copper rust in malachite form can be remotely and photo-chemically reduced to pure copper with sufficient photon energy.

Relationships between ozone and other photochemical products at Ll. Valby, Denmark

DEFF Research Database (Denmark)

Skov, H.; Egeløv, A.H.; Granby, K.

1997-01-01

literature results it is estimated that the non-photochemical background mixing ratio of O-3 in the Northern Hemisphere is 24+/-6 ppbv. The correlation of HCOOH and CH3COOH with Ox indicates that these acids are of photochemical origin. A high correlation of HNO3 with Ox is also found. The anti-correlation...

Splitting and non splitting are pollution models photochemical reactions in the urban areas of greater Tehran area

International Nuclear Information System (INIS)

Heidarinasab, A.; Dabir, B.; Sahimi, M.; Badii, Kh.

2003-01-01

During the past years, one of the most important problems has been air pollution in urban areas. In this regards, ozone, as one of the major products of photochemical reactions, has great importance. The term 'photochemical' is applied to a number of secondary pollutants that appear as a result of sun-related reactions, ozone being the most important one. So far various models have been suggested to predict these pollutants. In this paper, we developed the model that has been introduced by Dabir, et al. [4]. In this model more than 48 chemical species and 114 chemical reactions are involved. The result of this development, showed good to excellent agreement across the region for compounds such as O 3 , NO, NO 2 , CO, and SO 2 with regard to VOC and NMHC. The results of the simulation were compared with previous work [4] and the effects of increasing the number of components and reactions were evaluated. The results of the operator splitting method were compared with non splitting solving method. The result showed that splitting method with one-tenth time step collapsed with non splitting method (Crank-Nicolson, under-relaxation iteration method without splitting of the equation terms). Then we developed one dimensional model to 3-D and were compared with experimental data

Photochemical pollution indicators; Les indicateurs de la pollution photochimique. La mesure des composes azotes

Energy Technology Data Exchange (ETDEWEB)

Perros, P E; Marion, T [Paris-7 Univ., 75 (France). Laboratoire Interuniversitaire des Systemes Atmospheriques

1998-11-01

The number of photochemical pollution is generally based on the observation of ozone and nitrogen oxides concentration levels. So, the measurement of photochemical pollution indicators becomes essential to better understand the involved phenomena, and at the end to enable its reduction control and strategy. In this paper, we focus on the measurements of nitrogen compounds (NO{sub x} PAN, HNO{sub 3}). (authors) 24 refs.

International conference on the photochemical conversion and storage of solar energy

Energy Technology Data Exchange (ETDEWEB)

Hofman, M.Z.

1977-01-31

Abstracts are given for the eight formal lectures and the contributed papers from delegates which were presented in the form of posters. There were seven sessions divided by subject as follows: (1) photochemistry, (2) electron transfer mechanisms in photochemical energy conversion processes, (3) photoelectrolysis, (4) photogalvanics, (5) photochemical production of fuels in homogeneous solutions, (6) membranes for photosynthesis reactions, and (7) non-biological systems for organic molecular energy storage. (WHK)

The composition dependence of the photochemical reactivity of strontium barium titanate

Science.gov (United States)

Bhardwaj, Abhilasha

The efficiency of particulate water photolysis catalysts is impractically low due to the recombination of intermediate species and charge carriers. The back reaction can occur easily if the oxidation and reduction sites on the surface of the catalyst are not far enough apart. It is hypothesized that it will be possible to increase the separation of the sites of the two half reactions and reduce the recombination of photogenerated charge carriers by using a ferroelectric material with permanent internal dipolar fields. This separation of the reaction sites may significantly increase the efficiency of the process. The present work compares the photochemical reactivities of ferroelectric and nonferroelectric materials (SrxBa1-xTiO 3, 0.0≤ x ≤1.0) with similar composition and structure. The reactivities are compared by measuring the color change of methylene blue dye after the aqueous dye solution reacts on the surface of ceramic sample pellets as a result of exposure to UV light. The reactivities are also compared by measuring the amount of silver that is formed when an aqueous AgNO3 solution photochemically reacts on the surface. The change in the color of the dye is measured by diffuse reflectance spectroscopy and absorbance measurements. The amount of silver is measured by atomic force microscopy. The photochemical reactivity of SrxBa1-xTiO3 shows a local maximum at the composition of the ferroelectric to non-ferroelectric transition. Also, the reactivities decrease as BaTiO3 and SrTiO3 become less pure. The dominant factors causing this trend in reactivities of SrxBa1-xTiO3 are the dielectric constant and alloy scattering. It is found that higher values of the dielectric constant increase the photochemical reactivity by enlarging the space charge region. The increase in alloy scattering in SrxBa1-xTiO 3 solid solutions as x increases from zero or decreases from 1, has adverse effect on reactivity. There are other factors such as ferroelectric polarization

Ethylene Regulates Energy-Dependent Non-Photochemical Quenching in Arabidopsis through Repression of the Xanthophyll Cycle

Science.gov (United States)

Chen, Zhong; Gallie, Daniel R.

2015-01-01

Energy-dependent (qE) non-photochemical quenching (NPQ) thermally dissipates excess absorbed light energy as a protective mechanism to prevent the over reduction of photosystem II and the generation of reactive oxygen species (ROS). The xanthophyll cycle, induced when the level of absorbed light energy exceeds the capacity of photochemistry, contributes to qE. In this work, we show that ethylene regulates the xanthophyll cycle in Arabidopsis. Analysis of eto1-1, exhibiting increased ethylene production, and ctr1-3, exhibiting constitutive ethylene response, revealed defects in NPQ resulting from impaired de-epoxidation of violaxanthin by violaxanthin de-epoxidase (VDE) encoded by NPQ1. Elevated ethylene signaling reduced the level of active VDE through decreased NPQ1 promoter activity and impaired VDE activation resulting from a lower transthylakoid membrane pH gradient. Increasing the concentration of CO2 partially corrected the ethylene-mediated defects in NPQ and photosynthesis, indicating that changes in ethylene signaling affect stromal CO2 solubility. Increasing VDE expression in eto1-1 and ctr1-3 restored light-activated de-epoxidation and qE, reduced superoxide production and reduced photoinhibition. Restoring VDE activity significantly reversed the small growth phenotype of eto1-1 and ctr1-3 without altering ethylene production or ethylene responses. Our results demonstrate that ethylene increases ROS production and photosensitivity in response to high light and the associated reduced plant stature is partially reversed by increasing VDE activity. PMID:26630486

Ethylene Regulates Energy-Dependent Non-Photochemical Quenching in Arabidopsis through Repression of the Xanthophyll Cycle.

Directory of Open Access Journals (Sweden)

Zhong Chen

Full Text Available Energy-dependent (qE non-photochemical quenching (NPQ thermally dissipates excess absorbed light energy as a protective mechanism to prevent the over reduction of photosystem II and the generation of reactive oxygen species (ROS. The xanthophyll cycle, induced when the level of absorbed light energy exceeds the capacity of photochemistry, contributes to qE. In this work, we show that ethylene regulates the xanthophyll cycle in Arabidopsis. Analysis of eto1-1, exhibiting increased ethylene production, and ctr1-3, exhibiting constitutive ethylene response, revealed defects in NPQ resulting from impaired de-epoxidation of violaxanthin by violaxanthin de-epoxidase (VDE encoded by NPQ1. Elevated ethylene signaling reduced the level of active VDE through decreased NPQ1 promoter activity and impaired VDE activation resulting from a lower transthylakoid membrane pH gradient. Increasing the concentration of CO2 partially corrected the ethylene-mediated defects in NPQ and photosynthesis, indicating that changes in ethylene signaling affect stromal CO2 solubility. Increasing VDE expression in eto1-1 and ctr1-3 restored light-activated de-epoxidation and qE, reduced superoxide production and reduced photoinhibition. Restoring VDE activity significantly reversed the small growth phenotype of eto1-1 and ctr1-3 without altering ethylene production or ethylene responses. Our results demonstrate that ethylene increases ROS production and photosensitivity in response to high light and the associated reduced plant stature is partially reversed by increasing VDE activity.

Ethylene Regulates Energy-Dependent Non-Photochemical Quenching in Arabidopsis through Repression of the Xanthophyll Cycle.

Science.gov (United States)

Chen, Zhong; Gallie, Daniel R

2015-01-01

Energy-dependent (qE) non-photochemical quenching (NPQ) thermally dissipates excess absorbed light energy as a protective mechanism to prevent the over reduction of photosystem II and the generation of reactive oxygen species (ROS). The xanthophyll cycle, induced when the level of absorbed light energy exceeds the capacity of photochemistry, contributes to qE. In this work, we show that ethylene regulates the xanthophyll cycle in Arabidopsis. Analysis of eto1-1, exhibiting increased ethylene production, and ctr1-3, exhibiting constitutive ethylene response, revealed defects in NPQ resulting from impaired de-epoxidation of violaxanthin by violaxanthin de-epoxidase (VDE) encoded by NPQ1. Elevated ethylene signaling reduced the level of active VDE through decreased NPQ1 promoter activity and impaired VDE activation resulting from a lower transthylakoid membrane pH gradient. Increasing the concentration of CO2 partially corrected the ethylene-mediated defects in NPQ and photosynthesis, indicating that changes in ethylene signaling affect stromal CO2 solubility. Increasing VDE expression in eto1-1 and ctr1-3 restored light-activated de-epoxidation and qE, reduced superoxide production and reduced photoinhibition. Restoring VDE activity significantly reversed the small growth phenotype of eto1-1 and ctr1-3 without altering ethylene production or ethylene responses. Our results demonstrate that ethylene increases ROS production and photosensitivity in response to high light and the associated reduced plant stature is partially reversed by increasing VDE activity.

Synthesis of fluorescent metal nanoparticles in aqueous solution by photochemical reduction

KAUST Repository

Kshirsagar, Prakash

2014-01-06

A facile green chemistry approach for the synthesis of sub-5 nm silver and gold nanoparticles is reported. The synthesis was achieved by a photochemical method using tyrosine as the photoreducing agent. The size of the gold and silver nanoparticles was about 3 and 4 nm, respectively. The nanoparticles were characterized using x-ray diffraction, transmission electron microscopy, Fourier transform infrared spectroscopy and photoluminescence spectroscopy. Both silver and gold nanoparticles synthesized by this method exhibited fluorescence properties and their use for cell imaging applications has been demonstrated. © 2014 IOP Publishing Ltd.

Photochemical effects of sunlight.

Science.gov (United States)

Daniels, F

1972-07-01

The importance of sunlight in bringing about not only photosynthesis in plants, but also other photochemical effects, is reviewed. More effort should be devoted to photochemical storage of the sun's energy without the living plant. There is no theoretical reason to believe that such reactions are impossible. Ground rules for searching for suitable solar photochemical reactions are given, and a few attempts are described, but nothing successful has yet been found. Future possibilities are suggested. Photogalvanic cells which convert sunlight into electricity deserve further research. Eugene Rabinowitch has been an active pioneer in these fields.

Functional architecture of higher plant photosystem II supercomplexes.

Science.gov (United States)

Caffarri, Stefano; Kouril, Roman; Kereïche, Sami; Boekema, Egbert J; Croce, Roberta

2009-10-07

Photosystem II (PSII) is a large multiprotein complex, which catalyses water splitting and plastoquinone reduction necessary to transform sunlight into chemical energy. Detailed functional and structural studies of the complex from higher plants have been hampered by the impossibility to purify it to homogeneity. In this work, homogeneous preparations ranging from a newly identified particle composed by a monomeric core and antenna proteins to the largest C(2)S(2)M(2) supercomplex were isolated. Characterization by biochemical methods and single particle electron microscopy allowed to relate for the first time the supramolecular organization to the protein content. A projection map of C(2)S(2)M(2) at 12 A resolution was obtained, which allowed determining the location and the orientation of the antenna proteins. Comparison of the supercomplexes obtained from WT and Lhcb-deficient plants reveals the importance of the individual subunits for the supramolecular organization. The functional implications of these findings are discussed and allow redefining previous suggestions on PSII energy transfer, assembly, photoinhibition, state transition and non-photochemical quenching.

Respiratory processes in non-photosynthetic plastids

Science.gov (United States)

Renato, Marta; Boronat, Albert; Azcón-Bieto, Joaquín

2015-01-01

Chlororespiration is a respiratory process located in chloroplast thylakoids which consists in an electron transport chain from NAD(P)H to oxygen. This respiratory chain involves the NAD(P)H dehydrogenase complex, the plastoquinone pool and the plastid terminal oxidase (PTOX), and it probably acts as a safety valve to prevent the over-reduction of the photosynthetic machinery in stress conditions. The existence of a similar respiratory activity in non-photosynthetic plastids has been less studied. Recently, it has been reported that tomato fruit chromoplasts present an oxygen consumption activity linked to ATP synthesis. Etioplasts and amyloplasts contain several electron carriers and some subunits of the ATP synthase, so they could harbor a similar respiratory process. This review provides an update on the study about respiratory processes in chromoplasts, identifying the major gaps that need to be addressed in future research. It also reviews the proteomic data of etioplasts and amyloplasts, which suggest the presence of a respiratory electron transport chain in these plastids. PMID:26236317

Respiratory processes in non-photosynthetic plastids

Directory of Open Access Journals (Sweden)

Marta eRenato

2015-07-01

Full Text Available Chlororespiration is a respiratory process located in chloroplast thylakoids which consists in an electron transport chain from NAD(PH to oxygen. This respiratory chain involves the NAD(PH dehydrogenase complex, the plastoquinone pool and the plastid terminal oxidase (PTOX, and it probably acts as a safety valve to prevent the over-reduction of the photosynthetic machinery in stress conditions. The existence of a similar respiratory activity in non-photosynthetic plastids has been less studied. Recently, it has been reported that tomato fruit chromoplasts present an oxygen consumption activity linked to ATP synthesis. Etioplasts and amyloplasts contain several electron carriers and some subunits of the ATP synthase, so they could harbor a similar respiratory process. This review provides an update on the study about respiratory processes in chromoplasts, identifying the major gaps that need to be addressed in future research. It also reviews the proteomic data of etioplasts and amyloplasts, which suggest the presence of a respiratory electron transport chain in these plastids.

Determination of total mercury and methylmercury in biological samples by photochemical vapor generation

Energy Technology Data Exchange (ETDEWEB)

Vieira, Mariana A.; Ribeiro, Anderson S.; Curtius, Adilson J. [Universidade Federal de Santa Catarina, Departamento de Quimica, Florianopolis, SC (Brazil); Sturgeon, Ralph E. [National Research Council Canada, Institute for National Measurement Standards, Ottawa, ON (Canada)

2007-06-15

Cold vapor atomic absorption spectrometry (CV-AAS) based on photochemical reduction by exposure to UV radiation is described for the determination of methylmercury and total mercury in biological samples. Two approaches were investigated: (a) tissues were digested in either formic acid or tetramethylammonium hydroxide (TMAH), and total mercury was determined following reduction of both species by exposure of the solution to UV irradiation; (b) tissues were solubilized in TMAH, diluted to a final concentration of 0.125% m/v TMAH by addition of 10% v/v acetic acid and CH{sub 3}Hg{sup +} was selectively quantitated, or the initial digests were diluted to 0.125% m/v TMAH by addition of deionized water, adjusted to pH 0.3 by addition of HCl and CH{sub 3}Hg{sup +} was selectively quantitated. For each case, the optimum conditions for photochemical vapor generation (photo-CVG) were investigated. The photochemical reduction efficiency was estimated to be {proportional_to}95% by comparing the response with traditional SnCl{sub 2} chemical reduction. The method was validated by analysis of several biological Certified Reference Materials, DORM-1, DORM-2, DOLT-2 and DOLT-3, using calibration against aqueous solutions of Hg{sup 2+}; results showed good agreement with the certified values for total and methylmercury in all cases. Limits of detection of 6 ng/g for total mercury using formic acid, 8 ng/g for total mercury and 10 ng/g for methylmercury using TMAH were obtained. The proposed methodology is sensitive, simple and inexpensive, and promotes ''green'' chemistry. The potential for application to other sample types and analytes is evident. (orig.)

Utility of Photochemical Traits as Diagnostics of Thermal Tolerance amongst Great Barrier Reef Corals

Directory of Open Access Journals (Sweden)

Matthew R. Nitschke

2018-02-01

Full Text Available Light availability is considered a key factor regulating the thermal sensitivity of reef building corals, where excessive excitation of photosystem II (PSII further exacerbates pressure on photochemical pathways already compromised by heat stress. Coral symbionts acclimate to changes in light availability (photoacclimation by continually fine-tuning the photochemical operating efficiency of PSII. However, how this process adjusts throughout the warmest months in naturally heat-tolerant or sensitive species is unknown, and whether this influences the capacity to tolerate transient heat stress is untested. We therefore examined the PSII photophysiology of 10 coral species (with known thermal tolerances from shallow reef environments at Heron Island (Great Barrier Reef, Australia, in spring (October-November, 2015 vs. summer (February-March, 2016. Corals were maintained in flow-through aquaria and rapid light curve (RLC protocols using pulse amplitude modulated (PAM fluorometry captured changes in the PSII photoacclimation strategy, characterized as the minimum saturating irradiance (Ek, and the extent of photochemical ([1 – C], operating efficiency vs. non-photochemical ([1 – Q] energy dissipation. Values of Ek across species were >2-fold higher in all coral species in spring, consistent with a climate of higher overall light exposure (i.e., higher PAR from lower cloud cover, rainfall and wind speed compared with summer. Summer decreases in Ek were combined with a shift toward preferential photochemical quenching in all species. All coral species were subsequently subjected to thermal stress assays. An equivalent temperature-ramping profile of 1°C increase per day and then maintenance at 32°C was applied in each season. Despite the significant seasonal photoacclimation, the species hierarchy of thermal tolerance [maximum quantum yields of PSII (Fv/Fm, monitored at dawn and dusk] did not shift between seasons, except for Pocillopora

Synthesis of fluorescent metal nanoparticles in aqueous solution by photochemical reduction

International Nuclear Information System (INIS)

Kshirsagar, Prakash; Brunetti, Virgilio; Malvindi, Maria Ada; Pompa, Pier Paolo; Sangaru, Shiv Shankar

2014-01-01

A facile green chemistry approach for the synthesis of sub-5 nm silver and gold nanoparticles is reported. The synthesis was achieved by a photochemical method using tyrosine as the photoreducing agent. The size of the gold and silver nanoparticles was about 3 and 4 nm, respectively. The nanoparticles were characterized using x-ray diffraction, transmission electron microscopy, Fourier transform infrared spectroscopy and photoluminescence spectroscopy. Both silver and gold nanoparticles synthesized by this method exhibited fluorescence properties and their use for cell imaging applications has been demonstrated. (paper)

Mercury in Arctic snow: Quantifying the kinetics of photochemical oxidation and reduction

Energy Technology Data Exchange (ETDEWEB)

Mann, E.A. [Department of Environmental Science, Acadia University, Wolfville, NS (Canada); Environmental Science Programme, Memorial University of Newfoundland, St. John' s, NL (Canada); Mallory, M.L. [Department of Biology, Acadia University, Wolfville, NS (Canada); Ziegler, S.E. [Environmental Science Programme, Memorial University of Newfoundland, St. John' s, NL (Canada); Tordon, R. [Environment Canada, Dartmouth, NS (Canada); O' Driscoll, N.J., E-mail: nelson.odriscoll@acadiau.ca [Department of Environmental Science, Acadia University, Wolfville, NS (Canada)

2015-03-15

Controlled experiments were performed with frozen and melted Arctic snow to quantify relationships between mercury photoreaction kinetics, ultra violet (UV) radiation intensity, and snow ion concentrations. Frozen (− 10 °C) and melted (4 °C) snow samples from three Arctic sites were exposed to UV (280–400 nm) radiation (1.26–5.78 W · m{sup −2}), and a parabolic relationship was found between reduction rate constants in frozen and melted snow with increasing UV intensity. Total photoreduced mercury in frozen and melted snow increased linearly with greater UV intensity. Snow with the highest concentrations of chloride and iron had larger photoreduction and photooxidation rate constants, while also having the lowest Hg(0) production. Our results indicate that the amount of mercury photoreduction (loss from snow) is the highest at high UV radiation intensities, while the fastest rates of mercury photoreduction occurred at both low and high intensities. This suggests that, assuming all else is equal, earlier Arctic snow melt periods (when UV intensities are less intense) may result in less mercury loss to the atmosphere by photoreduction and flux, since less Hg(0) is photoproduced at lower UV intensities, thereby resulting in potentially greater mercury transport to aquatic systems with snowmelt. - Highlights: • Mercury photochemical kinetics were studied in frozen and melted Arctic snow. • UV-induced photoreduction and photooxidation rate constants were quantified. • Chloride ion, iron, and DOC influence mercury photoreactions in snow. • Frozen and melted snow have different mercury photoreduction characteristics. • Kinetic information provided can be used to model mercury fate in the Arctic.

Mercury in Arctic snow: Quantifying the kinetics of photochemical oxidation and reduction

International Nuclear Information System (INIS)

Mann, E.A.; Mallory, M.L.; Ziegler, S.E.; Tordon, R.; O'Driscoll, N.J.

2015-01-01

Controlled experiments were performed with frozen and melted Arctic snow to quantify relationships between mercury photoreaction kinetics, ultra violet (UV) radiation intensity, and snow ion concentrations. Frozen (− 10 °C) and melted (4 °C) snow samples from three Arctic sites were exposed to UV (280–400 nm) radiation (1.26–5.78 W · m −2 ), and a parabolic relationship was found between reduction rate constants in frozen and melted snow with increasing UV intensity. Total photoreduced mercury in frozen and melted snow increased linearly with greater UV intensity. Snow with the highest concentrations of chloride and iron had larger photoreduction and photooxidation rate constants, while also having the lowest Hg(0) production. Our results indicate that the amount of mercury photoreduction (loss from snow) is the highest at high UV radiation intensities, while the fastest rates of mercury photoreduction occurred at both low and high intensities. This suggests that, assuming all else is equal, earlier Arctic snow melt periods (when UV intensities are less intense) may result in less mercury loss to the atmosphere by photoreduction and flux, since less Hg(0) is photoproduced at lower UV intensities, thereby resulting in potentially greater mercury transport to aquatic systems with snowmelt. - Highlights: • Mercury photochemical kinetics were studied in frozen and melted Arctic snow. • UV-induced photoreduction and photooxidation rate constants were quantified. • Chloride ion, iron, and DOC influence mercury photoreactions in snow. • Frozen and melted snow have different mercury photoreduction characteristics. • Kinetic information provided can be used to model mercury fate in the Arctic

Photochemical hydrogen production system

International Nuclear Information System (INIS)

Copeland, R.J.

1990-01-01

Both technical and economic factors affect the cost of producing hydrogen by photochemical processes. Technical factors include the efficiency and the capital and operating costs of the renewable hydrogen conversion system; economic factors include discount rates, economic life, credit for co-product oxygen, and the value of the energy produced. This paper presents technical and economic data for a system that generates on-peak electric power form photochemically produced hydrogen

Photochemical decomposition of catecholamines

International Nuclear Information System (INIS)

Mol, N.J. de; Henegouwen, G.M.J.B. van; Gerritsma, K.W.

1979-01-01

During photochemical decomposition (lambda=254 nm) adrenaline, isoprenaline and noradrenaline in aqueous solution were converted to the corresponding aminochrome for 65, 56 and 35% respectively. In determining this conversion, photochemical instability of the aminochromes was taken into account. Irradiations were performed in such dilute solutions that the neglect of the inner filter effect is permissible. Furthermore, quantum yields for the decomposition of the aminochromes in aqueous solution are given. (Author)

Synthesis of silver nanoprisms: A photochemical approach using light emission diodes

International Nuclear Information System (INIS)

Saade, Jamil; Araújo, Cid B. de

2014-01-01

We report a simplified photochemical methodology for fabrication of silver nanoprisms (Ag-NPs). The particles, synthesized in aqueous solution, were produced by illumination with narrow band and low cost Light Emission Diodes (LEDs) and exhibit Localized Surface Plasmon Resonances (LSPR) from the blue to the near-infrared. The new methodology consists of one pot synthesis that uses only three chemical reagents and allows good control of the sizes and the aspect ratios of triangular Ag-NPs. Reduction of silver ions by trisodium citrate (TSC), catalyzed on silver seeds, is exploited to synthesize and to control the growth of the Ag-NPs. The growth kinetics of the particles was characterized by monitoring the LSPR absorption band during several hours under continuous illumination. Optical absorption, transmission electron microscopy (TEM), electron diffraction and zeta potential measurements were performed to characterize the shape and size of the Ag-NPs and the colloid stability during its synthesis and aging. The TEM images and extinction spectra revealed Ag-NPs with good size dispersion and narrow LSPR bands with great potential for applications in nanotechnology. - Highlights: • Efficient method to synthesize Ag nanoprisms using only three chemical reagents. • Practicality: it removes the needs for some steps used in photochemical synthesis. • Zeta Potential measurements revealed the best conditions for colloids stability. • Non-coherent-radiation-induced dipoles cause aggregation of similar nanoprisms. • Data confirmed step-like-structures on the nanoprisms surface due to their aging

[PS II photochemical efficiency in flag leaf of wheat varieties and its adaptation to strong sun- light intensity on farmland of Xiangride in Qinghai Province, Northwest China].

Science.gov (United States)

Shi, Sheng-Bo; Chen, Wen-Jie; Shi, Rui; Li, Miao; Zhang, Huai-Gang; Sun, Ya-Nan

2014-09-01

Taking four wheat varieties developed by Northwest Institute of Plateau Biology, Chinese Academy of Sciences, as test materials, with the measurement of content of photosynthetic pigments, leaf area, fresh and dry mass of flag leaf, the PS II photochemistry efficiency of abaxial and adaxial surface of flag leaf and its adaptation to strong solar radiation during the period of heading stage in Xiangride region were investigated with the pulse-modulated in-vivo chlorophyll fluorescence technique. The results indicated that flag leaf angle mainly grew in horizontal state in Gaoyuan 314, Gaoyuan 363 and Gaoyuan 584, and mainly in vertical state in Gaoyuan 913 because of its smaller leaf area and larger width. Photosynthetic pigments were different among the 4 varieties, and positively correlated with intrinsic PS II photochemistry efficiencies (Fv/Fm). In clear days, especially at noon, the photosynthetic photoinhibition was more serious in abaxial surface of flag leaf due to directly facing the solar radiation, but it could recover after reduction of sunlight intensity in the afternoon, which meant that no inactive damage happened in PS II reaction centers. There were significant differences of PS II actual and maximum photochemical efficiencies at the actinic light intensity (ΦPS II and Fv'/Fm') between abaxial and adaxial surface, and their relative variation trends were on the contrary. The photochemical and non-photochemical quenching coefficients (qP and NPQ) had a similar tendency in both abaxial and adaxial surfaces. Although ΦPS II and qP were lower in adaxial surface of flag leaf, the Fv'/Fm' was significantly higher, which indicated that the potential PS II capture efficiency of excited energy was higher. The results demonstrated that process of photochemical and non-photochemical quenching could effectively dissipate excited energy caused by strong solar radiation, and there were higher adaptation capacities in wheat varieties natively cultivated in

Modelling study of boundary-layer ozone over northern China - Part II: Responses to emission reductions during the Beijing Olympics

Science.gov (United States)

Tang, Guiqian; Zhu, Xiaowan; Xin, Jinyuan; Hu, Bo; Song, Tao; Sun, Yang; Wang, Lili; Wu, Fangkun; Sun, Jie; Cheng, Mengtian; Chao, Na; Li, Xin; Wang, Yuesi

2017-09-01

The implementation of emission reduction measures during the Olympics provided a valuable opportunity to study regional photochemical pollution over northern China. In this study, the fifth-generation Pennsylvania State University/National Centre for Atmospheric Research Mesoscale Model and Community Multiscale Air Quality model system was applied to conduct two sets of modelling analyses of the period from July 20 to September 20, 2008, to illustrate the influences of emission reduction measures on regional photochemical pollution over northern China during the Beijing Olympics. The results indicated that the implementation of emission control measures decreased the concentrations of ozone (O3) precursors, namely nitrogen oxide (NOx) and volatile organic compounds (VOCs), throughout the boundary layer. The concentrations of these compounds were reduced by 45% in the central urban area of Beijing at the ground level. Although the average O3 concentration in the central urban area increased by more than 8 ppbv, the total oxidant concentration decreased significantly by more than 5 ppbv. Greater O3 concentrations mainly occurred during periods with weak photochemical reactions. During periods of strong photochemical production, the O3 concentration decreased significantly due to a weakening vertical circulation between the lower and upper boundary layer. Consequently, the number of days when the O3 concentration exceeded 100 ppbv decreased by 25% in Beijing. The emission control measures altered the sensitivity of the regional O3 production. The coordinated control region of NOx and VOCs expanded, and the control region of VOCs decreased in size. The reduction of non-point-source emissions, such as fugitive VOCs and vehicles, was more useful for controlling regional photochemical pollution over northern China.

Photochemical smog and plants

Energy Technology Data Exchange (ETDEWEB)

Sawada, T.

1974-07-01

Surveys of plant damage due to photochemical smog are summarized. The components of smog which appear to be responsible for plant damage include ozone and peroxyacyl nitrates. Their phytotoxic effects are much greater than those due to sulfur oxides. Damage surveys since 1970 reveal the following symptoms appearing on herbaceous plants (morning glory, cocks comb, dahlia, knotweed, petunia, chickweed, Welsh onion, spinach, Chinese cabbage, chard, taro): yellowish-white leaf discoloration, white and brown spots on matured leaves, and silvering of the lower surfaces of young leaves. Symptoms which appear on arboraceous plants such as zelkova, poplar, ginkgo, planetree, rose mallow, magnolia, pine tree, and rhododendron include early yellowing and reddening, white or brown spots, and untimely leaf-fall. The above plants are now utilized as indicator plants of photochemical smog. Surveys covering a broad area of Tokyo and three other prefectures indicate that plant damage due to photochemical smog extends to relatively unpolluted areas.

Photosystem II-cyclic electron flow powers exceptional photoprotection and record growth in the microalga Chlorella ohadii.

Science.gov (United States)

Ananyev, Gennady; Gates, Colin; Kaplan, Aaron; Dismukes, G Charles

2017-11-01

The desert microalga Chlorella ohadii was reported to grow at extreme light intensities with minimal photoinhibition, tolerate frequent de/re-hydrations, yet minimally employs antenna-based non-photochemical quenching for photoprotection. Here we investigate the molecular mechanisms by measuring Photosystem II charge separation yield (chlorophyll variable fluorescence, Fv/Fm) and flash-induced O 2 yield to measure the contributions from both linear (PSII-LEF) and cyclic (PSII-CEF) electron flow within PSII. Cells grow increasingly faster at higher light intensities (μE/m 2 /s) from low (20) to high (200) to extreme (2000) by escalating photoprotection via shifting from PSII-LEF to PSII-CEF. This shifts PSII charge separation from plastoquinone reduction (PSII-LEF) to plastoquinol oxidation (PSII-CEF), here postulated to enable proton gradient and ATP generation that powers photoprotection. Low light-grown cells have unusually small antennae (332 Chl/PSII), use mainly PSII-LEF (95%) and convert 40% of PSII charge separations into O 2 (a high O 2 quantum yield of 0.06mol/mol PSII/flash). High light-grown cells have smaller antenna and lower PSII-LEF (63%). Extreme light-grown cells have only 42 Chl/PSII (no LHCII antenna), minimal PSII-LEF (10%), and grow faster than any known phototroph (doubling time 1.3h). Adding a synthetic quinone in excess to supplement the PQ pool fully uncouples PSII-CEF from its natural regulation and produces maximum PSII-LEF. Upon dark adaptation PSII-LEF rapidly reverts to PSII-CEF, a transient protection mechanism to conserve water and minimize the cost of antenna biosynthesis. The capacity of the electron acceptor pool (plastoquinone pool), and the characteristic times for exchange of (PQH 2 ) B with PQ pool and reoxidation of (PQH 2 ) pool were determined. Copyright © 2017. Published by Elsevier B.V.

Proposal to realize a cost breakthrough in carbon-13 production by photochemical separation

International Nuclear Information System (INIS)

Marling, J.B.

1979-10-01

A cost breakthrough can now be made in photochemical production of the rare stable isotope carbon-13. This cost breakthrough is achieved by CO 2 laser infrared multiple-photon dissociation of any of several halocarbons (Freon derivatives) such as CF 3 Cl, CF 3 Br, or CF 2 Cl 2 . The single-step carbon-13 enrichment factor for this process is approximately 50, yielding 30% pure C-13 in one step, or up to 97% pure C-13 in two steps. A three-fold carbon-13 cost reduction to below $20/gram is expected to be achieved in a small laboratory-scale demonstration facility capable of producing 4 to 8 kg/year of carbon-13, using presently available pulsed CO 2 TEA lasers at an average power level of 50 watts. Personnel costs dominate the attainable C-13 production costs in a small photochemical enrichment facility. A price reduction to $2/gm carbon-13 is feasible at carbon-13 production levels of 100 to 1000 kg/year, dominated by the Freon raw material costs

Thermo-cleavable polymers: Materials with enhanced photochemical stability

DEFF Research Database (Denmark)

Manceau, Matthieu; Petersen, Martin Helgesen; Krebs, Frederik C

2010-01-01

Photochemical stability of three thermo-cleavable polymers was investigated as thin films under atmospheric conditions. A significant increase in lifetime was observed once the side-chain was cleaved emphasizing the detrimental effect of solubilizing groups on the photochemical stability of conju......Photochemical stability of three thermo-cleavable polymers was investigated as thin films under atmospheric conditions. A significant increase in lifetime was observed once the side-chain was cleaved emphasizing the detrimental effect of solubilizing groups on the photochemical stability...... of conjugated polymers. In addition to their ease of processing, thermo-cleavable polymers thus also offer a greater intrinsic stability under illumination....

Identification of pH-sensing Sites in the Light Harvesting Complex Stress-related 3 Protein Essential for Triggering Non-photochemical Quenching in Chlamydomonas reinhardtii.

Science.gov (United States)

Ballottari, Matteo; Truong, Thuy B; De Re, Eleonora; Erickson, Erika; Stella, Giulio R; Fleming, Graham R; Bassi, Roberto; Niyogi, Krishna K

2016-04-01

Light harvesting complex stress-related 3 (LHCSR3) is the protein essential for photoprotective excess energy dissipation (non-photochemical quenching, NPQ) in the model green algaChlamydomonas reinhardtii Activation of NPQ requires low pH in the thylakoid lumen, which is induced in excess light conditions and sensed by lumen-exposed acidic residues. In this work we have used site-specific mutagenesisin vivoandin vitrofor identification of the residues in LHCSR3 that are responsible for sensing lumen pH. Lumen-exposed protonatable residues, aspartate and glutamate, were mutated to asparagine and glutamine, respectively. By expression in a mutant lacking all LHCSR isoforms, residues Asp(117), Glu(221), and Glu(224)were shown to be essential for LHCSR3-dependent NPQ induction inC. reinhardtii Analysis of recombinant proteins carrying the same mutations refoldedin vitrowith pigments showed that the capacity of responding to low pH by decreasing the fluorescence lifetime, present in the wild-type protein, was lost. Consistent with a role in pH sensing, the mutations led to a substantial reduction in binding the NPQ inhibitor dicyclohexylcarbodiimide. © 2016 by The American Society for Biochemistry and Molecular Biology, Inc.

A transthylakoid proton gradient and inhibitors induce a non-photochemical fluorescence quenching in unicellular algae Nannochloropsis sp.

Science.gov (United States)

Cao, Shaona; Zhang, Xiaowen; Xu, Dong; Fan, Xiao; Mou, Shanli; Wang, Yitao; Ye, Naihao; Wang, Wenqi

2013-05-02

Non-photochemical quenching (NPQ) of chlorophyll fluorescence is thought to be an indicator of an essential regulation and photoprotection mechanism against high-light stress in photosynthetic organisms. In this report, special chemicals were used to perturb the kinetics of the ΔpH build-up and the xanthophyll cycle (XC) in Nannochloropsis sp. We found that NPQ was stimulated rapidly on exposure to high light and relaxed rapidly in darkness. The ΔpH could be obligatory for NPQ and ΔpH alone was not sufficient to induce NPQ. The XC, being strictly mediated by ΔpH, was also essential for NPQ. The results demonstrate that the mechanism of NPQ in Nannochloropsis sp. resembled that of diatoms. Copyright © 2013 Federation of European Biochemical Societies. Published by Elsevier B.V. All rights reserved.

Damage to photosystem II due to heat stress without light-driven electron flow: involvement of enhanced introduction of reducing power into thylakoid membranes.

Science.gov (United States)

Marutani, Yoko; Yamauchi, Yasuo; Kimura, Yukihiro; Mizutani, Masaharu; Sugimoto, Yukihiro

2012-08-01

Under a moderately heat-stressed condition, the photosystems of higher plants are damaged in the dark more easily than they are in the presence of light. To obtain a better understanding of this heat-derived damage mechanism that occurs in the dark, we focused on the involvement of the light-independent electron flow that occurs at 40 °C during the damage. In various plant species, the maximal photochemical quantum yield of photosystem (PS) II (Fv/Fm) decreased as a result of heat treatment in the dark. In the case of wheat, the most sensitive plant species tested, both Fv/Fm and oxygen evolution rapidly decreased by heat treatment at 40 °C for 30 min in the dark. In the damage, specific degradation of D1 protein was involved, as shown by immunochemical analysis of major proteins in the photosystem. Because light canceled the damage to PSII, the light-driven electron flow may play a protective role against PSII damage without light. Light-independent incorporation of reducing power from stroma was enhanced at 40 °C but not below 35 °C. Arabidopsis mutants that have a deficit of enzymes which mediate the incorporation of stromal reducing power into thylakoid membranes were tolerant against heat treatment at 40 °C in the dark, suggesting that the reduction of the plastoquinone pool may be involved in the damage. In conclusion, the enhanced introduction of reducing power from stroma into thylakoid membranes that occurs around 40 °C causes over-reduction of plastoquinone, resulting in the damage to D1 protein under heat stress without linear electron flow.

Photochemical dynamics of surface oriented molecules

International Nuclear Information System (INIS)

Ho, W.

1992-01-01

The period 8/01/91-7/31/92 is the first year of a new project titled ''Photochemical Dynamics of Surface Oriented Molecules'', initiated with DOE Support. The main objective of this project is to understand the dynamics of elementary chemical reactions by studying photochemical dynamics of surface-oriented molecules. In addition, the mechanisms of photon-surface interactions need to be elucidated. The strategy is to carry out experiments to measure the translational energy distribution, as a function of the angle from the surface normal, of the photoproducts by time-of-flight (TOF) technique by varying the photon wavelength, intensity, polarization, and pulse duration. By choosing adsorbates with different bonding configuration, the effects of adsorbate orientation on surface photochemical dynamics can be studied

Decoupling photochemical Fe(II) oxidation from shallow-water BIF deposition

DEFF Research Database (Denmark)

Konhauser, Kurt; Amskold, Larry; Lalonde, Stefan

2007-01-01

to the rise of atmospheric oxygen and the development of a protective ozone layer, the Earth's surface was subjected to high levels of ultraviolet radiation. Bulk ocean waters that were anoxic at this time could have supported high concentrations of dissolved Fe(II). Under such conditions, dissolved ferrous...... for biology [Fran??ois, L.M., 1986, Extensive deposition of banded iron formations was possible without photosynthesis. Nature 320, 352-354]. Here, we evaluate the potential importance of photochemical oxidation using a combination of experiments and thermodynamic models. The experiments simulate......-type systems, then we are driven to conclude that oxide-facies BIF are the product of a rapid, non-photochemical oxidative process, the most likely candidates being direct or indirect biological oxidation, and that a significant fraction of BIF could have initially been deposited as ferrous minerals. ?? 2007...

Nickel films: Nonselective and selective photochemical deposition and properties

International Nuclear Information System (INIS)

Smirnova, N.V.; Boitsova, T.B.; Gorbunova, V.V.; Alekseeva, L.V.; Pronin, V.P.; Kon'uhov, G.S.

2006-01-01

Nickel films deposited on quartz surfaces by the photochemical reduction of a chemical nickel plating solution were studied. It was found that the deposition of the films occurs after an induction period, the length of which depends on the composition of the photolyte and the light intensity. Ni particles with a mean diameter of 20-30 nm were detected initially by transmission electron microscopy. The particles then increased in size (50 nm) upon irradiation and grouped into rings consisting of 4-5 particles. Irradiation with high-intensity light produces three-dimensional films. The calculated extinction coefficient of the nickel film was found to be 4800 L mol -1 cm -1 . Electron diffraction revealed that the prepared amorphous nickel films crystallize after one day of storage. It was determined that the films exhibit catalytic activity in the process of nickel deposition from nickel plating solution. The catalytic action remains for about 5-7 min after exposure of the films to air. The processes of selective and nonselective deposition of the nickel films are discussed. The use of poly(butoxy titanium) in the process of selective photochemical deposition enables negative and positive images to be prepared on quartz surfaces

Engineered Photosystem II reaction centers optimize photochemistry versus photoprotection at different solar intensities.

Science.gov (United States)

Vinyard, David J; Gimpel, Javier; Ananyev, Gennady M; Mayfield, Stephen P; Dismukes, G Charles

2014-03-12

The D1 protein of Photosystem II (PSII) provides most of the ligating amino acid residues for the Mn4CaO5 water-oxidizing complex (WOC) and half of the reaction center cofactors, and it is present as two isoforms in the cyanobacterium Synechococcus elongatus PCC 7942. These isoforms, D1:1 and D1:2, confer functional advantages for photosynthetic growth at low and high light intensities, respectively. D1:1, D1:2, and seven point mutations in the D1:2 background that are native to D1:1 were expressed in the green alga Chlamydomonas reinhardtii. We used these nine strains to show that those strains that confer a higher yield of PSII charge separation under light-limiting conditions (where charge recombination is significant) have less efficient photochemical turnover, measured in terms of both a lower WOC turnover probability and a longer WOC cycle period. Conversely, these same strains under light saturation (where charge recombination does not compete) confer a correspondingly faster O2 evolution rate and greater protection against photoinhibition. Taken together, the data clearly establish that PSII primary charge separation is a trade-off between photochemical productivity (water oxidation and plastoquinone reduction) and charge recombination (photoprotection). These trade-offs add up to a significant growth advantage for the two natural isoforms. These insights provide fundamental design principles for engineering of PSII reaction centers with optimal photochemical efficiencies for growth at low versus high light intensities.

Violaxanthin de-epoxidase is rate-limiting for non-photochemical quenching under subsaturating light or during chilling in Arabidopsis.

Science.gov (United States)

Chen, Zhong; Gallie, Daniel R

2012-09-01

In response to conditions of excess light energy, plants induce non-photochemical quenching (NPQ) as a protective mechanism to prevent over reduction of photosystem II and the generation of reactive oxygen species (ROS). The xanthophyll cycle, which contributes significantly to reversible NPQ to thermally dissipate excess absorbed light energy, involves de-epoxidation of violaxanthin and antheraxanthin to zeaxanthin in response to excess light energy. The activation of violaxanthin de-epoxidase (VDE), which catalyzes the de-epoxidation reaction, requires the generation of a light-induced, transthylakoid pH gradient. In this work, we overexpressed or repressed the expression of VDE in Arabidopsis (Arabidopsis thaliana) to examine whether VDE is rate-limiting for the induction of NPQ. Increasing VDE expression increased the de-epoxidation state of xanthophyll pigments, the rate of NPQ induction, and the level of NPQ achieved under subsaturating light. In saturating light, however, overexpression of VDE did not increase the xanthophyll pigment de-epoxidation state, the level of NPQ achieved following its initial induction, or substantially improve tolerance to high light. Only under chilling, which reduces VDE activity, did an increase in VDE expression provide slightly greater phototolerance. Repression of VDE expression impaired violaxanthin de-epoxidation, reduced the generation of NPQ, and lowered the level of NPQ achieved while increasing photosensitivity. These results demonstrate that the endogenous level of VDE is rate-limiting for NPQ in Arabidopsis under subsaturating but not saturating light and can become rate-limiting under chilling conditions. These results also show that increasing VDE expression confers greater phototolerance mainly under conditions which limit endogenous VDE activity. Copyright © 2012 Elsevier Masson SAS. All rights reserved.

Non-process instrumentation surveillance and test reduction

International Nuclear Information System (INIS)

Ferrell, R.; LeDonne, V.; Donat, T.; Thomson, I.; Sarlitto, M.

1993-12-01

Analysis of operating experience, instrument failure modes, and degraded instrument performance has led to a reduction in Technical Specification surveillance and test requirements for nuclear power plant process instrumentation. These changes have resulted in lower plant operations and maintenance (O ampersand M) labor costs. This report explores the possibility of realizing similar savings by reducing requirements for non-process instrumentation. The project team reviewed generic Technical Specifications for the four major US nuclear steam supply system (NSSS) vendors (Westinghouse, General Electric, Combustion Engineering, and Babcock ampersand Wilcox) to identify nonprocess instrumentation for which surveillance/test requirements could be reduced. The team surveyed 10 utilities to identify specific non-process instrumentation at their plants for which requirements could be reduced. The team evaluated utility analytic approaches used to justify changes in surveillance/test requirements for process equipment to determine their applicability to non-process instrumentation. The report presents a prioritized list of non-process instrumentation systems suitable for surveillance/test requirements reduction. The top three systems in the list are vibration monitors, leak detection monitors, and chemistry monitors. In general, most non-process instrumentation governed by Technical Specification requirements are candidates for requirements reduction. If statistical requirements are somewhat relaxed, the analytic approaches previously used to reduce requirements for process instrumentation can be applied to non-process instrumentation. The report identifies as viable the technical approaches developed and successfully used by Southern California Edison, Arizona Public Service, and Boston Edison

Creating Metamaterial Building Blocks with Directed Photochemical Metallization of Silver onto DNA Origami Templates.

Science.gov (United States)

Hossen, Md Mir; Bendickson, Lee; Palo, Pierre; Yao, Zhiqi; Nilsen-Hamilton, Marit; Hillier, Andrew C

2018-06-07

DNA origami can be used to create a variety of complex and geometrically unique nanostructures that can be further modified to produce building blocks for applications such as in optical metamaterials. We describe a method for creating metal-coated nanostructures using DNA origami templates and a photochemical metallization technique. Triangular DNA origami were fabricated and coated with a thin metal layer by photochemical silver reduction while either in solution or supported on a surface. The DNA origami template serves as a localized photosensitizer to facilitate reduction of silver ions directly from solution onto the DNA surface. The metallizing process is shown to result in a conformal metal coating, which grows in height to a self-limiting value with increasing photoreduction steps. Although this coating process results in a slight decrease in the triangle dimensions, the overall template shape is retained. Notably, this coating method exhibits characteristics of self-limiting and defect-filling growth, which results in a metal nanostructure that maps the shape of the original origami template with a continuous and uniform metal layer and stops growing once all available DNA sites are exhausted. © 2018 IOP Publishing Ltd.

A Universal Protocol for Photochemical Covalent Immobilization of Intact Carbohydrates for the Preparation of Carbohydrate Microarrays

Science.gov (United States)

Wang, Huibin; Zhang, Yiming; Yuan, Xun; Chen, Yi; Yan, Mingdi

2010-01-01

A universal photochemical method has been established for the immobilization of intact carbohydrates and their analogues, and for the fabrication of carbohydrate microarrays. The method features the use of perfluorophenyl azide (PFPA)-modified substrates and the photochemical reaction of surface azido groups with printed carbohydrates. Various aldoses, ketoses, non-reducing sugars such as alditols and their derivatives can be directly arrayed on the PFPA-modified chips. The lectin-recognition ability of arrayed mannose, glucose and their oligo- and polysaccharides were confirmed using surface plasmon resonance imaging and laser-induced fluorescence imaging. PMID:21138274

Monte Carlo variance reduction approaches for non-Boltzmann tallies

International Nuclear Information System (INIS)

Booth, T.E.

1992-12-01

Quantities that depend on the collective effects of groups of particles cannot be obtained from the standard Boltzmann transport equation. Monte Carlo estimates of these quantities are called non-Boltzmann tallies and have become increasingly important recently. Standard Monte Carlo variance reduction techniques were designed for tallies based on individual particles rather than groups of particles. Experience with non-Boltzmann tallies and analog Monte Carlo has demonstrated the severe limitations of analog Monte Carlo for many non-Boltzmann tallies. In fact, many calculations absolutely require variance reduction methods to achieve practical computation times. Three different approaches to variance reduction for non-Boltzmann tallies are described and shown to be unbiased. The advantages and disadvantages of each of the approaches are discussed

Use of Open Source Hardware and Software Platforms to Quantify Spectrally Dependent Differences in Photochemical Efficiency and Functional Absorption Cross Section within the Dinoflagellate Symbiodinium spp.

Directory of Open Access Journals (Sweden)

Kenneth D. Hoadley

2017-11-01

Full Text Available Active chlorophyll a fluorescence is an essential tool for understanding photosynthetic activity within cnidarian/dinoflagellate symbioses. Fluorescence measurement is typically achieved by utilizing a blue or red monochromatic excitation light source. However, algal photosynthetic pigments can differ in their absorption spectra, potentially leading to excitation wavelength dependent measurements of maximal and light acclimated PSII photosynthetic quantum yield (Fv/Fm or Fq′/Fm′ and functional absorption cross section (σPSII or σPSII′. Here we utilized an open source hardware development platform to construct a multispectral excitation fluorometer to assess spectrally dependent differences in photochemistry within four different Symbiodinium species (two of each ITS2-type A4 and B1. Multivariate analysis of light acclimated photochemical signatures showed separation between most alga types. These spectrally dependent differences in light acclimated PSII efficiency and PSII functional absorption cross section likely reflect changes in light harvesting compounds, their connectivity to the PSII reaction centers and the balance between photochemical and non-photochemical fluorescence quenching. Additionally, acclimation to low (20 μmol photons m−2 s−1 and high (200 μmol photons m−2 s−1 light conditions was examined in two of these symbionts types (ITS-2 type A4 and B1 As expected, chlorophyll a cell−1 decreased under high light acclimation in both symbionts. However, only A4 saw a subsequent reduction in absorbance whereas cellular volume decreased in the B1 (S. minutum symbiont. In response to high light acclimation, Fv/Fm was significantly lower at all excitation wavelengths for the B1 symbiont where as efficiencies remained the same for A4. However, high-light acclimated Fq′/Fm′ levels decreased in both symbionts, but only when measured using the 615 or 625 nm excitation wavelengths. Non-photochemical quenching within the

Photophysical and photochemical properties of novel metallophthalocyanines bearing 7-oxy-3-(m-methoxyphenyl)coumarin groups

International Nuclear Information System (INIS)

Taştemel, Ayşegül; Karaca, Birsen Yılmaz; Durmuş, Mahmut; Bulut, Mustafa

2015-01-01

Tetra-peripherally and non-peripherally 7-oxy-3-(m-methoxyphenyl)coumarin-substituted zinc(II) (4a and 5a), indium(III)acetate (4b and 5b) and magnesium(II) (4c and 5c) phthalocyanines were synthesized for the first time. These phthalocyanines were characterized by elemental analysis, FT-IR, 1 H NMR, UV–vis spectroscopy and mass spectra. The novel phthalocyanines showed excellent solubility in general organic solvents, such as dichloromethane, chloroform, tetrahydrofuran (THF), N,N-dimethylformamide (DMF) and dimethylsulfoxide (DMSO). The photophysical and photochemical properties of these phthalocyanines were investigated in DMF. The effects of the central metal ions (Zn 2+ , Mg 2+ , In +3 ) and the position (peripheral or non-peripheral) of the substituents on the photophysical and photochemical parameters were reported for comparison. The singlet oxygen quantum yield values of novel phthalocyanines ranged from 0.29 to 0.82 in DMF. In this study, the fluorescence quenching behavior of the studied zinc(II) and magnesium(II) phthalocyanine complexes was also described by the addition of 1,4-benzoquinone. - Highlights: • 7-oxy-3-(m-methoxyphenyl)coumarin-substituted Zn, In(III)OAc and Mg phthalocyanines. • Investigation of their photophysical and photochemical properties in DMF. • The effects of metal types and position of the substituents on these properties.

Emission sources of non-methane volatile organic compounds (NMVOCs) and their contribution to photochemical ozone (O3) formation at an urban atmosphere in western India.

Science.gov (United States)

Yadav, R.; Sahu, L. K.; Tripathi, N.; Pal, D.

2017-12-01

Atmospheric non-methane volatile organic compounds (NMVOCs) were measured at a sampling site in Udaipur city of western India during 2015 to recognize their pollution levels, variation characteristics, sources and photochemical reactivity. The samples were analyzed for NMVOCs using a Gas Chromatograph equipped with Flame Ionization Detector (GC/FID) and Thermal Desorption (TD) system. The main focus on understand the sources responsible for NMVOC emissions, and evaluating the role of the identified sources towards ozone formation. Hourly variations of various NMVOC species indicate that VOCs mixing ratios were influenced by photochemical removal with OH radicals for reactive species, secondary formation for oxygenated VOCs. In general, higher mixing ratios were observed during winter/pre-monsoon and lower levels during the monsoon season due to the seasonal change in meteorological, transport path of air parcel and boundary layer conditions. The high levels of propane (C3H8) and butane (C4H10) show the dominance of LPG over the study location. The correlation coefficients of typical NMVOC pairs (ethylene/propylene, propylene/isoprene, and ethane/propane) depicted that vehicular emission and natural gas leakages were important sources for atmospheric hydrocarbons in Udaipur. Based on the annual data, PMF analysis suggest the source factors namely biomass burning/ bio-fuel, automobile exhaust, Industrial/ natural gas/power plant emissions, petrol/Diesel, gasoline evaporation, and use of liquid petroleum gas (LPG) contribute to NMVOCs loading. The propylene-equivalent and ozone formation potential of NMVOCs have also been calculated in order to find out their OH reactivity and contribution to the photochemical ozone formation.

Sulfidic photochemical passivation of GaAs surfaces in alcoholic solutions

International Nuclear Information System (INIS)

Simonsmeier, T.; Ivankov, A.; Bauhofer, W.

2005-01-01

We report on a remarkable enhancement of the passivation effect of sulfidic solutions through illumination with above band gap light. Luminescence measurements on GaAs surfaces which have been illuminated during chemical passivation reveal in comparison to nonilluminated samples a further reduction of their surface density of states as well as a significantly increased stability of the passivation. Investigations with photoelectron spectroscopy show that illumination leads to a nearly complete removal of oxides on the surface. Measurements on Schottky diodes which have been manufactured with photochemically passivated GaAs indicate a noticeable decrease in band bending and a depinning of the Fermi level

Photochemical degradation of PCBs in snow.

Science.gov (United States)

Matykiewiczová, Nina; Klánová, Jana; Klán, Petr

2007-12-15

This work represents the first laboratory study known to the authors describing photochemical behavior of persistent organic pollutants in snow at environmentally relevant concentrations. The snow samples were prepared by shock freezing of the corresponding aqueous solutions in liquid nitrogen and were UV-irradiated in a photochemical cold chamber reactor at -25 degrees C, in which simultaneous monitoring of snow-air exchange processeswas also possible. The main photodegradation pathway of two model snow contaminants, PCB-7 and PCB-153 (c approximately 100 ng kg(-1)), was found to be reductive dehalogenation. Possible involvement of the water molecules of snow in this reaction has been excluded by performing the photolyses in D2O snow. Instead, trace amounts of volatile organic compounds have been proposed to be the major source of hydrogen atom in the reduction, and this hypothesis was confirmed by the experiments with deuterated organic cocontaminants, such as d6-ethanol or d8-tetrahydrofuran. It is argued that bimolecular photoreduction of PCBs was more efficient or feasible than any other phototransformations under the experimental conditions used, including the coupling reactions. The photodegradation of PCBs, however, competed with a desorption process responsible for the pollutant loss from the snow samples, especially in case of lower molecular-mass congeners. Organic compounds, apparently largely located or photoproduced on the surface of snow crystals, had a predisposition to be released to the air but, at the same time, to react with other species in the gas phase. It is concluded that physicochemical properties of the contaminants and trace co-contaminants, their location and local concentrations in the matrix, and the wavelength and intensity of radiation are the most important factors in the evaluation of organic contaminants' lifetime in snow. Based on the results, it has been estimated that the average lifetime of PCBs in surface snow, connected

EMERGING TECHNOLOGY PROJECT BULLETIN: LASER INDUCED PHOTOCHEMICAL OXIDATIVE DESTRUCTION

Science.gov (United States)

The process developed by Energy and Environmental Engineering, Incorporated, is designed to photochemically oxidize organic compounds in wastewater by applying ultraviolet radiation using an Excimer laser. The photochemical reactor can destroy low to moderate concentrations...

Photochemical reactions of neptunium in nitric acid solution containing photocatalyst

International Nuclear Information System (INIS)

Fukasawa, Tetsuo; Kawamura, Fumio

1991-01-01

Photochemical oxidation and reduction behaviors of neptunium were preliminarily investigated in 3 mol/l nitric acid solution. Nitric acid of 3 mol/l simulated the high level waste solution from a spent fuel reprocessing process. Concentrations of Np(V), Np(VI) and nitrous acid were determined with a photospectrometer, and solution potential with an electrode. Without additives, Np(VI) was reduced to Np(V) by nitrous acid which was photolytically generated from nitric acid. With a scavenger for nitrous acid, Np(V) was oxidized to extractable Np(VI) by a photolytically generated oxidizing reagent which were predicted by the solution potential measurement. The reduction rate was higher than the oxidation rate because of the larger quantity and higher reactivity of nitrous acid than an oxidizing reagent. Photocatalyst was proved to be effective for the oxidation of Np(V) to Np(VI). (author)

Photochemical generation of highly destabilized vinyl cations: the effects of alpha- and beta-trifluoromethyl versus alpha- and beta-methyl substituents

NARCIS (Netherlands)

Alem, van K.; Belder, G.; Lodder, G.; Zuilhof, H.

2005-01-01

The photochemical reactions in methanol of the vinylic halides 1-4, halostyrenes with a methyl or a trifluoromethyl substituent at the - or -position, have been investigated quantitatively. Next to E/Z isomerization, the reactions are formation of vinyl radicals, leading to reductive dehalogenation

Photochemical Assessment Monitoring Stations (PAMS)

Data.gov (United States)

U.S. Environmental Protection Agency — Photochemical Assessment Monitoring Stations (PAMS). This file provides information on the numbers and distribution (latitude/longitude) of air monitoring sites...

Influence of a photochemical reaction on the controlled potential coulometric determination of plutonium in a mixture with uranium

International Nuclear Information System (INIS)

Le Duigou, Y.; Leidert, W.

1976-01-01

Data are provided in support of a photochemical reaction which takes place simultaneously with the electrochemical reduction of quadrivalent plutonium during the controlled potential coulometric determination of plutonium in a mixture with uranium. The interfering effect of this reaction is overcome by placing the cell in a dark environment. (orig.) [de

Photochemically induced oscillations of aromatic pentazadienes

Energy Technology Data Exchange (ETDEWEB)

Kunz, T; Hahn, C; Wokaun, A [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

1997-06-01

Aromatic pentazadienes are used to enhance the laser induced ablation of standard polymers with low absorption in the UV. Therefore the photochemistry of substituted 1,5-diaryl-3-alkyl-1,4-pentazadiene monomers was studied with a pulsed excimer laser as irradiation source. The net photochemical reaction proceeds in an overall one-step pathway A{yields}B. Quantum yields for the laser decomposition were determined to be up to 10%. An oscillating behaviour of the absorption was found during the dark period following the irradiation. The temperature dependence of this dark reaction has been studied. An attempt to model this behaviour in terms of a non-linear coupling between heat released, heat transfer, and reaction kinetics will be described. (author) 4 figs., 4 refs.

Photochemical processes and ozone production in Finnish conditions

Energy Technology Data Exchange (ETDEWEB)

Laurila, T; Hakola, H [Finnish Meteorological Inst., Helsinki (Finland). Air Quality Dept.

1997-12-31

Photochemical ozone production is observed in March-September. Highest ozone concentrations and production efficiencies are observed in spring in the northern parts and in summer in the southern parts of the country. VOC concentrations are relatively low compared to continental areas in general. During the growing season a substantial part of the total reactive mass of VOCs is of biogenic origin. Large forest areas absorb ozone substantially, decreasing the ambient ozone concentrations in central and northern parts of Finland where long-range transport of ozone is relatively important compared to local production. The aim of the work conducted at Finnish Meteorological Institute has been to characterise concentrations of photochemically active species in the boundary layer and their photochemical formation and deposition including the effects on vegetation. Also interactions between the boundary layer and free troposphere of ozone have been studied. In the future, fluxes of both biogenic species and air pollutants will be measured and the models will be further developed so that the photochemical and micrometeorological processes could be better understood

Photochemical processes and ozone production in Finnish conditions

Energy Technology Data Exchange (ETDEWEB)

Laurila, T.; Hakola, H. [Finnish Meteorological Inst., Helsinki (Finland). Air Quality Dept.

1996-12-31

Photochemical ozone production is observed in March-September. Highest ozone concentrations and production efficiencies are observed in spring in the northern parts and in summer in the southern parts of the country. VOC concentrations are relatively low compared to continental areas in general. During the growing season a substantial part of the total reactive mass of VOCs is of biogenic origin. Large forest areas absorb ozone substantially, decreasing the ambient ozone concentrations in central and northern parts of Finland where long-range transport of ozone is relatively important compared to local production. The aim of the work conducted at Finnish Meteorological Institute has been to characterise concentrations of photochemically active species in the boundary layer and their photochemical formation and deposition including the effects on vegetation. Also interactions between the boundary layer and free troposphere of ozone have been studied. In the future, fluxes of both biogenic species and air pollutants will be measured and the models will be further developed so that the photochemical and micrometeorological processes could be better understood

Intraspecific variation in Pinus pinaster PSII photochemical efficiency in response to winter stress and freezing temperatures.

Directory of Open Access Journals (Sweden)

Leyre Corcuera

Full Text Available As part of a program to select maritime pine (Pinus pinaster Ait. genotypes for resistance to low winter temperatures, we examined variation in photosystem II activity by chlorophyll fluorescence. Populations and families within populations from contrasting climates were tested during two consecutive winters through two progeny trials, one located at a continental and xeric site and one at a mesic site with Atlantic influence. We also obtained the LT₅₀, or the temperature that causes 50% damage, by controlled freezing and the subsequent analysis of chlorophyll fluorescence in needles and stems that were collected from populations at the continental trial site.P. pinaster showed sensitivity to winter stress at the continental site, during the colder winter. The combination of low temperatures, high solar irradiation and low precipitation caused sustained decreases in maximal photochemical efficiency (F(v/F(m, quantum yield of non-cyclic electron transport (Φ(PSII and photochemical quenching (qP. The variation in photochemical parameters was larger among families than among populations, and population differences appeared only under the harshest conditions at the continental site. As expected, the environmental effects (winter and site on the photochemical parameters were much larger than the genotypic effects (population or family. LT₅₀ was closely related to the minimum winter temperatures of the population's range. The dark-adapted F(v/F(m ratio discriminated clearly between interior and coastal populations.In conclusion, variations in F(v/F(m, Φ(PSII, qP and non-photochemical quenching (NPQ in response to winter stress were primarily due to the differences between the winter conditions and the sites and secondarily due to the differences among families and their interactions with the environment. Populations from continental climates showed higher frost tolerance (LT₅₀ than coastal populations that typically experience mild

Intraspecific variation in Pinus pinaster PSII photochemical efficiency in response to winter stress and freezing temperatures.

Science.gov (United States)

Corcuera, Leyre; Gil-Pelegrin, Eustaquio; Notivol, Eduardo

2011-01-01

As part of a program to select maritime pine (Pinus pinaster Ait.) genotypes for resistance to low winter temperatures, we examined variation in photosystem II activity by chlorophyll fluorescence. Populations and families within populations from contrasting climates were tested during two consecutive winters through two progeny trials, one located at a continental and xeric site and one at a mesic site with Atlantic influence. We also obtained the LT₅₀, or the temperature that causes 50% damage, by controlled freezing and the subsequent analysis of chlorophyll fluorescence in needles and stems that were collected from populations at the continental trial site.P. pinaster showed sensitivity to winter stress at the continental site, during the colder winter. The combination of low temperatures, high solar irradiation and low precipitation caused sustained decreases in maximal photochemical efficiency (F(v)/F(m)), quantum yield of non-cyclic electron transport (Φ(PSII)) and photochemical quenching (qP). The variation in photochemical parameters was larger among families than among populations, and population differences appeared only under the harshest conditions at the continental site. As expected, the environmental effects (winter and site) on the photochemical parameters were much larger than the genotypic effects (population or family). LT₅₀ was closely related to the minimum winter temperatures of the population's range. The dark-adapted F(v)/F(m) ratio discriminated clearly between interior and coastal populations.In conclusion, variations in F(v)/F(m), Φ(PSII), qP and non-photochemical quenching (NPQ) in response to winter stress were primarily due to the differences between the winter conditions and the sites and secondarily due to the differences among families and their interactions with the environment. Populations from continental climates showed higher frost tolerance (LT₅₀) than coastal populations that typically experience mild winters

Photophysical and photochemical properties of novel metallophthalocyanines bearing 7-oxy-3-(m-methoxyphenyl)coumarin groups

Energy Technology Data Exchange (ETDEWEB)

Taştemel, Ayşegül; Karaca, Birsen Yılmaz [Marmara University, Faculty of Art and Science, Department of Chemistry, 34722 Kadıkoy-Istanbul (Turkey); Durmuş, Mahmut [Gebze Technical University, Department of Chemistry, P.O. Box 141, Gebze 41400, Kocaeli (Turkey); Bulut, Mustafa, E-mail: mbulut@marmara.edu.tr [Marmara University, Faculty of Art and Science, Department of Chemistry, 34722 Kadıkoy-Istanbul (Turkey)

2015-12-15

Tetra-peripherally and non-peripherally 7-oxy-3-(m-methoxyphenyl)coumarin-substituted zinc(II) (4a and 5a), indium(III)acetate (4b and 5b) and magnesium(II) (4c and 5c) phthalocyanines were synthesized for the first time. These phthalocyanines were characterized by elemental analysis, FT-IR, {sup 1}H NMR, UV–vis spectroscopy and mass spectra. The novel phthalocyanines showed excellent solubility in general organic solvents, such as dichloromethane, chloroform, tetrahydrofuran (THF), N,N-dimethylformamide (DMF) and dimethylsulfoxide (DMSO). The photophysical and photochemical properties of these phthalocyanines were investigated in DMF. The effects of the central metal ions (Zn{sup 2+}, Mg{sup 2+}, In{sup +3}) and the position (peripheral or non-peripheral) of the substituents on the photophysical and photochemical parameters were reported for comparison. The singlet oxygen quantum yield values of novel phthalocyanines ranged from 0.29 to 0.82 in DMF. In this study, the fluorescence quenching behavior of the studied zinc(II) and magnesium(II) phthalocyanine complexes was also described by the addition of 1,4-benzoquinone. - Highlights: • 7-oxy-3-(m-methoxyphenyl)coumarin-substituted Zn, In(III)OAc and Mg phthalocyanines. • Investigation of their photophysical and photochemical properties in DMF. • The effects of metal types and position of the substituents on these properties.

Photochemical oxidation: A solution for the mixed waste dilemma

Energy Technology Data Exchange (ETDEWEB)

Prellberg, J.W.; Thornton, L.M.; Cheuvront, D.A. [Vulcan Peroxidation Systems, Inc., Tucson, AZ (United States)] [and others

1995-12-31

Numerous technologies are available to remove organic contamination from water or wastewater. A variety of techniques also exist that are used to neutralize radioactive waste. However, few technologies can satisfactorily address the treatment of mixed organic/radioactive waste without creating unacceptable secondary waste products or resulting in extremely high treatment costs. An innovative solution to the mixed waste problem is on-site photochemical oxidation. Liquid-phase photochemical oxidation has a long- standing history of successful application to the destruction of organic compounds. By using photochemical oxidation, the organic contaminants are destroyed on-site leaving the water, with radionuclides, that can be reused or disposed of as appropriate. This technology offers advantages that include zero air emissions, no solid or liquid waste formation, and relatively low treatment cost. Discussion of the photochemical process will be described, and several case histories from recent design testing, including cost analyses for the resulting full-scale installations, will be presented as examples.

Method of making gold thiolate and photochemically functionalized microcantilevers

Science.gov (United States)

Boiadjiev, Vassil I [Knoxville, TN; Brown, Gilbert M [Knoxville, TN; Pinnaduwage, Lal A [Knoxville, TN; Thundat, Thomas G [Knoxville, TN; Bonnesen, Peter V [Knoxville, TN; Goretzki, Gudrun [Nottingham, GB

2009-08-25

Highly sensitive sensor platforms for the detection of specific reagents, such as chromate, gasoline and biological species, using microcantilevers and other microelectromechanical systems (MEMS) whose surfaces have been modified with photochemically attached organic monolayers, such as self-assembled monolayers (SAM), or gold-thiol surface linkage are taught. The microcantilever sensors use photochemical hydrosilylation to modify silicon surfaces and gold-thiol chemistry to modify metallic surfaces thereby enabling individual microcantilevers in multicantilever array chips to be modified separately. Terminal vinyl substituted hydrocarbons with a variety of molecular recognition sites can be attached to the surface of silicon via the photochemical hydrosilylation process. By focusing the activating UV light sequentially on selected silicon or silicon nitride hydrogen terminated surfaces and soaking or spotting selected metallic surfaces with organic thiols, sulfides, or disulfides, the microcantilevers are functionalized. The device and photochemical method are intended to be integrated into systems for detecting specific agents including chromate groundwater contamination, gasoline, and biological species.

Photoperiod and temperature constraints on the relationship between the photochemical reflectance index and the light use efficiency of photosynthesis in Pinus strobus

OpenAIRE

Fr?chette, Emmanuelle; Chang, Christine Yao-Yun; Ensminger, Ingo

2016-01-01

The photochemical reflectance index (PRI) is a proxy for the activity of the photoprotective xanthophyll cycle and photosynthetic light use efficiency (LUE) in plants. Evergreen conifers downregulate photosynthesis in autumn in response to low temperature and shorter photoperiod, and the dynamic xanthophyll cycle-mediated non-photochemical quenching (NPQ) is replaced by sustained NPQ. We hypothesized that this shift in xanthophyll cycle-dependent energy partitioning during the autumn is the c...

Reversible-Deactivation Radical Polymerization of Methyl Methacrylate Induced by Photochemical Reduction of Various Copper Catalysts

Directory of Open Access Journals (Sweden)

Jaroslav Mosnáček

2014-11-01

Full Text Available Photochemically mediated reversible-deactivation radical polymerization of methyl methacrylate was successfully performed using 50–400 ppm of various copper compounds such as CuSO4·5H2O, copper acetate, copper triflate and copper acetylacetonate as catalysts. The copper catalysts were reduced in situ by irradiation at wavelengths of 366–546 nm, without using any additional reducing agent. Bromopropionitrile was used as an initiator. The effects of various solvents and the concentration and structure of ligands were investigated. Well-defined polymers were obtained when at least 100 or 200 ppm of any catalyst complexed with excess tris(2-pyridylmethylamine as a ligand was used in dimethyl sulfoxide as a solvent.

Participation of the Halogens in Photochemical Reactions in Natural and Treated Waters

Directory of Open Access Journals (Sweden)

Yi Yang

2017-10-01

Full Text Available Halide ions are ubiquitous in natural waters and wastewaters. Halogens play an important and complex role in environmental photochemical processes and in reactions taking place during photochemical water treatment. While inert to solar wavelengths, halides can be converted into radical and non-radical reactive halogen species (RHS by sensitized photolysis and by reactions with secondary reactive oxygen species (ROS produced through sunlight-initiated reactions in water and atmospheric aerosols, such as hydroxyl radical, ozone, and nitrate radical. In photochemical advanced oxidation processes for water treatment, RHS can be generated by UV photolysis and by reactions of halides with hydroxyl radicals, sulfate radicals, ozone, and other ROS. RHS are reactive toward organic compounds, and some reactions lead to incorporation of halogen into byproducts. Recent studies indicate that halides, or the RHS derived from them, affect the concentrations of photogenerated reactive oxygen species (ROS and other reactive species; influence the photobleaching of dissolved natural organic matter (DOM; alter the rates and products of pollutant transformations; lead to covalent incorporation of halogen into small natural molecules, DOM, and pollutants; and give rise to certain halogen oxides of concern as water contaminants. The complex and colorful chemistry of halogen in waters will be summarized in detail and the implications of this chemistry for global biogeochemical cycling of halogen, contaminant fate in natural waters, and water purification technologies will be discussed.

Fibrillin 5 Is Essential for Plastoquinone-9 Biosynthesis by Binding to Solanesyl Diphosphate Synthases in Arabidopsis

Science.gov (United States)

Kim, Eun-Ha; Lee, Yongjik

2015-01-01

Fibrillins are lipid-associated proteins in plastids and are ubiquitous in plants. They accumulate in chromoplasts and sequester carotenoids during the development of flowers and fruits. However, little is known about the functions of fibrillins in leaf tissues. Here, we identified fibrillin 5 (FBN5), which is essential for plastoquinone-9 (PQ-9) biosynthesis in Arabidopsis thaliana. Homozygous fbn5-1 mutations were seedling-lethal, and XVE:FBN5-B transgenic plants expressing low levels of FBN5-B had a slower growth rate and were smaller than wild-type plants. In chloroplasts, FBN5-B specifically interacted with solanesyl diphosphate synthases (SPSs) 1 and 2, which biosynthesize the solanesyl moiety of PQ-9. Plants containing defective FBN5-B accumulated less PQ-9 and its cyclized product, plastochromanol-8, but the levels of tocopherols were not affected. The reduced PQ-9 content of XVE:FBN5-B transgenic plants was consistent with their lower photosynthetic performance and higher levels of hydrogen peroxide under cold stress. These results indicate that FBN5-B is required for PQ-9 biosynthesis through its interaction with SPS. Our study adds FBN5 as a structural component involved in the biosynthesis of PQ-9. FBN5 binding to the hydrophobic solanesyl moiety, which is generated by SPS1 and SPS2, in FBN5-B/SPS homodimeric complexes stimulates the enzyme activity of SPS1 and SPS2. PMID:26432861

A micellar model system for the role of zeaxanthin in the non-photochemical quenching process of photosynthesis--chlorophyll fluorescence quenching by the xanthophylls.

Science.gov (United States)

Avital, Shlomo; Brumfeld, Vlad; Malkin, Shmuel

2006-07-01

To get an insight to the mechanism of the zeaxanthin-dependent non-photochemical quenching in photosystem II of photosynthesis, we probed the interaction of some xanthophylls with excited chlorophyll-a by trapping both pigments in micelles of triton X-100. Optimal distribution of pigments among micelles was obtained by proper control of the micelle concentration, using formamide in the reaction mixture, which varies the micellar aggregation number over three orders of magnitude. The optimal reaction mixture was obtained around 40% (v/v) formamide in 0.2-0.4% (v/v) triton X-100 in water. Zeaxanthin in the micellar solution exhibited initially absorption and circular dichroism spectral features corresponding to a J-type aggregate. The spectrum was transformed over time (half-time values vary-an average characteristic figure is roughly 20 min) to give features representing an H-type aggregate. The isosbestic point in the series of spectral curves favors the supposition of a rather simple reaction between two pure J and H-types dimeric species. Violaxanthin exhibited immediately stable spectral features corresponding to a mixture of J-type and more predominately H-type dimers. Lutein, neoxanthin and beta-carotene did not show any aggregated spectral forms in micelles. The spectral features in micelles were compared to spectra in aqueous acetone, where the assignment to various aggregated types was established previously. The specific tendency of zeaxanthin to form the J-type dimer (or aggregate) could be important for its function in photosynthesis. The abilities of five carotenoids (zeaxanthin, violaxanthin, lutein, neoxanthin and beta-carotene) to quench chlorophyll-a fluorescence were compared. Zeaxanthin, in its two micellar dimeric forms, and beta-carotene were comparable good quenchers of chlorophyll-a fluorescence. Violaxanthin was a much weaker quencher, if at all. Lutein and neoxanthin rather enhanced the fluorescence. The implications to non-photochemical

40 CFR 52.2426 - Photochemical Assessment Monitoring Stations (PAMS) Program.

Science.gov (United States)

2010-07-01

... Stations (PAMS) Program. 52.2426 Section 52.2426 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... § 52.2426 Photochemical Assessment Monitoring Stations (PAMS) Program. On November 23, 1994 Virginia's... Photochemical Assessment Monitoring Stations (PAMS) Program as a state implementation plan (SIP) revision, as...

Iron oxides photochemical dissolution

International Nuclear Information System (INIS)

Blesa, M.A.; Litter, M.I.

1987-01-01

This work was intended to study the light irradiation influence of diverse wave-lengths on iron oxides dissolution in aqueous solutions. The objectives of this work were: the exploration of photochemical processes with the aim of its eventual application in: a) decontamination and chemical cleaning under special conditions; b) materials for solar energy conversion. (Author)

Inheritance of photochemical air pollution tolerance in petunias

Energy Technology Data Exchange (ETDEWEB)

Hanson, G.P.; Addis, D.H.; Thorne, L.

1976-12-01

Seven commercial inbred lines of pink flowered multiflora petunia (Petunia hybrida Vilm.) which differed widely in degrees of tolerance to photochemical oxidants were crossed in all possible combinations to yield a complete diallel cross. Sibling representatives of all 49 possible hybrids were then separately subjected to ozone (O/sub 3/), peroxyacetyl nitrate (PAN), and ambient oxidants at Arcadia, California. The seedlings were scored for tolerance to each pollutant and the inheritance of tolerance to each pollutant was studied. At the ambient levels of photochemical oxidants encountered, PAN more severely injured the petunias than did the O/sub 3/ component. Hybrids tolerant to one oxidant were not necessarily tolerant to the other. The genes which contributed photochemical oxidant tolerance in petunia acted primarily in an additive manner with some indication of partial dominance for tolerance. Gene interaction was evident in the expression of petunia sensitivity to PAN.

Simulation of photoreactive transients and of photochemical transformation of organic pollutants in sunlit boreal lakes across 14 degrees of latitude: A photochemical mapping of Sweden.

Science.gov (United States)

Koehler, Birgit; Barsotti, Francesco; Minella, Marco; Landelius, Tomas; Minero, Claudio; Tranvik, Lars J; Vione, Davide

2018-02-01

Lake water constituents, such as chromophoric dissolved organic matter (CDOM) and nitrate, absorb sunlight which induces an array of photochemical reactions. Although these reactions are a substantial driver of pollutant degradation in lakes they are insufficiently understood, in particular on large scales. Here, we provide for the first time comprehensive photochemical maps covering a large geographic region. Using photochemical kinetics modeling for 1048 lakes across Sweden we simulated the steady-state concentrations of four photoreactive transient species, which are continuously produced and consumed in sunlit lake waters. We then simulated the transient-induced photochemical transformation of organic pollutants, to gain insight into the relevance of the different photoreaction pathways. We found that boreal lakes were often unfavorable environments for photoreactions mediated by hydroxyl radicals (OH) and carbonate radical anions (CO 3 - ), while photoreactions mediated by CDOM triplet states ( 3 CDOM*) and, to a lesser extent, singlet oxygen ( 1 O 2 ) were the most prevalent. These conditions promote the photodegradation of phenols, which are used as plastic, medical drug and herbicide precursors. When CDOM concentrations increase, as is currently commonly the case in boreal areas such as Sweden, 3 CDOM* will also increase, promoting its importance in photochemical pathways even more. Copyright © 2017 Elsevier Ltd. All rights reserved.

Trends in photochemical smog in the Cape Peninsula and the ...

African Journals Online (AJOL)

There has been growing public concern over reports of increasing air pollution in the Cape Peninsula. Attention has been focused on the 'brown haze' and on photochemical smog. Because of deficiencies in the monitoring equipment, information on trends in photochemical smog levels over the past decade is limited.

Photochemically consumed hydrocarbons and their relationship with ozone formation in two megacities of China

Science.gov (United States)

Chang, C.; Wang, J.; Liu, S.; Shao, M.; Zhang, Y.; Zhu, T.; Shiu, C.; Lai, C.

2010-12-01

Two on-site continuous measurements of ozone and its precursors in two megacities of China were carried out in an urban site of Beijing and a suburban site near Guangzhou in the Pearl River Delta (PRD) to estimate precursor consumption and to assess its relationship with oxidant (O3+NO2) formation level. An observation-based method (OBM) with the precursor consumption concept was adopted to assess the relationship between oxidant production and amounts of photochemically consumed non-methane hydrocarbons (NMHCs). In this approach, the ratio of ethylbenzene to m,p-xylenes was used to estimate the degree of photochemical processing, as well as the amounts of photochemically consumed NMHCs by reacting with OH. By trying to correlate the observed oxidant with the observed NMHC concentration, the two areas both revealed nearly no to low correlation between them. However, it existed fair to good correlations (R2=0.68 for Beijing, 0.53 for PRD) between the observed oxidant level and the degree of photochemical processing (ethylbenzene/m,p-xylenes). Furthermore, after taking the approach of consumption to estimate the consumed amounts of NMHCs, an interesting finding reveals that the definite correlation existed between the observed oxidant level and the total consumed NMHCs. The good correlations (R2=0.83 for Beijing, 0.81 for PRD) implies that the ambient oxidant level correlated to the amount of consumed NMHCs. The results of the two megacities in China by using the OBM with the precursor consumption concept can provide another pathway to explore the relationship between photochemically produced oxidant and consumed precursors, and will be helpful to validate model results and to reduce uncertainty of model predictions. However, the method has some room for uncertainty, as injection of fresh precursor emissions and additional boundary ozone involved, etc. could affect the estimation of consumed NMHCs and observed oxidant levels. Assistance of approaches in assessing the

Nerium oleander indirect leaf photosynthesis and light harvesting reductions after clipping injury or Spodoptera eridania herbivory: high sensitivity to injury.

Science.gov (United States)

Delaney, Kevin J

2012-04-01

Variable indirect photosynthetic rate (P(n)) responses occur on injured leaves after insect herbivory. It is important to understand factors that influence indirect P(n) reductions after injury. The current study examines the relationship between gas exchange and chlorophyll a fluorescence parameters with injury intensity (% single leaf tissue removal) from clipping or Spodoptera eridania Stoll (Noctuidae) herbivory on Nerium oleander L. (Apocynaceae). Two experiments showed intercellular [CO(2)] increases but P(n) and stomatal conductance reductions with increasing injury intensity, suggesting non-stomatal P(n) limitation. Also, P(n) recovery was incomplete at 3d post-injury. This is the first report of a negative exponential P(n) impairment function with leaf injury intensity to suggest high N. oleander leaf sensitivity to indirect P(n) impairment. Negative linear functions occurred between most other gas exchange and chlorophyll a fluorescence parameters with injury intensity. The degree of light harvesting impairment increased with injury intensity via lower (1) photochemical efficiency indicated lower energy transfer efficiency from reaction centers to PSII, (2) photochemical quenching indicated reaction center closure, and (3) electron transport rates indicated less energy traveling through PSII. Future studies can examine additional mechanisms (mesophyll conductance, carbon fixation, and cardenolide induction) to cause N. oleander indirect leaf P(n) reductions after injury. Published by Elsevier Ireland Ltd.

Assessment of diphenylcyclopropenone for photochemically induced mutagenicity in the Ames assay

Energy Technology Data Exchange (ETDEWEB)

Wilkerson, M.G.; Connor, T.H.; Henkin, J.; Wilkin, J.K.; Matney, T.S.

1987-10-01

The photochemical conversion of diphenylcyclopropenone to diphenylacetylene has recently been reported. Diphenylcyclopropenone is used in the treatment of alopecia areata and is nonmutagenic in a limited Ames assay. We examined diphenylcyclopropenone and diphenylacetylene, as well as synthetic precursors of diphenylcyclopropenone--dibenzylketone and alpha,alpha'-dibromodibenzylketone--for mutagenicity against TA100, TA98, TA102, UTH8413, and UTH8414. All compounds were nonmutagenic except alpha,alpha'-dibromodibenzylketone, which was a potent mutagen in TA100 with and without S-9 activation. The effect of photochemical activation of diphenylcyclopropenone in the presence of bacteria demonstrated mutagenicity in UTH8413 (two times background) at 10 micrograms/plate with S-9 microsomal activation. 8-Methoxypsoralen produces a mutagenic response in TA102 at 0.1 microgram/plate with 60 seconds of exposure to 350 nm light. In vitro photochemically activated Ames assay with S-9 microsomal fraction may enhance the trapping of short-lived photochemically produced high-energy mutagenic intermediates. This technique offers exciting opportunities to trap high-energy intermediates that may play an important role in mutagenesis. This method can be applied to a variety of topically applied dermatologic agents, potentially subjected to photochemical changes in normal use.

Ultra-trace determination of iodine in sediments and biological material using UV photochemical generation-inductively coupled plasma mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Grinberg, Patricia [Institute for National Measurements Standards, National Research Council Canada, Ottawa, Ontario, K1A 0R6 (Canada)], E-mail: patricia.grinberg@nrc.ca; Sturgeon, Ralph E. [Institute for National Measurements Standards, National Research Council Canada, Ottawa, Ontario, K1A 0R6 (Canada)

2009-03-15

Several sample preparation techniques have been evaluated for the determination of iodine using UV-photochemical generation-quadrupole inductively coupled plasma mass spectrometry. Thermal decomposition of samples at 1000 {sup o}C followed by capture of the liberated iodine in dilute acetic acid permitted subsequent UV-photochemical generation of a volatile iodine species that serves to enhance sensitivity 25-fold over conventional solution nebulization, delivering reagent blank detection limits of 8.75 pg g{sup -1127}I and 0.075 pg g{sup -1129}I for solid samples (400 mg test mass). The methodology was validated through determination of total iodine in several Standard Reference Materials, including NIST 1572 Citrus leaves, NIST 1549 Non-fat milk powder, NIST 1566a Oyster tissue and NIST 2709 San Joaquin Soil. Liberation of iodine from samples and its collection as well as photochemical generation were quantitative, permitting calibration to be achieved using standards prepared in dilute acetic acid.

Redox reaction in photochemical and ionizing irradiation systems

International Nuclear Information System (INIS)

Slama-Schwok, A.

1985-09-01

This work presents a basic study of electron transfer reactions which could be involved in appropriate systems for photochemical conversion and storage of solar energy. The aim was to extend the knowledge to new photosensitizers and quenchers and to compare them with the most popular photosensitizers-quenchers system, i.e. a rubidium complex. The photosensitizer studied here is an irridium complex. We studied in this work the air oxidation of bromide to Br 3 - and H 2 O 2 using the irridium complex as the sensitizer. The reducing properties of the reduced irridium complex photosensitizer were studied, using the pulse radiolysis techniques. In conclusion, the oxidation reduction properties of the irridium and its lowest excited state correspond to most of the photosensitizer for electron transfer reactions. The energy temporary present in the charge separation products can be stored using appropriate environment such as polyelectrolytes

PHOTOCHEMICAL HEATING OF DENSE MOLECULAR GAS

Energy Technology Data Exchange (ETDEWEB)

Glassgold, A. E. [Astronomy Department, University of California, Berkeley, CA 94720 (United States); Najita, J. R. [National Optical Astronomy Observatory, 950 North Cherry Avenue, Tucson, AZ 85719 (United States)

2015-09-10

Photochemical heating is analyzed with an emphasis on the heating generated by chemical reactions initiated by the products of photodissociation and photoionization. The immediate products are slowed down by collisions with the ambient gas and then heat the gas. In addition to this direct process, heating is also produced by the subsequent chemical reactions initiated by these products. Some of this chemical heating comes from the kinetic energy of the reaction products and the rest from collisional de-excitation of the product atoms and molecules. In considering dense gas dominated by molecular hydrogen, we find that the chemical heating is sometimes as large, if not much larger than, the direct heating. In very dense gas, the total photochemical heating approaches 10 eV per photodissociation (or photoionization), competitive with other ways of heating molecular gas.

Photochemical heavy-atom effects

International Nuclear Information System (INIS)

Koziar, J.C.; Cowan, D.O.

1978-01-01

The effects of halogenated solvents such as n-butyl chloride, n-propyl bromide, and ethyl iodide, on the photochemistry of several aromatic compounds are reviewed. Dimerization of acenaphthylene is discussed in terms of spin -orbit coupling induced by the solvents. Appropriate wave functions are given for both the solvents and the compound. Cycloaddition reactions, electrocyclic rearrangements, and photochemical cis-trans isomerization are also considered

A conjugate of decyltriphenylphosphonium with plastoquinone can carry cyclic adenosine monophosphate, but not cyclic guanosine monophosphate, across artificial and natural membranes.

Science.gov (United States)

Firsov, Alexander M; Rybalkina, Irina G; Kotova, Elena A; Rokitskaya, Tatyana I; Tashlitsky, Vadim N; Korshunova, Galina A; Rybalkin, Sergei D; Antonenko, Yuri N

2018-02-01

The present study demonstrated for the first time the interaction between adenosine 3',5'-cyclic monophosphate (cAMP), one of the most important signaling compounds in living organisms, and the mitochondria-targeted antioxidant plastoquinonyl-decyltriphenylphosphonium (SkQ1). The data obtained on model liquid membranes and human platelets revealed the ability of SkQ1 to selectively transport cAMP, but not guanosine 3',5'-cyclic monophosphate (cGMP), across both artificial and natural membranes. In particular, SkQ1 elicited translocation of cAMP from the source to the receiving phase of a Pressman-type cell, while showing low activity with cGMP. Importantly, only conjugate with plastoquinone, but not dodecyl-triphenylphosphonium, was effective in carrying cAMP. In human platelets, SkQ1 also appeared to serve as a carrier of cAMP, but not cGMP, from outside to inside the cell, as measured by phosphorylation of the vasodilator stimulated phosphoprotein. The SkQ1-induced transfer of cAMP across the plasma membrane found here can be tentatively suggested to interfere with cAMP signaling pathways in living cells. Copyright © 2017 Elsevier B.V. All rights reserved.

Photochemical transformations accelerated in continuous-flow reactors: basic concepts and applications.

Science.gov (United States)

Su, Yuanhai; Straathof, Natan J W; Hessel, Volker; Noël, Timothy

2014-08-18

Continuous-flow photochemistry is used increasingly by researchers in academia and industry to facilitate photochemical processes and their subsequent scale-up. However, without detailed knowledge concerning the engineering aspects of photochemistry, it can be quite challenging to develop a suitable photochemical microreactor for a given reaction. In this review, we provide an up-to-date overview of both technological and chemical aspects associated with photochemical processes in microreactors. Important design considerations, such as light sources, material selection, and solvent constraints are discussed. In addition, a detailed description of photon and mass-transfer phenomena in microreactors is made and fundamental principles are deduced for making a judicious choice for a suitable photomicroreactor. The advantages of microreactor technology for photochemistry are described for UV and visible-light driven photochemical processes and are compared with their batch counterparts. In addition, different scale-up strategies and limitations of continuous-flow microreactors are discussed. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Photochemical fate of beta-blockers in NOM enriched waters

International Nuclear Information System (INIS)

Wang, Ling; Xu, Haomin; Cooper, William J.; Song, Weihua

2012-01-01

Beta-blockers, prescribed for the treatment of high blood pressure and for long-term use after a heart attack, have been detected in surface and ground waters. This study examines the photochemical fate of three beta-blockers, atenolol, metoprolol, and nadolol. Hydrolysis accounted for minor losses of these beta-blockers in the pH range 4–10. The rate of direct photolysis at pH 7 in a solar simulator varied from 6.1 to 8.9 h −1 at pH 7. However, the addition of a natural organic matter (NOM) isolate enhanced the photochemical loss of all three compounds. Indirect photochemical fate, generally described by reactions with hydroxyl radical (·OH) and singlet oxygen ( 1 ΔO 2 ), and, the direct reaction with the triplet excited state, 3 NOM ⁎ , also varied but collectively appeared to be the major loss factor. Bimolecular reaction rate constants of the three beta-blockers with 1 ΔO 2 and ·OH were measured and accounted for 0.02–0.04% and 7.2–38.9% of their loss, respectively. These data suggest that the 3 NOM ⁎ contributed 50.6–85.4%. Experiments with various 3 NOM ⁎ quenchers supported the hypothesis that it was singly the most important reaction. Atenolol was chosen for more detailed investigation, with the photoproducts identified by LC–MS analysis. The results suggested that electron-transfer could be an important mechanism in photochemical fate of beta-blockers in the presence of NOM. - Highlights: ► Photochemical degradation of beta-blockers in the simulated natural waters. ► Reactive Oxygen Species play a minor role in the indirect photodegradation. ► The loss of beta-blockers results from direct reaction with 3 DOM ⁎ .

Surface retention and photochemical reactivity of the diphenylether herbicide oxyfluorfen.

Science.gov (United States)

Scrano, Laura; Bufo, Sabino A; Cataldi, Tommaso R I; Albanis, Triantafyllos A

2004-01-01

The photochemical behavior of oxyfluorfen [2-chloro-1-(3-etoxy-4-nitrophenoxy)-4-(trifluoromethyl) benzene] on two Greek soils was investigated. Soils were sampled from Nea Malgara and Preveza regions, characterized by a different organic matter content. Soils were spiked with the diphenyl-ether herbicide and irradiation experiments were performed either in the laboratory with a solar simulator (xenon lamp) or outside, under natural sunlight irradiation; other soil samples were kept in the dark to control the retention reaction. Kinetic parameters of both retention and photochemical reactions were calculated using zero-, first- and second- (Langmuir-Hinshelwood) order equations, and best fit was checked through statistical analysis. The soil behaviors were qualitatively similar but quantitatively different, with the soil sampled from the Nea Malgara region much more sorbent as compared with Preveza soil. All studied reactions followed second-order kinetics and photochemical reactions were influenced by retaining capability of the soils. The contributions of the photochemical processes to the global dissipation rates were also calculated. Two main metabolites were identified as 2-chloro-1-(3-ethoxy-4-hydroxyphenoxy)-4-(trifluoromethyl)benzene and 2-chloro-1- (3-hydroxy-4-nitrophenoxy)-4-(trifluoromethyl)benzene.

An Integrative Study of Photochemical Air Pollution in Hong Kong: an Overview

Science.gov (United States)

Wang, T.

2014-12-01

Hong Kong is situated in the Pearl River delta of Southern China. This region has experienced phenomenal economic growth in the past 30 years. Emissions of large amount of pollutants from urban areas and various industries coupled with subtropical climate have led to frequent occurrences of severe photochemical air pollution. Despite the long-term control efforts of the Hong Kong government, the atmospheric levels of ozone have been increasing in the past decade. To obtain an updated and more complete understanding of photochemical smog, an integrative study has been conducted during 2010-2014. Several intensive measurement campaigns were carried out at urban, suburban and rural sites in addition to the routine observations at fourteen air quality monitoring stations in Hong Kong. Meteorological, photochemical, and chemical-transport modeling studies were conducted to investigate the causes/processes of elevated photochemical pollution . The main activities of this study were to (1) examine the situation and trends of photochemical air pollution in Hong Kong, (2) understand some underlying chemical processes in particular the poorly-understood heterogeneous processes of reactive nitrogen oxides, (3) quantify the local, regional, and super-regional contributions to the ozone pollution in Hong Kong, and (4) review the control policy and make further recommendations based on the science. This paper will give an overview of this study and present some key results on the trends and chemistry of the photochemical pollution in this polluted subtropical region.

Electro- and photochemical switching of dithienylethene self-assembled monolayers on gold electrodes

DEFF Research Database (Denmark)

Browne, W.R.; Kudernac, T.; Katsonis, N.

2008-01-01

forms of the dithienylethene SAMs is examined and found to be sensitive to the molecular structure of the switch. For the three dithienylethenes, the electrochemical behavior with respect to electrochemical ring opening/closing is retained in the SAMs. In contrast, a marked dependence on the nature...... of the anchoring group is observed upon immobilization in terms of the retention of the photochemical properties observed in solution. For the meta-thiophenol anchor both photochemical ring opening and closing are observed in the SAM, while for the thienyl-thiol-anchored switches the photochemically properties...

Photochemical organonitrate formation in wet aerosols

Science.gov (United States)

Lim, Yong Bin; Kim, Hwajin; Kim, Jin Young; Turpin, Barbara J.

2016-10-01

Water is the most abundant component of atmospheric fine aerosol. However, despite rapid progress, multiphase chemistry involving wet aerosols is still poorly understood. In this work, we report results from smog chamber photooxidation of glyoxal- and OH-containing ammonium sulfate or sulfuric acid particles in the presence of NOx and O3 at high and low relative humidity. Particles were analyzed using ultra-performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF-MS). During the 3 h irradiation, OH oxidation products of glyoxal that are also produced in dilute aqueous solutions (e.g., oxalic acids and tartaric acids) were formed in both ammonium sulfate (AS) aerosols and sulfuric acid (SA) aerosols. However, the major products were organonitrogens (CHNO), organosulfates (CHOS), and organonitrogen sulfates (CHNOS). These were also the dominant products formed in the dark chamber, indicating non-radical formation. In the humid chamber (> 70 % relative humidity, RH), two main products for both AS and SA aerosols were organonitrates, which appeared at m / z- 147 and 226. They were formed in the aqueous phase via non-radical reactions of glyoxal and nitric acid, and their formation was enhanced by photochemistry because of the photochemical formation of nitric acid via reactions of peroxy radicals, NOx and OH during the irradiation.

Photochemical Approaches to Complex Chemotypes: Applications in Natural Product Synthesis

Science.gov (United States)

2016-01-01

The use of photochemical transformations is a powerful strategy that allows for the formation of a high degree of molecular complexity from relatively simple building blocks in a single step. A central feature of all light-promoted transformations is the involvement of electronically excited states, generated upon absorption of photons. This produces transient reactive intermediates and significantly alters the reactivity of a chemical compound. The input of energy provided by light thus offers a means to produce strained and unique target compounds that cannot be assembled using thermal protocols. This review aims at highlighting photochemical transformations as a tool for rapidly accessing structurally and stereochemically diverse scaffolds. Synthetic designs based on photochemical transformations have the potential to afford complex polycyclic carbon skeletons with impressive efficiency, which are of high value in total synthesis. PMID:27120289

Southern Africa - a giant natural photochemical reactor

CSIR Research Space (South Africa)

Diab, RD

2006-04-01

Full Text Available photochemical reactor’ are abundant sources of ozone precursors (biomass burning, lightning, biogenic and urban-industrial sources), and meteorological conditions that promote anticyclonic recirculation on a subhemispheric scale....

Ozone modeling for compliance planning: A synopsis of ''The Use of Photochemical Air Quality Models for Evaluating Emission Control Strategies: A Synthesis Report''

International Nuclear Information System (INIS)

Blanchard, C.L.

1992-12-01

The 1990 federal Clean Air Act Amendments require that many nonattainment areas use gridded, photochemical air quality models to develop compliance plans for meeting the ambient ozone standard. Both industry and regulatory agencies will need to consider explicitly the strengths and limitations of the models. Photochemical air quality models constitute the principal tool available for evaluating the relative effectiveness of alternative emission control strategies. Limitations in the utility of modeling results stem from the uncertainty and bias of predictions for modeled episodes, possible compensating errors, limitations in the number of modeled episodes, and incompatibility between deterministic model predictions and the statistical form of the air quality standard for ozone. If emissions estimates (including naturally produced ''biogenic'' emissions) are accurate, intensive aerometric data are available, and an evaluation of performance (including diagnostic evaluations) is successfully completed, gridded photochemical airquality models can determine (1) the types of emission controls - VOC, NO x , or both - that would be most effective for reducing ozone concentrations, and (2) the approximate magnitudes - to within about 20--40% - of the estimated ozone reductions

Photochemically induced emission tuning of conductive polumers used in OLEDs

Energy Technology Data Exchange (ETDEWEB)

Vasilopoulou, M [NCSR ' Demokritos' , Institute of Microelectronics, POB 60228, 153 10 Agia Paraskevi, Attiki (Greece); Pistolis, G [Institute of Physical Chemistry, NCSR ' Demokritos' Athens 153 10 (Greece); Argitis, P [NCSR ' Demokritos' , Institute of Microelectronics, POB 60228, 153 10 Agia Paraskevi, Attiki (Greece)

2005-01-01

The present work focuses on the use of novel patterning technology schemes for the fabrication of OLED-based displays and in particular on the definition of two colour emitting pixels in one polymeric conducting layer. The approach adopted to this end is based on photochemically induced emition tuning. On the basis of this approach a novel photolithographic patterning technique was developed, aiming at the considerable simplification of the display fabrication process and on the performance improvement. We prepared electroluminescent devices that are emitting blue colour ({lambda}{sub max} 413 nm) with a turnon voltage about 12-15 V. In other devices we introduce a dispersed dye (1-[4-(dimethylamino)phenyl]-6-phenylhexatriene) and a series of photoacid generators (onium salts) in the polymeric layer and, by using an appropriate photochemical transformation through a photomask in a single layer, we were able to change the colour to desirable direction, since the parent compound and its photochemical product have distinguishable luminescence spectra (green and blue colour respectively). We were able to produce two of the three primary colours in a single layer of a conductive polymer by using a photochemical transformation based on photoacid induced emission change. A series of photoacid generators were evaluated.

Indications for chlororespiration in relation to light regime in the marine diatom Thalassiosira weissflogii.

Science.gov (United States)

Dijkman, Nicole A; Kroon, Bernd M A

2002-04-01

The marine diatom Thalassiosira weissflogii was cultured under a light regime simulating the daily rise and fall of the sun. The light regime caused a daily cycle in non-photochemical quenching. Remarkable were the changes in fluorescence directly after a light-to-dark transition that occurred in addition to the changes induced by non-photochemical quenching. A transient non-photochemical reduction of PQ and of Q(A) was indicated by a transient increase in apparent F(o) and by changes in the shape of the fluorescence induction curve. The observed changes developed approximately the first 100-120 s after a light-to-dark transition and could be reversed by the application of far-red illumination. Chlororespiration is thought to cause the reduction of PQ and, as the PQ-pool is in equilibrium with Q(A), also a reduction of Q(A). The function and ecological relevance of chlororespiration are discussed.

Isolation of a star-shaped uranium(V/VI) cluster from the anaerobic photochemical reduction of uranyl(VI)

International Nuclear Information System (INIS)

Chatelain, Lucile; White, Sarah; Scopelliti, Rosario; Mazzanti, Marinella

2016-01-01

Actinide oxo clusters are an important class of compounds due to their impact on actinide migration in the environment. The photolytic reduction of uranyl(VI) has potential application in catalysis and spent nuclear fuel reprocessing, but the intermediate species involved in this reduction have not yet been elucidated. Here we show that the photolysis of partially hydrated uranyl(VI) in anaerobic conditions leads to the reduction of uranyl(VI), and to the incorporation of the resulting U V species into the stable mixed-valent star-shaped U VI /U V oxo cluster [U(UO 2 ) 5 (μ 3 -O) 5 (PhCOO) 5 (Py) 7 ]. This cluster is only the second example of a U VI /U V cluster and the first one associating uranyl groups to a non-uranyl(V) center. The U V center in 1 is stable, while the reaction of uranyl(V) iodide with potassium benzoate leads to immediate disproportionation and formation of the U 12 IV U 4 V O 24 cluster {[K(Py) 2 ] 2 [K(Py)] 2 [U 16 O 24 (PhCOO) 24 (Py) 2 ]}.

Approximate photochemical dynamics of azobenzene with reactive force fields

Science.gov (United States)

Li, Yan; Hartke, Bernd

2013-12-01

We have fitted reactive force fields of the ReaxFF type to the ground and first excited electronic states of azobenzene, using global parameter optimization by genetic algorithms. Upon coupling with a simple energy-gap transition probability model, this setup allows for completely force-field-based simulations of photochemical cis→trans- and trans→cis-isomerizations of azobenzene, with qualitatively acceptable quantum yields. This paves the way towards large-scale dynamics simulations of molecular machines, including bond breaking and formation (via the reactive force field) as well as photochemical engines (presented in this work).

Photochemical synthesis of UO2 nanoparticles

International Nuclear Information System (INIS)

Rath, M.C.; Keny, Sangeeta; Naik, D.B.

2014-01-01

UO 2 nanoparticles have been recently synthesized by us from aqueous solutions of uranyl nitrate through radiolytic method on high-energy electron beam irradiation. In this study, the synthesis of UO 2 nanoparticles through photochemical method is reported which is a complementary route to radiation chemical method

Photochemical fate of beta-blockers in NOM enriched waters

Energy Technology Data Exchange (ETDEWEB)

Wang, Ling; Xu, Haomin; Cooper, William J. [Urban Water Research Center, Department of Civil and Environmental Engineering, University of California, Irvine, Irvine, CA 92697-2175 (United States); Song, Weihua, E-mail: wsong@fudan.edu.cn [Department of Environmental Science and Engineering, Fudan University, Shanghai 200433 (China)

2012-06-01

Beta-blockers, prescribed for the treatment of high blood pressure and for long-term use after a heart attack, have been detected in surface and ground waters. This study examines the photochemical fate of three beta-blockers, atenolol, metoprolol, and nadolol. Hydrolysis accounted for minor losses of these beta-blockers in the pH range 4-10. The rate of direct photolysis at pH 7 in a solar simulator varied from 6.1 to 8.9 h{sup -1} at pH 7. However, the addition of a natural organic matter (NOM) isolate enhanced the photochemical loss of all three compounds. Indirect photochemical fate, generally described by reactions with hydroxyl radical ({center_dot}OH) and singlet oxygen ({sup 1}{Delta}O{sub 2}), and, the direct reaction with the triplet excited state, {sup 3}NOM{sup Low-Asterisk }, also varied but collectively appeared to be the major loss factor. Bimolecular reaction rate constants of the three beta-blockers with {sup 1}{Delta}O{sub 2} and {center_dot}OH were measured and accounted for 0.02-0.04% and 7.2-38.9% of their loss, respectively. These data suggest that the {sup 3}NOM{sup Low-Asterisk} contributed 50.6-85.4%. Experiments with various {sup 3}NOM{sup Low-Asterisk} quenchers supported the hypothesis that it was singly the most important reaction. Atenolol was chosen for more detailed investigation, with the photoproducts identified by LC-MS analysis. The results suggested that electron-transfer could be an important mechanism in photochemical fate of beta-blockers in the presence of NOM. - Highlights: Black-Right-Pointing-Pointer Photochemical degradation of beta-blockers in the simulated natural waters. Black-Right-Pointing-Pointer Reactive Oxygen Species play a minor role in the indirect photodegradation. Black-Right-Pointing-Pointer The loss of beta-blockers results from direct reaction with {sup 3}DOM{sup Low-Asterisk }.

Photochemical reactions of nucleic acids and their constituents of photobiological relevance

International Nuclear Information System (INIS)

Saito, I.; Sugiyama, H.; Matsuura, T.

1983-01-01

A review is given of the papers published from 1977 to May 1983 on the UV-induced photochemical reactions of nucleic acids and their constituents of photobiological relevance where the structures of photoproducts have been fully characterized. Among the topics discussed are photoadditions relevant to nucleic acid-protein photocrosslinking, photoreactions with psoralens and nucleic acids and photochemical reactions of polynucleotides. (U.K.)

A review of post-column photochemical reaction systems coupled to electrochemical detection in HPLC

International Nuclear Information System (INIS)

Fedorowski, Jennifer; LaCourse, William R.

2010-01-01

Post-column photochemical reaction systems have developed into a common approach for enhancing conventional methods of detection in HPLC. Photochemical reactions as a means of 'derivatization' have a significant number of advantages over chemical reaction-based methods, and a significant effort has been demonstrated to develop an efficient photochemical reactor. When coupled to electrochemical (EC) detection, the technique allows for the sensitive and selective determination of a variety of compounds (e.g., organic nitro explosives, beta-lactam antibiotics, sulfur-containing antibiotics, pesticides and insecticides). This review will focus on developments and methods using post-column photochemical reaction systems followed by EC detection in liquid chromatography. Papers are presented in chronological order to emphasize the evolution of the approach and continued importance of the application.

The role of metals in production and scavenging of reactive oxygen species in photosystem II.

Science.gov (United States)

Pospíšil, Pavel

2014-07-01

Metal ions play a crucial role in enzymatic reactions in all photosynthetic organisms such as cyanobacteria, algae and plants. It well known that metal ions maintain the binding of substrate in the active site of the metalloenzymes and control the redox activity of the metalloenzyme in the enzymatic reaction. A large pigment-protein complex, PSII, known to serve as a water-plastoquinone oxidoreductase, contains three metal centers comprising non-heme iron, heme iron of Cyt b559 and the water-splitting manganese complex. Metal ions bound to PSII proteins maintain the electron transport from water to plastoquinone and regulate the pro-oxidant and antioxidant activity in PSII. In this review, attention is focused on the role of PSII metal centers in (i) the formation of superoxide anion and hydroxyl radicals by sequential one-electron reduction of molecular oxygen and the formation of hydrogen peroxide by incomplete two-electron oxidation of water; and (ii) the elimination of superoxide anion radical by one-electron oxidation and reduction (superoxide dismutase activity) and of hydrogen peroxide by two-electron oxidation and reduction (catalase activity). The balance between the formation and elimination of reactive oxygen species by PSII metal centers is discussed as an important aspect in the prevention of photo-oxidative damage of PSII proteins and lipids. © The Author 2014. Published by Oxford University Press on behalf of Japanese Society of Plant Physiologists. All rights reserved. For permissions, please email: journals.permissions@oup.com.

Highly efficient destruction of squamous carcinoma cells of the head and neck by photochemical internalization of Ranpirnase.

Science.gov (United States)

Liebers, Nora; Holland-Letz, Tim; Welschof, Mona; Høgset, Anders; Jäger, Dirk; Arndt, Michaela A E; Krauss, Jürgen

2017-11-01

Photochemical Internalization is a novel drug delivery technology for cancer treatment based on the principle of Photodynamic Treatment. Using a photosensitizer that locates in endocytic vesicles membranes of tumor cells, Photochemical internalization enables cytosolic release of endocytosed antitumor agents in a site-specific manner. The purpose of the present in-vitro study was to explore whether Photochemical Internalization is able to enhance the efficacy of Ranpirnase, a cytotoxic amphibian ribonuclease, for eradication of squamous cell carcinoma of the head and neck. Cell viability was measured in 8 primary human cell lines of squamous cell carcinoma of the head and neck after treatment with Ranpirnase and Photochemical Internalization. For Photochemical Internalization the photosensitizer disulfonated tetraphenyl porphine was incubated with tumor cells followed by exposure to blue light (435 nm). Our study demonstrates significant enhancement of antitumor activity of Ranpirnase by Photochemical Internalization. Treatment responses were heterogeneous between the primary cancer cell lines. Combining Photochemical Internalization with Ranpirnase resulted in 4.6 to 1,940-fold increased cytotoxicity when compared with the ribonuclease alone (P Internalization in squamous cell carcinoma of the head and neck.

Potential reduction of non-residential solid waste in Sukomanunggal district West Surabaya

Science.gov (United States)

Warmadewanthi, I. D. A. A.; Reswari, S. A.

2018-01-01

Sukomanunggal district a development unit 8 with the designation as a regional trade and services, industrial, education, healthcare, offices, and shopping center. The development of this region will make an increasing solid waste generation, especially waste from non-residential facilities. The aims of this research to know the potential reduction of waste source. The method used is the Likert scale questionnaire to determine the knowledge, attitude, and behavior of non-residential facilities manager. Results from this research are the existing reduction of non-residential solid waste is 5.34%, potential reduction of the waste source is optimization of plastic and paper waste with the reduction rate up to 19,52%. The level of public participation existing amounted to 46.79% with a willingness to increase recycling efforts amounted to 72.87%. Efforts that can be developed to increase public awareness of 3R are providing three types of bins, modification of solid waste collection schedule according to a type of waste that has been sorted, the provision of the communal bin.

Photosynthesis by isolated chloroplasts. IV. General concept and comparison of three photochemical reactions

Energy Technology Data Exchange (ETDEWEB)

Arnon, D I; Allen, M B; Whatley, F R

1956-01-01

Procedures are described for the preparation of chloroplasts capable of carrying out three photochemical reactions, each representing an increasingly complex phase of photosynthesis: photolysis of water (Hill reaction), esterification of inorganic phosphate into adenosine triphosphate (photosynthetic phosphorylation) and the reduction of carbon dioxide to the level of carbohydrates with a simultaneous evolution of oxygen. The three photochemical reactions were separable by variations in the technique for preparation of chloroplasts and by differential inhibition by several reagents. Inhibition of a more complex phase of photosynthesis does not affect the simpler one which precedes it and, conversely, the inhibition of a simpler phase of photosynthesis is paralleled by an inhibition of the more complex phase which follows. Reversible inhibition of CO/sub 2/ fixation and photosynthetic phosphorylation, but not of photolysis, by sulfhydryl group inhibitors suggests that sulfhydryl compounds (enzymes, cofactors, or both) are involved in phosphorylation and CO/sub 2/ fixation, but not in the primary conversion of light into chemical energy as measured by the Hill reaction. Evidence is presented in support of the conclusion that the synthesis of ATP by green cells occurs at two distinct sites: anaerobically in chloroplasts by photosynthetic phosphorylation, and acrobically in smaller cytoplasmic particles, presumably mitochondria, by oxidative phosphorylation independent of light. A general scheme of photosynthesis by chloroplasts, consistent with these findings, is presented. 44 references, 8 figures, 4 tables.

Exercise enhanced functional recovery and expression of GDNF after photochemically induced cerebral infarction in the rat.

Science.gov (United States)

Ohwatashi, Akihiko; Ikeda, Satoshi; Harada, Katsuhiro; Kamikawa, Yurie; Yoshida, Akira

2013-01-01

Exercise has been considered to affect the functional recovery from central nervous damage. Neurotrophic factors have various effects on brain damage. However, the effects of exercise for expression of GDNF on functional recovery with brain damage are not well known. We investigated the difference in functional recovery between non-exercise and beam-walking exercise groups, and the expression of GDNF in both groups after photochemical infarction. Adult male Wistar rats (N = 64) were used. Animals were divided into two groups: non-exercise (N = 35), and beam-walking exercise (N = 29). All rats underwent surgical photochemical infarction. The rats of the beam-walking group were trained every day to walk on a narrow beam after a one-day recovery period and those of the non-exercise group were left to follow a natural course. Animals were evaluated for hind limb function every day using a beam-walking task with an elevated narrow beam. The number of GDNF-like immunoreactive cells in the temporal cortex surrounding the lesion was counted 1, 3, 5, and 7 days after the infarction. Functional recovery of the beam-walking exercise group was significantly earlier than that of the non-exercise group. At 3 days after infarction, the number of GDNF-positive cells in the temporal cortex surrounding the infarction was significantly increased in the beam-walking exercise group compared with that in the non-exercise group. In the exercise group, motor function was remarkably recovered with the increased expression of GDNF-like immunoreactive cells. Our results suggested that a rehabilitative approach increased the expression of GDNF and facilitated functional recovery from cerebral infarction.

Non-local spatial frequency response of photopolymer materials containing chain transfer agents: I. Theoretical modelling

International Nuclear Information System (INIS)

Guo, Jinxin; Gleeson, Michael R; Liu, Shui; Sheridan, John T

2011-01-01

The non-local photopolymerization driven diffusion (NPDD) model predicts that a reduction in the non-local response length within a photopolymer material will improve its high spatial frequency response. The introduction of a chain transfer agent reduces the average molecular weight of polymer chains formed during free radical polymerization. Therefore a chain transfer agent (CTA) provides a practical method to reduce the non-local response length. An extended NPDD model is presented, which includes the chain transfer reaction and most major photochemical processes. The addition of a chain transfer agent into an acrylamide/polyvinyl alcohol photopolymer material is simulated and the predictions of the model are examined. The predictions of the model are experimentally examined in part II of this paper

Photochemical Haze Formation in the Atmospheres of Super-Earths and Mini-Neptunes

Science.gov (United States)

He, Chao; Hoerst, Sarah M.; Lewis, Nikole K.; Yu, Xinting; Moses, Julianne I.; Kempton, Eliza M.- R.; Marley, Mark S.; McGuiggan, Patricia; Morley, Caroline V.; Valenti, Jeff A.;

WATER DEFICIT ENSURES THE PHOTOCHEMICAL EFFICIENCY OF Copaifera langsdorffii Desf1

Directory of Open Access Journals (Sweden)

Angélica Lino Rodrigues

2017-02-01

Full Text Available ABSTRACT The intensity and frequency of drought periods has increased according to climate change predictions. The fast overcome and recovery are important adaptive features for plant species found in regions presenting water shortage periods. Copaifera langsdorffii is a neotropical species that has developed leaves presenting physiological mechanisms and morphological adaptations that allow its survival under seasonal water stress. We aimed in this work to observe substantial physiological responses for water saving and damage representative to the photochemical reaction after exposed plants to water stress and to subsequent recovery. We found in plants mechanisms to control water loss through the lower stomatal conductance, even after rehydration. It goes against the rapid recovery of leaves, indicated by the relative water content values restored to previously unstressed plants. Stomatal conductance was the only variable presenting high plasticity index. In photochemical activity, the species presented higher photochemical quenching, electron transport rate and effective quantum yield of photosystem II when they were subjected to rehydration after water stress period. Our results suggest that C. langsdorffii presented rapid rehydration and higher photochemical efficiency even after water restriction. These data demonstrate that this species can be used as a model for physiological studies due to the adjustment developed in response to different environmental schemes.

Photochemical Internalization of Bleomycin Before External-Beam Radiotherapy Improves Locoregional Control in a Human Sarcoma Model

International Nuclear Information System (INIS)

Norum, Ole-Jacob; Bruland, Oyvind Sverre; Gorunova, Ludmila; Berg, Kristian

2009-01-01

Purpose: The aim of this study was to explore the tumor growth response of the combination photochemical internalization and external-beam radiotherapy. Photochemical internalization is a technology to improve the utilization of therapeutic macromolecules in cancer therapy by photochemical release of endocytosed macromolecules into the cytosol. Methods and Materials: A human sarcoma xenograft TAX-1 was inoculated subcutaneously into nude mice. The photosensitizer AlPcS 2a and bleomycin were intraperitoneally administrated 48 h and 30 min, respectively, before diode laser light exposure at 670 nm (20 J/cm 2 ). Thirty minutes or 7 days after photochemical treatment, the animals were subjected to 4 Gy of ionizing radiation. Results: Using photochemical internalization of bleomycin as an adjunct to ionizing radiation increased the time to progression for the tumors from 17 to 33 days as compared with that observed with photodynamic therapy combined with ionizing radiation as well as for radiochemotherapy with bleomycin. The side effects observed when photochemical internalization of bleomycin was given shortly before ionizing radiation were eliminated by separating the treatment modalities in time. Conclusion: Photochemical internalization of bleomycin combined with ionizing radiation increased the time to progression and showed minimal toxicity and may therefore reduce the total radiation dose necessary to obtain local tumor control while avoiding long-term sequelae from radiotherapy.

Photochemical smog incident on June 30, 1973

Energy Technology Data Exchange (ETDEWEB)

Hata, S

1973-01-01

The first photochemical smog incident in Shizuoka prefecture (June 30, 1973) started in Hamamatsu and extended 100 km northeast as far as Fujinomiya city. This not only involved an extraordinarily large area, but the type of smog was different from that in Tokyo and Osaka. The victims were all pupils exercising at the time in the playgrounds. In Hamamatsu, 1050 children were involved and complained of eye irritation and pain, throat pain, coughs, and headaches between 2 and 3 pm, but there were no serious effects. The damages to agricultural produce were extensive and 70% of the total rice fields (1656 hectares), and 40 hectares of green scallions were affected. In Shizuoka, 716 children were affected about 5:30 pm, but in Fujinomiya, which is located further northeast, 16 children were affected about 4 pm. The movement of the damages, the locations, the extent of damages, and the direction of the wind, were puzzling in the light of the normal pattern of photochemical smogs, and the pollution sources could not be the coastal industrial area or automobile exhaust gases. Meteorological factors were similar to the usual photochemical smog conditions, but the locations of the cities involved and the wind direction from the sea suggested that the pollution source was the Pacific Ocean. Since the wind above 1000 m was northeast, circulation of industrial pollutants by the sea breeze is a possible explanation. The maximum concentration of oxidants was about 0.2 ppm in all areas except for Hamamatsu, where it was a little over 0.2 ppm.

SNCR technology for NO sub x reduction in the cement industry. [Selective non-catalytic reduction

Energy Technology Data Exchange (ETDEWEB)

Kupper, D; Brentrup, L [Krupp Polysius AG, Beckum (Germany)

1992-03-01

This article discusses the selective non-catalytic (SNCR) process for reducing nitrogen oxides in exhaust gases from cement plants. Topics covered include operating experience, injection of additives, selection of the additive, operating costs, reduction efficiency of SNCR, capital expenditure, secondary emissions and cycles of ammonium. (UK).

Isolation of a star-shaped uranium(V/VI) cluster from the anaerobic photochemical reduction of uranyl(VI)

Energy Technology Data Exchange (ETDEWEB)

Chatelain, Lucile; White, Sarah; Scopelliti, Rosario; Mazzanti, Marinella [Ecole Polytechnique Federale de Lausanne (EPFL) (Switzerland). Inst. de Sciences et Ingenierie Chimiques

2016-11-07

Actinide oxo clusters are an important class of compounds due to their impact on actinide migration in the environment. The photolytic reduction of uranyl(VI) has potential application in catalysis and spent nuclear fuel reprocessing, but the intermediate species involved in this reduction have not yet been elucidated. Here we show that the photolysis of partially hydrated uranyl(VI) in anaerobic conditions leads to the reduction of uranyl(VI), and to the incorporation of the resulting U{sup V} species into the stable mixed-valent star-shaped U{sup VI}/U{sup V} oxo cluster [U(UO{sub 2}){sub 5}(μ{sub 3}-O){sub 5}(PhCOO){sub 5}(Py){sub 7}]. This cluster is only the second example of a U{sup VI}/U{sup V} cluster and the first one associating uranyl groups to a non-uranyl(V) center. The U{sup V} center in 1 is stable, while the reaction of uranyl(V) iodide with potassium benzoate leads to immediate disproportionation and formation of the U{sub 12}{sup IV}U{sub 4}{sup V}O{sub 24} cluster {[K(Py)_2]_2[K(Py)]_2[U_1_6O_2_4(PhCOO)_2_4(Py)_2]}.

Understanding of the mode of action of Fe(III)-EDDHA as iron chlorosis corrector based on its photochemical and redox behavior.

Science.gov (United States)

Gómez-Gallego, Mar; Pellico, Daniel; Ramírez-López, Pedro; Mancheño, María J; Romano, Santiago; de la Torre, María C; Sierra, Miguel A

2005-10-07

The very low reduction potential of the chelate Fe(III)-EDDHA (EDDHA = ethylenediamine N,N'-bis(2-hydroxy)phenylacetic acid) makes it unreactive in photochemically or chemically induced electron transfer processes. The lack of reactivity of this complex toward light invalidates photodegradation as an alternative mechanism for environmental elimination. However, in spite of its low reduction potential, the biological reduction of Fe(III)-EDDHA is very effective. Based on electrochemical measurements, it is proposed that Fe(III)-EDDHA itself is not the substrate of the enzyme ferric chelate reductase. Likely, at the more acidic pH in the vicinity of the roots, the ferric chelate in a closed form (FeL-) could generate a vacant coordination site that leads to an open hexacoordinate species (FeHL) where the reduction of the metal by the enzyme takes place.

Synthesis, characterization, photophysical, and photochemical properties of novel zinc(II) and indium(III) phthalocyanines containing 2-phenylphenoxy units

Energy Technology Data Exchange (ETDEWEB)

Ali, Haytham Elzien Alamin [Department of Chemistry, Marmara University, Istanbul 34722 (Turkey); University of Khartoum, Department of Chemistry, Faculty of Science, P.O. Box 321, Khartoum, 11115 (Sudan); Pişkin, Mehmet [Çanakkale Onsekiz Mart University, Vocational School of Technical Sciences, Department of Food Technology, Çanakkale 17100 (Turkey); Altun, Selçuk [Department of Chemistry, Marmara University, Istanbul 34722 (Turkey); Durmuş, Mahmut [Gebze Technical University, Department of Chemistry, P.O. Box 141, Gebze, Kocaeli 41400 (Turkey); Odabaş, Zafer, E-mail: zodabas@marmara.edu.tr [Department of Chemistry, Marmara University, Istanbul 34722 (Turkey)

2016-05-15

The synthesis of highly soluble and non-aggregated peripherally/non-peripherally Zn and In(OAc) phthalocyanines was achieved by 3-/ and 4-(2-phenylphenoxy)phthalonitrile as starting materials. The novel compounds were characterized by elemental analyses, FT-IR, {sup 1}H-NMR (for phthalonitriles), UV–vis and MALDI-TOF mass (for Pcs) spectroscopic techniques. Additionally, photophysical, photochemical and spectral properties of the phthalocyanines were reported. Especially, the indium(OAc) phthalocyanines showed good singlet oxygen quantum yields in DMSO and they can be appropriate candidates as Type II photosensitizers in photodynamic therapy (PDT) applications.

Synthesis, characterization, photophysical, and photochemical properties of novel zinc(II) and indium(III) phthalocyanines containing 2-phenylphenoxy units

International Nuclear Information System (INIS)

Ali, Haytham Elzien Alamin; Pişkin, Mehmet; Altun, Selçuk; Durmuş, Mahmut; Odabaş, Zafer

2016-01-01

The synthesis of highly soluble and non-aggregated peripherally/non-peripherally Zn and In(OAc) phthalocyanines was achieved by 3-/ and 4-(2-phenylphenoxy)phthalonitrile as starting materials. The novel compounds were characterized by elemental analyses, FT-IR, 1 H-NMR (for phthalonitriles), UV–vis and MALDI-TOF mass (for Pcs) spectroscopic techniques. Additionally, photophysical, photochemical and spectral properties of the phthalocyanines were reported. Especially, the indium(OAc) phthalocyanines showed good singlet oxygen quantum yields in DMSO and they can be appropriate candidates as Type II photosensitizers in photodynamic therapy (PDT) applications.

Photochemical reaction products in air pollution

Energy Technology Data Exchange (ETDEWEB)

Stephens, E R; Darley, E F; Taylor, O C; Scott, W E

1961-01-01

Isolation and purification of peroxyacetyl nitrate (PAN) from artificial photochemical reaction of olefins and NO/sub x/ in air are analyzed. Olefin splits at the double bond, one end forming carbonyl compound and the other yielding PAN, among others. At concentrations below 1 ppM, PAN causes plant damage. At a concentration of about 1 ppM, PAN is a strong eye irritant.

Non-Cartesian MRI scan time reduction through sparse sampling

NARCIS (Netherlands)

Wajer, F.T.A.W.

2001-01-01

Non-Cartesian MRI Scan-Time Reduction through Sparse Sampling Magnetic resonance imaging (MRI) signals are measured in the Fourier domain, also called k-space. Samples of the MRI signal can not be taken at will, but lie along k-space trajectories determined by the magnetic field gradients. MRI

Photochemical internalisation of a macromolecular protein toxin using a cell penetrating peptide-photosensitiser conjugate.

Science.gov (United States)

Wang, Julie T-W; Giuntini, Francesca; Eggleston, Ian M; Bown, Stephen G; MacRobert, Alexander J

2012-01-30

Photochemical internalisation (PCI) is a site-specific technique for improving cellular delivery of macromolecular drugs. In this study, a cell penetrating peptide, containing the core HIV-1 Tat 48-57 sequence, conjugated with a porphyrin photosensitiser has been shown to be effective for PCI. Herein we report an investigation of the photophysical and photobiological properties of a water soluble bioconjugate of the cationic Tat peptide with a hydrophobic tetraphenylporphyrin derivative. The cellular uptake and localisation of the amphiphilic bioconjugate was examined in the HN5 human head and neck squamous cell carcinoma cell line. Efficient cellular uptake and localisation in endo/lysosomal vesicles was found using fluorescence detection, and light-induced, rupture of the vesicles resulting in a more diffuse intracellular fluorescence distribution was observed. Conjugation of the Tat sequence with a hydrophobic porphyrin thus enables cellular delivery of an amphiphilic photosensitiser which can then localise in endo/lysosomal membranes, as required for effective PCI treatment. PCI efficacy was tested in combination with a protein toxin, saporin, and a significant reduction in cell viability was measured versus saporin or photosensitiser treatment alone. This study demonstrates that the cell penetrating peptide-photosensitiser bioconjugation strategy is a promising and versatile approach for enhancing the therapeutic potential of bioactive agents through photochemical internalisation. Copyright © 2011 Elsevier B.V. All rights reserved.

New electrochemical and photochemical systems for water and wastewater treatment

International Nuclear Information System (INIS)

Sarria, Victor M; Parra, Sandra; Rincon, Angela G; Torres, Ricardo A; Pulgarin, Cesar

2005-01-01

With the increasing pressure on a more effective use of water resources, the development of appropriate water treatment technologies become more and more important. Photochemical and electrochemical oxidation processes have been proposed in recent years as an attractive alternative for the treatment of contaminated water containing anthropogenic substances hardly biodegradable as well as to purify and disinfect drinking waters. The aim of this paper is to present some of our last results demonstrating that electrochemical, photochemical, and the coupling of these processes with biological systems are very promising alternatives for the improvement of the water quality

Carrier-lifetime-controlled selective etching process for semiconductors using photochemical etching

International Nuclear Information System (INIS)

Ashby, C.I.H.; Myers, D.R.

1992-01-01

This patent describes a process for selectively photochemically etching a semiconductor material. It comprises introducing at least one impurity into at least one selected region of a semiconductor material to be etched to increase a local impurity concentration in the at least one selected region relative to an impurity concentration in regions of the semiconductor material adjacent thereto, for reducing minority carrier lifetimes within the at least one selected region relative to the adjacent regions for thereby providing a photochemical etch-inhibiting mask at the at least one selected region; and etching the semiconductor material by subjecting the surface of the semiconductor material to a carrier-driven photochemical etching reaction for selectively etching the regions of the semiconductor material adjacent the at least one selected region having the increase impurity concentration; wherein the step of introducing at least one impurity is performed so as not to produce damage to the at least one selected region before any etching is performed

Functional architecture of photosystem II supercomplexes

NARCIS (Netherlands)

Caffarri, S.; Kouril, R.; Kereiche, S.; Boekema, E.J.; Croce, R.

2009-01-01

Photosystem II (PSII) is a large multiprotein complex, which catalyses water splitting and plastoquinone reduction necessary to transform sunlight into chemical energy. Detailed functional and structural studies of the complex from higher plants have been hampered by the impossibility to purify it

Functional architecture of higher plant photosystem II supercomplexes

NARCIS (Netherlands)

Caffarri, Stefano; Kouril, Roman; Kereiche, Sami; Boekema, Egbert J.; Croce, Roberta; Kereïche, Sami

2009-01-01

Photosystem II ( PSII) is a large multiprotein complex, which catalyses water splitting and plastoquinone reduction necessary to transform sunlight into chemical energy. Detailed functional and structural studies of the complex from higher plants have been hampered by the impossibility to purify it

Reduction of Guanosyl Radical by Cysteine and Cysteine-Glycine Studied by Time-Resolved CIDNP

NARCIS (Netherlands)

Morozova, O.B.; Kaptein, R.; Yurkovskaya, A.V.

2012-01-01

As a model for chemical DNA repair, reduction of guanosyl radicals in the reaction with cysteine or the dipeptide cysteine-glycine has been studied by time-resolved chemically induced dynamic nuclear polarization (CIDNP). Radicals were generated photochemically by pulsed laser irradiation of a

Source apportionment of VOCs and the contribution to photochemical ozone formation during summer in the typical industrial area in the Yangtze River Delta, China

Science.gov (United States)

Shao, Ping; An, Junlin; Xin, Jinyuan; Wu, Fangkun; Wang, Junxiu; Ji, Dongsheng; Wang, Yuesi

2016-07-01

Volatile organic compounds (VOCs) were continuously observated in a northern suburb of Nanjing, a typical industrial area in the Yangtze River Delta, in a summer observation period from 15th May to 31st August 2013. The average concentration of total VOCs was (34.40 ± 25.20) ppbv, including alkanes (14.98 ± 12.72) ppbv, alkenes (7.35 ± 5.93) ppbv, aromatics (9.06 ± 6.64) ppbv and alkynes (3.02 ± 2.01) ppbv, respectively. Source apportionment via Positive Matrix Factorization was conducted, and six major sources of VOCs were identified. The industry-related sources, including industrial emissions and industrial solvent usage, occupied the highest proportion, accounting for about 51.26% of the VOCs. Vehicular emissions occupied the second highest proportion, accounting for about 34.08%. The rest accounted for about 14.66%, including vegetation emission and liquefied petroleum gas/natural gas usage. Contributions of VOCs to photochemical O3 formation were evaluated by the application of a detailed chemical mechanism model (NCAR MM). Alkenes were the dominant contributors to the O3 photochemical production, followed by aromatics and alkanes. Alkynes had a very small impact on photochemical O3 formation. Based on the outcomes of the source apportionment, a sensitivity analysis of relative O3 reduction efficiency (RORE), under different source removal regimes such as using the reduction of VOCs from 10% to 100% as input, was conducted. The RORE was the highest (~ 20%-40%) when the VOCs from solvent-related sources decreased by 40%. The highest RORE values for vegetation emissions, industrial emissions, vehicle exhaust, and LPG/NG usage were presented in the scenarios of 50%, 80%, 40% and 40%, respectively.

Bibliographic study of photophysical and photochemical properties of laser dyes

International Nuclear Information System (INIS)

Doizi, D.

1986-06-01

Laser isotope separation of uranium requires high power and precise wave length. This report is a bibliographic and experimental study of the photophysical and photochemical properties of seven commercial laser dyes which have an emission wavelength in the range 5500-6500 A: Rhodamine 110 or 560, rhodamine 6G or 590, rhodamine B or 610, rhodamine 101 or 640, sulforhodamine B or kiton red 620, sulforhodamine 101 or 640 and DCM or LC 6500. Absorption and emission cross section values, fluorescence lifetimes and quantum yields in various solvents are indicated. For each dye, a non exhaustive list of laboratory experiments made with two types of pump sources: Nd YAG (532) and copper vapor laser is given. When it is known, the toxicity of the dyes is mentioned [fr

Repair processes for photochemical damage in mammalian cells

International Nuclear Information System (INIS)

Cleaver, J.E.

1974-01-01

Repair processes for photochemical damage in cells following uv irradiation are reviewed. Cultured fibroblast cells from human patients with xeroderma pigmentosum were used as an example to illustrate aspects of repair of injuries to DNA and proteins. (250 references) (U.S.)

Photochemical decoration of gold nanoparticles on polymer stabilized magnetic microspheres for determination of adenine by surface-enhanced Raman spectroscopy

International Nuclear Information System (INIS)

Alula, Melisew Tadele; Yang, Jyisy

2015-01-01

Magnetic microspheres decorated with gold nanoparticles (AuNPs) were prepared and used for the determination of adenine by surface-enhanced Raman scattering (SERS). Magnetic particles were first synthesized by coprecipitation of solutions containing iron(II) and iron(III) ions with ammonium hydroxide. Subsequently, the magnetic particles were suspended into a solution of poly(divinylbenzene-co-methyl methacrylate) to yield polymer-stabilized magnetic microspheres. These were further decorated with AuNPs via a new photochemical reduction method. The magnetic microspheres were characterized by XRD patterns and SEM images. They are shown to represent highly SERS-active substrates by giving an enhancement by almost 7 orders of magnitude compared to conventional Raman spectroscopy. Several factors that affect the photochemical reduction to form the AuNPs were examined. It is found that the concentration of gold ion, UV irradiation time, and citrate concentration have more impact on the reaction rate than on the morphologies of the AuNPs. The gold-decorated magnetic microspheres are highly stable in aqueous solution and capable of concentrating nucleobases. A linear response of the SERS signal to adenine in concentrations up to 10 μM is found, with a linear regression coefficient of 0.997. The detection limit is estimated to a few hundreds of nM (at an SNR of 3). Based on its specific Raman peak at 734 cm −1 , adenine can be selectively determined without interference by other nucleobases, and a recovery higher than 95 % could be obtained. (author)

Near-field photochemical and radiation-induced chemical fabrication of nanopatterns of a self-assembled silane monolayer

Directory of Open Access Journals (Sweden)

Ulrich C. Fischer

2014-09-01

Full Text Available A general concept for parallel near-field photochemical and radiation-induced chemical processes for the fabrication of nanopatterns of a self-assembled monolayer (SAM of (3-aminopropyltriethoxysilane (APTES is explored with three different processes: 1 a near-field photochemical process by photochemical bleaching of a monomolecular layer of dye molecules chemically bound to an APTES SAM, 2 a chemical process induced by oxygen plasma etching as well as 3 a combined near-field UV-photochemical and ozone-induced chemical process, which is applied directly to an APTES SAM. All approaches employ a sandwich configuration of the surface-supported SAM, and a lithographic mask in form of gold nanostructures fabricated through colloidal sphere lithography (CL, which is either exposed to visible light, oxygen plasma or an UV–ozone atmosphere. The gold mask has the function to inhibit the photochemical reactions by highly localized near-field interactions between metal mask and SAM and to inhibit the radiation-induced chemical reactions by casting a highly localized shadow. The removal of the gold mask reveals the SAM nanopattern.

Photochemical oxidant transport - Mesoscale lake breeze and synoptic-scale aspects

Science.gov (United States)

Lyons, W. A.; Cole, H. S.

1976-01-01

Data from routine ozone monitoring in southeastern Wisconsin and limited monitoring of the Milwaukee area by the Environmental Protection Agency are examined. Hourly averages as high as 30 pphm have been recorded in southeastern Wisconsin, and high readings have been reported in rural regions throughout the state. The observations indicate that photochemical oxidants and their nitrogen oxide and reactive hydrocarbon precursers advect from Chicago and northern Indiana into southeastern Wisconsin. There is evidence that synoptic-scale transport of photochemical oxidants occurs, allowing the pollution of entire anticyclones. These results cast doubt on the validity of the Air Quality Control Regions established by amendment to the Clean Air Act of 1970.

Tropospheric Ozone and Photochemical Smog

Science.gov (United States)

Sillman, S.

2003-12-01

The question of air quality in polluted regions represents one of the issues of geochemistry with direct implications for human well-being. Human health and well-being, along with the well-being of plants, animals, and agricultural crops, are dependent on the quality of air we breathe. Since the start of the industrial era, air quality has become a matter of major importance, especially in large cities or urbanized regions with heavy automobile traffic and industrial activity.Concern over air quality existed as far back as the 1600s. Originally, polluted air in cities resulted from the burning of wood or coal, largely as a source of heat. The industrial revolution in England saw a great increase in the use of coal in rapidly growing cities, both for industrial use and domestic heating. London suffered from devastating pollution events during the late 1800s and early 1900s, with thousands of excess deaths attributed to air pollution (Brimblecombe, 1987). With increasing use of coal, other instances also occurred in continental Europe and the USA. These events were caused by directly emitted pollutants (primary pollutants), including sulfur dioxide (SO2), carbon monoxide (CO), and particulates. They were especially acute in cities with northerly locations during fall and winter when sunlight is at a minimum. These original pollution events gave rise to the term "smog" (a combination of smoke and fog). Events of this type have become much less severe since the 1950s in Western Europe and the US, as natural gas replaced coal as the primary source of home heating, industrial smokestacks were designed to emit at higher altitudes (where dispersion is more rapid), and industries were required to install pollution control equipment.Beginning in the 1950s, a new type of pollution, photochemical smog, became a major concern. Photochemical smog consists of ozone (O3) and other closely related species ("secondary pollutants") that are produced photochemically from directly

Photochemical Creation of Fluorescent Quantum Defects in Semiconducting Carbon Nanotube Hosts.

Science.gov (United States)

Wu, Xiaojian; Kim, Mijin; Kwon, Hyejin; Wang, YuHuang

2018-01-15

Quantum defects are an emerging class of synthetic single-photon emitters that hold vast potential for near-infrared imaging, chemical sensing, materials engineering, and quantum information processing. Herein, we show that it is possible to optically direct the synthetic creation of molecularly tunable fluorescent quantum defects in semiconducting single-walled carbon nanotube hosts through photochemical reactions. By exciting the host semiconductor with light that resonates with its electronic transition, we find that halide-containing aryl groups can covalently bond to the sp 2 carbon lattice. The introduced quantum defects generate bright photoluminescence that allows tracking of the reaction progress in situ. We show that the reaction is independent of temperature but correlates strongly with the photon energy used to drive the reaction, suggesting a photochemical mechanism rather than photothermal effects. This type of photochemical reactions opens the possibility to control the synthesis of fluorescent quantum defects using light and may enable lithographic patterning of quantum emitters with electronic and molecular precision. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A plasmaless, photochemical etch process for porous organosilicate glass films

Science.gov (United States)

Ryan, E. Todd; Molis, Steven E.

2017-12-01

A plasmaless, photochemical etch process using ultraviolet (UV) light in the presence of NH3 or O2 etched porous organosilicate glass films, also called pSiCOH films, in a two-step process. First, a UV/NH3 or UV/O2 treatment removed carbon (mostly methyl groups bonded to silicon) from a pSiCOH film by demethylation to a depth determined by the treatment exposure time. Second, aqueous HF was used to selectively remove the demethylated layer of the pSiCOH film leaving the methylated layer below. UV in the presence of inert gas or H2 did not demethylate the pSiCOH film. The depth of UV/NH3 demethylation followed diffusion limited kinetics and possible mechanisms of demethylation are presented. Unlike reactive plasma processes, which contain ions that can damage surrounding structures during nanofabrication, the photochemical etch contains no damaging ions. Feasibility of the photochemical etching was shown by comparing it to a plasma-based process to remove the pSiCOH dielectric from between Cu interconnect lines, which is a critical step during air gap fabrication. The findings also expand our understanding of UV photon interactions in pSiCOH films that may contribute to plasma-induced damage to pSiCOH films.

Controlling the photochemical reaction of an azastilbene derivative in water using a water-soluble pillar[6]arene.

Science.gov (United States)

Xia, Danyu; Wang, Pi; Shi, Bingbing

2017-09-20

Photochemistry plays an important role in our lives. It has also been a common tool in the laboratory to construct complicated systems from small molecules. Supramolecular chemistry provides an opportunity to solve some of the problems in controlling photochemical reactions via non-covalent interactions. By using confining media and weak interactions between the medium and the reactant molecule, the excited state behavior of molecules has been successfully manipulated. Pillararenes, a new class of macrocyclic hosts, have rarely been used in the field of photochemical investigations, such as the controlling of photo-induced reactions. Herein, we explore a synthetic macrocyclic host, a water-soluble pillar[6]arene, as a controlling tool to manipulate the photo-induced reactions (hydration) in water. A host-guest system in water based on a water-soluble pillar[6]arene and an azastilbene derivative, (E)-4,4'-dimethyl-4,4'-diazoniastilbene diiodide, has been constructed. Then this water-soluble pillar[6]arene was successfully employed to control the photohydration of the azastilbene derivative in water as a "protective agent".

Reduction and aggregation of silver in aqueous gelatin and silica suspensions

International Nuclear Information System (INIS)

Kapoor, S.; Lawless, D.; Kennepohl, P.; Meisel, D.; Serpone, N.

1994-01-01

The investigation of silver reduction and aggregation processes are of specific interest to the photographic industry, which relies heavily on photochemical equivalents of these reactions. Mechanistic insights into the formation of small silver clusters in aqueous solution have been obtained from both pulse and γ-radiolytic studies. This paper examines the reduction of silver ions and the subsequent formation of silver clusters in aqueous gelatin solutions and on colloidal silica particles using the pulse radiolysis technique. The aggregation processes are compared with the parallel reactions in aqueous solutions

The photochemical conversion of solar energy into electrical energy: Eosin-Arabinose system

Energy Technology Data Exchange (ETDEWEB)

Gangotri, K.M. [Department of Chemistry, Solar Energy Laboratory, Jai Narain Vyas University, Jodhpur 342 033, Rajasthan (India); Bhimwal, Mukesh Kumar [Solar Energy Laboratory, Jai Narain Vyas University, Jodhpur 342 033, Rajasthan (India)

2010-12-15

A photosensitizer -Eosin and a reductant- Arabinose have been used in the photogalvanic cell for photochemical conversion of solar energy into electrical energy. The generated photopotential and photocurrent are 679.0 mV and 240.0 {mu}A respectively. The maximum power of the cell is 162.96 {mu}W whereas the observed power at power point is 73.08 {mu}W. The conversion efficiency is 0.7026% and the fill factor is 0.2856 at the power point of the photogalvanic cell. The photogalvanic cell so developed can work for 85.0 min in dark if it is irradiated for 140.0 min i.e. the storage capacity of photogalvanic cell is 60.71%. The effects of different parameters on the electrical output of the photogalvanic cell have been observed. A mechanism has also been proposed for the photogeneration of electrical energy. (author)

Renormalization Group Reduction of Non Integrable Hamiltonian Systems

International Nuclear Information System (INIS)

Tzenov, Stephan I.

2002-01-01

Based on Renormalization Group method, a reduction of non integratable multi-dimensional Hamiltonian systems has been performed. The evolution equations for the slowly varying part of the angle-averaged phase space density and for the amplitudes of the angular modes have been derived. It has been shown that these equations are precisely the Renormalization Group equations. As an application of the approach developed, the modulational diffusion in one-and-a-half degrees of freedom dynamical system has been studied in detail

The chitosan - Porphyrazine hybrid materials and their photochemical properties.

Science.gov (United States)

Chełminiak-Dudkiewicz, Dorota; Ziegler-Borowska, Marta; Stolarska, Magdalena; Sobotta, Lukasz; Falkowski, Michal; Mielcarek, Jadwiga; Goslinski, Tomasz; Kowalonek, Jolanta; Węgrzynowska-Drzymalska, Katarzyna; Kaczmarek, Halina

2018-04-01

Three magnesium sulfanyl porphyrazines differing in the size of peripheral substituents (3,5-dimethoxybenzylsulfanyl, (3,5-dimethoxybenzyloxy)benzylsulfanyl, 3,5-bis[(3,5-bis[(3,5-dimethoxybenzyloxy)benzyloxy]benzylsulfanyl) were exposed to visible and ultraviolet radiation (UV A + B + C) in order to determine their photochemical properties. The course of photochemical reactions in dimethylformamide solutions and the ability of the systems to generate singlet oxygen were studied by UV-Vis spectroscopy, which additionally gave information on aggregation processes. The porphyrazines were found to be stable upon visible light irradiation conditions, but when exposed to high energy UV radiation, the efficient photodegradation of these macrocycles was observed. Therefore, these three magnesium sulfanyl porphyrazines were incorporated into chitosan matrix. The obtained thin films of chitosan doped with porphyrazines were subjected to polychromatic UV-radiation and studied by spectroscopic methods (UV-Vis, FTIR), scanning electron microscopy (SEM) and atomic force microscopy (AFM). Application of chitosan as a polymer matrix for porphyrazines was found to be successful method that effectively stopped the unwelcome degradation of macrocycles, thus worth considering for their photoprotection. In addition, the surface properties of the hybrid material were determined by contact angle measurements and calculation of surface free energy. Intermolecular interactions between these novel porphyrazines and chitosan were detected. The mechanism of photochemical reactions occurring in studied systems has been discussed. Copyright © 2018 Elsevier B.V. All rights reserved.

Enhanced Indirect Photochemical Transformation of Histidine and Histamine through Association with Chromophoric Dissolved Organic Matter.

Science.gov (United States)

Chu, Chiheng; Lundeen, Rachel A; Remucal, Christina K; Sander, Michael; McNeill, Kristopher

2015-05-05

Photochemical transformations greatly affect the stability and fate of amino acids (AAs) in sunlit aquatic ecosystems. Whereas the direct phototransformation of dissolved AAs is well investigated, their indirect photolysis in the presence of chromophoric dissolved organic matter (CDOM) is poorly understood. In aquatic systems, CDOM may act both as sorbent for AAs and as photosensitizer, creating microenvironments with high concentrations of photochemically produced reactive intermediates, such as singlet oxygen (1O2). This study provides a systematic investigation of the indirect photochemical transformation of histidine (His) and histamine by 1O2 in solutions containing CDOM as a function of solution pH. Both His and histamine showed pH-dependent enhanced phototransformation in the CDOM systems as compared to systems in which model, low-molecular-weight 1O2 sensitizers were used. Enhanced reactivity resulted from sorption of His and histamine to CDOM and thus exposure to elevated 1O2 concentrations in the CDOM microenvironment. The extent of reactivity enhancement depended on solution pH via its effects on the protonation state of His, histamine, and CDOM. Sorption-enhanced reactivity was independently supported by depressed rate enhancements in the presence of a cosorbate that competitively displaced His and histamine from CDOM. Incorporating sorption and photochemical transformation processes into a reaction rate prediction model improved the description of the abiotic photochemical transformation rates of His in the presence of CDOM.

Sunlight-Induced Photochemical Degradation of Methylene Blue by Water-Soluble Carbon Nanorods

Directory of Open Access Journals (Sweden)

Anshu Bhati

2016-01-01

Full Text Available Water-soluble graphitic hollow carbon nanorods (wsCNRs are exploited for their light-driven photochemical activities under outdoor sunlight. wsCNRs were synthesized by a simple pyrolysis method from castor seed oil, without using any metal catalyst or template. wsCNRs exhibited the light-induced photochemical degradation of methylene blue used as a model pollutant by the generation of singlet oxygen species. Herein, we described a possible degradation mechanism of methylene blue under the irradiation of visible photons via the singlet oxygen-superoxide anion pathway.

General Observation of Photocatalytic Oxygen Reduction to Hydrogen Peroxide by Organic Semiconductor Thin Films and Colloidal Crystals.

Science.gov (United States)

Gryszel, Maciej; Sytnyk, Mykhailo; Jakešová, Marie; Romanazzi, Giuseppe; Gabrielsson, Roger; Heiss, Wolfgang; Głowacki, Eric Daniel

2018-04-25

Low-cost semiconductor photocatalysts offer unique possibilities for industrial chemical transformations and energy conversion applications. We report that a range of organic semiconductors are capable of efficient photocatalytic oxygen reduction to H 2 O 2 in aqueous conditions. These semiconductors, in the form of thin films, support a 2-electron/2-proton redox cycle involving photoreduction of dissolved O 2 to H 2 O 2 , with the concurrent photooxidation of organic substrates: formate, oxalate, and phenol. Photochemical oxygen reduction is observed in a pH range from 2 to 12. In cases where valence band energy of the semiconductor is energetically high, autoxidation competes with oxidation of the donors, and thus turnover numbers are low. Materials with deeper valence band energies afford higher stability and also oxidation of H 2 O to O 2 . We found increased H 2 O 2 evolution rate for surfactant-stabilized nanoparticles versus planar thin films. These results evidence that photochemical O 2 reduction may be a widespread feature of organic semiconductors, and open potential avenues for organic semiconductors for catalytic applications.

Photochemical degradation of alachlor in water

Directory of Open Access Journals (Sweden)

Tajana Đurkić

2017-01-01

Full Text Available This study investigates the photochemical degradation of alachlor, a chloroacetanilide herbicide. All experiments were conducted in ultra-pure deionized water (ASTM Type I quality using direct ultraviolet (UV photolysis and the UV/H2O2 advanced oxidation process. The direct UV photolysis and UV/H2O2 experiments were conducted in a commercial photochemical reactor with a quartz reaction vessel equipped with a 253.7 nm UV low pressure mercury lamp (Philips TUV 16 W. The experimental results demonstrate that UV photolysis was very effective for alachlor degradation (up to 97% removal using a high UV fluence of 4200 mJ/cm2. The UV/H2O2 process promoted alachlor degradation compared to UV photolysis alone, with a high degree of decomposition (97% achieved at a significantly lower UV fluence of 600 mJ/cm2 when combined with 1 mg H2O2/L. The application of UV photolysis alone with a UV fluence of 600 mJ/cm2 gave a negligible 4% alachlor degradation. The photo degradation of alachlor, in both direct UV photolysis and the UV/H2O2 process, followed pseudo first-order kinetics. The degradation rate constant was about 6 times higher for the UV/H2O2 process than for UV photolysis alone.

[Photochemical internalisation (PCI): a further development of photodynamic therapy for the treatment of skin cancer].

Science.gov (United States)

Johansen, Pål; Berg, K; Selbo, P K; Hofbauer, G F L

2010-11-17

Recently, several new and non-invasive methods have been introduced for the treatment of skin cancers. Topical creams using the immune modulator imiquimod or the COX inhibitor diclofenac (with hyaluronic acid) are now registered for use against neoplasms such as basal or squamous cell carcinoma. Another modern treatment option is photodynamic therapy (PDT). A refined version of PDT, namely photochemical internalisation, is currently subject to a first clinical trial in patients with osteosarcoma, squamous cell carcinoma, head and neck cancer as well as adenocarcinoma of the breast. Preliminary results from this trial suggest that PCI seems to be a promising treatment.

Photochemically Synthesized Polyimides

Science.gov (United States)

Meador, Michael A.; Tyson, Daniel S.

2008-01-01

An alternative to the conventional approach to synthesis of polyimides involves the use of single monomers that are amenable to photopolymerization. Heretofore, the synthesis of polyimides has involved multiple-monomer formulations and heating to temperatures that often exceed 250 C. The present alternative approach enables synthesis under relatively mild conditions that can include room temperature. The main disadvantages of the conventional approach are the following: Elevated production temperatures can lead to high production costs and can impart thermal stresses to the final products. If the proportions of the multiple monomeric ingredients in a given batch are not exactly correct, the molecular weight and other physical properties of the final material could be reduced from their optimum or desired values. To be useful in the alternative approach, a monomer must have a molecular structure tailored to exploit Diels-Alder trapping of a photochemically generated ortho-quinodimethane. (In a Diels-Alder reaction, a diene combines with a dienophile to form molecules that contain six-membered rings.) In particular, a suitable monomer (see figure) contains ortho-methylbenzophenone connected to a dienophile (in this case, a maleimide) through a generic spacer group. Irradiation with ultraviolet light gives rise to a photochemical intermediate the aforementioned ortho-quinodimethane from the ortho-methylbenzophenone. This group may react with the dienophile on another such monomer molecule to produce an oligomer that, in turn may react in a stepgrowth manner to produce a polyimide. This approach offers several advantages in addition to those mentioned above: The monomer can be stored for a long time because it remains unreactive until exposed to light. Because the monomer is the only active starting ingredient, there is no need for mixing, no concern for ensuring correct proportions of monomers, and the purity of the final product material is inherently high. The use

Photochemical exchange reactions of thymine, uracil and their nucleosides with selected amino acids

International Nuclear Information System (INIS)

Shetlar, M.D.; Taylor, J.A.; Hom, K.

1984-01-01

The photoinduced exchange reactions of thymine with lysine at basic pH, using 254 nm light, have been studied. Three products have been isolated, namely, 6-amino-2-(1-thyminyl)hexanoic acid (Ia), 2-amino-6-(1-thyminyl)hexanoic acid (IIa) and 1-amino-5-(1-thyminyl)pentane (IIIa). Compound IIIa was shown to be a secondary product, produced by photochemical decarboxylation of Ia. Photochemical reaction of thymine with glycine and alanine at basic pH led, respectively, to formation of 2-(1-thyminyl)acetic acid (Ic) and 2-(1-thyminyl)propionic acid (Id). Compounds Ic and Id underwent photolysis to produce the decarboxylated secondary products 1-methylthymine and 1-ethylthymine, respectively. Thymidine reacts photochemically with glycine and alanine to produce the same products. Irradiation of DNA in the presence of lysine at basic pH led to the formation of the same products formed in the thymine-lysine system, namely Ia, IIa and IIIa. Uracil was found to undergo analogous photochemical exchange reactions with lysine to form 6-amino-2-(1-uracilyl)hexanoic acid (Ib), and 2-amino-6-(1-uracilyl)hexanoic acid (IIb). Compound Ib was found to undergo photodecarboxylation to form 1-amino-5-(1-uracilyl)pentane (IIIb), analogous to the secondary photoreaction of Ia. Photoreaction of uracil with 1,5-diaminopentane (cadaverine) likewise led to formation of IIIb. (author)

Wind Noise Reduction using Non-negative Sparse Coding

DEFF Research Database (Denmark)

Schmidt, Mikkel N.; Larsen, Jan; Hsiao, Fu-Tien

2007-01-01

We introduce a new speaker independent method for reducing wind noise in single-channel recordings of noisy speech. The method is based on non-negative sparse coding and relies on a wind noise dictionary which is estimated from an isolated noise recording. We estimate the parameters of the model ...... and discuss their sensitivity. We then compare the algorithm with the classical spectral subtraction method and the Qualcomm-ICSI-OGI noise reduction method. We optimize the sound quality in terms of signal-to-noise ratio and provide results on a noisy speech recognition task....

Dispersion and photochemical evolution of reactive pollutants in street canyons

Science.gov (United States)

Kwak, Kyung-Hwan; Baik, Jong-Jin; Lee, Kwang-Yeon

2013-05-01

Dispersion and photochemical evolution of reactive pollutants in street canyons with canyon aspect ratios of 1 and 2 are investigated using a computational fluid dynamics (CFD) model coupled with the carbon bond mechanism IV (CBM-IV). Photochemical ages of NOx and VOC are expressed as a function of the NO2-to-NOx and toluene-to-xylene ratios, respectively. These are found to be useful for analyzing the O3 and OH oxidation processes in the street canyons. The OH oxidation process (O3 oxidation process) is more pronounced in the upper (lower) region of the street canyon with a canyon aspect ratio of 2, which is characterized by more (less) aged air. In the upper region of the street canyon, O3 is chemically produced as well as transported downward across the roof level, whereas O3 is chemically reduced in the lower region of the street canyon. The O3 chemical production is generally favorable when the normalized photochemical ages of NOx and VOC are larger than 0.55 and 0.28, respectively. The sensitivities of O3 chemical characteristics to NOx and VOC emission rates, photolysis rate, and ambient wind speed are examined for the lower and upper regions of the street canyon with a canyon aspect ratio of 2. The O3 concentration and the O3 chemical production rate divided by the O3 concentration increase as the NOx emission rate decreases and the VOC emission rate and photolysis rate increase. The O3 concentration is less sensitive to the ambient wind speed than to other factors considered. The relative importance of the OH oxidation process compared to the O3 oxidation process increases with increasing NOx emission rate and photolysis rate and decreasing VOC emission rate. In this study, both O3 and OH oxidation processes are found to be important in street-canyon scale chemistry. The methodology of estimating the photochemical ages can potentially be adopted to neighborhood scale chemistry.

Photochemical production of ozone and control strategy for Southern Taiwan

Science.gov (United States)

Shiu, Chein-Jung; Liu, Shaw Chen; Chang, Chih-Chung; Chen, Jen-Ping; Chou, Charles C. K.; Lin, Chuan-Yao; Young, Chea-Yuan

An observation-based method (OBM) is developed to evaluate the ozone (O 3) production efficiency (O 3 molecules produced per NO x molecule consumed) and O 3 production rate ( P(O 3)) during a field campaign in southern Taiwan. The method can also provide an estimate of the concentration of OH. A key step in the method is to use observed concentrations of two aromatic hydrocarbons, namely ethylbenzene and m, p-xylene, to estimate the degree of photochemical processing and amounts of photochemically consumed NO x and NMHCs by OH. In addition, total oxidant (O 3+NO 2) instead of O 3 itself turns out to be very useful for representing ozone production in the OBM approach. The average O 3 production efficiency during the field campaign in Fall (2003) is found to be about 10.2±3.9. The relationship of P(O 3) with NO x is examined and compared with a one-dimensional (1D) photochemical model. Values of P(O 3) derived from the OBM are slightly lower than those calculated in the 1D model. However, OH concentrations estimated by the OBM are about a factor of 2 lower than the 1D model. Fresh emissions, which affect the degree of photochemical processing appear to be a major cause of the underestimate. We have developed a three-dimensional (3D) OBM O 3 production diagram that resembles the EKMA ozone isopleth diagram to study the relationship of the total oxidant versus O 3 precursors. The 3D OBM O 3 production diagram suggests that reducing emissions of NMHCs are more effective in controlling O 3 than reducing NO x. However, significant uncertainties remain in the OBM, and considerable more work is required to minimize these uncertainties before a definitive control strategy can be reached. The observation-based approach provides a good alternative to measuring peroxy radicals for evaluating the production of O 3 and formulating O 3 control strategy in urban and suburban environments.

Photochemical Reactions of Particulate Organic Matter: Deciphering the Role of Direct and Indirect Processes

Science.gov (United States)

Carrasquillo, A. J.; Gelfond, C. E.; Kocar, B. D.

2016-12-01

Photochemical reactions of natural organic matter (NOM) represent potentially important pathways for biologically recalcitrant material to be chemically altered in aquatic systems. Irradiation can alter the physical state of organic matter by facilitating the cycling between the particulate (POM) and dissolved (DOM) pools, however, a molecular level understanding of this chemically dynamic system is currently lacking. Photochemical reactions of a target molecule proceed by the direct absorption of a photon, or through reaction with a second photolytically generated species (i.e. the hydroxyl radical, singlet oxygen, excited triplet state NOM, hydrogen peroxide, etc.). Here, we isolate the major direct and indirect photochemical reactions of a lignocellulose-rich POM material (Phragmites australis) to determine their relative importance in changing the the chemical structure of the parent POM, and in the production of DOM. We measured POM molecular structure using a combination of NMR and FTIR for bulk analyses and scanning transmission x-ray microscopy (STXM) for spatially resolved chemistry, while the chemical composition of photo-produced DOM was measured using ultra-high resolution mass spectrometry. Results are discussed in the context of the differences in chemical composition of both NOM pools resulting from the isolated photochemical pathways. All treatments result in an increase in DOM with reaction time, indicating that the larger POM matrix is likely fragmenting into smaller more soluble species. Spectroscopic measurements, on the other hand, point to functionalization reactions which increase the abundance of alcohol, acid, and carbonyl moieties in both carbon pools. This unique dataset provides new insight into how photochemical reactions alter the chemical composition of NOM while highlighting the relative importance of indirect pathways.

Ammonia removal from leachate by photochemical process using H2O2

Directory of Open Access Journals (Sweden)

Giovani Archanjo Brota

2010-08-01

Full Text Available In this work, it was studied the optimization of the photochemical process using H2O2/UV in order to reduce the concentration of ammonia in leachate. It was used landfills leachate previously treated in the development of studies. A photochemical reactor with the capacity of 1.7 liters equipped with refrigeration system and recirculation of leachate was employed in the research. The influence of temperature, the light bulb power, the concentration of H2O2 and treatment time were tested during the study. A removal of 97% of ammonia was observed at 90 min.

Photochemical Aryl Radical Cyclizations to Give (E-3-Ylideneoxindoles

Directory of Open Access Journals (Sweden)

Michael Gurry

2014-09-01

Full Text Available (E-3-Ylideneoxindoles are prepared in methanol in reasonable to good yields, as adducts of photochemical 5-exo-trig of aryl radicals, in contrast to previously reported analogous radical cyclizations initiated by tris(trimethylsilylsilane and azo-initiators that gave reduced oxindole adducts.

Molecular-beam studies of primary photochemical processes

Energy Technology Data Exchange (ETDEWEB)

Lee, Y.T.

1982-12-01

Application of the method of molecular-beam photofragmentation translational spectroscopy to the investigation of primary photochemical processes of polyatomic molecules is described. Examples will be given to illustrate how information concerning the energetics, dynamics, and mechanism of dissociation processes can be obtained from the precise measurements of angular and velocity distributions of products in an experiment in which a well-defined beam of molecules is crossed with a laser.

Molecular-beam studies of primary photochemical processes

International Nuclear Information System (INIS)

Lee, Y.T.

1982-12-01

Application of the method of molecular-beam photofragmentation translational spectroscopy to the investigation of primary photochemical processes of polyatomic molecules is described. Examples will be given to illustrate how information concerning the energetics, dynamics, and mechanism of dissociation processes can be obtained from the precise measurements of angular and velocity distributions of products in an experiment in which a well-defined beam of molecules is crossed with a laser

Implications of imprecision in kinetic rate data for photochemical model calculations

Energy Technology Data Exchange (ETDEWEB)

Stewart, R.W.; Thompson, A.M. [National Aeronautics and Space Administration, Greenbelt, MD (United States). Goddard Space Flight Center

1997-12-31

Evaluation of uncertainties in photochemical model calculations is of great importance to scientists performing assessment modeling. A major source of uncertainty is the measurement imprecision inherent in photochemical reaction rate data that modelers rely on. A rigorous method of evaluating the impact of data imprecision on computational uncertainty is the study of error propagation using Monte Carlo techniques. There are two problems with the current implementation of the Monte Carlo method. First, there is no satisfactory way of accounting for the variation of imprecision with temperature in 1, 2, or 3D models; second, due to its computational expense, it is impractical in 3D model studies. These difficulties are discussed. (author) 4 refs.

Implications of imprecision in kinetic rate data for photochemical model calculations

Energy Technology Data Exchange (ETDEWEB)

Stewart, R W; Thompson, A M [National Aeronautics and Space Administration, Greenbelt, MD (United States). Goddard Space Flight Center

1998-12-31

Evaluation of uncertainties in photochemical model calculations is of great importance to scientists performing assessment modeling. A major source of uncertainty is the measurement imprecision inherent in photochemical reaction rate data that modelers rely on. A rigorous method of evaluating the impact of data imprecision on computational uncertainty is the study of error propagation using Monte Carlo techniques. There are two problems with the current implementation of the Monte Carlo method. First, there is no satisfactory way of accounting for the variation of imprecision with temperature in 1, 2, or 3D models; second, due to its computational expense, it is impractical in 3D model studies. These difficulties are discussed. (author) 4 refs.

Effects of the antioxidant moieties of dissolved organic matter on triplet-sensitized phototransformation processes: Implications for the photochemical modeling of sulfadiazine.

Science.gov (United States)

Vione, Davide; Fabbri, Debora; Minella, Marco; Canonica, Silvio

2018-01-01

Previous studies have shown that the photodegradation of some pollutants, induced by the excited triplet states of chromophoric dissolved organic matter ( 3 CDOM*), can be inhibited by back-reduction processes carried out by phenolic antioxidants occurring in dissolved organic matter (DOM). Here, for the first time to our knowledge, we included such an inhibition effect into a photochemical model and applied the model predictions to sulfadiazine (SDZ), a sulfonamide antibiotic that occurs in surface waters in two forms, neutral HSDZ and anionic SDZ - (pK a  = 6.5). The input parameters of the photochemical model were obtained by means of dedicated experiments, which showed that the inhibition effect was more marked for SDZ - than for HSDZ. Compared to the behavior of 2,4,6-trimethylphenol, which does not undergo antioxidant inhibition when irradiated in natural water samples, the back-reduction effect on the degradation of SDZ was proportional to the electron-donating capacity of the DOM. According to the model results, direct photolysis and OH reaction would account for the majority of both HSDZ and SDZ - photodegradation in waters having low dissolved organic carbon (DOC DOC values (>3-4 mgC L -1 ) and despite the back-reduction processes, the 3 CDOM* reactions are expected to account for the majority of HSDZ phototransformation. In the case of SDZ - at high DOC, most of the photodegradation would be accounted for by direct photolysis. The relative importance of the triplet-sensitized phototransformation of both SDZ - and (most importantly) HSDZ is expected to increase with increasing DOC, even in the presence of back reduction. An increase in water pH, favoring the occurrence of SDZ - with respect to HSDZ, would enhance direct photolysis at the expense of triplet sensitization. SDZ should be fairly photolabile under summertime sunlight, with predicted half-lives ranging from a few days to a couple of months depending on water conditions. Copyright © 2017

Bleaching herbicide norflurazon inhibits phytoene desaturase by competition with the cofactors.

Science.gov (United States)

Breitenbach, J; Zhu, C; Sandmann, G

2001-11-01

Cofactor requirement was determined for the heterologous expressed phytoene desaturases from the cyanobacterium Synechococcus and the higher plant Gentiana lutea. The cyanobacterial enzyme is dependent on either NAD(P) or plastoquinone, whereas only quinones such as plastoquinone can function as a cofactor for the phytoene desaturase from G. lutea. Enzyme kinetic studies were carried out to determine a possible competition between the cofactors and the bleaching herbicide norflurazon. For the Synechococcus enzyme, competition between norflurazon and NADP, as well as plastoquinone, could be demonstrated. The K(m) values for these cofactors were 6.6 mM and 0.23 microM, respectively. Inhibition of the phytoene desaturase from G. lutea by norflurazon was also competitive with respect to plastoquinone. The K(m) values of both enzymes for plastoquinone were very close.

The photochemical reaction of hydrocarbons under extreme thermobaric conditions

Science.gov (United States)

Serovaiskii, Aleksandr; Kolesnikov, Anton; Mukhina, Elena; Kutcherov, Vladimir

2017-10-01

The photochemical reaction of hydrocarbons was found to play an important role in the experiments with the synthetic petroleum conducted in Diamond Anvil Cell (DAC). Raman spectroscopy with a green laser (514.5 nm) was used for in situ sample analysis. This photochemical effect was investigated in the pressure range of 0.7-5 GPa, in the temperature interval from the ambient conditions to 450°C. The power of laser used in these experiment series was from 0.05 W to 0.6 W. The chemical transformation was observed when the necessary threshold pressure (~2.8 GPa) was reached. This transformation correlated with the luminescence appearance on the Raman spectra and a black opaque spot in the sample was observed in the place where the laser focus was forwarded. The exposure time and laser power (at least in the 0.1-0.5 W range) did not play a role in the 0.1-0.5 GPa range.

Reduction Assessment of Agricultural Non-Point Source Pollutant Loading

OpenAIRE

Fu, YiCheng; Zang, Wenbin; Zhang, Jian; Wang, Hongtao; Zhang, Chunling; Shi, Wanli

2018-01-01

NPS (Non-point source) pollution has become a key impact element to watershed environment at present. With the development of technology, application of models to control NPS pollution has become a very common practice for resource management and Pollutant reduction control in the watershed scale of China. The SWAT (Soil and Water Assessment Tool) model is a semi-conceptual model, which was put forward to estimate pollutant production & the influences on water quantity-quality under different...

Photochemical Reactivity of Dissolved Organic Matter in Boreal Lakes

Science.gov (United States)

Gu, Y.; Vuorio, K.; Tiirola, M.; Perämäki, S.; Vahatalo, A.

2016-12-01

Boreal lakes are rich in dissolved organic matter (DOM) that terrestrially derived from forest soil and wetland, yet little is known about potential for photochemical transformation of aquatic DOM in boreal lakes. Transformation of chromophoric dissolved organic matter (CDOM) can decrease water color and enhance microbial mineralization, affecting primary production and respiration, which both affect the CO2 balance of the lakes. We used laboratory solar radiation exposure experiments with lake water samples collected from 54 lakes located in Finland and Sweden, representing different catchment composition and watershed location to assess photochemical reactivity of DOM. The pH of water samples ranged from 5.4 to 8.3, and the concentrations of dissolved iron (Fe) were between samples received simulated solar radiation corresponding to a daily dose of sunlight, and photomineralization of dissolved organic carbon (DOC) to dissolved inorganic carbon (DIC) was measured for determination of spectral apparent quantum yields (AQY). During irradiation, photobleaching decreased the absorption coefficients of CDOM at 330 nm between 4.9 and 79 m-1 by 0.5 to 11 m-1. Irradiation generated DIC from 2.8 to 79 μmol C L-1. The AQY at 330 nm ranged between 31 and 273 ×10-6 mol C mol photons-1 h-1, which was correlated positively with concentration of dissolved Fe, and negatively with pH. Further statistical analyze indicated that the interaction between pH and Fe may explain much of the photochemical reactivity of DOM in the examined lakes, and land cover concerns main catchment areas also can have impact on the photoreaction process. This study may suggest how environmental conditions regulate DOM photomineralization in boreal lakes.

Effect of latitude on the potential for formation of photochemical smog

Energy Technology Data Exchange (ETDEWEB)

Neiboer, H [Central Laboratorium TNO, Delft, Netherlands; Carter, W P.L.; Lloyd, A C; Pitts, Jr, J N

1976-01-01

The effect of latitude on the potential for the formation of photochemical smog has been assessed. Calculations suggest that at the summer solstice, the integrated sunlight intensity at Rotterdam or Fairbanks (Alaska) is very similar to that in Los Angeles. Computations carried out, assuming the same pollutant emission inventory for the three locations, showed that ozone and PAN dosages depend more on the integrated light intensity than on the nature of the light intensity distribution with time. Therefore, if factors such as emissions and meteorological conditions are equal, the potential for significant photochemical smog formation during the summer months is similar for Los Angeles (34/sup 0/N) and northern cities such as Rotterdam (52/sup 0/N) and Nome or Fairbanks, Alaska (65/sup 0/N).

Seasonal and Diurnal Variations of Atmospheric Non-Methane Hydrocarbons in Guangzhou, China

Directory of Open Access Journals (Sweden)

Longfeng Li

2012-05-01

Full Text Available In recent decades, high ambient ozone concentrations have become one of the major regional air quality issues in the Pearl River Delta (PRD region. Non-methane hydrocarbons (NMHCs, as key precursors of ozone, were found to be the limiting factor in photochemical ozone formation for large areas in the PRD. For source apportioning of NMHCs as well as ozone pollution control strategies, it is necessary to obtain typical seasonal and diurnal patterns of NMHCs with a large pool of field data. To date, few studies have focused on seasonal and diurnal variations of NMHCs in urban areas of Guangzhou. This study explored the seasonal variations of most hydrocarbons concentrations with autumn maximum and spring minimum in Guangzhou. The diurnal variations of most anthropogenic NMHCs typically showed two-peak pattern with one at 8:00 in the morning and another at 20:00 in the evening, both corresponding to traffic rush hours in Guangzhou, whereas isoprene displayed a different bimodal diurnal curve. Propene, ethene, m, p-xylene and toluene were the four largest contributors to ozone formation in Guangzhou, based on the evaluation of individual NMHCs’ photochemical reactivity. Therefore, an effective strategy for controlling ozone pollution may be achieved by the reduction of vehicle emissions in Guangzhou.

Photochemical Synthesis and Properties of Colloidal Copper, Silver and Gold Adsorbed on Quartz

International Nuclear Information System (INIS)

Loginov, Anatoliy V.; Gorbunova, Valentina V.; Boitsova, Tatiana B.

2002-01-01

Original methods for the photochemical production of stable copper, silver and gold colloids in the form of films on quartz, and dispersion in liquids were devised. It is shown that photochemical synthesis of colloidal metals is a difficult multiphase process, and includes the formation of low-valence forms of Cu(I), Au(I) and nonmetal clusters, colloidal particles and their agglomerates. Cluster stabilization and further growth to colloidal particles are achieved by adsorption onto the solid surface (quartz) or by increasing the viscosity of photolyte. In the absence of these methods of stabilization, the processes of intermediate reoxidation to Cu(II) and Au(III) and agglomeration of Ag and Au colloids proceed in a photolyte. Adsorption and the rate of cluster growth on a quartz surface are speeded up by the action of monochromatic UV light. Experimental models of the mechanism of colloidal formation are suggested. The dependence of the growth rate and the properties of the colloids on conditions of the photochemical procedure (energy and light intensity, concentration of initial complex) has been established

Biochemical and photochemical feedbacks of acute Cd toxicity in Juncus acutus seedlings: The role of non-functional Cd-chlorophylls

Science.gov (United States)

Santos, D.; Duarte, B.; Caçador, I.

2015-12-01

The increasing metal pollution in salt marshes and its influence on the plants that inhabit these ecosystems, has become a major concern with serious implications on the species establishment. Juncus acutus is a highly common halophyte specie in Portuguese marshes. Seeds from his specie were exposed to a range of different Cd concentrations (0.05, 0.1, 0.5 and 1 μM) in order to evaluate the effects of acute Cd stress on seed germination and growth as well as on seedling pigment composition, photosynthetic apparatus and oxidative stress biomarkers. Seedling length was higher than in control in every Cd treatment, however biomass showed a decrease. It was also observed that increasing Cd treatments, lead to a proportional increase in the Cd tissue concentration. Also the Cd-substituted chlorophylls showed an increase with increasing Cd doses that were applied. This substitution results in a non-functional chlorophyll molecule, highly unstable under moderate light intensities which inevitably reduces the efficiency of the LHC II. As consequence, there was a decrease in the use-efficiency of the harvested energy, leading to a decay in the photosynthetic capacity and energy accumulation, which was dissipated as heat. As for the antioxidant enzymes, SOD and APX presented higher activity, responding to increasing cadmium concentrations. Thus, becomes evident that Cd affects negatively, both biochemically and photochemically, the establishment by seed process of J. acutus highlighting the potential of the use of this specie seed as potential sentinel and ecotoxicity test in extreme conditions.

Global emissions and models of photochemically active compounds

International Nuclear Information System (INIS)

Penner, J.E.; Atherton, C.S.; Graedel, T.E.

1993-01-01

Anthropogenic emissions from industrial activity, fossil fuel combustion, and biomass burning are now known to be large enough (relative to natural sources) to perturb the chemistry of vast regions of the troposphere. A goal of the IGAC Global Emissions Inventory Activity (GEIA) is to provide authoritative and reliable emissions inventories on a 1 degree x 1 degree grid. When combined with atmospheric photochemical models, these high quality emissions inventories may be used to predict the concentrations of major photochemical products. Comparison of model results with measurements of pertinent species allows us to understand whether there are major shortcomings in our understanding of tropospheric photochemistry, the budgets and transport of trace species, and their effects in the atmosphere. Through this activity, we are building the capability to make confident predictions of the future consequences of anthropogenic emissions. This paper compares IGAC recommended emissions inventories for reactive nitrogen and sulfur dioxide to those that have been in use previously. We also present results from the three-dimensional LLNL atmospheric chemistry model that show how emissions of anthropogenic nitrogen oxides might potentially affect tropospheric ozone and OH concentrations and how emissions of anthropogenic sulfur increase sulfate aerosol loadings

Photochemical and other air pollutions in the Netherlands

Energy Technology Data Exchange (ETDEWEB)

Floor, H.

1975-01-01

Together with the State Institute of Public Health and the Royal Dutch Meteorological Institute, the Institute of Phytopathological Research continued investigations on incidence of air pollution in the country. The main purpose is to measure the effects of air pollution on indicator plants and to detect over the years which components separately or perhaps together damage indicator plants. In 1974, the network of experimental fields in the Netherlands was completed. From April until October, 29 fields were inspected weekly for typical symptoms of air pollution. Just as in the preceding year O3 caused most injury of the photochemical air pollutants, as shown by Spinacia oleracea and Nicotiana tabacum. Other photochemical air pollutants like PAN, and the pollutants SO2, NO/sub x/ and ethylene caused little injury to the indicator plants Urtica urens, Poa annua, Medicago sativa, Petunia nyctaginiflora and Solanum tuberosum. Symptoms of damage on Tulipa gesneriana, Gladiolus gandavensis and Freesia refracta indicated air pollution by HF in all experimental fields, but especially in the south of the country. The F determination in the air by means of the limed paper method established the results with the indicator plants.

Photochemical stability of electrochromic polymers and devices

DEFF Research Database (Denmark)

Jensen, Jacob; Madsen, Morten Vesterager; Krebs, Frederik C

2013-01-01

The stability of fully printed flexible organic electrochromics based on 11 different conjugated polymers is explored from the fundamental chemical degradation level to the operational device level. The photochemical stability of the electrochromic polymers (ECPs) is studied enabling an analysis ...... based on flexible barrier substrates exhibit increased stability and are indeed viable in devices such as shading elements, light management systems, displays with low switching speed requirements and signage. © 2013 The Royal Society of Chemistry....

Cherenkov light as a source of photochemical reactions in irradiated solutions of nitrile of malachite green

Energy Technology Data Exchange (ETDEWEB)

Stuglik, Z; Grodkowski, J

1986-10-01

Experimental data on photochemical activity of Cherenkov light are presented. Malachite green leucocyanide was used to detect the photochemical effects. The G value of Cherenkov light from the region 200-330 nm (number of quanta formed per 100 eV absorbed energy of ionizing radiation) in ethanol was estimated to be in the range of 0.0027-0.049. 14 references.

Cherenkov light as a source of photochemical reactions in irradiated solutions of nitrile of malachite green

International Nuclear Information System (INIS)

Stuglik, Z.; Grodkowski, J.

1986-01-01

Experimental data on photochemical activity of Cherenkov light are presented. Malachite green leucocyanide was used to detect the photochemical effects. The G value of Cherenkov light from the region 200-330 nm (number of quanta formed per 100 eV absorbed energy of ionizing radiation) in ethanol was estimated to be in the range of 0.0027-0.049. (author)

Vertical observation of molecular hydrogen and carbon monoxide: Implication for non-photochemical H2 production at ocean surface and subsurface

Science.gov (United States)

Kawagucci, S.; Narita, T.; Obata, H.; Ogawa, H.; Gamo, T.

2009-12-01

Biological nitrogen fixation is a key metabolism controlling marine N-cycling and also known as a main H2 source. Recently, it was proposed that a monitoring of surface H2 concentration could be used quickly to figure out the spatial extent of biological nitrogen fixation activity without onboard incubation required for currently used methods for detecting the activity. However, H2 behavior in ocean water was still unresolved. This study carried out vertical observation of H2 and CO concentrations in south of Japan, western North Pacific. Because carbon monoxide, CO, in seawater has no relation with nitrogen fixation metabolism and is produced dominantly by the photochemical reaction, which is an altanative H2 source, simultaneous observation and comparison of H2 and CO concentration is helpful to investigate H2 behavior in ocean water. Reductive gases in seawater were observed during the R/V Tansei-maru KT-08-14 cruise by using a wired CTD-CMS (CTD-carousel multiple sampling) system to conduct vertical sampling (at most 200 m depth) and by using a plastic bucket for sampling surface seawater. The sample in the Niskin-X bottle was directed to the bottom of a 120 mL brown-colored glass vial allowed to overflow by 2 volumes before the tube was slowly withdrawn. After the addition of 0.5 mL HgCl2-saturated solution for poisoning, the PTFE-lined butyl-gum septum was used to cap the vials. Molecular hydrogen (H2) and carbon monoxide (CO) were analyzed at an onboard laboratory within 6 hours after subsampling. 20 mL of sample water was substituted by 20 mL of H2- and CO-free air using a gas-tight syringe; then the vial was put on an automatic shaker and shaken upside down for 6 minutes to achieve a complete equilibrium between the dissolved and head space gases in the vial. The equilibrated headspace was taken by another gas-tight syringe and then injected into a gas chromatograph equipped with a trace reduced gas detector. Vertical distribution of dissolved H2 and CO

Hydrogen production by Chlamydomonas reinhardtii: an elaborate interplay of electron sources and sinks

International Nuclear Information System (INIS)

Hemschemeier, A; Happe, T.; Fouchard, S; Cournac, L; Peltier, G.

2008-01-01

The unicellular green alga Chlamydomonas reinhardtii possesses a [FeFe]-hydrogenase HydA1 (EC 1.12.7.2), which is coupled to the photosynthetic electron transport chain. Large amounts of H 2 are produced in a light-dependent reaction for several days when C. reinhardtii cells are deprived of sulfur. Under these conditions, the cells drastically change their physiology from aerobic photosynthetic growth to an anaerobic resting state. The understanding of the underlying physiological processes is not only important for getting further insights into the adaptability of photosynthesis, but will help to optimize the biotechnological application of algae as H 2 producers. Two of the still most disputed questions regarding H 2 generation by C. reinhardtii concern the electron source for H 2 evolution and the competition of the hydrogenase with alternative electron sinks. We analyzed the H 2 metabolism of S-depleted C. reinhardtii cultures utilizing a special mass spectrometer setup and investigated the influence of photosystem II (PSII)- or ribulose-bisphosphate-carboxylase/oxygenase (Rubisco)-deficiency. We show that electrons for H 2 -production are provided both by PSII activity and by a non-photochemical plastoquinone reduction pathway, which is dependent on previous PSII activity. In a Rubisco-deficient strain, which produces H 2 also in the presence of sulfur, H 2 generation seems to be the only significant electron sink for PSII activity and rescues this strain at least partially from a light-sensitive phenotype.The latter indicates that the down-regulation of assimilatory pathways in S-deprived C. reinhardtii cells is one of the important prerequisites for a sustained H 2 evolution. (authors)

Photochemical smog modeling for assessment of potential impacts of different management strategies on air quality of the Bangkok Metropolitan Region, Thailand.

Science.gov (United States)

Oanh, Nguyen Thi Kim; Zhang, Baoning

2004-10-01

A photochemical smog model system, the Variable-Grid Urban Airshed Model/Systems Applications International Mesoscale Model (UAM-V/SAIMM), was used to investigate photochemical pollution in the Bangkok Metropolitan Region (BMR). The model system was first applied to simulate a historical photochemical smog episode of two days (January 13-14, 1997) using the 1997 anthropogenic emission database available at the Pollution Control Department and an estimated biogenic emission. The output 1-hr ozone (O3) for BMR, however, did not meet the U.S. Environmental Protection Agency suggested performance criteria. The simulated minimum and maximum O3 values in the domain were much higher than the observations. Multiple model runs with different precursor emission reduction scenarios showed that the best model performance with the simulated 1-hr O3 meeting all the criteria was obtained when the volatile organic compound (VOC) and oxides of nitrogen (NOx) emission from mobile source reduced by 50% and carbon monoxide by 20% from the original database. Various combinations of anthropogenic and biogenic emissions in Bangkok and surrounding provinces were simulated to assess the contribution of different sources to O3 pollution in the city. O3 formation in Bangkok was found to be more VOC-sensitive than NOx-sensitive. To attain the Thailand ambient air quality standard for 1-hr O3 of 100 ppb, VOC emission in BMR should be reduced by 50-60%. Management strategies considered in the scenario study consist of Stage I, Stage II vapor control, replacement of two-stroke by four-stroke motorcycles, 100% compressed natural gas bus, 100% natural gas-fired power plants, and replacement of methyltertiarybutylether by ethanol as an additive for gasoline.

40 CFR 52.430 - Photochemical Assessment Monitoring Stations (PAMS) Program.

Science.gov (United States)

2010-07-01

... 40 Protection of Environment 3 2010-07-01 2010-07-01 false Photochemical Assessment Monitoring Stations (PAMS) Program. 52.430 Section 52.430 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Natural Resources & Environmental Control submitted a plan for the establishment and implementation of a...

40 CFR 52.480 - Photochemical Assessment Monitoring Stations (PAMS) Program.

Science.gov (United States)

2010-07-01

... of Columbia's Department of Consumer and Regulatory Affairs submitted a plan for the establishment... 40 Protection of Environment 3 2010-07-01 2010-07-01 false Photochemical Assessment Monitoring Stations (PAMS) Program. 52.480 Section 52.480 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY...

40 CFR 52.1080 - Photochemical Assessment Monitoring Stations (PAMS) Program.

Science.gov (United States)

2010-07-01

... Stations (PAMS) Program. 52.1080 Section 52.1080 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... § 52.1080 Photochemical Assessment Monitoring Stations (PAMS) Program. On March 24, 1994 Maryland's... Assessment Monitoring Stations (PAMS) Program as a state implementation plan (SIP) revision, as required by...

Influence of photochemical transformations upon optic-spectral characteristics of iodine cadmium crystals with copper dopant

International Nuclear Information System (INIS)

Novosad, S.S.

2000-01-01

The influence of photochemical transformations upon absorption. X-ray, photo- and thermostimulated luminescence of crystals CdI 2 :CuI, CdI 2 :CuI and CdI 2 :CuO grown by Stockbarger - Czochralski method has been studied. The photochemical reactions in crystals of iodine cadmium with the dopant of copper leads to reducing the intensity of X-ray, photo- and thermostimulated luminescence, the appearance of new luminescent centers is not observed

Photocatalytic Reduction of Hexavalent Chromium Induced by Photolysis of Ferric/tartrate Complex

Energy Technology Data Exchange (ETDEWEB)

Feng, Xianghua; Ding, Shimin; Zhang, Lixian [Yangtze Normal Univ., Fuling (China)

2012-11-15

Photocatalytic reduction of hexavalent chromium (Cr(VI)) in ferric-tartrate system under irradiation of visible light was investigated. Effects of light resources, initial pH value and initial concentration of various reactants on Cr(VI) photocatalytic reduction were studied. Photoreaction kinetics was discussed and a possible photochemical pathway was proposed. The results indicate that Fe(III)-tartrate system is able to rapidly and effectively photocatalytically reduce Cr(VI) utilizing visible light. Initial pH variations results in the concentration changes of Fe(III)-tartrate complex in this system, and pH at 3.0 is optimal for Cr(VI) photocatalytic reduction. Efficiency of Cr(VI) photocatalytic reduction increases with increasing initial concentrations of Cr(VI), Fe(III) and tartrate. Kinetics analysis indicates that initial Fe(III) concentration affects Cr(VI) photoreduction most significantly.

Photocatalytic Reduction of Hexavalent Chromium Induced by Photolysis of Ferric/tartrate Complex

International Nuclear Information System (INIS)

Feng, Xianghua; Ding, Shimin; Zhang, Lixian

2012-01-01

Photocatalytic reduction of hexavalent chromium (Cr(VI)) in ferric-tartrate system under irradiation of visible light was investigated. Effects of light resources, initial pH value and initial concentration of various reactants on Cr(VI) photocatalytic reduction were studied. Photoreaction kinetics was discussed and a possible photochemical pathway was proposed. The results indicate that Fe(III)-tartrate system is able to rapidly and effectively photocatalytically reduce Cr(VI) utilizing visible light. Initial pH variations results in the concentration changes of Fe(III)-tartrate complex in this system, and pH at 3.0 is optimal for Cr(VI) photocatalytic reduction. Efficiency of Cr(VI) photocatalytic reduction increases with increasing initial concentrations of Cr(VI), Fe(III) and tartrate. Kinetics analysis indicates that initial Fe(III) concentration affects Cr(VI) photoreduction most significantly

Open burning of rice, corn and wheat straws: primary emissions, photochemical aging, and secondary organic aerosol formation

Science.gov (United States)

Fang, Zheng; Deng, Wei; Zhang, Yanli; Ding, Xiang; Tang, Mingjin; Liu, Tengyu; Hu, Qihou; Zhu, Ming; Wang, Zhaoyi; Yang, Weiqiang; Huang, Zhonghui; Song, Wei; Bi, Xinhui; Chen, Jianmin; Sun, Yele; George, Christian; Wang, Xinming

2017-12-01

Agricultural residues are among the most abundant biomass burned globally, especially in China. However, there is little information on primary emissions and photochemical evolution of agricultural residue burning. In this study, indoor chamber experiments were conducted to investigate primary emissions from open burning of rice, corn and wheat straws and their photochemical aging as well. Emission factors of NOx, NH3, SO2, 67 non-methane hydrocarbons (NMHCs), particulate matter (PM), organic aerosol (OA) and black carbon (BC) under ambient dilution conditions were determined. Olefins accounted for > 50 % of the total speciated NMHCs emission (2.47 to 5.04 g kg-1), indicating high ozone formation potential of straw burning emissions. Emission factors of PM (3.73 to 6.36 g kg-1) and primary organic carbon (POC, 2.05 to 4.11 gC kg-1), measured at dilution ratios of 1300 to 4000, were lower than those reported in previous studies at low dilution ratios, probably due to the evaporation of semi-volatile organic compounds under high dilution conditions. After photochemical aging with an OH exposure range of (1.97-4.97) × 1010 molecule cm-3 s in the chamber, large amounts of secondary organic aerosol (SOA) were produced with OA mass enhancement ratios (the mass ratio of total OA to primary OA) of 2.4-7.6. The 20 known precursors could only explain 5.0-27.3 % of the observed SOA mass, suggesting that the major precursors of SOA formed from open straw burning remain unidentified. Aerosol mass spectrometry (AMS) signaled that the aged OA contained less hydrocarbons but more oxygen- and nitrogen-containing compounds than primary OA, and carbon oxidation state (OSc) calculated with AMS resolved O / C and H / C ratios increased linearly (p < 0.001) with OH exposure with quite similar slopes.

The study on laser photochemical process of Diazonaphthoquinon-Cresol system

International Nuclear Information System (INIS)

Wei Jie; Huang Yu Li; Wang Wenke

1999-01-01

The kinetic process of laser photochemical reaction of diazonaphthoquinon-cresol system was studied by using laser spectrophotofluorimetry and laser induced fluorescence attenuation method. The nonlinear relationship between photodecomposition rate of the sensitizer and laser power, exposure time and concentration of solutions was discussed in detail

Photochemical reactions of aqueous plutonium systems

International Nuclear Information System (INIS)

Friedman, H.A.; Toth, L.M.; Bell, J.T.

1977-01-01

The photochemical shift of the Pu 4+ disproportionation equilibrium in aqueous perchloric acid solutions has been measured and shown to be reversible. Ratios of equilibrium quotients between light and dark conditions have been measured for 0.01 M Pu ion concentrations in 0.53 to 1.24 N acid solutions exposed to 0.5 Watt of UV light. The photodecomposition of time- and temperature-aged Pu(IV) polymers in perchloric and nitric acid solutions have been examined as a function of aging conditions. Effects similar to those seen previously for fresh polymers have been observed in the aged perchloric acid solutions. (author)

Highly uniform resistive switching properties of amorphous InGaZnO thin films prepared by a low temperature photochemical solution deposition method.

Science.gov (United States)

Hu, Wei; Zou, Lilan; Chen, Xinman; Qin, Ni; Li, Shuwei; Bao, Dinghua

2014-04-09

We report on highly uniform resistive switching properties of amorphous InGaZnO (a-IGZO) thin films. The thin films were fabricated by a low temperature photochemical solution deposition method, a simple process combining chemical solution deposition and ultraviolet (UV) irradiation treatment. The a-IGZO based resistive switching devices exhibit long retention, good endurance, uniform switching voltages, and stable distribution of low and high resistance states. Electrical conduction mechanisms were also discussed on the basis of the current-voltage characteristics and their temperature dependence. The excellent resistive switching properties can be attributed to the reduction of organic- and hydrogen-based elements and the formation of enhanced metal-oxide bonding and metal-hydroxide bonding networks by hydrogen bonding due to UV irradiation, based on Fourier-transform-infrared spectroscopy, X-ray photoelectron spectroscopy, and Field emission scanning electron microscopy analysis of the thin films. This study suggests that a-IGZO thin films have potential applications in resistive random access memory and the low temperature photochemical solution deposition method can find the opportunity for further achieving system on panel applications if the a-IGZO resistive switching cells were integrated with a-IGZO thin film transistors.

Strong Emergence as a Defese of Non-Reductive Physicalism

Directory of Open Access Journals (Sweden)

Carl Gillett

2002-06-01

Full Text Available Jaegwon Kim, and others, have recently posed a powerful challenge to both emergentism and nom-reductive physicalism by providing arguments that these positions are committed to an untenable combination of both ‘upward’ and ‘dounward’ determination. In section 1, I illuminate how the nature of the realization relation underlies such skeptical arguments However, in section 2, I suggest that such conclusions involve a confusion between the implications of physicalism and those of a related thesis the ‘Completeness of Physics' (Co? I show that the truth of CoP poses a very serious obstacle to realized properties being efficacious in a physicalist universe and suggest that abandoning CoP offers hope for defending non-reductive physicalism. I then formulate a schema for a physicalist metaphysics, in section 3, which rejects CoP. This scenario is one where microphysical properties have a few conditional powers that they contribute to individuals when they realize certain properties In such a situation, I argue, though physicalism holds true there is still plausibly both ‘upward’ and ‘downward’ determination, where the latter is crucially an underappreciated form of determination I temn 'non- causal'. Ultimately, I conclude that this metaphysical schema offers a coherent account of Strongly emergent properties that preserves the truth of NRP albeit, in a form that is purged of any commitment to CoP. Finally, in section: 4, I carefully explore which of Kim's assumptions and arguments this metaphysics undermines.

Fabrication of self-written waveguide in photosensitive polyimide resin by controlling photochemical reaction of photosensitizer

International Nuclear Information System (INIS)

Yamashita, K.; Kuro, T.; Oe, K.; Mune, K.; Tagawa, K.; Naitou, R.; Mochizuki, A.

2004-01-01

We have investigated optical properties of photosensitive polyimide appropriating for long self-written waveguide fabrication. From systematic measurements of absorption properties, it was found that photochemical reaction of photosensitizer dissolved in the photosensitive polyimide resins relates to transparency after the exposure, which limits the length of the fabricated self-written waveguide. By controlling the photochemical reaction, in which the photosensitive polyimide resin has sufficient transparency during exposure, four times longer self-written waveguide core was fabricated

Light-induced hysteresis and recovery behaviors in photochemically activated solution-processed metal-oxide thin-film transistors

Energy Technology Data Exchange (ETDEWEB)

Jo, Jeong-Wan; Park, Sung Kyu, E-mail: yhkim76@skku.edu, E-mail: skpark@cau.ac.kr [School of Electrical and Electronics Engineering, Chung-Ang University, Seoul 156-756 (Korea, Republic of); Kim, Yong-Hoon, E-mail: yhkim76@skku.edu, E-mail: skpark@cau.ac.kr [School of Advanced Materials Science and Engineering, Sungkyunkwan University, Suwon 440-746 (Korea, Republic of); SKKU Advanced Institute of Nanotechnology (SAINT), Sungkyunkwan University, Suwon 440-746 (Korea, Republic of)

2014-07-28

In this report, photo-induced hysteresis, threshold voltage (V{sub T}) shift, and recovery behaviors in photochemically activated solution-processed indium-gallium-zinc oxide (IGZO) thin-film transistors (TFTs) are investigated. It was observed that a white light illumination caused negative V{sub T} shift along with creation of clockwise hysteresis in electrical characteristics which can be attributed to photo-generated doubly ionized oxygen vacancies at the semiconductor/gate dielectric interface. More importantly, the photochemically activated IGZO TFTs showed much reduced overall V{sub T} shift compared to thermally annealed TFTs. Reduced number of donor-like interface states creation under light illumination and more facile neutralization of ionized oxygen vacancies by electron capture under positive gate potential are claimed to be the origin of the less V{sub T} shift in photochemically activated TFTs.

Sensitivity evaluation of the green alga Chlamydomonas reinhardtii to uranium by pulse amplitude modulated (PAM) fluorometry

International Nuclear Information System (INIS)

Herlory, Olivier; Bonzom, Jean-Marc; Gilbin, Rodolphe

2013-01-01

Highlights: •Our study addressed the toxicity thresholds of uranium on microalgae using PAM fluorometry. •The oxygen-evolving complex (OEC) of PSII was identified as the primary action site of uranium. •Uranium impaired the electron flux between the photosystems until almost complete inhibition. •Non-photochemical quenching was identified as the most sensitive fluorescence parameter. •PAM fluorometry provided a rapid and reasonably sensitive method for assessing stress response. -- Abstract: Although ecotoxicological studies tend to address the toxicity thresholds of uranium in freshwaters, there is a lack of information on the effects of the metal on physiological processes, particularly in aquatic plants. Knowing that uranium alters photosynthesis via impairment of the water photo-oxidation process, we determined whether pulse amplitude modulated (PAM) fluorometry was a relevant tool for assessing the impact of uranium on the green alga Chlamydomonas reinhardtii and investigated how and to what extent uranium hampered photosynthetic performance. Photosynthetic activity and quenching were assessed from fluorescence induction curves generated by PAM fluorometry, after 1 and 5 h of uranium exposure in controlled conditions. The oxygen-evolving complex (OEC) of PSII was identified as the primary action site of uranium, through alteration of the water photo-oxidation process as revealed by F 0 /F v . Limiting re-oxidation of the plastoquinone pool, uranium impaired the electron flux between the photosystems until almost complete inhibition of the PSII quantum efficiency (F ′ q /F ′ m , EC 50 = 303 ± 64 μg U L −1 after 5 h of exposure) was observed. Non-photochemical quenching (qN) was identified as the most sensitive fluorescence parameter (EC 50 = 142 ± 98 μg U L −1 after 5 h of exposure), indicating that light energy not used in photochemistry was dissipated in non-radiative processes. It was shown that parameters which stemmed from

Effect of photochemical ageing on the ice nucleation properties of diesel and wood burning particles

Directory of Open Access Journals (Sweden)

C. Chou

2013-01-01

Full Text Available A measurement campaign (IMBALANCE conducted in 2009 was aimed at characterizing the physical and chemical properties of freshly emitted and photochemically aged combustion particles emitted from a log wood burner and diesel vehicles: a EURO3 Opel Astra with a diesel oxidation catalyst (DOC but no particle filter and a EURO2 Volkswagen Transporter TDI Syncro without emission aftertreatment. Ice nucleation experiments in the deposition and condensation freezing modes were conducted with the Portable Ice Nucleation Chamber (PINC at three nominal temperatures, −30 °C, −35 °C and −40 °C. Freshly emitted diesel particles showed ice formation only at −40 °C in the deposition mode at 137% relative humidity with respect to ice (RH_i and 92% relative humidity with respect to water (RH_w, and photochemical ageing did not play a role in modifying their ice nucleation behaviour. Only one diesel experiment where α-pinene was added for the ageing process, showed an ice nucleation enhancement at −35 °C. Wood burning particles also act as ice nuclei (IN at −40 °C in the deposition mode at the same conditions as for diesel particles and photochemical ageing also did not alter the ice formation properties of the wood burning particles. Unlike diesel particles, wood burning particles form ice via condensation freezing at −35 °C whereas no ice nucleation was observed at −30 °C. Photochemical ageing did not affect the ice nucleation ability of the diesel and wood burning particles at the three different temperatures investigated but a broader range of temperatures below −40 °C need to be investigated in order to draw an overall conclusion on the effect of photochemical ageing on deposition/condensation ice nucleation across the entire temperature range relevant to cold clouds.

40 CFR 52.2035 - Photochemical Assessment Monitoring Stations (PAMS) Program.

Science.gov (United States)

2010-07-01

... Stations (PAMS) Program. 52.2035 Section 52.2035 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY...) Pennsylvania § 52.2035 Photochemical Assessment Monitoring Stations (PAMS) Program. On September 23, 1994... (PAMS) Program as a state implementation plan (SIP) revision, as required by section 182(c)(1) of the...

Enhancing photophysical and photochemical properties of zinc(II) phthalocyanine dyes by substitution of triptycene moieties

Energy Technology Data Exchange (ETDEWEB)

Al-Sohaimi, Bander Roshadan [Department of Chemistry, Faculty of Science, Taibah University, P.O. Box 344, Al-Madinah Al Munawwrah (Saudi Arabia); Pişkin, Mehmet [Çanakkale Onsekiz Mart University, Vocational School of Technical Sciences, Department of Food Technology, Çanakkale 17100 (Turkey); Aljuhani, Ateyatallah; Al-Raqa, Shaya Y. [Department of Chemistry, Faculty of Science, Taibah University, P.O. Box 344, Al-Madinah Al Munawwrah (Saudi Arabia); Durmuş, Mahmut, E-mail: durmus@gtu.edu.tr [Gebze Technical University, Department of Chemistry, P.O. Box 141, Gebze 41400, Kocaeli (Turkey)

2016-05-15

The symmetrical zinc(II) phthalocyanines conjugated with 9,10-dioctyl-6,7-dimethoxy-2,3-dioxytriptycene or 9,10-diundecyl-6,7-dimethoxy-2,3-dioxytriptycene moieties were synthesized in this study. These novel phthalocyanines were characterized by standard characterization techniques such as {sup 1}H-NMR, FT-IR, UV–vis, Mass and Elemental Analysis. All these phthalocyanines showed highly solubility and formed non-aggregated monomeric species in most of the organic solvents. Their photochemical properties such as singlet oxygen, and photodegradation quantum yields, and photophysical properties including fluorescence quantum yields and lifetimes were investigated in toluene. The fluorescence quenching behavior of the studied zinc(II) phthalocyanines by the addition of 1,4-benzoquinone were also described in toluene.

Enhancing photophysical and photochemical properties of zinc(II) phthalocyanine dyes by substitution of triptycene moieties

International Nuclear Information System (INIS)

Al-Sohaimi, Bander Roshadan; Pişkin, Mehmet; Aljuhani, Ateyatallah; Al-Raqa, Shaya Y.; Durmuş, Mahmut

2016-01-01

The symmetrical zinc(II) phthalocyanines conjugated with 9,10-dioctyl-6,7-dimethoxy-2,3-dioxytriptycene or 9,10-diundecyl-6,7-dimethoxy-2,3-dioxytriptycene moieties were synthesized in this study. These novel phthalocyanines were characterized by standard characterization techniques such as 1 H-NMR, FT-IR, UV–vis, Mass and Elemental Analysis. All these phthalocyanines showed highly solubility and formed non-aggregated monomeric species in most of the organic solvents. Their photochemical properties such as singlet oxygen, and photodegradation quantum yields, and photophysical properties including fluorescence quantum yields and lifetimes were investigated in toluene. The fluorescence quenching behavior of the studied zinc(II) phthalocyanines by the addition of 1,4-benzoquinone were also described in toluene.

Heparin Assisted Photochemical Synthesis of Gold Nanoparticles and Their Performance as SERS Substrates

Science.gov (United States)

Rodríguez-Torres, Maria del Pilar; Díaz-Torres, Luis Armando; Romero-Servin, Sergio

2014-01-01

Reactive and pharmaceutical-grade heparins were used as biologically compatible reducing and stabilizing agents to photochemically synthesize colloidal gold nanoparticles. Aggregates and anisotropic shapes were obtained photochemically under UV black-light lamp irradiation (λ = 366 nm). Heparin-functionalized gold nanoparticles were characterized by Scanning Electron Microscopy and UV-Vis spectroscopy. The negatively charged colloids were used for the Surface Enhanced Raman Spectroscopy (SERS) analysis of differently charged analytes (dyes). Measurements of pH were taken to inspect how the acidity of the medium affects the colloid-analyte interaction. SERS spectra were taken by mixing the dyes and the colloidal solutions without further functionalization or addition of any aggregating agent. PMID:25342319

Quantifying non-energy benefits of a carbon reduction initiative for a glassware company

Energy Technology Data Exchange (ETDEWEB)

Willoughb-y, Sheri (World Wildlife Fund (United States)); Guo, Stephan (IKEA Trading (Hongkong) Ltd. (China)); Dahlgren, Maja (IKEA Trading Services Sp. z o.o. (Poland)); Schaefer, Thomas (IKEA of Sweden (Sweden)); Jia, Hongming (Hongwei Glassware Co. Ltd. (China))

2011-07-01

A glassware company in Yuncheng, China, which supplies to IKEA, upgraded its furnaces and switched the fuel source from coal to natural gas as a participant in an IKEA and WWF-led carbon reduction project. In addition to reducing its greenhouse gas emissions by 35 % (approx7,000 tons CO{sub 2}e) between 2009 and 2010, the company realized numerous non-energy benefits (NEBs) which improved the business case for their investment. While many NEBs can be difficult to quantify, the company calculated that improvements in product quality related to switching the pot furnaces from coal to natural gas directly reduced cost of products by 17 %. This cost reduction was realized from two primary NEBs: 1. Rate of available material: For one product, improved temperature stability in the natural gas furnace increased the output rate from 1,200 to 1,350 pieces, reducing each product's cost 12.5 %. 2. Improvement of qualified rate (non-rejects): For another product output increased from 900 to 1,050 pieces and the qualified rate increased from 75 to 80 percent. This gain was also due to increased temperature stability in the natural gas furnace which made the melted color and the material quality more stable. This resulted in a cost reduction of 5 % compared to the daily output from the coal furnace. While the glassware company had not yet broke even on its investment in the first year, the management had a very favourable view on this project due to the NEBs listed above as well as increased labor productivity due to improved working conditions (cleaner and cooler) and reduced risk of fines due to environmental regulation of coal. If a source of biogas could be secured, further carbon reductions could be realized while maintaining the NEBs achieved by switching to natural gas. This paper will further examine these and other non-energy benefits realized by the glassware company through the IKEA-WWF carbon reduction project

Silencing of the violaxanthin de-epoxidase gene in the diatom Phaeodactylum tricornutum reduces diatoxanthin synthesis and non-photochemical quenching.

Directory of Open Access Journals (Sweden)

Johann Lavaud

Full Text Available Diatoms are a major group of primary producers ubiquitous in all aquatic ecosystems. To protect themselves from photooxidative damage in a fluctuating light climate potentially punctuated with regular excess light exposures, diatoms have developed several photoprotective mechanisms. The xanthophyll cycle (XC dependent non-photochemical chlorophyll fluorescence quenching (NPQ is one of the most important photoprotective processes that rapidly regulate photosynthesis in diatoms. NPQ depends on the conversion of diadinoxanthin (DD into diatoxanthin (DT by the violaxanthin de-epoxidase (VDE, also called DD de-epoxidase (DDE. To study the role of DDE in controlling NPQ, we generated transformants of P. tricornutum in which the gene (Vde/Dde encoding for DDE was silenced. RNA interference was induced by genetic transformation of the cells with plasmids containing either short (198 bp or long (523 bp antisense (AS fragments or, alternatively, with a plasmid mediating the expression of a self-complementary hairpin-like construct (inverted repeat, IR. The silencing approaches generated diatom transformants with a phenotype clearly distinguishable from wildtype (WT cells, i.e. a lower degree as well as slower kinetics of both DD de-epoxidation and NPQ induction. Real-time PCR based quantification of Dde transcripts revealed differences in transcript levels between AS transformants and WT cells but also between AS and IR transformants, suggesting the possible presence of two different gene silencing mediating mechanisms. This was confirmed by the differential effect of the light intensity on the respective silencing efficiency of both types of transformants. The characterization of the transformants strengthened some of the specific features of the XC and NPQ and confirmed the most recent mechanistic model of the DT/NPQ relationship in diatoms.

Silencing of the Violaxanthin De-Epoxidase Gene in the Diatom Phaeodactylum tricornutum Reduces Diatoxanthin Synthesis and Non-Photochemical Quenching

Science.gov (United States)

Vugrinec, Sascha; Kroth, Peter G.

2012-01-01

Diatoms are a major group of primary producers ubiquitous in all aquatic ecosystems. To protect themselves from photooxidative damage in a fluctuating light climate potentially punctuated with regular excess light exposures, diatoms have developed several photoprotective mechanisms. The xanthophyll cycle (XC) dependent non-photochemical chlorophyll fluorescence quenching (NPQ) is one of the most important photoprotective processes that rapidly regulate photosynthesis in diatoms. NPQ depends on the conversion of diadinoxanthin (DD) into diatoxanthin (DT) by the violaxanthin de-epoxidase (VDE), also called DD de-epoxidase (DDE). To study the role of DDE in controlling NPQ, we generated transformants of P. tricornutum in which the gene (Vde/Dde) encoding for DDE was silenced. RNA interference was induced by genetic transformation of the cells with plasmids containing either short (198 bp) or long (523 bp) antisense (AS) fragments or, alternatively, with a plasmid mediating the expression of a self-complementary hairpin-like construct (inverted repeat, IR). The silencing approaches generated diatom transformants with a phenotype clearly distinguishable from wildtype (WT) cells, i.e. a lower degree as well as slower kinetics of both DD de-epoxidation and NPQ induction. Real-time PCR based quantification of Dde transcripts revealed differences in transcript levels between AS transformants and WT cells but also between AS and IR transformants, suggesting the possible presence of two different gene silencing mediating mechanisms. This was confirmed by the differential effect of the light intensity on the respective silencing efficiency of both types of transformants. The characterization of the transformants strengthened some of the specific features of the XC and NPQ and confirmed the most recent mechanistic model of the DT/NPQ relationship in diatoms. PMID:22629333

Engineering photochemical smog through convection towers

Energy Technology Data Exchange (ETDEWEB)

Elliott, S.; Prueitt, M.L.; Bossert, J.E.; Mroz, E.J.; Krakowski, R.A.; Miller, R.L. [Los Alamos National Lab., NM (United States); Jacobson, M.Z.; Turco, R.P. [Los Alamos National Lab., NM (United States)]|[Univ. of California, Los Angeles, CA (United States). Atmospheric Sciences Dept.

1995-02-01

Reverse convection towers have attracted attention as a medium for cleansing modern cities. Evaporation of an aqueous mist injected at the tower opening could generate electrical power by creating descent, and simultaneously scavenge unsightly and unhealthful particulates. The study offered here assesses the influence to tower water droplets on the photochemical component of Los Angeles type smog. The primary radical chain initiator OH is likely removed into aqueous phases well within the residence time of air in the tower, and then reacts away rapidly. Organics do not dissolve, but nighttime hydrolysis of N{sub 2}O{sub 5} depletes the nitrogen oxides. A lack of HOx would slow hydrocarbon oxidation and so also ozone production. Lowering of NOx would also alter ozone production rates, but the direction is uncertain. SO{sub 2} is available in sufficient quantities in some urban areas to react with stable oxidants, and if seawater were the source of the mist, the high pH would lead to fast sulfur oxidation kinetics. With an accommodation coefficient of 10{sup {minus}3}, however, ozone may not enter the aqueous phase efficiently. Even if ozone is destroyed or its production suppressed, photochemical recovery times are on the order of hours, so that tower processing must be centered on a narrow midday time window. The cost of building the number of structures necessary for this brief turnover could be prohibitive. The increase in humidity accompanying mist evaporation could be controlled with condensers, but might otherwise counteract visibility enhancements by recreating aqueous aerosols. Quantification of the divergent forcings convection towers must exert upon the cityscape would call for coupled three dimensional modeling of transport, microphysics, and photochemistry. 112 refs.

Photochemical transformations accelerated in continuous-flow reactors : basic concepts and applications

NARCIS (Netherlands)

Su, Y.; Straathof, N.J.W.; Hessel, V.; Noel, T.

2014-01-01

Continuous-flow photochemistry is used increasingly by researchers in academia and industry to facilitate photochemical processes and their subsequent scale-up. However, without detailed knowledge concerning the engineering aspects of photochemistry, it can be quite challenging to develop a suitable

Reduction of Acid-Fast and Non-Acid-Fast Bacteria by Point of Use Coagulation-Flocculation-Disinfection

Directory of Open Access Journals (Sweden)

Lisa M. Casanova

2015-11-01

Full Text Available Point of use (POU household water treatment is increasingly being adopted as a solution for access to safe water. Non-tuberculous Mycobacteria (NTM are found in water, but there is little research on whether NTM survive POU treatment. Mycobacteria may be removed by multi-barrier treatment systems that combine processes such as coagulation, settling and disinfection. This work evaluated removal of a non-tuberculous Mycobacterium (Mycobaterium terrae and a Gram-negative non-acid-fast environmental bacterium (Aeromonas hydrophila by combined coagulation-flocculation disinfection POU treatment. Aeromonas hydrophila showed 7.7 log10 reduction in demand free buffer, 6.8 log10 in natural surface water, and 4 log10 reduction in fecally contaminated surface water. Turbidity after treatment was <1 NTU. There was almost no reduction in levels of viable M. terrae by coagulant-flocculant-disinfectant in natural water after 30 minutes. The lack of Mycobacteria reduction was similar for both combined coagulant-flocculant-disinfectant and hypochlorite alone. A POU coagulant-flocculant-disinfectant treatment effectively reduced A. hydrophila from natural surface waters but not Mycobacteria. These results reinforce previous findings that POU coagulation-flocculation-disinfection is effective against gram-negative enteric bacteria. POU treatment and safe storage interventions may need to take into account risks from viable NTM in treated stored water and consider alternative treatment processes to achieve NTM reductions.

Photochemical synthesis of biomolecules under anoxic conditions

Science.gov (United States)

Folsome, C.; Brittain, A.; Zelko, M.

1983-01-01

The long-wavelength UV anoxic photosynthesis of uracil, various sugars (including deoxyribose and glycoaldehyde), amino acids, and other organic photoproducts is reported. The reactions were conducted in a mixture of water, calcium carbonate, hydrazine, and formaldehyde which were subjected to 24 hr or 72 hr radiation. Product yields were greatest when the hydrazine/formaldehyde ratio was one, and when the reactant concentrations were low. These data suggest that organic products can be formed in variety from those amounts of formaldehyde and hydazine precursors which are themselves formed under anoxic UV photochemical conditions.

Fusarium solani Infection Depressed Photosystem Performance by Inducing Foliage Wilting in Apple Seedlings

Directory of Open Access Journals (Sweden)

Kun Yan

2018-05-01

Full Text Available Fusarium fungi are soil-borne pathogens, and the pathological effects on plant photosystems remain unclear. This study aimed to deeply reveal pathological characterization in apple seedlings infected with Fusarium solani by investigating photosystems performance and interaction. Roots were immersed in conidial suspension for inoculation. Thereafter, prompt and delayed chlorophyll a fluorescence and modulated 820 nm reflection were simultaneously detected. After 30 days of infection, leaf relative water content and dry weight were remarkably decreased by 55.7 and 47.1%, suggesting that the infected seedlings were subjected to Fusarium-induced water deficit stress. PSI reaction center was more susceptible than PSII reaction center in infected seedlings due to greater decrease in the maximal photochemical efficiency of PSI than that of PSII, but PSI reaction center injury was aggravated slowly, as PSII injury could partly protect PSI by restricting electron donation. PSII donor and acceptor sides were also damaged after 20 days of infection, and the restricted electron donation induced PSII and PSI disconnection by blocking PSI re-reduction. In accordance with greater damage of PSI reaction center, PSI oxidation was also suppressed. Notably, significantly increased efficiency of electron transport from plastoquinone (PQ to PSI acceptors (REo/ETo after 20 days of infection suggested greater inhibition on PQ reduction than re-oxidation, and the protection for PSI acceptors might alleviate the reduction of electron transport efficiency beyond PQ upon damaged PSI reaction center. Lowered delayed fluorescence in microsecond domain verified PSII damage in infected seedlings, and elevated delayed fluorescence in sub-millisecond domain during PQ reduction process conformed to increased REo/ETo. In conclusion, F. solani infection depressed PSII and PSI performance and destroyed their coordination by inducing pathological wilting in apple seedlings. It may

Photochemical epoxidation of olefins by visible light in a redox system involving Sb(V) tetraphenylporphyrin and water

Energy Technology Data Exchange (ETDEWEB)

Inoue, Haruo; Hida, Mitsuhiko (Tokyo Metropolitan Univ. (Japan))

1989-03-25

The authors explore electron donors from the viewpoint of solar energy storage. Much attention has been focused on how a water molecule can be incorporated into electron donor system. In this paper, the authors describe a photochemical epoxidation of alkene sensitized by Sb(V)-, P(V)-, Sn(IV)-, Ge(IV)- tetraphenylporphyrin (TPP) with higher oxidation potential than 1.0 Volts vs. NHE in redox systems with a water molecule as an electron donor. The water molecule acts as an electron donor, and alkene acts as an oxygen atom acceptor in this photoredox system. Epoxidation of alkenes usually requires strong oxidizing agents either by the thermal or photochemical method. This is the first example of the photochemical epoxide formation from alkene and water without any strong oxidizing agent. 1 fig.

L-Cysteine Capped CdSe Quantum Dots Synthesized by Photochemical Route.

Science.gov (United States)

Singh, Avinash; Kunwar, Amit; Rath, M C

2018-05-01

L-cysteine capped CdSe quantum dots were synthesized via photochemical route in aqueous solution under UV photo-irradiation. The as grown CdSe quantum dots exhibit broad fluorescence at room temperature. The CdSe quantum dots were found to be formed only through the reactions of the precursors, i.e., Cd(NH3)2+4 and SeSO2-3 with the photochemically generated 1-hydroxy-2-propyl radicals, (CH3)2COH radicals, which are formed through the process of H atom abstraction by the photoexcited acetone from 2-propanol. L-Cysteine was found to act as a suitable capping agent for the CdSe quantum dots and increases their biocompatability. Cytotoxicty effects of these quantum dots were evaluated in Chinese Hamster Ovary (CHO) epithelial cells, indicated a significant lower level for the L-cysteine capped CdSe quantum dots as compare to the bare ones.

Study of greenhouse gases reduction alternatives for the exploitation of non conventional oil sands in Canada

Energy Technology Data Exchange (ETDEWEB)

Bouchonneau, Deborah [Institut Francais du Petrole (IFP), Paris (France)

2008-07-01

High energy prices and greenhouse gases reduction represent the main challenges the current worldwide energetic situation has to face. As a consequence, paradox strategies can be highlighted: oil prices are sufficiently high to exploit non conventional oil resources, like extra heavy oils and oil sands. But the production of these resources emits larger GHG than the conventional oil path and implies other major environmental issues (water management, risks of soil pollution, destruction of the boreal forest), incompatible with the rules validated by the protocol of Kyoto. At the light of the new greenhouse gases reduction regulation framework announced by the Canadian Federal government, this work focuses on the study of greenhouse gases reduction alternatives applied to the non conventional oil sands exploitation in Canada. (author)

Photochemical Hydrogen Doping Induced Embedded Two-Dimensional Metallic Channel Formation in InGaZnO at Room Temperature.

Science.gov (United States)

Kim, Myeong-Ho; Lee, Young-Ahn; Kim, Jinseo; Park, Jucheol; Ahn, Seungbae; Jeon, Ki-Joon; Kim, Jeong Won; Choi, Duck-Kyun; Seo, Hyungtak

2015-10-27

The photochemical tunability of the charge-transport mechanism in metal-oxide semiconductors is of great interest since it may offer a facile but effective semiconductor-to-metal transition, which results from photochemically modified electronic structures for various oxide-based device applications. This might provide a feasible hydrogen (H)-radical doping to realize the effectively H-doped metal oxides, which has not been achieved by thermal and ion-implantation technique in a reliable and controllable way. In this study, we report a photochemical conversion of InGaZnO (IGZO) semiconductor to a transparent conductor via hydrogen doping to the local nanocrystallites formed at the IGZO/glass interface at room temperature. In contrast to thermal or ionic hydrogen doping, ultraviolet exposure of the IGZO surface promotes a photochemical reaction with H radical incorporation to surface metal-OH layer formation and bulk H-doping which acts as a tunable and stable highly doped n-type doping channel and turns IGZO to a transparent conductor. This results in the total conversion of carrier conduction property to the level of metallic conduction with sheet resistance of ∼16 Ω/□, room temperature Hall mobility of 11.8 cm(2) V(-1) sec(-1), the carrier concentration at ∼10(20) cm(-3) without any loss of optical transparency. We demonstrated successful applications of photochemically highly n-doped metal oxide via optical dose control to transparent conductor with excellent chemical and optical doping stability.

Photochemical immobilization of anthraquinone conjugated oligonucleotides and PCR amplicons on solid surfaces

DEFF Research Database (Denmark)

Koch, T.; Jacobsen, N.; Fensholdt, J.

2000-01-01

Ligand immobilization on solid surfaces is an essential step in fields such as diagnostics, bio sensor manufacturing, and new material sciences in general. In this paper a photochemical approach based on anthraquinone as the chromophore is presented. Photochemical procedures offer special...... advantages as they are able to generate highly reactive species in an orientation specific manner. As presented here, anthraquinone (AQ) mediated covalent DNA immobilization appears to be superior to currently known procedures. A synthetic procedure providing AQ-phosphoramidites is presented. These reagents...... facilitate AQ conjugation during routine DNA synthesis, thus enabling the AQ-oligonucleotides to be immobilized in a very convenient and efficient manner. AQ-conjugated PCR primers can be used directly in PCR. When the PCR is performed in solution, the amplicons can be immobilized after the PCR. Moreover...

Studies on the photochemical and thermal dissociation synthesis of krypton difluoride

Energy Technology Data Exchange (ETDEWEB)

Kinkead, S.A.; FitzPatrick, J.R.; Foropoulos, J. Jr.; Kissane, R.J.; Purson, J.D.

1993-08-01

Like dioxygen difluoride (O{sub 2}F{sub 2}), KrF{sub 2} can be produced by thermal dissociation or photochemical synthesis from the elements; however, the yields are invariably much less than those obtained for O{sub 2}F{sub 2}. For example, while irradiation of liquid O{sub 2}/F{sub 2} mixtures at {minus}196{degrees}C through a sapphire window with an unfiltered 1,000W uv lamp provides in excess of 3g of O{sub 2}F{sub 2} per hour, the yield of KrF{sub 2} under identical circumstances is approximately 125 mg/hr. In this report, the yield of KrF{sub 2} in quartz and Pyrex{trademark} photochemical reactors has been examined as a function of irradiation wavelength, irradiation power, and Kr: F{sub 2} mole ratio. The uv-visible spectrum of KrF{sub 2} has also been recorded for comparison with earlier work, and the quantum yield for photodissociation at two wavelengths determined. The synthesis of KrF{sub 2} using large thermal gradients has also been examined using resistively heated nickel filaments to thermally dissociate the F{sub 2} in close proximity to liquid nitrogen-cooled metal surfaces. As a net result, KrF{sub 2} has been produced in yields in excess of 1.75 g/hr for extended periods in photochemical systems, and 2.3 g/hr for shorter periods in thermally dissociative reactors. This paper summarizes the results of examining parametrically several different types of reactors for efficiency of producing krypton difluoride.

Photochemical hydrogen production through solar radiation by means of the membrane principle

International Nuclear Information System (INIS)

Broda, E.

1976-01-01

This report was written by Enelbert Broda from the University of Vienna for the UNESCO-Solar-Energy-Symposium in Geneva in 1976. Nuclear experts are considering a 'hydrogen economy' where H 2 serves as a fuel to make electricity, as a chemical reactant, as a metallurgical reductant and as a source of food. Now H 2 could also be made by photolysis of water. Theoretically, a quantum of green light carries enough energy for the reaction H 2 0 = H 2 + 0.5 0 2 . With long-wave light, photolysis could be achieved by combination of 2 quanta. Yet attempts to photolyze water, in presence of sensitizers (photocatalysts), have failed. In the last analysis, this is due to re-combination of the primary, highly reactive, products of the photochemical reaction. A solution of the problem is to be found by the spatial separation of the primary production by development of suitable membranes where these products, and therefore also the stable gases H 2 and 0 2 , come out on opposite sides. The feasibility of this 'membrane principle' has been shown in Nature for 3 giga-years. Using membranes, all photosynthetic cells (photosynthetic bacteria and plants) succeed in the photo-production of a reductant (in many cases at least ferredoxin in the reduced form) with a redox potential equal to that of H 2 in neutral solution (-0.4 v). The reductant can, but need not, be used by the cells for C0 2 assimilation. In man-made technology, the reducing power would be diverted as H 2 . Here it is not suggested to use or copy living cells. Rather their operation is to be studied so that technically useful membranes for water photolysis can be constructed abiotically. The scientific and practical aspects of large-scale photolytic H 2 production are discussed. (author)

Photochemical versus biological production of methyl iodide during Meteor 55

Science.gov (United States)

Richter, U.; Wallace, D.

2003-04-01

The flux of methyl iodide from sea to air represents the largest flux of iodine from the ocean to the atmosphere. Surface water concentrations and hence fluxes are particularly high in tropical regions. This flux may be responsible for the enrichment of iodine in the marine aerosol and may contribute to important processes in the marine boundary layer, including particle formation. Methyl iodide is commonly referred to as a biogenic gas, with both macroalgae and phytoplankton identified as important sources. On the other hand experimental and field data have shown the importance of photochemical production that is not necessarily associated directly with biological activity. During the Meteor cruise 55 along 11°N in the tropical Atlantic Ocean, a series of experiments were conducted to examine the biological vs. photochemical production of methyl iodide. A total of eight separate experiments were conducted. Production of CH3I in quartz glass flasks during 24 hour incubations (dark and natural sunlight) was measured under three experimental treatments: untreated seawater, filtered seawater (0.1 um pore size filter to exclude most phytoplankton and bacteria), and seawater that was poisoned with mercuric chloride. There were two clear findings from these experiments: (1) methyl iodide production was significantly higher in all the incubations that were exposed to the light than in the dark incubations; (2) there was no significant difference between CH3I production under the three experimental treatments. These results argue very strongly for the primary importance of photochemical production of CH3I as opposed to biogenic production at least for the tropical open ocean surface waters. Further experiments are required to investigate the reactants involved, their sources, the wavelength and depth dependence of production, etc. as well as (possibly related) sink processes.

Oxyfluorfen toxic effect on S. obliquus evaluated by different photosynthetic and enzymatic biomarkers.

Science.gov (United States)

Geoffroy, L; Dewez, D; Vernet, G; Popovic, R

2003-11-01

The effect of oxyfluorfen was investigated when alga Scenedesmus obliquus has been exposed to different concentrations (7.5, 15, and 22.5 microg x L(-1)) at 12, 24, and 48 hours of exposure. Toxicity test was done by using 13 biomarkers concerning growth rate, chlorophyll content and indicators of photosynthetic and antioxidant enzyme activities. The change of the 13 parameters showed a great variation of sensitivity indicating differences in parameters' suitability to be used as biomarkers when alga culture was exposed to oxyfluorfen toxicity. The order of sensitivity between those biomarkers was: Antenna size (ABS/RC) > Chlorophyll content > Catalase (CAT) > Operational PSII quantum yield (phiS(PSII)) > Glutathione S-transferase (GST) > Functional plastoquinone pool (Q(PQ)) > Glutathione reductase (GR) > Growth rate > Nonphotochemical quenching (QN) > Proton gradient quenching (Q(Emax)) > Ascorbate peroxidase (APX) > Photochemical quenching (Q(p)) > Maximum PSII quantum yield (Phi(PSII)). The effect of oxyfluorfen on the changes of those parameters was interpreted as a result of herbicide mode of action at molecular level of alga cellular system. This study indicated for some photosynthetic and enzymatic biomarkers to be useful indicators of toxicity effect induced in non-target alga species. Determination of biomarkers' sensitivity order may facilitate their selection to be used in environmental risk assessment of polluted water.

Dispersive kinetic model for the non-isothermal reduction of nickel oxide by hydrogen

International Nuclear Information System (INIS)

Adnadevic, Borivoj; Jankovic, Bojan

2008-01-01

The kinetics of the non-isothermal reduction process of powder nickel oxide samples using hydrogen was investigated by temperature-programmed experiments at the different constant heating rates. The new procedure for the determination of density distribution function of activation energies (ddfE a ), evaluated from the experimentally obtained non-isothermal conversion curves, was developed. The analytical relationships between the corresponding thermo-kinetic parameters for the investigated reduction process were established. From the influence of heating rate on the basic characteristics of ddfE a 's, it was concluded that the evaluated ddfE a 's are completely independent of the heating rate (v h ). It was found that the value of activation energy at the peak of the distribution curve (E a,max ), at all considered heating rates, is in good agreement with the value of E a,0 (96.6 kJ mol -1 ) calculated from the isoconversional dependence of activation energy, in the conversion range of 0.20≤α≤0.60. From the appearances of the true compensation effect, it was concluded that the factor that produces the changes of kinetic parameter values is a conversion fraction (α). Using the model prediction, the experimentally obtained conversion curves are completely described by the evaluated distribution curves (g(E a ) vhj ) at all considered heating rates. It was concluded that the assumption about the distribution of potential energies of oxygen vacancies presented in NiO samples leads to the distribution of activation energies, which determine the kinetics of non-isothermal reduction processes

A new approach of the understanding of sulfur dioxide reduction in non-aqueous solvent; Une nouvelle approche de la comprehension de la reduction du dioxyde de soufre en solvant non aqueux

Energy Technology Data Exchange (ETDEWEB)

Potteau, E.; Levillain, E.; Lelieur, J.P. [Laboratoire de Spectrochimie Infrarouge et Raman (LASIR, UPR 2631 CNRS) Haute Etudes Industrielles (HEI), 59 - Lille (France)

1996-12-31

The study of SO{sub 2} reduction in non-aqueous solvent can help to understand the functioning of Li/SO{sub 2} batteries and to find a simpler way for the synthesis of Li{sub 2}S{sub 2}O{sub 4} dithionite. This paper presents the results of electrochemical studies (cycle volt-amperometry in semi-infinite and thin film diffusion conditions, visible spectro-electrochemistry) and spectroscopic studies (UV, visible and RPE) performed on SO{sub 2} solutions. A mechanism of SO{sub 2} reduction is proposed and discussed. (J.S.) 18 refs.

A new approach of the understanding of sulfur dioxide reduction in non-aqueous solvent; Une nouvelle approche de la comprehension de la reduction du dioxyde de soufre en solvant non aqueux

Energy Technology Data Exchange (ETDEWEB)

Potteau, E; Levillain, E; Lelieur, J P [Laboratoire de Spectrochimie Infrarouge et Raman (LASIR, UPR 2631 CNRS) Haute Etudes Industrielles (HEI), 59 - Lille (France)

1997-12-31

The study of SO{sub 2} reduction in non-aqueous solvent can help to understand the functioning of Li/SO{sub 2} batteries and to find a simpler way for the synthesis of Li{sub 2}S{sub 2}O{sub 4} dithionite. This paper presents the results of electrochemical studies (cycle volt-amperometry in semi-infinite and thin film diffusion conditions, visible spectro-electrochemistry) and spectroscopic studies (UV, visible and RPE) performed on SO{sub 2} solutions. A mechanism of SO{sub 2} reduction is proposed and discussed. (J.S.) 18 refs.

Light-induced reduction of rhodium(III) and palladium(II) on titanium dioxide dispersions and the selective photochemical separation and recovery of gold(III), platinum(IV), and rhodium(III) in chloride media

Energy Technology Data Exchange (ETDEWEB)

Borgarello, E.; Serpone, N.; Emo, G.; Harris, R.; Pelizzetti, E.; Minero, C.

1986-12-03

Irradiation of aqueous TiO/sub 2/ dispersions containing palladium(II) or rhodium(III) chloride salts with AM1 simulated sunlight leads to the photoreduction of these metals, which are deposited on the semiconductor particle surface. Oxygen is detrimental to the photoreduction of rhodium(III) but not the photoreduction of palladium(II). However, in both cases the reduction process is most efficient if the solution contains CH/sub 3/OH, which acts to scavenge valence band holes of the illuminated TiO/sub 2/ semiconductor. The selective photoreduction and recovery of precious metals from a dilute solution (as might be found in industrial wastes) have been investigated for a mixture of gold(III), platinum(IV), and rhodium(III) chloride salts as a function of various parameters (pH, presence or absence of O/sub 2/, presence or absence of a hole scavenger, and the concentration of the semiconductor). At pH 0, gold is easily separated from platinum and rhodium. The rate of photoreduction of gold(III) on TiO/sub 2/ is nearly independent of the concentration of the semiconductor, under the experimental conditions employed; the limiting rate is 2.7 x 10/sup -7/ M s/sup -1/. The potential utility of this selective photochemical technique is discussed.

No-lose targets as an option to integrate non-Annex I countries in global emission reduction efforts. A game-theoretical analysis

Energy Technology Data Exchange (ETDEWEB)

Duscha, Vicki

2012-07-01

Substantial greenhouse gas emission reductions of 50% and more below 1990 levels by 2050 are necessary, to limit mean temperature increase below 2 C above pre-industrial levels. While the Kyoto Protocol foresees emission reduction targets for Annex I countries only, current and projected greenhouse gas emissions, as well as the growing economic importance of emerging economies call for an integration of non-Annex I countries in global reduction efforts. No-lose targets set emission reduction targets and define incentives for meeting the target, in contrast to binding reduction targets that use penalties to ensure compliance. One form of incentive is the participation in an international emissions trading market. While a few conceptual and quantitative analyses of no-lose targets can be found in the literature, economic analyses have not been carried out so far. In this thesis, two theoretical frameworks are introduced to analyze the potential of no-lose targets to contribute to global emission reduction efforts. First, a two-player, two-stage model is developed to model a non-Annex I country's participation decision and derive the contribution to global emission reductions. Then a two-player participation game is introduced to analyze the effects that the participation decision of one non-Annex I country has on another non-Annex I country also facing a no-lose target. Two market forms, a perfectly competitive market, and a market with market power on the side of the non-Annex I country are analyzed. In order to complement the highly stylized theoretical frameworks, a quantitative analysis applying marginal abatement cost curves is conducted to estimate the contribution of no-lose targets to reaching the 2 C target. The analyses show that no-lose targets can result in substantial contributions from non-Annex I countries to global emission reductions, in particular if the reduction potential in the non-Annex I countries is large, compared to that of the Annex I

Light-driven dinitrogen reduction catalyzed by a CdS:nitrogenase MoFe protein biohybrid

Energy Technology Data Exchange (ETDEWEB)

Brown, K. A.; Harris, D. F.; Wilker, M. B.; Rasmussen, A.; Khadka, N.; Hamby, H.; Keable, S.; Dukovic, G.; Peters, J. W.; Seefeldt, L. C.; King, P. W.

2016-04-21

The splitting of dinitrogen (N2) and reduction to ammonia (NH3) is a kinetically complex and energetically challenging multistep reaction. In the Haber-Bosch process, N2 reduction is accomplished at high temperature and pressure, whereas N2 fixation by the enzyme nitrogenase occurs under ambient conditions using chemical energy from adenosine 5'-triphosphate (ATP) hydrolysis. We show that cadmium sulfide (CdS) nanocrystals can be used to photosensitize the nitrogenase molybdenum-iron (MoFe) protein, where light harvesting replaces ATP hydrolysis to drive the enzymatic reduction of N2 into NH3. The turnover rate was 75 per minute, 63% of the ATP-coupled reaction rate for the nitrogenase complex under optimal conditions. Inhibitors of nitrogenase (i.e., acetylene, carbon monoxide, and dihydrogen) suppressed N2 reduction. The CdS:MoFe protein biohybrids provide a photochemical model for achieving light-driven N2 reduction to NH3.

Modeling of photochemical air pollution in the Barcelona area with highly disaggregated anthropogenic and biogenic emissions

International Nuclear Information System (INIS)

Toll, I.; Baldasano, J.M.

2000-01-01

The city of Barcelona and its surrounding area, located in the western Mediterranean basin, can reach high levels of O 3 in spring and summertime. To study the origin of this photochemical pollution, a numerical modeling approach was adopted and the episode that took place between 3 and 5 August 1990 was chosen. The main meteorological mesoscale flows were reproduced with the meteorological non-hydrostatic mesoscale model MEMO for 5 August 1990, when weak pressure synoptic conditions took place. The emissions inventory was calculated with the EIM-LEM model, giving highly disaggregated anthropogenic and biogenic emissions in the zone studied, an 80 x 80 km 2 area around the city of Barcelona. Major sources of VOC were road traffic (51%) and vegetation (34%), while NO x were mostly emitted by road traffic (88%). However, emissions from some industrial stacks can be locally important and higher than those from road traffic. Photochemical simulation with the MARS model revealed that the combination of mesoscale wind flows and the above-mentioned local emissions is crucial in the production and transport of O 3 in the area. On the other hand, the geostrophic wind also played an important role in advecting the air masses away from the places O 3 had been generated. The model simulations were also evaluated by comparing meteorological measurements from nine surface stations and concentration measurements from five surface stations, and the results proved to be fairly satisfactory. (author)

The Support Reduction Algorithm for Computing Non-Parametric Function Estimates in Mixture Models

OpenAIRE

GROENEBOOM, PIET; JONGBLOED, GEURT; WELLNER, JON A.

2008-01-01

In this paper, we study an algorithm (which we call the support reduction algorithm) that can be used to compute non-parametric M-estimators in mixture models. The algorithm is compared with natural competitors in the context of convex regression and the ‘Aspect problem’ in quantum physics.

Water Treatment Process Intensification by Combination of Electrochemical and Photochemical Methods

Czech Academy of Sciences Publication Activity Database

Krystyník, Pavel; Klusoň, Petr; Tito, D.N.

2015-01-01

Roč. 94, SI (2015), s. 85-92 ISSN 0255-2701 R&D Projects: GA MPO(CZ) FR-TI1/065; GA TA ČR TA03010548 Institutional support: RVO:67985858 Keywords : electrocoagulation * photochemical oxidation * TOC removal Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 2.154, year: 2015

Far-red light is needed for efficient photochemistry and photosynthesis.

Science.gov (United States)

Zhen, Shuyang; van Iersel, Marc W

2017-02-01

The efficiency of monochromatic light to drive photosynthesis drops rapidly at wavelengths longer than 685nm. The photosynthetic efficiency of these longer wavelengths can be improved by adding shorter wavelength light, a phenomenon known as the Emerson enhancement effect. The reverse effect, the enhancement of photosynthesis under shorter wavelength light by longer wavelengths, however, has not been well studied and is often thought to be insignificant. We quantified the effect of adding far-red light (peak at 735nm) to red/blue or warm-white light on the photosynthetic efficiency of lettuce (Lactuca sativa). Adding far-red light immediately increased quantum yield of photosystem II (Φ PSII ) of lettuce by an average of 6.5 and 3.6% under red/blue and warm-white light, respectively. Similar or greater increases in Φ PSII were observed after 20min of exposure to far-red light. This longer-term effect of far-red light on Φ PSII was accompanied by a reduction in non-photochemical quenching of fluorescence (NPQ), indicating that far-red light reduced the dissipation of absorbed light as heat. The increase in Φ PSII and complementary decrease in NPQ is presumably due to preferential excitation of photosystem I (PSI) by far-red light, which leads to faster re-oxidization of the plastoquinone pool. This facilitates reopening of PSII reaction centers, enabling them to use absorbed photons more efficiently. The increase in Φ PSII by far-red light was associated with an increase in net photosynthesis (P n ). The stimulatory effect of far-red light increased asymptotically with increasing amounts of far-red. Overall, our results show that far-red light can increase the photosynthetic efficiency of shorter wavelength light that over-excites PSII. Copyright © 2016 Elsevier GmbH. All rights reserved.

Chemical degradation of proteins in the solid state with a focus on photochemical reactions.

Science.gov (United States)

Mozziconacci, Olivier; Schöneich, Christian

2015-10-01

Protein pharmaceuticals comprise an increasing fraction of marketed products but the limited solution stability of proteins requires considerable research effort to prepare stable formulations. An alternative is solid formulation, as proteins in the solid state are thermodynamically less susceptible to degradation. Nevertheless, within the time of storage a large panel of kinetically controlled degradation reactions can occur such as, e.g., hydrolysis reactions, the formation of diketopiperazine, condensation and aggregation reactions. These mechanisms of degradation in protein solids are relatively well covered by the literature. Considerably less is known about oxidative and photochemical reactions of solid proteins. This review will provide an overview over photolytic and non-photolytic degradation reactions, and specially emphasize mechanistic details on how solid structure may affect the interaction of protein solids with light. Copyright © 2014 Elsevier B.V. All rights reserved.

Enhancing endosomal escape of transduced proteins by photochemical internalisation.

Directory of Open Access Journals (Sweden)

Kevin Mellert

Full Text Available Induced internalisation of functional proteins into cultured cells has become an important aspect in a rising number of in vitro and in vivo assays. The endo-lysosomal entrapment of the transduced proteins remains the major problem in all transduction protocols. In this study we compared the efficiency, cytotoxicity and protein targeting of different commercially available transduction reagents by transducing a well-studied fluorescently labelled protein (Atto488-bovine serum albumin into cultured human sarcoma cells. The amount of internalised protein and toxicity differed between the different reagents, but the percentage of transduced cells was consistently high. Furthermore, in all protocols the signals of the transduced Atto488-BSA were predominantly punctual consistent with an endosomal localisation. To overcome the endosomal entrapment, the transduction protocols were combined with a photochemical internalisation (PCI treatment. Using this combination revealed that an endosomal disruption is highly effective in cell penetrating peptide (CPP mediated transduction, whereas lipid-mediated transductions lead to a lower signal spreading throughout the cytosol. No change in the signal distribution could be achieved in treatments using non-lipid polymers as a transduction reagent. Therefore, the combination of protein transduction protocols based on CPPs with the endosomolytic treatment PCI can facilitate protein transduction experiments in vitro.

Enhancing endosomal escape of transduced proteins by photochemical internalisation.

Science.gov (United States)

Mellert, Kevin; Lamla, Markus; Scheffzek, Klaus; Wittig, Rainer; Kaufmann, Dieter

2012-01-01

Induced internalisation of functional proteins into cultured cells has become an important aspect in a rising number of in vitro and in vivo assays. The endo-lysosomal entrapment of the transduced proteins remains the major problem in all transduction protocols. In this study we compared the efficiency, cytotoxicity and protein targeting of different commercially available transduction reagents by transducing a well-studied fluorescently labelled protein (Atto488-bovine serum albumin) into cultured human sarcoma cells. The amount of internalised protein and toxicity differed between the different reagents, but the percentage of transduced cells was consistently high. Furthermore, in all protocols the signals of the transduced Atto488-BSA were predominantly punctual consistent with an endosomal localisation. To overcome the endosomal entrapment, the transduction protocols were combined with a photochemical internalisation (PCI) treatment. Using this combination revealed that an endosomal disruption is highly effective in cell penetrating peptide (CPP) mediated transduction, whereas lipid-mediated transductions lead to a lower signal spreading throughout the cytosol. No change in the signal distribution could be achieved in treatments using non-lipid polymers as a transduction reagent. Therefore, the combination of protein transduction protocols based on CPPs with the endosomolytic treatment PCI can facilitate protein transduction experiments in vitro.

Ozonolysis and Subsequent Photolysis of unsaturated organic molecules: Model Systems for Photochemical Aging of Organic Aerosol Particles

Science.gov (United States)

Park, J.; Gomez, A. L.; Walser, M. L.; Lin, A.; Nizkorodov, S. A.

2005-12-01

Chemical and photochemical aging of organic species adsorbed on aerosol particle surfaces is believed to have a significant effect on cloud condensation properties of atmospheric aerosols. Ozone initiated oxidation reactions of thin films of undecylenic acid and alkene-terminated self assembled monolayers (SAMs) on SiO2 surface were investigated using a combination of spectroscopic and mass spectrometric techniques. Photolysis of the oxidized film in the tropospheric actinic region (λ>290 nm) readily produces formaldehyde and formic acid as gas-phase products. Photodissociation action spectra of the oxidized film suggest that organic peroxides are responsible for the enhanced photochemical activity. The presence of peroxides in the oxidized sample was confirmed by mass-spectrometric analysis and by an iodometric test. Significant polymerization resulting from secondary reactions of Criegee radicals during ozonolysis of the film is also observed. The reaction mechanism and its implications for photochemical aging of atmospheric aerosol particles will be discussed.

Organic photochemical reactions on solid surfaces: Enrichment and separation of isotopes. Final report. SBIR-1988, Phase 2

International Nuclear Information System (INIS)

Ruderman, W.; Fehlner, J.; Spencer, J.

1988-01-01

The objectives of the Phase II program were to: (1) investigate organic photochemical reactions on solid porous silica surfaces, (2) utilize the magnetic isotope effect to develop a (13)C enrichment process using a fluidized bed reactor, and (3) investigate the possibility of enrichment of heavier isotopes having a nuclear spin. Although researchers were able to demonstrate a continuous fluidized bed (13)C enrichment process, analysis showed that the process could not compete with low temperature distillation of CO because of the high cost of the starting material, dibenzylketone (DBK), and the difficulty of converting the photochemical decomposition products back to DBK. However, the process shows promise for the separation of heavier isotopes such as (29)Si. The photochemical studies led to the discovery that the selectivity for terminal chlorination of alkanes can be increased more than 25 fold by sorbing the alkanes on ZSM-5 zeolites in a fluidized bed. The selectivity is ascribed to the presence of interfaces within the crystals

Particle number concentration, size distribution and chemical composition during haze and photochemical smog episodes in Shanghai.

Science.gov (United States)

Wang, Xuemei; Chen, Jianmin; Cheng, Tiantao; Zhang, Renyi; Wang, Xinming

2014-09-01

The aerosol number concentration and size distribution as well as size-resolved particle chemical composition were measured during haze and photochemical smog episodes in Shanghai in 2009. The number of haze days accounted for 43%, of which 30% was severe (visibilitysmog episodes, about 5.89 times and 4.29 times those of clean days. The particle volume concentration and surface concentration in haze, photochemical smog and clean days were 102, 49, 15μm(3)/cm(3) and 949, 649, 206μm(2)/cm(3), respectively. As haze events got more severe, the number concentration of particles smaller than 50nm decreased, but the particles of 50-200nm and 0.5-1μm increased. The diurnal variation of particle number concentration showed a bimodal pattern in haze days. All soluble ions were increased during haze events, of which NH4(+), SO4(2-) and NO3(-) increased greatly, followed by Na(+), K(+), Ca(2+) and Cl(-). These ions were very different in size-resolved particles during haze and photochemical smog episodes. Copyright © 2014. Published by Elsevier B.V.

Photochemical recombination of deep centers in silicon: decay of donor-acceptor pairs

International Nuclear Information System (INIS)

Adilov, K.A.

1991-01-01

Processes of photochemical recombination of deep impurity centers (DIC) in p-Si alloyed by Te, Zn and Fe occuring at 300-350 K under irradiation by super-low-energy light from δ 14 -10 17 quantum/cm 2 )Xs intensity impurity absorption range, are considered

Atmospheric photochemical reactivity and ozone production at two sites in Hong Kong: Application of a Master Chemical Mechanism-photochemical box model

Science.gov (United States)

Ling, Z. H.; Guo, H.; Lam, S. H. M.; Saunders, S. M.; Wang, T.

2014-09-01

A photochemical box model incorporating the Master Chemical Mechanism (v3.2), constrained with a full suite of measurements, was developed to investigate the photochemical reactivity of volatile organic compounds at a semirural site (Mount Tai Mo Shan (TMS)) and an urban site (Tsuen Wan (TW)) in Hong Kong. The levels of ozone (O3) and its precursors, and the magnitudes of the reactivity of O3 precursors, revealed significant differences in the photochemistry at the two sites. Simulated peak hydroperoxyl radical (HO2) mixing ratios were similar at TW and TMS (p = 0.05), while the simulated hydroxyl radical (OH) mixing ratios were much higher at TW (p TMS, but at TW, both HCHO and O3 photolyses were found to be major contributors. By contrast, radical-radical reactions governed HOx radical losses at TMS, while at TW, the OH + NO2 reaction was found to dominate in the morning and the radical-radical reactions at noon. Overall, the conversion of NO to NO2 by HO2 dictated the O3 production at the two sites, while O3 destruction was dominated by the OH + NO2 reaction at TW, and at TMS, O3 photolysis and the O3 + HO2 reaction were the major mechanisms. The longer OH chain length at TMS indicated that more O3 was produced for each radical that was generated at this site.

Accounting for the decrease of photosystem photochemical efficiency with increasing irradiance to estimate quantum yield of leaf photosynthesis.

Science.gov (United States)

Yin, Xinyou; Belay, Daniel W; van der Putten, Peter E L; Struik, Paul C

2014-12-01

Maximum quantum yield for leaf CO2 assimilation under limiting light conditions (Φ CO2LL) is commonly estimated as the slope of the linear regression of net photosynthetic rate against absorbed irradiance over a range of low-irradiance conditions. Methodological errors associated with this estimation have often been attributed either to light absorptance by non-photosynthetic pigments or to some data points being beyond the linear range of the irradiance response, both causing an underestimation of Φ CO2LL. We demonstrate here that a decrease in photosystem (PS) photochemical efficiency with increasing irradiance, even at very low levels, is another source of error that causes a systematic underestimation of Φ CO2LL. A model method accounting for this error was developed, and was used to estimate Φ CO2LL from simultaneous measurements of gas exchange and chlorophyll fluorescence on leaves using various combinations of species, CO2, O2, or leaf temperature levels. The conventional linear regression method under-estimated Φ CO2LL by ca. 10-15%. Differences in the estimated Φ CO2LL among measurement conditions were generally accounted for by different levels of photorespiration as described by the Farquhar-von Caemmerer-Berry model. However, our data revealed that the temperature dependence of PSII photochemical efficiency under low light was an additional factor that should be accounted for in the model.

Photochemical and Spectroscopic Effects Resulting from Excimer Laser Excitation.

Science.gov (United States)

Wang, Xuan Xiao

I. Photochemical production of ozone from pure oxygen using excimer lasers. Production of ozone was observed from experiments when oxygen was under a broadband pulsed KrF laser radiation. The production process was found to be autocatalytic. Mechanisms for the ozone formation were proposed. Experimental results over a range of oxygen pressure and laser pulse energy (irradiance) provided evidences in favor of the proposed mechanisms. Experiments were also numerically modeled. Good agreement between the experimental and the numerical results were observed, which provided further evidence to support the proposed mechanisms. Cross sections for some photochemical processes in the mechanisms were estimated. Production of ozone from pure oxygen under a ArF excimer laser radiation (193 nm) was also studied and numerically modeled. Effects of ambient water vapor on ozone production were investigated. Experimental results showed a fast ozone destruction when water vapor was present in the cell. However, numerical results obtained from the well-known OH and HO _2 chain ozone destruction mechanism predicted a slower ozone destruction. Possible reasons for the discrepancy are discussed. II. Resonance-enhanced multiphoton ionization of N_2 at 193 and 248 nm detected by N_sp{2}{+} fluorescence. Using a broadband excimer laser operating at 193 and 248 nm multiphoton ionization at high pressures in air and pure nitrogen has been detected by fluorescence from N_sp{2}{+} in the B-X firstnegative system. Measurements of the fluorescence intensity as a function of beam irradiance indicate resonance in N_2 at the energy of two 193 nm photons (2 + 1 REMPI) and three 248 nm photons (3 + 1 REMPI). Possible intermediate states are discussed. III. Excimer laser-induced fluorescence from some organic solvents. Fluorescence was observed from vapor phase benzene, toluene, p-xylene, benzyl chloride, methyl benzoate, acetic anhydride, ether, methanol, ethyl acetone, acetone, and 2-butanone using

Organic reactions for the electrochemical and photochemical production of chemical fuels from CO2--The reduction chemistry of carboxylic acids and derivatives as bent CO2 surrogates.

Science.gov (United States)

Luca, Oana R; Fenwick, Aidan Q

2015-11-01

The present review covers organic transformations involved in the reduction of CO2 to chemical fuels. In particular, we focus on reactions of CO2 with organic molecules to yield carboxylic acid derivatives as a first step in CO2 reduction reaction sequences. These biomimetic initial steps create opportunities for tandem electrochemical/chemical reductions. We draw parallels between long-standing knowledge of CO2 reactivity from organic chemistry, organocatalysis, surface science and electrocatalysis. We point out some possible non-faradaic chemical reactions that may contribute to product distributions in the production of solar fuels from CO2. These reactions may be accelerated by thermal effects such as resistive heating and illumination. Copyright © 2015 Elsevier B.V. All rights reserved.

Studies of Silyl-Transfer Photochemical Reactions of N-[(Trimethylsilyl)alkyl]saccharins

Energy Technology Data Exchange (ETDEWEB)

Cho, Dae Won; Oh, Sun Wha; Park, Hea Jung; Yoon, Ung Chan [Pusan National University, Busan (Korea, Republic of); Kim, Dong Uk [Daegu National University of Education, Daegu (Korea, Republic of); Xue, Jin Ying [Harbin Normal University, Harbin (China); Mariano, Patrick S. [University of New Mexico, Albuquerque (United States)

2010-09-15

Photochemical studies of N-[(trimethylsilyl)alkyl]saccharins were carried out to investigate their photochemical behavior. Depending on the nature of the substrate and the solvent system employed, reactions of these substances can take place by either SET-promoted silyl migration from carbon to either the amide carbonyl or sulfonyl oxygen or by a N-S homolysis route. The results of the current studies show that an azomethine ylide, arising from a SET-promoted silyl migration pathway, is generated in photoreactions of N-[(trimethylsilyl)methyl]saccharin and this intermediate reacts to give various photoproducts depending on the conditions employed. In addition, irradiation of N-[(trimethylsily)ethyl]saccharin produces an excited state that reacts through two pathways, the relative importance is governed by solvent polarity and protic nature. Finally, photoirradiation of N-[(trimethylsilyl)propyl]saccharin in a highly polar solvent system comprised of 35% aqueous MeOH gives rise to formation of a tricyclic pyrrolizidine and saccharin that generated via competitive SET-promoted silyl transfer and γ-hydrogen abstraction pathways.

Studies of Silyl-Transfer Photochemical Reactions of N-[(Trimethylsilyl)alkyl]saccharins

International Nuclear Information System (INIS)

Cho, Dae Won; Oh, Sun Wha; Park, Hea Jung; Yoon, Ung Chan; Kim, Dong Uk; Xue, Jin Ying; Mariano, Patrick S.

2010-01-01

Photochemical studies of N-[(trimethylsilyl)alkyl]saccharins were carried out to investigate their photochemical behavior. Depending on the nature of the substrate and the solvent system employed, reactions of these substances can take place by either SET-promoted silyl migration from carbon to either the amide carbonyl or sulfonyl oxygen or by a N-S homolysis route. The results of the current studies show that an azomethine ylide, arising from a SET-promoted silyl migration pathway, is generated in photoreactions of N-[(trimethylsilyl)methyl]saccharin and this intermediate reacts to give various photoproducts depending on the conditions employed. In addition, irradiation of N-[(trimethylsily)ethyl]saccharin produces an excited state that reacts through two pathways, the relative importance is governed by solvent polarity and protic nature. Finally, photoirradiation of N-[(trimethylsilyl)propyl]saccharin in a highly polar solvent system comprised of 35% aqueous MeOH gives rise to formation of a tricyclic pyrrolizidine and saccharin that generated via competitive SET-promoted silyl transfer and γ-hydrogen abstraction pathways

Light-driven dinitrogen reduction catalyzed by a CdS:nitrogenase MoFe protein biohybrid.

Science.gov (United States)

Brown, Katherine A; Harris, Derek F; Wilker, Molly B; Rasmussen, Andrew; Khadka, Nimesh; Hamby, Hayden; Keable, Stephen; Dukovic, Gordana; Peters, John W; Seefeldt, Lance C; King, Paul W

2016-04-22

The splitting of dinitrogen (N2) and reduction to ammonia (NH3) is a kinetically complex and energetically challenging multistep reaction. In the Haber-Bosch process, N2 reduction is accomplished at high temperature and pressure, whereas N2 fixation by the enzyme nitrogenase occurs under ambient conditions using chemical energy from adenosine 5'-triphosphate (ATP) hydrolysis. We show that cadmium sulfide (CdS) nanocrystals can be used to photosensitize the nitrogenase molybdenum-iron (MoFe) protein, where light harvesting replaces ATP hydrolysis to drive the enzymatic reduction of N2 into NH3 The turnover rate was 75 per minute, 63% of the ATP-coupled reaction rate for the nitrogenase complex under optimal conditions. Inhibitors of nitrogenase (i.e., acetylene, carbon monoxide, and dihydrogen) suppressed N2 reduction. The CdS:MoFe protein biohybrids provide a photochemical model for achieving light-driven N2 reduction to NH3. Copyright © 2016, American Association for the Advancement of Science.

Photochemical oxygen reduction by zinc phthalocyanine and silver/gold nanoparticle incorporated silica thin films

Energy Technology Data Exchange (ETDEWEB)

Pal, Manas; Ganesan, Vellaichamy, E-mail: velganesh@yahoo.com; Azad, Uday Pratap

2012-12-15

Silver or gold nanoparticles are synthesized using a borohydride reduction method and are anchored simultaneously into/onto the mercaptopropyl functionalized silica. Later, zinc phthalocyanine is adsorbed onto the above materials. Thin films of these materials are prepared by coating an aqueous colloidal suspension of the respective material onto glass plates. Visible light irradiation of these films in oxygen saturated, stirred aqueous solutions effectively reduces oxygen to hydrogen peroxide. The photocatalytic reduction of oxygen is explained on the basis of the semiconducting properties of the silica films. The back electron transfer reaction is largely prevented by means of a sacrificial electron donor, triethanolamine. - Highlights: Black-Right-Pointing-Pointer Zinc phthalocyanine adsorbed silica materials were prepared. Black-Right-Pointing-Pointer Thin films of these materials photocatalytically reduce oxygen. Black-Right-Pointing-Pointer The photocatalysis is explained based on semiconductor properties of the materials. Black-Right-Pointing-Pointer Metal nanoparticles increase the photocatalytic efficiency of the materials.

Photochemical Cyclopolymerization of Polyimides in Ultraviolet Ridgidizing Composites for Use in Inflatable Structures, Phase I

Data.gov (United States)

National Aeronautics and Space Administration — This innovation uses photochemical cyclopolymerization of polyimides to manufacture ultraviolet rigidizable composites for use in RIS (ridgidizing inflatable)...

A Highly Effective Photochemical System for Complex Treatment of Heavily Contaminated Wastewaters

Czech Academy of Sciences Publication Activity Database

Krystyník, Pavel; Klusoň, Petr; Hejda, S.; Mašín, P.; Tito, D.N.

2014-01-01

Roč. 86, č. 11 (2014), s. 2212-2220 ISSN 1061-4303 R&D Projects: GA MPO(CZ) FR-TI1/065 Institutional support: RVO:67985858 Keywords : advanced oxidation processes * photochemical oxidation * wastewater treatment Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 0.865, year: 2014

Photoperiod and temperature constraints on the relationship between the photochemical reflectance index and the light use efficiency of photosynthesis in Pinus strobus.

Science.gov (United States)

Fréchette, Emmanuelle; Chang, Christine Yao-Yun; Ensminger, Ingo

2016-03-01

The photochemical reflectance index (PRI) is a proxy for the activity of the photoprotective xanthophyll cycle and photosynthetic light use efficiency (LUE) in plants. Evergreen conifers downregulate photosynthesis in autumn in response to low temperature and shorter photoperiod, and the dynamic xanthophyll cycle-mediated non-photochemical quenching (NPQ) is replaced by sustained NPQ. We hypothesized that this shift in xanthophyll cycle-dependent energy partitioning during the autumn is the cause for variations in the PRI-LUE relationship. In order to test our hypothesis, we characterized energy partitioning and pigment composition during a simulated summer-autumn transition in a conifer and assessed the effects of temperature and photoperiod on the PRI-LUE relationship. We measured gas exchange, chlorophyll fluorescence and leaf reflectance during the photosynthetic downregulation in Pinus strobus L. seedlings exposed to low temperature/short photoperiod or elevated temperature/short photoperiod conditions. Shifts in energy partitioning during simulated autumn were observed when the pools of chlorophylls decreased and pools of photoprotective carotenoids increased. On a seasonal timescale, PRI was controlled by carotenoid pool sizes rather than xanthophyll cycle dynamics. Photochemical reflectance index variation under cold autumn conditions mainly reflected long-term pigment pool adjustments associated with sustained NPQ, which impaired the PRI-LUE relationship. Exposure to warm autumn conditions prevented the induction of sustained NPQ but still impaired the PRI-LUE relationship. We therefore conclude that alternative zeaxanthin-independent NPQ mechanisms, which remain undetected by the PRI, are present under both cold and warm autumn conditions, contributing to the discrepancy in the PRI-LUE relationship during autumn. © The Author 2016. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Polymers designed for laser ablation-influence of photochemical properties

International Nuclear Information System (INIS)

Lippert, T.; Dickinson, J.T.; Hauer, M.; Kopitkovas, G.; Langford, S.C.; Masuhara, H.; Nuyken, O.; Robert, J.; Salmio, H.; Tada, T.; Tomita, K.; Wokaun, A.

2002-01-01

The ablation characteristics of various polymers were studied at low and high fluences. The polymers can be divided into three groups, i.e. polymers containing triazene and ester groups, the same polymers without the triazene group, and polyimide as reference polymer. At high fluences similar ablation parameters, i.e. etch rates and effective absorption coefficients, were obtained for all polymers. The main difference is the absence of carbon deposits for the designed polymers. At low fluences (at 308 nm) very pronounced differences are detected. The polymers containing the photochemically most active group (triazene) exhibit the lowest threshold of ablation (as low as 25 mJ cm -2 ) and the highest etch rates (up to 3 μm/pulse), followed by the designed polyesters and then polyimide. The laser-induced decomposition of the designed polymers was studied by nanosecond-interferometry. Only the triazene-polymer reveals etching without any sign of surface swelling, which is observed for all other polymers. The etching of the triazene-polymer starts and ends with the laser pulse, clearly indicating photochemical etching. The triazene-polymer was also studied by time-of-flight mass spectrometry (TOF-MS). The intensities of the ablation fragments show pronounced differences between irradiation at the absorption band of the triazene group (308 nm) and irradiation at a shorter wavelength (248 nm)

Photochemical degradation of the carbapenem antibiotics imipenem and meropenem in aqueous solutions under solar radiation.

Science.gov (United States)

Reina, Alejandro Cabrera; Martínez-Piernas, Ana B; Bertakis, Yannis; Brebou, Christina; Xekoukoulotakis, Nikolaos P; Agüera, Ana; Sánchez Pérez, José Antonio

2018-01-01

This paper deals with the photochemical fate of two representative carbapenem antibiotics, namely imipenem and meropenem, in aqueous solutions under solar radiation. The analytical method employed for the determination of the target compounds in various aqueous matrices, such as ultrapure water, municipal wastewater treatment plant effluents, and river water, at environmentally relevant concentrations, was liquid chromatography coupled with hybrid triple quadrupole-linear ion trap-mass spectrometry. The absorption spectra of both compounds were measured in aqueous solutions at pH values from 6 to 8, and both compounds showed a rather strong absorption band centered at about 300 nm, while their molar absorption coefficient was in the order from 9 × 10 3 -10 4  L mol -1  cm -1 . The kinetics of the photochemical degradation of the target compounds was studied in aqueous solutions under natural solar radiation in a solar reactor with compound parabolic collectors. It was found that the photochemical degradation of both compounds at environmentally relevant concentrations follows first order kinetics and the quantum yield was in the order of 10 -3  mol einsten -1 . Several parameters were studied, such as solution pH, the presence of nitrate ions and humic acids, and the effect of water matrix. In all cases, it was found that the presence of various organic and inorganic constituents in the aqueous matrices do not contribute significantly, either positively or negatively, to the photochemical degradation of both compounds under natural solar radiation. In a final set of photolysis experiments, the effect of the level of irradiance was studied under simulated solar radiation and it was found that the quantum yield for the direct photodegradation of both compounds remained practically constant by changing the incident solar irradiance from 28 to 50 W m -2 . Copyright © 2017 Elsevier Ltd. All rights reserved.

Photochemical reaction of Si-substituted ethynylsilanes with 1,2-ethanedithiol

Energy Technology Data Exchange (ETDEWEB)

Voronkov, M.G.; Brodskaya, E.I.; Kalabin, G.A.; Vlasova, N.N.; Yarosh, O.G.; Zhila, G.Y.

1985-12-01

The authors investigate the chief products of the photochemical reactions of Si-substituted ethynylsilanes with 1,2,-ethanedithiol at 60-70 C. It is found that the chief products are 2-triorganylsilyl-substituted 1,4-dithiacyclopentanes and 1,4-dithiacyclohexanes. On lowering the temperature to -30 C, formation of bis (triorganylsilyl)-substituted 1,4,7,10-tetrathiacyclododecanes occurs along with the abo ve-mentioned five- and six-membered heterocycles.

Heterologous Expression of Moss Light-harvesting Complex Stress-related 1 (LHCSR1), the Chlorophyll a-Xanthophyll Pigment-protein Complex Catalyzing Non-photochemical Quenching, in Nicotiana sp.*

Science.gov (United States)

Pinnola, Alberta; Ghin, Leonardo; Gecchele, Elisa; Merlin, Matilde; Alboresi, Alessandro; Avesani, Linda; Pezzotti, Mario; Capaldi, Stefano; Cazzaniga, Stefano; Bassi, Roberto

2015-01-01

Oxygenic photosynthetic organisms evolved mechanisms for thermal dissipation of energy absorbed in excess to prevent formation of reactive oxygen species. The major and fastest component, called non-photochemical quenching, occurs within the photosystem II antenna system by the action of two essential light-harvesting complex (LHC)-like proteins, photosystem II subunit S (PSBS) in plants and light-harvesting complex stress-related (LHCSR) in green algae and diatoms. In the evolutionary intermediate Physcomitrella patens, a moss, both gene products are active. These proteins, which are present in low amounts, are difficult to purify, preventing structural and functional analysis. Here, we report on the overexpression of the LHCSR1 protein from P. patens in the heterologous systems Nicotiana benthamiana and Nicotiana tabacum using transient and stable nuclear transformation. We show that the protein accumulated in both heterologous systems is in its mature form, localizes in the chloroplast thylakoid membranes, and is correctly folded with chlorophyll a and xanthophylls but without chlorophyll b, an essential chromophore for plants and algal LHC proteins. Finally, we show that recombinant LHCSR1 is active in quenching in vivo, implying that the recombinant protein obtained is a good material for future structural and functional studies. PMID:26260788

Photochemical alteration of organic carbon draining permafrost soils shifts microbial metabolic pathways and stimulates respiration.

Science.gov (United States)

Ward, Collin P; Nalven, Sarah G; Crump, Byron C; Kling, George W; Cory, Rose M

2017-10-03

In sunlit waters, photochemical alteration of dissolved organic carbon (DOC) impacts the microbial respiration of DOC to CO 2 . This coupled photochemical and biological degradation of DOC is especially critical for carbon budgets in the Arctic, where thawing permafrost soils increase opportunities for DOC oxidation to CO 2 in surface waters, thereby reinforcing global warming. Here we show how and why sunlight exposure impacts microbial respiration of DOC draining permafrost soils. Sunlight significantly increases or decreases microbial respiration of DOC depending on whether photo-alteration produces or removes molecules that native microbial communities used prior to light exposure. Using high-resolution chemical and microbial approaches, we show that rates of DOC processing by microbes are likely governed by a combination of the abundance and lability of DOC exported from land to water and produced by photochemical processes, and the capacity and timescale that microbial communities have to adapt to metabolize photo-altered DOC.The role of dissolved organic carbon (DOC) photo-alteration in the microbial respiration of DOC to CO 2 is unclear. Here, the authors show that the impact of this mechanism depends on whether photo-alteration of DOC produces or removes molecules used by native microbial communities prior to light exposure.

A review of photochemical approaches for the treatment of a wide range of pesticides.

Science.gov (United States)

Reddy, P Venkata Laxma; Kim, Ki-Hyun

2015-03-21

Pesticides are renowned as some of the most pernicious chemicals known to humankind. Nine out of twelve most hazardous and persistent organic chemicals on planet have been identified as pesticides and their derivatives. Because of their strong recalcitrant nature, it often becomes a difficult task to treat them by conventional approaches. It is well perceived that many factors can interfere with the degradation of pesticides under ambient conditions, e.g., media, light intensity, humic content, and other biological components. However, for the effective treatment of pesticides, photochemical methods are viewed as having clear and perceivable advantages. In this article, we provide a review of the fundamental characteristics of photochemical approaches for pesticide treatment and the factors governing their capacity and potential in such a process. Copyright © 2014 Elsevier B.V. All rights reserved.

Photochemical removal of NpF6 and PuF6 from UF6 gas streams

International Nuclear Information System (INIS)

Beitz, J.V.; Williams, C.W.

1990-01-01

A novel photochemical method of removing reactive fluorides from UF 6 gas has been discovered. This method reduces generated waste to little more than the volume of the removed impurities, minimizes loss of UF 6 , and can produce a recyclable by-product, fluorine gas. In our new method, impure UF 6 , is exposed to ultraviolet light which dissociates the UF 6 to UF 5 and fluorine atom. Impurities which chemically react with UF 5 are reduced and form solid compounds easily removed from the gas while UF 5 is converted back to UF 6 . Proof-of-concept testing involved UF 6 containing NpF 6 and PuF 6 with CO added as a fluorine atom scavenger. In a single photolysis step, greater than 5000-fold reduction of PuF 6 was demonstrated while reducing NpF 6 by more than 40-fold. This process is likely to remove corrosion and fission product fluorides that are more reactive than UF 6 and has been demonstrated without an added fluorine atom scavenger by periodically removing photogenerated fluorine gas. 44 refs., 3 figs., 2 tabs

Estimating CO2 Emission Reduction of Non-capture CO2 Utilization (NCCU) Technology

International Nuclear Information System (INIS)

Lee, Ji Hyun; Lee, Dong Woog; Gyu, Jang Se; Kwak, No-Sang; Lee, In Young; Jang, Kyung Ryoung; Shim, Jae-Goo; Choi, Jong Shin

2015-01-01

Estimating potential of CO 2 emission reduction of non-capture CO 2 utilization (NCCU) technology was evaluated. NCCU is sodium bicarbonate production technology through the carbonation reaction of CO 2 contained in the flue gas. For the estimating the CO 2 emission reduction, process simulation using process simulator (PRO/II) based on a chemical plant which could handle CO 2 of 100 tons per day was performed, Also for the estimation of the indirect CO 2 reduction, the solvay process which is a conventional technology for the production of sodium carbonate/sodium bicarbonate, was studied. The results of the analysis showed that in case of the solvay process, overall CO 2 emission was estimated as 48,862 ton per year based on the energy consumption for the production of NaHCO 3 (7.4 GJ/tNaHCO 3 ). While for the NCCU technology, the direct CO 2 reduction through the CO 2 carbonation was estimated as 36,500 ton per year and the indirect CO 2 reduction through the lower energy consumption was 46,885 ton per year which lead to 83,385 ton per year in total. From these results, it could be concluded that sodium bicarbonate production technology through the carbonation reaction of CO 2 contained in the flue was energy efficient and could be one of the promising technology for the low CO 2 emission technology.

Photochemical production of ozone in Beijing during the 2008 Olympic Games

Science.gov (United States)

Chou, C. C.-K.; Tsai, C.-Y.; Chang, C.-C.; Lin, P.-H.; Liu, S. C.; Zhu, T.

2011-09-01

As a part of the CAREBeijing-2008 campaign, observations of O3, oxides of nitrogen (NOx and NOy), CO, and hydrocarbons (NMHCs) were carried out at the air quality observatory of the Peking University in Beijing, China during August 2008, including the period of the 29th Summer Olympic Games. The measurements were compared with those of the CAREBeijing-2006 campaign to evaluate the effectiveness of the air pollution control measures, which were conducted for improving the air quality in Beijing during the Olympics. The results indicate that significant reduction in the emissions of primary air pollutants had been achieved; the monthly averaged mixing ratios of NOx, NOy, CO, and NMHCs decreased by 42.2, 56.5, 27.8, and 49.7 %, respectively. In contrast to the primary pollutants, the averaged mixing ratio of O3 increased by 42.2 %. Nevertheless, it was revealed that the ambient levels of total oxidant (Ox = O3+NO2+1.5 NOz) and NOz were reduced by 21.3 and 77.4 %, respectively. The contradictions between O3 and Ox were further examined in two case studies. Ozone production rates of 30-70 ppbv h-1 and OPEx of ~8 mole mole-1 were observed on a clear-sky day in spite of the reduced levels of precursors. In that case, it was found that the mixing ratio of O3 increased with the increasing NO2/NO ratio, whereas the NOz mixing ratio leveled off when NO2/NO>8. Consequently, the ratio of O3 to NOz increased to above 10, indicating the shift from VOC-sensitive regime to NOx-sensitive regime. However, in the other case, it was found that the O3 production was inhibited significantly due to substantial reduction in the NMHCs. According to the observations, it was suggested that the O3 and/or Ox production rates in Beijing should have been reduced as a result of the reduction in the emissions of precursors during the Olympic period. However, the nighttime O3 levels increased due to a decline in the NO-O3 titration, and the midday O3 peak levels were elevated because of the shift in

Sensitivity evaluation of the green alga Chlamydomonas reinhardtii to uranium by pulse amplitude modulated (PAM) fluorometry

Energy Technology Data Exchange (ETDEWEB)

Herlory, Olivier, E-mail: olivier.herlory@gmail.com [IRSN-Laboratoire d’Ecotoxicologie des Radionucléides, Centre de Cadarache, BP3, 13115 Saint Paul lez Durance (France); Bonzom, Jean-Marc, E-mail: jean-marc.bonzom@irsn.fr [IRSN-Laboratoire d’Ecotoxicologie des Radionucléides, Centre de Cadarache, BP3, 13115 Saint Paul lez Durance (France); Gilbin, Rodolphe, E-mail: rodolphe.gilbin@irsn.fr [IRSN-Laboratoire de Biogéochimie, Biodisponibilité et Transferts des Radionucléides, Centre de Cadarache, BP3, 13115 Saint Paul lez Durance (France)

2013-09-15

Highlights: •Our study addressed the toxicity thresholds of uranium on microalgae using PAM fluorometry. •The oxygen-evolving complex (OEC) of PSII was identified as the primary action site of uranium. •Uranium impaired the electron flux between the photosystems until almost complete inhibition. •Non-photochemical quenching was identified as the most sensitive fluorescence parameter. •PAM fluorometry provided a rapid and reasonably sensitive method for assessing stress response. -- Abstract: Although ecotoxicological studies tend to address the toxicity thresholds of uranium in freshwaters, there is a lack of information on the effects of the metal on physiological processes, particularly in aquatic plants. Knowing that uranium alters photosynthesis via impairment of the water photo-oxidation process, we determined whether pulse amplitude modulated (PAM) fluorometry was a relevant tool for assessing the impact of uranium on the green alga Chlamydomonas reinhardtii and investigated how and to what extent uranium hampered photosynthetic performance. Photosynthetic activity and quenching were assessed from fluorescence induction curves generated by PAM fluorometry, after 1 and 5 h of uranium exposure in controlled conditions. The oxygen-evolving complex (OEC) of PSII was identified as the primary action site of uranium, through alteration of the water photo-oxidation process as revealed by F{sub 0}/F{sub v}. Limiting re-oxidation of the plastoquinone pool, uranium impaired the electron flux between the photosystems until almost complete inhibition of the PSII quantum efficiency (F{sup ′}{sub q}/F{sup ′}{sub m}, EC{sub 50} = 303 ± 64 μg U L{sup −1} after 5 h of exposure) was observed. Non-photochemical quenching (qN) was identified as the most sensitive fluorescence parameter (EC{sub 50} = 142 ± 98 μg U L{sup −1} after 5 h of exposure), indicating that light energy not used in photochemistry was dissipated in non-radiative processes. It was shown

Bioavialability of Dom Photochemically Released from Resuspended Sediments

Science.gov (United States)

Avery, G. B., Jr.; Rainey, D. H.; Mead, R. N.; Skrabal, S. A.; Kieber, R. J.; Felix, J. D.; Helms, J. R.

2016-02-01

Little is known regarding the bioavailability of dissolved organic matter (DOM) released photochemically from resuspended estuarine sediments. Sediments were collected from two sites along the Cape Fear River estuary, NC, USA, size fractionated in 0.2 µm filtered Gulf Stream seawater and exposed to simulated sunlight for six hours. Light exposed samples resulted in increases of dissolved organic carbon (DOC) (34 ± 3 µM), chromophoric dissolved organic matter (CDOM) (a300nm, 2.7 m-1), and fluorescent dissolved organic matter (FDOM) (78.6 quinine sulfate equivalents (QSE)) compared to dark controls. Ultra high resolution mass spectrometric characterization indicated the photoreleased DOM was more oxidized and condensed based upon van Kreevlan analysis. Samples were then filtered and inoculated to a final ratio of 4% with coastal water sample filtered through a100 µm net to remove larger grazing organisms and particles while keeping most of bacterial community intact. All three parameters were monitored during a 30 day-long incubation in the dark to assess biological consumption and alteration. Previously light exposed samples had double (20 vs. 9 µM) the amount of DOC consumed compared to samples not previously exposed to light and twice the loss of CDOM (a300nm, 0.6 vs. 0.3 m-1) compared to samples not previously exposed to light. Previously light exposed samples resulted in a threefold loss of FDOM (9.5 QSE) compared to samples not previously exposed to light (2.8 QSE). Results of this study are important because they demonstrate dissolved organic matter released photochemically from resuspended sediments is more bioavailable than ambient material likely fueling secondary productivity and impacting ecosystem functioning in coastal regions.

Separation of the mercury isotopes by the indirect photochemical method

International Nuclear Information System (INIS)

Botter nee Bergheaud, F.; Scaringella nee Desnoyer, M.; Wacongne, M.

1976-01-01

A method of photochemical separation of the mercury isotopes by the so-called indirect route in which a gas stream of oxygen and butadiene containing a mixture of mercury isotopes is passed through one or a number of vessels placed in series. The gas stream is irradiated by a lamp containing mercury which is depleted in one or a number of the isotopes and said isotopes are recovered in a trap placed downstream of the vessel or vessels

APEX (Aqueous Photochemistry of Environmentally occurring Xenobiotics): a free software tool to predict the kinetics of photochemical processes in surface waters.

Science.gov (United States)

Bodrato, Marco; Vione, Davide

2014-04-01

The APEX software predicts the photochemical transformation kinetics of xenobiotics in surface waters as a function of: photoreactivity parameters (direct photolysis quantum yield and second-order reaction rate constants with transient species, namely ˙OH, CO₃(-)˙, (1)O₂ and the triplet states of chromophoric dissolved organic matter, (3)CDOM*), water chemistry (nitrate, nitrite, bicarbonate, carbonate, bromide and dissolved organic carbon, DOC), and water depth (more specifically, the optical path length of sunlight in water). It applies to well-mixed surface water layers, including the epilimnion of stratified lakes, and the output data are average values over the considered water column. Based on intermediate formation yields from the parent compound via the different photochemical pathways, the software can also predict intermediate formation kinetics and overall yield. APEX is based on a photochemical model that has been validated against available field data of pollutant phototransformation, with good agreement between model predictions and field results. The APEX software makes allowance for different levels of knowledge of a photochemical system. For instance, the absorption spectrum of surface water can be used if known, or otherwise it can be modelled from the values of DOC. Also the direct photolysis quantum yield can be entered as a detailed wavelength trend, as a single value (constant or average), or it can be defined as a variable if unknown. APEX is based on the free software Octave. Additional applications are provided within APEX to assess the σ-level uncertainty of the results and the seasonal trend of photochemical processes.

5-FU resistant EMT-like pancreatic cancer cells are hypersensitive to photochemical internalization of the novel endoglin-targeting immunotoxin CD105-saporin.

Science.gov (United States)

Lund, Kaja; Olsen, Cathrine Elisabeth; Wong, Judith Jing Wen; Olsen, Petter Angell; Solberg, Nina Therese; Høgset, Anders; Krauss, Stefan; Selbo, Pål Kristian

2017-12-19

-expressing 5-FUR cells, whereas little effect was seen in the CD105-negative non-resistant parental cancer cell lines. Strikingly, using the intracellular drug delivery method photochemical internalization (PCI) by combining light-controlled activation of the TPCS 2a with nanomolar levels of CD105-saporin resulted in strong cytotoxic effects in the 5-FUR cell population. Our findings suggested that autophagy is an important resistance mechanism against the chemotherapeutic drug 5-FU in pancreatic cancer cells, and that inhibition of the autophagy process, either by CQ or lysosomal photodamage, can contribute to increased sensitivity to 5-FU. For the first time, we demonstrate the promise of PCI-based targeting of CD105 in site-specific elimination of 5-FU resistant pancreatic cancer cells in vitro. In conclusion, PCI-based targeting of CD105 may represent a potent anticancer strategy and should be further evaluated in pre-clinical models.

Enhanced cellular delivery of cell-penetrating peptide-peptide nucleic acid conjugates by photochemical internalization

DEFF Research Database (Denmark)

Shiraishi, Takehiko; Nielsen, Peter E

2011-01-01

(antisense activity) is still limited by endocytotic entrapment. We have shown that this low bioavailability can be greatly improved by combining CPP-PNA conjugate administration with a photochemical internalization technique using photosensitizers such as aluminum phthalocyanine (AlPcS(2a...

Summary of photochemical and radiative data used in the LLNL one-dimensional transport-kinetics model of the troposphere and stratosphere: 1982

International Nuclear Information System (INIS)

Connell, P.S.; Wuebbles, D.J.

1983-01-01

This report summarizes the contents and sources of the photochemical and radiative segment of the LLNL one-dimensional transport-kinetics model of the troposphere and stratosphere. Data include the solar flux incident at the top of the atmosphere, absorption spectra for O 2 , O 3 and NO 2 , and effective absorption coefficients for about 40 photolytic processes as functions of wavelength and, in a few cases, temperature and pressure. The current data set represents understanding of atmospheric photochemical processes as of late 1982 and relies largely on NASA Evaluation Number 5 of Chemical Kinetics and Photochemical Data for Use in Stratospheric Modeling, JPL Publication 82-57 (DeMore et al., 1982). Implementation in the model, including the treatment of multiple scattering and cloud cover, is discussed in Wuebbles (1981)

Photochemically induced carbon dioxide production as a mechanism for carbon loss from plant litter in arid ecosystems

Science.gov (United States)

Brandt, L. A.; Bohnet, C.; King, J. Y.

2009-06-01

We investigated the potential for abiotic mineralization to carbon dioxide (CO2) via photodegradation to account for carbon (C) loss from plant litter under conditions typical of arid ecosystems. We exposed five species of grass and oak litter collected from arid and mesic sites to a factorial design of ultraviolet (UV) radiation (UV pass, UV block), and sterilization under dry conditions in the laboratory. UV pass treatments produced 10 times the amount of CO2 produced in UV block treatments. CO2 production rates were unaffected by litter chemistry or sterilization. We also exposed litter to natural solar radiation outdoors on clear, sunny days close to the summer solstice at midlatitudes and found that UV radiation (280-400 nm) accounted for 55% of photochemically induced CO2 production, while shortwave visible radiation (400-500 nm) accounted for 45% of CO2 production. Rates of photochemically induced CO2 production on a per-unit-mass basis decreased with litter density, indicating that rates depend on litter surface area. We found no evidence for leaching, methane production, or facilitation of microbial decomposition as alternative mechanisms for significant photochemically induced C loss from litter. We conclude that abiotic mineralization to CO2 is the primary mechanism by which C is lost from litter during photodegradation. We estimate that CO2 production via photodegradation could be between 1 and 4 g C m-2 a-1 in arid ecosystems in the southwestern United States. Taken together with low levels of litter production in arid systems, photochemical mineralization to CO2 could account for a significant proportion of annual carbon loss from litter in arid ecosystems.

Volatile organic compounds (VOCs) in photochemically aged air from the eastern and western Mediterranean

Science.gov (United States)

Derstroff, Bettina; Hüser, Imke; Bourtsoukidis, Efstratios; Crowley, John N.; Fischer, Horst; Gromov, Sergey; Harder, Hartwig; Janssen, Ruud H. H.; Kesselmeier, Jürgen; Lelieveld, Jos; Mallik, Chinmay; Martinez, Monica; Novelli, Anna; Parchatka, Uwe; Phillips, Gavin J.; Sander, Rolf; Sauvage, Carina; Schuladen, Jan; Stönner, Christof; Tomsche, Laura; Williams, Jonathan

2017-08-01

During the summertime CYPHEX campaign (CYprus PHotochemical EXperiment 2014) in the eastern Mediterranean, multiple volatile organic compounds (VOCs) were measured from a 650 m hilltop site in western Cyprus (34° 57' N/32° 23' E). Periodic shifts in the northerly Etesian winds resulted in the site being alternately impacted by photochemically processed emissions from western (Spain, France, Italy) and eastern (Turkey, Greece) Europe. Furthermore, the site was situated within the residual layer/free troposphere during some nights which were characterized by high ozone and low relative humidity levels. In this study we examine the temporal variation of VOCs at the site. The sparse Mediterranean scrub vegetation generated diel cycles in the reactive biogenic hydrocarbon isoprene, from very low values at night to a diurnal median level of 80-100 pptv. In contrast, the oxygenated volatile organic compounds (OVOCs) methanol and acetone exhibited weak diel cycles and were approximately an order of magnitude higher in mixing ratio (ca. 2.5-3 ppbv median level by day, range: ca. 1-8 ppbv) than the locally emitted isoprene and aromatic compounds such as benzene and toluene. Acetic acid was present at mixing ratios between 0.05 and 4 ppbv with a median level of ca. 1.2 ppbv during the daytime. When data points directly affected by the residual layer/free troposphere were excluded, the acid followed a pronounced diel cycle, which was influenced by various local effects including photochemical production and loss, direct emission, dry deposition and scavenging from advecting air in fog banks. The Lagrangian model FLEXPART was used to determine transport patterns and photochemical processing times (between 12 h and several days) of air masses originating from eastern and western Europe. Ozone and many OVOC levels were ˜ 20 and ˜ 30-60 % higher, respectively, in air arriving from the east. Using the FLEXPART calculated transport time, the contribution of photochemical

Physiological validation of photochemical reflectance index (PRI) as a photosynthetic parameter using Arabidopsis thaliana mutants.

Science.gov (United States)

Kohzuma, Kaori; Hikosaka, Kouki

2018-03-25

Non-photochemical quenching (NPQ) is the most important photoprotective system in higher plants. NPQ can be divided into several steps according to the timescale of relaxation of chlorophyll fluorescence after reaching a steady state (i.e., the fast phase, qE; middle phase, qZ or qT; and slow phase, qI). The dissipation of excess energy as heat during the xanthophyll cycle, a large component of NPQ, is detectable during the fast to middle phase (sec to min). Although thermal dissipation is primarily investigated using indirect methods such as chlorophyll a fluorescence measurements, such analyses require dark adaptation or the application of a saturating pulse during measurement, making it difficult to continuously monitor this process. Here, we designed an unconventional technique for real-time monitoring of changes in thylakoid lumen pH (as reflected by changes in xanthophyll pigment content) based on the photochemical reflectance index (PRI), which we estimated by measuring light-driven leaf reflectance at 531 nm. We analyzed two Arabidopsis thaliana mutants, npq1 (unable to convert violaxanthin to zeaxanthin due to inhibited violaxanthin de-epoxidase [VDE] activity) and npq4 (lacking PsbS protein), to uncover the regulator of the PRI. The PRI was variable in wild-type and npq4 plants, but not in npq1, indicating that the PRI is related to xanthophyll cycle-dependent thermal energy quenching (qZ) rather than the linear electron transport rate or NPQ. In situ lumen pH substitution using a pH-controlled buffer solution caused a shift in PRI. These results suggest that the PRI reflects only xanthophyll cycle conversion and is therefore a useful parameter for monitoring thylakoid lumen pH (reflecting VDE activity) in vivo. Copyright © 2018 The Authors. Published by Elsevier Inc. All rights reserved.

Photochemical fate and eco-genotoxicity assessment of the drug etodolac

Energy Technology Data Exchange (ETDEWEB)

Passananti, Monica [Dipartimento di Scienze Chimiche, Università di Napoli Federico II, Complesso Universitario Monte S. Angelo, via Cintia, 4, 80126 Napoli (Italy); Clermont Université, Université Blaise Pascal, Institut de Chimie de Clermont-Ferrand (ICCF) UMR 6296, BP 10448, F-63000 Clermont-Ferrand (France); Lavorgna, Margherita [Dipartimento di Scienze e Tecnologie Ambientali, Biologiche e Farmaceutiche, Seconda Università di Napoli, Via Vivaldi 43, I-81100 Caserta (Italy); Iesce, Maria Rosaria, E-mail: iesce@unina.it [Dipartimento di Scienze Chimiche, Università di Napoli Federico II, Complesso Universitario Monte S. Angelo, via Cintia, 4, 80126 Napoli (Italy); DellaGreca, Marina [Dipartimento di Scienze Chimiche, Università di Napoli Federico II, Complesso Universitario Monte S. Angelo, via Cintia, 4, 80126 Napoli (Italy); Brigante, Marcello [Clermont Université, Université Blaise Pascal, Institut de Chimie de Clermont-Ferrand (ICCF) UMR 6296, BP 10448, F-63000 Clermont-Ferrand (France); Criscuolo, Emma [Dipartimento di Scienze e Tecnologie Ambientali, Biologiche e Farmaceutiche, Seconda Università di Napoli, Via Vivaldi 43, I-81100 Caserta (Italy); Cermola, Flavio [Dipartimento di Scienze Chimiche, Università di Napoli Federico II, Complesso Universitario Monte S. Angelo, via Cintia, 4, 80126 Napoli (Italy); Isidori, Marina, E-mail: marina.isidori@unina2.it [Dipartimento di Scienze e Tecnologie Ambientali, Biologiche e Farmaceutiche, Seconda Università di Napoli, Via Vivaldi 43, I-81100 Caserta (Italy)

2015-06-15

The photochemical behavior of etodolac was investigated under various irradiation conditions. Kinetic data were obtained after irradiation of 10{sup −4} M aqueous solutions by UVB, UVA and direct exposure to sunlight. The Xenon lamp irradiation was used in order to determine the photodegradation quantum yield under sun-simulated condition (ϕ{sub sun}). The value was determined to be = 0.10 ± 0.01. In order to obtain photoproducts and for mechanistic purposes, experiments were carried out on more concentrated solutions by exposure to sunlight and to UVA and UVB lamps. The drug underwent photooxidative processes following an initial oxygen addition to the double bond of the five membered ring and was mainly converted into a spiro compound and a macrolactam. Ecotoxicity tests were performed on etodolac, its photostable spiro derivative and its sunlight irradiation mixture on two different aquatic trophic levels, plants (algae) and invertebrates (rotifers and crustaceans). Mutagenesis and genotoxicity were detected on bacterial strains. The results showed that only etodolac had long term effects on rotifers although at concentrations far from environmental detection values. A mutagenic and genotoxic potential was found for its derivative. - Highlights: • Photochemical transformation of etodolac occurs in the environment. • Etodolac was slightly toxic in the long term for some aquatic organisms. • A mutagenic and genotoxic potential was found for etodolac photostable derivative.

Water soluble peripheral and non-peripheral tetrasubstituted zinc phthalocyanines: Synthesis, photochemistry and bovine serum albumin binding behavior

Energy Technology Data Exchange (ETDEWEB)

Çakır, Volkan; Çakır, Dilek [Department of Chemistry, Faculty of Sciences, Karadeniz Technical University, 61080 Trabzon (Turkey); Pişkin, Mehmet [Department of Food Technology, Çanakkale Vocational School of Technical Sciences, Çanakkale Onsekiz Mart University, 17100 Çanakkale (Turkey); Durmuş, Mahmut [Gebze Institute of Technology, Department of Chemistry, PO Box 141, Gebze 41400, Kocaeli (Turkey); Bıyıklıoğlu, Zekeriya, E-mail: zekeriya_61@yahoo.com [Department of Chemistry, Faculty of Sciences, Karadeniz Technical University, 61080 Trabzon (Turkey)

2014-10-15

The new peripherally and non-peripherally tetra-1,3-bis[3-(diethylamino)phenoxy]propan-2-ol substituted zinc(II) phthalocyanine complexes (2a and 3a) and their quaternized amphiphilic derivatives (2b and 3b) have been synthesized and characterized using UV–vis, FT-IR, {sup 1}H-NMR, {sup 13}C-NMR, MS spectroscopic data and elemental analysis for the first time. The quaternized complexes (2b and 3b) show excellent solubility in water and DMSO which makes them potential photosensitizers for use in photodynamic therapy (PDT) of cancer. The photochemical (singlet oxygen generation and photodegradation under light irradiation) properties of these novel phthalocyanines are investigated in dimethylsulfoxide (DMSO) for non-quaternized complexes and in DMSO, phosphate buffered solution (PBS) or PBS+triton X-100 (TX) solution for quaternized complexes. In this study, the effects of the aggregation of the molecules, quaternization, position of the substituents (peripherally or non-peripherally) and nature of the solvents (DMSO, PBS or PBS+triton X-100) on the photochemical parameters of the zinc (II) phthalocyanines are also reported. In addition, a spectroscopic investigation of the binding behavior of the quaternized zinc(II) phthalocyanine complexes to bovine serum albumin (BSA) is also presented in this work. - Highlights: • Synthesis of zinc phthalocyanines is performed. • Photophysical and photochemical properties of phthalocyanines are studied. • Photodynamic therapy studies are performed.

Water soluble peripheral and non-peripheral tetrasubstituted zinc phthalocyanines: Synthesis, photochemistry and bovine serum albumin binding behavior

International Nuclear Information System (INIS)

Çakır, Volkan; Çakır, Dilek; Pişkin, Mehmet; Durmuş, Mahmut; Bıyıklıoğlu, Zekeriya

2014-01-01

The new peripherally and non-peripherally tetra-1,3-bis[3-(diethylamino)phenoxy]propan-2-ol substituted zinc(II) phthalocyanine complexes (2a and 3a) and their quaternized amphiphilic derivatives (2b and 3b) have been synthesized and characterized using UV–vis, FT-IR, 1 H-NMR, 13 C-NMR, MS spectroscopic data and elemental analysis for the first time. The quaternized complexes (2b and 3b) show excellent solubility in water and DMSO which makes them potential photosensitizers for use in photodynamic therapy (PDT) of cancer. The photochemical (singlet oxygen generation and photodegradation under light irradiation) properties of these novel phthalocyanines are investigated in dimethylsulfoxide (DMSO) for non-quaternized complexes and in DMSO, phosphate buffered solution (PBS) or PBS+triton X-100 (TX) solution for quaternized complexes. In this study, the effects of the aggregation of the molecules, quaternization, position of the substituents (peripherally or non-peripherally) and nature of the solvents (DMSO, PBS or PBS+triton X-100) on the photochemical parameters of the zinc (II) phthalocyanines are also reported. In addition, a spectroscopic investigation of the binding behavior of the quaternized zinc(II) phthalocyanine complexes to bovine serum albumin (BSA) is also presented in this work. - Highlights: • Synthesis of zinc phthalocyanines is performed. • Photophysical and photochemical properties of phthalocyanines are studied. • Photodynamic therapy studies are performed

Investigation of the photochemical changes of chlorogenic acids induced by ultraviolet light in model systems and in agricultural practice with Stevia rebaudiana cultivation as an example.

Science.gov (United States)

Karaköse, Hande; Jaiswal, Rakesh; Deshpande, Sagar; Kuhnert, Nikolai

2015-04-08

Mono- and diacyl chlorogenic acids undergo photochemical trans-cis isomerization under ultraviolet (UV) irradiation. The photochemical equilibrium composition was established for eight selected derivatives. In contrast to all other dicaffeoylquinic acid derivatives, cynarin (1,3-dicaffeoylquinic acid) undergoes a [2 + 2] photochemical cycloaddition reaction, constituting a first example of Schmidt's law in a natural product family. The relevance of photochemical isomerization in agricultural practice was investigated using 120 samples of Stevia rebaudiana leave samples grown under defined cultivation conditions. Ratios of cis to trans chlorogenic acids were determined in leaf samples and correlated with climatic and harvesting conditions. The data indicate a clear correlation between the formation of cis-caffeoyl derivatives and sunshine hours prior to harvesting and illustrate the relevance of UV exposure to plant material affecting its phytochemical composition.

Lipid antioxidant and galactolipid remodeling under temperature stress in tomato plants

Directory of Open Access Journals (Sweden)

Livia eSpicher

2016-02-01

Full Text Available Increased temperatures are a major scenario in climate change and present a threat to plant growth and agriculture. Plant growth depends on photosynthesis. To function optimally the photosynthetic machinery at the thylakoid membrane in chloroplasts continuously adapts to changing conditions. Here, we set out to discover the most important changes arising at the lipid level under high temperature (38°C in comparison to mild (20°C and moderately cold temperature (10°C using a non-targeted lipidomics approach. To our knowledge, no comparable experiment at the level of the whole membrane system has been documented. Here, 791 molecular species were detected by mass spectrometry and ranged from membrane lipids, prenylquinones (tocopherols, phylloquinone, plastoquinone, plastochromanol, carotenoids (β-carotene, xanthophylls to numerous unidentified compounds. At high temperatures, the most striking changes were observed for the prenylquinones (α-tocopherol and plastoquinone/-ol and the degree of saturation of fatty acids in galactolipids and phosphatidyl ethanolamine. Photosynthetic efficiency at high temperature was not affected but at moderately cold temperature mild photoinhibition occurred. The results indicate that the thylakoid membrane is remodeled with regard to fatty acid saturation in galactolipids and lipid antioxidant concentrations under high temperature stress. The data strongly suggest that massively increased concentrations of α-tocopherol and plastoquinone are important for protection against high temperature stress and proper function of the photosynthetic apparatus.

Kinetic analyses and mathematical modeling of primary photochemical and photoelectrochemical processes in plant photosystems

NARCIS (Netherlands)

Vredenberg, W.J.

2011-01-01

In this paper the model and simulation of primary photochemical and photo-electrochemical reactions in dark-adapted intact plant leaves is presented. A descriptive algorithm has been derived from analyses of variable chlorophyll a fluorescence and P700 oxidation kinetics upon excitation with

A single exposure to photochemical smog causes airway irritation and cardiac dysrhythmia in mice

Science.gov (United States)

The data presented here shows that a single exposure to photochemical smog causes airway irritation and cardiac dysrhythmia in mice. Smog, which is a complex mixture of particulate matter and gaseous irritants (ozone, sulfur dioxide, reactive aldehydes), as well as components whi...

APPLICATION OF BAYESIAN MONTE CARLO ANALYSIS TO A LAGRANGIAN PHOTOCHEMICAL AIR QUALITY MODEL. (R824792)

Science.gov (United States)

Uncertainties in ozone concentrations predicted with a Lagrangian photochemical air quality model have been estimated using Bayesian Monte Carlo (BMC) analysis. Bayesian Monte Carlo analysis provides a means of combining subjective "prior" uncertainty estimates developed ...

Non-catalyzed cathodic oxygen reduction at graphite granules in microbial fuel cells

International Nuclear Information System (INIS)

Freguia, Stefano; Rabaey, Korneel; Yuan Zhiguo; Keller, Juerg

2007-01-01

Oxygen is the most sustainable electron acceptor currently available for microbial fuel cell (MFC) cathodes. However, its high overpotential for reduction to water limits the current that can be produced. Several materials and catalysts have previously been investigated in order to facilitate oxygen reduction at the cathode surface. This study shows that significant stable currents can be delivered by using a non-catalyzed cathode made of granular graphite. Power outputs up to 21 W m -3 (cathode total volume) or 50 W m -3 (cathode liquid volume) were attained in a continuous MFC fed with acetate. These values are higher than those obtained in several other studies using catalyzed graphite in various forms. The presence of nanoscale pores on granular graphite provides a high surface area for oxygen reduction. The current generated with this cathode can sustain an anodic volume specific COD removal rate of 1.46 kg COD m -3 d -1 , which is higher than that of a conventional aerobic process. This study demonstrates that microbial fuel cells can be operated efficiently using high surface graphite as cathode material. This implies that research on microbial fuel cell cathodes should not only focus on catalysts, but also on high surface area materials

Non-catalyzed cathodic oxygen reduction at graphite granules in microbial fuel cells

Energy Technology Data Exchange (ETDEWEB)

Freguia, Stefano; Rabaey, Korneel; Yuan, Zhiguo; Keller, Juerg [The University of Queensland, St. Lucia, Qld (Australia). Advanced Wastewater Management Centre

2007-12-01

Oxygen is the most sustainable electron acceptor currently available for microbial fuel cell (MFC) cathodes. However, its high overpotential for reduction to water limits the current that can be produced. Several materials and catalysts have previously been investigated in order to facilitate oxygen reduction at the cathode surface. This study shows that significant stable currents can be delivered by using a non-catalyzed cathode made of granular graphite. Power outputs up to 21 W m{sup -3} (cathode total volume) or 50 W m{sup -3} (cathode liquid volume) were attained in a continuous MFC fed with acetate. These values are higher than those obtained in several other studies using catalyzed graphite in various forms. The presence of nanoscale pores on granular graphite provides a high surface area for oxygen reduction. The current generated with this cathode can sustain an anodic volume specific COD removal rate of 1.46 kg{sub COD} m{sup -3} d{sup -1}, which is higher than that of a conventional aerobic process. This study demonstrates that microbial fuel cells can be operated efficiently using high surface graphite as cathode material. This implies that research on microbial fuel cell cathodes should not only focus on catalysts, but also on high surface area materials. (author)

Stacking effect on the ferroelectric properties of PZT/PLZT multilayer thin films formed by photochemical metal-organic deposition

International Nuclear Information System (INIS)

Park, Hyeong-Ho; Park, Hyung-Ho; Hill, Ross H.

2004-01-01

The ferroelectric properties of lead zirconate titanate (PZT) and lanthanum-doped lead zirconate titanate (PLZT) multilayer films formed by photochemical metal-organic deposition (PMOD) using photosensitive precursors have been characterized. The substitution of La for Pb was reported to induce improved ferroelectric properties, especially fatigue resistance, through the reduction of oxygen vacancies. The relation between La-substitution and the ferroelectric properties was investigated by characterization of the effect of the order of stacking four ferroelectric layers of PZT or PLZT in the multilayer films 4-PZT, PZT/2-PLZT/PZT, PLZT/2-PZT/PLZT, and 4-PLZT. The films with the PLZT layer at the top and bottom showed an improvement in the fatigue resistance. It was revealed that defect dipole such as O vacancy was reduced at the ferroelectric/Pt interface by doping with La. Also, the bottom layer, just on Pt substrate had a significant influence on the surface microstructure and growth orientation of ferroelectric film

Radiolytic and photochemical reduction of carbon dioxide in solution catalyzed by transition metal complexes with some selected macrocycles

International Nuclear Information System (INIS)

Grodkowski, J.

2004-01-01

The main goal of the work presented in this report is an explanation of the mechanism of carbon dioxide (CO 2 ) reduction catalyzed by transition metal complexes with some selected macrocycles. The catalytic function of two electron exchange centers in the reduction of CO 2 , an inner metal and a macrocycle ring, was defined. Catalytic effects of rhodium, iron and cobalt porphyrins, cobalt and iron phthalocyanines and corroles as well as cobalt corrins have been investigated. CO 2 reduction by iron ions without presence of macrocycles and also in presence of copper compounds in aqueous solutions have been studied as well

Chloroplastic and stomatal aspects of ozone-induced reduction of net photosynthesis in plants

Energy Technology Data Exchange (ETDEWEB)

Torsethaugen, Gro

1998-09-01

The present thesis relates to ozone-induced reduction of photosynthesis in plants. As a photochemical oxidant O{sub 3} is formed by the interaction of hydrocarbons, nitrogen oxides and oxygen in sunlight. Ozone (O{sub 3}) is the most phytotoxic of all the air pollutants and is known to reduce plant growth and net photosynthesis, cause stomatal closure, induce visible injury, accelerate senescence and induce or inhibit transcription of a variety of genes with a corresponding increase/decrease in protein products. The underlying cellular mechanisms for many of these changes are unknown. Following fields are investigated: Ozone-induced reduction of net photosynthesis; ozone and the photosynthetic apparatus in the chloroplasts; ozone and stomata; ozone effects on plant membranes; protection against ozone injury in plants. 249 refs., 22 figs., 4 tabs.

Photochemical cycle of bacteriorhodopsin studied by resonance Raman spectroscopy.

Science.gov (United States)

Stockburger, M; Klusmann, W; Gattermann, H; Massig, G; Peters, R

1979-10-30

Individual species of the photochemical cycle of bacteriorhodopsin, a retinal-protein complex of Halobacteria, were studied in aqueous suspensions of the "purple membrane" at room temperature by resonance Raman (RR) spectroscopy with flow systems. Two pronounced deuterium shifts were found in the RR spectra of the all-trans complex BR-570 in H2O-D2O suspensions. The first is ascribed to C=NH+ (C=ND+) stretching vibrations of the protonated Schiff base which links retinal to opsin. The second is assigned tentatively to an "X-H" ("X-D") bending mode, where "X" is an atom which carries an exchangeable proton. A RR spectrum of the 13-cis-retinal complex "BR-548" could be deduced from spectra of the dark-adapted purple membrane. The RR spectrum of the M-412 intermediate was monitored in a double-beam pump-probe experiment. The main vibrational features of the intermediate M' in the reaction M-412 in equilibrium hv M' leads to delta BR-570 could be deduced from a photostationary mixture of M-412 and M'. Difference procedures were applied to obtain RR spectra of the L-550 intermediate and of two new long-lived species, R1'-590 and R2-550. From kinetic data it is suggested that T1'-590 links the proton-translocating cycle to the "13-cis" cycle of BR-548. The protonation and isomeric states of the different species are discussed in light of the new spectroscopic and kinetic data. It is found that conformational changes during the photochemical cycle play an important role.

The reduction of retinal autofluorescence caused by light exposure.

Science.gov (United States)

Morgan, Jessica I W; Hunter, Jennifer J; Merigan, William H; Williams, David R

2009-12-01

A prior study showed that long exposure to 568-nm light at levels below the maximum permissible exposure safety limit produces retinal damage preceded by a transient reduction in the autofluorescence of retinal pigment epithelial (RPE) cells in vivo. The present study shows how the effects of exposure power and duration combine to produce this autofluorescence reduction and find the minimum exposure causing a detectable autofluorescence reduction. Macaque retinas were imaged using a fluorescence adaptive optics scanning laser ophthalmoscope to resolve individual RPE cells in vivo. The retina was exposed to 568-nm light over a square subtending 0.5 degrees with energies ranging from 1 to 788 J/cm(2), where power and duration were independently varied. In vivo exposures of 5 J/cm(2) and higher caused an immediate decrease in autofluorescence followed by either full autofluorescence recovery (exposures or= 247 J/cm(2)). No significant autofluorescence reduction was observed for exposures of 2 J/cm(2) and lower. Reciprocity of exposure power and duration held for the exposures tested, implying that the total energy delivered to the retina, rather than its distribution in time, determines the amount of autofluorescence reduction. That reciprocity held is consistent with a photochemical origin, which may or may not cause retinal degeneration. The implementation of safe methods for delivering light to the retina requires a better understanding of the mechanism causing autofluorescence reduction. Finally, RPE imaging was demonstrated using light levels that do not cause a detectable reduction in autofluorescence.

Effects of Biological and Photochemical Degradation on the Optical Properties of CDOM Exported to Coastal Marine Environments

National Research Council Canada - National Science Library

Moran, Mary

2004-01-01

.... This project quantitatively assessed the ability of coastal ocean bacteria to degrade and produce CDOM and investigated the synergistic interactions between bacterial degradation and photochemical...

Effect of heavy atoms on photochemically induced dynamic nuclear polarization in liquids

Science.gov (United States)

Okuno, Yusuke; Cavagnero, Silvia

2018-01-01

Given its short hyperpolarization time (∼10-6 s) and mostly non-perturbative nature, photo-chemically induced dynamic nuclear polarization (photo-CIDNP) is a powerful tool for sensitivity enhancement in nuclear magnetic resonance. In this study, we explore the extent of 1H-detected 13C nuclear hyperpolarization that can be gained via photo-CIDNP in the presence of small-molecule additives containing a heavy atom. The underlying rationale for this methodology is the well-known external-heavy-atom (EHA) effect, which leads to significant enhancements in the intersystem-crossing rate of selected photosensitizer dyes from photoexcited singlet to triplet. We exploited the EHA effect upon addition of moderate amounts of halogen-atom-containing cosolutes. The resulting increase in the transient triplet-state population of the photo-CIDNP sensitizer fluorescein resulted in a significant increase in the nuclear hyperpolarization achievable via photo-CIDNP in liquids. We also explored the internal-heavy-atom (IHA) effect, which is mediated by halogen atoms covalently incorporated into the photosensitizer dye. Widely different outcomes were achieved in the case of EHA and IHA, with EHA being largely preferable in terms of net hyperpolarization.

Photochemical redox reactions of copper(II)-alanine complexes in aqueous solutions.

Science.gov (United States)

Lin, Chen-Jui; Hsu, Chao-Sheng; Wang, Po-Yen; Lin, Yi-Liang; Lo, Yu-Shiu; Wu, Chien-Hou

2014-05-19

The photochemical redox reactions of Cu(II)/alanine complexes have been studied in deaerated solutions over an extensive range of pH, Cu(II) concentration, and alanine concentration. Under irradiation, the ligand-to-metal charge transfer results in the reduction of Cu(II) to Cu(I) and the concomitant oxidation of alanine, which produces ammonia and acetaldehyde. Molar absorptivities and quantum yields of photoproducts for Cu(II)/alanine complexes at 313 nm are characterized mainly with the equilibrium Cu(II) speciation where the presence of simultaneously existing Cu(II) species is taken into account. By applying regression analysis, individual Cu(I) quantum yields are determined to be 0.094 ± 0.014 for the 1:1 complex (CuL) and 0.064 ± 0.012 for the 1:2 complex (CuL2). Individual quantum yields of ammonia are 0.055 ± 0.007 for CuL and 0.036 ± 0.005 for CuL2. Individual quantum yields of acetaldehyde are 0.030 ± 0.007 for CuL and 0.024 ± 0.007 for CuL2. CuL always has larger quantum yields than CuL2, which can be attributed to the Cu(II) stabilizing effect of the second ligand. For both CuL and CuL2, the individual quantum yields of Cu(I), ammonia, and acetaldehyde are in the ratio of 1.8:1:0.7. A reaction mechanism for the formation of the observed photoproducts is proposed.

Photochemical oxidants: state of the science.

Science.gov (United States)

Kley, D; Kleinmann, M; Sanderman, H; Krupa, S

1999-01-01

Atmospheric photochemical processes resulting in the production of tropospheric ozone (O(3)) and other oxidants are described. The spatial and temporal variabilities in the occurrence of surface level oxidants and their relationships to air pollution meteorology are discussed. Models of photooxidant formation are reviewed in the context of control strategies and comparisons are provided of the air concentrations of O(3) at select geographic locations around the world. This overall oxidant (O(3)) climatology is coupled to human health and ecological effects. The discussion of the effects includes both acute and chronic responses, mechanisms of action, human epidemiological and plant population studies and briefly, efforts to establish cause-effect relationships through numerical modeling. A short synopsis is provided of the interactive effects of O(3) with other abiotic and biotic factors. The overall emphasis of the paper is on identifying the current uncertainties and gaps in our understanding of the state of the science and some suggestions as to how they may be addressed.

Spatially controlled synthesis of silver nanoparticles and nanowires by photosensitized reduction

Energy Technology Data Exchange (ETDEWEB)

Jradi, S; Zeng, X H; Plain, J; Royer, P; Bachelot, R; Akil, S [Laboratoire de Nanotechnologie et d' Instrumentation Optique, ICD CNRS FRE 2848, Universite de Technologie de Troyes, 12 rue Marie Curie, BP 2060, 10010 Troyes (France); Balan, L; Lougnot, D J; Soppera, O; Vidal, L, E-mail: lavinia.balan@uha.fr [Institut de Science des Materiaux de Mulhouse CNRS LRC 7228, 15 rue Jean Starcky, 68057 Mulhouse (France)

2010-03-05

The present paper reports on the spatially controlled synthesis of silver nanoparticles (NPs) and silver nanowires by photosensitized reduction. In a first approach, direct photogeneration of silver NPs at the end of an optical fiber was carried out. Control of both size and density of silver NPs was possible by changing the photonic conditions. In a further development, a photochemically assisted procedure allowing silver to be deposited at the surface of a polymer microtip was implemented. Finally, polymer tips terminated by silver nanowires were fabricated by simultaneous photopolymerization and silver photoreduction. The silver NPs were characterized by UV-visible spectroscopy and scanning electron microscopy.

Efficient photochemical generation of peroxycarboxylic nitric anhydrides with ultraviolet light-emitting diodes

Science.gov (United States)

Rider, N. D.; Taha, Y. M.; Odame-Ankrah, C. A.; Huo, J. A.; Tokarek, T. W.; Cairns, E.; Moussa, S. G.; Liggio, J.; Osthoff, H. D.

2015-07-01

Photochemical sources of peroxycarboxylic nitric anhydrides (PANs) are utilized in many atmospheric measurement techniques for calibration or to deliver an internal standard. Conventionally, such sources rely on phosphor-coated low-pressure mercury (Hg) lamps to generate the UV light necessary to photo-dissociate a dialkyl ketone (usually acetone) in the presence of a calibrated amount of nitric oxide (NO) and oxygen (O2). In this manuscript, a photochemical PAN source in which the Hg lamp has been replaced by arrays of ultraviolet light-emitting diodes (UV-LEDs) is described. The output of the UV-LED source was analyzed by gas chromatography (PAN-GC) and thermal dissociation cavity ring-down spectroscopy (TD-CRDS). Using acetone, diethyl ketone (DIEK), diisopropyl ketone (DIPK), or di-n-propyl ketone (DNPK), respectively, the source produces peroxyacetic (PAN), peroxypropionic (PPN), peroxyisobutanoic (PiBN), or peroxy-n-butanoic nitric anhydride (PnBN) from NO in high yield (> 90 %). Box model simulations with a subset of the Master Chemical Mechanism (MCM) were carried out to rationalize product yields and to identify side products. The present work demonstrates that UV-LED arrays are a viable alternative to current Hg lamp setups.

Role of nitrite in the photochemical formation of radicals in the snow.

Science.gov (United States)

Jacobi, Hans-Werner; Kleffmann, Jörg; Villena, Guillermo; Wiesen, Peter; King, Martin; France, James; Anastasio, Cort; Staebler, Ralf

2014-01-01

Photochemical reactions in snow can have an important impact on the composition of the atmosphere over snow-covered areas as well as on the composition of the snow itself. One of the major photochemical processes is the photolysis of nitrate leading to the formation of volatile nitrogen compounds. We report nitrite concentrations determined together with nitrate and hydrogen peroxide in surface snow collected at the coastal site of Barrow, Alaska. The results demonstrate that nitrite likely plays a significant role as a precursor for reactive hydroxyl radicals as well as volatile nitrogen oxides in the snow. Pollution events leading to high concentrations of nitrous acid in the atmosphere contributed to an observed increase in nitrite in the surface snow layer during nighttime. Observed daytime nitrite concentrations are much higher than values predicted from steady-state concentrations based on photolysis of nitrate and nitrite indicating that we do not fully understand the production of nitrite and nitrous acid in snow. The discrepancy between observed and expected nitrite concentrations is probably due to a combination of factors, including an incomplete understanding of the reactive environment and chemical processes in snow, and a lack of consideration of the vertical structure of snow.

Applications of the Regional Atmospheric Modeling System (RAMS) to provide input to photochemical grid models for the Lake Michigan Ozone Study (LMOS)

Energy Technology Data Exchange (ETDEWEB)

Lyons, W.A.; Tremback, C.J.; Pielke, R.A. [ASTeR, Inc., Ft. Collins, CO (United States); Eastman, J.L. [Colorado State Univ., Ft. Collins, CO (United States)

1994-12-31

In spite of stringent emission controls, numerous exceedances of the US ozone air quality standard have continued in the Lake Michigan region, especially during the very hot summers of 1987 and 1988. Analyses revealed that exceedances of the 120 PPB hourly standard were 400% more likely at monitors located within 20 km of the lakeshore. While the role of Lake Michigan in exacerbating regional air quality problems has been investigated for almost 20 years, the relative impacts of various phenomena upon regional photochemical air quality have yet to be quantified. In order to design a defensible regional emission control policy, LMOS sponsored the development of a comprehensive regional photochemical modeling system. This is comprised of an emission model, an advanced regional photochemical model, and a prognostic meteorological model.

Systems and methods for solar energy storage, transportation, and conversion utilizing photochemically active organometallic isomeric compounds and solid-state catalysts

Science.gov (United States)

Vollhardt, K. Peter C.; Segalman, Rachel A; Majumdar, Arunava; Meier, Steven

2015-02-10

A system for converting solar energy to chemical energy, and, subsequently, to thermal energy includes a light-harvesting station, a storage station, and a thermal energy release station. The system may include additional stations for converting the released thermal energy to other energy forms, e.g., to electrical energy and mechanical work. At the light-harvesting station, a photochemically active first organometallic compound, e.g., a fulvalenyl diruthenium complex, is exposed to light and is photochemically converted to a second, higher-energy organometallic compound, which is then transported to a storage station. At the storage station, the high-energy organometallic compound is stored for a desired time and/or is transported to a desired location for thermal energy release. At the thermal energy release station, the high-energy organometallic compound is catalytically converted back to the photochemically active organometallic compound by an exothermic process, while the released thermal energy is captured for subsequent use.

Chemical Kinetics and Photochemical Data for Use in Stratospheric Modeling. Evaluation No. 12

Science.gov (United States)

DeMore, W. B.; Sander, S. P.; Golden, D. M.; Hampson, R. F.; Kurylo, M. J.; Howard, C. J.; Ravishankara, A. R.; Kolb, C. E.; Molina, M. J.

1997-01-01

This is the twelfth in a series of evaluated sets of rate constants and photochemical cross sections compiled by the NASA Panel for Data Evaluation. The primary application of the data is in the modeling of stratospheric processes, with special emphasis on the ozone layer and its possible perturbation by anthropogenic and natural phenomena.

Interaction of light and atmospheric photochemical products (smog) within plants. [Phaseolius vulgaris; Petunia hydrida

Energy Technology Data Exchange (ETDEWEB)

Taylor, O C; Dugger, W M; Cardiff, E A; Darley, E F

1961-12-02

Damage to plants from ozone and peroxyacetyl nitrate, two photochemically formed components of smog, has been described. However, variations in symptom expression and the degree of damage caused by a given concentration of these components, whether of synthetic or natural origin, have complicated development of an adequate biological assay method for these materials. These observed variations in symptomatology have implicated stomatal action, inorganic nutrition temperature, genetics, ascorbic acid content, physiological age of tissue and photoperiod. Plants grown under artificial illumination differ in their response to the photochemically formed pollutants as compared with plants grown in the greenhouse. Interactions between light and oxidants from the polluted atmosphere within plants, as reported here, might well explain some of the variabilities in symptomatology observed in earlier controlled experiments as well as the unexplained natural variability observed in the Los Angeles area. The results presented also emphasize the importance of standardizing plant growth conditions for future work of this nature. 10 references.

Utilization of Photochemically Induced Fluorescence Detection for HPLC Determination of Genotoxic Impurities in the Vortioxetine Manufacturing Process.

Science.gov (United States)

Douša, Michal; Doubský, Jan; Srbek, Jan

2016-07-01

An analytical reversed-phase high-performance liquid chromatography (HPLC) method for the detection and quantitative determination of two genotoxic impurities at ppm level present in the vortioxetine manufacturing process is described. Applying the concept of threshold of toxicological concern, a limit of 75 ppm each for both genotoxic impurities was calculated based on the maximum daily dose of active pharmaceutical ingredients. The novel reversed-phase HPLC method with photochemically induced fluorescence detection was developed on XSELECT Charged Surface Hybrid Phenyl-Hexyl column using the mobile phase consisted a mixture of 10 mM ammonium formate pH 3.0 and acetonitrile. The elution was performed using an isocratic composition of 48:52 (v/v) at a flow rate of 1.0 mL/min. The photochemically induced fluorescence detection is based on the use of UV irradiation at 254 nm through measuring the fluorescence intensity at 300 nm and an excitation wavelength of 272 nm to produce fluorescent derivatives of both genotoxic impurities. The online photochemical conversion and detection is easily accomplished for two expected genotoxic impurities and provides a sufficiently low limit detection and quantification for the target analysis. © The Author 2016. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Size-controlled synthesis of transition metal nanoparticles through chemical and photo-chemical routes

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Tangeysh, Behzad

The central objective of this work is developing convenient general procedures for controlling the formation and stabilization of nanoscale transition metal particles. Contemporary interest in developing alternative synthetic approaches for producing nanoparticles arises in large part from expanding applications of the nanomaterials in areas such as catalysis, electronics and medicine. This research focuses on advancing the existing nanoparticle synthetic routes by using a new class of polymer colloid materials as a chemical approach, and the laser irradiation of metal salt solution as a photo-chemical method to attain size and shape selectivity. Controlled synthesis of small metal nanoparticles with sizes ranging from 1 to 5nm is still a continuing challenge in nanomaterial synthesis. This research utilizes a new class of polymer colloid materials as nano-reactors and protective agents for controlling the formation of small transition metal nanoparticles. The polymer colloid particles were formed from cross-linking of dinegatively charged metal precursors with partially protonated poly dimethylaminoethylmethacrylate (PDMAEMA). Incorporation of [PtCl6]2- species into the colloidal particles prior to the chemical reduction was effectively employed as a new strategy for synthesis of unusually small platinum nanoparticles with narrow size distributions (1.12 +/-0.25nm). To explore the generality of this approach, in a series of proof-of-concept studies, this method was successfully employed for the synthesis of small palladium (1.4 +/-0.2nm) and copper nanoparticles (1.5 +/-0.6nm). The polymer colloid materials developed in this research are pH responsive, and are designed to self-assemble and/or disassemble by varying the levels of protonation of the polymer chains. This unique feature was used to tune the size of palladium nanoparticles in a small range from 1nm to 5nm. The procedure presented in this work is a new convenient room temperature route for synthesis of

Volatile organic compounds (VOCs in photochemically aged air from the eastern and western Mediterranean

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B. Derstroff

2017-08-01

Full Text Available During the summertime CYPHEX campaign (CYprus PHotochemical EXperiment 2014 in the eastern Mediterranean, multiple volatile organic compounds (VOCs were measured from a 650 m hilltop site in western Cyprus (34° 57′ N/32° 23′ E. Periodic shifts in the northerly Etesian winds resulted in the site being alternately impacted by photochemically processed emissions from western (Spain, France, Italy and eastern (Turkey, Greece Europe. Furthermore, the site was situated within the residual layer/free troposphere during some nights which were characterized by high ozone and low relative humidity levels. In this study we examine the temporal variation of VOCs at the site. The sparse Mediterranean scrub vegetation generated diel cycles in the reactive biogenic hydrocarbon isoprene, from very low values at night to a diurnal median level of 80–100 pptv. In contrast, the oxygenated volatile organic compounds (OVOCs methanol and acetone exhibited weak diel cycles and were approximately an order of magnitude higher in mixing ratio (ca. 2.5–3 ppbv median level by day, range: ca. 1–8 ppbv than the locally emitted isoprene and aromatic compounds such as benzene and toluene. Acetic acid was present at mixing ratios between 0.05 and 4 ppbv with a median level of ca. 1.2 ppbv during the daytime. When data points directly affected by the residual layer/free troposphere were excluded, the acid followed a pronounced diel cycle, which was influenced by various local effects including photochemical production and loss, direct emission, dry deposition and scavenging from advecting air in fog banks. The Lagrangian model FLEXPART was used to determine transport patterns and photochemical processing times (between 12 h and several days of air masses originating from eastern and western Europe. Ozone and many OVOC levels were  ∼  20 and  ∼  30–60 % higher, respectively, in air arriving from the east. Using the FLEXPART

Functional architecture of higher plant photosystem II supercomplexes

OpenAIRE

Caffarri, Stefano; Kouřil, Roman; Kereïche, Sami; Boekema, Egbert J; Croce, Roberta

2009-01-01

Photosystem II (PSII) is a large multiprotein complex, which catalyses water splitting and plastoquinone reduction necessary to transform sunlight into chemical energy. Detailed functional and structural studies of the complex from higher plants have been hampered by the impossibility to purify it to homogeneity. In this work, homogeneous preparations ranging from a newly identified particle composed by a monomeric core and antenna proteins to the largest C2S2M2 supercomplex were isolated. Ch...

SMOG CHAMBERS: A TOOL TO EXAMINE EFFECTS OF PHOTOCHEMICALLY AGED AIR POLLUTANTS ON BIOLOGICAL SYSTEMS

Science.gov (United States)

Irradiative exposure chambers or 'Smog chambers' have been used at the University of North Carolina for over 30 years to study photochemically active mixtures of volatile organic compounds and their transformation products (a significant sub-set of Hazardous Air Pollutants, HAPs)...

Effect of Photochemical Transformation on Dissolved Organic Carbon Concentration and Bioavailability from Watersheds with Varying Landcover

Science.gov (United States)

Vermilyea, A.; Sanders, A.; Vazquez, E.

2017-12-01

The transformation of freshwater dissolved organic carbon (DOC) can have important implications for water quality, aquatic ecosystem health, and our climate. DOC is an important nutrient for heterotrophic microorganisms near the base of the aquatic food chain and the extent of conversion of DOC to CO2 is a critical piece of the global carbon cycle. Photochemical pathways have the potential to transform recalcitrant DOC into more labile forms that can then be converted to smaller DOC molecules and eventually be completely mineralized to CO2. This may lead to a DOC pool with different bioavailability depending on the structural composition of the original DOC pool and the mechanistic pathways undergone during transformation. This study aimed to measure the changes in DOC concentration and bioavailability due solely to photochemical processes in three watersheds of northern Vermont, USA that have varied land cover, land use (LCLU) attributes. Our hypothesis was that photochemical transformations will lead to (1) an overall loss of DOC due to mineralization to CO2 and (2) a relative increase in the bioavailable fraction of DOC. Additionally, the influence of LCLU and base flow versus storm flow on both mineralization rates and changes in DOC bioavailability was investigated. Irradiation of filtered samples in quartz vessels under sunlight led to small changes in DOC concentration over time, but significant changes in DOC bioavailability. In general, fluorescence excitation-emission matrices (EEMs) showed a shift from an initially more humic-like DOC pool, to a more protein-like (bioavailable) DOC pool. Specific UV index (SUVA) along with bioavailable DOC (BDOC) incubations were also used to characterize DOC and its bioavailability. There were only small differences in the DOC transformation that took place among sites, possibly due to only small differences in the initial bioavailability and fluorescent properties between water samples. Photochemical transformation

HANDBOOK ON ADVANCED PHOTOCHEMICAL OXIDATION ...

Science.gov (United States)

This handbook summarizes commercial-scale system performance and cost data for advanced photochemical oxidation (APO) treatment of contaminated water, air, and solids. Similar information from pilot- and bench-scale evaluations of APO processes is also included to supplement the commercial-scale data. Performance and cost data is summarized for various APO processes, including vacuum ultraviolet (VUV) photolysis, ultraviolet (UV)/oxidation, photo-Fenton, and dye- or semiconductor-sensitized APO processes. This handbook is intended to assist engineering practitioners in evaluating the applicability of APO processes and in selecting one or more such processes for site-specific evaluation.APO has been shown to be effective in treating contaminated water and air. Regarding contaminated water treatment, UV/oxidation has been evaluated for the most contaminants, while VUV photolysis has been evaluated for the fewest. Regarding contaminated air treatment, the sensitized APO processes have been evaluated for the most contaminants, while VUV photolysis has been evaluated for the fewest.APO processes for treating contaminated solids generally involve treatment of contaminated slurry or leachate generated using an extraction process such as soil washing. APO has been shown to be effective in treating contaminated solids, primarily at the bench-scale level. Information

Application of photochemical technologies for treatment of landfill leachate

International Nuclear Information System (INIS)

Meeroff, Daniel E.; Bloetscher, Frederick; Reddy, D.V.; Gasnier, François; Jain, Swapnil; McBarnette, André; Hamaguchi, Hatsuko

2012-01-01

Highlights: ► Photochemical iron-mediated aeration and TiO 2 photocatalysis for leachate treatment. ► Removal efficiency tested on COD, BOD 5 , color, ammonia, and lead. ► Contact times for 90% removal were 10–200 h for PIMA ► Contact times for 90% removal were 3–37 h for TiO 2 photocatalysis. ► Pre-filtration is not necessary. - Abstract: Because of widely varying practices in solid waste management, an all-inclusive solution to long-term management of landfill leachate is currently not available. There is a major technological need for sustainable, economical options for safe discharge of leachate to the environment. Two potential on-site pretreatment technologies, photochemical iron-mediated aeration (PIMA) and TiO 2 photocatalysis were compared for treatment of landfill leachate at laboratory scale. Results of bench scale testing of real landfill leachate with PIMA and TiO 2 photocatalysis showed up to 86% conversion of refractory COD to complete mineralization, up to 91% removal of lead, up to 71% removal of ammonia without pH adjustment, and up to 90% effective color removal with detention times between 4 and 6 h, in field samples. The estimated contact times for 90% removal of COD, ammonia, lead, and color were found to be on the order of 10–200 h for PIMA and 3–37 h for TiO 2 photocatalysis. Testing with actual leachate samples showed 85% TiO 2 photocatalyst recovery efficiency with no loss in performance after multiple (n > 4 uses). Pre-filtration was not found to be necessary for effective treatment using either process.

Photophysical, Photochemical, and BQ Quenching Properties of Zinc Phthalocyanines with Fused or Interrupted Extended Conjugation

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Gülşah Gümrükçü

2014-01-01

Full Text Available The effects of substituents and solvents on the photophysical and photochemical parameters of zinc(II phthalocyanines containing four Schiff’s base substituents attached directly and through phenyleneoxy-bridges on peripheral positions are reported. The group effects on peripheral position and the continual and intermittent conjugation of the phthalocyanine molecules on the photophysical and photochemical properties are also investigated. General trends are described for photodegradation, singlet oxygen, and fluorescence quantum yields of these compounds in dimethylsulfoxide (DMSO, dimethylformamide (DMF, and tetrahydrofurane (THF. Among the different substituents, phthalocyanines with cinnamaldimine moieties (1c and 2c have the highest singlet oxygen quantum yields (ΦΔ and those with nitro groups (1a and 2a have the highest fluorescence quantum yields in all the solvents used. The fluorescence of the substituted zinc(II phthalocyanine complexes is effectively quenched by 1,4-benzoquinone (BQ in these solvents.

In-situ sequential laser transfer and laser reduction of graphene oxide films

Science.gov (United States)

Papazoglou, S.; Petridis, C.; Kymakis, E.; Kennou, S.; Raptis, Y. S.; Chatzandroulis, S.; Zergioti, I.

2018-04-01

Achieving high quality transfer of graphene on selected substrates is a priority in device fabrication, especially where drop-on-demand applications are involved. In this work, we report an in-situ, fast, simple, and one step process that resulted in the reduction, transfer, and fabrication of reduced graphene oxide-based humidity sensors, using picosecond laser pulses. By tuning the laser illumination parameters, we managed to implement the sequential printing and reduction of graphene oxide flakes. The overall process lasted only a few seconds compared to a few hours that our group has previously published. DC current measurements, X-Ray Photoelectron Spectroscopy, X-Ray Diffraction, and Raman Spectroscopy were employed in order to assess the efficiency of our approach. To demonstrate the applicability and the potential of the technique, laser printed reduced graphene oxide humidity sensors with a limit of detection of 1700 ppm are presented. The results demonstrated in this work provide a selective, rapid, and low-cost approach for sequential transfer and photochemical reduction of graphene oxide micro-patterns onto various substrates for flexible electronics and sensor applications.

Non-Isothermal Gas-Based Direct Reduction Behavior of High Chromium Vanadium-Titanium Magnetite Pellets and the Melting Separation of Metallized Pellets

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Jue Tang

2017-04-01

Full Text Available The non-isothermal reduction behavior of high chromium vanadium-titanium magnetite (HCVTM pellets by gas mixtures was investigated using different heating rates (4, 8, and 12 K/min and varied gas compositions (H2/CO = 2/5, H2/CO = 1/1, and H2/CO = 5/2 volume ratios; the pellets were then used for melting separation. It was observed that the temperature corresponding to the maximum reduction ratio increased with the increasing heating rate. The HCVTM pellets reached the same final reduction ratio under a given reducing gas composition, although the heating rates were different. Under the same heating rate, the gas mixture with more H2 was conducive for obtaining a higher reduction ratio. The phase transformations during the non-isothermal reduction were ordered as follows: Fe2O3 → Fe3O4 → FeO → Fe; Fe9TiO15 + Fe2Ti3O9 → Fe2.75Ti0.25O4 → FeTiO3 → TiO2; V1.7Cr0.3O3 → V2O3 → Fe2VO4; Fe1.2Cr0.8O3 → Cr2O3 → FeCr2O4. The non-isothermal reduction kinetic model was established based on the unreacted core model with multiple reaction interfaces. The correlation coefficients were greater than 0.99, revealing that this kinetic model could properly describe the non-isothermal reduction of the HCVTM pellets by gas mixtures. Iron containing V and Cr along with the Ti-rich slag was obtained through the melting separation of the metallized HCVTM pellets. The mass fractions and recovery rates of Fe, V, and Cr in the iron were 93.87% and 99.45%, 0.91% and 98.83%, and 0.72% and 95.02%, respectively. The mass fraction and recovery rate of TiO2 in the slag were 38.12% and 95.08%, respectively.

Pressure Dependent Product Formation in the Photochemically Initiated Allyl + Allyl Reaction

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Thomas Zeuch

2013-11-01

Full Text Available Photochemically driven reactions involving unsaturated radicals produce a thick global layer of organic haze on Titan, Saturn’s largest moon. The allyl radical self-reaction is an example for this type of chemistry and was examined at room temperature from an experimental and kinetic modelling perspective. The experiments were performed in a static reactor with a volume of 5 L under wall free conditions. The allyl radicals were produced from laser flash photolysis of three different precursors allyl bromide (C3H5Br, allyl chloride (C3H5Cl, and 1,5-hexadiene (CH2CH(CH22CHCH2 at 193 nm. Stable products were identified by their characteristic vibrational modes and quantified using FTIR spectroscopy. In addition to the (re- combination pathway C3H5+C3H5 → C6H10 we found at low pressures around 1 mbar the highest final product yields for allene and propene for the precursor C3H5Br. A kinetic analysis indicates that the end product formation is influenced by specific reaction kinetics of photochemically activated allyl radicals. Above 10 mbar the (re- combination pathway becomes dominant. These findings exemplify the specificities of reaction kinetics involving chemically activated species, which for certain conditions cannot be simply deduced from combustion kinetics or atmospheric chemistry on Earth.

Okadaic acid inhibits cell growth and photosynthetic electron transport in the alga Dunaliella tertiolecta

Energy Technology Data Exchange (ETDEWEB)

Perreault, Francois; Matias, Marcelo Seleme; Oukarroum, Abdallah [Department of Chemistry, Universite du Quebec a Montreal, 2101, Rue Jeanne Mance, Montreal, QC, Canada H2X 2J6 (Canada); Matias, William Gerson [Department of Chemistry, Universite du Quebec a Montreal, 2101, Rue Jeanne Mance, Montreal, QC, Canada H2X 2J6 (Canada); Laboratorio de Toxicologia Ambiental, LABTOX, Depto. de Engenharia Sanitaria e Ambiental, Universidade Federal de Santa Catarina, Campus Universitario, CEP: 88040-970, Florianopolis, SC (Brazil); Popovic, Radovan, E-mail: popovic.radovan@uqam.ca [Department of Chemistry, Universite du Quebec a Montreal, 2101, Rue Jeanne Mance, Montreal, QC, Canada H2X 2J6 (Canada)

2012-01-01

Okadaic acid (OA), which is produced by several dinoflagellate species, is a phycotoxin known to induce a decrease of biomass production in phytoplankton. However, the mechanisms of OA cytotoxicity are still unknown in microalgae. In this study, we exposed the green microalga Dunaliella tertiolecta to OA concentrations of 0.05 to 0.5 {mu}M in order to evaluate its effects on cell division, reactive oxygen species production and photosynthetic electron transport. After 72 h of treatment under continuous illumination, OA concentrations higher than 0.10 {mu}M decreased culture cell density, induced oxidative stress and inhibited photosystem II electron transport capacity. OA effect in D. tertiolecta was strongly light dependent since no oxidative stress was observed when D. tertiolecta was exposed to OA in the dark. In the absence of light, the effect of OA on culture cell density and photosystem II activity was also significantly reduced. Therefore, light appears to have a significant role in the toxicity of OA in microalgae. Our results indicate that the site of OA interaction on photosynthetic electron transport is likely to be at the level of the plastoquinone pool, which can lead to photo-oxidative stress when light absorbed by the light-harvesting complex of photosystem II cannot be dissipated via photochemical pathways. These findings allowed for a better understanding of the mechanisms of OA toxicity in microalgae. - Highlights: Black-Right-Pointing-Pointer Exposition of Dunaliella tertiolecta to okadaic acid in light conditions results in reactive oxygen species formation. Black-Right-Pointing-Pointer Inhibition of photosystem II is dependent on oxidative stress and effects of okadaic acid on the plastoquinone pool. Black-Right-Pointing-Pointer Oxidative stress and inhibition of photosynthesis increase okadaic acid effect on cell density in light conditions. Black-Right-Pointing-Pointer Okadaic acid induces toxicity in algae via both light-dependent and light

Action spectrum for photochemical retinal pigment epithelium (RPE) disruption in an in vivo monkey model

Science.gov (United States)

Zhang, Jie; Sabarinathan, Ranjani; Bubel, Tracy; Williams, David R.; Hunter, Jennifer J.

2016-03-01

Observations of RPE disruption and autofluorescence (AF) photobleaching at light levels below the ANSI photochemical maximum permissible exposure (MPE) (Morgan et al., 2008) indicates a demand to modify future light safety standards to protect the retina from harm. To establish safe light exposures, we measured the visible light action spectrum for RPE disruption in an in vivo monkey model with fluorescence adaptive optics retinal imaging. Using this high resolution imaging modality can provide insight into the consequences of light on a cellular level and allow for longitudinal monitoring of retinal changes. The threshold retinal radiant exposures (RRE) for RPE disruption were determined for 4 wavelengths (460, 488, 544, and 594 nm). The anaesthetized macaque retina was exposed to a uniform 0.5° × 0.5° field of view (FOV). Imaging within a 2° × 2° FOV was performed before, immediately after and at 2 week intervals for 10 weeks. At each wavelength, multiple RREs were tested with 4 repetitions each to determine the threshold for RPE disruption. For qualitative analysis, RPE disruption is defined as any detectable change from the pre exposure condition in the cell mosaic in the exposed region relative to the corresponding mosaic in the immediately surrounding area. We have tested several metrics to evaluate the RPE images obtained before and after exposure. The measured action spectrum for photochemical RPE disruption has a shallower slope than the current ANSI photochemical MPE for the same conditions and suggests that longer wavelength light is more hazardous than other measurements would suggest.

RP-UHPLC-UV-ESI-MS/MS analysis of LPMO generated C4-oxidized gluco-oligosaccharides after non-reductive labeling with 2-aminobenzamide.

Science.gov (United States)

Frommhagen, Matthias; van Erven, Gijs; Sanders, Mark; van Berkel, Willem J H; Kabel, Mirjam A; Gruppen, Harry

2017-08-07

Lytic polysaccharide monooxygenases (LPMOs) are able to cleave recalcitrant polysaccharides, such as cellulose, by oxidizing the C1 and/or C4 atoms. The analysis of the resulting products requires a variety of analytical techniques. Up to now, these techniques mainly focused on the identification of non-oxidized and C1-oxidized oligosaccharides. The analysis of C4-oxidized gluco-oligosaccharides is mostly performed by using high pressure anion exchange chromatography (HPAEC). However, the alkaline conditions used during HPAEC analysis lead to tautomerization of C4-oxidized gluco-oligosaccharides, which limits the use of this technique. Here, we describe the use of reverse phase-ultra high performance liquid chromatography (RP-UHPLC) in combination with non-reductive 2-aminobenzamide (2-AB) labeling. Non-reductive 2-AB labeling enabled separation of C4-oxidized gluco-oligosaccharides from their non-oxidized counterparts. Moreover, RP-UHPLC does not require buffered mobile phases, which reduce mass spectrometry (MS) sensitivity. The latter is seen as an advantage over other techniques such as hydrophilic interaction liquid chromatography and porous graphitized carbon coupled to MS. RP-UHPLC coupled to UV detection and mass spectrometry allowed the identification of both labeled non-oxidized and C4-oxidized oligosaccharides. Non-reductive labeling kept the ketone at the C4-position of LPMO oxidized oligosaccharides intact, while selective reducing agents such as sodium triacetoxyborohydride (STAB) reduced this ketone group. Our results show that RP-UHPLC-UV-ESI-MS in combination with non-reductively 2-AB labeling is a suitable technique for the separation and identification of LPMO-generated C4-oxidized gluco-oligosaccharides. Copyright © 2017 The Authors. Published by Elsevier Ltd.. All rights reserved.

Kinetics of U(VI) reduction by a dissimilatory Fe(III)-reducing bacterium under non-growth conditions

International Nuclear Information System (INIS)

Truex, M.J.; Peyton, B.M.; Valentine, N.B.; Gorby, Y.A.

1997-01-01

Dissimilatory metal-reducing microorganisms may be useful in processes designed for selective removal of uranium from aqueous streams. These bacteria can use U(VI) as an electron acceptor and thereby reduce soluble U(VI) to insoluble U(IV). While significant research has been devoted to demonstrating and describing the mechanism of dissimilatory metal reduction, the reaction kinetics necessary to apply this for remediation processes have not been adequately defined. In this study, pure culture Shewanella alga strain BrY reduced U(VI) under non-growth conditions in the presence of excess lactate as the electron donor. Initial U(VI) concentrations ranged from 13 to 1,680microM. A maximum specific U(VI) reduction rate of 2.37 micromole-U(VI)/(mg-biomass h) and Monod half-saturation coefficient of 132 microM-U(VI) were calculated from measured U(VI) reduction rates. U(VI) reduction activity was sustained at 60% of this rate for at least 80 h. The initial presence of oxygen at a concentration equal to atmospheric saturation at 22 C delays but does not prevent U(VI) reduction. The rate of U(VI) reduction by BrY is comparable or better than rates reported for other metal reducing species. BrY reduces U(VI) at a rate that is 30% of its Fe(III) reduction rate

HYBRID SELECTIVE NON-CATALYTIC REDUCTION (SNCR)/SELECTIVE CATALYTIC REDUCTION (SCR) DEMONSTRATION FOR THE REMOVAL OF NOx FROM BOILER FLUE GASES

Energy Technology Data Exchange (ETDEWEB)

Jerry B. Urbas

1999-05-01

The U. S. Department of Energy (DOE), Electric Power Research Institute (EPRI), Pennsylvania Electric Energy Research Council, (PEERC), New York State Electric and Gas and GPU Generation, Inc. jointly funded a demonstration to determine the capabilities for Hybrid SNCR/SCR (Selective Non-Catalytic Reduction/Selective Catalytic Reduction) technology. The demonstration site was GPU Generation's Seward Unit No.5 (147MW) located in Seward Pennsylvania. The demonstration began in October of 1997 and ended in December 1998. DOE funding was provided through Grant No. DE-FG22-96PC96256 with T. J. Feeley as the Project Manager. EPRI funding was provided through agreements TC4599-001-26999 and TC4599-002-26999 with E. Hughes as the Project Manager. This project demonstrated the operation of the Hybrid SNCR/SCR NO{sub x} control process on a full-scale coal fired utility boiler. The hybrid technology was expected to provide a cost-effective method of reducing NO{sub x} while balancing capital and operation costs. An existing urea based SNCR system was modified with an expanded-duct catalyst to provide increased NO{sub x} reduction efficiency from the SNCR while producing increased ammonia slip levels to the catalyst. The catalyst was sized to reduce the ammonia slip to the air heaters to less than 2 ppm while providing equivalent NO{sub x} reductions. The project goals were to demonstrate hybrid technology is capable of achieving at least a 55% reduction in NO{sub x} emissions while maintaining less than 2ppm ammonia slip to the air heaters, maintain flyash marketability, verify the cost benefit and applicability of Hybrid post combustion technology, and reduce forced outages due to ammonium bisulfate (ABS) fouling of the air heaters. Early system limitations, due to gas temperature stratification, restricted the Hybrid NO{sub x} reduction capabilities to 48% with an ammonia slip of 6.1 mg/Nm{sup 3} (8 ppm) at the catalyst inlet. After resolving the stratification

Effect of process parameters and injector position on the efficiency of NOx reduction by selective non catalytic reduction technique

International Nuclear Information System (INIS)

Hamid, A.; Mehmood, M.A.; Irfan, N.; Javed, M.T.; Waheed, K.

2009-01-01

An experimental investigation has been performed to study the effect of atomizer pressure dilution of the reducing reagent and the injector position on the efficiency or the NOx reduction by a selective non-catalytic reduction technique using urea as a reducing agent. Experiments were performed with a flow reactor in which flue gas was generated by the combustion of methane in air at stoichiometric amount of oxygen and the desired levels of initial NOx (400-450 ppm) were achieved by doping the flame with ammonia. The work was directed to investigate the effect of atomizer pressure, dilution of urea reagent and the injector position. The atomizer pressure was varied from 1 to 3bar and 20-25% increase in efficiency was observed by decreasing the pressure. Effect of dilution of urea solution was investigated by varying the strength of the solution from the 8 to 32% and 40-45% increase in the efficiency was observed. Effects of injector position was investigated by injecting the urea solution both in co current and counter current direction of the flue gases and 20-25% increase in the efficiency was observed in counter current direction. (author)

Localized, Non-Harmonic Active Flap Motions for Low Frequency In-Plane Rotor Noise Reduction

Science.gov (United States)

Sim, Ben W.; Potsdam, Mark; Kitaplioglu, Cahit; LeMasurier, Philip; Lorber, Peter; Andrews, Joseph

2012-01-01

A first-of-its-kind demonstration of the use of localized, non-harmonic active flap motions, for suppressing low frequency, in-plane rotor noise, is reported in this paper. Operational feasibility is verified via testing of the full-scale AATD/Sikorsky/UTRC active flap demonstration rotor in the NFAC's 40- by 80-Foot anechoic wind tunnel. Effectiveness of using localized, non-harmonic active flap motions are compared to conventional four-per-rev harmonic flap motions, and also active flap motions derived from closed-loop acoustics implementations. All three approaches resulted in approximately the same noise reductions over an in-plane three-by-three microphone array installed forward and near in-plane of the rotor in the nearfield. It is also reported that using an active flap in this localized, non-harmonic manner, resulted in no more that 2% rotor performance penalty, but had the tendency to incur higher hub vibration levels.

Efficient photochemical generation of peroxycarboxylic nitric anhydrides with ultraviolet light emitting diodes

Science.gov (United States)

Rider, N. D.; Taha, Y. M.; Odame-Ankrah, C. A.; Huo, J. A.; Tokarek, T. W.; Cairns, E.; Moussa, S. G.; Liggio, J.; Osthoff, H. D.

2015-01-01

Photochemical sources of peroxycarboxylic nitric anhydrides (PANs) are utilized in many atmospheric measurement techniques for calibration or to deliver an internal standard. Conventionally, such sources rely on phosphor-coated low-pressure mercury (Hg) lamps to generate the UV light necessary to photo-dissociate a dialkyl ketone (usually acetone) in the presence of a calibrated amount of nitric oxide (NO) and oxygen (O2). In this manuscript, a photochemical PAN source in which the Hg lamp has been replaced by arrays of ultraviolet light-emitting diodes (UV-LEDs) is described. The output of the UV-LED source was analyzed by gas chromatography (PAN-GC) and thermal dissociation cavity ring-down spectroscopy (TD-CRDS). Using acetone, diethyl ketone (DIEK), diisopropyl ketone (DIPK), or di-n-propyl ketone (DNPK), respectively, the source produces peroxyacetic (PAN), peroxypropionic (PPN), peroxyisobutanoic (PiBN), or peroxy-n-butanoic nitric anhydride (PnBN) from NO in high yield (> 90%). Box model simulations with a subset of the Master Chemical Mechanism (MCM) were carried out to rationalize products yields and to identify side products. The use of UV-LED arrays offers many advantages over conventional Hg lamp setups, including greater light output over a narrower wavelength range, lower power consumption, and minimal generation of heat.

Photochemical immobilization of bovine serum albumin on Ti-O and evaluations in vitro and in vivo

International Nuclear Information System (INIS)

Weng, Y.J.; Qi, F.; Huang, N.; Wang, J.; Cheng, J.Y.; Leng, Y.X.

2008-01-01

Antithrombogenic biomaterials have been of great interest in the development of artificial organs and devices. In this study, titanium oxide coatings were used as the basis for covalent immobilization of a BSA layer by a photochemical method. BSA was first modified with azidophenyl group on the side chain, so it (AZ-BSA) has the property of photo-reactivity. Simultaneously, an organic monolayer of 3-aminopropylphosphonic acid (APP) was introduced on the Ti-O film by self-assembling, and then UV irradiation was used to couple AZ-BSA with APP. FTIR, XPS and contact angle measurements confirmed the occurrence of the modification. Additionally, a surface with both BSA immobilized and non-BSA immobilized regions was prepared by using a mask when irradiating, thus the interactions of materials and platelets were visualized. Platelet experiments of both qualitative and quantitative analysis showed that BSA immobilized surface was effective to inhibit platelet adhesion in vitro. In vivo study also confirmed better hemocompatibility of BSA immobilized surface after 90 days implantation

Photochemical synthesis of copper nanoparticles incorporated in poly(vinyl pyrrolidone)

International Nuclear Information System (INIS)

Giuffrida, Salvatore; Costanzo, Lucia L.; Ventimiglia, Giorgio; Bongiorno, Corrado

2008-01-01

The effect of the presence of poly(vinyl pyrrolidone) (PVP) on the copper nanoparticle formation, obtained by UV irradiation of ethanol solution of Cu(acac) 2 (acac = 2,4-pentanedionato), was investigated. At 254 nm, in conditions of light completely absorbed by complex, the PVP exhibited protective and stabilizing effects, as shown by the formation of a colloidal copper solution and by a block of the heterogeneous process, which leads to thin film formation on the quartz walls. The colloidal solution was tested for several months by plasmon position and it was found that it remained unaltered in inert atmosphere, but returned to the starting complex on contact with air. The PVP ability to control the particle size was investigated by carrying out photoreduction sensitized by Hacac at 254 and 300 nm, in the presence of PVP concentration varying from 0 to 0.2 M. In this range it was possible to obtain copper nanoparticles of dimensions decreasing from 30 to 4 nm. Besides this, the PVP (0.005-0.05 M) role as sensitizer was investigated by irradiating solutions of Cu(acac) 2 at 300 nm which is an inactive wavelength for copper reduction by direct light absorption. It was found that the PVP was an efficient sensitizer of the copper photoreduction. The nanoparticles were characterized by plasmon band, Trasmission Electron Microscope (TEM) as well as Dynamic Light Scattering (DSL) analysis. The overall results evidence the advantages of the PVP use in the nanoparticle copper formation through the photochemical technique such as the exclusive formation of colloidal copper, their size control, stable colloidal solution and complete return to the starting complex.

The Photochemical Conversion of Surrogate Emissions for Use in Toxicological Studies: Role of Particulate- and Gas-Phase Products

Data.gov (United States)

U.S. Environmental Protection Agency — The production of photochemical atmospheres under controlled conditions in an irradiation chamber permits the manipulation of parameters that influence the resulting...

Is the ipsilateral cortex surrounding the lesion or the non-injured contralateral cortex important for motor recovery in rats with photochemically induced cortical lesions?

Science.gov (United States)

Takata, Kotaro; Yamauchi, Hideki; Tatsuno, Hisashi; Hashimoto, Keiji; Abo, Masahiro

2006-01-01

To determine whether the ipsilateral cortex surrounding the lesion or the non-injured contralateral cortex is important for motor recovery after brain damage in the photochemically initiated thrombosis (PIT) model. We induced PIT in the sensorimotor cortex in rats and examined the recovery of motor function using the beam-walking test. In 24 rats, the right sensorimotor cortex was lesioned after 2 days of training for the beam-walking test (group 1). After 10 days, PIT was induced in the left sensorimotor cortex. Eight additional rats (group 2) received 2 days training in beam walking, then underwent the beam-walking test to evaluate function. After 10 days of testing, the left sensorimotor cortex was lesioned and recovery was monitored by the beam-walking test for 8 days. In group 1 animals, left hindlimb function caused by a right sensorimotor cortex lesion recovered within 10 days after the operation. Right hindlimb function caused by the left-side lesion recovered within 6 days. In group 2, right hindlimb function caused by induction of the left-side lesion after a total of 12 days of beam-walking training and testing recovered within 6 days as with the double PIT model. The training effect may be relevant to reorganization and neuromodulation. Motor recovery patterns did not indicate whether motor recovery was dependent on the ipsilateral cortex surrounding the lesion or the cortex of the contralateral side. The results emphasize the need for selection of appropriate programs tailored to the area of cortical damage in order to enhance motor functional recovery in this model. Copyright 2006 S. Karger AG, Basel.

Integrated Science Assessment (ISA) of Ozone and Related Photochemical Oxidants (Second External Review Draft, Sep 2011)

Science.gov (United States)

EPA has released the Integrated Science Assessment of Ozone and Related Photochemical Oxidants (Second External Review Draft) for independent peer review and public review. This draft document represents a concise synthesis and evaluation of the most policy-relevant scienc...

Photochemical Synthesis of Silver Nanodecahedrons and Related Nanostructures for Plasmonic Field Enhancement Applications

Science.gov (United States)

Lu, Haifei

Noble-metal nanocrystals have received considerable attention in recent years for their size and shape dependent localized surface Plasmon resonances (LSPR). Various applications based on colloidal nanoparticles, such as surface enhanced Raman scattering (SERS), surface enhanced fluorescence (SEF), plasmonic sensing, photothermal therapy etc., have been broadly explored in the field of biomedicine, because of their extremely large optical scattering and absorption cross sections, as well as giant electric field enhancement on their surface. However, despite its high chemical stability, gold exhibits quite large losses and electric field enhancement is comparatively weaker than silver. Silver nanoparticles synthesized by the traditional technique only cover an LSPR ranged from 420~500 nm. On the other hand, the range of 500~660 nm, which is covered by several easily available commercial laser lines, very limited colloidal silver nanostructures with controllable size and shape have been reported, and realization of tuning the resonance to longer wavelengths is very important for the practical applications. In this thesis, a systematic study on photochemical synthesis of silver nanodecahedrons (NDs) and related nanostructures, and their plasmonic field enhancements are presented. First, the roles of chemicals and the light source during the formation of silver nanoparticles have been studied. We have also developed a preparation route for the production size-controlled silver nanodecahedrons (LSPR range 420 ~ 660 nm) in high purity. Indeed our experiments indicate that both the chemicals and the light sources can affect the shape and purity of final products. Adjusting the molar ratio between sodium citrate and silver nitrate can help to control the crystal structure following rapid reduction from sodium borohydride. Light from a blue LED (465 nm) can efficiently transform the polyvinylpyrrolidone stabilized small silver nanoparticles into silver NDs through photo

Application of a Three-Layer Photochemical Box Model in an Athens Street Canyon.

Science.gov (United States)

Proyou, Athena G; Ziomas, Loannis C; Stathopoulos, Antony

1998-05-01

The aim of this paper is to show that a photochemical box model could describe the air pollution diurnal profiles within a typical street canyon in the city of Athens. As sophisticated three-dimensional dispersion models are computationally expensive and they cannot serve to simulate pollution levels in the scale of an urban street canyon, a suitably modified three-layer photochemical box model was applied. A street canyon of Athens with heavy traffic was chosen to apply the aforementioned model. The model was used to calculate pollutant concentrations during two days with meteorological conditions favoring pollutant accumulation. Road traffic emissions were calculated based on existing traffic load measurements. Meteorological data, as well as various pollutant concentrations, in order to compare with the model results, were provided by available measurements. The calculated concentrations were found to be in good agreement with measured concentration levels and show that, when traffic load and traffic composition data are available, this model can be used to predict pollution episodes. It is noteworthy that high concentrations persisted, even after additional traffic restriction measures were taken on the second day because of the high pollution levels.

Partial coupling and differential regulation of biologically and photochemically labile dissolved organic carbon across boreal aquatic networks

Science.gov (United States)

Lapierre, J.-F.; del Giorgio, P. A.

2014-10-01

Despite the rapidly increasing volume of research on the biological and photochemical degradation of DOC (dissolved organic carbon) in aquatic environments, little is known of the large-scale patterns in biologically and photochemically degradable DOC (BDOC and PDOC, respectively) in continental watersheds, and on the links that exist between these two key properties that greatly influence the flow of carbon from continents to oceans. Here we explored the patterns in the concentrations and proportions of BDOC and PDOC across hundreds of boreal lakes, rivers and wetlands spanning a large range of system trophic status and terrestrial influence, and compared the drivers of these two reactive pools of DOC at the landscape level. Using standardized incubations of natural waters, we found that the concentrations of BDOC and PDOC covaried across all systems studied but were nevertheless related to different pools of dissolved organic matter (DOM; identified by fluorescence analyses) in ambient waters. Concentrations of nutrients and protein-like fluorescent DOM (FDOM) explained nearly half of the variation in BDOC, whereas PDOC was exclusively predicted by DOM optical properties, consistent with the photochemical degradability of specific FDOM pools that we experimentally determined. The concentrations of colored DOM (CDOM), which we use here as a proxy of terrestrial influence, almost entirely accounted for the observed relationship between FDOM and the concentrations of both BDOC and PDOC. The concentrations of CDOM and of the putative biolabile fluorescence component shifted from complete decoupling in clear-water environments to strong coupling in darker streams and wetlands. This suggests a baseline autochthonous BDOC pool fueled by internal production that is gradually overwhelmed by land-derived BDOC as terrestrial influence increases across landscape gradients. The importance of land as a major source of both biologically and photochemically degradable DOC for

Photochemical degradation of chromophoric-dissolved organic matter exposed to simulated UV-B and natural solar radiation

NARCIS (Netherlands)

Zhang, Y.; Liu, M.; Qin, B.; Feng, S.

2009-01-01

Photochemical degradation of chromophoric-dissolved organic matter (CDOM) by UV-B radiation decreases CDOM absorption in the UV region and fluorescence intensity, and alters CDOM composition. CDOM absorption, fluorescence, and the spectral slope indicating the CDOM composition were studied using

Diagnostic Evaluation of Ozone Production and Horizontal Transport in a Regional Photochemical Air Quality Modeling System

Science.gov (United States)

A diagnostic model evaluation effort has been performed to focus on photochemical ozone formation and the horizontal transport process since they strongly impact the temporal evolution and spatial distribution of ozone (O3) within the lower troposphere. Results from th...

Simulations of photochemical smog formation in complex urban areas

Science.gov (United States)

Muilwijk, C.; Schrijvers, P. J. C.; Wuerz, S.; Kenjereš, S.

2016-12-01

In the present study we numerically investigated the dispersion of photochemical reactive pollutants in complex urban areas by applying an integrated Computational Fluid Dynamics (CFD) and Computational Reaction Dynamics (CRD) approach. To model chemical reactions involved in smog generation, the Generic Reaction Set (GRS) approach is used. The GRS model was selected since it does not require detailed modeling of a large set of reactive components. Smog formation is modeled first in the case of an intensive traffic emission, subjected to low to moderate wind conditions in an idealized two-dimensional street canyon with a building aspect ratio (height/width) of one. It is found that Reactive Organic Components (ROC) play an important role in the chemistry of smog formation. In contrast to the NOx/O3 photochemical steady state model that predicts a depletion of the (ground level) ozone, the GRS model predicts generation of ozone. Secondly, the effect of direct sunlight and shadow within the street canyon on the chemical reaction dynamics is investigated for three characteristic solar angles (morning, midday and afternoon). Large differences of up to one order of magnitude are found in the ozone production for different solar angles. As a proof of concept for real urban areas, the integrated CFD/CRD approach is applied for a real scale (1 × 1 km2) complex urban area (a district of the city of Rotterdam, The Netherlands) with high traffic emissions. The predicted pollutant concentration levels give realistic values that correspond to moderate to heavy smog. It is concluded that the integrated CFD/CRD method with the GRS model of chemical reactions is both accurate and numerically robust, and can be used for modeling of smog formation in complex urban areas.

Application of photochemical technologies for treatment of landfill leachate

Energy Technology Data Exchange (ETDEWEB)

Meeroff, Daniel E., E-mail: dmeeroff@fau.edu [Department of Civil, Environmental and Geomatics Engineering, Florida Atlantic University, Boca Raton, FL (United States); Bloetscher, Frederick; Reddy, D.V.; Gasnier, Francois; Jain, Swapnil; McBarnette, Andre; Hamaguchi, Hatsuko [Department of Civil, Environmental and Geomatics Engineering, Florida Atlantic University, Boca Raton, FL (United States)

2012-03-30

Highlights: Black-Right-Pointing-Pointer Photochemical iron-mediated aeration and TiO{sub 2} photocatalysis for leachate treatment. Black-Right-Pointing-Pointer Removal efficiency tested on COD, BOD{sub 5}, color, ammonia, and lead. Black-Right-Pointing-Pointer Contact times for 90% removal were 10-200 h for PIMA Black-Right-Pointing-Pointer Contact times for 90% removal were 3-37 h for TiO{sub 2} photocatalysis. Black-Right-Pointing-Pointer Pre-filtration is not necessary. - Abstract: Because of widely varying practices in solid waste management, an all-inclusive solution to long-term management of landfill leachate is currently not available. There is a major technological need for sustainable, economical options for safe discharge of leachate to the environment. Two potential on-site pretreatment technologies, photochemical iron-mediated aeration (PIMA) and TiO{sub 2} photocatalysis were compared for treatment of landfill leachate at laboratory scale. Results of bench scale testing of real landfill leachate with PIMA and TiO{sub 2} photocatalysis showed up to 86% conversion of refractory COD to complete mineralization, up to 91% removal of lead, up to 71% removal of ammonia without pH adjustment, and up to 90% effective color removal with detention times between 4 and 6 h, in field samples. The estimated contact times for 90% removal of COD, ammonia, lead, and color were found to be on the order of 10-200 h for PIMA and 3-37 h for TiO{sub 2} photocatalysis. Testing with actual leachate samples showed 85% TiO{sub 2} photocatalyst recovery efficiency with no loss in performance after multiple (n > 4 uses). Pre-filtration was not found to be necessary for effective treatment using either process.

Using of Photochemical H2O2/UVC Decontamination Cell for Heavily Polluted Waters

Czech Academy of Sciences Publication Activity Database

Žebrák, R.; Mašín, P.; Klusoň, Petr; Krystyník, Pavel

2014-01-01

Roč. 2014, č. 2 (2014), s. 55-62 ISSN 1804-0195. [Symposium ODPADOVÉ FÓRUM 2014. Hustopeče u Brna, 23.042014-23.04.2013] R&D Projects: GA MPO(CZ) FR-TI1/065 Institutional support: RVO:67985858 Keywords : photochemical oxidation * remediation * pilot scale Subject RIV: CI - Industrial Chemistry, Chemical Engineering http://www.wasteforum.cz/

Photochemical Energy Storage and Electrochemically Triggered Energy Release in the Norbornadiene-Quadricyclane System: UV Photochemistry and IR Spectroelectrochemistry in a Combined Experiment.

Science.gov (United States)

Brummel, Olaf; Waidhas, Fabian; Bauer, Udo; Wu, Yanlin; Bochmann, Sebastian; Steinrück, Hans-Peter; Papp, Christian; Bachmann, Julien; Libuda, Jörg

2017-07-06

The two valence isomers norbornadiene (NBD) and quadricyclane (QC) enable solar energy storage in a single molecule system. We present a new photoelectrochemical infrared reflection absorption spectroscopy (PEC-IRRAS) experiment, which allows monitoring of the complete energy storage and release cycle by in situ vibrational spectroscopy. Both processes were investigated, the photochemical conversion from NBD to QC using the photosensitizer 4,4'-bis(dimethylamino)benzophenone (Michler's ketone, MK) and the electrochemically triggered cycloreversion from QC to NBD. Photochemical conversion was obtained with characteristic conversion times on the order of 500 ms. All experiments were performed under full potential control in a thin-layer configuration with a Pt(111) working electrode. The vibrational spectra of NBD, QC, and MK were analyzed in the fingerprint region, permitting quantitative analysis of the spectroscopic data. We determined selectivities for both the photochemical conversion and the electrochemical cycloreversion and identified the critical steps that limit the reversibility of the storage cycle.

Evaluation of model-based versus non-parametric monaural noise-reduction approaches for hearing aids.

Science.gov (United States)

Harlander, Niklas; Rosenkranz, Tobias; Hohmann, Volker

2012-08-01

Single channel noise reduction has been well investigated and seems to have reached its limits in terms of speech intelligibility improvement, however, the quality of such schemes can still be advanced. This study tests to what extent novel model-based processing schemes might improve performance in particular for non-stationary noise conditions. Two prototype model-based algorithms, a speech-model-based, and a auditory-model-based algorithm were compared to a state-of-the-art non-parametric minimum statistics algorithm. A speech intelligibility test, preference rating, and listening effort scaling were performed. Additionally, three objective quality measures for the signal, background, and overall distortions were applied. For a better comparison of all algorithms, particular attention was given to the usage of the similar Wiener-based gain rule. The perceptual investigation was performed with fourteen hearing-impaired subjects. The results revealed that the non-parametric algorithm and the auditory model-based algorithm did not affect speech intelligibility, whereas the speech-model-based algorithm slightly decreased intelligibility. In terms of subjective quality, both model-based algorithms perform better than the unprocessed condition and the reference in particular for highly non-stationary noise environments. Data support the hypothesis that model-based algorithms are promising for improving performance in non-stationary noise conditions.

Evaluated kinetic and photochemical data for atmospheric chemistry: Supplement VIII, halogen species evaluation for atmospheric chemistry

International Nuclear Information System (INIS)

Atkinson, R.; Baulch, D.L.; Cox, R.A.; Hampson, R.F. Jr.; Kerr, J.A.; Rossi, M.J.; Troe, J.

2000-01-01

This paper updates and extends part of the previous data base of critical evaluations of the kinetics and photochemistry of gas-phase chemical reactions of neutral species involved in atmospheric chemistry [J. Phys. Chem. Ref. Data 9, 295 (1980); 11, 327 (1982); 13, 1259 (1984); 18, 881 (1989); 21, 1125 (1992); 26, 521 (1997); 26, 1329 (1997); 28, 191 (1999)]. The present evaluation is limited to the inorganic halogen family of atmospherically important reactions. The work has been carried out by the authors under the auspices of the IUPAC Subcommittee on Gas Phase Kinetic Data Evaluation for Atmospheric Chemistry. Data sheets have been prepared for 102 thermal and photochemical reactions, containing summaries of the available experimental data with notes giving details of the experimental procedures. For each thermal reaction, a preferred value of the rate coefficient at 298 K is given together with a temperature dependence where possible. The selection of the preferred value is discussed and estimates of the accuracies of the rate coefficients and temperature coefficients have been made for each reaction. For each photochemical reaction the data sheets list the preferred values of the photoabsorption cross sections and the quantum yields of the photochemical reactions together with comments on how they were selected. The data sheets are intended to provide the basic physical chemical data needed as input for calculations that model atmospheric chemistry. A table summarizing the preferred rate data is provided, together with an appendix listing the available values of enthalpies of formation of the reactant and product species

HYBRID SELECTIVE NON-CATALYTIC REDUCTION (SNCR)/SELECTIVE CATALYTIC REDUCTION (SCR) DEMONSTRATION FOR THE REMOVAL OF NOx FROM BOILER FLUE GASES; FINAL

International Nuclear Information System (INIS)

Jerry B. Urbas

1999-01-01

The U. S. Department of Energy (DOE), Electric Power Research Institute (EPRI), Pennsylvania Electric Energy Research Council, (PEERC), New York State Electric and Gas and GPU Generation, Inc. jointly funded a demonstration to determine the capabilities for Hybrid SNCR/SCR (Selective Non-Catalytic Reduction/Selective Catalytic Reduction) technology. The demonstration site was GPU Generation's Seward Unit No.5 (147MW) located in Seward Pennsylvania. The demonstration began in October of 1997 and ended in December 1998. DOE funding was provided through Grant No. DE-FG22-96PC96256 with T. J. Feeley as the Project Manager. EPRI funding was provided through agreements TC4599-001-26999 and TC4599-002-26999 with E. Hughes as the Project Manager. This project demonstrated the operation of the Hybrid SNCR/SCR NO(sub x) control process on a full-scale coal fired utility boiler. The hybrid technology was expected to provide a cost-effective method of reducing NO(sub x) while balancing capital and operation costs. An existing urea based SNCR system was modified with an expanded-duct catalyst to provide increased NO(sub x) reduction efficiency from the SNCR while producing increased ammonia slip levels to the catalyst. The catalyst was sized to reduce the ammonia slip to the air heaters to less than 2 ppm while providing equivalent NO(sub x) reductions. The project goals were to demonstrate hybrid technology is capable of achieving at least a 55% reduction in NO(sub x) emissions while maintaining less than 2ppm ammonia slip to the air heaters, maintain flyash marketability, verify the cost benefit and applicability of Hybrid post combustion technology, and reduce forced outages due to ammonium bisulfate (ABS) fouling of the air heaters. Early system limitations, due to gas temperature stratification, restricted the Hybrid NO(sub x) reduction capabilities to 48% with an ammonia slip of 6.1 mg/Nm(sup 3) (8 ppm) at the catalyst inlet. After resolving the stratification problem

Considerations on photochemical genotoxicity. II: Report of the 2009 International Workshop on Genotoxicity Testing Working Group

NARCIS (Netherlands)

Lynch, A.M.; Guzzie, P.J.; Bauer, D.; Gocke, E.; Itoh, S.; Jacobs, A.; Krul, C.A.M.; Schepky, A.; Tanaka, N.; Kasper, P.

2011-01-01

A workshop to reappraise the previous IWGT recommendations for photogenotoxicity testing [E. Gocke, L. Muller, P.J. Guzzie, S. Brendler-Schwaab, S. Bulera, C.F. Chignell, L.M. Henderson, A. Jacobs, H. Murli, R.D. Snyder, N. Tanaka, Considerations on photochemical genotoxicity: report of the

1H-NMR and photochemically-induced dynamic nuclear polarization studies on bovine pancreatic phospholipase A2

NARCIS (Netherlands)

Egmond, M.R.; Slotboom, A.J.; Haas, G.H. de; Dijkstra, Klaas; Kaptein, R.

1980-01-01

Proton-NMR resonances of trytophan 3 and tyrosine 69 in bovine pancreatic phospholipase A2, its pro-enzyme and in Ala1-transaminated protein were assigned using photochemically-induced dynamic nuclear polarization (photo-CIDNP) as such or in combination with spin-echo measurements. In addition

Photoreduction of chromium(VI) in the presence of algae, Chlorella vulgaris

International Nuclear Information System (INIS)

Deng Lin; Wang Hongli; Deng Nansheng

2006-01-01

In this thesis, the photochemical reduction of hexavalent chromium Cr(VI) in the presence of algae, Chlorella vulgaris, was investigated under the irradiation of metal halide lamps (λ=365nm, 250W). The affecting factors of photochemical reduction were studied in detail, such as exposure time, initial Cr(VI) concentration, initial algae concentration and pH. The rate of Cr(VI) photochemical reduction increased with algae concentration increasing, exposure time increasing, initial Cr(VI) concentration decreasing and the decrease of pH. When pH increased to 6, the rate of Cr(VI) photochemical reduction nearly vanished. When initial Cr(VI) concentration ranged from 0.4 to 1.0mgL -1 and initial algae concentration ranged from ABS algae (the absorbency of algae)=0.025 to ABS algae =0.180, According to the results of kinetic analyses, the kinetic equation of Cr(VI) photochemical reduction in aqueous solution with algae under 250W metal halide lamps was V 0 =kC 0 0.1718 A algae 0.5235 (C 0 was initial concentration of Cr(VI); A algae was initial concentration of algae) under the condition of pH 4

N = 2 local and N = 4 non-local reductions of supersymmetric KP hierarchy in N = 2 superspace

International Nuclear Information System (INIS)

Delduc, F.; Gallot, L.; Sorin, A.

1999-01-01

An N = 4 supersymmetric matrix KP hierarchy is proposed and a wide class of its reductions which are characterized by a finite number of fields are described. This class includes the one-dimensional reduction of the two-dimensional N = (2,2) superconformal Toda lattice hierarchy possessing the N = 4 supersymmetry -- the N = 4 Toda chain hierarchy - which may be relevant in the construction of supersymmetric matrix models. The Lax-pair representations of the bosonic and fermionic flows, corresponding local and non-local Hamiltonians, finite and infinite discrete symmetries, the first two Hamiltonian structures and the recursion operator connecting all evolution equations and the Hamiltonian structures of the N = 4 Toda chain hierarchy are constructed in explicit form. Is secondary reduction to the N 4 supersymmetric α = - 2 KdV hierarchy is

The Social Network of Tracer Variations and O(100) Uncertain Photochemical Parameters in the Community Atmosphere Model

Science.gov (United States)

Lucas, D. D.; Labute, M.; Chowdhary, K.; Debusschere, B.; Cameron-Smith, P. J.

2014-12-01

Simulating the atmospheric cycles of ozone, methane, and other radiatively important trace gases in global climate models is computationally demanding and requires the use of 100's of photochemical parameters with uncertain values. Quantitative analysis of the effects of these uncertainties on tracer distributions, radiative forcing, and other model responses is hindered by the "curse of dimensionality." We describe efforts to overcome this curse using ensemble simulations and advanced statistical methods. Uncertainties from 95 photochemical parameters in the trop-MOZART scheme were sampled using a Monte Carlo method and propagated through 10,000 simulations of the single column version of the Community Atmosphere Model (CAM). The variance of the ensemble was represented as a network with nodes and edges, and the topology and connections in the network were analyzed using lasso regression, Bayesian compressive sensing, and centrality measures from the field of social network theory. Despite the limited sample size for this high dimensional problem, our methods determined the key sources of variation and co-variation in the ensemble and identified important clusters in the network topology. Our results can be used to better understand the flow of photochemical uncertainty in simulations using CAM and other climate models. This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344 and supported by the DOE Office of Science through the Scientific Discovery Through Advanced Computing (SciDAC).

Disruption of the ndhF1 gene affects Chl fluorescence through state transition in the Cyanobacterium Synechocystis sp. PCC 6803, resulting in apparent high efficiency of photosynthesis.

Science.gov (United States)

Ogawa, Takako; Harada, Tetsuyuki; Ozaki, Hiroshi; Sonoike, Kintake

2013-07-01

In Synechocystis sp. PCC 6803, the disruption of the ndhF1 gene (slr0844), which encodes a subunit of one of the NDH-1 complexes (NDH-1L complex) serving for respiratory electron transfer, causes the largest change in Chl fluorescence induction kinetics among the kinetics of 750 disruptants searched in the Fluorome, the cyanobacterial Chl fluorescence database. The cause of the explicit phenotype of the ndhF1 disruptant was examined by measurements of the photosynthetic rate, Chl fluorescence and state transition. The results demonstrate that the defects in respiratory electron transfer obviously have great impact on Chl fluorescence in cyanobacteria. The inactivation of NDH-1L complexes involving electron transfer from NDH-1 to plastoquinone (PQ) would result in the oxidation of the PQ pool, leading to the transition to State 1, where the yield of Chl fluorescence is high. Apparently, respiration, although its rate is far lower than that of photosynthesis, could affect Chl fluorescence through the state transition as leverage. The disruption of the ndhF1 gene caused lower oxygen-evolving activity but the estimated electron transport rate from Chl fluorescence measurements was faster in the mutant than in the wild-type cells. The discrepancy could be ascribed to the decreased level of non-photochemical quenching due to state transition. One must be cautious when using the Chl fluorescence parameter to estimate photosynthesis in mutants defective in state transition.

Use of fluorescent probes for ROS to tease apart Type I and Type II photochemical pathways in photodynamic therapy

DEFF Research Database (Denmark)

Garcia-Diaz, Maria; Huang, Ying-Ying; Hamblin, Michael R

2016-01-01

) include superoxide, hydrogen peroxide and hydroxyl radical (HO), while singlet oxygen ((1)O2) is produced by energy transfer. Diverse methods exist to distinguish between these two pathways, some of which are more specific or more sensitive than others. In this review we cover the use of two fluorescence...... probes: singlet oxygen sensor green (SOSG) detects (1)O2; and 4-hydroxyphenyl-fluorescein (HPF) that detects HO. Interesting data was collected concerning the photochemical pathways of functionalized fullerenes compared to tetrapyrroles, stable synthetic bacteriochlorins with and without central metals......Photodynamic therapy involves the excitation of a non-toxic dye by harmless visible light to produce a long-lived triplet state that can interact with molecular oxygen to produce reactive oxygen species (ROS), which can damage biomolecules and kill cells. ROS produced by electron transfer (Type 1...

Estimating CO{sub 2} Emission Reduction of Non-capture CO{sub 2} Utilization (NCCU) Technology

Energy Technology Data Exchange (ETDEWEB)

Lee, Ji Hyun; Lee, Dong Woog; Gyu, Jang Se; Kwak, No-Sang; Lee, In Young; Jang, Kyung Ryoung; Shim, Jae-Goo [KEPCO Research Institute, Daejon (Korea, Republic of); Choi, Jong Shin [Korea East-West Power Co., LTD(ETP), Ulsan (Korea, Republic of)

2015-10-15

Estimating potential of CO{sub 2} emission reduction of non-capture CO{sub 2} utilization (NCCU) technology was evaluated. NCCU is sodium bicarbonate production technology through the carbonation reaction of CO{sub 2} contained in the flue gas. For the estimating the CO{sub 2} emission reduction, process simulation using process simulator (PRO/II) based on a chemical plant which could handle CO{sub 2} of 100 tons per day was performed, Also for the estimation of the indirect CO{sub 2} reduction, the solvay process which is a conventional technology for the production of sodium carbonate/sodium bicarbonate, was studied. The results of the analysis showed that in case of the solvay process, overall CO{sub 2} emission was estimated as 48,862 ton per year based on the energy consumption for the production of NaHCO{sub 3} (7.4 GJ/tNaHCO{sub 3}). While for the NCCU technology, the direct CO{sub 2} reduction through the CO{sub 2} carbonation was estimated as 36,500 ton per year and the indirect CO{sub 2} reduction through the lower energy consumption was 46,885 ton per year which lead to 83,385 ton per year in total. From these results, it could be concluded that sodium bicarbonate production technology through the carbonation reaction of CO{sub 2} contained in the flue was energy efficient and could be one of the promising technology for the low CO{sub 2} emission technology.

State of the direct reduction and reduction smelting processes

Directory of Open Access Journals (Sweden)

Markotić A.

2002-01-01

Full Text Available For quite a long time efforts have been made to develop processes for producing iron i.e. steel without employing conventional procedures - from ore, coke, blast furnace, iron, electric arc furnace, converter to steel. The insufficient availability and the high price of the coking coals have forced many countries to research and adopt the non-coke-consuming reduction and metal manufacturing processes (non-coke metallurgy, direct reduction, direct processes. This paper represents a survey of the most relevant processes from this domain by the end of 2000, which display a constant increase in the modern process metallurgy.

The photochemical stability of the Venus atmosphere against UV radiation

International Nuclear Information System (INIS)

Mills, F.P.; Slanger, T.G.; Allen, M.

2004-01-01

Full text: One unresolved question regarding the Venus atmosphere is what chemical mechanism(s) stabilize its primary constituent (CO 2 ) against UV radiation. CO 2 photolyzes on the day side into CO and O after absorbing photons at 2 rather than recombining with CO to form CO 2 , and the intense night side O 2 airglow observed quantitatively supports this. CO and O 2 are photochemically stable in an otherwise pure CO 2 atmosphere so significant abundances of CO and O 2 could accumulate on Venus if no catalytic mechanism existed to speed the reformation of CO 2 . However, the observational upper limit on ground state O 2 is equivalent to 2 from CO and O 2 . Recent laboratory work verified the existence of the ClC(O)OO catalytic mechanism that has been used in photochemical models since the early 1980s. However, there are significant uncertainties in the rates for the component steps of this catalytic mechanism. An alternative mechanism for production of CO 2 that has not previously been modeled but which could be competitive with the ClCO(O)O mechanism is the reaction CO + O 2 (c 1 Σ - u ) → CO 2 + O( 1 D) or O( 1 S), Reaction (1). A range of values for Reaction (1) will be examined in model calculations to compare with observational (UV to IR) constraints and to assess under what conditions this mechanism is competitive with the ClC(O)OO catalytic mechanism. The sensitivity of the results to uncertainties in the CO 2 UV absorption cross section also will be examined

Volatile Organic Compounds from Logwood Combustion: Emissions and Transformation under Dark and Photochemical Aging Conditions in a Smog Chamber.

Science.gov (United States)

Hartikainen, Anni; Yli-Pirilä, Pasi; Tiitta, Petri; Leskinen, Ari; Kortelainen, Miika; Orasche, Jürgen; Schnelle-Kreis, Jürgen; Lehtinen, Kari E J; Zimmermann, Ralf; Jokiniemi, Jorma; Sippula, Olli

2018-04-17

Residential wood combustion (RWC) emits high amounts of volatile organic compounds (VOCs) into ambient air, leading to formation of secondary organic aerosol (SOA), and various health and climate effects. In this study, the emission factors of VOCs from a logwood-fired modern masonry heater were measured using a Proton-Transfer-Reactor Time-of-Flight Mass Spectrometer. Next, the VOCs were aged in a 29 m 3 Teflon chamber equipped with UV black lights, where dark and photochemical atmospheric conditions were simulated. The main constituents of the VOC emissions were carbonyls and aromatic compounds, which accounted for 50%-52% and 30%-46% of the detected VOC emission, respectively. Emissions were highly susceptible to different combustion conditions, which caused a 2.4-fold variation in emission factors. The overall VOC concentrations declined considerably during both dark and photochemical aging, with simultaneous increase in particulate organic aerosol mass. Especially furanoic and phenolic compounds decreased, and they are suggested to be the major precursors of RWC-originated SOA in all aging conditions. On the other hand, dark aging produced relatively high amounts of nitrogen-containing organic compounds in both gas and particulate phase, while photochemical aging increased especially the concentrations of certain gaseous carbonyls, particularly acid anhydrides.

Reduction of non-point source contaminants associated with road-deposited sediments by sweeping.

Science.gov (United States)

Kim, Do-Gun; Kang, Hee-Man; Ko, Seok-Oh

2017-09-19

Road-deposited sediments (RDS) on an expressway, residual RDS collected after sweeping, and RDS removed by means of sweeping were analyzed to evaluate the degree to which sweeping removed various non-point source contaminants. The total RDS load was 393.1 ± 80.3 kg/km and the RDS, residual RDS, and swept RDS were all highly polluted with organics, nutrients, and metals. Among the metals studied, Cu, Zn, Pb, Ni, Ca, and Fe were significantly enriched, and most of the contaminants were associated with particles within the size range from 63 μm to 2 mm. Sweeping reduced RDS and its associated contaminants by 33.3-49.1% on average. We also measured the biological oxygen demand (BOD) of RDS in the present work, representing to our knowledge the first time that this has been done; we found that RDS contains a significant amount of biodegradable organics and that the reduction of BOD by sweeping was higher than that of other contaminants. Significant correlations were found between the contaminants measured, indicating that the organics and the metals originated from both exhaust and non-exhaust particles. Meanwhile, the concentrations of Cu and Ni were higher in 63 μm-2 mm particles than in smaller particles, suggesting that some metals in RDS likely exist intrinsically in particles, rather than only as adsorbates on particle surfaces. Overall, the results in this study showed that sweeping to collect RDS can be a good alternative for reduction of contaminants in runoff.

A box model study on photochemical interactions between VOCs and reactive halogen species in the marine boundary layer

Directory of Open Access Journals (Sweden)

K. Toyota

2004-01-01

Full Text Available A new chemical scheme is developed for the multiphase photochemical box model SEAMAC (size-SEgregated Aerosol model for Marine Air Chemistry to investigate photochemical interactions between volatile organic compounds (VOCs and reactive halogen species in the marine boundary layer (MBL. Based primarily on critically evaluated kinetic and photochemical rate parameters as well as a protocol for chemical mechanism development, the new scheme has achieved a near-explicit description of oxidative degradation of up to C3-hydrocarbons (CH4, C2H6, C3H8, C2H4, C3H6, and C2H2 initiated by reactions with OH radicals, Cl- and Br-atoms, and O3. Rate constants and product yields for reactions involving halogen species are taken from the literature where available, but the majority of them need to be estimated. In particular, addition reactions of halogen atoms with alkenes will result in forming halogenated organic intermediates, whose photochemical loss rates are carefully evaluated in the present work. Model calculations with the new chemical scheme reveal that the oceanic emissions of acetaldehyde (CH3CHO and alkenes (especially C3H6 are important factors for regulating reactive halogen chemistry in the MBL by promoting the conversion of Br atoms into HBr or more stable brominated intermediates in the organic form. The latter include brominated hydroperoxides, bromoacetaldehyde, and bromoacetone, which sequester bromine from a reactive inorganic pool. The total mixing ratio of brominated organic species thus produced is likely to reach 10-20% or more of that of inorganic gaseous bromine species over wide regions over the ocean. The reaction between Br atoms and C2H2 is shown to be unimportant for determining the degree of bromine activation in the remote MBL. These results imply that reactive halogen chemistry can mediate a link between the oceanic emissions of VOCs and the behaviors of compounds that are sensitive to halogen chemistry such as dimethyl

Partial coupling and differential regulation of biologically and photo-chemically labile dissolved organic carbon across boreal aquatic networks

Science.gov (United States)

Lapierre, J.-F.; del Giorgio, P. A.

2014-05-01

Despite the rapidly increasing volume of research on the biological and photochemical degradation of DOC in aquatic environments, little is known on the large-scale patterns in biologically and photo-chemically degradable DOC (Bd-DOC and Pd-DOC, respectively) in continental watersheds, and on the links that exist between these two key properties that greatly influence the flow of carbon from continents to oceans. Here we explore the patterns of Bd- and Pd-DOC across hundreds of boreal lakes, rivers and wetlands spanning a large range of system trophy and terrestrial influence, and compared the drivers of these two reactive pools of DOC at the landscape level. Using standardized incubations of natural waters, we found that the concentrations of Bd- and Pd-DOC co-varied across all systems studied but were nevertheless related to different pools of dissolved organic matter (DOM, identified by fluorescence analyses) in ambient waters. A combination of nutrients and protein-like DOM explained nearly half of the variation in Bd-DOC, whereas Pd-DOC was exclusively predicted by DOM optical properties, consistent with the photochemical degradability of specific fluorescent DOM (FDOM) pools that we experimentally determined. The concentrations of colored DOM (CDOM), a proxy of terrestrial influence, almost entirely accounted for the observed relationship between FDOM and the concentrations of both Bd- and Pd-DOC. The concentrations of CDOM and of the putative bio-labile fluorescence component shifted from complete decoupling in clear-water environments to strong coupling in browner streams and wetlands. This suggests a baseline autochthonous Bd-DOC pool fuelled by internal production that is gradually overwhelmed by land-derived Bd-DOC as terrestrial influence increases across landscape gradients. The importance of land as a major source of both biologically and photo-chemically degradable DOC for continental watersheds resulted in a partial coupling of those carbon pools in

Revisiting the O(3) non-linear sigma model and its Pohlmeyer reduction

Energy Technology Data Exchange (ETDEWEB)

Pastras, Georgios [NCSR ' ' Demokritos' ' , Institute of Nuclear and Particle Physics, Attiki (Greece)

2018-01-15

It is well known that sigma models in symmetric spaces accept equivalent descriptions in terms of integrable systems, such as the sine-Gordon equation, through Pohlmeyer reduction. In this paper, we study the mapping between known solutions of the Euclidean O(3) non-linear sigma model, such as instantons, merons and elliptic solutions that interpolate between the latter, and solutions of the Pohlmeyer reduced theory, namely the sinh-Gordon equation. It turns out that instantons do not have a counterpart, merons correspond to the ground state, while the class of elliptic solutions is characterized by a two to one correspondence between solutions in the two descriptions. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Photochemical Formation and Transformation of Birnessite: Effects of Cations on Micromorphology and Crystal Structure.

Science.gov (United States)

Zhang, Tengfei; Liu, Lihu; Tan, WenFeng; Suib, Steven L; Qiu, Guohong; Liu, Fan

2018-05-24

As important components with excellent oxidation and adsorption activity in soils and sediments, manganese oxides affect the transportation and fate of nutrients and pollutants in natural environments. In this work, birnessite was formed by photocatalytic oxidation of Mn2+aq in the presence of nitrate under solar irradiation. The effects of concentrations and species of interlayer cations (Na+, Mg2+, and K+) on birnessite crystal structure and micromorphology were investigated. The roles of adsorbed Mn2+ and pH in the transformation of the photosynthetic birnessite were further studied. The results indicated that Mn2+aq was oxidized to birnessite by superoxide radicals (O2•-) generated from the photolysis of NO3- under UV irradiation. The particle size and thickness of birnessite decreased with increasing cation concentration. The birnessite showed a plate-like morphology in the presence of K+, while exhibited a rumpled sheet-like morphology when Na+ or Mg2+ was used. The different micromorphologies of birnessites could be ascribed to the position of cations in the interlayer. The adsorbed Mn2+ and high pH facilitated the reduction of birnessite to low-valence manganese oxides including hausmannite, feitknechtite, and manganite. This study suggests that interlayer cations and Mn2+ play essential roles in the photochemical formation and transformation of birnessite in aqueous environments.

Transfusion of pooled buffy coat platelet components prepared with photochemical pathogen inactivation treatment: the euroSPRITE trial

NARCIS (Netherlands)

D.J. van Rhenen (Dirk Jan); S. Marblie (Stephane); M. Laforet (Michel); K. Davis (Kathryn); M. Conlan (Maureen); B. Lioure (Bruno); H. Gulliksson (Hans); J.P. Cazenave; P. Metzel (Peyton); D. Pamphilon (Derwood); L. Corash (Laurence); J. Flament (Jocelyne); P. Ljungman (Per); H. Kluter; H. Vermeij (Hans); V. Mayaudon (Veronique); L. Lin (Lily); M.C. Kappers-Klunne (Mies); D. Buchholz (Don); G.E. de Greef (Georgine)

2003-01-01

textabstractA nucleic acid-targeted photochemical treatment (PCT) using amotosalen HCl (S-59) and ultraviolet A (UVA) light was developed to inactivate viruses, bacteria, protozoa, and leukocytes in platelet components. We conducted a controlled, randomized, double-blinded trial in thrombocytopenic

Bacterial assimilation reduction of iron in the treatment of non-metallics

Directory of Open Access Journals (Sweden)

Peter Malachovský

2005-11-01

Full Text Available Natural non-metallics, including granitoide and quartz sands, often contain iron which decreases the whiteness of these raw materials. Insoluble Fe3+ in these samples could be reduced to soluble Fe2+ by bacteria of Bacillus spp. and Saccharomyces spp. The leaching effect, observed by the measurement of Fe2+concentration in a solution, showed higher activities of a bacterial kind isolated from the Bajkal lake and also by using of yeast Saccharomyces sp. during bioleaching of quartz sands. However, allkinds of Bacillus spp. isolated from the Slovak deposit and from Bajkal lake were very active in the iron reduction during bioleaching of the feldspar raw material. This metal was efficiently removed from quartz sands as documented by the Fe2O3 decrease (from 0,317 % to 0,126 % and from feldpars raw materials by the Fe2O3 decrease (from 0,288 % to 0,115 % after bioleaching. The whiteness of these non-metallics was increased during a visual comparison of samples before and after bioleaching but samples contain selected magnetic particles. A removal of iron as well as a release of iron minerals from silicate matrix should increase the effect of the magnetic separation and should give a product which is suitable for industrial applications.

Reductive and oxidative degradation of iopamidol, iodinated X-ray contrast media, by Fe(III)-oxalate under UV and visible light treatment.

Science.gov (United States)

Zhao, Cen; Arroyo-Mora, Luis E; DeCaprio, Anthony P; Sharma, Virender K; Dionysiou, Dionysios D; O'Shea, Kevin E

2014-12-15

Iopamidol, widely employed as iodinated X-ray contrast media (ICM), is readily degraded in a Fe(III)-oxalate photochemical system under UV (350 nm) and visible light (450 nm) irradiation. The degradation is nicely modeled by pseudo first order kinetics. The rates of hydroxyl radical (OH) production for Fe(III)-oxalate/H2O2/UV (350 nm) and Fe(III)-oxalate/H2O2/visible (450 nm) systems were 1.19 ± 0.12 and 0.30 ± 0.01 μM/min, respectively. The steady-state concentration of hydroxyl radical (OH) for the Fe(III)-oxalate/H2O2/UV (350 nm) conditions was 10.88 ± 1.13 × 10(-14) M and 2.7 ± 0.1 × 10(-14) M for the Fe(III)-oxalate/H2O2/visible (450 nm). The rate of superoxide anion radical (O2(-)) production under Fe(III)-oxalate/H2O2/UV (350 nm) was 0.19 ± 0.02 μM/min with a steady-state concentration of 5.43 ± 0.473 × 10(-10) M. Detailed product studies using liquid chromatography coupled to Q-TOF/MS demonstrate both reduction (multiple dehalogenations) and oxidation (aromatic ring and side chains) contribute to the degradation pathways. The reduction processes appear to be initiated by the carbon dioxide anion radical (CO2(-)) while oxidation processes are consistent with OH initiated reaction pathways. Unlike most advanced oxidation processes the Fe(III)-oxalate/H2O2/photochemical system can initiate to both reductive and oxidative degradation processes. The observed reductive dehalogenation is an attractive remediation strategy for halogenated organic compounds as the process can dramatically reduce the formation of the problematic disinfection by-products often associated with oxidative treatment processes. Copyright © 2014 Elsevier Ltd. All rights reserved.

Photochemical water splitting mediated by a C1 shuttle

KAUST Repository

Alderman, N. P.

2016-10-31

The possibility of performing photochemical water splitting in a two-stage system, separately releasing the H and O components, has been probed with two separate catalysts and in combination with a formaldehyde/formate shuttling redox couple. In the first stage, formaldehyde releases hydrogen vigorously in the presence of an Na[Fe(CN)]·10HO catalyst, selectively affording the formate anion. In the second stage, the formate anion is hydro-genated back to formaldehyde by water and in the presence of a BiWO photocatalyst whilst releasing oxygen. Both stages operate at room temperature and under visible light irradiation. The two separate photocatalysts are compatible since water splitting can also be obtained in one-pot experiments with simultaneous H/O evolution.

Energy and Molecules from Photochemical/Photocatalytic Reactions. An Overview

Directory of Open Access Journals (Sweden)

Davide Ravelli

2015-01-01

Full Text Available Photocatalytic reactions have been defined as those processes that require both a (not consumed catalyst and light. A previous definition was whether such reactions brought a system towards or away from the (thermal equilibrium. This consideration brings in the question whether a part of the photon energy is incorporated into the photochemical reaction products. Data are provided for representative organic reactions involving or not molecular catalysts and show that energy storage occurs only when a heavily strained structure is generated, and in that case only a minor part of photon energy is actually stored (ΔG up to 25 kcal·mol−1. The green role of photochemistry/photocatalysis is rather that of forming highly reactive intermediates under mild conditions.

Photochemical water splitting mediated by a C1 shuttle

KAUST Repository

Alderman, N. P.; Sommers, J. M.; Viasus, C. J.; Wang, C. H T; Peneau, V.; Gambarotta, S.; Vidjayacoumar, B.; Al-Bahily, K. A.

2016-01-01

The possibility of performing photochemical water splitting in a two-stage system, separately releasing the H and O components, has been probed with two separate catalysts and in combination with a formaldehyde/formate shuttling redox couple. In the first stage, formaldehyde releases hydrogen vigorously in the presence of an Na[Fe(CN)]·10HO catalyst, selectively affording the formate anion. In the second stage, the formate anion is hydro-genated back to formaldehyde by water and in the presence of a BiWO photocatalyst whilst releasing oxygen. Both stages operate at room temperature and under visible light irradiation. The two separate photocatalysts are compatible since water splitting can also be obtained in one-pot experiments with simultaneous H/O evolution.

Temporal Changes in Photochemically Labile DOM and Implications for Carbon Budgets in Peatland Aquatic Systems

Science.gov (United States)

Pickard, A.

2015-12-01

Aquatic systems in peatland catchments are subject to high loading of dissolved organic matter (DOM) from surrounding terrestrial environments. However the significance of photochemical transformation of DOM in peatland carbon budgets remains poorly constrained. In this study UV irradiation experiments were conducted on water samples collected over one year from two contrasting systems in Scotland: a stream draining a peatland with high levels of DOM and a reservoir draining a peat catchment with low levels of DOM. Further samples were collected from the high DOM system during two storm events. After experimental exposure, optical and chemical analyses were employed to determine photochemical lability of the DOM pool. At both sites irradiation-induced decreases in dissolved organic carbon (DOC) as a percentage of the total carbon pool were greatest in winter, suggesting that DOM was depleted in photo-reactive molecules in summer. Seasonal variability in DOC was high at the stream site and was positively correlated with CO₂ and CO photoproduction (r2 = 0.81 and 0.83, respectively; pLignin phenol analyses indicate considerable contribution of peat to the DOM pool at the stream site, particularly during summer. Whilst DOC concentrations did not vary greatly during storm events, UV-Vis absorbance indicators did, signifying changing DOM source material from activation of different hydrological pathways. The most photo-reactive DOM occurred 5-10 hours after peak discharge, suggesting that storms replenish photochemically labile DOM in headwater streams. Conservative estimates using data from this study suggest that up to 7% of the DOM pool of peatland streams can be lost (primarily as CO₂ and CO) upon exposure to 8 hours of environmentally representative UV irradiation. Further investigation in field campaigns under natural UV exposure are underway to assess the importance of photodegradation of DOM as a loss pathway of carbon based gases from aquatic systems.

Photochemical reactions between mercury (Hg) and dissolved organic matter decrease Hg bioavailability and methylation.

Science.gov (United States)

Luo, Hong-Wei; Yin, Xiangping; Jubb, Aaron M; Chen, Hongmei; Lu, Xia; Zhang, Weihua; Lin, Hui; Yu, Han-Qing; Liang, Liyuan; Sheng, Guo-Ping; Gu, Baohua

2017-01-01

Atmospheric deposition of mercury (Hg) to surface water is one of the dominant sources of Hg in aquatic environments and ultimately drives methylmercury (MeHg) toxin accumulation in fish. It is known that freshly deposited Hg is more readily methylated by microorganisms than aged or preexisting Hg; however the underlying mechanism of this process is unclear. We report that Hg bioavailability is decreased by photochemical reactions between Hg and dissolved organic matter (DOM) in water. Photo-irradiation of Hg-DOM complexes results in loss of Sn(II)-reducible (i.e. reactive) Hg and up to an 80% decrease in MeHg production by the methylating bacterium Geobacter sulfurreducens PCA. Loss of reactive Hg proceeded at a faster rate with a decrease in the Hg to DOM ratio and is attributed to the possible formation of mercury sulfide (HgS). These results suggest a new pathway of abiotic photochemical formation of HgS in surface water and provide a mechanism whereby freshly deposited Hg is readily methylated but, over time, progressively becomes less available for microbial uptake and methylation. Copyright © 2016 Elsevier Ltd. All rights reserved.

Sequential fermentation using non-Saccharomyces yeasts for the reduction of alcohol content in wine

Directory of Open Access Journals (Sweden)

Ciani Maurizio

2014-01-01

Full Text Available Over the last few decades there has been a progressive increase in wine ethanol content due to global climate change and modified wine styles that involved viticulture and oenology practices. Among the different approaches and strategies to reduce alcohol content in wine we propose a sequential fermentation using immobilized non-Saccharomyces wine yeasts. Preliminary results showed that sequential fermentations with Hanseniaspora osmophila, Hanseniaspora uvarum, Metschnikowia pulcherrima, Starmerella bombicola and Saccharomyces cerevisiae strains showed an ethanol reduction when compared with pure S. cerevisiae fermentation trials.

Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies: Evaluation Number 18

Science.gov (United States)

Burkholder, J. B.; Sander, S. P.; Abbatt, J. P. D.; Barker, J. R.; Huie, R. E.; Kolb, C. E.; Kurylo, M. J.; Orkin, V. L.; Wilmouth, D. M.; Wine, P. H.

2015-01-01

This is the eighteenth in a series of evaluated sets of rate constants, photochemical cross sections, heterogeneous parameters, and thermochemical parameters compiled by the NASA Panel for Data Evaluation. The data are used primarily to model stratospheric and upper tropospheric processes, with particular emphasis on the ozone layer and its possible perturbation by anthropogenic and natural phenomena. The evaluation is available in electronic form from the following Internet URL: http://jpldataeval.jpl.nasa.gov/

Sensitivity evaluation of the green alga Chlamydomonas reinhardtii to uranium by pulse amplitude modulated (PAM) fluorometry.

Science.gov (United States)

Herlory, Olivier; Bonzom, Jean-Marc; Gilbin, Rodolphe

2013-09-15

Although ecotoxicological studies tend to address the toxicity thresholds of uranium in freshwaters, there is a lack of information on the effects of the metal on physiological processes, particularly in aquatic plants. Knowing that uranium alters photosynthesis via impairment of the water photo-oxidation process, we determined whether pulse amplitude modulated (PAM) fluorometry was a relevant tool for assessing the impact of uranium on the green alga Chlamydomonas reinhardtii and investigated how and to what extent uranium hampered photosynthetic performance. Photosynthetic activity and quenching were assessed from fluorescence induction curves generated by PAM fluorometry, after 1 and 5h of uranium exposure in controlled conditions. The oxygen-evolving complex (OEC) of PSII was identified as the primary action site of uranium, through alteration of the water photo-oxidation process as revealed by F0/Fv. Limiting re-oxidation of the plastoquinone pool, uranium impaired the electron flux between the photosystems until almost complete inhibition of the PSII quantum efficiency ( [Formula: see text] , EC50=303 ± 64 μg UL(-1) after 5h of exposure) was observed. Non-photochemical quenching (qN) was identified as the most sensitive fluorescence parameter (EC50=142 ± 98 μg UL(-1) after 5h of exposure), indicating that light energy not used in photochemistry was dissipated in non-radiative processes. It was shown that parameters which stemmed from fluorescence induction kinetics are valuable indicators for evaluating the impact of uranium on PSII in green algae. PAM fluorometry provided a rapid and reasonably sensitive method for assessing stress response to uranium in microalgae. Copyright © 2013 Elsevier B.V. All rights reserved.

Interfacial electrochemistry of colloidal ruthenium dioxide and catalysis of the photochemical generation of hydrogen from water

NARCIS (Netherlands)

Kleijn, J.M.

1987-01-01

The formation of hydrogen from water using solar energy is a very attractive research topic, because of the potential use of hydrogen as an alternative, clean fuel. It has been shown by many workers in the field that photochemical hydrogen generation can be achieved in an aqueous system,

Photochemical internalisation of chemotherapy potentiates killing of multidrug-resistant breast and bladder cancer cells

OpenAIRE

Adigbli, D. K.; Wilson, D. G. G.; Farooqui, N.; Sousi, E.; Risley, P.; Taylor, I.; MacRobert, A. J.; Loizidou, M.

2007-01-01

Multidrug resistance (MDR) is the major confounding factor in adjuvant solid tumour chemotherapy. Increasing intracellular amounts of chemotherapeutics to circumvent MDR may be achieved by a novel delivery method, photochemical internalisation (PCI). PCI consists of the co-administration of drug and photosensitiser; upon light activation the latter induces intracellular release of organelle-bound drug. We investigated whether co-administration of hypericin ( photosensitiser) with mitoxantrone...

Photochemical internalisation of chemotherapy potentiates killing of multidrug-resistant breast and bladder cancer cells

OpenAIRE

Adigbli, D K; Wilson, D G G; Farooqui, N; Sousi, E; Risley, P; Taylor, I; MacRobert, A J; Loizidou, M

2007-01-01

Multidrug resistance (MDR) is the major confounding factor in adjuvant solid tumour chemotherapy. Increasing intracellular amounts of chemotherapeutics to circumvent MDR may be achieved by a novel delivery method, photochemical internalisation (PCI). PCI consists of the co-administration of drug and photosensitiser; upon light activation the latter induces intracellular release of organelle-bound drug. We investigated whether co-administration of hypericin (photosensitiser) with mitoxantrone ...

High performance oligomers: synthesis and photochemical properties of calix(n)arene containing various photoreactive groups

International Nuclear Information System (INIS)

Nishikubo, T.; Kameyama, A.

1999-01-01

Photoreactive calix(n)arenes containing radical polymerizable (meth)acrylate groups, and catatonically polymerizable vinyl ether, propargyl ether, oxirane and oxetane groups were synthesized by certain reactions of calix(n)arenes with the corresponding (meth)acrylic acid derivatives, vinyl ether compound, epibromohydrin and oxetane derivatives, respectively. The photochemical reaction of these calix(n)arene derivatives were also examined

Integrating transient heterogeneity of non-photochemical quenching in shade-grown heterobaric leaves of avocado (Persea americana L.): responses to CO2 concentration, stomatal occlusion, dehydration and relative humidity.

Science.gov (United States)

Takayama, Kotaro; King, Diana; Robinson, Sharon A; Osmond, Barry

2013-11-01

Long-lived shade leaves of avocado had extremely low rates of photosynthesis. Gas exchange measurements of photosynthesis were of limited use, so we resorted to Chl fluorescence imaging (CFI) and spot measurements to evaluate photosynthetic electron transport rates (ETRs) and non-photochemical quenching (NPQ). Imaging revealed a remarkable transient heterogeneity of NPQ during photosynthetic induction in these hypostomatous, heterobaric leaves, but was adequately integrated by spot measurements, despite long-lasting artifacts from repeated saturating flashes during assays. Major veins (mid-vein, first- and second-order veins) defined areas of more static large-scale heterogeneous NPQ, with more dynamic small-scale heterogeneity most strongly expressed in mesophyll cells between third- and fourth-order veins. Both responded to external CO2 concentration ([CO2]), occlusion of stomata with Vaseline™, leaf dehydration and relative humidity (RH). We interpreted these responses in terms of independent behavior of stomata in adjacent areoles that was largely expressed through CO2-limited photosynthesis. Heterogeneity was most pronounced and prolonged in the absence of net CO2 fixation in 100 p.p.m. [CO2] when respiratory and photorespiratory CO2 cycling constrained the inferred ETR to ~75% of values in 400 or 700 p.p.m. [CO2]. Likewise, sustained higher NPQ under Vaseline™, after dehydration or at low RH, also restricted ETR to ~75% of control values. Low NPQ in chloroplast-containing cells adjacent to major veins but remote from stomata suggested internal sources of high [CO2] in these tissues.

Chemical characteristics of fulvic acids from Arctic surface waters: Microbial contributions and photochemical transformations

Science.gov (United States)

Cory, Rose M.; McKnight, Diane M.; Chin, Yu-Ping; Miller, Penney; Jaros, Chris L.

2007-12-01

Dissolved organic matter (DOM) originating from the extensive Arctic tundra is an important source of organic material to the Arctic Ocean. Chemical characteristics of whole water dissolved organic matter (DOM) and the fulvic acid fraction of DOM were studied from nine surface waters in the Arctic region of Alaska to gain insight into the extent of microbial and photochemical transformation of this DOM. All the fulvic acids had a strong terrestrial/higher plant signature, with uniformly depleted δ13C values of -28‰, and low fluorescence indices around 1.3. Several of the measured chemical characteristics of the Arctic fulvic acids were related to water residence time, a measure of environmental exposure to sunlight and microbial activity. For example, fulvic acids from Arctic streams had higher aromatic contents, higher specific absorbance values, lower nitrogen content, lower amino acid-like fluorescence and were more depleted in δ15N relative to fulvic acids isolated from lake and coastal surface waters. The differences in the nitrogen signature between the lake and coastal fulvic acids compared to the stream fulvic acids indicated that microbial contributions to the fulvic acid pool increased with increasing water residence time. The photo-lability of the fulvic acids was positively correlated with water residence time, suggesting that the fulvic acids isolated from source waters with larger water residence times (i.e., lakes and coastal waters) have experienced greater photochemical degradation than the stream fulvic acids. In addition, many of the initial differences in fulvic acid chemical characteristics across the gradient of water residence times were consistent with changes observed in fulvic acid photolysis experiments. Taken together, results from this study suggest that photochemical processes predominantly control the chemical character of fulvic acids in Arctic surface waters. Our findings show that hydrologic transport in addition to

Symbiont shuffling linked to differential photochemical dynamics of Symbiodinium in three Caribbean reef corals

Science.gov (United States)

Cunning, Ross; Silverstein, Rachel N.; Baker, Andrew C.

2018-03-01

Dynamic symbioses with functionally diverse dinoflagellate algae in the genus Symbiodinium may allow some reef corals to alter their phenotypes through `symbiont shuffling', or changes in symbiont community composition. In particular, corals may become more bleaching resistant by increasing the relative abundance of thermally tolerant Symbiodinium in clade D after bleaching. Despite the immediate relevance of this phenomenon to corals living in warming oceans—and to interventions aimed at boosting coral resilience—the mechanisms governing how, why, and when symbiont shuffling occurs are still poorly understood. Here, we performed controlled thermal bleaching and recovery experiments on three species of Caribbean corals hosting mixtures of D1a ( S. trenchii) and other symbionts in clades B or C. We show that the degree of symbiont shuffling is related to (1) the duration of stress exposure and (2) the difference in photochemical efficiency ( F v /F m) of co-occurring symbionts under stress (i.e., the `photochemical advantage' of one symbiont over the other). The advantage of D1a under stress was greatest in Montastraea cavernosa, intermediate in Siderastrea siderea, and lowest in Orbicella faveolata and correlated positively with the magnitude of shuffling toward D1a. In holobionts where D1a had less of an advantage over co-occurring symbionts (i.e., only slightly higher F v /F m under stress), a longer stress duration was required to elicit commensurate increases in D1a abundance. In fact, across these three coral species, 92.9% of variation in the degree of symbiont shuffling could be explained by the time-integrated photochemical advantage of D1a under heat stress. Although F v /F m is governed by numerous factors that this study is unable to resolve mechanistically, its strong empirical relationship with symbiont shuffling helps elucidate general features that govern this process in reef corals, which will help refine predictions of coral responses to

The evolution of photochemical smog in a power plant plume

Science.gov (United States)

Luria, Menachem; Valente, Ralph J.; Tanner, Roger L.; Gillani, Noor V.; Imhoff, Robert E.; Mueller, Stephen F.; Olszyna, Kenneth J.; Meagher, James F. Present address: Aeronomy Laboratory, NOAA, 325 Broadway, Boulder CO 80303, USA.)

The evolution of photochemical smog in a plant plume was investigated with the aid of an instrumented helicopter. Air samples were taken in the plume of the Cumberland Power Plant, located in central Tennessee, during the afternoon of 16 July 1995 as part of the Southern Oxidants Study - Nashville Middle Tennessee Ozone Study. Twelve cross-wind air sampling traverses were made at six distance groups from 35 to 116 km from the source. During the sampling period the winds were from the west-northwest and the plume drifted towards the city of Nashville TN. Ten of the traverses were made upwind of the city, where the power plant plume was isolated, and two traverses downwind of the city when the plumes were possibly mixed. The results revealed that even six hours after the release, excess ozone production was limited to the edges of the plume. Only when the plume was sufficiently dispersed, but still upwind of Nashville, was excess ozone (up to 109 ppbv, 50-60 ppbv above background levels) produced in the center of the plume. The concentrations image of the plume and a Lagrangian particle model suggests that portions of the power plant plume mixed with the urban plume. The mixed urban power plant plume began to regenerate O 3 that peaked at 120 ppbv at a short distance (15-25 km) downwind of Nashville. Ozone productivity (the ratio of excess O 3 to NO y and NO z) in the isolated plume was significantly lower compared with that found in the city plume. The production of nitrate, a chain termination product, was significantly higher in the power plant plume compared to the mixed plume, indicating shorter chain length of the photochemical smog chain reaction mechanism.

The evolution of photochemical smog in a power plant plume

International Nuclear Information System (INIS)

Luria, M.; The Hebrew University, Jerusalem; Valente, R.J.; Tanner, R.L.; Imhoff, R.E.; Mueller, S.F.; Olszyna, K.J.; Meagher, J.F.; Gillani, N.V.; University of Alabama, Huntsville, AL

1999-01-01

The evolution of photochemical smog in a plant plume was investigated with the aid of an instrumented helicopter. Air samples were taken in the plume of the Cumberland Power Plant, located in central Tennessee, during the afternoon of 16 July 1995 as part of the Southern Oxidants Study - Nashville Middle Tennessee Ozone Study. Twelve cross-wind air sampling traverses were made at six distance groups from 35 to 116 km from the source. During the sampling period the winds were from the west-northwest and the plume drifted towards the city of Nashville TN. Ten of the traverses were made upwind of the city, where the power plant plume was isolated, and two traverses downwind of the city when the plumes were possibly mixed. The results revealed that even six hours after the release, excess ozone production was limited to the edges of the plume. Only when the plume was sufficiently dispersed, but still upwind of Nashville, was excess ozone (up to 109 ppbv, 50-60 ppbv above background levels) produced in the center of the plume. The concentrations image of the plume and a Lagrangian particle model suggests that portions of the power plant plume mixed with the urban plume. The mixed urban power plant plume began to regenerate O 3 that peaked at 120 ppbv at a short distance (15-25 km) downwind of Nashville. Ozone productivity (the ratio of excess O 3 to NO y and NO z ) in the isolated plume was significantly lower compared with that found in the city plume. The production of nitrate, a chain termination product, was significantly higher in the power plant plume compared to the mixed plume, indicating shorter chain length of the photochemical smog chain reaction mechanism. (author)

Photophysics of conjugated polymers: interplay between Förster energy migration and defect concentration in shaping a photochemical funnel in PPV.

Science.gov (United States)

Saini, Sangeeta; Bagchi, Biman

2010-07-21

Recent single molecule experiments have suggested the existence of a photochemical funnel in the photophysics of conjugated polymers, like poly[2-methoxy-5-(2'-ethylhexyl)oxy-1,4-phenylenevinylene] (MEH-PPV). The funnel is believed to be a consequence of the presence of conformational or chemical defects along the polymer chain and efficient non-radiative energy transfer among different chromophore segments. Here we address the effect of the excitation energy dynamics on the photophysics of PPV. The PPV chain is modeled as a polymer with the length distribution of chromophores given either by a Gaussian or by a Poisson distribution. We observe that the Poisson distribution of the segment lengths explains the photophysics of PPV better than the Gaussian distribution. A recently proposed version of an extended 'particle-in-a-box' model is used to calculate the exciton energies and the transition dipole moments of the chromophores, and a master equation to describe the excitation energy transfer among different chromophores. The rate of energy transfer is assumed to be given here, as a first approximation, by the well-known Förster expression. The observed excitation population dynamics confirms the photochemical funneling of excitation energy from shorter to longer chromophores of the polymer chain. The time scale of spectral shift and energy transfer for our model polymer, with realistic values of optical parameters, is in the range of 200-300 ps. We find that the excitation energy may not always migrate towards the longest chromophore segments in the polymer chain as the efficiency of energy transfer between chromophores depends on the separation distance between the two and their relative orientation.

Long-term reduction in infrared autofluorescence caused by infrared light below the maximum permissible exposure.

Science.gov (United States)

Masella, Benjamin D; Williams, David R; Fischer, William S; Rossi, Ethan A; Hunter, Jennifer J

2014-05-20

Many retinal imaging instruments use infrared wavelengths to reduce the risk of light damage. However, we have discovered that exposure to infrared illumination causes a long-lasting reduction in infrared autofluorescence (IRAF). We have characterized the dependence of this effect on radiant exposure and investigated its origin. A scanning laser ophthalmoscope was used to obtain IRAF images from two macaques before and after exposure to 790-nm light (15-450 J/cm(2)). Exposures were performed with either raster-scanning or uniform illumination. Infrared autofluorescence images also were obtained in two humans exposed to 790-nm light in a separate study. Humans were assessed with direct ophthalmoscopy, Goldmann visual fields, multifocal ERG, and photopic microperimetry to determine whether these measures revealed any effects in the exposed locations. A significant decrease in IRAF after exposure to infrared light was seen in both monkeys and humans. In monkeys, the magnitude of this reduction increased with retinal radiant exposure. Partial recovery was seen at 1 month, with full recovery within 21 months. Consistent with a photochemical origin, IRAF decreases caused by either raster-scanning or uniform illumination were not significantly different. We were unable to detect any effect of the light exposure with any measure other than IRAF imaging. We cannot exclude the possibility that changes could be detected with more sensitive tests or longer follow-up. This long-lasting effect of infrared illumination in both humans and monkeys occurs at exposure levels four to five times below current safety limits. The photochemical basis for this phenomenon remains unknown. Copyright 2014 The Association for Research in Vision and Ophthalmology, Inc.

Potential biosignatures in super-Earth atmospheres II. Photochemical responses.

Science.gov (United States)

Grenfell, J L; Gebauer, S; Godolt, M; Palczynski, K; Rauer, H; Stock, J; von Paris, P; Lehmann, R; Selsis, F

2013-05-01

Spectral characterization of super-Earth atmospheres for planets orbiting in the habitable zone of M dwarf stars is a key focus in exoplanet science. A central challenge is to understand and predict the expected spectral signals of atmospheric biosignatures (species associated with life). Our work applies a global-mean radiative-convective-photochemical column model assuming a planet with an Earth-like biomass and planetary development. We investigated planets with gravities of 1g and 3g and a surface pressure of 1 bar around central stars with spectral classes from M0 to M7. The spectral signals of the calculated planetary scenarios have been presented by in an earlier work by Rauer and colleagues. The main motivation of the present work is to perform a deeper analysis of the chemical processes in the planetary atmospheres. We apply a diagnostic tool, the Pathway Analysis Program, to shed light on the photochemical pathways that form and destroy biosignature species. Ozone is a potential biosignature for complex life. An important result of our analysis is a shift in the ozone photochemistry from mainly Chapman production (which dominates in Earth's stratosphere) to smog-dominated ozone production for planets in the habitable zone of cooler (M5-M7)-class dwarf stars. This result is associated with a lower energy flux in the UVB wavelength range from the central star, hence slower planetary atmospheric photolysis of molecular oxygen, which slows the Chapman ozone production. This is important for future atmospheric characterization missions because it provides an indication of different chemical environments that can lead to very different responses of ozone, for example, cosmic rays. Nitrous oxide, a biosignature for simple bacterial life, is favored for low stratospheric UV conditions, that is, on planets orbiting cooler stars. Transport of this species from its surface source to the stratosphere where it is destroyed can also be a key process. Comparing 1g with

Photoreduction of chromium(VI) in the presence of algae, Chlorella vulgaris

Energy Technology Data Exchange (ETDEWEB)

Deng Lin [School of Resources and Environmental Science, Wuhan University, Wuhan 430072 (China); Wang Hongli [School of Resources and Environmental Science, Wuhan University, Wuhan 430072 (China); Deng Nansheng [School of Resources and Environmental Science, Wuhan University, Wuhan 430072 (China)]. E-mail: nsdengwhu@163.com

2006-11-16

In this thesis, the photochemical reduction of hexavalent chromium Cr(VI) in the presence of algae, Chlorella vulgaris, was investigated under the irradiation of metal halide lamps ({lambda}=365nm, 250W). The affecting factors of photochemical reduction were studied in detail, such as exposure time, initial Cr(VI) concentration, initial algae concentration and pH. The rate of Cr(VI) photochemical reduction increased with algae concentration increasing, exposure time increasing, initial Cr(VI) concentration decreasing and the decrease of pH. When pH increased to 6, the rate of Cr(VI) photochemical reduction nearly vanished. When initial Cr(VI) concentration ranged from 0.4 to 1.0mgL{sup -1} and initial algae concentration ranged from ABS{sub algae} (the absorbency of algae)=0.025 to ABS{sub algae}=0.180, According to the results of kinetic analyses, the kinetic equation of Cr(VI) photochemical reduction in aqueous solution with algae under 250W metal halide lamps was V{sub 0}=kC{sub 0}{sup 0.1718}A{sub algae}{sup 0.5235} (C{sub 0} was initial concentration of Cr(VI); A{sub algae} was initial concentration of algae) under the condition of pH 4.

Nanoparticle-based photodynamic therapy on non-melanoma skin cancer

Science.gov (United States)

Fanjul-Vélez, F.; Arce-Diego, J. L.

2018-02-01

There are several advantages of Photodynamic Therapy (PDT) for nonmelanoma skin cancer treatment compared to conventional treatment techniques such as surgery, radiotherapy or chemotherapy. Among these advantages its noninvasive nature, the use of non ionizing radiation and its high selectivity can be mentioned. Despite all these advantages, the therapeutic efficiency of the current clinical protocol is not complete in all the patients and depends on the type of pathology. An adequate dosimetry is needed in order to personalize the protocol. There are strategies that try to overcome the current PDT shortcomings, such as the improvement of the photosensitizer accumulation in the target tissue, optical radiation distribution optimization or photochemical reactions maximization. These strategies can be further complemented by the use of nanostructures with conventional PDT. Customized dosimetry for nanoparticle-based PDT requires models in order to adjust parameters of different nature to get an optimal tumor removal. In this work, a predictive model of nanoparticle-based PDT is proposed and analyzed. Dosimetry in nanoparticle-based PDT is going to be influenced by photosensitizer-nanoparticle distribution in the malignant tissue, its influence in the optical radiation distribution and the subsequent photochemical reactions. Nanoparticles are considered as photosensitizer carriers on several types of non-melanoma skin cancer. Shielding effects are taken into account. The results allow to compare the estimated treatment outcome with and without nanoparticles.

Thermal and Mechanical Non-Equilibrium Effects on Turbulent Flows: Fundamental Studies of Energy Exchanges Through Direct Numerical Simulations, Molecular Simulations and Experiments

Science.gov (United States)

2016-02-26

photochemical TNE generation, and chemistry of non- equilibrium phenomena. We have investigated a new concept to generate turbulence using photo-initiated...AFRL-AFOSR-VA-TR-2016-0104 Thermal and mechanical non- equilibrium effects on turbulent flows:fundamental studies of energy exchanges through direct...Performance 3. DATES COVERED (From - To) 15-09-2012 to 14-11-2015 4. TITLE AND SUBTITLE Thermal and mechanical non- equilibrium effects on turbulent

Photochemically enhanced microbial degradation of environmental pollutants

International Nuclear Information System (INIS)

Katayama, A.; Matsumura, F.

1991-01-01

Biodegradation of persistent halogenated organic pollutants is of great interest from the viewpoint of its potential use to cleanup the contaminated sites and industrial waste streams on-site (i.e., in situ remediation). Recent studies have shown that lignin-degrading white rot fungi possess capabilities to degrade a variety of highly recalcitrant and toxic compounds. On the other hand, photodegradation by sunlight or ultraviolet light (UV) has not been considered as a potential technology to detoxify the contaminated sites, in spite of the availability of extensive research data, because of its limited reaching ability to subsurface locations. In view of the urgent needs for the development of technology to deal with mounting problems of toxic wastes, the authors have decided to experiment with the ideas of combining photochemical and microbial technologies. The main obstacle in developing such simultaneous combination systems has been the susceptibilities of microorganisms in general to UV irradiation. To overcome this problem, the authors have developed an ultraviolet- and fungicide-resistant strain of white rot fungus and now report their results

Decomposition of oxalate precipitates by photochemical reaction

International Nuclear Information System (INIS)

Yoo, J.H.; Kim, E.H.

1998-01-01

A photo-radiation method was applied to decompose oxalate precipitates so that it can be dissolved into dilute nitric acid. This work has been studied as a part of partitioning of minor actinides. Minor actinides can be recovered from high-level wastes as oxalate precipitates, but they tend to be coprecipitated together with lanthanide oxalates. This requires another partitioning step for mutual separation of actinide and lanthanide groups. In this study, therefore, the photochemical decomposition mechanism of oxalates in the presence of nitric acid was elucidated by experimental work. The decomposition of oxalates was proved to be dominated by the reaction with hydroxyl radical generated from the nitric acid, rather than with nitrite ion also formed from nitrate ion. The decomposition rate of neodymium oxalate, which was chosen as a stand-in compound representing minor actinide and lanthanide oxalates, was found to be 0.003 M/hr at the conditions of 0.5 M HNO 3 and room temperature when a mercury lamp was used as a light source. (author)

Decomposition of oxalate precipitates by photochemical reaction

International Nuclear Information System (INIS)

Jae-Hyung Yoo; Eung-Ho Kim

1999-01-01

A photo-radiation method was applied to decompose oxalate precipitates so that it can be dissolved into dilute nitric acid. This work has been studied as a part of partitioning of minor actinides. Minor actinides can be recovered from high-level wastes as oxalate precipitates, but they tend to be coprecipitated together with lanthanide oxalates. This requires another partitioning step for mutual separation of actinide and lanthanide groups. In this study, therefore, some experimental work of photochemical decomposition of oxalate was carried out to prove its feasibility as a step of partitioning process. The decomposition of oxalic acid in the presence of nitric acid was performed in advance in order to understand the mechanistic behaviour of oxalate destruction, and then the decomposition of neodymium oxalate, which was chosen as a stand-in compound representing minor actinide and lanthanide oxalates, was examined. The decomposition rate of neodymium oxalate was found as 0.003 mole/hr at the conditions of 0.5 M HNO 3 and room temperature when a mercury lamp was used as a light source. (author)

Photochemical studies on aromatic γ,δ-epoxy ketones: efficient synthesis of benzocyclobutanones and indanones.

Science.gov (United States)

Shao, Yutian; Yang, Chao; Gui, Weijun; Liu, Yang; Xia, Wujiong

2012-04-11

Irradiation of terminal aromatic γ,δ-epoxy ketones with a 450 W UV lamp led to Norrish type II cyclization/semi-pinacol rearrangement cascade reaction which formed the benzocyclobutanones containing a full-carbon quaternary center, whereas irradiation of substituted aromatic γ,δ-epoxy ketones led to the indanones through a photochemical epoxy rearrangement and 1,5-biradicals cyclization tandem reaction. This journal is © The Royal Society of Chemistry 2012

Molecular orbital study of iron pentacarbonyl and its photochemical fragments Fe(CO) sub(n)

International Nuclear Information System (INIS)

Guenzburger, D.J.R.; Saitovitch, E.M.B.; De Paoli, M.-A.; Manella, H.

1982-01-01

Self-consistent Molecular Orbital calculations were performed for Fe(CO) 5 and its photofragments Fe(CO) sub(n), 1 5 , photoelectron and optical spectra are analysed, and photochemical behaviour is discussed. The Moessbauer isomer shifts and quadrupole splittings are investigated. In the case of Fe(CO) 5 and Fe(CO) 4 , the values derived for these hyperfine interactions are compared to experimental measurements reported in a polyethylene matrix. (Author) [pt

Large-scale photochemical reactions of nanocrystalline suspensions: a promising green chemistry method.

Science.gov (United States)

Veerman, Marcel; Resendiz, Marino J E; Garcia-Garibay, Miguel A

2006-06-08

Photochemical reactions in the solid state can be scaled up from a few milligrams to 10 grams by using colloidal suspensions of a photoactive molecular crystal prepared by the solvent shift method. Pure products are recovered by filtration, and the use of H(2)O as a suspension medium makes this method a very attractive one from a green chemistry perspective. Using the photodecarbonylation of dicumyl ketone (DCK) as a test system, we show that reaction efficiencies in colloidal suspensions rival those observed in solution. [reaction: see text

Catalysis of photochemical hydrogen production by metal dithiolenes in aqueous organic solvents

International Nuclear Information System (INIS)

Zeug, N.

1983-01-01

Photolysis(lambda>=248 nm) of zinc ditetrabutylammonium-bis(cis-1,2-dicyano-1,2-dithiol-ethylene) in mixtures of water with 2,5-dihydrofuran (2,5-DHF) or tetrahydroguran (THF) gives rise to catalytic production of hydrogen. The mechanisms of this process were studied here. The photochemical and thermal properties of zinc dithiolene were studied along with the analogous cadmium and mercury complexes. It could be shown that zinc dithiolene is in fact only the precursor to the actual catalyst which has been identified elsewhere as zinc sulphide. (orig./GG) [de

UV-photochemical vapor generation of selenium for atomic absorption spectrometry: Optimization and 75Se radiotracer efficiency study

Czech Academy of Sciences Publication Activity Database

Rybínová, M.; Musil, Stanislav; Červený, J.; Vobecký, Miloslav; Rychlovský, P.

2016-01-01

Roč. 123, SEP (2016), s. 134-142 ISSN 0584-8547 R&D Projects: GA ČR GA14-23532S Institutional support: RVO:68081715 Keywords : UV-photochemical vapor generation * Selenium * 75Se radiotracer Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 3.241, year: 2016

Development of advanced technologies for photochemical tritium recovery. Bi-quarterly program report, 1 April-30 September 1980

International Nuclear Information System (INIS)

Herman, I.P.; Marling, J.B.

1980-01-01

The laboratory facility for photochemical tritium separation research has been completed. Methods for synthesizing the mono-tritiated halogenated methanes have been developed. Notably, CTF 3 has been synthesized and spectrally analyzed. The CTF 3 vibrational frequencies are found to be in quite good agreement with earlier calculations

Non-uniform crosstalk reduction for dynamic scenes

NARCIS (Netherlands)

Smit, F.A.; Liere, van R.; Fröhlich, B.

2007-01-01

Stereo displays suffer from crosstalk, an effect that reduces or even inhibits the viewer's ability to correctly perceive depth. Previous work on software crosstalk reduction focussed on the preprocessing of static scenes which are viewed from a fixed viewpoint. However, in virtual environments

Risk-based enteric pathogen reduction targets for non-potable and direct potable use of roof runoff, stormwater, and greywater

Science.gov (United States)

This paper presents risk-based enteric pathogen log reduction targets for non-potable and potable uses of a variety of alternative source waters (i.e., locally-collected greywater, roof runoff, and stormwater). A probabilistic Quantitative Microbial Risk Assessment (QMRA) was use...

Photoreduction of CO{sub 2} using metal complexes

Energy Technology Data Exchange (ETDEWEB)

Fujita, Etsuko [Brookhaven National Laboratory, Upton, NY (United States)

1996-09-01

Photochemical reduction of CO{sub 2} to fuels and chemicals is a challenging task. Work in the area of photochemical CO{sub 2} reduction from the early 1980s to the present is summarized to provide a perspective on the achievements and problems involved in the process.

Photoreduction of CO{sub 2} using metal complexes

Energy Technology Data Exchange (ETDEWEB)

Fujita, Etsuko

1996-04-01

Photochemical reduction of CO{sub 2} to fuels and chemicals is a challenging task. Work in the area of photochemical CO{sub 2} reduction from the early 1980s to the present is summarized to provide a perspective on the achievements and problems involved in the process.

Quantum Mechanics/Molecular Mechanics Free Energy Maps and Nonadiabatic Simulations for a Photochemical Reaction in DNA: Cyclobutane Thymine Dimer.

Science.gov (United States)

Mendieta-Moreno, Jesús I; Trabada, Daniel G; Mendieta, Jesús; Lewis, James P; Gómez-Puertas, Paulino; Ortega, José

2016-11-03

The absorption of ultraviolet radiation by DNA may result in harmful genetic lesions that affect DNA replication and transcription, ultimately causing mutations, cancer, and/or cell death. We analyze the most abundant photochemical reaction in DNA, the cyclobutane thymine dimer, using hybrid quantum mechanics/molecular mechanics (QM/MM) techniques and QM/MM nonadiabatic molecular dynamics. We find that, due to its double helix structure, DNA presents a free energy barrier between nonreactive and reactive conformations leading to the photolesion. Moreover, our nonadiabatic simulations show that most of the photoexcited reactive conformations return to standard B-DNA conformations after an ultrafast nonradiative decay to the ground state. This work highlights the importance of dynamical effects (free energy, excited-state dynamics) for the study of photochemical reactions in biological systems.

Investigations of oxygen reduction reactions in non-aqueous electrolytes and the lithium-air battery

Science.gov (United States)

O'Laoire, Cormac Micheal

Unlocking the true energy capabilities of the lithium metal negative electrode in a lithium battery has until now been limited by the low capacity intercalation and conversion reactions at the positive electrodes. This is overcome by removing these electrodes and allowing lithium to react directly with oxygen in the atmosphere forming the Li-air battery. Chapter 2 discusses the intimate role of electrolyte, in particular the role of ion conducting salts on the mechanism and kinetics of oxygen reduction in non-aqueous electrolytes designed for such applications and in determining the reversibility of the electrode reactions. Such fundamental understanding of this high energy density battery is crucial to harnessing its full energy potential. The kinetics and mechanisms of O2 reduction in solutions of hexafluorophosphate salts of the general formula X+ PF6-, where, X = tetra butyl ammonium (TBA), K, Na and Li, in acetonitrile have been studied on glassy carbon electrodes using cyclic voltammetry (CV) and rotating disk electrode (RDE) techniques. Our results show that cation choice strongly influences the reduction mechanism of O2. Electrochemical data supports the view that alkali metal oxides formed via electrochemical and chemical reactions passivate the electrode surface inhibiting the kinetics and reversibility of the processes. The O2 reduction mechanisms in the presence of the different cations have been supplemented by kinetic parameters determined from detailed analyses of the CV and RDE data. The organic solvent present in the Li+-conducting electrolyte has a major role on the reversibility of each of the O2 reduction products as found from the work discussed in the next chapter. A fundamental study of the influence of solvents on the oxygen reduction reaction (ORR) in a variety of non-aqueous electrolytes was conducted in chapter 4. In this work special attention was paid to elucidate the mechanism of the oxygen electrode processes in the rechargeable Li

Photochemical induced growth and aggregation of metal nanoparticles in diode-array spectrophotometer via excited dimethyl-sulfoxide.

Science.gov (United States)

Zidki, Tomer; Cohen, Haim; Meyerstein, Dan

2010-10-21

Ag(0) and Au(0) nanoparticles suspended in dilute aqueous solutions containing (CH(3))(2)SO are photochemically unstable. The light source of a diode-array spectrophotometer induces, within less than a minute, particle growth and aggregation. The results indicate that this process is triggered by UV light absorption by the (CH(3))(2)SO.

Chemical composition and photochemical reactivity of exhaust from aircraft turbine engines

Directory of Open Access Journals (Sweden)

C. W. Spicer

1994-08-01

Full Text Available Assessment of the environmental impact of aircraft emissions is required by planners and policy makers. Seveal areas of concern are: 1. exposure of airport workers and urban residents to toxic chemicals emitted when the engines operate at low power (idle and taxi on the ground; 2. contributions to urban photochemical air pollution of aircraft volatile organic and nitrogen oxides emissions from operations around airports; and 3. emissions of nitrogen oxides and particles during high-altitude operation. The environmental impact of chemicals emitted from jet aircraft turbine engines has not been firmly established due to lack of data regarding emission rates and identities of the compounds emitted. This paper describes an experimental study of two different aircraft turbine engines designed to determine detailed organic emissions, as well as emissions of inorganic gases. Emissions were measured at several engine power settings. Measurements were made of detailed organic composition from C1 through C17, CO, CO2, NO, NOx, and polycyclic aromatic hydrocarbons. Measurements were made using a multi-port sampling pro be positioned directly behind the engine in the exhaust exit plane. The emission measurements have been used to determine the organic distribution by carbon number and the distribution by compound class at each engine power level. The sum of the organic species was compared with an independent measurement of total organic carbon to assess the carbon mass balance. A portion of the exhaust was captured and irradiated in outdoor smog chambers to assess the photochemical reactivity of the emissions with respect to ozone formation. The reactivity of emissions from the two engines was apportioned by chemical compound class.

Solitons, τ-functions and hamiltonian reduction for non-Abelian conformal affine Toda theories

Science.gov (United States)

Ferreira, L. A.; Miramontes, J. Luis; Guillén, Joaquín Sánchez

1995-02-01

We consider the Hamiltonian reduction of the "two-loop" Wess-Zumino-Novikov-Witten model (WZNW) based on an untwisted affine Kac-Moody algebra G. The resulting reduced models, called Generalized Non-Abelian Conformal Affine Toda (G-CAT), are conformally invariant and a wide class of them possesses soliton solutions; these models constitute non-Abelian generalizations of the conformal affine Toda models. Their general solution is constructed by the Leznov-Saveliev method. Moreover, the dressing transformations leading to the solutions in the orbit of the vacuum are considered in detail, as well as the τ-functions, which are defined for any integrable highest weight representation of G, irrespectively of its particular realization. When the conformal symmetry is spontaneously broken, the G-CAT model becomes a generalized affine Toda model, whose soliton solutions are constructed. Their masses are obtained exploring the spontaneous breakdown of the conformal symmetry, and their relation to the fundamental particle masses is discussed. We also introduce what we call the two-loop Virasoro algebra, describing extended symmetries of the two-loop WZNW models.

Ferric ion mediated photochemical decomposition of perfluorooctanoic acid (PFOA) by 254 nm UV light

International Nuclear Information System (INIS)

Wang Yuan; Zhang Pengyi; Pan Gang; Chen Hao

2008-01-01

The great enhancement of ferric ion on the photochemical decomposition of environmentally persistent perfluorooctanoic acid (PFOA) under 254 nm UV light was reported. In the presence of 10 μM ferric ion, 47.3% of initial PFOA (48 μM) was decomposed and the defluorination ratio reached 15.4% within 4 h reaction time. While the degradation and defluorination ratio greatly increased to 80.2% and 47.8%, respectively, when ferric ion concentration increased to 80 μM, and the corresponding half-life was shortened to 103 min. Though the decomposition rate was significantly lowered under nitrogen atmosphere, PFOA was efficiently decomposed too. Other metal ions like Cu 2+ and Zn 2+ also slightly improved the photochemical decomposition of PFOA under irradiation of 254 nm UV light. Besides fluoride ion, other intermediates during PFOA decomposition including formic acid and five shorter-chain perfluorinated carboxylic acids (PFCAs) with C7, C6, C5, C4 and C3, respectively, were identified and quantified by IC or LC/MS. The mixture of PFOA and ferric ion had strong absorption around 280 nm. It is proposed that PFOA coordinates with ferric ion to form a complex, and its excitation by 254 nm UV light leads to the decomposition of PFOA in a stepwise way

Investigating the pathway for the photochemical formation of VOCs in presence of an organic monolayer at the air/water interface.

Science.gov (United States)

Tinel, Liselotte; Rossignol, Stéphanie; Ciuraru, Raluca; George, Christian

2015-04-01

Investigating the pathway for the photochemical formation of VOCs in presence of an organic monolayer at the air/water interface. Liselotte Tinel, Stéphanie Rossignol, Raluca Ciuraru and Christian George Université de Lyon, Université Lyon 1, CNRS, UMR5256, IRCELYON, Institut de recherches sur la catalyse et l'environnement de Lyon, Villeurbanne, F-69626, France Recently the surface microlayer (SML) has received growing attention for its role in the deposition and emission of trace gases. This SML is presumably a highly efficient environment for photochemical reactions thanks to its physical and chemical properties, showing enrichment in chromophores [1]. Still, little is known about the possible photochemical processes that could influence the emission and deposition of volatile organic compounds (VOCs) in the SML. A recent study underlines the particularity of the presence of an organic microlayer, showing enhanced formation of peptide bonds at the air-water interface, although this reaction is thermodynamically disfavoured in bulk water [2]. Also, emissions of small gas phase carbonyl compounds formed photochemically by dissolved organic matter have been measured above natural water and glyoxal, for example, measured above the open ocean is thought to be photochemically produced [3, 4]. This study presents the results of a set of laboratory studies set up in order to better understand the role of the SML in the photochemical production of VOCs. Recently, our group has shown the formation of VOCs by light driven reactions in a small quartz reactor (14mL) containing aqueous solutions of humic acids (HA) in the presence of an organic (artificial or natural) microlayer [5]. The main VOCs produced were oxidized species, such as aldehydes, ketones and alcohols, as classically can be expected by the oxidation of the organics present at the interface initiated by triplet excited chromophores present in the HA. But also alkenes, dienes, including isoprene and

Blood pressure reduction in patients with irreversible pulpitis teeth treated by non-surgical root canal treatment

Directory of Open Access Journals (Sweden)

James I-Sheng Huang

2017-12-01

Full Text Available Background/purpose: The hypotension in patients during non-surgical root canal treatment (NSRCT has not yet investigated. This study aimed to assess the mean systolic blood pressure (MSBP, mean diastolic blood pressure (MDBP, and mean arterial blood pressure (MABP reduction percentages in patients with irreversible pulpitis teeth treated by NSRCT. Materials and methods: We prospectively recruited 111 patients with a total of 138 irreversible pulpitis teeth. All patients underwent two NSRCT sessions. The first NSRCT session involved mainly the removal of vital pulp tissue with the direct stimulation of the dental branches of the trigeminal nerve, and the second NSRCT session included the root canal debridement and enlargement with minimal disturbance to the dental nerves. The blood pressure of each patient was recorded before and during both NSRCT sessions. Results: There were significantly higher reduction percentages of MSBP, MDBP, and MABP in the first NSRCT session than in the second NSRCT session for all treated patients (all the P-values < 0.001. If the patients were divided into 2 or more groups according to the clinical variables including the patients' gender, age, tooth type, and anesthesia type, we also found significantly higher reduction percentages of MSBP, MDBP, and MABP in the first NSRCT session than in the second NSRCT session for all treated patients except for patients below 40 years of age and for patients with lower anterior teeth treated (all the P-values < 0.05. Conclusion: The decrease in blood pressure in patients receiving vital pulpal extirpation is a relatively common phenomenon. Keywords: hypotension, irreversible pulpitis teeth, non-surgical root canal treatment, blood pressure, parasympathetic effect, vital pulpal extirpation

Graphene layer encapsulated metal nanoparticles as a new type of non-precious metal catalysts for oxygen reduction

DEFF Research Database (Denmark)

Hu, Yang; Zhong, Lijie; Jensen, Jens Oluf

2016-01-01

Cheap and efficient non-precious metal catalysts for oxygen reduction have been a focus of research in the field of low-temperature fuel cells. This review is devoted to a brief summary of the recent work on a new type of catalysts, i.e., the graphene layer encapsulated metal nanoparticles....... The discussion is focused on the synthesis, structure, mechanism, performance, and further research....

Effects of Photo-chemically Activated Alkylating Agents of the FR900482 Family on Chromatin

OpenAIRE

Subramanian, Vidya; Ducept, Pascal; Williams, Robert M.; Luger, Karolin

2007-01-01

Bioreductive alkylating agents are an important class of clinical antitumor antibiotics that cross-link and mono-alkylate DNA. Here we use a synthetic photochemically activated derivative of FR400482 to investigate the molecular mechanism of this class of drugs in a biologically relevant context. We find that the organization of DNA into nucleosomes effectively protects it against drug-mediated cross-linking, while permitting mono-alkylation. This modification has the potential to form covale...

Effect of fluid velocity, temperature, and concentration of non-ionic surfactants on drag reduction

International Nuclear Information System (INIS)

Cho, Sung-Hwan; Tae, Choon-Seob; Zaheeruddin, M.

2007-01-01

The drag reduction (DR) and heat transfer efficiency reduction (ER) of non-ionic surfactant as a function of fluid velocity, temperature, and surfactant concentration were investigated. Several types of new surfactants, which contain amine-oxide and betaine, were developed. An experimental apparatus consisting of two temperature controlled water storage tanks, pumps, test specimen pipe and the piping network, two flow meters, two pressure gauges, a heat exchanger, and data logging system was built. From the experimental results, it was concluded that existing alkyl ammonium surfactant (CTAC; cethyl trimethyl ammonium chloride) had DR of 0.6-0.8 at 1000-2000 ppm concentration with fluid temperature ranging between 50 and 60 o C. However, the DR was very low when the fluid temperature was 70-80 o C. The new amine oxide and betaine surfactant (SAOB; stearyl amine oxide + betaine) had lower DR at fluid temperatures ranging between 50 and 60 o C compared with CTAC. However, with fluid temperature ranging between 70 and 80 o C the DR was 0.6-0.8 when the concentration level was between 1000 and 2000 ppm

C60H- an intermediate in the photochemical reduction of C60 fullerene with triethylamine

International Nuclear Information System (INIS)

Stasko, A.; Brezova, V.; Neudeck, A.; Bartl, A.; Dunsch, L.

1999-01-01

The systematic investigations on the photo reduction of C 60 fullerene and its derivatives using triethylamine and TiO 2 donors, and also other techniques, verified the formation of C 60 .- . Formation of the mono-anion a narrow EPR line (pp A = 0.1 mT) was observed. During a continuous irradiation line A is replaced with line B having g B - 2.0006 and pp B = 0.04 mT which also vanished under prolonged irradiation. But lines A and B repeated after stopping irradiation. This unusual behaviour was re-investigated in analogous EPR-NIR experiments using now a rapid NIR spectrometer. The band at 996 nm was assigned to C 60 H - . The mechanism of C 60 H - formation is discussed

Reduction of symplectic principal R-bundles

International Nuclear Information System (INIS)

Lacirasella, Ignazio; Marrero, Juan Carlos; Padrón, Edith

2012-01-01

We describe a reduction process for symplectic principal R-bundles in the presence of a momentum map. These types of structures play an important role in the geometric formulation of non-autonomous Hamiltonian systems. We apply this procedure to the standard symplectic principal R-bundle associated with a fibration π:M→R. Moreover, we show a reduction process for non-autonomous Hamiltonian systems on symplectic principal R-bundles. We apply these reduction processes to several examples. (paper)

Diurnal changes in the xanthophyll cycle pigments of freshwater algae correlate with the environmental hydrogen peroxide concentration rather than non-photochemical quenching

Science.gov (United States)

Roach, Thomas; Miller, Ramona; Aigner, Siegfried; Kranner, Ilse

2015-01-01

Background and Aims In photosynthetic organisms exposure to high light induces the production of reactive oxygen species (ROS), such as hydrogen peroxide (H2O2), which in part is prevented by non-photochemical quenching (NPQ). As one of the most stable and longest-lived ROS, H2O2 is involved in key signalling pathways in development and stress responses, although in excess it can induce damage. A ubiquitous response to high light is the induction of the xanthophyll cycle, but its role in algae is unclear as it is not always associated with NPQ induction. The aim of this study was to reveal how diurnal changes in the level of H2O2 are regulated in a freshwater algal community. Methods A natural freshwater community of algae in a temporary rainwater pool was studied, comprising photosynthetic Euglena species, benthic Navicula diatoms, Chlamydomonas and Chlorella species. Diurnal measurements were made of photosynthetic performance, concentrations of photosynthetic pigments and H2O2. The frequently studied model organisms Chlamydomonas and Chlorella species were isolated to study photosynthesis-related H2O2 responses to high light. Key Results NPQ was shown to prevent H2O2 release in Chlamydomonas and Chlorella species under high light; in addition, dissolved organic carbon excited by UV-B radiation was probably responsible for a part of the H2O2 produced in the water column. Concentrations of H2O2 peaked at 2 µm at midday and algae rapidly scavenged H2O2 rather than releasing it. A vertical H2O2 gradient was observed that was lowest next to diatom-rich benthic algal mats. The diurnal changes in photosynthetic pigments included the violaxanthin and diadinoxanthin cycles; the former was induced prior to the latter, but neither was strictly correlated with NPQ. Conclusions The diurnal cycling of H2O2 was apparently modulated by the organisms in this freshwater algal community. Although the community showed flexibility in its levels of NPQ, the diurnal changes in

Photochemical and microbial alterations of DOM spectroscopic properties in the estuarine system Ria de Aveiro.

Science.gov (United States)

Santos, L; Santos, E B H; Dias, J M; Cunha, A; Almeida, A

2014-08-01

The influence of photochemical transformations of chromophoric dissolved organic matter (CDOM) on microbial communities was evaluated in the estuarine system Ria de Aveiro. Two sites, representative of the marine and brackish water zones of the estuary, were surveyed regularly in order to determine seasonal and vertical profiles of variation of CDOM properties. Optical parameters of CDOM indicative of aromaticity and molecular weight were used to establish CDOM sources, and microbial abundance and activity was characterized. Additionally, microcosm experiments were performed in order to simulate photochemical reactions of CDOM and to evaluate microbial responses to light-induced changes in CDOM composition. The CDOM of the two estuarine zones showed different spectral characteristics, with significantly higher values of the specific ultra-violet absorbance at 254 nm (SUVA254) (5.5 times) and of the absorption coefficient at 350 nm (a350) (12 times) and lower SR (S275-295/S350-400) ratio at brackish water compared with the marine zone, reflecting the different amounts and prevailing sources of organic matter, as well as distinct riverine and oceanic influences. At the marine zone, the abundance of bacteria and the activity of Leu-AMPase correlated with a350 and a254, suggesting a microbial contribution to the HMW CDOM pool. The irradiation of DOM resulted in a decrease of the values of a254 and a350 and an increase of the slope S275-295 and of the ratios E2 : E3 (a250/a365) and SR, which in turn increase its bioavailability. However, the extent of photoinduced transformations and microbial responses was dependent on the initial optical characteristics of CDOM. In Ria de Aveiro both photochemical and microbial processes yielded optical changes in CDOM and the overall results of these combined processes determine the fate of CDOM in the estuarine system and have an influence on local productivity and in adjacent coastal areas.

Non linear optical investigations of silver nanoparticles synthesised by curcumin reduction

Science.gov (United States)

Dhanya, N. P.

2017-11-01

Metal nanoparticles have considerable applications in assorted fields like medicine, biology, photonics, metallurgy etc. Optical applications of Silver nanoparticles are of significant interest among researchers nowadays. In this paper, we report a single step chemical reduction of silver nanoparticles with Curcumin both as a reducing and stabilising agent at room temperature. Structural, plasmonic and non linear optical properties of the prepared nanoparticles are explored using Scanning Electron Microscope, Transmission Electron Microscope, UV absorption spectrometry, Spectroflurometry and Z scan. UV-Vis absorption studies affirm the Surface Plasmon Resonance (SPR) absorption and spectroflurometric studies announce the emission spectrum of the prepared silvernanoparticles at 520 nm. SEM and TEM images uphold the existence of uniform sized, spherical silvernanoparticles. Nonlinear optical studies are accomplished with the open aperture z scan technique in the nanosecond regime. The nonlinearity is in virtue of saturable absorption, two-photon absorption and excited state absorption. The marked nonlinearity and optical limiting of the Curcumin reduced silvernanoparticles enhances its photonic applications.

Investigation on Surface Roughness of Inconel 718 in Photochemical Machining

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Nitin D. Misal

2017-01-01

Full Text Available The present work is focused on estimating the optimal machining parameters required for photochemical machining (PCM of an Inconel 718 and effects of these parameters on surface topology. An experimental analysis was carried out to identify optimal values of parameters using ferric chloride (FeCl3 as an etchant. The parameters considered in this analysis are concentration of etchant, etching time, and etchant temperature. The experimental analysis shows that etching performance as well as surface topology improved by appropriate selection of etching process parameters. Temperature of the etchant found to be dominant parameter in the PCM of Inconel 718 for surface roughness. At optimal etching conditions, surface roughness was found to be 0.201 μm.

Synthesis, optical properties and residual strain effect of GaN nanowires generated via metal-assisted photochemical electroless etching

KAUST Repository

Najar, Adel; Shafa, Muhammad; Anjum, Dalaver H.

2017-01-01

Herein, we report on the studies of GaN nanowires (GaN NWs) prepared via a metal-assisted photochemical electroless etching method with Pt as the catalyst. It has been found that etching time greatly influences the growth of GaN NWs. The density

Minimally invasive non-surgical lung volume reduction

International Nuclear Information System (INIS)

Shen Liming; Zhou Dayong; Shen Junkang

2006-01-01

Minimally invasive treatment with lung volume reduction is the promising future for severe pulmonary emphysema patients. With emerging and improving of new techniques and instruments, it would become an important choice for managing severe emphysema. A comprehensive review is here documented through the correlative techniques, instruments, new achievements and latest research work. (authors)

Random resampling masks: a non-Bayesian one-shot strategy for noise reduction in digital holography.

Science.gov (United States)

Bianco, V; Paturzo, M; Memmolo, P; Finizio, A; Ferraro, P; Javidi, B

2013-03-01

Holographic imaging may become severely degraded by a mixture of speckle and incoherent additive noise. Bayesian approaches reduce the incoherent noise, but prior information is needed on the noise statistics. With no prior knowledge, one-shot reduction of noise is a highly desirable goal, as the recording process is simplified and made faster. Indeed, neither multiple acquisitions nor a complex setup are needed. So far, this result has been achieved at the cost of a deterministic resolution loss. Here we propose a fast non-Bayesian denoising method that avoids this trade-off by means of a numerical synthesis of a moving diffuser. In this way, only one single hologram is required as multiple uncorrelated reconstructions are provided by random complementary resampling masks. Experiments show a significant incoherent noise reduction, close to the theoretical improvement bound, resulting in image-contrast improvement. At the same time, we preserve the resolution of the unprocessed image.

Ferredoxin-dependent and antimycin A-sensitive reduction of cytochrome b-559 by far-red light in maize [Zea mays] thylakoids; participation of a meladiol-reducible cytochrome b-559 in cyclic electron flow

International Nuclear Information System (INIS)

Miyake, C.; Schreiber, U.; Asada, K.

1995-01-01

Thylakoids from mesophyll cells of maize showed a high rate of the ferredoxin (Fd)-dependent and antimycin A (AntiA)-sensitive cyclic electron flow as determined by the quenching of 9-aminoacridine fluorescence which indicates the formation of ΔpH across the membranes. Spectrophotometric survey of the thylakoids showed the reduction of a Cyt having an α-peak at 559 nm [Cyt b-559(Fd)] by far-red light, which depended on Fd and was sensitive to AntiA. Dose dependencies of Fd and AntiA on the photoreduction of Cyt b-559(Fd) were the same as those of the formation of ΔpH. Cyt b-559(Fd) occurred in an oxidized form even in the presence of ascorbate and was reduced by far-red light. In darkness, it was reduced only by menadiol (E m,7 = –10mV). Thus, Cyt b-559(Fd) was distinguished from Cyt b-559 in the PSII complex by its low redox potential. The present results indicate that Cyt b-559(Fd) mediates electron transfer from Fd to plastoquinone during Fd-dependent cyclic electron flow around PSI. (author)

Photochemical key steps in the synthesis of surfactants from furfural-derived intermediates.

Science.gov (United States)

Gassama, Abdoulaye; Ernenwein, Cédric; Hoffmann, Norbert

2009-01-01

Furfural is oxidized to 2[5H]-furanone by using hydrogen peroxide or to 5-hydroxy-2[5H]-furanone by using photo-oxygenation. An amine function is introduced by photochemically induced radical addition of tertiairy amines, some of which carry an n-alkyl side chain as hydrophobic moiety. These amines are produced from fatty aldehydes and cyclic secondary amines. The resulting adducts are transformed into amphoteric surfactants possessing an ammonium and a carboxylate function. Amphoteric (pK(N) and isoelectric point) and surfactant properties such as the critical micelle concentration and the adsorption efficiency are determined.

A novel photochemical machining process for magnesium aerospace and biomedical microengineering applications

International Nuclear Information System (INIS)

Allen, D M; Simpkins, M; Almond, H

2010-01-01

Research was carried out to evaluate the feasibility of fabricating perforated (filigree) magnesium microcomponents with metal wire widths of the order of the metal thickness using a photochemical machining (PCM) process. Experimentally, it has been demonstrated for the first time that metal wire widths of 0.15 mm can be achieved within a 2D, 0.25 mm thick magnesium foil to fabricate microcomponents for use as micro air vehicle (MAV) wings or stents through a bespoke PCM process. This etching process differs significantly from the industrial etching process used currently to manufacture magnesium letterpress printing plates and embossing dies

Photochemical products causing fluorescence enhancement for 6H-benzo[cd]pyren-6-one in de-aerated and pre-irradiated solutions

Energy Technology Data Exchange (ETDEWEB)

Yagishita, M., E-mail: yagishita.mayuko@nies.go.jp [Department of Environmental Science, Faculty of Science, Toho University, 2-2-1 Miyama, Funabashi, Chiba 274-8510 (Japan); National Institute for Environmental Studies, 16-2 Onogawa, Tsukuba-City, Ibaraki 305-8506 (Japan); Nakajima, D. [National Institute for Environmental Studies, 16-2 Onogawa, Tsukuba-City, Ibaraki 305-8506 (Japan); Ohshima, S. [Department of Environmental Science, Faculty of Science, Toho University, 2-2-1 Miyama, Funabashi, Chiba 274-8510 (Japan)

2016-11-15

Polycyclic aromatic ketones emit very weak fluorescence, but their fluorescence is significantly enhanced by about one hundred times after preliminary irradiation of their degassed solution. To investigate the mechanism of such fluorescence enhancement, liquid chromatography/time-of-flight mass spectrometry measurements were performed for degassed methanol, ethanol, and acetonitrile solutions of 6H-benzo[cd]pyren-6-one (naphthanthrone), in which fluorescence enhancement had been induced. As a result, two kinds of photochemical products were identified as the substance causing fluorescence enhancement: they were produced by dehydrogenation and dehydration of adducts of a solvent molecule to naphthanthrone. On the basis of the findings, the mechanism of the fluorescence enhancement of naphthanthrone was discussed. Fluorescence enhancement; 6H-benzo[cd]pyren-6-one; Polycyclic aromatic ketones; Liquid chromatography-mass spectrometry; Photochemical reaction.

Photochemical products causing fluorescence enhancement for 6H-benzo[cd]pyren-6-one in de-aerated and pre-irradiated solutions

International Nuclear Information System (INIS)

Yagishita, M.; Nakajima, D.; Ohshima, S.

2016-01-01

Polycyclic aromatic ketones emit very weak fluorescence, but their fluorescence is significantly enhanced by about one hundred times after preliminary irradiation of their degassed solution. To investigate the mechanism of such fluorescence enhancement, liquid chromatography/time-of-flight mass spectrometry measurements were performed for degassed methanol, ethanol, and acetonitrile solutions of 6H-benzo[cd]pyren-6-one (naphthanthrone), in which fluorescence enhancement had been induced. As a result, two kinds of photochemical products were identified as the substance causing fluorescence enhancement: they were produced by dehydrogenation and dehydration of adducts of a solvent molecule to naphthanthrone. On the basis of the findings, the mechanism of the fluorescence enhancement of naphthanthrone was discussed. Fluorescence enhancement; 6H-benzo[cd]pyren-6-one; Polycyclic aromatic ketones; Liquid chromatography-mass spectrometry; Photochemical reaction

Characterization of photochemical pollution at different elevations in mountainous areas in Hong Kong

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H. Guo

2013-04-01

Full Text Available To advance our understanding on the factors that affect photochemical pollution at different elevations in mountainous areas, concurrent systematic field measurements (September to November 2010 were conducted at a mountain site and at an urban site at the foot of the mountain in Hong Kong. The mixing ratios of air pollutants were greater at the foot of the mountain (i.e., Tsuen Wan urban site, TW than near the summit (i.e., Tai Mao Shan mountain site, TMS, expect for ozone. In total, only one O3 episode day was observed at TW, whereas twenty-one (21 O3 episode days were observed at TMS. The discrepancy of O3 at the two sites was attributed to the mixed effects of NO titration, vertical meteorological conditions, regional transport and mesoscale circulations. The lower NO levels at TMS and the smaller differences of "oxidant" Ox (O3 + NO2 between the two sites suggested that variations of O3 at the two sites were partly attributed to different degree of NO titration. In addition, analysis of vertical structure of meteorological variables revealed that the inversion layer at the range of altitudes of 500–1000 m might be another factor that caused the high O3 levels at TMS. Furthermore, analyses of the wind fields, the levels of air pollutants in different air flows, ratios of different trace gases and the correlation between variability and the lifetime of VOCs (volatile organic compounds indicated that high O3 concentrations at TMS were somewhat influenced by regional air masses from the highly polluted Pearl River delta (PRD region. In particular, the diurnal profiles and correlations of gaseous pollutants suggested influence of mesoscale circulations, which is confirmed using the Master Chemical Mechanism moving box model (Mbox and the Weather Research and Forecasting (WRF model. By investigating the correlations of observed O3 and NOx* and the relationships of O3 and its precursors by an observation-based model (OBM, as well as the ratios

Photochemical decoration of silver nanoparticles on graphene oxide nanosheets and their optical characterization

Energy Technology Data Exchange (ETDEWEB)

Lan, Nguyen Thi; Chi, Do Thi; Dinh, Ngo Xuan; Hung, Nguyen Duy; Lan, Hoang [Department of Nanoscience and Nanotechnology, Advanced Institute for Science and Technology (AIST), Hanoi University of Science and Technology (HUST), No. 1 Dai Co Viet Street, Hai Ba Trung District, Hanoi (Viet Nam); Tuan, Pham Anh [Vietnam Metrology Institute, 08 Hoang Quoc Viet Road, Cau Giay District, Hanoi (Viet Nam); Thang, Le Hong [School of Materials Science and Engineering, Hanoi University of Science and Technology (HUST), 01 Dai Co Viet Street, Hai Ba Trung District, Hanoi (Viet Nam); Trung, Nguyen Ngoc [School of Engineering Physics, Hanoi University of Science and Technology (HUST), 01 Dai Co Viet Street, Hai Ba Trung District, Hanoi (Viet Nam); Hoa, Nguyen Quang [Department of Physics, Hanoi University of Science, 334 Nguyen Trai, Thanh Xuan, Hanoi (Viet Nam); Huy, Tran Quang [Laboratory for Ultrastructure and Bionanotechnology (LUBN), National Institute of Hygiene and Epidemiology (NIHE), No. 1 Yecxanh Street, Hai Ba Trung District, Hanoi (Viet Nam); Quy, Nguyen Van [International Training Institute for Materials Science (ITIMS), Hanoi University of Science and Technology (HUST), 01 Dai Co Viet Street, Hai Ba Trung District, Hanoi (Viet Nam); Duong, Thanh-Tung [Department of Materials Engineering, Chungnam National University, Daeduk Science Town, 305-764 Daejeon (Korea, Republic of); Phan, Vu Ngoc [Department of Nanoscience and Nanotechnology, Advanced Institute for Science and Technology (AIST), Hanoi University of Science and Technology (HUST), No. 1 Dai Co Viet Street, Hai Ba Trung District, Hanoi (Viet Nam); Le, Anh-Tuan, E-mail: tuan.leanh1@hust.edu.vn [Department of Nanoscience and Nanotechnology, Advanced Institute for Science and Technology (AIST), Hanoi University of Science and Technology (HUST), No. 1 Dai Co Viet Street, Hai Ba Trung District, Hanoi (Viet Nam)

2014-12-05

Highlights: • A photochemical method for effective decoration of the Ag-NPs on GO nanosheets is presented. • The average size of the Ag-NPs on the GO nanosheets obtained ∼6–7 nm with uniform size distribution. • Surface interaction of Ag-NPs with GO nanosheets leads to surface plasmon-enhanced luminescence. - Abstract: Nanohybrid materials based on silver nanoparticles (Ag-NPs) and graphene oxide (GO) are attracting considerable research interest because of their potential many applications including surface-enhanced Raman scattering, catalysis, sensors, biomedicine and antimicrobials. In this study, we established a simple and effective method of preparing a finely dispersed Ag-GO aqueous solution using modified Hummer and photochemical technique. The Ag-NPs formation on GO nanosheets was analyzed by X-ray diffraction, transmission electron microscopy, Raman spectroscopy, and Fourier-transform infrared spectroscopy. The average size of Ag-NPs on the GO nanosheets was approximately 6–7 nm with nearly uniform size distribution. The Ag-GO nanohybrid also exhibits an adsorption band at 435 nm because of the presence of Ag-NPs on the GO nanosheets. Photoluminescence emission of the Ag-GO nanohybrid was found at 400 and 530 nm, which can be attributed to the interaction between the luminescence of exploited GO nanosheets and localized surface plasmon resonance from metallic Ag-NPs. The observed excellent optical properties of the as-prepared Ag-GO nanohybrid showed a significant potential for optoelectronics applications.

PHOTOCHEMICAL AIR POLLUTION IN THE NORTH OF PORTUGAL: A HIGH TROPOSHERIC OZONE EPISODE

Science.gov (United States)

Monteiro, A.; Carvalho, A.; Tchepel, O.; Ferreira, J.; Martins, H.; Miranda, A.; Borrego, C.; Saavedra, S.; Rodríguez, A.; Souto, J. A.

2009-12-01

Very high concentrations of ozone are continuously measured at the monitoring station at Lamas d’Olo, located at the North of Portugal,. A particular high photochemical episode occurred between 11 and 13 of July 2005, registering ozone hourly maximum values above 350 µg.m-3. This ozone-rich episode is investigated in this paper, in order to identify its origin and formation. Besides the analysis of both meteorological and air quality monitoring datasets, a numerical modelling approach, based on MM5-CAMx system, was used to simulate the dispersion and transport (horizontal and vertical) of the photochemical pollutants and its precursors. A cross spectrum analysis of the meteorological and air quality time series was performed, in the frequency domain, to establish the relationships between ozone data measured at Lamas d’Olo with air quality data from neighbourhood stations and meteorological parameters. Results point out different behaviour/contribution between the analysed sites. Moreover, different contributions of the u and v wind component on the ozone concentration fluctuations were found suggesting the presence a mountain breeze circulation and a north synoptic transport. The preliminary modelling results pointed out that the vertical transport of pollutants are responsible for the measured high concentrations, combined with particular meteorological conditions, related to the planetary boundary layer (PBL) development. The pollutants transported and existent at high vertical levels are captured/trapped when the PBL height reaches its daily maximum, and extremely high ozone ground level concentrations are consequently measured.

Photochemical decoration of silver nanoparticles on graphene oxide nanosheets and their optical characterization

International Nuclear Information System (INIS)

Lan, Nguyen Thi; Chi, Do Thi; Dinh, Ngo Xuan; Hung, Nguyen Duy; Lan, Hoang; Tuan, Pham Anh; Thang, Le Hong; Trung, Nguyen Ngoc; Hoa, Nguyen Quang; Huy, Tran Quang; Quy, Nguyen Van; Duong, Thanh-Tung; Phan, Vu Ngoc; Le, Anh-Tuan

2014-01-01

Highlights: • A photochemical method for effective decoration of the Ag-NPs on GO nanosheets is presented. • The average size of the Ag-NPs on the GO nanosheets obtained ∼6–7 nm with uniform size distribution. • Surface interaction of Ag-NPs with GO nanosheets leads to surface plasmon-enhanced luminescence. - Abstract: Nanohybrid materials based on silver nanoparticles (Ag-NPs) and graphene oxide (GO) are attracting considerable research interest because of their potential many applications including surface-enhanced Raman scattering, catalysis, sensors, biomedicine and antimicrobials. In this study, we established a simple and effective method of preparing a finely dispersed Ag-GO aqueous solution using modified Hummer and photochemical technique. The Ag-NPs formation on GO nanosheets was analyzed by X-ray diffraction, transmission electron microscopy, Raman spectroscopy, and Fourier-transform infrared spectroscopy. The average size of Ag-NPs on the GO nanosheets was approximately 6–7 nm with nearly uniform size distribution. The Ag-GO nanohybrid also exhibits an adsorption band at 435 nm because of the presence of Ag-NPs on the GO nanosheets. Photoluminescence emission of the Ag-GO nanohybrid was found at 400 and 530 nm, which can be attributed to the interaction between the luminescence of exploited GO nanosheets and localized surface plasmon resonance from metallic Ag-NPs. The observed excellent optical properties of the as-prepared Ag-GO nanohybrid showed a significant potential for optoelectronics applications

Study of the photochemical isomerization of ergosterol

International Nuclear Information System (INIS)

Mermet-Bouvier, Rene

1972-01-01

The photochemical reaction scheme of Ergosterol-Vitamin D 2 was studied. The schemes proposed in published literature are described together with earlier methods used for the analysis and determination. The method used is then discussed. In the first part, the factors concerning the changes occurring in molecular systems exposed to radiation, and the formalism used, are examined. Investigations of linear molecular systems and their applications to the reaction scheme of Ergosterol-Vitamin D 2 are discussed. The properties which enable the last three reaction schemes proposed in the literature to be distinguished are described. In the second part, the experimental analytical methods and the determinations made of the different isomers formed are presented. Chromatographic techniques (thin films, columns, gaseous phase) suitable for separating the various isomeric species are used. The existence of 8 isomers was established as well as a transformation occurring in one of them. The ultraviolet and infrared spectra were obtained. A reaction scheme is proposed (in which all the quantum yield values are given) from comparisons between the calculated and experimental values of the eigenvalue of the absolute minimum value λ m and the eigenvector corresponding to V m . (author) [fr

Chemical composition and photochemical reactivity of exhaust from aircraft turbine engines

Directory of Open Access Journals (Sweden)

T. F. Lyon

Full Text Available Assessment of the environmental impact of aircraft emissions is required by planners and policy makers. Seveal areas of concern are: 1. exposure of airport workers and urban residents to toxic chemicals emitted when the engines operate at low power (idle and taxi on the ground; 2. contributions to urban photochemical air pollution of aircraft volatile organic and nitrogen oxides emissions from operations around airports; and 3. emissions of nitrogen oxides and particles during high-altitude operation. The environmental impact of chemicals emitted from jet aircraft turbine engines has not been firmly established due to lack of data regarding emission rates and identities of the compounds emitted. This paper describes an experimental study of two different aircraft turbine engines designed to determine detailed organic emissions, as well as emissions of inorganic gases. Emissions were measured at several engine power settings. Measurements were made of detailed organic composition from C₁ through C₁₇, CO, CO₂, NO, NO_x, and polycyclic aromatic hydrocarbons. Measurements were made using a multi-port sampling pro be positioned directly behind the engine in the exhaust exit plane. The emission measurements have been used to determine the organic distribution by carbon number and the distribution by compound class at each engine power level. The sum of the organic species was compared with an independent measurement of total organic carbon to assess the carbon mass balance. A portion of the exhaust was captured and irradiated in outdoor smog chambers to assess the photochemical reactivity of the emissions with respect to ozone formation. The reactivity of emissions from the two engines was apportioned by chemical compound class.

The susceptibility of the retina to photochemical damage from visible light

Science.gov (United States)

Hunter, Jennifer J; Morgan, Jessica I W; Merigan, William H; Sliney, David H; Sparrow, Janet R; Williams, David R

2011-01-01

The photoreceptor/RPE complex must maintain a delicate balance between maximizing the absorption of photons for vision and retinal image quality while simultaneously minimizing the risk of photodamage when exposed to bright light. We review the recent discovery of two new effects of light exposure on the photoreceptor/RPE complex in the context of current thinking about the causes of retinal phototoxicity. These effects are autofluorescence photobleaching in which exposure to bright light reduces lipofuscin autofluorescence and, at higher light levels, RPE disruption in which the pattern of autofluorescence is permanently altered following light exposure. Both effects occur following exposure to visible light at irradiances that were previously thought to be safe. Photopigment, retinoids involved in the visual cycle, and bisretinoids in lipofuscin have been implicated as possible photosensitizers for photochemical damage. The mechanism of RPE disruption may follow either of these paths. On the other hand, autofluorescence photobleaching is likely an indicator of photooxidation of lipofuscin. The permanent changes inherent in RPE disruption might require modification of the light safety standards. AF photobleaching recovers after several hours although the mechanisms by which this occurs are not yet clear. Understanding the mechanisms of phototoxicity is all the more important given the potential for increased susceptibility in the presence of ocular diseases that affect either the visual cycle and/or lipofuscin accumulation. In addition, knowledge of photochemical mechanisms can improve our understanding of some disease processes that may be influenced by light exposure, such as some forms of Leber’s congenital amaurosis, and aid in the development of new therapies. Such treatment prior to intentional light exposures, as in ophthalmic examinations or surgeries, could provide an effective preventative strategy. PMID:22085795

Controlling cyanobacterial blooms in hypertrophic Lake Taihu, China: will nitrogen reductions cause replacement of non-N2 fixing by N2 fixing taxa?

Directory of Open Access Journals (Sweden)

Hans W Paerl

Full Text Available Excessive anthropogenic nitrogen (N and phosphorus (P inputs have caused an alarming increase in harmful cyanobacterial blooms, threatening sustainability of lakes and reservoirs worldwide. Hypertrophic Lake Taihu, China's third largest freshwater lake, typifies this predicament, with toxic blooms of the non-N2 fixing cyanobacteria Microcystis spp. dominating from spring through fall. Previous studies indicate N and P reductions are needed to reduce bloom magnitude and duration. However, N reductions may encourage replacement of non-N2 fixing with N2 fixing cyanobacteria. This potentially counterproductive scenario was evaluated using replicate, large (1000 L, in-lake mesocosms during summer bloom periods. N+P additions led to maximum phytoplankton production. Phosphorus enrichment, which promoted N limitation, resulted in increases in N2 fixing taxa (Anabaena spp., but it did not lead to significant replacement of non-N2 fixing with N2 fixing cyanobacteria, and N2 fixation rates remained ecologically insignificant. Furthermore, P enrichment failed to increase phytoplankton production relative to controls, indicating that N was the most limiting nutrient throughout this period. We propose that Microcystis spp. and other non-N2 fixing genera can maintain dominance in this shallow, highly turbid, nutrient-enriched lake by outcompeting N2 fixing taxa for existing sources of N and P stored and cycled in the lake. To bring Taihu and other hypertrophic systems below the bloom threshold, both N and P reductions will be needed until the legacy of high N and P loading and sediment nutrient storage in these systems is depleted. At that point, a more exclusive focus on P reductions may be feasible.

Advanced oxidation treatment and photochemical fate of selected antidepressant pharmaceuticals in solutions of Suwannee River humic acid

Energy Technology Data Exchange (ETDEWEB)

Santoke, Hanoz, E-mail: hsantoke@uci.edu [Urban Water Research Center, Department of Civil and Environmental Engineering, University of California, Irvine, Irvine, CA 92697-2175 (United States); Song, Weihua, E-mail: wsong@uci.edu [Urban Water Research Center, Department of Civil and Environmental Engineering, University of California, Irvine, Irvine, CA 92697-2175 (United States); Department of Environmental Science and Engineering, Fudan University, Shanghai, 200433 (China); Cooper, William J., E-mail: wcooper@uci.edu [Urban Water Research Center, Department of Civil and Environmental Engineering, University of California, Irvine, Irvine, CA 92697-2175 (United States); Peake, Barrie M., E-mail: bpeake@chemistry.otago.ac.nz [Chemistry Department, University of Otago, P.O. Box 56, Dunedin 9054 (New Zealand)

2012-05-30

Highlights: Black-Right-Pointing-Pointer We elucidate the photochemical degradation of three antidepressant pharmaceuticals. Black-Right-Pointing-Pointer Hydroxyl radical is the most significant contributor to the degradation. Black-Right-Pointing-Pointer Excited state dissolved organic matter also plays a significant role for duloxetine. Black-Right-Pointing-Pointer Tentative reaction byproducts are identified. - Abstract: Antidepressant pharmaceuticals have recently been detected at low concentrations in wastewater and surface water. This work reports studies of the direct and indirect photochemical fate and treatment by advanced oxidation of three antidepressant compounds (duloxetine, venlafaxine and bupropion) in solutions of humic acid in order to elucidate their behavior in the natural environment prior to reaching a water treatment facility and potentially entering a potable water supply. Humic acid solution was prepared by adding to distilled water a known amount of organic matter as a photosensitizer. All three antidepressants react very rapidly with hydroxyl radicals ({center_dot}OH) and hydrated electrons (e{sup -}{sub aq}) with rate constants of {approx}10{sup 8} to 10{sup 10} M{sup -1} s{sup -1}, but significantly slower with singlet oxygen ({sup 1}{Delta}O{sub 2}) ({approx}10{sup 3} to 10{sup 5} M{sup -1} s{sup -1}). The steady-state concentrations of {center_dot}OH and {sup 1}{Delta}O{sub 2}, in a sample of humic acid solution were measured and used with the second order rate constants to show that the hydroxyl radical was an order of magnitude more effective than the singlet oxygen in the solar-induced photochemical degradation of the antidepressants. Excited state dissolved organic matter also accounted for a substantial portion of degradation of duloxetine, decreasing its half-life by 27% under solar irradiation. Several reaction pathways and by-products arising from the photodegradation were identified using gamma-irradiation followed by LC

Reduction of Non-stationary Noise using a Non-negative Latent Variable Decomposition

DEFF Research Database (Denmark)

Schmidt, Mikkel Nørgaard; Larsen, Jan

2008-01-01

We present a method for suppression of non-stationary noise in single channel recordings of speech. The method is based on a non-negative latent variable decomposition model for the speech and noise signals, learned directly from a noisy mixture. In non-speech regions an over complete basis...... is learned for the noise that is then used to jointly estimate the speech and the noise from the mixture. We compare the method to the classical spectral subtraction approach, where the noise spectrum is estimated as the average over non-speech frames. The proposed method significantly outperforms...

Singlet Oxygen Sensor Green: Photochemical Behavior in Solution and in a Mammalian Cell

DEFF Research Database (Denmark)

Gollmer, Anita; Arnbjerg, Jacob; Blaikie, Frances Helen

2011-01-01

The development of efficient and selective luminescent probes for reactive oxygen species, particularly for singlet molecular oxygen, is currently of great importance. In this study, the photochemical behavior of Singlet Oxygen Sensor Green® (SOSG), a commercially available fluorescent probe...... of the reaction between SOSG and singlet oxygen is, itself, an efficient singlet oxygen photosensitizer. Second, SOSG appears to efficiently bind to proteins which, in turn, can influence uptake by a cell as well as behavior in the cell. As such, incorrect use of SOSG can yield misleading data on yields...

Photophysical and photochemical effects in ultrafast laser patterning of CVD graphene

International Nuclear Information System (INIS)

Bobrinetskiy, Ivan; Otero, Nerea; Romero, Pablo M; Emelianov, Aleksei; Komarov, Ivan; Nasibulin, Albert

2016-01-01

The micro-scale patterns in graphene on Si/SiO 2 substrate were fabricated using ultrashort 515 nm laser pulses. For both picosecond and femtosecond laser pulses two competitive processes, based on photo-thermal (ablation) and photochemical (oxidation/etching) effects, were observed. The laser-induced etching of graphene starts just below the threshold energy of graphene ablation: 1.7 nJ per 280 fs pulse and 2.7 µ J per 30 ps pulse. Whilst etching is not sensitive to thermal properties of graphene and provides uniform patterns, the ablation, in contrast, is highly affected by defects in the graphene structure like wrinkles and bilayer islands. The mechanisms of ultrafast laser interaction with graphene are discussed. (letter)

Photochemical addition of amino acids and peptides to homopolyribonucleotides of the major DNA bases

International Nuclear Information System (INIS)

Shetlar, M.D.; Hom, K.; Carbone, J.; Moy, D.; Steady, E.; Watanabe, M.

1984-01-01

The photochemical quantum yields for addition of glycine and the L-amino acids commonly occurring in proteins to polyadenylic acid, polycytidylic acid, polyguanylic acid and polyribothymidylic acid have been determined in deoxygenated phosphate buffer using a fluorescamine assay technique. Polyadenylic acid was reactive with eleven of the twenty amino acids tested, with phenylalanine, tyrosine, glutamine, lysine and asparagine having the highest quantum yields. Polyguanylic acid reacted with sixteen amino acids; phenylalanine, arginine, cysteine, tyrosine, and lysine displayed the largest quantum yields. Polycytidylic acid showed reactivity with fifteen amino acids with lysine, phenylalanine, cysteine, tyrosine and arginine having the greatest quantum yields. Polyribothymidylic acid, reactive with fifteen of nineteen amino acids surveyed, showed the highest quantum yields for cysteine, phenylalanine, tyrosine, lysine and asparagine. None of the polynucleotides were reactive with aspartic acid or glutamic acid. The quantum yields for photoaddition of eighteen dipeptides of the form gycyl X (X being an amino acid), and of L-alanyl-L-tryptophan, L-seryl-L-seryl-L-serine, L-threonyl-L-threonyl-L-threonine, L-cystine-bis-glycine, and Nsup(α)-acetyllysine to polyadenylic acid, polycytidylic acid and polyguanylic acid were measured. All were found to add photochemically to each of these polymers. Polyribothymidylic acid, tested with eleven peptides and with Nsup(α)-acetyllysine, was found to be reactive with all. (author)

Photochemical transformation of phenylurea herbicides in surface waters: a model assessment of persistence, and implications for the possible generation of hazardous intermediates.

Science.gov (United States)

Fabbri, Debora; Minella, Marco; Maurino, Valter; Minero, Claudio; Vione, Davide

2015-01-01

This work models the phototransformation kinetics in surface waters of five phenylurea herbicides (diuron, fenuron, isoproturon, metoxuron and chlortoluron), for which important photochemical parameters are available in the literature (direct photolysis quantum yields and reaction rate constants with ·OH, CO3(-·) and the triplet states of chromophoric dissolved organic matter, (3)CDOM*). Model calculations suggest that isoproturon and metoxuron would be the least photochemically persistent and diuron the most persistent compound. Reactions with ·OH and (3)CDOM* would be the main phototransformation pathways for all compounds in the majority of environmental conditions. Reaction with CO3(-) could be important in waters with low dissolved organic carbon (DOC), while direct photolysis would be negligible for fenuron, quite important for chlortoluron, and somewhat significant for the other compounds. The direct photolysis of metoxuron and diuron is known to increase toxicity, and such a photoreaction pathway would be enhanced at intermediate DOC values (1-4 mg C L(1)). The reaction between phenylureas and ·OH is known to produce toxic intermediates, differently from (3)CDOM*. Therefore, the shift of reactivity from ·OH to (3)CDOM* with increasing DOC could reduce the environmental impact of photochemical transformation. Copyright © 2014 Elsevier Ltd. All rights reserved.

Photochemical and microbial degradation technologies to remove toxic chemicals

International Nuclear Information System (INIS)

Matsumura, F.; Katayama, A.

1992-01-01

An effort was made to apply photochemical degradation technology on biodegradation processes to increase the bioremediation potential of microbial actions. For this purpose, we have chosen Phanerochaete chrysosporium, a wood decaying white-rot fungus and a variety of chlorinated pesticides and aromatics as study materials. By using UV-irradiation and benomyl (a commonly used fungicide) as selection methods, a strain of UV-resistant P. chrysosporium was developed. This strain was found to be capable of rapidly degrading these chlorinated chemicals when they were incubated in N-deficient medium which received 1 hr/day of UV-irradiation. UV-irradiation either at 300 or 254 nm showed the beneficial effect of speeding up the rate of degradation on most of test chemicals with the exception of toxaphene and HCH (hexachlorocyclohexane). By adding fresh glucose to the medium it was possible to maintain high degradation capacity for several weeks

Photochemical and microbial degradation technologies to remove toxic chemicals

Energy Technology Data Exchange (ETDEWEB)

Matsumura, F.; Katayama, A.

1992-07-01

An effort was made to apply photochemical degradation technology on biodegradation processes to increase the bioremediation potential of microbial actions. For this purpose, we have chosen Phanerochaete chrysosporium, a wood decaying white-rot fungus and a variety of chlorinated pesticides and aromatics as study materials. By using UV-irradiation and benomyl (a commonly used fungicide) as selection methods, a strain of UV-resistant P. chrysosporium was developed. This strain was found to be capable of rapidly degrading these chlorinated chemicals when they were incubated in N-deficient medium which received 1 hr/day of UV-irradiation. UV-irradiation either at 300 or 254 nm showed the beneficial effect of speeding up the rate of degradation on most of test chemicals with the exception of toxaphene and HCH (hexachlorocyclohexane). By adding fresh glucose to the medium it was possible to maintain high degradation capacity for several weeks.

Laboratory investigation of photochemical oxidation of organic aerosol from wood fires 2: analysis of aerosol mass spectrometer data

Directory of Open Access Journals (Sweden)

A. P. Grieshop

2009-03-01

Full Text Available Experiments were conducted to investigate the effects of photo-oxidation on organic aerosol (OA in dilute wood smoke by exposing emissions from soft- and hard-wood fires to UV light in a smog chamber. This paper focuses on changes in OA composition measured using a unit-mass-resolution quadrupole Aerosol Mass Spectrometer (AMS. The results highlight how photochemical processing can lead to considerable evolution of the mass, volatility and level of oxygenation of biomass-burning OA. Photochemical oxidation produced substantial new OA, more than doubling the OA mass after a few hours of aging under typical summertime conditions. Aging also decreased the volatility of the OA and made it progressively more oxygenated. The results also illustrate strengths of, and challenges with, using AMS data for source apportionment analysis. For example, the mass spectra of fresh and aged BBOA are distinct from fresh motor-vehicle emissions. The mass spectra of the secondary OA produced from aging wood smoke are very similar to those of the oxygenated OA (OOA that dominates ambient AMS datasets, further reinforcing the connection between OOA and OA formed from photo-chemistry. In addition, aged wood smoke spectra are similar to those from OA created by photo-oxidizing dilute diesel exhaust. This demonstrates that the OOA observed in the atmosphere can be produced by photochemical aging of dilute emissions from different types of combustion systems operating on fuels with modern or fossil carbon. Since OOA is frequently the dominant component of ambient OA, the similarity of spectra of aged emissions from different sources represents an important challenge for AMS-based source apportionment studies.

Wind Noise Reduction in a Non-Porous Subsurface Windscreen

Science.gov (United States)

Zuckerwar, Allan J.; Shams, Qamar A.; Knight, H. Keith

2012-01-01

Measurements of wind noise reduction were conducted on a box-shaped, subsurface windscreen made of closed cell polyurethane foam. The windscreen was installed in the ground with the lid flush with the ground surface. The wind was generated by means of a fan, situated on the ground, and the wind speed was measured at the center of the windscreen lid with an ultrasonic anemometer. The wind speed was controlled by moving the fan to selected distances from the windscreen. The wind noise was measured on a PCB Piezotronics 3†electret microphone. Wind noise spectra were measured with the microphone exposed directly to the wind (atop the windscreen lid) and with the microphone installed inside the windscreen. The difference between the two spectra comprises the wind noise reduction. At wind speeds of 3, 5, and 7 m/s, the wind noise reduction is typically 15 dB over the frequency range of 0.1-20 Hz.

Photochemical modeling in California with two chemical mechanisms: model intercomparison and response to emission reductions.

Science.gov (United States)

Cai, Chenxia; Kelly, James T; Avise, Jeremy C; Kaduwela, Ajith P; Stockwell, William R

2011-05-01

An updated version of the Statewide Air Pollution Research Center (SAPRC) chemical mechanism (SAPRC07C) was implemented into the Community Multiscale Air Quality (CMAQ) version 4.6. CMAQ simulations using SAPRC07C and the previously released version, SAPRC99, were performed and compared for an episode during July-August, 2000. Ozone (O3) predictions of the SAPRC07C simulation are generally lower than those of the SAPRC99 simulation in the key areas of central and southern California, especially in areas where modeled concentrations are greater than the federal 8-hr O3 standard of 75 parts per billion (ppb) and/or when the volatile organic compound (VOC)/nitrogen oxides (NOx) ratio is less than 13. The relative changes of ozone production efficiency (OPE) against the VOC/NOx ratio at 46 sites indicate that the OPE is reduced in SAPRC07C compared with SAPRC99 at most sites by as much as approximately 22%. The SAPRC99 and SAPRC07C mechanisms respond similarly to 20% reductions in anthropogenic VOC emissions. The response of the mechanisms to 20% NOx emissions reductions can be grouped into three cases. In case 1, in which both mechanisms show a decrease in daily maximum 8-hr O3 concentration with decreasing NOx emissions, the O3 decrease in SAPRC07C is smaller. In case 2, in which both mechanisms show an increase in O3 with decreasing NOx emissions, the O3 increase is larger in SAPRC07C. In case 3, SAPRC07C simulates an increase in O3 in response to reduced NOx emissions whereas SAPRC99 simulates a decrease in O3 for the same region. As a result, the areas where NOx controls would be disbeneficial are spatially expanded in SAPRC07C. Although the results presented here are valuable for understanding differences in predictions and model response for SAPRC99 and SAPRC07C, the study did not evaluate the impact of mechanism differences in the context of the U.S. Environmental Protection Agency's guidance for using numerical models in demonstrating air quality attainment

Photochemical degradation of atenolol, carbamazepine, meprobamate, phenytoin and primidone in wastewater effluents

Energy Technology Data Exchange (ETDEWEB)

Dong, Mei Mei [Civil, Environmental and Architectural Engineering, 428 UCB, University of Colorado, Boulder, CO 80309 (United States); Southern Nevada Water Authority (SNWA), P.O. Box 99954, Las Vegas, NV 89193-9954 (United States); Trenholm, Rebecca [Southern Nevada Water Authority (SNWA), P.O. Box 99954, Las Vegas, NV 89193-9954 (United States); Rosario-Ortiz, Fernando L., E-mail: Fernando.rosario@colorado.edu [Civil, Environmental and Architectural Engineering, 428 UCB, University of Colorado, Boulder, CO 80309 (United States)

2015-01-23

Highlights: • The photochemical degradation of 5 compounds was evaluated in wastewater effluents. • Attenuation by sensitized photolysis was the most important degradation pathway. • Hydroxyl radical accounted for most of the degradation for aliphatic compounds. • Other transient oxidants could also significantly impact the degradation of the compounds. - Abstract: The photochemical degradation of five pharmaceuticals was examined in two secondary wastewater effluents. The compounds, which included atenolol, carbamazepine, meprobamate, phenytoin and primidone, were evaluated for both direct and sensitized photolysis. In the two wastewaters, direct photolysis did not lead to significant compound degradation; however, sensitized photolysis was an important removal pathway for the five pharmaceuticals. Upon solar irradiation, hydroxyl radical (HO·) was quantified using the hydroxylation of benzene and singlet oxygen ({sup 1}O{sub 2}) formation was monitored following the degradation of furfuryl alcohol. Degradation via sensitized photolysis was observed following five-day exposures for atenolol (69–91%), carbamazepine (67–98%), meprobamate (16–52%), phenytoin (44–85%), and primidone (34–88%). Varying removal is likely a result of the differences in reactivity with transient oxidants. Averaged steady state HO· concentrations ranged from 1.2 to 4.0 × 10{sup −16} M, whereas the concentrations of {sup 1}O{sub 2} were 6.0–7.6 × 10{sup −14} M. Partial removal due to presence of HO· indicates it was not the major sink for most compounds examined. Other transient oxidants, such as {sup 1}O{sub 2} and triplet state effluent organic matter, are likely to play important roles in fates of these compounds.

A CsPbBr3 Perovskite Quantum Dot/Graphene Oxide Composite for Photocatalytic CO2 Reduction.

Science.gov (United States)

Xu, Yang-Fan; Yang, Mu-Zi; Chen, Bai-Xue; Wang, Xu-Dong; Chen, Hong-Yan; Kuang, Dai-Bin; Su, Cheng-Yong

2017-04-26

Halide perovskite quantum dots (QDs), primarily regarded as optoelectronic materials for LED and photovoltaic devices, have not been applied for photochemical conversion (e.g., water splitting or CO 2 reduction) applications because of their insufficient stability in the presence of moisture or polar solvents. Herein, we report the use of CsPbBr 3 QDs as novel photocatalysts to convert CO 2 into solar fuels in nonaqueous media. Under AM 1.5G simulated illumination, the CsPbBr 3 QDs steadily generated and injected electrons into CO 2 , catalyzing CO 2 reduction at a rate of 23.7 μmol/g h with a selectivity over 99.3%. Additionally, through the construction of a CsPbBr 3 QD/graphene oxide (CsPbBr 3 QD/GO) composite, the rate of electron consumption increased 25.5% because of improved electron extraction and transport. This study is anticipated to provide new opportunities to utilize halide perovskite QD materials in photocatalytic applications.

Assessing the Effect of Potential Reductions in Non-Hepatic Mortality on the Estimated Cost-Effectiveness of Hepatitis C Treatment in Early Stages of Liver Disease

Science.gov (United States)

Chesson, Harrell W.; Spradling, Philip R.; Holmberg, Scott D.

2018-01-01

Background Most cost-effectiveness analyses of hepatitis C (HCV) therapy focus on the benefits of reducing liver-related morbidity and mortality. Objectives Our objective was to assess how cost-effectiveness estimates of HCV therapy can vary depending on assumptions regarding the potential impact of HCV therapy on non-hepatic mortality. Methods We adapted a state-transition model to include potential effects of HCV therapy on non-hepatic mortality. We assumed successful treatment could reduce non-hepatic mortality by as little as 0 % to as much as 100 %. Incremental cost-effectiveness ratios were computed comparing immediate treatment versus delayed treatment and comparing immediate treatment versus non-treatment. Results Comparing immediate treatment versus delayed treatment, when we included a 44 % reduction in nonhepatic mortality following successful HCV treatment, the incremental cost per quality-adjusted life year (QALY) gained by HCV treatment fell by 76 % (from US$314,100 to US$76,900) for patients with no fibrosis and by 43 % (from US$62,500 to US$35,800) for patients with moderate fibrosis. Comparing immediate treatment versus non-treatment, assuming a 44 % reduction in non-hepatic mortality following successful HCV treatment, the incremental cost per QALY gained by HCV treatment fell by 64 % (from US$186,700 to US$67,300) for patients with no fibrosis and by 27 % (from US$35,000 to US$25,500) for patients with moderate fibrosis. Conclusion Including reductions in non-hepatic mortality from HCV treatment can have substantial effects on the estimated cost-effectiveness of treatment. PMID:27480538

Source reconciliation of atmospheric gas-phase and particle-phase pollutants during a severe photochemical smog episode.

Science.gov (United States)

Schauer, James J; Fraser, Matthew P; Cass, Glen R; Simoneit, Bernd R T

2002-09-01

A comprehensive organic compound-based receptor model is developed that can simultaneously apportion the source contributions to atmospheric gas-phase organic compounds, semivolatile organic compounds, fine particle organic compounds, and fine particle mass. The model is applied to ambient data collected at four sites in the south coast region of California during a severe summertime photochemical smog episode, where the model determines the direct primary contributions to atmospheric pollutants from 11 distinct air pollution source types. The 11 sources included in the model are gasoline-powered motor vehicle exhaust, diesel engine exhaust, whole gasoline vapors, gasoline headspace vapors, organic solvent vapors, whole diesel fuel, paved road dust, tire wear debris, meat cooking exhaust, natural gas leakage, and vegetative detritus. Gasoline engine exhaust plus whole gasoline vapors are the predominant sources of volatile organic gases, while gasoline and diesel engine exhaust plus diesel fuel vapors dominate the emissions of semivolatile organic compounds from these sources during the episode studied at all four air monitoring sites. The atmospheric fine particle organic compound mass was composed of noticeable contributions from gasoline-powered motor vehicle exhaust, diesel engine exhaust, meat cooking, and paved road dust with smaller but quantifiable contributions from vegetative detritus and tire wear debris. In addition, secondary organic aerosol, which is formed from the low-vapor pressure products of gas-phase chemical reactions, is found to be a major source of fine particle organic compound mass under the severe photochemical smog conditions studied here. The concentrations of secondary organic aerosol calculated in the present study are compared with previous fine particle source apportionment results for less intense photochemical smog conditions. It is shown that estimated secondary organic aerosol concentrations correlate fairly well with the

UV-Assisted Photochemical Synthesis of Reduced Graphene Oxide/ZnO Nanowires Composite for Photoresponse Enhancement in UV Photodetectors

Directory of Open Access Journals (Sweden)

Changsong Chen

2018-01-01

Full Text Available The weak photon absorption and high recombination rate of electron-hole pairs in disordered zinc oxide nanowires (ZNWs limit its application in UV photodetection. This limitation can be overcome by introducing graphene sheets to the ZNWs. Herein we report a high-performance photodetector based on one-dimensional (1D wide band-gap semiconductor disordered ZNWs composited with reduced graphene oxide (RGO for ultraviolet (UV photoresponse enhancement. The RGO/ZNWs composites have been successfully synthetized through UV-assisted photochemical reduction of GO in ZNWs suspension. The material characterizations in morphology, Raman scattering, and Ultraviolet-visible light absorption verified the formation of graphene sheets attached in ZNWs network and the enhancement of UV absorption due to the introduction of graphene. In comparison with photodetectors based on pure ZNWs, the photodetectors based on RGO/ZNWs composite exhibit enhanced photoresponse with photocurrent density of 5.87 mA·cm−2, on/off current ratio of 3.01 × 104, and responsivity of 1.83 A·W−1 when a UV irradiation of 3.26 mW·cm−2 and 1.0 V bias were used. Theory analysis is also presented to get insight into the inherent mechanisms of separation and transportation of photo-excited carriers in RGO/ZNWs composite.

UV-Assisted Photochemical Synthesis of Reduced Graphene Oxide/ZnO Nanowires Composite for Photoresponse Enhancement in UV Photodetectors.

Science.gov (United States)

Chen, Changsong; Zhou, Peng; Wang, Na; Ma, Yang; San, Haisheng

2018-01-05

The weak photon absorption and high recombination rate of electron-hole pairs in disordered zinc oxide nanowires (ZNWs) limit its application in UV photodetection. This limitation can be overcome by introducing graphene sheets to the ZNWs. Herein we report a high-performance photodetector based on one-dimensional (1D) wide band-gap semiconductor disordered ZNWs composited with reduced graphene oxide (RGO) for ultraviolet (UV) photoresponse enhancement. The RGO/ZNWs composites have been successfully synthetized through UV-assisted photochemical reduction of GO in ZNWs suspension. The material characterizations in morphology, Raman scattering, and Ultraviolet-visible light absorption verified the formation of graphene sheets attached in ZNWs network and the enhancement of UV absorption due to the introduction of graphene. In comparison with photodetectors based on pure ZNWs, the photodetectors based on RGO/ZNWs composite exhibit enhanced photoresponse with photocurrent density of 5.87 mA·cm -2 , on/off current ratio of 3.01 × 10⁴, and responsivity of 1.83 A·W -1 when a UV irradiation of 3.26 mW·cm -2 and 1.0 V bias were used. Theory analysis is also presented to get insight into the inherent mechanisms of separation and transportation of photo-excited carriers in RGO/ZNWs composite.

Results of photochemical modeling sensitivity analyses in the Lake Michigan region: Current status of Lake Michigan Ozone Control Program (LMOP) modeling

Energy Technology Data Exchange (ETDEWEB)

Dolwick, P.D. [Lake Michigan Air Directors Consortium, Des Plaines, IL (United States); Kaleel, R.J. [Illinois Environmental Protection Agency, Springfield, IL (United States); Majewski, M.A. [Wisconsin Dept. of Natural Resources, Madison, WI (United States)

1994-12-31

The four states that border Lake Michigan are cooperatively applying a state-of-the-art nested photochemical grid model to assess the effects of potential emission control strategies on reducing elevated tropospheric ozone concentrations in the region to levels below the national ambient air quality standard. In order to provide an extensive database to support the application of the photochemical model, a substantial data collection effort known as the Lake Michigan Ozone Study (LMOS) was completed during the summer of 1991. The Lake Michigan Ozone Control Program (LMOP) was established by the States of Illinois, Wisconsin, Michigan, and Indiana to carry out the application of the modeling system developed from the LMOS, in terms of developing the attainment demonstrations required from this area by the Clean Air Act Amendments of 1990.

Biologically labile photoproducts from riverine non-labile dissolved organic carbon in the coastal waters

Science.gov (United States)

Kasurinen, V.; Aarnos, H.; Vähätalo, A.

2015-06-01

In order to assess the production of biologically labile photoproducts (BLPs) from non-labile riverine dissolved organic carbon (DOC), we collected water samples from ten major rivers, removed labile DOC and mixed the residual non-labile DOC with artificial seawater for microbial and photochemical experiments. Bacteria grew on non-labile DOC with a growth efficiency of 11.5% (mean; range from 3.6 to 15.3%). Simulated solar radiation transformed a part of non-labile DOC into BLPs, which stimulated bacterial respiration and production, but did not change bacterial growth efficiency (BGE) compared to the non-irradiated dark controls. In the irradiated water samples, the amount of BLPs stimulating bacterial production depended on the photochemical bleaching of chromophoric dissolved organic matter (CDOM). The apparent quantum yields for BLPs supporting bacterial production ranged from 9.5 to 76 (mean 39) (μmol C mol photons-1) at 330 nm. The corresponding values for BLPs supporting bacterial respiration ranged from 57 to 1204 (mean 320) (μmol C mol photons-1). According to the calculations based on spectral apparent quantum yields and local solar radiation, the annual production of BLPs ranged from 21 (St. Lawrence) to 584 (Yangtze) mmol C m-2 yr-1 in the plumes of the examined rivers. Complete photobleaching of riverine CDOM in the coastal ocean was estimated to produce 10.7 Mt C BLPs yr-1 from the rivers examined in this study and globally 38 Mt yr-1 (15% of riverine DOC flux from all rivers), which support 4.1 Mt yr-1 of bacterial production and 33.9 Mt yr-1 bacterial respiration.

Numerical simulation of urea based selective non-catalytic reduction deNOx process for industrial applications

International Nuclear Information System (INIS)

Baleta, Jakov; Mikulčić, Hrvoje; Vujanović, Milan; Petranović, Zvonimir; Duić, Neven

2016-01-01

Highlights: • SNCR is a simple method for the NOx reduction from large industrial facilities. • Capabilities of the developed mathematical framework for SNCR simulation were shown. • Model was used on the geometry of experimental reactor and municipal incinerator. • Results indicate suitability of the developed model for real industrial cases. - Abstract: Industrial processes emit large amounts of diverse pollutants into the atmosphere, among which NOx takes a significant portion. Selective non-catalytic reduction (SNCR) is a relatively simple method for the NOx reduction in large industrial facilities such as power plants, cement plants and waste incinerator plants. It consists of injecting the urea-water solution in the hot flue gas stream and its reaction with the NOx. During this process flue gas enthalpy is used for the urea-water droplet heating and for the evaporation of water content. After water evaporates, thermolysis of urea occurs, during which ammonia, a known NO_x reductant, and isocyanic acid are generated. In order to cope with the ever stringent environmental norms, equipment manufacturers need to develop energy efficient products that are at the same time benign to environment. This is becoming increasingly complicated and costly, and one way to reduce production costs together with the maintaining the same competitiveness level is to employ computational fluid dynamics (CFD) as a tool, in a process today commonly known under the term “virtual prototyping”. The aim of this paper is to show capabilities of the developed mathematical framework implemented in the commercial CFD code AVL FIRE®, to simulate physical processes of all relevant phenomena occurring during the SNCR process. First, mathematical models for description of SNCR process are presented and afterwards, models are used on the 3D geometry of an industrial reactor and a real industrial case to predict SNCR efficiency, temperature and velocity field. Influence of the main

Synthesis of self-supported non-precious metal catalysts for oxygen reduction reaction with preserved nanostructures from the polyaniline nanofiber precursor

DEFF Research Database (Denmark)

Hu, Yang; Zhao, Xiao; Huang, Yunjie

2013-01-01

Non-precious metal catalysts (NPMCs) for the oxygen reduction reaction (ORR) are an active subject of recent research on proton exchange membrane fuel cells. In this study, we report a new approach to preparation of self-supported and nano-structured NPMCs using pre-prepared polyaniline (PANI...

Eficiência fotoquímica de gramíneas forrageiras tropicais submetidas à deficiência hídrica Photochemical efficiency of tropical forage grasses submitted to water deficit

Directory of Open Access Journals (Sweden)

Manoel Messias Pereira da Silva

2006-02-01

, nilograss (Acroceras macrum Stapf. and angola grass (Brachiaria purpurascens [Raddi] Henr. were submitted to moderate drought. The characteristics of chlorophyll a fluorescence (inicial fluorescence, Fo; maximum fluorescence, Fm; photochemistry efficiency, Fv/F­m; photochemical quenching, qP; non-photochemical quenching, qN and relative electron transport rate, ETR were investigated in an experiment carried out in greenhouse, using plastic pots. The experimental treatments were allocated in a randomized complete blocks design, with three replications. The values of Fo and Fm decreased in all species after 10 days of drought, this effect being more evident in nilograss and setariagrass. The Fv/Fm values for nilograss and setariagrass decreased dramatically while that one for hemarthriagrass did not differ from the control. This results suggest a lower photochemical efficiency of photosynthesis in nilograss and setariagrass under water stress compared to hemarthriagrass and to the hea,lthy plants. The highest values of qN were observed for hemarthriagraas and angolagrass. This showed that the increased capacity to dissipate the excessive energy to drive photosynthesis was satisfactory to maintain a low reduction state of the primary electron acceptor of the photosystem II (measured as qP. In general, ETR curves in response to increasing photosynthetic photon flux differed from control to stressed plants, especially for nilograss. In this species, a serious damage caused by water stress provoked a significant reduction to the efficiency of the electron transporters of PSII.

European scale modeling of sulfur, oxidized nitrogen and photochemical oxidants. Model development and evaluation for the 1994 growing season

Energy Technology Data Exchange (ETDEWEB)

Langner, J.; Bergstroem, R. [Swedish Meteorological and Hydrological Inst., Norrkoeping (Sweden); Pleijel, K. [Swedish Environmental Research Inst., Goeteborg (Sweden)

1998-09-01

A chemical mechanism, including the relevant reactions leading to the production of ozone and other photochemical oxidants, has been implemented in the MATCH regional tracer transport/chemistry/deposition model. The aim has been to develop a model platform that can be used as a basis for a range of regional scale studies involving atmospheric chemistry, including assessment of the importance of different sources of pollutants to the levels of photochemical oxidants and air pollutant forecasting. Meteorological input data to the model were taken from archived output from the operational version of HIRLAM at SMHI. Evaluation of model calculations over Europe for a six month period in 1994 for a range of chemical components show good results considering known sources of error and uncertainties in input data and model formulation. With limited further work the system is sufficiently good to be applied for scenario studies and for regional scale air pollutant forecasts 42 refs, 24 figs, 17 tabs

Photochemical Study of Silver Nanoparticles Formed from the Reduction of Silver Ions by Humic Acid

Science.gov (United States)

Leslie, Renee M.

This study focuses on the ability of silver ions and humic acid to form silver nanoparticles in the presence of UV and visible light. Silver nanoparticles have a number of industrial applications due primarily to their antimicrobial properties, but these properties pose an environmental threat. Silver nanoparticles can directly disrupt sensitive ecosystems by harming bacteria. Consumption of silver nanoparticles results in silver ions and silver nanoparticles entering waterways; the presence of silver ions raises the question of whether nanoparticles can reform in environmental waters. As our data show, silver nanoparticles can form from the reduction of silver ions by humic acid after irradiation with UV and visible light. In order to better understand the mechanism of these naturally synthesized silver nanoparticles, we investigated the effects of reactant concentration, experimental conditions and presence of ions/reactive species. We monitored silver nanoparticle growth with UV-visible spectroscopy. The evolution in time of nanoparticle size was monitored by dynamic light scattering (DLS).

Photochemical stability of π-conjugated polymers for polymer solar cells: a rule of thumb

DEFF Research Database (Denmark)

Manceau, Matthieu; Bundgaard, Eva; Carlé, Jon Eggert

2011-01-01

A comparative photochemical stability study of a wide range of π-conjugated polymers relevant to polymer solar cells is presented. The behavior of each material has been investigated under simulated sunlight (1 sun, 1000 W m−2, AM 1.5G) and ambient atmosphere. Degradation was monitored during age...... ageing combining UV-visible and infrared spectroscopies. From the comparison of the collected data, the influence of the polymer chemical structure on its stability has been discussed. General rules relative to the polymer structure–stability relationship are proposed....

Aqueous photochemical degradation of hydroxylated PAHs: Kinetics, pathways, and multivariate effects of main water constituents

Energy Technology Data Exchange (ETDEWEB)

Ge, Linke; Na, Guangshui [Key Laboratory for Ecological Environment in Coastal Areas (SOA), National Marine Environmental Monitoring Center, Dalian 116023 (China); Chen, Chang-Er [Lancaster Environment Centre, Lancaster University, Lancaster LA1 4YQ (United Kingdom); Li, Jun [Key Laboratory for Ecological Environment in Coastal Areas (SOA), National Marine Environmental Monitoring Center, Dalian 116023 (China); College of Marine Science, Shanghai Ocean University, Shanghai 201306 (China); Ju, Maowei; Wang, Ying; Li, Kai [Key Laboratory for Ecological Environment in Coastal Areas (SOA), National Marine Environmental Monitoring Center, Dalian 116023 (China); Zhang, Peng, E-mail: pzhang@nmemc.org.cn [Key Laboratory for Ecological Environment in Coastal Areas (SOA), National Marine Environmental Monitoring Center, Dalian 116023 (China); Yao, Ziwei [Key Laboratory for Ecological Environment in Coastal Areas (SOA), National Marine Environmental Monitoring Center, Dalian 116023 (China)

2016-03-15

Hydroxylated polycyclic aromatic hydrocarbons (OH-PAHs) are contaminants of emerging concern in the aquatic environment, so it is of great significance to understand their environmental transformation and toxicity. This study investigated the aqueous photochemical behavior of four OH-PAHs, 9-Hydroxyfluorene (9-OHFL), 2-Hydroxyfluorene, 9-Hydroxyphenanthrene and 1-Hydroxypyrene, under simulated sunlight irradiation (λ > 290 nm). It was observed that their photodegradation followed the pseudo-first-order kinetics. Based on the determined quantum yields, their calculated solar apparent photodegradation half-lives in surface waters at 45° N latitude ranged from 0.4 min for 9-Hydroxyphenanthrene to 7.5 × 10{sup 3} min for 9-OHFL, indicating that the OH-PAHs would intrinsically photodegrade fast in sunlit surface waters. Furthermore, 9-OHFL as an example was found to undergo direct photolysis, and self-sensitized photooxidation via ·OH rather than {sup 1}O{sub 2} in pure water. The potential photoreactions involved photoinduced hydroxylation, dehydrogenation and isomerization based on product identification by GC–MS/MS. 9-OHFL photodegraded slower in natural waters than in pure water, which was attributed to the integrative effects of the most photoreactive species, such as Fe(III), NO{sub 3}{sup −}, Cl{sup −} and humic acid. The photomodified toxicity was further examined using Vibrio fischeri, and it was found that the toxicity of photolyzed 9-OHFL did not decrease significantly (p > 0.05) either in pure water or in seawater, implying the comparable or higher toxicity of some intermediates. These results are important for assessing the fate and risks of OH-PAHs in surface waters. - Graphical abstract: Aqueous photochemical behavior of 4 hydroxylated PAHs is first reported on revealing the kinetics, mechanisms, toxicity, and multivariate effects of water constituents. - Highlights: • It is first reported on aqueous photochemical behavior of 4 hydroxylated

Applying green chemistry to the photochemical route to artemisinin

Science.gov (United States)

Amara, Zacharias; Bellamy, Jessica F. B.; Horvath, Raphael; Miller, Samuel J.; Beeby, Andrew; Burgard, Andreas; Rossen, Kai; Poliakoff, Martyn; George, Michael W.

2015-06-01

Artemisinin is an important antimalarial drug, but, at present, the environmental and economic costs of its semi-synthetic production are relatively high. Most of these costs lie in the final chemical steps, which follow a complex acid- and photo-catalysed route with oxygenation by both singlet and triplet oxygen. We demonstrate that applying the principles of green chemistry can lead to innovative strategies that avoid many of the problems in current photochemical processes. The first strategy combines the use of liquid CO2 as solvent and a dual-function solid acid/photocatalyst. The second strategy is an ambient-temperature reaction in aqueous mixtures of organic solvents, where the only inputs are dihydroartemisinic acid, O2 and light, and the output is pure, crystalline artemisinin. Everything else—solvents, photocatalyst and aqueous acid—can be recycled. Some aspects developed here through green chemistry are likely to have wider application in photochemistry and other reactions.

Applying green chemistry to the photochemical route to artemisinin.

Science.gov (United States)

Amara, Zacharias; Bellamy, Jessica F B; Horvath, Raphael; Miller, Samuel J; Beeby, Andrew; Burgard, Andreas; Rossen, Kai; Poliakoff, Martyn; George, Michael W

2015-06-01

Artemisinin is an important antimalarial drug, but, at present, the environmental and economic costs of its semi-synthetic production are relatively high. Most of these costs lie in the final chemical steps, which follow a complex acid- and photo-catalysed route with oxygenation by both singlet and triplet oxygen. We demonstrate that applying the principles of green chemistry can lead to innovative strategies that avoid many of the problems in current photochemical processes. The first strategy combines the use of liquid CO2 as solvent and a dual-function solid acid/photocatalyst. The second strategy is an ambient-temperature reaction in aqueous mixtures of organic solvents, where the only inputs are dihydroartemisinic acid, O2 and light, and the output is pure, crystalline artemisinin. Everything else-solvents, photocatalyst and aqueous acid-can be recycled. Some aspects developed here through green chemistry are likely to have wider application in photochemistry and other reactions.

Laser-induced photochemical enrichment of boron isotopes

International Nuclear Information System (INIS)

Freund, S.M.; Ritter, J.J.

1976-01-01

A boron trichloride starting material containing both boron-10 isotopes and boron-11 isotopes is selectively enriched in one or the other of these isotopes by a laser-induced photochemical method involving the reaction of laser-excited boron trichloride with either H 2 S or D 2 S. The method is carried out by subjecting a low pressure gaseous mixture of boron trichloride starting material and the sulfide to infrared radiation from a carbon dioxide TE laser. The wave length of the radiation is selected so as to selectively excite one or the other of boron-10 BCl 3 molecules or boron-11 BCl 3 molecules, thereby making them preferentially more reactive with the sulfide. The laser-induced reaction produces both a boron-containing solid phase reaction product and a gaseous phase containing mostly unreacted BCl 3 and small amounts of sulfhydroboranes. Pure boron trichloride selectively enriched in one of the isotopes is recovered as the primary product of the method from the gaseous phase by a multi-step recovery procedure. Pure boron trichloride enriched in the other isotope is recovered as a secondary product of the method by the subsequent chlorination of the solid phase reaction product followed by separation of BCl 3 from the mixture of gaseous products resulting from the chlorination

Changes in optical characteristics of surface microlayers in the Peruvian upwelling region hint to photochemically and microbially-mediated DOM turnover

Science.gov (United States)

Engel, A.; Galgani, L.

2016-02-01

The coastal upwelling system off Peru is characterized by high biological activity and associated subsurface oxygen minimum zone, leading to an enhanced emission of atmospheric trace gases. High biological productivity in the water column may promote the establishment of enriched organic surface films, key environments for processes regulating gas fluxes across the water-air interface. During M91 cruise to the Peruvian upwelling, we focused our attention on the composition of the sea-surface microlayer (SML), the oceanic uppermost boundary directly subject to high solar radiation, often enriched in specific organic compounds of biological origin like Chromophoric Dissolved Organic Matter (CDOM) and marine gels. In the SML, the continuous photochemical and microbial recycling of organic matter may strongly influence gas exchange between marine systems and the atmosphere. In order to understand organic matter cycling in surface films, we analyzed SML and underlying water samples in 38 stations determining DOC concentrations, amino acids composition, marine gels, CDOM and bacterial abundance as indicators of photochemical and microbial alteration processes. CDOM composition was characterized by spectral slopes (S) values and Excitation-Emission Matrix fluorescence (EEMs), which allow to track changes in molecular weight (MW) of DOM, and to determine potential DOM sources. Profound changes in spectral slope properties were observed suggesting smaller MW CDOM in the SML compared to underlying water. Microbial and photochemical degradation are likely the main drivers for organic matter cycling in the top layer of the ocean. Consequences on the formation of inorganic and organic species highly relevant for air-sea gas exchange and for climate dynamics will be discussed.

Atmospheric carbon dioxide changes photochemical activity, soluble sugars and volatile levels in broccoli (Brassica oleracea var. italica).

Science.gov (United States)

Krumbein, Angelika; Kläring, Hans-Peter; Schonhof, Ilona; Schreiner, Monika

2010-03-24

Atmospheric carbon dioxide (CO(2)) concentration is an environmental factor currently undergoing dramatic changes. The objective of the present study was to determine the effect of doubling the ambient CO(2) concentration on plant photochemistry as measured by photochemical quenching coefficient (qP), soluble sugars and volatiles in broccoli. Elevated CO(2) concentration increased qP values in leaves by up to 100% and 89% in heads, while glucose and sucrose in leaves increased by about 60%. Furthermore, in broccoli heads elevated CO(2) concentration induced approximately a 2-fold increase in concentrations of three fatty acid-derived C(7) aldehydes ((E)-2-heptenal, (E,Z)-2,4-heptadienal, (E,E)-2,4-heptadienal), two fatty acid-derived C(5) alcohols (1-penten-3-ol, (Z)-2-pentenol), and two amino acid-derived nitriles (phenyl propanenitrile, 3-methyl butanenitrile). In contrast, concentrations of the sulfur-containing compound 2-ethylthiophene and C(6) alcohol (E)-2-hexenol decreased. Finally, elevated CO(2) concentration increased soluble sugar concentrations due to enhanced photochemical activity in leaves and heads, which may account for the increased synthesis of volatiles.

Dual active layer a-IGZO TFT via homogeneous conductive layer formation by photochemical H-doping.

Science.gov (United States)

Jeong, Seung-Ki; Kim, Myeong-Ho; Lee, Sang-Yeon; Seo, Hyungtak; Choi, Duck-Kyun

2014-01-01

In this study, InGaZnO (IGZO) thin film transistors (TFTs) with a dual active layer (DAL) structure are fabricated by inserting a homogeneous embedded conductive layer (HECL) in an amorphous IGZO (a-IGZO) channel with the aim of enhancing the electrical characteristics of conventional bottom-gate-structure TFTs. A highly conductive HECL (carrier concentration at 1.6 × 10(13) cm(-2), resistivity at 4.6 × 10(-3) Ω∙cm, and Hall mobility at 14.6 cm(2)/Vs at room temperature) is fabricated using photochemical H-doping by irradiating UV light on an a-IGZO film. The electrical properties of the fabricated DAL TFTs are evaluated by varying the HECL length. The results reveal that carrier mobility increased proportionally with the HECL length. Further, a DAL TFT with a 60-μm-long HECL embedded in an 80-μm-long channel exhibits comprehensive and outstanding improvements in its electrical properties: a saturation mobility of 60.2 cm(2)/Vs, threshold voltage of 2.7 V, and subthreshold slope of 0.25 V/decade against the initial values of 19.9 cm(2)/Vs, 4.7 V, and 0.45 V/decade, respectively, for a TFT without HECL. This result confirms that the photochemically H-doped HECL significantly improves the electrical properties of DAL IGZO TFTs.

Strategy to Identify and Test Putative Light-Sensitive Non-Opsin G-Protein-Coupled Receptors: A Case Study.

Science.gov (United States)

Faggionato, Davide; Serb, Jeanne M

2017-08-01

The rise of high-throughput RNA sequencing (RNA-seq) and de novo transcriptome assembly has had a transformative impact on how we identify and study genes in the phototransduction cascade of non-model organisms. But the advantage provided by the nearly automated annotation of RNA-seq transcriptomes may at the same time hinder the possibility for gene discovery and the discovery of new gene functions. For example, standard functional annotation based on domain homology to known protein families can only confirm group membership, not identify the emergence of new biochemical function. In this study, we show the importance of developing a strategy that circumvents the limitations of semiautomated annotation and apply this workflow to photosensitivity as a means to discover non-opsin photoreceptors. We hypothesize that non-opsin G-protein-coupled receptor (GPCR) proteins may have chromophore-binding lysines in locations that differ from opsin. Here, we provide the first case study describing non-opsin light-sensitive GPCRs based on tissue-specific RNA-seq data of the common bay scallop Argopecten irradians (Lamarck, 1819). Using a combination of sequence analysis and three-dimensional protein modeling, we identified two candidate proteins. We tested their photochemical properties and provide evidence showing that these two proteins incorporate 11-cis and/or all-trans retinal and react to light photochemically. Based on this case study, we demonstrate that there is potential for the discovery of new light-sensitive GPCRs, and we have developed a workflow that starts from RNA-seq assemblies to the discovery of new non-opsin, GPCR-based photopigments.

Construction of a photochemical reactor combining a CCD spectrophotometer and a LED radiation source.

Science.gov (United States)

Gombár, Melinda; Józsa, Éva; Braun, Mihály; Ősz, Katalin

2012-10-01

An inexpensive photoreactor using LED light sources and a fibre-optic CCD spectrophotometer as a detector was built by designing a special cell holder for standard 1.000 cm cuvettes. The use of this device was demonstrated by studying the aqueous photochemical reaction of 2,5-dichloro-1,4-benzoquinone. The developed method combines the highly quantitative data collection of CCD spectrophotometers with the possibility of illuminating the sample independently of the detecting light beam, which is a substantial improvement of the method using diode array spectrophotometers as photoreactors.

Disulfonated tetraphenyl chlorin (TPCS2a)-induced photochemical internalisation of bleomycin in patients with solid malignancies: a phase 1, dose-escalation, first-in-man trial.

Science.gov (United States)

Sultan, Ahmed A; Jerjes, Waseem; Berg, Kristian; Høgset, Anders; Mosse, Charles A; Hamoudi, Rifat; Hamdoon, Zaid; Simeon, Celia; Carnell, Dawn; Forster, Martin; Hopper, Colin

2016-09-01

Photochemical internalisation, a novel minimally invasive treatment, has shown promising preclinical results in enhancing and site-directing the effect of anticancer drugs by illumination, which initiates localised chemotherapy release. We assessed the safety and tolerability of a newly developed photosensitiser, disulfonated tetraphenyl chlorin (TPCS2a), in mediating photochemical internalisation of bleomycin in patients with advanced and recurrent solid malignancies. In this phase 1, dose-escalation, first-in-man trial, we recruited patients (aged ≥18 to internalisation were either local, resulting from the local inflammatory process, or systemic, mostly as a result of the skin-photosensitising effect of TPCS2a. The most common grade 3 or worse adverse events were unexpected higher transient pain response (grade 3) localised to the treatment site recorded in nine patients, and respiratory failure (grade 4) noted in two patients. One dose-limiting toxicity was reported in the 1·0 mg/kg cohort (skin photosensitivity [grade 2]). Dose-limiting toxicities were reported in two of three patients at a TPCS2a dose of 1·5 mg/kg (skin photosensitivity [grade 3] and wound infection [grade 3]); thus, the maximum tolerated dose of TPCS2a was 1·0 mg/kg. Administration of TPCS2a was found to be safe and tolerable by all patients. No deaths related to photochemical internalisation treatment occurred. TPCS2a-mediated photochemical internalisation of bleomycin is safe and tolerable. We identified TPCS2a 0·25 mg/kg as the recommended treatment dose for future trials. PCI Biotech. Copyright © 2016 Elsevier Ltd. All rights reserved.

Experimental Study of Nonequilibrium Electrodeposition of Nanostructures on Copper and Nickel for Photochemical Fuel Cell Application

Directory of Open Access Journals (Sweden)

Rajesh K. Shanmugam

2011-01-01

Full Text Available To increase the performance of photochemical fuel cells, nonequilibrium electrodeposition has been performed on Cu and Ni to make photosensitive anodes. Processing parameters including electrolyte concentration, and electrode potential were studied using cyclic voltammetry. Scanning electron microscopy (SEM and X-ray Spectroscopy (EDS were performed to understand the formation of the nanostructures during the nonequilibrium deposition of copper fractals. An increase in the deposition rate was observed with the increase in electrolyte concentration (from 0.05 M to 1.0 M. Similar trend was found when the cathode potential was decreased from −0.5 V to −4.5 V. The effect of substrate material was also examined. Porous fractal structures on copper were achieved, while the deposited material showed high density of surface cracks on nickel. The fractal structures deposited on copper electrode with the increased surface area were converted into copper oxide by oxidation in air. Such oxide samples were made into anodes for photochemical fuel cell application. We demonstrated that an increase in the magnitude of open circuit output voltage is associated with the increase in the fractal surface area under the ultraviolet irradiation test conditions. However, the electrodeposited fractals on nickel showed very limited increase in the magnitude of open circuit voltage.

Leaf and canopy photosynthesis of a chlorophyll deficient soybean mutant.

Science.gov (United States)

Sakowska, Karolina; Alberti, Giorgio; Genesio, Lorenzo; Peressotti, Alessandro; Delle Vedove, Gemini; Gianelle, Damiano; Colombo, Roberto; Rodeghiero, Mirco; Panigada, Cinzia; Juszczak, Radosław; Celesti, Marco; Rossini, Micol; Haworth, Matthew; Campbell, Benjamin W; Mevy, Jean-Philippe; Vescovo, Loris; Cendrero-Mateo, M Pilar; Rascher, Uwe; Miglietta, Franco

2018-03-02

The photosynthetic, optical, and morphological characteristics of a chlorophyll-deficient (Chl-deficient) "yellow" soybean mutant (MinnGold) were examined in comparison with 2 green varieties (MN0095 and Eiko). Despite the large difference in Chl content, similar leaf photosynthesis rates were maintained in the Chl-deficient mutant by offsetting the reduced absorption of red photons by a small increase in photochemical efficiency and lower non-photochemical quenching. When grown in the field, at full canopy cover, the mutants reflected a significantly larger proportion of incoming shortwave radiation, but the total canopy light absorption was only slightly reduced, most likely due to a deeper penetration of light into the canopy space. As a consequence, canopy-scale gross primary production and ecosystem respiration were comparable between the Chl-deficient mutant and the green variety. However, total biomass production was lower in the mutant, which indicates that processes other than steady state photosynthesis caused a reduction in biomass accumulation over time. Analysis of non-photochemical quenching relaxation and gas exchange in Chl-deficient and green leaves after transitions from high to low light conditions suggested that dynamic photosynthesis might be responsible for the reduced biomass production in the Chl-deficient mutant under field conditions. © 2018 John Wiley & Sons Ltd.

Reduction of radio-contamination of vines by the method of 'non-lethal defoliation'

International Nuclear Information System (INIS)

Arapis, G.

1998-01-01

This study is included in the European Commission Programme RESSAC (Rehabilitation of Soils and Surfaces after a nuclear Accident). Its objective is to investigate the possibility of using 'non-lethal defoliation' as a countermeasure to mitigate the foliar uptake of radionuclides by plant leaves. We experimented on vines in productive agricultural fields in Spata - Attica, Greece. Interception factors and translocation of radionuclides studies were performed by using 134 Cs as marker. The deposition of 134 Cs was dry. Two pesticides, Harvade 60% FL and Basta 20 S.L., were used as defoliants. Our data showed that the recommended commercial doses of these chemicals resulted in defoliating up to 80% of the plants. We observed a reduction of radioactivity translocation to grapes by half, related to the defoliating degree. The efficacy of Harvade seemed higher than that of Basta. (authors)

Photochemical oxidants injury in rice plants. III. Effect of ozone on physiological activities in rice plants

Energy Technology Data Exchange (ETDEWEB)

Nakamura, H; Saka, H

1978-01-01

Experiments were made to determine the effect of photochemical oxidants on physiological activities of rice plants. Rice plants were fumigated with ozone at concentrations of 0.12-0.20 ppm for 2-3 hr to investigate acute injury and at 0.05 and 0.09 ppm for daily exposure from 3.0 leaf stage to assess the effect of ozone on growth. It was observed that malondialdehyde produced by disruption of the components of the membrane increased in the leaves exposed to ozone. Ozone reduced the RuBP-carboxylase activity in both young and old leaves 12-24 hr after fumigation. In the young leaves the activity of this enzyme recovered to some extent after 48 hr, but it did not show any recovery in the old leaves. On the other hand, ozone remarkably increased the peroxidase activity and slightly increased acid phosphatase in all leaves. Abnormally high ethylene evolution and oxygen uptake were detected in leaves soon after ozone fumigation. In general, high molecular protein and chlorophyll contents in the detached leaves decreased with incubation in dark, particularly in the old ones. These phenomena were more accelerated by ozone fumigation. Kinetin and benzimidazole showed significant effects on chlorophyll retention in ozone-exposed leaves. Reduction of plant growth and photosynthetic rate was recognized even in low concentration of ozone in daily exposure at 0.05 and 0.09 ppm. From these results it was postulated that ozone may cause the senescence of leaves in rice plants.

Photochemical stability of random poly(3-hexylthiophene-co-3-cyanothiophene) and its use in roll coated ITO-free organic photovoltaics

DEFF Research Database (Denmark)

Roth, Bérenger; Rudenko, Andrey E.; Thompson, Barry C.

2015-01-01

The photochemical stability of the active layer blend for organic solar cells was explored by introducing electron withdrawing cyano groups into the backbone of poly-3-hexylthiophene (P3HT). Random copolymerization of 2-bromo-3-hexyl-5-trimethylstannylthiophene and 2-bromo-3-cyano-5-trimethylstan...

Catalytic/non-catalytic combination process for nitrogen oxides reduction

International Nuclear Information System (INIS)

Luftglass, B.K.; Sun, W.H.; Hofmann, J.E.

1992-01-01

This patent describes a process for the reduction of nitrogen oxides in the effluent from the combustion of a carbonaceous fuel. It comprises introducing a nitrogenous treatment agent comprising urea, one or more of the hydrolysis products of urea, ammonia, compounds which produce ammonia as a by-product, ammonium salts of organic acids, 5- or 6-membered heterocyclic hydrocarbons having at least one cyclic nitrogen, hydroxy amino hydrocarbons, or mixtures thereof into the effluent at an effluent temperature between about 1200 degrees F and about 2100 degrees F; and contacting the treated effluent under conditions effective to reduce the nitrogen oxides in the effluent with a catalyst effective for the reduction of nitrogen oxides in the presence of ammonia

Photochemical surface modification of PP for abrasion resistance

International Nuclear Information System (INIS)

Bahners, Thomas; Haessler, Ruediger; Gao Shanglin; Maeder, Edith; Wego, Andreas; Schollmeyer, Eckhard

2009-01-01

The potential of a photo-chemical approach to increase the surface hardness of polypropylene (PP) has been studied. Using a 222 nm excimer lamp, fibers and film were irradiated in the presence of multi-functional substances diallylphthalate (DAP), tetraallyloxyethane (TAE), and pentaerithritoltriacylate (PETA) and characterized with regard to the resulting effect on abrasion resistance. AFM-based methods were employed to analyze thermo-mechanical surface properties. Nanoindentation and microthermal analyses of the outermost surface layers of UV treated fibers gave clear indications of an effective cross-linking of reactive substances present during irradiation. One may assume that the reactive media polymerize on top of the surface of the PP substrate and form a thin-layer. The abrasion resistance of the PP fibers was tested by applying stress through a rotating and axially oscillating roller of defined roughness and measuring the mass loss as a function of time. The abrasion resistance was found to be remarkably improved compared to the untreated fiber. Best effects were achieved using PETA as reactive substance. The experiments clearly showed the influence of processing conditions, namely with regard to homogeneous coverage of the substrate surface with the reactive medium.

[Sequential degradation of p-cresol by photochemical and biological methods].

Science.gov (United States)

Karetnikova, E A; Chaĭkovskaia, O N; Sokolova, I V; Nikitina, L I

2008-01-01

Sequential photo- and biodegradation of p-cresol was studied using a mercury lamp, as well as KrCl and XeCl excilamps. Preirradiation of p-cresol at a concentration of 10(-4) M did not affect the rate of its subsequent biodegradation. An increase in the concentration of p-cresol to 10(-3) M and in the duration preliminary UV irradiation inhibited subsequent biodegradation. Biodegradation of p-cresol was accompanied by the formation of a product with a fluorescence maximum at 365 nm (lambdaex 280 nm), and photodegradation yielded a compound fluorescing at 400 nm (lambdaex 330 nm). Sequential UV and biodegradation led to the appearance of bands in the fluorescence spectra that were ascribed to p-cresol and its photolysis products. It was shown that sequential use of biological and photochemical degradation results in degradation of not only the initial toxicant but also the metabolites formed during its biodegradation.

Rhodium-Coordinated Poly(arylene-ethynylene)-alt-Poly(arylene-vinylene) Copolymer Acting as Photocatalyst for Visible-Light-Powered NAD+/NADH Reduction

Science.gov (United States)

2014-01-01

A 2,2′-bipyridyl-containing poly(arylene-ethynylene)-alt-poly(arylene-vinylene) polymer, acting as a light-harvesting ligand system, was synthesized and coupled to an organometallic rhodium complex designed for photocatalytic NAD+/NADH reduction. The material, which absorbs over a wide spectral range, was characterized by using various analytical techniques, confirming its chemical structure and properties. The dielectric function of the material was determined from spectroscopic ellipsometry measurements. Photocatalytic reduction of nucleotide redox cofactors under visible light irradiation (390–650 nm) was performed and is discussed in detail. The new metal-containing polymer can be used to cover large surface areas (e.g. glass beads) and, due to this immobilization step, can be easily separated from the reaction solution after photolysis. Because of its high stability, the polymer-based catalyst system can be repeatedly used under different reaction conditions for (photo)chemical reduction of NAD+. With this concept, enzymatic, photo-biocatalytic systems for solar energy conversion can be facilitated, and the precious metal catalyst can be recycled. PMID:25130570

Discrete Routh reduction

International Nuclear Information System (INIS)

Jalnapurkar, Sameer M; Leok, Melvin; Marsden, Jerrold E; West, Matthew

2006-01-01

This paper develops the theory of Abelian Routh reduction for discrete mechanical systems and applies it to the variational integration of mechanical systems with Abelian symmetry. The reduction of variational Runge-Kutta discretizations is considered, as well as the extent to which symmetry reduction and discretization commute. These reduced methods allow the direct simulation of dynamical features such as relative equilibria and relative periodic orbits that can be obscured or difficult to identify in the unreduced dynamics. The methods are demonstrated for the dynamics of an Earth orbiting satellite with a non-spherical J 2 correction, as well as the double spherical pendulum. The J 2 problem is interesting because in the unreduced picture, geometric phases inherent in the model and those due to numerical discretization can be hard to distinguish, but this issue does not appear in the reduced algorithm, where one can directly observe interesting dynamical structures in the reduced phase space (the cotangent bundle of shape space), in which the geometric phases have been removed. The main feature of the double spherical pendulum example is that it has a non-trivial magnetic term in its reduced symplectic form. Our method is still efficient as it can directly handle the essential non-canonical nature of the symplectic structure. In contrast, a traditional symplectic method for canonical systems could require repeated coordinate changes if one is evoking Darboux' theorem to transform the symplectic structure into canonical form, thereby incurring additional computational cost. Our method allows one to design reduced symplectic integrators in a natural way, despite the non-canonical nature of the symplectic structure

Breast cancer prevention knowledge, beliefs, and information sources between non-Hispanic and Hispanic college women for risk reduction focus.

Science.gov (United States)

Kratzke, Cynthia; Amatya, Anup; Vilchis, Hugo

2015-02-01

Although growing research focuses on breast cancer screenings, little is known about breast cancer prevention with risk reduction awareness for ethnic differences among college-age women. This study examined breast cancer prevention knowledge, beliefs, and information sources between non-Hispanic and Hispanic college women. Using a cross-sectional study, women at a university in the Southwest completed a 51-item survey about breast cancer risk factors, beliefs, and media and interpersonal information sources. The study was guided by McGuire's Input Output Persuasion Model. Of the 546 participants, non-Hispanic college women (n = 277) and Hispanic college women (n = 269) reported similar basic knowledge levels of modifiable breast cancer risk factors for alcohol consumption (52 %), obesity (72 %), childbearing after age 35 (63 %), and menopausal hormone therapy (68 %) using bivariate analyses. Most common information sources were Internet (75 %), magazines (69 %), provider (76 %) and friends (61 %). Least common sources were radio (44 %), newspapers (34 %), and mothers (36 %). Non-Hispanic college women with breast cancer family history were more likely to receive information from providers, friends, and mothers. Hispanic college women with a breast cancer family history were more likely to receive information from their mothers. Breast cancer prevention education for college women is needed to include risk reduction for modifiable health behavior changes as a new focus. Health professionals may target college women with more information sources including the Internet or apps.

Photochemical stability of conjugated polymers, electron acceptors and blends for polymer solar cells resolved in terms of film thickness and absorbance

DEFF Research Database (Denmark)

Tromholt, Thomas; Vesterager Madsen, Morten; Carlé, Jon Eggert

2012-01-01

Photochemical degradation at 1 sun under AM1.5G illumination was performed on six conjugated polymers and five different electron acceptors. Additionally, the respective polymer:PC60BM and P3HT:electron acceptor blends were studied, and all degradations were resolved in terms of film thickness...... within each material group were found to vary for both the pure polymers and the blends. The stability ranking between the materials of the pure polymers was found to be similar to the ranking for their respective blends, implying that the photochemical stability of a pure polymer is a good measure...... of its associated blend stability. Different electron acceptors were found to stabilize P3HT decreasingly with decreasing donor–acceptor LUMO–LUMO gap. Destabilization of P3HT was observed in the case of the electron acceptor ICBA. Additionally, the decreased stabilization of P3HT by high LUMO electron...

Reduction of nitric oxide level enhances the radiosensitivity of hypoxic non-small cell lung cancer

International Nuclear Information System (INIS)

Saleem, Wael; Suzuki, Yoshiyuki; Mobaraki, Abdulelah; Yoshida, Yukari; Noda, Shinei; Saitoh, Jun-ichi; Nakano, Takashi

2011-01-01

The epidermal growth factor receptor (EGFR) tyrosine kinase inhibitor (E-TKI) resistance has emerged as an important clinical issue. To overcome this resistance, researchers have examined different modalities, either for use as a monotherapy or in combination with E-TKI therapy. In the present study, we investigated whether a decrease in nitric oxide (NO) levels affects the radiosensitization of non-small cell lung cancer (NSCLC) cell lines. A549 and H3255 NSCLC cells were examined. They were subjected to hypoxic conditions and monotherapy, or combined therapy using radiation and N G -monomethyl- L -arginine, monoacetate (LNMMA). Reductions in nitric oxide levels enhanced the radiosensitivity of both cell lines and significantly reduced the expression of both hypoxia-inducible factor-1α (HIF-1α) and EGFR in H3255 cells compared to A549 cells. Since NO is significantly associated with cell metabolism, we measured the levels of pyruvate dehydrogenase kinase-1 (PDK-1), reactive oxygen species, and oxygen and observed that the expression of PDK-1 was significantly reduced. This reduction was seen simultaneously after the silencing of HIF-1α; however, not following LNMMA treatment. The oxygen concentration was significantly increased in the treated cells, and their viability decreased in parallel. Reactive oxygen species were decreased after LNMMA and radiation treatment. Adding EGFR-TKI to cells with reduced NO levels further suppressed cell viability when combined with radiation. This study suggests that a reduction in the NO level might substantially overcome the radioresistance of mutant NSCLC cells. (author)

Generating and measuring photochemical changes inside the brain using optical fibers: exploring stroke.

Science.gov (United States)

Tsiminis, Georgios; Klarić, Thomas S; Schartner, Erik P; Warren-Smith, Stephen C; Lewis, Martin D; Koblar, Simon A; Monro, Tanya M

2014-11-01

We report here on the development of a method for inducing a stroke in a specific location within a mouse brain through the use of an optical fiber. By capturing the emitted fluorescence signal generated using the same fiber it is possible to monitor photochemical changes within the brain in real-time, and directly measure the concentration of the stroke-inducing dye, Rose Bengal, at the infarct site. This technique reduces the requirement for post-operative histology to determine if a stroke has successfully been induced within the animal, and therefore opens up the opportunity to explore the recovery of the brain after the stroke event.

The kinetics of the photochemical reaction cycle of deuterated bacteriorhodopsin and pharaonis halorhodopsin

International Nuclear Information System (INIS)

Szakacs, Julianna; Lakatos, Melinda; Varo, Gy.; Ganea, Constanta

2005-01-01

Kinetic isotope effects in the photochemical reaction cycle of bacteriorhodopsin and pharaonis halorhodopsin were determined in H 2 O and D 2 O at normal pH, to get insight in the proton dependent steps of the transport process. All the steps of the bacteriorhodopsin photocycle at normal pH exhibited a strong isotope effect. In the case of halorhodopsin in both the chloride and nitrate transporting conditions the photocycle was not strongly affected by the deuterium exchange. In the case of chloride, a slight slow down of the photocycle could be observed. On the opposite, in the nitrate transport conditions a reverse effect is present. (author)

Photochemical ozone production in tropical squall line convection during NASA Global Tropospheric Experiment/Amazon Boundary Layer Experiment 2A

Science.gov (United States)

Pickering, Kenneth E.; Thompson, Anne M.; Tao, Wei-Kuo; Simpson, Joanne; Scala, John R.

1991-01-01

The role of convection was examined in trace gas transport and ozone production in a tropical dry season squall line sampled on August 3, 1985, during NASA Global Tropospheric Experiment/Amazon Boundary Layer Experiment 2A (NASA GTE/ABLE 2A) in Amazonia, Brazil. Two types of analyses were performed. Transient effects within the cloud are examined with a combination of two-dimensional cloud and one-dimensional photochemical modeling. Tracer analyses using the cloud model wind fields yield a series of cross sections of NO(x), CO, and O3 distribution during the lifetime of the cloud; these fields are used in the photochemical model to compute the net rate of O3 production. At noon, when the cloud was mature, the instantaneous ozone production potential in the cloud is between 50 and 60 percent less than in no-cloud conditions due to reduced photolysis and cloud scavenging of radicals. Analysis of cloud inflows and outflows is used to differentiate between air that is undisturbed and air that has been modified by the storm. These profiles are used in the photochemical model to examine the aftereffects of convective redistribution in the 24-hour period following the storm. Total tropospheric column O3 production changed little due to convection because so little NO(x) was available in the lower troposphere. However, the integrated O3 production potential in the 5- to 13-km layer changed from net destruction to net production as a result of the convection. The conditions of the August 3, 1985, event may be typical of the early part of the dry season in Amazonia, when only minimal amounts of pollution from biomass burning have been transported into the region.

Aqueous-phase photochemical oxidation and direct photolysis of vanillin - a model compound of methoxy phenols from biomass burning

Science.gov (United States)

Li, Y. J.; Huang, D. D.; Cheung, H. Y.; Lee, A. K. Y.; Chan, C. K.

2014-03-01

We present here experimental results on aqueous-phase (A) photochemical oxidation (with UV and OH radicals generated from H2O2 photolysis) and (B) direct photolysis (with only UV irradiation) of a methoxy phenol, vanillin (VL), as a model compound from biomass burning. Both on-line aerosol mass spectrometric (AMS) characterization and off-line chemical analyses were performed. AMS analyses of dried atomized droplets of the bulk reacting mixtures showed that VL almost entirely evaporates during the drying process. Large amounts of organic mass remained in the particle phase after reactions under both conditions. Under condition (A), AMS measured organic mass first increased rapidly and then decreased, attributable to the formation of non-volatile products and subsequent formation of smaller and volatile products, respectively. The oxygen-to-carbon (O : C) ratio of the products reached 1.5 after about 80 min, but dropped substantially thereafter. In contrast, organic mass increased slowly under condition (B). The O : C ratio reached 1.0 after 180 min. In off-line analyses, small oxygenates were detected under condition (A), while hydroxylated products and dimers of VL were detected under condition (B). Particle hygroscopic growth factor (GF) and cloud condensation nuclei (CCN) activity of the reacting mixtures were found to depend on both organic volume fraction and the degree of oxygenation of organics. Results show that (1) aqueous-phase processes can lead to the retention of a large portion of the organic mass in the particle phase; (2) once retained, this portion of organic mass significantly changes the hygroscopicity and CCN activity of the aerosol particles; (3) intensive photochemical oxidation gave rise to an O : C ratio as high as 1.5 but the ratio decreased as further oxidation led to smaller and more volatile products; and (4) polymerization occurred with direct photolysis, resulting in high-molecular-weight products of a yellowish color. This study

Aqueous-phase photochemical oxidation and direct photolysis of vanillin - a model compound of methoxy-phenols from biomass burning

Science.gov (United States)

Li, Y. J.; Huang, D. D.; Cheung, H. Y.; Lee, A. K. Y.; Chan, C. K.

2013-10-01

We present here experimental results on aqueous-phase (A) photochemical oxidation (with UV and OH radicals generated from H2O2 photolysis) and (B) direct photolysis (with only UV irradiation) of a methoxy-phenol, vanillin (VL), as a model compound from biomass burning. Both on-line aerosol mass spectrometric (AMS) characterization and off-line chemical analyses were performed. AMS analyses of dried atomized droplets of the bulk reacting mixtures showed that VL almost entirely evaporates during the drying process. Large amounts of organic mass remained in the particle phase after reactions under both conditions. Under condition (A), AMS measured organic mass first increased rapidly and then decreased, attributable to the formation of non-volatile products and subsequent formation of smaller and volatile products, respectively. The oxygen-to-carbon (O:C) ratio of the products reached 1.5 after about 80 min, but dropped substantially thereafter. In contrast, organic mass increased slowly under condition (B). The O:C ratio reached 1.0 after 180 min. In off-line analyses, small oxygenates were detected under condition (A), while hydroxylated products and dimers of VL were detected under condition (B). Particle hygroscopic growth factor (GF) and cloud condensation nuclei (CCN) activity of the reacting mixtures were found to be dependent on both organic volume fraction and the degree of oxygenation of organics. Results show that (1) aqueous-phase processes can lead to the retention of a large portion of the organic mass in the particle phase; (2) once retained, this portion of organic mass significantly changes the hygroscopicity and CCN activity of the aerosol particles; (3) intensive photochemical oxidation gave rise to an O:C ratio as high as 1.5 but the ratio decreased as further oxidation led to smaller and more volatile products; and (4) polymerization occurred with direct photolysis, resulting in high-molecular-weight products of a yellowish color. This study

An optimal photochemical energy conversion and environmental effects in the reactive molecular dynamics; Optimale Photochemische Energiekonversion und Umgebungseffekte in Reaktiver Molekueldynamik

Energy Technology Data Exchange (ETDEWEB)

Fingerhut, Benjamin Philipp

2011-02-08

One of the main challenges in photochemical energy conversion is the design of charge separating units which are able to generate a long lived charge separated state, and to couple efficiently to an energy storage state. In part I of this work the energy conversion efficiency of a photochemical unit inspired by bacterial photosynthesis is investigated. The developed model is based on non-adiabatic multi step electron transfer to generate a trans-membrane potential gradient. Upon optimization with multi objective genetic algorithms, the biological strategies for high quantum efficiency in photosynthetic reaction centers are derived, which have to suppress loss channels such as charge recombination. The concepts of bacterial photosynthesis are extended to the design of artificial photochemical devices. The unified model consists of a charge separation unit and an energy storing system whereby the coupling between both units is assured by thermal repopulation according to the principle of detailed balance. The complete photosynthetic unit is characterized by the respective current-voltage relation and an upper limit for the overall energy efficiency is derived under AM1.5 global conditions. Such a realistic chemical solar energy conversion system can reach efficiencies, which are comparable to the limits of an ideal single-junction solar cell. In Part II of this work the reactive dynamics of two surrounding controlled photoreactions is investigated on a microscopic scale. In general the effect of the surrounding can be classified into intramolecular contributions, like steric or electronic effects, and intermolecular contributions like the solvent or the embedding in an enzyme. Both limiting cases are examined on the basis of two generic photoreactions. The Dewar DNA lesion follows quantitatively from the 6-4 lesion by UV-A/B irradiation and constitutes the stable end product of continuous solar irradiation. Here the detailed mechanism of the formally 4{pi

Sources and Potential Photochemical Roles of Formaldehyde in an Urban Atmosphere in South China

Science.gov (United States)

Wang, Chuan; Huang, Xiao-Feng; Han, Yu; Zhu, Bo; He, Ling-Yan

2017-11-01

Formaldehyde (HCHO) is an important intermediate in tropospheric photochemistry. However, study of its evolution characteristics under heavy pollution conditions in China is limited, especially for high temporal resolutions, making it difficult to analyze its sources and environmental impacts. In this study, ambient levels of HCHO were monitored using a proton-transfer reaction mass spectrometer at an urban site in the Pearl River Delta of China. Continuous monitoring campaigns were conducted in the spring, summer, fall, and winter in 2016. The highest averaged HCHO concentrations were observed in autumn (5.1 ± 3.1 ppbv) and summer (5.0 ± 4.4 ppbv), followed by winter (4.2 ± 2.2 ppbv) and spring (3.4 ± 1.6 ppbv). The daily maximum of HCHO occurs in the early afternoon and shows good correlations with O3 and the secondary organic aerosol tracer during the day, revealing close relationships between ambient HCHO and secondary formations in Shenzhen, especially in summer and autumn. The daytime HCHO is estimated to be the major contributor to O3 formation and OH radical production, indicating that HCHO plays a key role in the urban atmospheric photochemical reactions. Anthropogenic secondary formation was calculated to be the dominant source of HCHO using a photochemical age-based parameterization method, with an average proportion of 39%. The contributions of biogenic sources in summer (41%) and autumn (39%) are much higher than those in spring (26%) and winter (28%), while the contributions of anthropogenic primary sources in spring (20%) and winter (18%) are twice those in summer (9%) and autumn (9%).

Photochemical and photocatalytic evaluation of 1D titanate/TiO{sub 2} based nanomaterials

Energy Technology Data Exchange (ETDEWEB)

Conceição, D.S.; Ferreira, D.P. [Centro de Química-Física Molecular and IN-Institute of Nanoscience and Nanotechnology Instituto Superior Técnico, Universidade de Lisboa Av. Rovisco Pais, 1049-001 Lisboa (Portugal); Graça, C.A.L. [Universidade de São Paulo, Avenida Prof. Luciano Gualberto, tr. 3, 380 São Paulo (Brazil); Júlio, M.F.; Ilharco, L.M. [Centro de Química-Física Molecular and IN-Institute of Nanoscience and Nanotechnology Instituto Superior Técnico, Universidade de Lisboa Av. Rovisco Pais, 1049-001 Lisboa (Portugal); Velosa, A.C. [Instituto Nacional de Tecnologia, Av. Venezuela 82, Rio de Janeiro (Brazil); Santos, P.F. [Centro de Química, Vila Real Universidade de Trás-os-Montes e Alto Douro, 5001-801 Vila Real (Portugal); Vieira Ferreira, L.F., E-mail: lfvieiraferreira@tecnico.ulisboa.pt [Centro de Química-Física Molecular and IN-Institute of Nanoscience and Nanotechnology Instituto Superior Técnico, Universidade de Lisboa Av. Rovisco Pais, 1049-001 Lisboa (Portugal)

2017-01-15

Highlights: • 1D titanate based nanomaterials were prepared via a hydrothermal approach. • The structural and photochemical evaluation of the nanomaterials was performed. • A fluorescent dye was used as a surface probe in visible excitation conditions. • Amicarbazone was used as the model contaminant for photodegradation studies. - Abstract: One-dimensional (1D) titanate based nanomaterials were synthesized following an alkaline hydrothermal approach of commercial TiO{sub 2} nanopowder. The morphological features of all materials were monitored by means of scanning electron microscopy (SEM), transmission electron microscopy (TEM), and also Brunauer-Emmett-Teller (BET) technique. In addition the photochemical behaviour of these nanostructured materials were evaluated with the use of laser induced luminescence (LIL), ground-state diffuse reflectance (GSDR), and laser-flash photolysis in diffuse reflectance mode (DRLFP). The mixed titanate/TiO{sub 2} nanowires presented the least intense fluorescence spectra, suggesting the presence of surficial defects that can extend the lifetime of the excited charge carriers. A fluorescent ‘rhodamine-like’ dye was adsorbed onto different materials and examined via photoexcitation in the visible range to study the self-photosensitization mechanism. The presence of the radical cation of the dye and the degradation kinetics, when compared with a neutral substrate—cellulose, provided significant evidences regarding the photoactivity of the different materials. Regarding all the materials under study, the nanowires exhibited a strong photocatalytic efficiency, for the adsorbed fluorescent probe. The photocatalytic mechanism was also considered by studying the photodegradation capability of the titanate based materials in the presence of an herbicide, Amicarbazone, after ultraviolet (UVA) photoexcitation.

Selective laser-induced photochemical dry etching of semiconductors controlled by ion-bombardment-induced damage

International Nuclear Information System (INIS)

Ashby, C.I.H.; Myers, D.R.; Vook, F.L.

1987-01-01

When a photochemical dry etching process requires direct participation of photogenerated carriers in the chemical reaction, it is sensitive to the electronic properties of the semiconductor. For such solid-excitation-based dry etching processes, the balance between reaction and carrier recombination rates determines the practical utility of a particular reaction for device fabrication. The distance from the surface at which the photocarriers are generated by light adsorption is determined by the absorption coefficient. In the absence of an external bias potential, only those carriers formed within a diffusion length of the surface space-charge region will have an opportunity to drive the dry etching reaction. When the absorption coefficient is high, most of the photons generate carriers within a diffusion length from the surface space-charge region, and the etching rate is largely determined by the balance between the rate of the carrier-driven reaction and the surface recombination velocity. When the recombination rate of free carriers in the bulk of the semiconductor is high, the effective diffusion length is reduced and fewer of the carriers generated in the subsurface region ever reach the surface. An important effect of ion bombardment is the creation of many lattice defects that increase the rate of recombination of electrons and holes. When a sufficient number of defects, which act as recombination sites, are formed during ion implantation, the recombination of photogenerated carriers at these defects in the subsurface region can greatly reduce the number of carriers which can reach the surface and drive a photochemical etching reaction

Instantaneous global nitrous oxide photochemical rates

International Nuclear Information System (INIS)

Johnston, H.S.; Serang, O.; Podolske, J.

1979-01-01

In recent years, vertical profiles of nitrous oxide have been measured by balloon up to midstratosphere at several latitudes between 63 0 N and 73 0 S, including one profile in the tropical zone at 9 0 N. Two rocket flights measured nitrous oxide mixing ratios at 44 and 49 km. From these experimental data plus a large amount of interpolation and extrapolation, we have estimated a global distribution of nitrous oxide up to the altitude of 50 km. With standard global distributions of oxygen and ozone we carried out instantaneous, three-dimensional, global photochemical calculations, using recently measured temperature-dependent cross sections for nitrous oxide. The altitude of maximum photolysis rate of N 2 O is about 30 km at all latitudes, and the rate of photolysis is a maximum in tropical latitudes. The altitude of maximum rate of formation of nitric oxide is latitude dependent, about 26 km at the equator, about 23 km over temperate zones, and 20 km at the summer pole. The global rate of N 2 O destruction is 6.2 x 10 27 molecules s -1 , and the global rate of formation of NO from N 2 O is 1.4 x 10 27 molecules s -1 . The global N 2 O inventory divided by the stratospheric loss rate gives a residence time of about 175 years with respect to this loss process. From the global average N 2 O profile a vertical eddy diffusion profile was derived, and this profile agrees very closely with that of Stewart and Hoffert

QSARs for phenols and phenolates: oxidation potential as a predictor of reaction rate constants with photochemically produced oxidants.

Science.gov (United States)

Arnold, William A; Oueis, Yan; O'Connor, Meghan; Rinaman, Johanna E; Taggart, Miranda G; McCarthy, Rachel E; Foster, Kimberley A; Latch, Douglas E

2017-03-22

Quantitative structure-activity relationships (QSARs) for prediction of the reaction rate constants of phenols and phenolates with three photochemically produced oxidants, singlet oxygen, carbonate radical, and triplet excited state sensitizers/organic matter, are developed. The predictive variable is the one-electron oxidation potential (E 1 ), which is calculated for each species using density functional theory. The reaction rate constants are obtained from the literature, and for singlet oxygen, are augmented with new experimental data. Calculated E 1 values have a mean unsigned error compared to literature values of 0.04-0.06 V. For singlet oxygen, a single linear QSAR that includes both phenols and phenolates is developed that predicts experimental rate constants, on average, to within a factor of three. Predictions for only 6 out of 87 compounds are off by more than a factor of 10. A more limited data set for carbonate radical reactions with phenols and phenolates also gives a single linear QSAR with prediction of rate constant being accurate to within a factor of three. The data for the reactions of phenols with triplet state sensitizers demonstrate that two sensitizers, 2-acetonaphthone and methylene blue, most closely predict the reactivity trend of triplet excited state organic matter with phenols. Using sensitizers with stronger reduction potentials could lead to overestimation of rate constants and thus underestimation of phenolic pollutant persistence.

Photochirogenesis: Photochemical Models on the Origin of Biomolecular Homochirality

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Cornelia Meinert

2010-05-01

Full Text Available Current research focuses on a better understanding of the origin of biomolecular asymmetry by the identification and detection of the possibly first chiral molecules that were involved in the appearance and evolution of life on Earth. We have reasons to assume that these molecules were specific chiral amino acids. Chiral amino acids have been identified in both chondritic meteorites and simulated interstellar ices. Present research reasons that circularly polarized electromagnetic radiation was identified in interstellar environments and an asymmetric interstellar photon-molecule interaction might have triggered biomolecular symmetry breaking. We review on the possible prebiotic interaction of ‘chiral photons’ in the form of circularly polarized light, with early chiral organic molecules. We will highlight recent studies on enantioselective photolysis of racemic amino acids by circularly polarized light and experiments on the asymmetric photochemical synthesis of amino acids from only one C and one N containing molecules by simulating interstellar environments. Both approaches are based on circular dichroic transitions of amino acids that will be presented as well.

Potential of plug-in hybrid electric vehicle for reduction of CO2 emission and role of non-fossil power plant

International Nuclear Information System (INIS)

Hiwatari, R.; Okano, K.; Yamamoto, H.

2009-01-01

A method to analyze the demand of electricity and the reduction of CO 2 emission and oil consumption by PHEV is established. Using the performance of PHEV optimized by EPRI and an estimation on the pattern of driving and charging in Japan, the following results are obtained. The electric demand for PHEV60(which has 60mile EV range) and PHEV20(which has 20mile EV range) is evaluated at 79.3 billion kWh and 41.2 billion kWh, respectively, in case that all vehicles in Japan (80 million cars) would be replaced by PHEV. The load leveling effect on the Japanese grid, which is hypothetically considered as one electric grid system, is evaluated at about 30 million kW, in case that all vehicles in Japan are replaced by PHEV60 and charged in the midnight. However, when the charge of PHEVs starts in the evening, that effect is not obtained. The reduction of CO 2 emission results in 64 million ton by the averaged CO 2 emissions intensity (emissions per unit of user end electricity) in Japan, and 98 million ton by electricity from the non-fossil power plant such as nuclear energy or renewable one. Those values are equivalent to 25% and 38% of CO 2 emission from the transport sector in Japan in 2003. Hence, non-fossil power plant enhances the reduction of CO 2 emission by the PHEV introduction. (author)

Environmental and economic evaluation of selective non-catalytic reduction of nitrogen oxides

Science.gov (United States)

Parchevskii, V. M.; Shchederkina, T. E.; Proshina, A. O.

2017-11-01

There are two groups of atmosphere protecting measures: technology (primary) and treatment (secondary). When burning high-calorie low-volatile brands of coals in the furnaces with liquid slag removal to achieve emission standards required joint use of these two methods, for example, staged combustion and selective non-catalytic reduction recovery (SNCR). For the economically intelligent combination of these two methods it is necessary to have information not only about the environmental performance of each method, but also the operating costs per unit of reduced emission. The authors of this report are made an environmental-economic analysis of SNCR on boiler Π-50P Kashirskaya power station. The obtained results about the dependence of costs from the load of the boiler and the mass emissions of nitrogen oxides then approximates into empirical formulas, is named as environmental and economic characteristics, which is suitable for downloading into controllers and other control devices for subsequent implementation of optimal control of emissions to ensure compliance with environmental regulations at the lowest cost at any load of the boiler.

Chemical and photochemical properties of a ruthenium nitrosyl complex with the N-monosubstituted cyclam 1-(3-Propylammonium)-1,4,8,11-tetraazacyclotetradecane

International Nuclear Information System (INIS)

Ferreira, Kleber Q.; Tfouni, Elia

2010-01-01

The amine-functionalized trans-[Ru(NO)Cl(1-pramcyH)](PF 6 ) 3 complex (1-pramcyH = 1-(3-propylammonium)-1,4,8,11-tetraazacyclotetradecane) was synthesized from trans-[Ru Cl(tfms) (1-pramcyH)](tfms) 2 (tfms trifluoromethanesulfonate) in acidic aqueous solution in the presence of nitric oxide (NO). The complex was characterized by elemental, spectroscopic (UV-Vis, IR, 1 H and 13 C NMR) and electrochemical analyses. Two pKa values (7.0 and 8.2) were estimated for trans-[Ru(NO)Cl(1-pramcyH)](PF 6 ) 3 and were assigned to one of the cyclam nitrogen protons and to the protonated aminopropyl group. Reduction of trans-[Ru(NO)Cl(1-pramcyH)] 3+ results in rapid loss of chloride followed by slower loss of NO, while irradiation of the complex in aqueous deaerated conditions suggests photochemical labilization of NO. The quantum yields for NO photoaquation decrease as the irradiation wavelength increases, being noticeable only at λ irr 3+ , which contains an aminopropyl substituted cyclam, parallels that reported for the analogous complex with the unsubstituted ligand, but differs from that described for the complex in which carboxypropyl is the substituent. (author)

Photoclickable dendritic molecular glue: noncovalent-to-covalent photochemical transformation of protein hybrids.

Science.gov (United States)

Uchida, Noriyuki; Okuro, Kou; Niitani, Yamato; Ling, Xiao; Ariga, Takayuki; Tomishige, Michio; Aida, Takuzo

2013-03-27

A water-soluble dendron with a fluorescein isothiocyanate (FITC) fluorescent label and bearing nine pendant guanidinium ion (Gu(+))/benzophenone (BP) pairs at its periphery (Glue(BP)-FITC) serves as a "photoclickable molecular glue". By multivalent salt-bridge formation between Gu(+) ions and oxyanions, Glue(BP)-FITC temporarily adheres to a kinesin/microtubule hybrid. Upon subsequent exposure to UV light, this noncovalent binding is made permanent via a cross-linking reaction mediated by carbon radicals derived from the photoexcited BP units. This temporal-to-permanent transformation by light occurs quickly and efficiently in this preorganized state, allowing the movements of microtubules on a kinesin-coated glass plate to be photochemically controlled. A fundamental difference between such temporal and permanent bindings was visualized by the use of "optical tweezers".