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Sample records for actual photochemical efficiency

  1. Characterization of one- and two-photon photochemical uncaging efficiency.

    PubMed

    Specht, Alexandre; Bolze, Frederic; Nicoud, Jean Francois; Goeldner, Maurice

    2013-01-01

    The idea of using light to unleash biologically active compounds from inert precursors (uncaging) was introduced over 30 years ago. Recent efforts prompted the development of photoremovable protecting groups that have increased photochemical efficiencies for one- and two-photon excitation to allow more sophisticated applications. This requires characterization of one- and two-photon photochemical efficiencies of the uncaging processes.The present chapter focuses on the characterization of one-photon quantum yields and two-photon cross-sections. PMID:23494373

  2. Quantum efficiencies of bacteriorhodopsin photochemical reactions

    SciTech Connect

    Xie, A.H. )

    1990-11-01

    Determination of quantum efficiencies of bacteriorhodopsin (bR) photoreactions is an essential step toward a full understanding of its light-driven proton-pumping mechanism. The bR molecules can be photoconverted into and from a K state, which is stable at 110 K. I measured the absorption spectra of pure bR, and the photoequilibrium states of bR and K generated with 420, 460, 500, 510, 520, 540, 560, 570, 580, 590, and 600 nm illumination at 110 K. The fraction of the K population in the photoequilibrium state, fk, is determined by AbR and AK the absorbances of the bR and K states at the excitation wavelengths, and also by phi 1 and phi 2, the quantum efficiencies for the bR to K and K to bR photoconversion: fK = phi 1 AbR/(phi 1AbR + phi 2Ak). By assuming that the ratio phi 1/phi 2 is the same at two different but close wavelengths, for example 570 and 580 nm, the value of phi 1/phi 2 at 570 and 580 nm was determined to be 0.55 +/- 0.02, and the spectrum of the K state was obtained with the peak absorbance at 607 nm. The values of phi 1/phi 2 at the other excitation wavelengths were then evaluated using the known K spectrum, and show almost no dependence on the excitation wavelength within the main band. The result phi 1/phi 2 = 0.55 +/- 0.02 disagrees with those of many other groups. The advantages of this method over others are its minimal assumptions and its straightforward procedure.

  3. on the growth and photochemical efficiency of Acropora cervicornis

    NASA Astrophysics Data System (ADS)

    Enochs, I. C.; Manzello, D. P.; Carlton, R.; Schopmeyer, S.; van Hooidonk, R.; Lirman, D.

    2014-06-01

    The effects of light and elevated pCO2 on the growth and photochemical efficiency of the critically endangered staghorn coral, Acropora cervicornis, were examined experimentally. Corals were subjected to high and low treatments of CO2 and light in a fully crossed design and monitored using 3D scanning and buoyant weight methodologies. Calcification rates, linear extension, as well as colony surface area and volume of A. cervicornis were highly dependent on light intensity. At pCO2 levels projected to occur by the end of the century from ocean acidification (OA), A. cervicornis exhibited depressed calcification, but no change in linear extension. Photochemical efficiency ( F v / F m ) was higher at low light, but unaffected by CO2. Amelioration of OA-depressed calcification under high-light treatments was not observed, and we suggest that the high-light intensity necessary to reach saturation of photosynthesis and calcification in A. cervicornis may limit the effectiveness of this potentially protective mechanism in this species. High CO2 causes depressed skeletal density, but not linear extension, illustrating that the measurement of extension by itself is inadequate to detect CO2 impacts. The skeletal integrity of A. cervicornis will be impaired by OA, which may further reduce the resilience of the already diminished populations of this endangered species.

  4. Mechanistic details for cobalt catalyzed photochemical hydrogen production in aqueous solution: Efficiencies of the photochemical and non-photochemical steps

    DOE PAGESBeta

    Shan, Bing; Baine, Teera; Ma, Xuan Anh N.; Zhao, Xuan; Schmehl, Russell H.

    2013-04-17

    The use of sunlight to drive chemical reactions that lead to the reduction of water to produce hydrogen is a potential avenue of solar energy utilization. There are many individual steps that take place in this process. This paper reports the investigation of a particular system that involves light absorbing molecules, electron donating agents and a catalyst for water reduction to hydrogen. We evaluated the efficiency of the light induced formation of a strong electron donor, the use of this donor to reduce the catalyst and finally the efficiency of the catalyst to produce hydrogen from water. From this, themore » sources of loss of efficiency could be clearly identified and used in the design of better systems to produce hydrogen from water.« less

  5. Mechanistic details for cobalt catalyzed photochemical hydrogen production in aqueous solution: Efficiencies of the photochemical and non-photochemical steps

    SciTech Connect

    Shan, Bing; Baine, Teera; Ma, Xuan Anh N.; Zhao, Xuan; Schmehl, Russell H.

    2013-04-17

    The use of sunlight to drive chemical reactions that lead to the reduction of water to produce hydrogen is a potential avenue of solar energy utilization. There are many individual steps that take place in this process. This paper reports the investigation of a particular system that involves light absorbing molecules, electron donating agents and a catalyst for water reduction to hydrogen. We evaluated the efficiency of the light induced formation of a strong electron donor, the use of this donor to reduce the catalyst and finally the efficiency of the catalyst to produce hydrogen from water. From this, the sources of loss of efficiency could be clearly identified and used in the design of better systems to produce hydrogen from water.

  6. Efficiency of photochemical stages of photosynthesis in purple bacteria (a critical survey).

    PubMed

    Borisov, A Yu

    2014-03-01

    Based on currently available data, the energy transfer efficiency in the successive photophysical and photochemical stages has been analyzed for purple bacteria. This analysis covers the stages starting from migration of the light-induced electronic excitations from the bulk antenna pigments to the reaction centers up to irreversible stage of the electron transport along the transmembrane chain of cofactors-carriers. Some natural factors are revealed that significantly increase the rates of efficient processes in these stages. The influence on their efficiency by the "bottleneck" in the energy migration chain is established. The overall quantum yield of photosynthesis in these stages is determined. PMID:24821449

  7. Isoprene improves photochemical efficiency and enhances heat dissipation in plants at physiological temperatures.

    PubMed

    Pollastri, Susanna; Tsonev, Tsonko; Loreto, Francesco

    2014-04-01

    Isoprene-emitting plants are better protected against thermal and oxidative stresses. Isoprene may strengthen membranes avoiding their denaturation and may quench reactive oxygen and nitrogen species, achieving a similar protective effect. The physiological role of isoprene in unstressed plants, up to now, is not understood. It is shown here, by monitoring the non-photochemical quenching (NPQ) of chlorophyll fluorescence of leaves with chemically or genetically altered isoprene biosynthesis, that chloroplasts of isoprene-emitting leaves dissipate less energy as heat than chloroplasts of non-emitting leaves, when exposed to physiologically high temperatures (28-37 °C) that do not impair the photosynthetic apparatus. The effect was especially remarkable at foliar temperatures between 30 °C and 35 °C, at which isoprene emission is maximized and NPQ is quenched by about 20%. Isoprene may also allow better stability of photosynthetic membranes and a more efficient electron transfer through PSII at physiological temperatures, explaining most of the NPQ reduction and the slightly higher photochemical quenching that was also observed in isoprene-emitting leaves. The possibility that isoprene emission helps in removing thermal energy at the thylakoid level is also put forward, although such an effect was calculated to be minimal. These experiments expand current evidence that isoprene is an important trait against thermal and oxidative stresses and also explains why plants invest resources in isoprene under unstressed conditions. By improving PSII efficiency and reducing the need for heat dissipation in photosynthetic membranes, isoprene emitters are best fitted to physiologically high temperatures and will have an evolutionary advantage when adapting to a warming climate. PMID:24676032

  8. A novel microfluidic approach for extremely fast and efficient photochemical transformations in fluoropolymer microcapillary films.

    PubMed

    Reis, N M; Li Puma, G

    2015-05-18

    The unique optical properties of the fluoropolymer microcapillary film (MCF) material combined with the extremely fast photoinactivation of Herpes HSV-1 virus, and photodegradation of indigo carmine, diclofenac and benzoylecgonine in the MCF array photoreactor, demonstrate a new, flexible and inexpensive platform for rapid photochemical transformations, high-throughput process analytics and photochemical synthesis. PMID:25849647

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

    PubMed

    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. PMID:25149653

  10. Explaining the variability of Photochemical Reflectance Index (PRI): deconvolution of variability related to Light Use Efficiency and Canopy attributes.

    NASA Astrophysics Data System (ADS)

    Merlier, Elodie; Hmimina, Gabriel; Dufrêne, Eric; Soudani, Kamel

    2014-05-01

    The Photochemical Reflectance Index (PRI) was designed as a proxy of the state of xanthophyll cycle which is used as a response of plants to excess of light (Gamon et al., 1990; 1992). Strong relationships between PRI and LUE were shown at leaf and canopy scales and over a wide range of species (Garbulsky et al., 2011). However, its use at canopy scale was shown to be significantly hampered by effects of confounding factors such as the PRI sensitivity to leaf pigment content (Gamon et al. 2001; Nakaji et al. 2006) and to canopy structure (Hilker et al. 2008). Several approaches aimed at correcting such effects and recent works focused on the deconvolution of LUE related and LUE unrelated PRI variability (Rahimzadeh-Bajgiran et al. 2012).In this study, the PRI variability at canopy scale is investigated over two years on three species (Fagus sylvatica, Quercus robur and Pinus sylvestris) growing under two water regimes. At daily scale, PRI variability is mainly explained by radiation conditions. As already reported at leaf scale in Hmimina et al. (2014), analysis of PRI responses to incoming photosynthetically active radiation over seasonal scale allowed to separate two sources of variability : a constitutive variability mainly related to canopy structure and leaf chlorophyll content and a facultative variability mainly related to LUE and soil moisture content. These results highlight the composite nature of PRI signal measured at canopy scale and the importance of disentangling its sources of variability in order to accurately assess ecosystem light use efficiency. Gamon JA, Field CB, Bilger W, Björkman O, Fredeen AL, Peñuelas J. 1990. Remote sensing of the xanthophyll cycle and chlorophyll fluorescence in sunflower leaves and canopies. Oecologia 85, 1-7. Gamon JA, Field CB, Fredeen A AL, Thayer S. 2001. Assessing photosynthetic downregulation in sunflower stands with an optically-based model. Photosynthesis Research 67, 113-125. Gamon JA, Peñuelas J, Field CB

  11. An efficient photochemical route to Pd nanoparticles; application to the one-step synthesis of Pd@polymer nanocomposite films.

    PubMed

    Wolak, Séverine; Vidal, Loïc; Becht, Jean-Michel; Michelin, Laure; Balan, Lavinia

    2016-08-26

    We have developed a facile, efficient, low cost and 'green' photochemical approach to preparing surfactant-free Pd nanoparticles and Pd-immobilized@acrylate photo-polymer films at room temperature, under air and without any additional treatment. The reaction system only includes a photo-initiator used as a generator of free radicals and a Pd(II) salt. In ethanol solution, the photochemical reduction of Pd(II) to Pd(0) generates very small metal particles with a narrow size distribution (2-4 nm). Furthermore, we have shown that the formation of Pd nanoparticles from a Pd(II) salt can be reversible thus allowing easy handling and safe storage with the possibility of generating the nanoparticles just before use. In the presence of an acrylate bifunctional monomer, Pd@polymer film was obtained through a 'one-pot, one-step' process resulting from a simultaneous photo-reduction of Pd(II) and photo-polymerization of acrylate units. The simultaneous generation of a 3D polymer network and of metal particles leads to a homogeneous distribution of Pd nanoparticles in the photo-polymer matrix with an average diameter of approximately 3.7 ± 1.1 nm. Such as-prepared Pd@polymer films were found to efficiently catalyze the Mizoroki-Heck reaction in the presence of only 0.9 mequiv. of supported palladium. The major interest of this arrangement is its recoverability and reusability, which makes it very attractive both from a practical and economical viewpoint. Finally, it is worth noting that this innovation offers a great advantage over concurrent methods in that it is simply generated within minutes, it is highly stable, and there is sharp monodispersity in the size of the Pd nanoparticles that can be stored for months without alteration of their physico-chemical properties and catalytic activity. PMID:27418591

  12. An efficient photochemical route to Pd nanoparticles; application to the one-step synthesis of Pd@polymer nanocomposite films

    NASA Astrophysics Data System (ADS)

    Wolak, Séverine; Vidal, Loïc; Becht, Jean-Michel; Michelin, Laure; Balan, Lavinia

    2016-08-01

    We have developed a facile, efficient, low cost and ‘green’ photochemical approach to preparing surfactant-free Pd nanoparticles and Pd-immobilized@acrylate photo-polymer films at room temperature, under air and without any additional treatment. The reaction system only includes a photo-initiator used as a generator of free radicals and a Pd(II) salt. In ethanol solution, the photochemical reduction of Pd(II) to Pd(0) generates very small metal particles with a narrow size distribution (2–4 nm). Furthermore, we have shown that the formation of Pd nanoparticles from a Pd(II) salt can be reversible thus allowing easy handling and safe storage with the possibility of generating the nanoparticles just before use. In the presence of an acrylate bifunctional monomer, Pd@polymer film was obtained through a ‘one-pot, one-step’ process resulting from a simultaneous photo-reduction of Pd(II) and photo-polymerization of acrylate units. The simultaneous generation of a 3D polymer network and of metal particles leads to a homogeneous distribution of Pd nanoparticles in the photo-polymer matrix with an average diameter of approximately 3.7 ± 1.1 nm. Such as-prepared Pd@polymer films were found to efficiently catalyze the Mizoroki–Heck reaction in the presence of only 0.9 mequiv. of supported palladium. The major interest of this arrangement is its recoverability and reusability, which makes it very attractive both from a practical and economical viewpoint. Finally, it is worth noting that this innovation offers a great advantage over concurrent methods in that it is simply generated within minutes, it is highly stable, and there is sharp monodispersity in the size of the Pd nanoparticles that can be stored for months without alteration of their physico-chemical properties and catalytic activity.

  13. Highly efficient photochemical HCOOH production from CO{sub 2} and water using an inorganic system

    SciTech Connect

    Yotsuhashi, Satoshi; Hashiba, Hiroshi; Deguchi, Masahiro; Zenitani, Yuji; Hinogami, Reiko; Yamada, Yuka; Deura, Momoko; Ohkawa, Kazuhiro

    2012-12-15

    We have constructed a system that uses solar energy to react CO{sub 2} with water to generate formic acid (HCOOH) at an energy conversion efficiency of 0.15%. It consists of an AlGaN/GaN anode photoelectrode and indium (In) cathode that are electrically connected outside of the reactor cell. High energy conversion efficiency is realized due to a high quantum efficiency of 28% at 300 nm, attributable to efficient electron-hole separation in the semiconductor's heterostructure. The efficiency is close to that of natural photosynthesis in plants, and what is more, the reaction product (HCOOH) can be used as a renewable energy source.

  14. Estimating Light Use Efficiency Of A Pine And Beech Forest From Leaf To Ecosystem Scale Using The Photochemical Reflectance Index

    NASA Astrophysics Data System (ADS)

    Vanikiotis, Theofilos; Markos, Nikos; Stagakis, Stavros; Tzotsos, Angelos; Sykioti, Olga; Kyparissis, Aris

    2013-12-01

    The prospect of accurately tracking photosynthetic processes using satellite observations is very important for understanding and monitoring global carbon cycle and climate change. The present study investigates the efficiency of the Photochemical Reflectance Index (PRI) in detecting light use efficiency (ɛ) in different spatial scales. The study sites concern two dense and homogenous forests in the region of Epirus (Greece), one evergreen coniferous forest dominated by Pinus nigra species and one deciduous forest dominated by Fagus sylvatica. Field and laboratory measurements of canopy structure (Leaf Area Index - LAI, needle and shoot structure characteristics), leaf pigment concentrations, leaf photosynthesis and water potential were performed throughout the growth period. These measurements were used for an accurate description of the ecophysiological characteristics of the two species and thus the parameterization of a Canopy Photosynthesis Model in order to estimate canopy photosynthesis. During the same period, leaf and canopy reflectance measurements were performed in the field to test and evaluate PRI regarding it's efficiency to track ɛ in leaf and canopy scale. In order to investigate the potential application of PRI for estimating ɛ in a broader spatial scale, satellite hyperspectral or superspectral sensors can be used. Compact High Resolution Imaging Spectrometer (CHRIS) and Moderate Resolution Imaging Spectroradiometer (MODIS) are currently available for this purpose and their performances were tested within the present study. An agreement between the fluctuations of CHRIS PRI and the field measured canopy PRI has been found, with both of them appearing to track the ɛ fluctuation efficiently. However, MODIS PRI shows no intense fluctuation and no relationship with ɛ and field measured PRI, probably due to lack of atmospheric correction and the effects of viewing and illumination geometry.

  15. In vitro estimations of in vivo jet nebulizer efficiency using actual and simulated tidal breathing patterns.

    PubMed

    Bosco, Andrew P; Rhem, Rod G; Dolovich, Myrna B

    2005-01-01

    In vivo aerosol delivery efficiency was estimated in vitro for two jet nebulizers using a breath monitor (Breathe!; Pari GmbH, Germany) and breath simulator (COMPAS; Pari GmbH) to reproduce subject tidal breathing patterns. The AeroEclipse (Trudell Medical International, Canada), a breath-actuated nebulizer, and the LC Star (Pari GmbH), a breath-enhanced nebulizer, were filled with levalbuterol HCl solution (Sepracor, USA) and operated with compressed O(2) at 8 lpm. Tidal breathing patterns of 20 adult subjects were digitally recorded with the Breathe! Breath Monitor. Subjects then breathed tidally from each nebulizer separately for 1 minute and to nebulizer dryness. Levalbuterol aerosol collected on filters placed between the nebulizer and mouth was chemically assayed to determine the inspired mass (IM), wasted mass (WM) and total emitted mass (TM). Measurements were repeated using the COMPAS Breath Simulator to simulate each subject's tidal breathing pattern. IM, WM, and TM measurements using actual versus simulated tidal breathing were highly comparable for each nebulizer, except the IM (p < 0.05) from LC Star measured at nebulizer dryness. Breath simulation was an inaccurate tool for estimating the time to nebulizer dryness as simulated measurements to nebulizer dryness took significantly longer than measurements preformed with actual tidal breathing (p < 0.001). While breath simulation provides an accurate in vitro tool for estimating in vivo aerosol delivery, it should not completely replace in vivo measurements until inherent limitations in simulator operation can be overcome to provide a more clinically realistic simulation. PMID:16379618

  16. Remote sensing of assimilating branch light use efficiency using the photochemical reflectance index in Haloxylon ammodendron forest

    NASA Astrophysics Data System (ADS)

    Nyongesah, Maina John; Quan, Wang; Lu, Xu

    2016-04-01

    Five healthy Haloxylon ammodendron trees were randomly selected to monitor the photochemical reflectance index (PRI) and its relation to light use efficiency (LUE) in shaded and sunlit assimilating branches. Linear regression was performed where the results revealed that LUE decreased with seasonal courses with vivid midday depression regardless of light variation within canopies. PRI and LUE decoupled in early spring when the foliage was deeply downregulated, with high correlation (R2=0.8, p<0.001) during most parts of the year. Measured and estimated LUE were highly correlated for the July to September dataset (R2=0.73, p<0.001) compared to May to June datasets (R2=0.35, p<0.001). The estimated LUE for young assimilating branches could be obtained with a high RMSE of 0.01, compared to mature branches with an RMSE of 0.003. The measured LUE values were ˜20% higher than estimated LUE during the period from May to June, and values were slightly lower at the end of the growing season. This was attributed to differences in the physiological and biochemical mechanisms controlling the seasonal dynamics of PRI. Therefore, PRI is the best estimator of LUE when age-related changes and canopy light partitioning are considered in assimilating organs. Combined use of PRI with pigments could improve the remote evaluation of LUE.

  17. Efficient Bimolecular Mechanism of Photochemical Hydrogen Production Using Halogenated Boron-Dipyrromethene (Bodipy) Dyes and a Bis(dimethylglyoxime) Cobalt(III) Complex.

    PubMed

    Sabatini, Randy P; Lindley, Brian; McCormick, Theresa M; Lazarides, Theodore; Brennessel, William W; McCamant, David W; Eisenberg, Richard

    2016-01-28

    A series of Boron-dipyrromethene (Bodipy) dyes were used as photosensitizers for photochemical hydrogen production in conjunction with [Co(III)(dmgH)2pyCl] (where dmgH = dimethylglyoximate, py = pyridine) as the catalyst and triethanolamine (TEOA) as the sacrificial electron donor. The Bodipy dyes are fully characterized by electrochemistry, X-ray crystallography, quantum chemistry calculations, femtosecond transient absorption, and time-resolved fluorescence, as well as in long-term hydrogen production assays. Consistent with other recent reports, only systems containing halogenated chromophores were active for hydrogen production, as the long-lived triplet state is necessary for efficient bimolecular electron transfer. Here, it is shown that the photostability of the system improves with Bodipy dyes containing a mesityl group versus a phenyl group, which is attributed to increased electron donating character of the mesityl substituent. Unlike previous reports, the optimal ratio of chromophore to catalyst is established and shown to be 20:1, at which point this bimolecular dye/catalyst system performs 3-4 times better than similar chemically linked systems. We also show that the hydrogen production drops dramatically with excess catalyst concentration. The maximum turnover number of ∼ 700 (with respect to chromophore) is obtained under the following conditions: 1.0 × 10(-4) M [Co(dmgH)2pyCl], 5.0 × 10(-6) M Bodipy dye with iodine and mesityl substituents, 1:1 v:v (10% aqueous TEOA):MeCN (adjusted to pH 7), and irradiation by light with λ > 410 nm for 30 h. This system, containing discrete chromophore and catalyst, is more active than similar linked Bodipy-Co(dmg)2 dyads recently published, which, in conjunction with our other measurements, suggests that the nominal dyads actually function bimolecularly. PMID:26730460

  18. Highly efficient photochemically induced thiyl radical-mediated racemization of aliphatic amines at 30 degrees C.

    PubMed

    Routaboul, Lucie; Vanthuyne, Nicolas; Gastaldi, Stéphane; Gil, Gérard; Bertrand, Michèle

    2008-01-18

    UV irradiation in the presence of thiol enables the performance of highly efficient aliphatic amines racemization, under mild conditions at 30 degrees C. The reaction proceeds via the reversible generation of prochiral alpha-aminoalkyl radicals. The latter may result either from a redox process between the thiyl radical and the amine or from direct hydrogen atom abstraction by thiyl radical. As hydrogen atom donor, the thiol plays a crucial role. While the racemization of both primary and secondary amines were fast processes, the racemization of tertiary amines was sluggish. A tentative rationale is based on the photostimulated amine-catalyzed oxidation of the thiol into the corresponding disulfide, which makes the hydrogen atom donor concentration in the reaction medium drop up to trace amount at a rate that depends on the nature of the amine. PMID:18076189

  19. Transformation efficiency and formation of transformation products during photochemical degradation of TCE and PCE at micromolar concentrations

    PubMed Central

    2014-01-01

    Background Trichloroethene and tetrachloroethene are the most common pollutants in groundwater and two of the priority pollutants listed by the U.S. Environmental Protection Agency. In previous studies on TCE and PCE photolysis and photochemical degradation, concentration ranges exceeding environmental levels by far with millimolar concentrations of TCE and PCE have been used, and it is not clear if the obtained results can be used to explain the degradation of these contaminants at more realistic environmental concentration levels. Methods Experiments with micromolar concentrations of TCE and PCE in aqueous solution using direct photolysis and UV/H2O2 have been conducted and product formation as well as transformation efficiency have been investigated. SPME/GC/MS, HPLC/UV and ion chromatography with conductivity detection have been used to determine intermediates of degradation. Results The results showed that chloride was a major end product in both TCE and PCE photodegradation. Several intermediates such as formic acid, dichloroacetic acid, dichloroacetaldehyede, chloroform, formaldehyde and glyoxylic acid were formed during both, UV and UV/H2O2 treatment of TCE. However chloroacetaldehyde and chloroacetic acid were only detected during direct UV photolysis of TCE and oxalic acid was only formed during the UV/H2O2 process. For PCE photodegradation, formic acid, di- and trichloroacetic acids were detected in both UV and UV/H2O2 systems, but formaldehyde and glyoxylic acid were only detected during direct UV photolysis. Conclusions For water treatment UV/H2O2 seems to be favorable over direct UV photolysis because of its higher degradation efficiency and lower risk for the formation of harmful intermediates. PMID:24401763

  20. Light Use Efficiency and Photochemical Reflectance Index: do we have a common basis defining them? Implications for productivity estimation (Invited)

    NASA Astrophysics Data System (ADS)

    Gitelson, A. A.; Gamon, J. A.

    2013-12-01

    There are at least three commonly used definitions of photosynthetic Light Use Efficiency (LUE) based on: (a) incident radiation (LUEinc); (b) total absorbed light (LUEtotal); and (c) radiation absorbed by photosynthetically active vegetation (LUEps). Consequently, LUE values reported do not have a common basis, bringing confusion and limiting the utility of reported LUE values for comparative analyses. Not surprisingly, the value of LUE reported in literature varies by a factor of three. Similarly, the Photochemical Reflectance Index (PRI) has different operational definitions, resulting in a wide range of reported values for comparable conditions. The objectives of this paper are to investigate (a) temporal behavior of each definition of LUE; and (b) factors affecting PRI, often used as a surrogate of LUE at leaf and canopy levels. We focused on annual and winter-deciduous vegetation where total chlorophyll content is closely tied to the seasonal dynamics of GPP. In these conditions, LUEinc is closely related to total plant chlorophyll (Chl) content. LUEtotal oscillates around a constant value during the vegetative stage, depending mainly on plant physiological status, PAR composition and magnitude, while in reproductive and senescence stages it relates closely to Chl content. LUEps may vary 2- to 3-fold during the growing season with no clear seasonal pattern, and does not seem to be related to any biophysical characteristic studied; rather, it depends on the physiological status of vegetation, PAR composition and magnitude as well as air temperature and soil moisture. At the leaf level, PRI depends greatly on pigment content and composition and relates closely to the ratio of Chl to carotenoid content. At the canopy and stand levels, both total plant Chl content and green LAI are responsible for more than 95% of PRI variation, demonstrating that PRI is confounded by pigment pool sizes and canopy structure in these conditions. Importantly, the close relationship

  1. Efficient blind dereverberation and echo cancellation based on independent component analysis for actual acoustic signals.

    PubMed

    Takeda, Ryu; Nakadai, Kazuhiro; Takahashi, Toru; Komatani, Kazunori; Ogata, Tetsuya; Okuno, Hiroshi G

    2012-01-01

    This letter presents a new algorithm for blind dereverberation and echo cancellation based on independent component analysis (ICA) for actual acoustic signals. We focus on frequency domain ICA (FD-ICA) because its computational cost and speed of learning convergence are sufficiently reasonable for practical applications such as hands-free speech recognition. In applying conventional FD-ICA as a preprocessing of automatic speech recognition in noisy environments, one of the most critical problems is how to cope with reverberations. To extract a clean signal from the reverberant observation, we model the separation process in the short-time Fourier transform domain and apply the multiple input/output inverse-filtering theorem (MINT) to the FD-ICA separation model. A naive implementation of this method is computationally expensive, because its time complexity is the second order of reverberation time. Therefore, the main issue in dereverberation is to reduce the high computational cost of ICA. In this letter, we reduce the computational complexity to the linear order of the reverberation time by using two techniques: (1) a separation model based on the independence of delayed observed signals with MINT and (2) spatial sphering for preprocessing. Experiments show that the computational cost grows in proportion to the linear order of the reverberation time and that our method improves the word correctness of automatic speech recognition by 10 to 20 points in a RT₂₀= 670 ms reverberant environment. PMID:22023192

  2. Decreased photochemical efficiency of photosystem II following sunlight exposure of shade-grown leaves of avocado: because of, or in spite of, two kinetically distinct xanthophyll cycles?

    PubMed

    Jia, Husen; Förster, Britta; Chow, Wah Soon; Pogson, Barry James; Osmond, C Barry

    2013-02-01

    This study resolved correlations between changes in xanthophyll pigments and photosynthetic properties in attached and detached shade-grown avocado (Persea americana) leaves upon sun exposure. Lutein epoxide (Lx) was deepoxidized to lutein (L), increasing the total pool by ΔL over 5 h, whereas violaxanthin (V) conversion to antheraxanthin (A) and zeaxanthin (Z) ceased after 1 h. During subsequent dark or shade recovery, de novo synthesis of L and Z continued, followed by epoxidation of A and Z but not of L. Light-saturated nonphotochemical quenching (NPQ) was strongly and linearly correlated with decreasing [Lx] and increasing [L] but showed a biphasic correlation with declining [V] and increasing [A+Z] separated when V deepoxidation ceased. When considering [ΔL+Z], the monophasic linear correlation was restored. Photochemical efficiency of photosystem II (PSII) and photosystem (PSI; deduced from the delivery of electrons to PSI in saturating single-turnover flashes) showed a strong correlation in their continuous decline in sunlight and an increase in NPQ capacity. This decrease was also reflected in the initial reduction of the slope of photosynthetic electron transport versus photon flux density. Generally longer, stronger sun exposures enhanced declines in both slope and maximum photosynthetic electron transport rates as well as photochemical efficiency of PSII and PSII/PSI more severely and prevented full recovery. Interestingly, increased NPQ capacity was accompanied by slower relaxation. This was more prominent in detached leaves with closed stomata, indicating that photorespiratory recycling of CO(2) provided little photoprotection to avocado shade leaves. Sun exposure of these shade leaves initiates a continuum of photoprotection, beyond full engagement of the Lx and V cycle in the antenna, but ultimately photoinactivated PSII reaction centers. PMID:23213134

  3. Research opportunities in photochemical sciences

    SciTech Connect

    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.

  4. Proton-transfer and hydrogen-bond interactions determine fluorescence quantum yield and photochemical efficiency of bacteriophytochrome

    PubMed Central

    Toh, K. C.; Stojković, Emina A.; van Stokkum, Ivo H. M.; Moffat, Keith; Kennis, John T. M.

    2010-01-01

    Phytochromes are red-light photoreceptor proteins that regulate a variety of responses and cellular processes in plants, bacteria, and fungi. The phytochrome light activation mechanism involves isomerization around the C15═C16 double bond of an open-chain tetrapyrrole chromophore, resulting in a flip of its D-ring. In an important new development, bacteriophytochrome (Bph) has been engineered for use as a fluorescent marker in mammalian tissues. Here we report that an unusual Bph, RpBphP3 from Rhodopseudomonas palustris, denoted P3, is fluorescent. This Bph modulates synthesis of light-harvesting complex in combination with a second Bph exhibiting classical photochemistry, RpBphP2, denoted P2. We identify the factors that determine the fluorescence and isomerization quantum yields through the application of ultrafast spectroscopy to wild-type and mutants of P2 and P3. The excited-state lifetime of the biliverdin chromophore in P3 was significantly longer at 330–500 ps than in P2 and other classical phytochromes and accompanied by a significantly reduced isomerization quantum yield. H/D exchange reduces the rate of decay from the excited state of biliverdin by a factor of 1.4 and increases the isomerization quantum yield. Comparison of the properties of the P2 and P3 variants shows that the quantum yields of fluorescence and isomerization are determined by excited-state deprotonation of biliverdin at the pyrrole rings, in competition with hydrogen-bond rupture between the D-ring and the apoprotein. This work provides a basis for structure-based conversion of Bph into an efficient near-IR fluorescent marker. PMID:20435909

  5. Photochemical Synthesis of Nepetanudone.

    PubMed

    Jayan, Swapna; Jones, Paul B

    2015-06-26

    Nepetanudone and nepetaparnone have been suspected of being the products of a photochemical dimerization of nepetapyrone. Both are natural products found in a variety of Nepeta species. The synthesis of (±)-nepetapyrone and subsequent photochemical experiments are described. (±)-Nepetanudone was produced upon irradiation of (±)-nepetapyrone, while (±)-nepetaparnone, a diastereomer of nepetanudone, was not observed. PMID:25978278

  6. A highly efficient polyampholyte hydrogel sorbent based fixed-bed process for heavy metal removal in actual industrial effluent.

    PubMed

    Zhou, Guiyin; Luo, Jinming; Liu, Chengbin; Chu, Lin; Ma, Jianhong; Tang, Yanhong; Zeng, Zebing; Luo, Shenglian

    2016-02-01

    High sorption capacity, high sorption rate, and fast separation and regeneration for qualified sorbents used in removing heavy metals from wastewater are urgently needed. In this study, a polyampholyte hydrogel was well designed and prepared via a simple radical polymerization procedure. Due to the remarkable mechanical strength, the three-dimensional polyampholyte hydrogel could be fast separated, easily regenerated and highly reused. The sorption capacities were as high as 216.1 mg/g for Pb(II) and 153.8 mg/g for Cd(II) owing to the existence of the large number of active groups. The adsorption could be conducted in a wide pH range of 3-6 and the equilibrium fast reached in 30 min due to its excellent water penetration for highly accessible to metal ions. The fixed-bed column sorption results indicated that the polyampholyte hydrogel was particularly effective in removing Pb(II) and Cd(II) from actual industrial effluent to meet the regulatory requirements. The treatment volumes of actual smelting effluent using one fixed bed column were as high as 684 bed volumes (BV) (7736 mL) for Pb(II) and 200 BV (2262 mL) for Cd(II). Furthermore, the treatment volumes of actual smelting effluent using tandem three columns reached 924 BV (31,351 mL) for Pb(II) and 250 BV (8483 mL) for Cd(II), producing only 4 BV (136 mL) eluent. Compared with the traditional high density slurry (HDS) process with large amount of sludge, the proposed process would be expected to produce only a small amount of sludge. When the treatment volume was controlled below 209.3 BV (7103 mL), all metal ions in the actual industrial effluent could be effectively removed (<0.01 mg/L). This wok develops a highly practical process based on polyampholyte hydrogel sorbents for the removal of heavy metal ions from practical wastewater. PMID:26650450

  7. Is less really more: Does a prefrontal efficiency genotype actually confer better performance when working memory becomes difficult?

    PubMed

    Ihne, Jessica L; Gallagher, Natalie M; Sullivan, Marie; Callicott, Joseph H; Green, Adam E

    2016-01-01

    Perhaps the most widely studied effect to emerge from the combination of neuroimaging and human genetics is the association of the COMT-Val(108/158)Met polymorphism with prefrontal activity during working memory. COMT-Val is a putative risk factor in schizophrenia, which is characterized by disordered prefrontal function. Work in healthy populations has sought to characterize mechanisms by which the valine (Val) allele may lead to disadvantaged prefrontal cognition. Lower activity in methionine (Met) carriers has been interpreted as advantageous neural efficiency. Notably, however, studies reporting COMT effects on neural efficiency have generally not reported working memory performance effects. Those studies have employed relatively low/easy working memory loads. Higher loads are known to elicit individual differences in working memory performance that are not visible at lower loads. If COMT-Met confers greater neural efficiency when working memory is easy, a reasonable prediction is that Met carriers will be better able to cope with increasing demand for neural resources when working memory becomes difficult. To our knowledge, this prediction has thus far gone untested. Here, we tested performance on three working memory tasks. Performance on each task was measured at multiple levels of load/difficulty, including loads more demanding than those used in prior studies. We found no genotype-by-load interactions or main effects of COMT genotype on accuracy or reaction time. Indeed, even testing for performance differences at each load of each task failed to find a single significant effect of COMT genotype. Thus, even if COMT genotype has the effects on prefrontal efficiency that prior work has suggested, such effects may not directly impact high-load working memory ability. The present findings accord with previous evidence that behavioral effects of COMT are small or nonexistent and, more broadly, with a growing consensus that substantial effects on phenotype will

  8. Integrated adsorptive technique for efficient recovery of m-cresol and m-toluidine from actual acidic and salty wastewater.

    PubMed

    Chen, Da; Liu, Fuqiang; Zong, Lidan; Sun, Xiaowen; Zhang, Xiaopeng; Zhu, Changqing; Tao, Xuewen; Li, Aimin

    2016-07-15

    An integrated adsorptive technique combining an m-cresol adsorption unit, an acid retardation unit and an m-toluidine adsorption unit in sequence was designed to recover m-cresol and m-toluidine from highly acidic and salty m-cresol manufacturing wastewater. In the first column packed with hypercrosslinked polymeric resin (NDA-99), most m-cresol was captured through π-π and hydrogen-bonding interactions as well as the salting-out effect, while m-toluidine was not absorbed due to protonation. To separate acid from salt, an acid retardation unit was introduced successively to adsorb sulfuric acid by strong base anion exchange resin (201×7). After the acid retardation unit and mild neutralization reaction, the last column filled with NDA-99 was applied to trap neutral m-toluidine from the salty effluent. Moreover, the eluent of the acid retardation unit was utilized as the regenerant to recover m-toluidine, and the recycled high-acidity and low-salinity solution of m-toluidine was directly used to produce m-cresol as the raw material. Therefore, the proposed method not only efficiently recycled m-cresol and m-toluidine, but also reduced the consumption of alkali dramatically (saving 0.1628t/t wastewater). These findings will inspire design of integrated adsorptive techniques for treating complex organic wastewater with high efficiency and low cost. PMID:27037473

  9. PHOTOCHEMICAL BOX MODEL (PBM)

    EPA Science Inventory

    This magnetic tape contains the FORTRAN source code, sample input data, and sample output data for the Photochemical Box Model (PBM). The PBM is a simple stationary single-cell model with a variable height lid designed to provide volume-integrated hour averages of O3 and other ph...

  10. PHOTOCHEMICAL REACTIVITY OF PERCHLOROETHYLENE

    EPA Science Inventory

    Perchloroethylene (PCE), a solvent used in dry cleaning, has been suspected of contributing significantly to photochemical ozone/oxidant (O3/Ox) problems in urban atmospheres. Past evidence, however, was neither complete nor consistent. To interpret more conclusively the past evi...

  11. Photochemical tissue bonding

    DOEpatents

    Redmond, Robert W.; Kochevar, Irene E.

    2012-01-10

    Photochemical tissue bonding methods include the application of a photosensitizer to a tissue and/or tissue graft, followed by irradiation with electromagnetic energy to produce a tissue seal. The methods are useful for tissue adhesion, such as in wound closure, tissue grafting, skin grafting, musculoskeletal tissue repair, ligament or tendon repair and corneal repair.

  12. PHOTOCHEMICAL AEROSOL DYNAMICS

    EPA Science Inventory

    New data are reported on (1) the rate of formation of condensable chemical species by photochemical reactions, (2) the effect of the reaction products on the particle size distribution and (3) the distribution of reaction products as a function of particle size. Gas-to-particle c...

  13. Methods for the photochemical utilization of solar energy

    NASA Technical Reports Server (NTRS)

    Schwerzel, R. E.

    1978-01-01

    The paper considers the 'ground rules' which govern the efficiency of photochemical solar energy conversion and then summarizes the most promising approaches in each of three categories: photochemically assisted thermal systems for the heating and/or cooling of structures; photogalvanic systems for the production of electrical power in applications, such as photorechargeable batteries or inexpensive 'solar cells'; and photochemical formation of fuels for combustion and for use as chemical feedstocks or foods. Three concepts for the photochemical utilization of solar energy in space are found to be particularly promising: (1) photochemical trans-cis isomerization of indigold dyes for photoassisted heating or cooling, (2) the redox stabilized photoelectrolysis cell for the production of hydrogen (and/or oxygen or other useful chemicals), and (3) the liquid-junction photovoltaic cell for the production of electrical power.

  14. Decreased Photochemical Efficiency of Photosystem II following Sunlight Exposure of Shade-Grown Leaves of Avocado: Because of, or in Spite of, Two Kinetically Distinct Xanthophyll Cycles?1[W

    PubMed Central

    Jia, Husen; Förster, Britta; Chow, Wah Soon; Pogson, Barry James; Osmond, C. Barry

    2013-01-01

    This study resolved correlations between changes in xanthophyll pigments and photosynthetic properties in attached and detached shade-grown avocado (Persea americana) leaves upon sun exposure. Lutein epoxide (Lx) was deepoxidized to lutein (L), increasing the total pool by ΔL over 5 h, whereas violaxanthin (V) conversion to antheraxanthin (A) and zeaxanthin (Z) ceased after 1 h. During subsequent dark or shade recovery, de novo synthesis of L and Z continued, followed by epoxidation of A and Z but not of L. Light-saturated nonphotochemical quenching (NPQ) was strongly and linearly correlated with decreasing [Lx] and increasing [∆L] but showed a biphasic correlation with declining [V] and increasing [A+Z] separated when V deepoxidation ceased. When considering [ΔL+∆Z], the monophasic linear correlation was restored. Photochemical efficiency of photosystem II (PSII) and photosystem (PSI; deduced from the delivery of electrons to PSI in saturating single-turnover flashes) showed a strong correlation in their continuous decline in sunlight and an increase in NPQ capacity. This decrease was also reflected in the initial reduction of the slope of photosynthetic electron transport versus photon flux density. Generally longer, stronger sun exposures enhanced declines in both slope and maximum photosynthetic electron transport rates as well as photochemical efficiency of PSII and PSII/PSI more severely and prevented full recovery. Interestingly, increased NPQ capacity was accompanied by slower relaxation. This was more prominent in detached leaves with closed stomata, indicating that photorespiratory recycling of CO2 provided little photoprotection to avocado shade leaves. Sun exposure of these shade leaves initiates a continuum of photoprotection, beyond full engagement of the Lx and V cycle in the antenna, but ultimately photoinactivated PSII reaction centers. PMID:23213134

  15. Photochemical isotope separation

    DOEpatents

    Robinson, C. Paul; Jensen, Reed J.; Cotter, Theodore P.; Greiner, Norman R.; Boyer, Keith

    1987-01-01

    A process for separating isotopes by selective excitation of isotopic species of a volatile compound by tuned laser light. A highly cooled gas of the volatile compound is produced in which the isotopic shift is sharpened and defined. Before substantial condensation occurs, the cooled gas is irradiated with laser light precisely tuned to a desired wavelength to selectively excite a particular isotopic species in the cooled gas. The laser light may impart sufficient energy to the excited species to cause it to undergo photochemical reaction or even to photoionize. Alternatively, a two-photon irradiation may be applied to the cooled gas to induce photochemical reaction or photoionization. The process is particularly applicable to the separation of isotopes of uranium and plutonium.

  16. Photochemical isotope separation

    DOEpatents

    Robinson, C.P.; Jensen, R.J.; Cotter, T.P.; Greiner, N.R.; Boyer, K.

    1987-04-28

    A process is described for separating isotopes by selective excitation of isotopic species of a volatile compound by tuned laser light. A highly cooled gas of the volatile compound is produced in which the isotopic shift is sharpened and defined. Before substantial condensation occurs, the cooled gas is irradiated with laser light precisely tuned to a desired wavelength to selectively excite a particular isotopic species in the cooled gas. The laser light may impart sufficient energy to the excited species to cause it to undergo photochemical reaction or even to photoionize. Alternatively, a two-photon irradiation may be applied to the cooled gas to induce photochemical reaction or photoionization. The process is particularly applicable to the separation of isotopes of uranium and plutonium. 8 figs.

  17. Materials Integrating Photochemical Upconversion.

    PubMed

    McCusker, Catherine E; Castellano, Felix N

    2016-04-01

    This review features recent experimental work focused on the preparation and characterization of materials that integrate photochemical upconversion derived from sensitized triplet-triplet annihilation, resulting in the conversion of low energy photons to higher energy light, thereby enabling numerous wavelength-shifting applications. Recent topical developments in upconversion include encapsulating or rigidifying fluid solutions to give them mechanical strength, adapting inert host materials to enable upconversion, and using photoactive materials that incorporate the sensitizer and/or the acceptor. The driving force behind translating photochemical upconversion from solution into hard and soft materials is the incorporation of upconversion into devices and other applications. At present, some of the most promising applications of upconversion materials include imaging and fluorescence microscopy, photoelectrochemical devices, water disinfection, and solar cell enhancement. PMID:27573144

  18. Photochemical cutting of fabrics

    DOEpatents

    Piltch, Martin S.

    1994-01-01

    Apparatus for the cutting of garment patterns from one or more layers of fabric. A laser capable of producing laser light at an ultraviolet wavelength is utilized to shine light through a pattern, such as a holographic phase filter, and through a lens onto the one or more layers of fabric. The ultraviolet laser light causes rapid photochemical decomposition of the one or more layers of fabric, but only along the pattern. The balance of the fabric of the one or more layers of fabric is undamaged.

  19. Photochemical cutting of fabrics

    SciTech Connect

    Piltch, M.S.

    1994-11-22

    Apparatus is described for the cutting of garment patterns from one or more layers of fabric. A laser capable of producing laser light at an ultraviolet wavelength is utilized to shine light through a pattern, such as a holographic phase filter, and through a lens onto the one or more layers of fabric. The ultraviolet laser light causes rapid photochemical decomposition of the one or more layers of fabric, but only along the pattern. The balance of the fabric of the one or more layers of fabric is undamaged. 1 fig.

  20. PHOTOCHEMICAL MODELING APPLIED TO NATURAL WATERS

    EPA Science Inventory

    The study examines the application of modeling photochemical processes in natural water systems. For many photochemical reactions occurring in natural waters, a simple photochemical model describing reaction rate as a function of intensity, radiation attenuation, reactant absorpt...

  1. Polyimides by Photochemical Cyclopolymerization

    NASA Technical Reports Server (NTRS)

    Meador, Michael A. (Inventor)

    2005-01-01

    The novel polyimides of this invention are derived from Diels-Alder cyclopolymerization of photochemically generated bisdienes with dienophiles, such as bismaleimides, trismaleimides and mixtures thereof with maleimide endcaps. Irradiation of one or more diketones produces two distinct hydroxy o-quinodimethane (photoenol) intermediates. These intermediates are trapped via Diels-Alder cycloaddition with appropriate dienophiles, e.g., bismaleimide and/or trismaleimides to give the corresponding polyimides in quantitative yields. When bismaleimides, trismaleimides or mixtures thereof with maleimide end-caps are used as the dienophile, the resulting polyimides have glass transition temperatures (Tg) as high as 300 C. Polyimide films can be prepared by ultraviolet irradiation of high solids content varnishes of the monomers in a small amount of solvent, e.g., cyclohexanone, dimethyl formamide, N-methylpyrollidone and the like. These novel polyimides are characterized as having high glass transition temperatures, good mechanical properties and improved processing in the manufacture of adhesives, electronic materials and films.

  2. Polyimides by photochemical cyclopolymerization

    NASA Technical Reports Server (NTRS)

    Meador, Michael A. (Inventor)

    2005-01-01

    The novel polyimides of this invention are derived from Diels-Alder cyclopolymerization of photochemically generated bisdienes with dienophiles, such as bismaleimides, trismaleimides and mixtures thereof with maleimide end-caps. Irradiation of one or more diketones produces two distinct hydroxy o-quinodimethane (photoenol) intermediates. These intermediates are trapped via Diels-Alder cycloaddition with appropriate dienophiles, e.g., bismaleimide and/or trismaleimides to give the corresponding polyimides in quantitative yields. When bismaleimides, trismaleimides or mixtures thereof with maleimide end-caps are used as the dienophile, the resulting polyimides have glass transition temperatures (Tg) as high as 300? C. Polyimide films can be prepared by ultraviolet irradiation of high solids content varnishes of the monomers in a small amount of solvent, e.g., cyclohexanone, dimethyl formamide, N-methylpyrollidone and the like. These novel polyimides are characterized as having high glass transition temperatures, good mechanical properties and improved processing in the manufacture of adhesives, electronic materials and films.

  3. Photochemically Synthesized Polyimides

    NASA Technical Reports Server (NTRS)

    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

  4. Polyesters by Photochemical Cyclopolymerization

    NASA Technical Reports Server (NTRS)

    Meador, Michael A. (Inventor)

    2002-01-01

    The polyesters of this invention are derived from a Diels-Alder cyclopolymerization of a photochemically generated bisdiene with dienophiles, such as di(acrylates), tri (acrylates), di(methacrylates), tri(methacrylates) and mixtures thereof with mono(methacrylates) or mono(acrylate) end-caps. Irradiation of one or more diketones produces two distinct hydroxy o-quinodimethane (photoenol) intermediates. These intermediates are trapped via a Diels-Alder cycloaddition with appropriate dienophiles, e.g., di(acrylates) to give the corresponding in polyesters quantitative yields. When di(acrylates), tri(acrylates) and di and tri(methacrylates) or mixtures thereof with monoacrylate end-caps are used as the dienophile, the resulting polyesters have glass transition temperatures (Tg) as high as 200 C. Polyesters films can be prepared by ultraviolet irradiation of high solids content varnishes of the monomers in a small amount of solvent, e.g., cyclohexanone, dimethyl formamide, N-methylpyrollidone and the like. These polyesters, i.e. polyesters are characterized as having high glass transition temperatures, good mechanical properties and improved processing in the manufacture of composites, adhesives, electronic materials and films.

  5. Plasmonic antenna effects on photochemical reactions.

    PubMed

    Gao, Shuyan; Ueno, Kosei; Misawa, Hiroaki

    2011-04-19

    Efficient solar energy conversion has been vigorously pursued since the 1970s, but its large-scale implementation hinges on the availability of high-efficiency modules. For maximum efficiency, it is important to absorb most of the incoming radiation, which necessitates both efficient photoexcitation and minimal electron-hole recombination. To date, researchers have primarily focused on the latter difficulty: finding a strategy to effectively separate photoinduced electrons and holes. Very few reports have been devoted to broadband sunlight absorption and photoexcitation. However, the currently available photovoltaic cells, such as amorphous silicon, and even single-crystal silicon and sensitized solar cells, cannot respond to the wide range of the solar spectrum. The photoelectric conversion characteristics of solar cells generally decrease in the infrared wavelength range. Thus, the fraction of the solar spectrum absorbed is relatively poor. In addition, the large mismatch between the diffraction limit of light and the absorption cross-section makes the probability of interactions between photons and cell materials quite low, which greatly limits photoexcitation efficiency. Therefore, there is a pressing need for research aimed at finding conditions that lead to highly efficient photoexcitation over a wide spectrum of sunlight, particularly in the visible to near-infrared wavelengths. As characterized in the emerging field of plasmonics, metallic nanostructures are endowed with optical antenna effects. These plasmonic antenna effects provide a promising platform for artificially sidestepping the diffraction limit of light and strongly enhancing absorption cross-sections. Moreover, they can efficiently excite photochemical reactions between photons and molecules close to an optical antenna through the local field enhancement. This technology has the potential to induce highly efficient photoexcitation between photons and molecules over a wide spectrum of sunlight

  6. Crassulacean Acid Metabolism and Photochemical Efficiency of Photosystem II in the Adaxial and Abaxial Parts of the Succulent Leaves of Kalanchoë daigremontiana Grown at Four Photon Flux Densities.

    PubMed

    Winter, K; Awender, G

    1989-07-01

    Kalanchoë daigremontiana, a species possessing crassulacean acid metabolism, was grown at four photon flux densities (1300, 400, 60, and 25 micromole photons per square meter per second). In leaves which had developed at 1300 and 400 micromole photons per square meter per second, CO(2) was mainly incorporated through the lower, shaded leaf surfaces, and the chlorenchyma adjacent to the lower surfaces showed a higher degree of nocturnal acid synthesis than the chlorenchyma adjacent to the upper surfaces. In leaves acclimated to 60 and 25 micromole photons per square meter per second, the gradient in CAM activity was reversed, i.e. more CO(2) was taken up through the upper than through the lower surfaces and nocturnal acidification was higher in the tissue next to the upper surfaces. Total net carbon gain and total nocturnal acid synthesis were highest in leaves which had developed at 400 micromole photons per square meter per second. Chlorophyll content was markedly reduced in leaves which had developed at 1300 micromole photons per square meter per second, especially in the exposed adaxial parts. There was also a sustained reduction in photosystem II photochemical efficiency as indicated by measurements of the ratio of variable over maximum chlorophyll a fluorescence. These findings suggest that, at high growth photon flux densities, the reduced activity of the exposed portions of these succulent leaves is caused by (a) the adverse effects of excess light, (b) together with a genotypic component which favors CO(2) uptake and acid synthesis in the abaxial (lower) leaf parts even when light is not or only marginally excessive. This latter component is predominant at medium photon flux densities, e.g. at 400 micromole photons per square meter per second. It becomes overridden, however, under conditions of deep shade when strongly reduced light levels in the abaxial parts of the leaf chlorenchyma severely limit photosynthesis. PMID:16666903

  7. Hairlike Percutaneous Photochemical Sensors

    NASA Technical Reports Server (NTRS)

    George, Thomas; Loeb, Gerald

    2004-01-01

    Instrumentation systems based on hairlike fiber-optic photochemical sensors have been proposed as minimally invasive means of detecting biochemicals associated with cancer and other diseases. The fiber-optic sensors could be mass-produced as inexpensive, disposable components. The sensory tip of a fiber-optic sensor would be injected through the patient's skin into subcutaneous tissue. A biosensing material on the sensory tip would bind or otherwise react with the biochemical(s) of interest [the analyte(s)] to produce a change in optical properties that would be measured by use of an external photonic analyzer. After use, a fiber-optic sensor could be simply removed by plucking it out with tweezers. A fiber-optic sensor according to the proposal would be of the approximate size and shape of a human hair, and its sensory tip would resemble a follicle. Once inserted into a patient's subcutaneous tissue, the sensor would even more closely resemble a hair growing from a follicle (see Figure 1). The biosensing material on the sensory tip could consist of a chemical and/or cells cultured and modified for the purpose. The biosensing material would be contained within a membrane that would cover the tip. If the membrane were not permeable by an analyte, then it would be necessary to create pores in the membrane that would be large enough to allow analyte molecules to diffuse to the biosensing material, but not so large as to allow cells (if present as part of the biosensing material) to diffuse out. The end of the fiber-optic sensor opposite the sensory tip would be inserted in a fiberoptic socket in the photonic analyzer.

  8. Gated photochemical hole burning in photoadducts of polyacenes

    NASA Technical Reports Server (NTRS)

    Iannone, Mark; Scott, Gary W.; Brinza, David; Coulter, Daniel R.

    1986-01-01

    A photoadduct of anthracene and tetracene (A-T) in a polymer matrix at 1.5 K generates an absorption spectrum which exhibits two-color, photon-gated photochemical hole burning (PHB) when irradiated with narrowband exciting light into the 0-0 band of the S1-S0 absorption. The efficiency of this PHB process is found to be enhanced by simultaneous irradiation near the maximum of the Tn-T1 absorption of A-T; hole widths of less than 0.07/cm have been observed for this photochemical cleavage of A-T.

  9. A critical review on photochemical conversions in flow analysis.

    PubMed

    Rocha, Diogo L; Kamogawa, Marcos Y; Rocha, Fábio R P

    2015-10-01

    Photochemical conversions are cost-effective and environmental friendly processes that require mild experimental conditions and avoid generation of highly acidic wastes. Treated samples are then compatible with most of the analytical techniques. These characteristics become more relevant when the photoconversions are accomplished to flow analysis, thus allowing exploitation of incomplete reactions, the effective use of the photogenerated unstable radicals and in-line sample treatment. Decreasing of reagent consumption and waste generation, sample processing in a closed environment, and improvement of efficiency of the photochemical processes are other inherent advantages. These aspects are critically reviewed in this article, which emphasizes applications to fractionation and speciation analysis, photo-induced luminescence, miniaturization, and in-line waste treatment. Design of flow-through photochemical cells, use of auxiliary reagents in homogeneous and heterogeneous media, and configurations of flow manifolds are also discussed. PMID:26481985

  10. An Apparatus for Photochemical Studies.

    ERIC Educational Resources Information Center

    Winter, M. J.; Winter, P. V.

    1984-01-01

    Describes an apparatus developed for photochemical studies, particularly those involving the fluorescence of halogenated acetones. The apparatus is constructed from equipment normally found in a moderately sized physical chemical laboratory. Also provides background information on some aspects of the photophysics of halogenated propanones. (JN)

  11. VALIDATION DATA FOR PHOTOCHEMICAL MECHANISMS

    EPA Science Inventory

    The report describes the Quality Assurance and data processing procedures and systems used at the UNC outdoor smog chamber facility. The facility is used to measure the reactants and products that participate in the photochemical smog formation process. The intent of the Quality ...

  12. Photochemical grid model implementation and application of VOC, NOx, and O3 source apportionment

    EPA Science Inventory

    For the purposes of developing optimal emissions control strategies, efficient approaches are needed to identify the major sources or groups of sources that contribute to elevated ozone (O3) concentrations. Source-based apportionment techniques implemented in photochemical grid m...

  13. The Photochemical Cycle of Halorhodopsin

    PubMed Central

    Tittor, J.; Oesterhelt, D.; Maurer, R.; Desel, H.; Uhl, R.

    1987-01-01

    Results of experiments using flash photolysis and fast difference spectroscopy suggest an extended version of the earlier published scheme of the photochemical cycle of halorhodopsin. Detailed experimental verification of the suggested photocycle is given. Due to the high resolution of the time-resolved difference spectra, absolute spectra of the intermediates in the photocycle were derived, allowing the interpretation of complex kinetic absorbance changes. PMID:19431713

  14. Photochemical synthesis of gold nanorods.

    PubMed

    Kim, Franklin; Song, Jae Hee; Yang, Peidong

    2002-12-01

    Gold nanorods have been synthesized by photochemically reducing gold ions within a micellar solution. The aspect ratio of the rods can be controlled with the addition of silver ions. This process reported here is highly promising for producing uniform nanorods, and more importantly it will be useful in resolving the growth mechanism of anisotropic metal nanoparticles due to its simplicity and the relatively slow growth rate of the nanorods. PMID:12452700

  15. Photochemical air pollution. Part I

    SciTech Connect

    Goldstein E.; Hackney, J.D.; Rokaw, S.N.

    1985-03-01

    In this paper, epidemiologic studies are reported which indicate that high photochemical oxidant exposures: do not cause mortality or serious illness; may increase the risk of asthmatic attacks in a small percentage of asthmatic patients; appear to reduce pulmonary function in smokers and nonsmokers after long-term exposure; cause acute discomfort of eye and throat, chest irritation and cough; and interfere with athletic performance. Exposure to high ambient levels of NO/sub 2/ is not associated with mortality, serious disease or respiratory dysfunction, but self-limiting symptoms of respiratory irritation or illness may develop in children. 106 references, 2 figures, 1 table.

  16. Engineering photochemical smog through convection towers

    SciTech Connect

    Elliott, S.; Prueitt, M.L.; Bossert, J.E.; Mroz, E.J.; Krakowski, R.A.; Miller, R.L.; Jacobson, M.Z.; Turco, R.P. |

    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.

  17. Photochemical Ablation of Organic Solids

    NASA Astrophysics Data System (ADS)

    Garrison, Barbara

    2004-03-01

    As discovered by Srinivasan in 1982, irradiation of materials by far UV laser light can lead to photochemical ablation, a process distinct from normal thermal ablation in which the laser primarily heats the material. A versatile mesoscopic model for molecular dynamics simulations of the laser ablation phenomena is presented. The model incorporates both the thermal and photochemical events, that is, both heating of the system and UV induced bond-cleavage followed by abstraction and radical-radical recombination reactions. The results from the simulations are compared to experimental data and the basic physics and chemistry for each irradiation regime are discussed. Initial results from polymer ablation simulations will be presented. L. V. Zhigilei, P. B. S. Kodali and B. J. Garrison, J. Phys. Chem. B, 102, 2845-2853 (1998); L. V. Zhigilei and B. J. Garrison, Journal of Applied Physics, 88, 1281-1298 (2000). Y. G. Yingling, L. V. Zhigilei and B. J. Garrison, J. Photochemistry and Photobiology A: Chemistry, 145, 173-181 (2001); Y. G. Yingling and B. J. Garrison, Chem. Phys. Lett., 364, 237-243 (2002).

  18. The Self Actualized Reader.

    ERIC Educational Resources Information Center

    Marino, Michael; Moylan, Mary Elizabeth

    A study examined the commonalities that "voracious" readers share, and how their experiences can guide parents, teachers, and librarians in assisting children to become self-actualized readers. Subjects, 25 adults ranging in age from 20 to 67 years, completed a questionnaire concerning their reading histories and habits. Respondents varied in…

  19. Tropospheric Ozone and Photochemical Smog

    NASA Astrophysics Data System (ADS)

    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

  20. Solar photochemical process engineering for production of fuels and chemicals

    NASA Technical Reports Server (NTRS)

    Biddle, J. R.; Peterson, D. B.; Fujita, T.

    1984-01-01

    The engineering costs and performance of a nominal 25,000 scmd (883,000 scfd) photochemical plant to produce dihydrogen from water were studied. Two systems were considered, one based on flat-plate collector/reactors and the other on linear parabolic troughs. Engineering subsystems were specified including the collector/reactor, support hardware, field transport piping, gas compression equipment, and balance-of-plant (BOP) items. Overall plant efficiencies of 10.3 and 11.6% are estimated for the flat-plate and trough systems, respectively, based on assumed solar photochemical efficiencies of 12.9 and 14.6%. Because of the opposing effects of concentration ratio and operating temperature on efficiency, it was concluded that reactor cooling would be necessary with the trough system. Both active and passive cooling methods were considered. Capital costs and energy costs, for both concentrating and non-concentrating systems, were determined and their sensitivity to efficiency and economic parameters were analyzed. The overall plant efficiency is the single most important factor in determining the cost of the fuel.

  1. Solar photochemical process engineering for production of fuels and chemicals

    NASA Technical Reports Server (NTRS)

    Biddle, J. R.; Peterson, D. B.; Fujita, T.

    1985-01-01

    The engineering costs and performance of a nominal 25,000 scmd (883,000 scfd) photochemical plant to produce dihydrogen from water were studied. Two systems were considered, one based on flat-plate collector/reactors and the other on linear parabolic troughs. Engineering subsystems were specified including the collector/reactor, support hardware, field transport piping, gas compression equipment, and balance-of-plant (BOP) items. Overall plant efficiencies of 10.3 and 11.6 percent are estimated for the flat-plate and trough systems, respectively, based on assumed solar photochemical efficiencies of 12.9 and 14.6 percent. Because of the opposing effects of concentration ratio and operating temperature on efficiency, it was concluded that reactor cooling would be necessary with the trough system. Both active and passive cooling methods were considered. Capital costs and energy costs, for both concentrating and non-concentrating systems, were determined and their sensitivity to efficiency and economic parameters were analyzed. The overall plant efficiency is the single most important factor in determining the cost of the fuel.

  2. Photochemical degradation of PCBs in snow.

    PubMed

    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

  3. Photochemical grafting of diazonium salts on metals.

    PubMed

    Busson, Mathilde; Berisha, Avni; Combellas, Catherine; Kanoufi, Frédéric; Pinson, Jean

    2011-12-21

    4-Nitrobenzenediazonium may be photochemically grafted onto gold, copper and iron under visible and UV light. Thin nanometre layers are obtained and characterized by IRRAS, electrochemistry and ellipsometry. PMID:22031299

  4. Photochemical Degradation Of Organic-Solvent Fumes

    NASA Technical Reports Server (NTRS)

    Herzstock, James J.

    1990-01-01

    Quality of air in laboratory or industrial ventilation airstream enhanced by proposed technique. Source of ultraviolet light placed in airstream to degrade fumes photochemically. If fumes acceptable in degraded form, no further processing needed.

  5. The photochemical smog pollution in Beijing

    SciTech Connect

    Xiaoyan Tang

    1996-12-31

    The photochemical smog pollution in summer time has been studied in Beijing area. The systematic field measurements associated with meteorological observation was conducted in 1986, 1987 and 1993. The spatial and temporal distribution of O{sub 3} and specific formation condition of photochemical smog, including vehicle emission sources and meteorological factors etc. in summer were studied and discussed. The prediction of O{sub 3} ambient air concentration in Beijing area in 2000, 2005 and 2010 by model simulation were also discussed.

  6. Photochemical modeling of Titan's atmosphere

    PubMed

    Toublanc, D; Parisot, J P; Brillet, J; Gautier, D; Raulin, F; McKay, C P

    1995-01-01

    We have developed a new photochemical model of Titan's atmosphere which includes all the important compounds and reactions in spherical geometry from the surface to 1240 km. Compared to the previous model of Yung et al. (1984, Astrophys. J. Suppl. 55, 465-506), the most significant recent change in the reactions used is the updated methane photodissociation scheme (Mordaunt et al. 1993, J. Chem. Phys. 98(3), 2054-2065). Moreover, the transfer of the solar radiation in the atmosphere and the photolysis rates have been calculated by using a Monte Carlo code. Finally, the eddy diffusion coefficient profile is adjusted in order to fit the mean vertical distribution of HCN retrieved from millimeter groundbased observations of Tanguy et al. (1990, Icarus, 85, 43-57) using new values for the boundary flux of atomic nitrogen (Strobel et al. 1992, Icarus 100, 512-526). We have run the model in both steady-state and diurnal modes, with 62 speices involved in 249 reactions. There is little difference between diurnal and steady-state results. Overall our results are in a closer agreement with the abundances inferred from the Voyager infrared measurements at the equator than the Yung et al. results. We find that the catalytic scheme for H recombination invoked by Yung et al. only slightly improves the model results and we conclude that this scheme is not essential to fit observations. PMID:11538950

  7. Photochemical reduction of uranyl nitrate

    SciTech Connect

    Duerksen, W.K.

    1993-10-20

    The photochemical reduction of uranyl nitrate solutions to tetravalent uranium was investigated as a means of producing uranium dioxide feed for the saltless direct oxide reduction (SDOR) process. At high uranium concentrations, reoxidation of U{sup +4} occurs rapidly. The kinetics of the nitric oxidation of tetravalent uranium depend on the concentrations of hydrogen ion, nitrate ion, nitrous acid, and tetravalent uranium in the same manner as was reported elsewhere for the nitrate oxidation of PU{sup +3}. Reaction rate data were successfully correlated with a mechanism in which nitrogen dioxide is the reactive intermediate. Addition of a nitrous acid scavenger suppresses the reoxidation reaction. An immersion reactor employing a mercury vapor lamp gave reduction times fast enough for routine production usage. Precipitation techniques for conversion of aqueous U(NO{sub 3}){sub 4} to hydrous UO{sub 2} were evaluated. Prolonged dewatering times tended to make the process time consuming. Use of 3- to 4-M aqueous NaOH gave the best dewatering times observed. Reoxidation of the UO{sub 2} by water of hydration was encountered, which required the drying process to be carried out under a reducing atmosphere.

  8. Photochemical transformations of diazocarbonyl compounds: expected and novel reactions

    NASA Astrophysics Data System (ADS)

    Galkina, O. S.; Rodina, L. L.

    2016-05-01

    Photochemical reactions of diazocarbonyl compounds are well positioned in synthetic practice as an efficient method for ring contraction and homologation of carboxylic acids and as a carbene generation method. However, interpretation of the observed transformations of diazo compounds in electronically excited states is incomplete and requires a careful study of the fine mechanisms of these processes specific to different excited states of diazo compounds resorting to modern methods of investigation, including laser technology. The review is devoted to analysis of new data in the chemistry of excited states of diazocarbonyl compounds. The bibliography includes 155 references.

  9. Actualizing the Learning Community.

    ERIC Educational Resources Information Center

    Braman, Dave

    Where conditions are right, continuing education (CE) staff working in true collaboration with campus-based credit staff can meet the learning needs of the community and improve instructional quality with greater resource efficiency. CE staff must become learning strategists who bring ideas from their marketplace experience to the instructional…

  10. Photochemical vapor deposition of amorphous silicon photovoltaic devices. Semiannual subcontract report, 1 May 1985-31 October 1985

    SciTech Connect

    Baron, B.N.; Rocheleau, R.E.; Hegedus, S.S.

    1986-06-01

    Intrinsic, p-type, and n-type hydrogenated amorphous silicon thin-films have been deposited by mercury-sensitized photochemical vapor deposition (photo-CVD) from disilane. The photochemical reactor design includes two chambers separated by a movable uv-transparent Teflon curtain to eliminate deposition on the reactor window. Glass/TCO/p-i-n/metal photovoltaic devices were fabricated by photo-CVD. The efficiency at 87.5 MW/cm/sup 2/(ELH) was 5.1%.

  11. Photochemical dynamics of surface oriented molecules

    SciTech Connect

    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.

  12. Stratospheric Ozone: Transport, Photochemical Production and Loss

    NASA Technical Reports Server (NTRS)

    Douglass, A. R.; Kawa, S. R.; Jackman, C. H.

    2003-01-01

    Observations from various satellite instruments (e.g., Total Ozone Mapping Spectrometer (TOMS), Halogen Occultation Experiment (HALOE), Microwave Limb Sounder (MLS)) specify the latitude and seasonal variations of total ozone and ozone as a function of altitude. These seasonal variations change with latitude and altitude partly due to seasonal variation in transport and temperature, partly due to differences in the balance between photochemical production and loss processes, and partly due to differences in the relative importance of the various ozone loss processes. Comparisons of modeled seasonal ozone behavior with observations test the following: the seasonal dependence of dynamical processes where these dominate the ozone tendency; the seasonal dependence of photochemical processes in the upper stratosphere; and the seasonal change in the balance between photochemical and dynamical processes.

  13. Formation and inhibition of photochemical smog

    SciTech Connect

    Heicklen, J.

    1987-01-01

    Photochemical smog is caused by a free-radical chain mechanism which converts NO to NO/sub 2/. The NO/sub 2/ further reacts to produce ozone, nitric acid, and peracylnitrates. This chain mechanism can be inhibited by suitable free-radical scavengers. The chemistry and toxicology of one such free-radical scavenger, diethylhydroxylamine, has been studied in depth. It has been shown to be effective, safe, and practical for use in urban atmospheres to prevent photochemical smog formation. 42 references.

  14. Photochemical Production of Oligothiophene and Polythiophene Micropatterns from 2,5-diiodothiophene on Au in UHV

    SciTech Connect

    Liu,G.; Natarajan, S.; Kim, S.

    2005-01-01

    Fabrication of oligothiophene and polythiophene micropatterns is demonstrated by photochemical reactions of 2, 5-diiodothiophene adsorbed on an Au coated Si wafer under UHV conditions. For patterning, a TEM grid is utilized as a model stencil mask. Fluorescence microscopic analysis shows that polymer microstructures with good pattern fidelity are attained over a large area. RAIRS and NEXAFS analyses indicate that the electronic and molecular structures of the produced polymer are similar to those of chemically synthesized polythiophene. The structural defects of the photochemically produced polymer are negligible. The present procedure provides a very efficient strategy for growth and patterning of conjugated polymer microstructures with high quality in one step.

  15. 40 CFR 52.1877 - Control strategy: Photochemical oxidants (hydrocarbons).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... oxidants (hydrocarbons). 52.1877 Section 52.1877 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY....1877 Control strategy: Photochemical oxidants (hydrocarbons). (a) The requirements of Subpart G of this... national standard for photochemical oxidants (hydrocarbons) in the Metropolitan Cincinnati...

  16. 40 CFR 52.1877 - Control strategy: Photochemical oxidants (hydrocarbons).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... oxidants (hydrocarbons). 52.1877 Section 52.1877 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY....1877 Control strategy: Photochemical oxidants (hydrocarbons). (a) The requirements of Subpart G of this... national standard for photochemical oxidants (hydrocarbons) in the Metropolitan Cincinnati...

  17. 40 CFR 52.1877 - Control strategy: Photochemical oxidants (hydrocarbons).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... oxidants (hydrocarbons). 52.1877 Section 52.1877 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY....1877 Control strategy: Photochemical oxidants (hydrocarbons). (a) The requirements of Subpart G of this... national standard for photochemical oxidants (hydrocarbons) in the Metropolitan Cincinnati...

  18. 40 CFR 52.1877 - Control strategy: Photochemical oxidants (hydrocarbons).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... oxidants (hydrocarbons). 52.1877 Section 52.1877 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY....1877 Control strategy: Photochemical oxidants (hydrocarbons). (a) The requirements of Subpart G of this... national standard for photochemical oxidants (hydrocarbons) in the Metropolitan Cincinnati...

  19. 40 CFR 52.1877 - Control strategy: Photochemical oxidants (hydrocarbons).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... oxidants (hydrocarbons). 52.1877 Section 52.1877 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY....1877 Control strategy: Photochemical oxidants (hydrocarbons). (a) The requirements of Subpart G of this... national standard for photochemical oxidants (hydrocarbons) in the Metropolitan Cincinnati...

  20. A Simple Parallel Photochemical Reactor for Photodecomposition Studies

    ERIC Educational Resources Information Center

    Xiaobo Chen; Halasz, Sarah M.; Giles, Eric C.; Mankus, Jessica V.; Johnson, Joseph C.; Burda, Clemens

    2006-01-01

    A simple and useful parallel photochemical reactor intended to study the photodecomposition of dyes using semiconductor photocatalysis is presented. The photochemical reactions are followed through time-dependent changes in the ground-state absorption spectra of the dyes.

  1. Photochemical instability of the ancient Martian atmosphere

    NASA Astrophysics Data System (ADS)

    Zahnle, Kevin; Haberle, Robert M.; Catling, David C.; Kasting, James F.

    2008-11-01

    We develop a 1-D steady state photochemical model of the modern Martian atmosphere and apply it to possible Martian atmospheres present and past. A unique feature of our model is that the major current sink of oxygen is dry deposition (surface reactions) of highly reactive, oxidized molecules (chiefly H2O2), rather than oxygen escape to space. Another difference is that we allow hydrogen to escape to space at the diffusion limit, which gives H escape fluxes ~70% higher than in other models. What results is a model with one free parameter: a dry deposition velocity to describe the surface sink of reactive molecules. An effective global average deposition velocity of 0.02 cm s-1 for H2O2 and O3 gives a good match to the observed abundances of O2, CO, and H2, the three abundant photochemical trace gases. We then apply our model to Martian atmospheres with different amounts of CO2, H2O, and solar forcing. We find that thick, cold, dry CO2 atmospheres are photochemically unstable with respect to conversion to CO. This may be pertinent to ancient Mars when the Sun was faint and O escape rates were likely high, for which the tipping point is computed to be ~10 mbar of CO2. The possible photochemical instability of cold thick CO2 atmospheres, and the high likelihood that CO was abundant even if CO2 were stable, has broad implications for early Mars.

  2. Photochemical reactions of anthropogenic chemicals in seawater

    SciTech Connect

    Toole, A.P.; Crosby, D.G. )

    1988-09-01

    Sunlight-driven, photochemical reactions can be a major degradative force for anthropogenic organic compounds in the aquatic environment. Chlorinated phenols, various classes of pesticides, and polycyclic aromatic hydrocarbons are among some examples of the compounds shown to be degraded by sunlight. Most environmental photochemistry has been studied in fresh water, despite the fact that the oceans cover more than 70% of the earths surface and receive large inputs of anthropogenic chemicals via atmospheric transport, runoff, and coastal outfalls. This fact, along with increasing pressure for ocean waste disposal as land options dwindle, present a need for information on the photochemical reactions of anthropogenic organic chemicals in seawater. Several probable seawater pollutants were selected as probes for studying photochemical reactions including, 2-nitrotoluene, 4-nitrotoluene, styrene, 4,5-dichloroguaiacol, 4,5,6-trichloroguaiacol and tetrachloroguaiacol. Dilute solutions of each probe were prepared in buffered (pH 8), distilled water (DW), synthetic seawater (SSW) and natural seawater (NSW), then irradiated in a temperature-controlled photoreactor fitted with a General Electric F40BL fluorescent lamp to simulate sunlight. Samples were taken at regular intervals, concentrated using solid phase extraction techniques and analyzed by gas chromatography. Photolysis rates were determined assuming first, or pseudo-first, order kinetics. Photoproducts were identified by gas chromatography;mass spectrometry and confirmed by comparison to standards when available. By determining rates in DW containing selected components of SSW, at SSW concentrations, the inorganic compounds mediating the photochemical reactions in seawater could be determined.

  3. Photochemical Transformation of Graphene Oxide in Sunlight

    EPA Science Inventory

    Graphene oxide (GO) is a graphene derivative that is more easily manufactured in large scale and used to synthesize reduced graphene oxide (rGO) with properties analogous to graphene. In this study, we investigate the photochemical fate of GO under sunlight conditions. The resu...

  4. PHOTOCHEMICAL REACTIVITY OF PERCHLOROETHYLENE: A NEW APPRAISAL

    EPA Science Inventory

    Perchloroethylene (PCE), a solvent used in dry cleaning, has been suspected of contributing significantly to photochemical ozone/oxidant (O3/O(x)) problems in urban atmospheres. Past evidence, however, was neither complete nor consistent. To interpret more conclusively the past e...

  5. HANDBOOK ON ADVANCED PHOTOCHEMICAL OXIDATION PROCESSES

    EPA Science Inventory

    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...

  6. VALIDATION DATA FOR PHOTOCHEMICAL MECHANISMS: EXPERIMENTAL RESULTS

    EPA Science Inventory

    The smog chamber facility of the University of North Carolina (UNC) was used to provide experimental data for the EPA and atmospheric model developers for testing and validating kinetic mechanisms of photochemical smog formation. In the study, 71 dual-experiments were performed u...

  7. Photochemical synthesis of disilane from silane with infrared laser radiation

    SciTech Connect

    Zavelovich, J. ); Lyman, J.L. )

    1989-07-27

    The authors report the clean and efficient conversion of silane to disilane by CO{sub 2} laser irradiation. The direct irradiation of pure silane at high pressures (from 75 to 1,700 Torr) converts silane to disilane with high selectivity and with efficient use of the absorbed laser radiation. Hydrogen is the only other major volatile product, and the production of solid products is minimal. The proposed mechanism of the photochemical reaction includes (1) collisionally enhanced absorption of the laser radiation by silane, (2) collisional deexcitation of the vibrationally excited silane, (3) concurrent decomposition to SiH{sub 2} and H{sub 2}, (4) production of vibrationally excited disilane by SiH{sub 2} insertion into a silane Si-H bond, (5) collisional quenching of the excited disilane, and (6) rapid cooling of the irradiated gas by thermal expansion. They support the proposed mechanism by additional experiments and model calculations.

  8. A photochemical approach to aromatic extension of the corannulene nucleus.

    PubMed

    Rajeshkumar, Venkatachalam; Stuparu, Mihaiela C

    2016-08-01

    A high yielding, general, and mild synthetic strategy is established for aromatic annulation of the corannulene scaffold. In this approach, a corannulene-based aldehyde, ylide, or ketone compound is conjugated with an aromatic unit of choice through a Wittig reaction. The resulting stilbene-like precursor can be subjected to a photochemically induced oxidative-cyclization process to yield a corannulene structure with an extended π-framework. The generality of synthesis allows for preparation of a wide range of polycyclic aromatic arene as well as heteroarene structures. Meanwhile, the mild nature of the developed protocol permits for incorporation of reactive and functional substituents onto the fused aromatic scaffold. Furthermore, efficient and simple synthesis ensures access to significant amounts of the material in a facile manner. In essence, this work demonstrates, for the first time, that photochemical synthesis is a highly practical alternative to the known flash vacuum pyrolysis and metal catalyzed processes for the aromatic extension of the bucky-bowl structure. PMID:27440449

  9. Fate and implication of acetylacetone in photochemical processes for water treatment.

    PubMed

    Wu, Bingdang; Zhang, Guoyang; Zhang, Shujuan

    2016-09-15

    Acetylacetone (AA), due to the peculiar enol-keto structures, has attracted wide scientific interests. In terms of photo-decolorization, it works much more efficiently than the well-known H2O2. However, there is very limited information on the photochemistry of AA in aqueous solutions. Herein, the photolysis kinetics, quantum yield, mass balance, decomposition pathway, and bioavailability of AA during UV irradiation were systematically investigated. It seems that photophysical processes predominated over photochemical ones when AA was irradiated with UV light. Although the quantum yield of AA (0.116) was much lower than that of H2O2 (1.0), the stronger light absorption of AA and the better overlap of the AA absorption spectrum with the solar emission spectrum, as well as the direct energy/electron transfer mechanisms, ensured its high efficiency in photochemical processes. The main degradation products of AA in photochemical processes were similar to the metabolic products in bio-fermentation. Besides, the irradiated AA solution showed a high bioavailability to the cells in activated sludge. Therefore, the UV/AA process might be a promising pre-treatment approach for bio-treatment. The results provide new insights into the photochemical fate and implication of β-diketones in aqueous solutions. PMID:27262551

  10. Enhanced aqueous photochemical reaction rates after freezing.

    PubMed

    Grannas, Amanda M; Bausch, Alexandra R; Mahanna, Kendell M

    2007-11-01

    Sunlit snow/ice is known to play an important role in the processing of atmospheric species, including photochemical production of NO(x), HONO, molecular halogens, alkyl halides, and carbonyl compounds, among others. It has been shown that a liquid-like (quasi-liquid or disordered) layer exists on the surface of pure ice and that this quasi-liquid layer is also found on the surface of ambient snow crystals and ice at temperatures similar to polar conditions. However, it is unclear what role the liquid-like fractions present in and on frozen water play in potential photochemical reactions, particularly with regard to organic substrates. Here, we report a detailed study of enhanced rates of photochemical nucleophilic substitution of p-nitroanisole (PNA) with pyridine, a well-characterized and commonly used actinometer system. Reaction rates were enhanced by a factor of up to approximately 40 when frozen at temperatures between 236 and 272 K. Reaction rates were dependent on temperature and solute concentration, both variables that control the nature of the liquid-like fraction in frozen water. The results obtained indicate that a major portion of the organic solutes is excluded to the liquid-like layer, significantly impacting the rate of the photochemical nucleophilic substitution reaction studied here. Also, the direct comparison of liquid-phase kinetics to reactions occurring in frozen water systems is drawn into question, indicating that a simple extrapolation of liquid-phase mechanisms to snow/ice may not be valid for certain reactions. PMID:17918916

  11. A Photochemical Route to Metal Chalcogenide Nanomaterials

    NASA Astrophysics Data System (ADS)

    Warwick, P. C. Temple

    Semiconducting nanoscale metal chaicogenides are an important class of materials used in optoelectronics, photovoltaics, and thermoelectric applications. The properties of nanomaterials are directly influenced by their size and shape. Because of this a great deal of research has been focused on the size-controllable synthesis of these materials. Metal chalcogenide nanomaterial:; have been synthesized using solvothermal, sonochemical, pyrolysis, and microwave heating methods, which require high temperature and pressure. Furthermore, the reactants, solvents, and reaction conditions are highly specific for each method as well as the desired nanomaterial. We have developed a unique photochemical method for the generalized synthesis of metal chalcogenide nanomateri GIs. The photolysis is conducted at 20° C, which is substantially lower than current solution based methods. Furthermore, the low temperature allows conventional solvents to be used. We have synthesized Culn2, InS, SbSe, and E2S3 (where E = Sb and Bi) nanopz,rticles with sizes ranging from 5 - 100 nm by photolysis of photoreactive single source precursors (SSPs). The SSPs are designed to photochemically decompose to yield the desired material with the proper stoichiometry. Our SSPs contain photoactive benzyl-X ligands (where X = S or Se), which are known to undergo bond homolysis at the benzyl-X bond. The results indicate that the reactions proceed by bond homolysis to produce reactive radicals species that self-assemble to yield the desired nanomaterials. Furthermore, we have used the same photochemical method as a route to functiorialize a Si surface with bismuth sulfide. We have also investigated the photochemistry of Ph2PBn (where Bn = CH2Ph). Upon photolysis, the P-Bn bond cleaves and yields tetraphenyl diphosphine (Ph4P2) and bibenzyl (PhCH2CH2Ph). These results support the observations made during the photochemical metal chalcogenide nanomaterials synthesis.

  12. Photochemical aspects related to humic substances

    SciTech Connect

    Frimmel, F.H. )

    1994-01-01

    Dissolved humic substances (HS) show yellow color and relatively strong absorption in the UV range [a(254 nm) ca. 0.04 cm[sup [minus]1] for c(DOC) = 1 mg/L]. This is the basis for photochemical reactions in the photic zone of aquatic systems and in water treatment using IV sources. Even though understanding the mechanisms involved in the energy transfer and the resulting reactions is hampered by the poorly defined structure of HS, reliable information has been gathered on some typical aspects of their photochemistry. The luminescence of HS can be influenced and partly quenched by molecular interactions with other water constituents (e.g., heavy metals and organic micropollutants). The presence of oxygen may lead to the sensitized production of singlet oxygen (O[sub 2]), that can react specifically with substances containing diene structures or low valent sulfur. Because of the presence of these structures in HS, humic molecules will also react with the sensitized products. As a consequence, their biological, chemical, and physical properties are influenced. In addition, HS have a significant impact on the photochemical treatment of organic micropollutants in water. This has to be kept in mind when using photochemical steps for water treatment. The results from model experiments reflecting the conditions in surface water and in water treatment are given and discussed. In the presence of H[sub 2]O[sub 2], irradiation led to a transformation and partial degradation of HS. The rate of photochemical degradation of pesticides (e.g., atrazine) was decreased in the presence of HS. Fe and Mn quenched the luminescence. From this, a decrease of excited states of HS for sensitizing reactions can be deduced. The results suggest the manyfold and significant influences of HS on the photochemistry of aquatic systems. 66 refs., 9 figs., 7 tabs.

  13. Photochemical Phenomenology Model for the New Millennium

    NASA Technical Reports Server (NTRS)

    Bishop, James; Evans, J. Scott

    2001-01-01

    The "Photochemical Phenomenology Model for the New Millennium" project tackles the issue of reengineering and extension of validated physics-based modeling capabilities ("legacy" computer codes) to application-oriented software for use in science and science-support activities. While the design and architecture layouts are in terms of general particle distributions involved in scattering, impact, and reactive interactions, initial Photochemical Phenomenology Modeling Tool (PPMT) implementations are aimed at construction and evaluation of photochemical transport models with rapid execution for use in remote sensing data analysis activities in distributed systems. Current focus is on the Composite Infrared Spectrometer (CIRS) data acquired during the CASSINI flyby of Jupiter. Overall, the project has stayed on the development track outlined in the Year 1 annual report and most Year 2 goals have been met. The issues that have required the most attention are: implementation of the core photochemistry algorithms; implementation of a functional Java Graphical User Interface; completion of a functional CORBA Component Model framework; and assessment of performance issues. Specific accomplishments and the difficulties encountered are summarized in this report. Work to be carried out in the next year center on: completion of testing of the initial operational implementation; its application to analysis of the CASSINI/CIRS Jovian flyby data; extension of the PPMT to incorporate additional phenomenology algorithms; and delivery of a mature operational implementation.

  14. Photochemical modulation of DNA conformation by organic dications.

    PubMed

    Zinchenko, Anatoly A; Tanahashi, Mao; Murata, Shizuaki

    2012-01-01

    A group of azobenzene derivatives containing two quaternary ammonium groups with various intercharge distances between them was synthesised and used to control photochemically the conformation of genomic DNA by switching the distance between cationic ammonium groups in the dications. It was found that isomerisation of either dication from the trans form to cis resulted in an increase in the dication's efficiency for DNA compaction; this is associated with a decrease in intercharge distance between ammonium groups and leads to a better match of the binder's cationic groups to adjacent phosphate groups of DNA. Ammonium dications have several important advantages over the photosensitive surfactant type of diazobenzene reported earlier: they can be used at significantly lower (>100-fold) concentrations than photosensitive surfactants, and DNA conformation control can be performed over a broader concentration range of dications. The influence of intercharge distance in photosensitive dications on photo-induced DNA binding discrimination is discussed, and the molecular mechanism is proposed. PMID:22109974

  15. Photochemical Attenuation of Pesticides in Prairie Potholes

    NASA Astrophysics Data System (ADS)

    Zeng, T.; Arnold, W. A.

    2013-12-01

    Prairie potholes are small, shallow, glacially-derived wetlands scattered across a vast region extending from Midwestern United States into south central Canada known as the Prairie Pothole Region (PPR). They constitute one of the largest inland wetland systems on Earth and play a prominent role in sustaining the regional biodiversity and productivity. Throughout the PPR, historic and contemporary conversion of native prairie for agriculture resulted in a pronounced loss of potholes. Remaining potholes have become interspersed within a matrix of agricultural landscape and trap nonpoint source pollutants such as pesticides from adjacent farmland, which has raised concerns regarding negative impacts on the water quality of downstream water bodies. The fate and persistence of pesticides in potholes, however, remains largely unexplored. Prairie potholes are typically characterized by shallow depth (i.e., large photic zone) and high levels of dissolved organic matter (DOM), making them ideal for photochemical reactions. In this context, we collected pothole water samples from North Dakota to investigate the rates and mechanisms of sunlight-induced attenuation of pesticides. The photodegradation kinetics and pathways of sixteen pesticides in the pothole water were monitored under both simulated and natural sunlight. For most pesticides, photolysis accelerated in the pothole water relative to the buffer control, which pointed to the importance of photosensitized processes (i.e., indirect photolysis). Upon solar irradiation, a mixture of photochemically produced reactive intermediates (PPRIs), such as carbonate radical, hydroxyl radical, singlet oxygen, and triplet-excited state DOM, formed in the pothole water. The major pathways through which pesticides degraded were inferred from the relative contribution attributable to specific PPRIs via quencher experiments. Different classes of pesticides exhibited contrasting photochemical behavior, but singlet oxygen and triplet

  16. The actual goals of geoethics

    NASA Astrophysics Data System (ADS)

    Nemec, Vaclav

    2014-05-01

    The most actual goals of geoethics have been formulated as results of the International Conference on Geoethics (October 2013) held at the geoethics birth-place Pribram (Czech Republic): In the sphere of education and public enlightenment an appropriate needed minimum know how of Earth sciences should be intensively promoted together with cultivating ethical way of thinking and acting for the sustainable well-being of the society. The actual activities of the Intergovernmental Panel of Climate Changes are not sustainable with the existing knowledge of the Earth sciences (as presented in the results of the 33rd and 34th International Geological Congresses). This knowledge should be incorporated into any further work of the IPCC. In the sphere of legislation in a large international co-operation following steps are needed: - to re-formulate the term of a "false alarm" and its legal consequences, - to demand very consequently the needed evaluation of existing risks, - to solve problems of rights of individuals and minorities in cases of the optimum use of mineral resources and of the optimum protection of the local population against emergency dangers and disasters; common good (well-being) must be considered as the priority when solving ethical dilemmas. The precaution principle should be applied in any decision making process. Earth scientists presenting their expert opinions are not exempted from civil, administrative or even criminal liabilities. Details must be established by national law and jurisprudence. The well known case of the L'Aquila earthquake (2009) should serve as a serious warning because of the proven misuse of geoethics for protecting top Italian seismologists responsible and sentenced for their inadequate superficial behaviour causing lot of human victims. Another recent scandal with the Himalayan fossil fraud will be also documented. A support is needed for any effort to analyze and to disclose the problems of the deformation of the contemporary

  17. Photochemical synthesis of biomolecules under anoxic conditions

    NASA Technical Reports Server (NTRS)

    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.

  18. Recent laboratory photochemical studies and their relationship to the photochemical formation of cometary radicals

    NASA Technical Reports Server (NTRS)

    Jackson, William M.

    1991-01-01

    Experimental laboratory techniques used in studying the photochemistry of stable and unstable molecules are discussed. The laboratory evidence for the photochemical formation of C2 from C2H, C3 from C3H2, and NH from NH2 is presented. Other recent results obtained in laboratory studies of H2O, H2S, NH3, and HCN are reported.

  19. Surface chemistry for stable and smart molecular and biomolecular interfaces via photochemical grafting of alkenes.

    PubMed

    Wang, Xiaoyu; Landis, Elizabeth C; Franking, Ryan; Hamers, Robert J

    2010-09-21

    Many emerging fields such as biotechnology and renewable energy require functionalized surfaces that are "smart" and highly stable. Surface modification schemes developed previously have often been limited to simple molecules or have been based on weakly bound layers that have limited stability. In this Account, we report on recent developments enabling the preparation of molecular and biomolecular interfaces that exhibit high selectivity and unprecedented stability on a range of covalent materials including diamond, vertically aligned carbon nanofibers, silicon, and metal oxides. One particularly successful pathway to ultrastable interfaces involves the photochemical grafting of organic alkenes to the surfaces. Bifunctional alkenes with a suitable functional group at the distal end can directly impart functionality and can serve as attachment points for linking complex structures such as DNA and proteins. The successful application of photochemical grafting to a surprisingly wide range of materials has motivated researchers to better understand the underlying photochemical reaction mechanisms. The resulting studies using experimental and computational methods have provided fundamental insights into the electronic structure of the molecules and the surface control photochemical reactivity. Such investigations have revealed the important role of a previously unrecognized process, photoelectron emission, in initiating photochemical grafting of alkenes to surfaces. Molecular and biomolecular interfaces formed on diamond and other covalent materials are leading to novel types of molecular electronic interfaces. For example, electrical, optical, or electromechanical structures that convert biological information directly into analytical signals allow for direct label-free detection of DNA and proteins. Because of the preferential adherence of molecules to graphitic edge-plane sites, the grafting of redox-active species to vertically aligned carbon nanofibers leads to

  20. Heterogeneous Photochemical Oxidation of Sulfur Dioxide

    NASA Astrophysics Data System (ADS)

    El-Zanan, H. S.; Stockwell, W. R.

    2007-12-01

    The gas phase oxidation of sulfur dioxide by the hydroxyl radical is a significant source of sulfate aerosol in the troposphere and stratosphere. Stockwell and Calvert (1983) performed fifteen chamber experiments where mixtures of HONO, NO, NO2, H2O, SO2 and CO were photolyzed in synthetic air or in nitrogen containing approximately 50 ppm oxygen. They found that the atmospheric oxidation of SO2 by hydroxyl radical was a chain process that occurs through the production of an HO2 radical followed by reaction with NO to reproduce HO. We have reanalyzed this dataset and we have found that a very large amount of the observed SO2 oxidation (70.0 ± 9.1 %) is not explained through the HO + SO2 reaction alone. The Regional Atmospheric Chemistry Mechanism (RACM2) was used to investigate additional chemical pathways for the oxidation of SO2. A mechanism consisting of photochemical heterogeneous reactions is proposed to account for the observed additional sulfur dioxide oxidation not accounted for by gas phase oxidation. The analysis showed that the measured time dependent SO2, CO2 and nitrogenous compound concentrations could be simulated by the photochemical heterogeneous mechanism in conjunction with the RACM2 mechanism.

  1. Linguistic Theory and Actual Language.

    ERIC Educational Resources Information Center

    Segerdahl, Par

    1995-01-01

    Examines Noam Chomsky's (1957) discussion of "grammaticalness" and the role of linguistics in the "correct" way of speaking and writing. It is argued that the concern of linguistics with the tools of grammar has resulted in confusion, with the tools becoming mixed up with the actual language, thereby becoming the central element in a metaphysical…

  2. A PHOTOCHEMICAL BOX MODEL FOR URBAN AIR QUALITY SIMULATION

    EPA Science Inventory

    A simple 'box-approach' to air quality simulation modeling has been developed in conjunction with a newly formulated photochemical kinetic mechanism to produce an easily applied Photochemical Box Model (PBM). This approach represents an urban area as a single cell 20 km in both l...

  3. Solar Irradiation of Bilirubin: An Experiment in Photochemical Oxidation

    ERIC Educational Resources Information Center

    Pillay A. E.; Salih, F. M.

    2006-01-01

    An experiment in photochemical oxidation, which deals with bilirubin, a well-known light-sensitive biological compound that is pedagogically ideal for photochemical experiments at tertiary institutes, is presented. The experiment would benefit students in chemistry who eventually branch out into the health sciences or biochemistry.

  4. Photochemical vapor deposition of amorphous silicon photovoltaic devices: Annual subcontract report, 1 May 1985-30 April 1986

    SciTech Connect

    Baron, B.N.; Rocheleau, R.E.; Hegedus, S.S.

    1987-02-01

    Intrinsic, p-type, and n-type a-Si:H and p-type a-SiC:H thin-films have been deposited by Hg-sensitized photochemical vapor depositions (photo-CVD) from disilane. The photochemical reactor design includes two chambers separated by a movable uv-transparent Teflon curtain, which eliminates deposition on the reactor window. Photovoltaic devices of the type glass/TCO/p-i-n/metal were fabricated by photo-CVD. The device efficiency obtained at 87.5 mW/cm/sup 2/ and ELH illumination was 6.4%.

  5. Photochemical coal dissolution. Quarterly technical progress report, April 1, 1995--June 30, 1995

    SciTech Connect

    Doetschman, D.C.

    1996-01-01

    Research continued on coal photochemical dissolution. Experiments were performed in a newly constructed, computerized, coal photochemical reactor. The experiments demonstrated the active participation of coal in photochemistry.

  6. UV-induced photochemical heterogeneity of dissolved and attached organic matter associated with cyanobacterial blooms in a eutrophic freshwater lake.

    PubMed

    Xu, Huacheng; Jiang, Helong

    2013-11-01

    Cyanobacterial blooms represent a significant ecological and human health problem worldwide. In aquatic environments, cyanobacterial blooms are actually surrounded by dissolved organic matter (DOM) and attached organic matter (AOM) that bind with algal cells. In this study, DOM and AOM fractionated from blooming cyanobacteria in a eutrophic freshwater lake (Lake Taihu, China) were irradiated with a polychromatic UV lamp, and the photochemical heterogeneity was investigated using fluorescence excitation-emission matrix (EEM)-parallel factor (PARAFAC) analysis and synchronous fluorescence (SF)-two dimensional correlation spectroscopy (2DCOS). It was shown that a 6-day UV irradiation caused more pronounced mineralization for DOM than AOM (59.7% vs. 41.9%). The EEM-PARAFAC analysis identified one tyrosine-, one humic-, and two tryptophan-like components in both DOM and AOM, and high component photodegradation rates were observed for DOM versus AOM (k > 0.554 vs. <0.519). Moreover, SF-2DCOS found that the photodegradation of organic matters followed the sequence of tyrosine-like > humic-like > tryptophan-like substances. Humic-like substances promoted the indirect photochemical reactions, and were responsible for the higher photochemical rate for DOM. The lower photodegradation of AOM benefited the integrality of cells in cyanobacterial blooms against the negative impact of UV irradiation. Therefore, the photochemical behavior of organic matter was related to the adaptation of enhanced-duration cyanobacterial blooms in aquatic environments. PMID:24041526

  7. Photochemical Isomerization and Topochemical Polymerization of the Programmed Asymmetric Amphiphiles.

    PubMed

    Kim, Dae-Yoon; Lee, Sang-A; Jung, Daseal; Jeong, Kwang-Un

    2016-01-01

    For the advancement in multi-stimuli responsive optical devices, we report the elaborate molecular engineering of the dual photo-functionalized amphiphile (abbreviated as AZ1DA) containing both a photo-isomerizable azobenzene and a photo-polymerizable diacetylene. To achieve the efficient photochemical reactions in thin solid films, the self-assembly of AZ1DA molecules into the ordered phases should be precisely controlled and efficiently utilized. First, the remote-controllable light shutter is successfully demonstrated based on the reversible trans-cis photo-isomerization of azobenzene group in the smectic A mesophase. Second, the self-organized monoclinic crystal phase allows us to validate the photo-polymerization of diacetylene moiety for the photo-patterned thin films and the thermo-responsible color switches. From the demonstrations of optically tunable thin films, it is realized that the construction of strong relationships between chemical structures, molecular packing structures and physical properties of the programmed molecules is the core research for the development of smart and multifunctional soft materials. PMID:27339163

  8. Photochemical Isomerization and Topochemical Polymerization of the Programmed Asymmetric Amphiphiles

    NASA Astrophysics Data System (ADS)

    Kim, Dae-Yoon; Lee, Sang-A.; Jung, Daseal; Jeong, Kwang-Un

    2016-06-01

    For the advancement in multi-stimuli responsive optical devices, we report the elaborate molecular engineering of the dual photo-functionalized amphiphile (abbreviated as AZ1DA) containing both a photo-isomerizable azobenzene and a photo-polymerizable diacetylene. To achieve the efficient photochemical reactions in thin solid films, the self-assembly of AZ1DA molecules into the ordered phases should be precisely controlled and efficiently utilized. First, the remote-controllable light shutter is successfully demonstrated based on the reversible trans-cis photo-isomerization of azobenzene group in the smectic A mesophase. Second, the self-organized monoclinic crystal phase allows us to validate the photo-polymerization of diacetylene moiety for the photo-patterned thin films and the thermo-responsible color switches. From the demonstrations of optically tunable thin films, it is realized that the construction of strong relationships between chemical structures, molecular packing structures and physical properties of the programmed molecules is the core research for the development of smart and multifunctional soft materials.

  9. Photochemical Isomerization and Topochemical Polymerization of the Programmed Asymmetric Amphiphiles

    PubMed Central

    Kim, Dae-Yoon; Lee, Sang-A; Jung, Daseal; Jeong, Kwang-Un

    2016-01-01

    For the advancement in multi-stimuli responsive optical devices, we report the elaborate molecular engineering of the dual photo-functionalized amphiphile (abbreviated as AZ1DA) containing both a photo-isomerizable azobenzene and a photo-polymerizable diacetylene. To achieve the efficient photochemical reactions in thin solid films, the self-assembly of AZ1DA molecules into the ordered phases should be precisely controlled and efficiently utilized. First, the remote-controllable light shutter is successfully demonstrated based on the reversible trans-cis photo-isomerization of azobenzene group in the smectic A mesophase. Second, the self-organized monoclinic crystal phase allows us to validate the photo-polymerization of diacetylene moiety for the photo-patterned thin films and the thermo-responsible color switches. From the demonstrations of optically tunable thin films, it is realized that the construction of strong relationships between chemical structures, molecular packing structures and physical properties of the programmed molecules is the core research for the development of smart and multifunctional soft materials. PMID:27339163

  10. Mars atmospheric loss and isotopic fractionation by solar-wind-induced sputtering and photochemical escape

    NASA Technical Reports Server (NTRS)

    Jakosky, B. M.; Pepin, R. O.; Johnson, R. E.; Fox, J. L.

    1993-01-01

    We examine the effects of loss of Mars atmospheric constituents by solar-wind-induced sputtering and by photochemical escape during the last 3.8 b.y. Sputtering is capable of efficiently removing all species from the upper atmosphere including the light noble gases; N is removed by photochemical processes as well. Due to diffusive separation (by mass) above the homopause, removal from the top of the atmosphere will fractionate the isotopes of each species with the lighter mass being preferentially lost. For C and O, this allows us to determine the size of nonatmospheric reservoirs that mix with the atmosphere; these reservoirs can be CO2 adsorbed in the regolith or H2O in the polar ice caps. We have constructed both simple analytical models and time-dependent models of the loss from and supply of volatiles to the Martian atmosphere.

  11. Mars atmosphere loss and isotopic fractionation by solar-wind-induced sputtering and photochemical escape

    NASA Technical Reports Server (NTRS)

    Jakosky, B. M.; Pepin, R. O.; Johnson, R. E.; Fox, J. L.

    1993-01-01

    The effects of loss of Mars atmospheric constituents by solar-wind-induced sputtering and by photochemical escape during the last 3.8 b.y. were examined. Sputtering is capable of efficiently removing all species from the upper atmosphere, including the light noble gases; N also is removed by photochemical processes. Due to the diffusive separation by mass above the homopause, removal from the top of the atmosphere will fractionate the isotopes of each species, with the lighter mass being preferentially lost. For C and O, this allows us to determine the size of nonatmospheric reservoirs that mix with the atmosphere; these reserviors can be accounted for by exchange with CO2 adsorbed in the regolith and with H2O in the polar ice deposits. Both simple analytical models and time-dependent models of the loss of volatiles from and supply to the Martian atmosphere were constructed. Both Ar and Ne require continued replenishment from outgassing over geologic time.

  12. Effect of the Hydrogen Bond on Photochemical Synthesis of Silver Nanoparticles.

    PubMed

    Zhao, Feng-jiao; Liu, Lei; Yang, Yang; Zhang, Rui-ling; Ren, Guang-hua; Xu, Da-li; Zhou, Pan-wang; Han, Ke-li

    2015-12-17

    The effect of a hydrogen bond on the photochemical synthesis of silver nanoparticles has been investigated via experimental and theoretical methods. In a benzophenone system, the photochemical synthesis process includes two steps, which are that hydrogen abstraction reaction and the following reduction reaction. We found that for the first step, an intermolecular hydrogen bond enhances the proton transfer. The efficiency of hydrogen abstraction increases with the hydrogen bond strength. For the second step, the hydrogen-bonded ketyl radical complex shows higher reducibility than the ketyl radical. The inductively coupled plasma-optical emission spectroscopy (ICP-OES) measurement exhibits a 2.49 times higher yield of silver nanoparticles in the hydrogen bond ketyl radical complex system than that for the ketyl radical system. Theoretical calculations show that the hydrogen bond accelerates electron transfer from the ketyl radical to the silver ion by raising the SOMO energy of the ketyl radical; thus, the SOMO-LUMO interaction is more favorable. PMID:26562362

  13. THE PHOTOCHEMICAL NATURE OF THE PHOTOSENSORY PROCESS.

    PubMed

    Hecht, S

    1920-01-20

    1. In order to produce a response in Mya, the minimum amount of light energy required is 5.62 meter candle seconds. This energy follows the Bunsen-Roscoe law for the relation between intensity and time of exposure. 2. The necessary minimum amount of energy varies but little with the temperature; the temperature coefficient for 10 degrees C. is 1.06. 3. In view of these facts it is concluded that the initial action of the light is photochemical in nature. This substantiates the hypothesis previously suggested to account for the mechanism of photoreception. 4. The constant energy requirement for stimulation of Mya shows that the traditional division of animals into those which respond to a constant source of light and those which respond to a rapidly augmented light is without any fundamental significance for sensory physiology. PMID:19871805

  14. Photochemical Microcontact Printing by Tetrazole Chemistry.

    PubMed

    Vonhören, Benjamin; Roling, Oliver; Buten, Christoph; Körsgen, Martin; Arlinghaus, Heinrich F; Ravoo, Bart Jan

    2016-03-01

    We developed a simple method to pattern self-assembled monolayers of tetrazole triethoxylsilane with a variety of different molecules by photochemical microcontact printing. Under irradiation, tetrazoles form highly reactive nitrile imines, which react with alkenes, alkynes, and thiols. The covalent linkage to the surface could be unambiguously demonstrated by fluorescence microscopy, because the reaction product is fluorescent in contrast to tetrazole. The modified surfaces were further analyzed by X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), atomic force microscopy (AFM), and contact angle goniometry. Protein-repellent micropatterns, a biotin-streptavidin array, and structured polymer brushes could be fabricated with this straightforward method for surface functionalization. PMID:26886297

  15. The photochemical role of tropospheric nitrogen oxides

    NASA Technical Reports Server (NTRS)

    Chameides, W. L.

    1978-01-01

    The role of nitrogen oxides in the tropospheric photochemical system is re-evaluated in the light of recent measurements of the rate constants for two key reactions. A model for nitrogen oxides is discussed which yields surface NO(x) (NO+NO2) levels approaching 1 ppb in NO(x) source regions but less than 0.1 ppb outside source regions. Applying the new rate coefficients implies increased radical concentrations and a more intense O3 and CO photochemistry. Even for densities of 0.1 ppb or less, NO(x) still leads to significant local O3 production and conversion of HO2 to OH. Unrealistic O3 profiles are obtained with the new rate coefficients for surface NO(x) densities of about 1 ppb, while reasonable agreement with observation is obtained with lower NO(x) densities. Feedback processes between CO, NO(x), OH, and CH4 are also discussed.

  16. Multidimensional Electronic Spectroscopy of Photochemical Reactions.

    PubMed

    Nuernberger, Patrick; Ruetzel, Stefan; Brixner, Tobias

    2015-09-21

    Coherent multidimensional electronic spectroscopy can be employed to unravel various channels in molecular chemical reactions. This approach is thus not limited to analysis of energy transfer or charge transfer (i.e. processes from photophysics), but can also be employed in situations where the investigated system undergoes permanent structural changes (i.e. in photochemistry). Photochemical model reactions are discussed by using the example of merocyanine/spiropyran-based molecular switches, which show a rich variety of reaction channels, in particular ring opening and ring closing, cis-trans isomerization, coherent vibrational wave-packet motion, radical ion formation, and population relaxation. Using pump-probe, pump-repump-probe, coherent two-dimensional and three-dimensional, triggered-exchange 2D, and quantum-control spectroscopy, we gain intuitive pictures on which product emerges from which reactant and which reactive molecular modes are associated. PMID:26382095

  17. [Photochemical degradation of chlorothalonil in aqueous solution].

    PubMed

    Li, Xuede; Hua, Rimao; Yue, Yongde; Li, Ying; Tang, Feng; Tang, Jun

    2006-06-01

    The study on the effects of light source, solution pH and temperature, and surfactant on the photochemical degradation of chlorothalonil showed that the half-life of chlorothalonil photodegradation under high pressure mercury lamp (HPML), UV lamp and sunlight was 22.4, 82.5 and 123.8 min, respectively. Under HPML and sunlight, chlorothalonil had a higher photolysis rate in alkaline solution than in neutral and acid solution. The photolysis rate increased with increasing solution temperature in the range of 10 degrees C - 40 degrees C, which was doubled when the temperature increased every 10 degrees C. Sodium laurylsulfonate (SDS), sodium dodecylbenzene sulfonate (SDBS), Tween 60 and Span 20 showed significant photosensitizing effects, while cetyltrimethylammonium bromide (CTAB) had significant photoquench effect on the photolysis of chlorothalonil. PMID:16964947

  18. Fibre-optic photochemical stroke: generating and measuring photochemical changes inside the brain

    NASA Astrophysics Data System (ADS)

    Tsiminis, G.; Klarić, T. S.; Schartner, E. P.; Warren-Smith, S. C.; Lewis, M. D.; Koblar, S. A.; Monro, T. M.

    2014-05-01

    We report here on the development of a method to induce a stroke in a specific location within a mouse brain through the use of an optical fibre. By capturing the emitted fluorescence signal generated using the same fibre it is then possible to monitor photochemical changes within the brain in real-time, potentially reducing the requirement for post-operative histology to determine if a stroke has successfully been induced within the animal.

  19. Photochemical Aging of Organic Aerosol Particles

    NASA Astrophysics Data System (ADS)

    Nizkorodov, S. A.; Bateman, A. P.; Dailo, M.; Do, T.; Mang, S. A.; Pan, X.; Underwood, J. S.; Walser, M. L.

    2007-05-01

    Secondary Organic Aerosol (SOA) particles are produced in the atmosphere as a result of oxidation of volatile organic compounds (VOC). Primary Organic Aerosol (POA) particles are directly emitted in the atmosphere by their sources. This research focuses on the mechanisms of direct photochemical processes taking place in model SOA and POA particles, the role of such processes in aging of organic aerosol particles, and the effect of photochemistry on particles' physicochemical properties. To address these questions, artificial SOA and POA particles are investigated with several laboratory-based approaches relying on cavity ring-down spectroscopy and mass-spectrometry. SOA particles generated by dark oxidation of d-Limonene, alpha-Pinene, and beta-Pinene by ozone are all found to absorb radiation in the tropospheric actinic window. The UV absorption photolyzes SOA constituents resulting in a release of small VOC molecules back in the gas-phase, and considerable change in SOA chemical composition. For terpenes featuring a terminal double bond, the main SOA photolysis products are invariably found to be formaldehyde and formic acid. Similar observations are obtained for products of ozonolysis of thin films of unsaturated fatty acids and self-assembled monolayers of unsaturated alkenes. For the case of fatty acids, a very detailed mechanism of ozonolysis and subsequent photolysis is proposed. The photolytic activity is primarily attributed to organic peroxides and aldehydes. These results convincingly demonstrate that photochemical processes occurring inside SOA and POA particles age the particles on time scales that are shorter than typical lifetimes of aerosol particles in the atmosphere.

  20. Photochemical processing of aqueous atmospheric brown carbon

    NASA Astrophysics Data System (ADS)

    Zhao, R.; Lee, A. K. Y.; Huang, L.; Li, X.; Yang, F.; Abbatt, J. P. D.

    2015-06-01

    Atmospheric brown carbon (BrC) is a collective term for light absorbing organic compounds in the atmosphere. While the identification of BrC and its formation mechanisms is currently a central effort in the community, little is known about the atmospheric removal processes of aerosol BrC. As a result, we report on a series of laboratory studies of photochemical processing of BrC in the aqueous phase, by direct photolysis and OH oxidation. Solutions of ammonium sulfate mixed with glyoxal (GLYAS) or methylglyoxal (MGAS) are used as surrogates for a class of secondary BrC mediated by imine intermediates. Three nitrophenol species, namely 4-nitrophenol, 5-nitroguaiacol and 4-nitrocatechol, were investigated as a class of water-soluble BrC originating from biomass burning. Photochemical processing induced significant changes in the absorptive properties of BrC. The imine-mediated BrC solutions exhibited rapid photo-bleaching with both direct photolysis and OH oxidation, with atmospheric half-lives of minutes to a few hours. The nitrophenol species exhibited photo-enhancement in the visible range during direct photolysis and the onset of OH oxidation, but rapid photo-bleaching was induced by further OH exposure on an atmospheric timescale of an hour or less. To illustrate the atmospheric relevance of this work, we also performed direct photolysis experiments on water-soluble organic carbon extracted from biofuel combustion samples and observed rapid changes in the optical properties of these samples as well. Overall, these experiments indicate that atmospheric models need to incorporate representations of atmospheric processing of BrC species to accurately model their radiative impacts.

  1. Photochemical processing of aqueous atmospheric brown carbon

    NASA Astrophysics Data System (ADS)

    Zhao, R.; Lee, A. K. Y.; Huang, L.; Li, X.; Yang, F.; Abbatt, J. P. D.

    2015-01-01

    Atmospheric Brown Carbon (BrC) is a collective term for light absorbing organic compounds in the atmosphere. While the identification of BrC and its formation mechanisms is currently a central effort in the community, little is known about the atmospheric removal processes of aerosol BrC. As a result, we report a series of laboratory studies of photochemical processing of BrC in the aqueous phase, by direct photolysis and OH oxidation. Solutions of ammonium sulfate mixed with glyoxal (GLYAS) or methylglyoxal (MGAS) are used as surrogates for a class of secondary BrC mediated by imine intermediates. Three nitrophenol species, namely 4-nitrophenol, 5-nitroguaiacol and 4-nitrocatechol, were investigated as a class of water soluble BrC originating from biomass burning. Photochemical processing induced significant changes in the absorptive properties of BrC. The imine-mediated BrC solutions exhibited rapid photo-bleaching with both direct photolysis and OH oxidation, with atmospheric half-lives of minutes to a few hours. The nitrophenol species exhibited photo-enhancement in the visible range during direct photolysis and the onset of OH oxidation, but rapid photo-bleaching was induced by further OH exposure on an atmospheric timescale of an hour or less. To illustrate atmospheric relevance of this work, we also performed direct photolysis experiments on water soluble organic carbon extracted from biofuel combustion samples and observed rapid changes in optical properties of these samples as well. Overall, these experiments indicate that atmospheric models need to incorporate representations of atmospheric processing of BrC species to accurately model their radiative impacts.

  2. Photochemical activity in waters of the Great Barrier Reef

    NASA Astrophysics Data System (ADS)

    Szymczak, R.; Waite, T. D.

    1991-12-01

    Photochemical activity in waters of the Great Barrier Reef was investigated through studies on the vertical, horizontal and temporal distribution of hydrogen peroxide and factors influencing its generation and decay processes. Surface hydrogen peroxide concentrations varied from 15 to 110 nM and generally decreased with depth, though a number of anomalies were detected. Photochemical activity decreased with increasing distance from the coast reflecting the positive influence of terrestrial inputs to the hydrogen peroxide generation and decay processes. Increases in photochemical activity were observed in the proximity of coral reefs. Hydrogen peroxide concentrations in the region were influenced by wind-induced mixing processes, atmospheric inputs, anthropogenic activity and seasonal light regimes.

  3. Photochemical weathering and contemporary volatile loss on Mars

    NASA Technical Reports Server (NTRS)

    Huguenin, R. L.

    1987-01-01

    In an earlier series of papers by the author it was proposed that photochemical weathering of Fe(2+) in magnetite and in mafic silicates may be occurring in the contemporary surface environment with a resultant loss of O2 from the atmosphere. Morris and Lauer challenged the photochemical weathering model, proposing that oxidation by radiant heating rather than UV photoelectron emission induced oxidation may have dominated in the authors experiments. Subsequent laboratory studies of photochemical weathering of magnetite described here support the authors original proposal that UV illunimation can indeed drive the oxidation of magnetite under contemporary Martian surface conditions. The negative results of the Morris and Lauer study can now be explained.

  4. How People Actually Use Thermostats

    SciTech Connect

    Meier, Alan; Aragon, Cecilia; Hurwitz, Becky; Mujumdar, Dhawal; Peffer, Therese; Perry, Daniel; Pritoni, Marco

    2010-08-15

    Residential thermostats have been a key element in controlling heating and cooling systems for over sixty years. However, today's modern programmable thermostats (PTs) are complicated and difficult for users to understand, leading to errors in operation and wasted energy. Four separate tests of usability were conducted in preparation for a larger study. These tests included personal interviews, an on-line survey, photographing actual thermostat settings, and measurements of ability to accomplish four tasks related to effective use of a PT. The interviews revealed that many occupants used the PT as an on-off switch and most demonstrated little knowledge of how to operate it. The on-line survey found that 89% of the respondents rarely or never used the PT to set a weekday or weekend program. The photographic survey (in low income homes) found that only 30% of the PTs were actually programmed. In the usability test, we found that we could quantify the difference in usability of two PTs as measured in time to accomplish tasks. Users accomplished the tasks in consistently shorter times with the touchscreen unit than with buttons. None of these studies are representative of the entire population of users but, together, they illustrate the importance of improving user interfaces in PTs.

  5. Metal hybrid nanoparticles for catalytic organic and photochemical transformations.

    PubMed

    Song, Hyunjoon

    2015-03-17

    In order to understand heterogeneous catalytic reactions, model catalysts such as a single crystalline surface have been widely studied for many decades. However, catalytic systems that actually advance the reactions are three-dimensional and commonly have multiple components including active metal nanoparticles and metal oxide supports. On the other hand, as nanochemistry has rapidly been developed and been applied to various fields, many researchers have begun to discuss the impact of nanochemistry on heterogeneous catalysis. Metal hybrid nanoparticles bearing multiple components are structurally very close to the actual catalysts, and their uniform and controllable morphology is suitable for investigating the relationship between the structure and the catalytic properties in detail. In this Account, we introduce four typical structures of metal hybrid nanoparticles that can be used to conduct catalytic organic and photochemical reactions. Metal@silica (or metal oxide) yolk-shell nanoparticles, in which metal cores exist in internal voids surrounded by thin silica (or metal oxide) shells, exhibited extremely high thermal and chemical stability due to the geometrical protection of the silica layers against the metal cores. The morphology of the metal cores and the pore density of the hollow shells were precisely adjusted to optimize the reaction activity and diffusion rates of the reactants. Metal@metal oxide core-shell nanoparticles and inverted structures, where the cores supported the shells serving an active surface, exhibited high activity with no diffusion barriers for the reactants and products. These nanostructures were used as effective catalysts for various organic and gas-phase reactions, including hydrogen transfer, Suzuki coupling, and steam methane reforming. In contrast to the yolk- and core-shell structures, an asymmetric arrangement of distinct domains generated acentric dumbbells and tipped rods. A large domain of each component added multiple

  6. Photochemical model for NH3 in an early Martian atmosphere

    NASA Technical Reports Server (NTRS)

    Brown, L. L.; Kasting, J. F.

    1992-01-01

    A warm and wet climate scenario for early Mars has been explained by invoking a 5-bar CO2 atmosphere; however, Kasting has shown that CO2 will condense in the Martian atmosphere at these pressures. The formation of CO2 clouds will reduce the convection lapse rate and reduce the magnitude of the greenhouse effect. It is possible that additional greenhouse gases such as methane and ammonia were present in the early Mars atmosphere. We are using a one dimensional photochemical model to estimate the magnitude of the ammonia source required to maintain a given ammonia concentration in a dense CO2 atmosphere. Because CO2 is 2.5 times more efficient at Rayleigh scattering than Earth's N2 atmosphere, we anticipate increased scattering opacities and decreased photolytic destruction rates of ammonia on early Mars. The reduced gravity on Mars means that a 1 bar atmosphere will be approximately 3 times as thick as on Earth. It is possible that ammonia could have been shielded from photolysis by hydrocarbon aerosols which form as a product of methane photolysis.

  7. Surface and Interface Control on Photochemically Initiated Immobilization

    SciTech Connect

    Liu, Li; Engelhard, Mark H.; Yan, Mingdi

    2006-11-01

    Surface and interface properties are important in controlling the yield and efficiency of the photochemically initiated immobilization. Using a silane-functionalized perfluorophenylazide (PFPA-silane) as the photoactive crosslinker, the immobilization of polymers was studied by adjusting the density of the surface azido groups. Dilution of the photolinker resulted in a gradual decrease in the density of surface azido groups as well as the thickness of the immobilized film. When a non-photoactive silane was added to PFPA-silane, the film thickness decreased more rapidly, indicating that the additive competed with PFPA-silane and effectively reduced the density of the surface azido groups. The effect of surface topography was studied by adding a non-photoactive silane with either a shorter (n-propyltrimethoxysilane (PTMS)) or a longer spacer (n-octadecyltrimethoxysilane (ODTMS)). In most cases the long chain ODTMS shielded the surface azido groups resulting in more rapid decrease in film thickness as compared to PTMS treated under the same conditions. As the density of the surface azido groups decreased, the immobilized polymer changed from smooth films to patched structures, and eventually single polymer molecules.

  8. Promoting Photochemical Water Oxidation with Metallic Band Structures.

    PubMed

    Liu, Hongfei; Moré, René; Grundmann, Henrik; Cui, Chunhua; Erni, Rolf; Patzke, Greta R

    2016-02-10

    The development of economic water oxidation catalysts is a key step toward large-scale water splitting. However, their current exploration remains empirical to a large extent. Elucidating the correlations between electronic properties and catalytic activity is crucial for deriving general and straightforward catalyst design principles. Herein, strongly correlated electronic systems with abundant and easily tunable electronic properties, namely La(1-x)Sr(x)BO3 perovskites and La(2-x)Sr(x)BO4 layered perovskites (B = Fe, Co, Ni, or Mn), were employed as model systems to identify favorable electronic structures for water oxidation. We established a direct correlation between the enhancement of catalytic activity and the insulator to metal transition through tuning the electronic properties of the target perovskite families via the La(3+)/Sr(2+) ratio. Their improved photochemical water oxidation performance was clearly linked to the increasingly metallic character. These electronic structure-activity relations provide a promising guideline for constructing efficient water oxidation catalysts. PMID:26771537

  9. Formation of smooth, conformal molecular layers on ZnO surfaces via photochemical grafting.

    PubMed

    Ruther, Rose E; Franking, Ryan; Huhn, Alex M; Gomez-Zayas, Jaritza; Hamers, Robert J

    2011-09-01

    We have investigated the photochemical grafting of organic alkenes to atomically flat ZnO(10 ̅10) single crystals and ZnO nanorods as a way to produce functional molecule-semiconductor interfaces. Atomic force microscopy shows that photochemical grafting produces highly conformal, smooth molecular layers with no detectable changes in the underlying structure of the ZnO terraces or steps. X-ray photoelectron spectroscopy measurements show that grafting of a methyl ester-terminated alkene terminates near one monolayer, while alkenes bearing a trifluoroacetamide-protected amine form very smooth multilayers. Even with multilayers, it is possible to deprotect the amines and to link a second molecule to the surface with excellent efficiency and without significant loss of molecules from the surface. This demonstrates that the use of photochemical grafting, even in the case of multilayer formation, enables multistep chemical processes to be conducted on the ZnO surface. Photoresponse measurements demonstrate that functionalization of the surface does not affect the ability to induce field effects in the underlying ZnO, thereby suggesting that this approach to functionalization may be useful for applications in sensing and in hybrid organic-inorganic transistors and related devices. PMID:21777005

  10. Photochemical sample treatment for extracts clean up in PCB analysis from sediments.

    PubMed

    Barreca, Salvatore; Orecchio, Santino; Pace, Andrea

    2013-01-15

    Sample purification can be considered the most polluting step of the whole analytical process for PCBs determination in sediment samples. The use of photochemical sample treatment represents an alternative methodology for extracts clean up allowing for a reduction of the used amount of organic solvents. The first application of a photochemical sample treatment for the selective removal or reduction of organic substances interfering with PCBs analyses in sediments is reported. The method's efficiency and robustness were compared with currently used chromatographic purification. Quality parameters such as recovery, linearity and reproducibility were studied. The entire procedure was validated by four replicate analysis of certified reference sediment. The quantification limits (LOQ) obtained by us ranged from 1 to 3.1 ng g(-1). The RSD for each congener was below 15% and recoveries were in the range 40-130%. Results based on the analysis of real and certified samples showed similar or improved detection thresholds and pointed out the advantages of the photochemical methodology in terms of costs and environmental friendly conditions. PMID:23200398

  11. Photochemical Reaction Altered Cardiac Toxicity of Diesel Exhaust Inhalation

    EPA Science Inventory

    Rationale: Epidemiological studies have indicated an association between urban air pollution exposure and cardiovascular morbidity and mortality. The present study was designed to evaluate the cardiac effects of inhaled diesel exhaust and compared with photochemically altered d...

  12. Chemical kinetics and photochemical data for use in stratospheric modeling

    NASA Technical Reports Server (NTRS)

    Demore, W. B.; Margitan, J. J.; Molina, M. J.; Watson, R. T.; Golden, D. M.; Hampson, R. F.; Kurylo, M. J.; Howard, C. J.; Ravishankara, A. R.

    1985-01-01

    Rate constants and photochemical cross sections are presented. The primary application of the data is for modeling of the stratospheric processes, with particular emphasis on the ozone layer and its possible perturbation by anthropogenic and natural phenomena.

  13. Method of making gold thiolate and photochemically functionalized microcantilevers

    SciTech Connect

    Boiadjiev, Vassil I; Brown, Gilbert M; Pinnaduwage, Lal A; Thundat, Thomas G; Bonnesen, Peter V; Goretzki, Gudrun

    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.

  14. CHEMICAL AND PHOTOCHEMICAL TRANSFORMATION OF SELECTED PESTICIDES IN AQUATIC SYSTEMS

    EPA Science Inventory

    This report presents the results of laboratory studies to quantitatively predict chemical and photochemical transformation rates and products of pesticides in water. It includes a general discussion of relevant transformation processes and associated kinetic expressions. The proc...

  15. PREDICTION OF PHOTOCHEMICAL TRANSFORMATION OF POLLUTANTS IN THE AQUATIC ENVIRONMENT

    EPA Science Inventory

    Discussion in this paper focuses on methods for prediction of one important transformation process, photolysis by the action of sunlight. Two general classes of photochemical transformation are direct photolysis, initiated by direct absorption of light by the pollutant, and indir...

  16. PHOTOCHEMICAL REACTIONS AMONG FORMALDEHYDE, CHLORINE, AND NITROGEN DIOXIDE IN AIR

    EPA Science Inventory

    Photochemical reactions among chlorine, nitrogen dioxide, and formaldehyde were studied, using parts-per-million concentrations in 1 atm of air. The reactant mixtures were irradiated by ultraviolet fluorescent lamps and simultaneously analyzed by the Fourier transform infrared te...

  17. PHOTOCHEMICAL URBAN AIRSHED MODELING USING DIAGNOSTIC AND DYNAMIC METEOROLOGICAL FIELDS

    EPA Science Inventory

    Spatial pollutant patterns and peak concentrations are strongly influenced by meteorological parameters. herefore, accurate hourly, gridded meteorological data sets are crucial inputs for photochemical modeling. n effort has been underway to apply both diagnostic and dynamic mete...

  18. Solid State Photochemical Isomerization: A Convenient Laboratory Experiment.

    ERIC Educational Resources Information Center

    Burton, W. B.

    1979-01-01

    Describes the use of benzophenone in the role of a solid state sensitizer in a photochemical isomerization and as an indicator in preparative layer chromatography for purification of the isomeride. (Author/SA)

  19. Photochemical oxidation: A solution for the mixed waste dilemma

    SciTech Connect

    Prellberg, J.W.; Thornton, L.M.; Cheuvront, D.A.

    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.

  20. Oxidation photochemistry in the Southern Atlantic boundary layer: unexpected deviations of photochemical steady state

    NASA Astrophysics Data System (ADS)

    Hosaynali Beygi, Z.; Fischer, H.; Harder, H. D.; Martinez, M.; Sander, R.; Williams, J.; Brookes, D. M.; Monks, P. S.; Lelieveld, J.

    2011-03-01

    Ozone (O3) is a photochemical oxidant, an air pollutant and a greenhouse gas. As the main precursor of the hydroxyl radical (OH) it strongly affects the oxidation power of the atmosphere. The remote marine boundary layer (MBL) is considered an important region in terms of chemical O3 loss; however surface-based atmospheric observations are sparse and the photochemical processes are not well understood. To investigate the photochemistry under the clean background conditions of the Southern Atlantic Ocean, ship measurements of NO, NO2, O3, JNO2, J(O1D), HO2, OH, ROx and a range of meteorological parameters were carried out. The concentrations of NO and NO2 measured on board the French research vessel Marion-Dufresne (28° S-57° S, 46° W-34° E) in March 2007, are among the lowest yet observed. The data is evaluated for consistency with photochemical steady state (PSS) conditions, and the calculations indicate substantial deviations from PSS (Φ>1). The deviations observed under low NOx conditions (5-25 pptv) demonstrate a remarkable upward tendency in the Leighton ratio (used to characterize PSS) with increasing NOx mixing ratio and JNO2 intensity. It is a paradigm in atmospheric chemistry that OH largely controls the oxidation efficiency of the atmosphere. However, evidence is growing that for unpolluted low-NOx (NO + NO2) conditions the atmospheric oxidant budget is poorly understood. Nevertheless, for the very cleanest conditions, typical for the remote marine boundary layer, good model agreement with measured OH and HO2 radicals has been interpreted as accurate understanding of baseline photochemistry. Here we show that such agreement can be deceptive and that a yet unidentified oxidant is needed to explain the photochemical conditions observed at 40°-60° S over the Atlantic Ocean.

  1. Oxidation photochemistry in the Southern Atlantic boundary layer: unexpected deviations of photochemical steady state

    NASA Astrophysics Data System (ADS)

    Hosaynali Beygi, Z.; Fischer, H.; Harder, H. D.; Martinez, M.; Sander, R.; Williams, J.; Brookes, D. M.; Monks, P. S.; Lelieveld, J.

    2011-08-01

    Ozone (O3) is a photochemical oxidant, an air pollutant and a greenhouse gas. As the main precursor of the hydroxyl radical (OH) it strongly affects the oxidation power of the atmosphere. The remote marine boundary layer (MBL) is considered an important region in terms of chemical O3 loss; however surface-based atmospheric observations are sparse and the photochemical processes are not well understood. To investigate the photochemistry under the clean background conditions of the Southern Atlantic Ocean, ship measurements of NO, NO2, O3, JNO2, J(O1D), HO2, OH, ROx and a range of meteorological parameters were carried out. The concentrations of NO and NO2 measured on board the French research vessel Marion-Dufresne (28° S-57° S, 46° W-34° E) in March 2007, are among the lowest yet observed. The data is evaluated for consistency with photochemical steady state (PSS) conditions, and the calculations indicate substantial deviations from PSS (Φ>1). The deviations observed under low NOx conditions (5-25 pptv) demonstrate a remarkable upward tendency in the Leighton ratio (used to characterize PSS) with increasing NOx mixing ratio and JNO2 intensity. It is a paradigm in atmospheric chemistry that OH largely controls the oxidation efficiency of the atmosphere. However, evidence is growing that for unpolluted low-NOx (NO + NO2) conditions the atmospheric oxidant budget is poorly understood. Nevertheless, for the very cleanest conditions, typical for the remote marine boundary layer, good model agreement with measured OH and HO2 radicals has been interpreted as accurate understanding of baseline photochemistry. Here we show that such agreement can be deceptive and that a yet unidentified oxidant is needed to explain the photochemical conditions observed at 40°-60° S over the Atlantic Ocean.

  2. Investigation of the Photochemical Method for Uranium Isotope Separation

    DOE R&D Accomplishments Database

    Urey, H. C.

    1943-07-10

    To find a process for successful photochemical separation of isotopes several conditions have to be fulfilled. First, the different isotopes have to show some differences in the spectrum. Secondly, and equally important, this difference must be capable of being exploited in a photochemical process. Parts A and B outline the physical and chemical conditions, and the extent to which one might expect to find them fulfilled. Part C deals with the applicability of the process.

  3. Photochemical properties of multi-azobenzene compounds.

    PubMed

    Bahrenburg, Julia; Sievers, Claudia M; Schönborn, Jan Boyke; Hartke, Bernd; Renth, Falk; Temps, Friedrich; Näther, Christian; Sönnichsen, Frank D

    2013-03-01

    A systematic study is reported of the photochemical properties of the multi-azobenzene compounds bis[4-(phenylazo)phenyl]amine (BPAPA) and tris[4-(phenylazo)phenyl]amine (TPAPA) compared to the parent molecule 4-aminoazobenzene (AAB). The bis- and tris-azobenzenes were synthesised by a variant of the Ullmann reaction and exist in their stable all-E forms at room temperature. Striking changes in the spectral positions and intensities of their first ππ* absorption bands compared to AAB reveal strong electronic coupling between the AB units. The nature of the excited states was explored by quantum chemical calculations at the approximate coupled-cluster (CC2) level. Upon UV/VIS irradiation, the molecules isomerise to the Z-isomer (AAB), ZE- and ZZ-isomers (BPAPA), and ZEE-, ZZE- and ZZZ-isomers (TPAPA), respectively. The photoswitching behaviours were investigated by UV/VIS and NMR spectroscopies. All individual isomers were detected by one-dimensional (1D) (1)H NMR spectroscopy (BPAPA) and two-dimensional (2D) HSQC NMR spectroscopy (TPAPA). A kinetic analysis provided the isomer-specific thermal lifetimes. The variance of the thermal lifetimes demonstrates a dependence of the Z-E isomerisation on the chromophore size and number of AB units. PMID:23224342

  4. A photochemical model of the martian atmosphere

    NASA Technical Reports Server (NTRS)

    Nair, Hari; Allen, Mark; Anbar, Ariel D.; Yung, Yuk L; Clancy, R. Todd

    1994-01-01

    The factors governing the amounts of CO, O2, and O3 in the martian atmposphere are investigated using a minimally constrained, one-dimensional photochemical model. We find that the incorporation of temperature-dependent CO2 absorption cross sections leads to an enhancement in the water photolysis rate, increasing the abundance of OH radicals to the point where the model CO abundance is smaller that observed. Good agreement between models and observations of CO, O2, O3, and the escape flux of atomic hydrogen can be achieved, using only gas-phase chemistry, by varying the recommended rate constraints for the reaction CO + OH and OH + HO2 within their specified uncertainties. The oxygen escape flux plays a key role in the oxygen budget on Mars; as inferred from the observed atomic hydrogen escape, it is much larger than recent calculations of the exospheric escape rate for oxygen. Weathering of the surface may account for the imbalance. We also consider the possiblity that HO(x) radicals may be catalytically destroyed on dust grains suspended in the atmosphere. Good agreement with the observed CO mixing ratio can be achieved via this mechanism, but the resulting ozone column is much higher than the observed quantity.

  5. Solar photochemical and thermochemical splitting of water.

    PubMed

    Rao, C N R; Lingampalli, S R; Dey, Sunita; Roy, Anand

    2016-02-28

    Artificial photosynthesis to carry out both the oxidation and the reduction of water has emerged to be an exciting area of research. It has been possible to photochemically generate oxygen by using a scheme similar to the Z-scheme, by using suitable catalysts in place of water-oxidation catalyst in the Z-scheme in natural photosynthesis. The best oxidation catalysts are found to be Co and Mn oxides with the e(1) g configuration. The more important aspects investigated pertain to the visible-light-induced generation of hydrogen by using semiconductor heterostructures of the type ZnO/Pt/Cd1-xZnxS and dye-sensitized semiconductors. In the case of heterostructures, good yields of H2 have been obtained. Modifications of the heterostructures, wherein Pt is replaced by NiO, and the oxide is substituted with different anions are discussed. MoS2 and MoSe2 in the 1T form yield high quantities of H2 when sensitized by Eosin Y. Two-step thermochemical splitting of H2O using metal oxide redox pairs provides a strategy to produce H2 and CO. Performance of the Ln0.5A0.5MnO3 (Ln = rare earth ion, A = Ca, Sr) family of perovskites is found to be promising in this context. The best results to date are found with Y0.5Sr0.5MnO3. PMID:26755752

  6. Photochemical transformation of graphene oxide in sunlight.

    PubMed

    Hou, Wen-Che; Chowdhury, Indranil; Goodwin, David G; Henderson, W Matthew; Fairbrother, D Howard; Bouchard, Dermont; Zepp, Richard G

    2015-03-17

    Graphene oxide (GO) is promising in scalable production and has useful properties that include semiconducting behavior, catalytic reactivity, and aqueous dispersibility. In this study, we investigated the photochemical fate of GO under environmentally relevant sunlight conditions. The results indicate that GO readily photoreacts under simulated sunlight with the potential involvement of electron-hole pair creation. GO was shown to photodisproportionate to CO2, reduced materials similar to reduced GO (rGO) that are fragmented compared to the starting material, and low molecular-weight (LMW) species. Kinetic studies show that the rate of the initially rapid photoreaction of GO is insensitive to the dissolved oxygen content. In contrast, at longer time points (>10 h), the presence of dissolved oxygen led to a greater production of CO2 than the same GO material under N2-saturated conditions. Regardless, the rGO species themselves persist after extended irradiation equivalent to 2 months in natural sunlight, even in the presence of dissolved oxygen. Overall, our findings indicate that GO phototransforms rapidly under sunlight exposure, resulting in chemically reduced and persistent photoproducts that are likely to exhibit transport and toxic properties unique from parent GO. PMID:25671674

  7. Photochemical oxidants: state of the science.

    PubMed

    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. PMID:15093111

  8. Photochemical Phenomenology Model for the New Millenium

    NASA Technical Reports Server (NTRS)

    Bishop, James; Evans, J. Scott

    2000-01-01

    This project tackles the problem of conversion of validated a priori physics-based modeling capabilities, specifically those relevant to the analysis and interpretation of planetary atmosphere observations, to application-oriented software for use in science and science-support activities. The software package under development, named the Photochemical Phenomenology Modeling Tool (PPMT), has particular focus on the atmospheric remote sensing data to be acquired by the CIRS instrument during the CASSINI Jupiter flyby and orbital tour of the Saturnian system. Overall, the project has followed the development outline given in the original proposal, and the Year 1 design and architecture goals have been met. Specific accomplishments and the difficulties encountered are summarized in this report. Most of the effort has gone into complete definition of the PPMT interfaces within the context of today's IT arena: adoption and adherence to the CORBA Component Model (CCM) has yielded a solid architecture basis, and CORBA-related issues (services, specification options, development plans, etc.) have been largely resolved. Implementation goals have been redirected somewhat so as to be more relevant to the upcoming CASSINI flyby of Jupiter, with focus now being more on data analysis and remote sensing retrieval applications.

  9. Remotely Sensing the Photochemical Reflectance Index (PRI)

    NASA Technical Reports Server (NTRS)

    Vanderbilt, Vern

    2015-01-01

    In remote sensing, the Photochemical Reflectance Index (PRI) provides insight into physiological processes occurring inside the leaves in a stand of plants. Developed by Gamon et al., (1990 and 1992), PRI evolved from laboratory measurements of the reflectance of individual leaves (Bilger et al.,1989). Yet in a remotely sensed image, a pixel measurement may include light from both reflecting and transmitting leaves. We conducted laboratory experiments comparing values of PRI based upon polarized reflectance and transmittance measurements of water and nutrient stressed leaves. We illuminated single detached leaves using a current controlled light source (Oriel model 66881) and measured the leaf weight using an analytical balance (Mettler model AE 260) and the light reflected and transmitted by the leaf during dry down using two Analytical Spectral Devices spectroradiometers. Polarizers on the incident and reflected light beams allowed us to divide the leaf reflectance into two parts: a polarized surface reflectance and a non-polarized 'leaf interior' reflectance. Our results underscore the importance when calculating PRI of removing the leaf surface reflection, which contains no information about physiological processes ongoing in the leaf interior. The results show that the leaf physiology information is in the leaf interior reflectance, not the leaf transmittance. Applied to a plant stand, these results suggest use of polarization measurements in sun-view directions that minimize the number of sunlit transmitting leaves in the sensor field of view.

  10. Degradation of artificial sweeteners via direct and indirect photochemical reactions.

    PubMed

    Perkola, Noora; Vaalgamaa, Sanna; Jernberg, Joonas; Vähätalo, Anssi V

    2016-07-01

    We studied the direct and indirect photochemical reactivity of artificial sweeteners acesulfame, saccharin, cyclamic acid and sucralose in environm entally relevant dilute aqueous solutions. Aqueous solutions of sweeteners were irradiated with simulated solar radiation (>290 nm; 96 and 168 h) or ultraviolet radiation (UVR; up to 24 h) for assessing photochemical reactions in surface waters or in water treatment, respectively. The sweeteners were dissolved in deionised water for examination of direct photochemical reactions. Direct photochemical reactions degraded all sweeteners under UVR but only acesulfame under simulated solar radiation. Acesulfame was degraded over three orders of magnitude faster than the other sweeteners. For examining indirect photochemical reactions, the sweeteners were dissolved in surface waters with indigenous dissolved organic matter or irradiated with aqueous solutions of nitrate (1 mg N/L) and ferric iron (2.8 mg Fe/L) introduced as sensitizers. Iron enhanced the photodegradation rates but nitrate and dissolved organic matter did not. UVR transformed acesulfame into at least three products: iso-acesulfame, hydroxylated acesulfame and hydroxypropanyl sulfate. Photolytic half-life was one year for acesulfame and more than several years for the other sweeteners in surface waters under solar radiation. Our study shows that the photochemical reactivity of commonly used artificial sweeteners is variable: acesulfame may be sensitive to photodegradation in surface waters, while saccharin, cyclamic acid and sucralose degrade very slowly even under the energetic UVR commonly used in water treatment. PMID:27023816

  11. Tracing Gas and Particle Phase Oxidation From Engine Sources as a Function of Fuel Type, Load, and Photochemical Age

    NASA Astrophysics Data System (ADS)

    Friedman, B.; Farmer, D.; Jathar, S.; Galang, A.; Fulgham, R.; Link, M.; Brophy, P.

    2015-12-01

    Motor vehicle emissions are an important source of anthropogenic gases and particles in the atmosphere. To study the gas and particle phase emissions, an HR-TOF-AMS and HR-TOF-CIMS were deployed at the CSU Engines Lab, along with an oxidative flow reactor, to measure emissions from a 4.5 L John Deere engine, which ran either diesel or biodiesel fuel. Concurrent gas-phase and particle-phase measurements allowed determination of the gas-phase and particle-phase oxidation properties as a function of fuel type, fuel load, and photochemical age. The impacts of particulate filers on composition and oxidation state were also assessed. While aerosol composition and associated oxidation properties for the biodiesel and diesel fuel types were similar, differences in photochemical production existed for the amount of load, or efficiency of the engine. The mean particulate oxygen to carbon ratios (O:C) and mean hydrogen to carbon ratios (H:C) moved from an initial 0.1 and 2 to a final 0.55 and 1.6, respectively, upon idle biodiesel and diesel engine exhaust exposure to approximately 7 days of OH exposure. The more efficient higher load biodiesel and diesel engine exhaust experienced less changes in the mean O:C and H:C values (an initial 0.1 and 2 to a final 0.3 and 1.7, respectively) with approximately the same amount of OH exposure. Despite largely scrubbing the majority of particles from the engine exhaust, experiments with engine particulate filters still showed photochemical production of oxidized particle-phase species at high photochemical ages, similar to that of idle engine exhaust without any particulate filters. Bulk gas-phase data was compared to bulk aerosol data in Van Krevelen space in order to understand how particle-phase oxidation traces gas-phase oxidation as a function of fuel type, engine load, and photochemical age.

  12. Photochemical internalization of bleomycin for glioma treatment

    NASA Astrophysics Data System (ADS)

    Mathews, Marlon S.; Blickenstaff, Joseph W.; Shih, En-Chung; Zamora, Genesis; Vo, Van; Sun, Chung-Ho; Hirschberg, Henry; Madsen, Steen J.

    2012-05-01

    We study the use of photochemical internalization (PCI) for enhancing chemotherapeutic response to malignant glioma cells in vitro. Two models are studied: monolayers consisting of F98 rat glioma cells and human glioma spheroids established from biopsy-derived glioma cells. In both cases, the cytotoxicity of aluminum phthalocyanine disulfonate (AlPcS2a)-based PCI of bleomycin was compared to AlPcS2a-photodynamic therapy (PDT) and chemotherapy alone. Monolayers and spheroids were incubated with AlPcS2a (PDT effect), bleomycin (chemotherapy effect), or AlPcS2a+bleomycin (PCI effect) and were illuminated (670 nm). Toxicity was evaluated using colony formation assays or spheroid growth kinetics. F98 cells in monolayer/spheroids were not particularly sensitive to the effects of low radiant exposure (1.5 J/cm2 @ 5 mW/cm2) AlPcS2a-PDT. Bleomycin was moderately toxic to F98 cells in monolayer at relatively low concentrations-incubation of F98 cells in 0.1 μg/ml for 4 h resulted in 80% survival, but less toxic in human glioma spheroids respectively. In both in vitro systems investigated, a significant PCI effect is seen. PCI using 1.5 J/cm2 together with 0.25 μg/ml bleomycin resulted in approximately 20% and 18% survival of F98 rat glioma cells and human glioma spheroids, respectively. These results show that AlPcS2a-mediated PCI can be used to enhance the efficacy of chemotherapeutic agents such as bleomycin in malignant gliomas.

  13. Photochemical Transformation and Phototoxicity of 1-Aminopyrene

    PubMed Central

    Zeng, Kui; Hwang, Huey-Min; Dong, Shiming; Shi, Xiaochun; Wilson, Kaneytta; Green, Jacinta; Jiao, Yuguo; Yu, Hongtao

    2013-01-01

    1-Aminopyrene (1-AP) is an environmental mutagen and a metabolite of the mutagenic environmental pollutant, 1-nitropyrene (1-NO2P). Upon light irradiation, 1-AP transforms into oxidation products with a half-life of 7.1 min in 10% methanolic buffer. The presence of free radical/singlet oxygen scavengers DTT, histidine, or NaN3, slows down 1-AP photochemical reaction. The reaction is also slower in the presence of DNA. The photoproducts identified include 1-hydroxyaminopyrene, 1-nitrosopyrene, 1-NO2P, 1-amino-x-hydroxypyrene, and three covalent dimers. The progressive oxidation of the amino group to hydroxyamino, nitroso, and finally nitro is the reverse of the enzymatic reduction of 1-NO2P in living systems. Since it is known that 1-NO2P and 1-nitrosopyrene are genotoxic and 1-hydroxyaminopyrnene can react with DNA to form covalent adducts, the toxicity of 1-AP and its photoproducts and light-induced DNA covalent adduct formation were studied. Using Mutatox® Test, it is found that the lowest effective observable concentrations for 1-AP, 1-AP photoproducts, and 1-NO2P are 1.25, 10, and NA (not applicable) in the direct medium (no S-9) and NA, 5, and 0.625 μM in the S-9 medium, respectively. Therefore, 1-AP photoproducts are more genotoxic than 1-AP itself in the S-9 medium and more mutagenic than 1-NO2P in the direct medium. Thus 1-NO2P alone cannot account for all the mutagenicity of the photoproducts. Irradiation of 1-AP together with DNA leads to covalent DNA adduct formation possibly via the 1-hydroxyaminopyrene intermediate. This suggests that photolysis not only transforms 1-AP into more mutagenic compounds, but also forms DNA covalent adducts. PMID:15376525

  14. A photochemical model of the martian atmosphere.

    PubMed

    Nair, H; Allen, M; Anbar, A D; Yung, Y L; Clancy, R T

    1994-09-01

    The factors governing the amounts of CO, O2, and O3 in the martian atmosphere are investigated using a minimally constrained, one-dimensional photochemical model. We find that the incorporation of temperature-dependent CO2 absorption cross sections leads to an enhancement in the water photolysis rate, increasing the abundance of OH radicals to the point where the model CO abundance is smaller than observed. Good agreement between models and observations of CO, O2, O3, and the escape flux of atomic hydrogen can be achieved, using only gas-phase chemistry, by varying the recommended rate constants for the reactions CO + OH and OH + HO2 within their specified uncertainties. Similar revisions have been suggested to resolve discrepancies between models and observations of the terrestrial mesosphere. The oxygen escape flux plays a key role in the oxygen budget on Mars; as inferred from the observed atomic hydrogen escape, it is much larger than recent calculations of the exospheric escape rate for oxygen. Weathering of the surface may account for the imbalance. Quantification of the escape rates of oxygen and hydrogen from Mars is a worthwhile objective for an upcoming martian upper atmospheric mission. We also consider the possibility that HOx radicals may be catalytically destroyed on dust grains suspended in the atmosphere. Good agreement with the observed CO mixing ratio can be achieved via this mechanism, but the resulting ozone column is much higher than the observed quantity. We feel that there is no need at this time to invoke heterogeneous processes to reconcile models and observations. PMID:11539176

  15. Photochemical flocculation of terrestrial dissolved organic matter and iron

    NASA Astrophysics Data System (ADS)

    Helms, John R.; Mao, Jingdong; Schmidt-Rohr, Klaus; Abdulla, Hussain; Mopper, Kenneth

    2013-11-01

    Dissolved organic matter (DOM) rich water samples (Great Dismal Swamp, Virginia) were 0.1-μm filtered and UV-irradiated in a solar simulator for 30 days. During the irradiation, pH increased, particulate organic matter (POM) and particulate iron formed. After 30 days, 7% of the dissolved organic carbon (DOC) was converted to POC while 75% was remineralized. Approximately 87% of the iron was removed from the dissolved phase after 30 days, but iron did not flocculate until a major fraction of DOM was removed by photochemical degradation and flocculation (>10 days); thus, during the initial 10 days, there were sufficient organic ligands present or the pH was low enough to keep iron in solution. Nuclear magnetic resonance and Fourier transform infrared spectroscopies indicated that photochemically flocculated POM was more aliphatic than the residual non-flocculated DOM. Photochemically flocculated POM was also enriched in amide functionality, while carbohydrate-like material was resistant to both photochemical degradation and flocculation. Abiotic photochemical flocculation likely removes a significant fraction of terrestrial DOM from the upper water column between headwaters and the ocean, but has previously been ignored. Preliminary evidence suggests that this process may significantly impact the transport of DOM and POM in ocean margin environments including estuaries.

  16. A photochemical answer to the 'xenon paradox'

    NASA Astrophysics Data System (ADS)

    Hébrard; Marty, B.

    2012-12-01

    Xenon is depleted by one order of magnitude relative to other volatile elements when normalized to the chondritic composition. Furthermore, atmospheric xenon is far more enriched in the heavy isotopes relatively to chondritic and solar compositions (3-4%.amu-1) than atmospheric krypton (< 1%.amu-1). This discrepancy, known as the 'xenon paradox', has led to sophisticated models of atmospheric evolution coupled with mantle geodynamics (Pepin, 1991; Tolstikhin and Marty, 1998) and cometary contributions (Dauphas, 2003; Owen et al., 1992) that could explain terrestrial noble gas patterns under ad hoc conditions during the building stages of the Earth, no more than ~200 Ma following the beginning of solar system formation. Yet, xenon having an isotopic composition intermediate between the atmospheric and the chondritic ones has been recently documented in Archean (≤3 Ga-old) sedimentary rocks (Pujol et al., 2011), suggesting that isotopic fractionation of Xe occurred over a much longer period of time than previously thought, during the Hadean and the Archean eons. In that case, assuming a Rayleigh type isotope evolution for atmospheric Xe requires an enrichment fractionation factor of 1.3% in heavy isotopes for Xe remaining in the atmosphere. This is clearly within the range of values observed in laboratory experiments aimed at trapping and fractionating Xe isotopes in solids, which is only effective upon ionization (Marrocchi et al., 2011; Kuga et al., 2012). We report here a possibility for explaining the 'xenon paradox' through interaction of the Hadean/Archean atmosphere with EUV light from the young Sun. By using a new photochemical model, we have found out that atmospheric Xe depletion and enrichment in heavy Xe isotopes could be achieved by EUV photoionization deep enough in the atmosphere to allow the preferential implantation of the heavier Xe isotopes in organic aerosols, the formation of which is itself triggered by UV photochemistry. Most of the ionized

  17. Actinometric measurement of solar ultraviolet and development of a weighted solar UV integral. [photochemical reaction rate determination

    NASA Technical Reports Server (NTRS)

    Gupta, A.; Coulbert, C.

    1978-01-01

    An actinometer has been developed to measure outdoor irradiance in the range 295-400 nm. Actinometric measurements of radiation are based on determination of photochemical reaction rates for reactions of known quantum efficiency. Actinometers have the advantage of providing irradiance data over surfaces of difficult accessibility; in addition, actinometrically determined irradiance data are wavelength weighted and therefore provide a useful means of assessing the degradation rates of polymers employed in solar energy systems.

  18. Photochemical hydrogen production from water catalyzed by CdTe quantum dots/molecular cobalt catalyst hybrid systems.

    PubMed

    Han, Kai; Wang, Mei; Zhang, Shuai; Wu, Suli; Yang, Yong; Sun, Licheng

    2015-04-25

    A hybrid system with a coordinative interaction between a cobalt complex of a N2S2-tetradentate ligand and CdTe quantum dots displayed a high activity (initial TOF 850 h(-1)) and improved stability (TON 1.44 × 10(4) based on catalyst over 30 h) for the photochemical H2 generation from water, with a quantum efficiency of 5.32% at 400 nm. PMID:25800286

  19. Application of photochemical reaction in electrochemical detection of DNA intercalation.

    PubMed

    Pandey, P C; Weetall, H H

    1994-04-15

    A flow injection analysis (FIA) system for the detection of the compounds that intercalate within DNA is reported. A derivative of 9,10-anthraquinone has been used as the reference compound for photoelectrochemical detection. The sodium salts of 9,10-anthraquinone-2,6-disulfonic acid and 9,10-anthraquinone-2-sulfonic acid are photochemically activated and then reduced in the presence of an electron donor (glucose). The electrochemical signal is based on the measurement of the anodic current resulting from the oxidation of the reduced form of 9,10-anthraquinone. The reduced form of the 9,10-anthraquinone is oxidized through a mediated mechanism at the surface of a tetracyanoquinodimethane-(TCNQ)-modified graphite paste electrode covered by a Nucleopore membrane. TCNQ acts as an efficient mediator for the oxidation of reduced 9,10-anthraquinone. Cyclic voltammetry, photocyclic voltammetry, and the photoelectrochemical FIA response of 9,10-anthraquinone are reported. Experimental results show that these anthraquinones can be intercalated within the helix of double-stranded calf thymus DNA. The anthraquinone molecules that are intercalated within DNA cannot be oxidized due to their limited transport to the modified electrode surface. This results in a decrease in the anodic current at a constant concentration of anthraquinone after intercalation. There is a linear relation between the decrease in electrochemical response and the DNA concentration at a constant concentration of anthraquinone. The intercalated anthraquinone molecules can be completely replaced by another intercalating agent (i.e., ethidium bromide) that is more strongly intercalated within DNA, thereby regenerating the electrochemical response.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:8210041

  20. Evaluation of the photochemical reflectance index in AVIRIS imagery

    NASA Technical Reports Server (NTRS)

    Gamon, John A.; Roberts, Dar A.; Green, Robert O.

    1995-01-01

    In this paper, we evaluate the potential for extracting the 'photochemical reflectance index' (PRI; previously called the 'physiological reflectance index') from AVIRIS data. This index, which is derived from narrow-band reflectance at 531 and 570 nm, has proven to be a useful indicator of photosynthetic function at the leaf and canopy scales. At the leaf level, PRI varies with photosynthetic capacity, radiation-use efficiency, and vegetation type (unpublished data). This finding is consistent with the hypothesis that vegetation types exhibiting chronically reduced photosynthesis during periods of stress (e.g. drought-tolerant evergreens) invest proportionally more in photoprotective processes than vegetation with high photosynthetic capacity (e.g. crops or deciduous perennials). Vertical transects in tropical and boreal forest canopies have indicated declines in PRI associated with downregulation of photosynthesis at the canopy tops under sunny, dry midday conditions (unpublished data). This reduced PRI in upper canopy levels provides a further basis for examining this signal with the 'view from above' afforded by aircraft overflights. Although many factors could confound interpretation of a subtle physiological signal at the landscape scale, we conducted a preliminary examination of PRI extracted from existing, AVIRIS imagery of Stanford University's Jasper Ridge Biological Preserve obtained on the June 2nd, 1992, overflight. The goal was to use the hyperspectral capabilities of AVIRIS to evaluate the potential of this index for obtaining useful physiological data at the landscape scale. The expectation based on leaf- and canopy-level studies was that regions containing vegetation of reduced photosynthetic capacity (e.g. chaparral or evergreen woodland) would exhibit lower PRI values than regions of high capacity (e.g. deciduous woodland).

  1. Versatile thin-film reactor for photochemical vapor generation.

    PubMed

    Zheng, Chengbin; Sturgeon, Ralph E; Brophy, Christine; Hou, Xiandeng

    2010-04-01

    A novel thin-film reactor is described and evaluated for its analytical performance with photochemical vapor generation (TF-PVG). The device, comprising both the generator and a gas-liquid separator, utilizes a vertical central quartz rod onto which the sample is pumped to yield a thin liquid film conducive to the rapid escape of generated hydrophobic species. The rod is housed within a concentric quartz tube through which a flow of argon carrier/stripping gas is passed to remove and transport the generated species to a detector, which in this study is an inductively coupled argon plasma optical emission spectrometer (ICP-OES). The concentric quartz tube is itself surrounded by a 78-turn 0.5 m long quartz coil low-pressure mercury discharge lamp operating at 20 W. The performance of this thin-film photoreactor was evaluated through comparison of analytical figures of merit for detection of a number of elements undergoing PVG in the presence of formic or acetic acid with those arising from conventional solution nebulization under optimized conditions. The TF-PVG reactor provided sensitivity enhancements, of 110-, 120-, 130-, 250-, 120-, 230-, 78-, 1.3-, 16-, and 32-fold for As, Sb, Bi, Se, Te, Hg, Ni, Co, Fe, and I, respectively, and detection limit enhancements of 110-, 140-, 170-, 270-, 200-, 300-, 160-, 2.7-, 50-, and 44-fold for these same elements. Vapor generation efficiencies ranged from 20-100% for this suite of analytes. The utility of this technique was demonstrated by the determination of Fe and Ni in Certified Reference Materials DORM-3 (fish protein) and DOLT-4 (dogfish liver tissue). PMID:20225824

  2. Photochemical Behavior of Beryllium Complexes with Subporphyrazines and Subphthalocyanines.

    PubMed

    Montero-Campillo, M Merced; Lamsabhi, Al Mokhtar; Mó, Otilia; Yáñez, Manuel

    2016-07-14

    Structures of beryllium subphthalocyanines and beryllium subporphyrazines complexes with different substituents are explored for the first time. Their photochemical properties are studied using time-dependent density functional theory calculations and compared to boron-related compounds for which their photochemical activity is already known. These beryllium compounds were found to be thermodynamically stable in a vacuum and present features similar to those of boron-containing analogues, although the nature of bonding between the cation and the macrocycle presents subtle differences. Most important contributions to the main peak in the Q-band region arise from HOMO to LUMO transitions in the case of subphthalocyanines and alkyl subporphyrazine complexes, whereas a mixture of that contribution and a HOMO-2 to LUMO contribution are present in the case of thioalkyl subporphyrazines. The absorption in the visible region could make these candidates suitable for photochemical devices if combined with appropriate donor groups. PMID:26812068

  3. Why thiocolchicine does not undergo photochemical isomerization: A theoretical study

    NASA Astrophysics Data System (ADS)

    Cacelli, Ivo; D'Auria, Maurizio; Villani, Vincenzo

    2008-06-01

    The reasons why colchicine undergoes photochemical cyclization to give lumicolchicine, whereas thiocolchicine does not, are investigated by theoretical methods. The relative stability of the reagent and of the products is computed at DFT level of theory and indicates that such a photochemical reaction is energetically possible. The photochemical reaction path of thiocolchicine is studied within the relaxed energy scan, at MC-SCF level of theory. The results are again rather similar to those of colchicine. Finally, the spin-orbit coupling between S 1 and T 1 has been computed and are two order of magnitude greater than those of colchicine, that makes plausible that spin-orbit is the main reason of the observed reaction quenching.

  4. A flight experiment to determine GPS photochemical contamination accumulation rates

    NASA Technical Reports Server (NTRS)

    Tribble, A. C.; Haffner, J. W.

    1990-01-01

    It was recently suggested that photochemically deposited contamination, originating from volatiles outgassed by a spacecraft, may be responsible for the anomalous degradation in power seen on the GPS Block 1 vehicles. In an attempt to confirm, or deny, the photochemical deposition rates predicted, a study was undertaken to design a flight experiment to be incorporated on the GPS vehicles currently in production. The objective was to develop an inexpensive, light weight instrument package that would give information on the contamination levels within a few months of launch. Three types of apparatus were studied, Quartz Crystal Microbalances, (QCM's), modified solar cells, and calorimeters. A calorimeter was selected due primarily to its impact on the production schedule of the GPS vehicles. An analysis of the sensitivity of the final design is compared to the predicted contamination accumulation rates in order to determine how long after launch it will take the experiment to show the effects of photochemical contamination.

  5. Approximate photochemical dynamics of azobenzene with reactive force fields

    SciTech Connect

    Li, Yan; Hartke, Bernd

    2013-12-14

    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)

  6. Electrolytic photodissociation of chemical compounds by iron oxide photochemical diodes

    DOEpatents

    Somorjai, Gabor A.; Leygraf, Christofer H.

    1985-01-01

    Chemical compounds can be dissociated by contacting the same with a p/n type semi-conductor photochemical diode having visible light as its sole source of energy. The photochemical diode consists of low cost, readily available materials, specifically polycrystalline iron oxide doped with silicon in the case of the n-type semi-conductor electrode, and polycrystalline iron oxide doped with magnesium in the case of the p-type electrode. So long as the light source has an energy greater than 2.2 electron volts, no added energy source is needed to achieve dissociation.

  7. Photochemical synthesis of mono and bimetallic nanoparticles and their use in catalysis

    NASA Astrophysics Data System (ADS)

    Pardoe, Andrea

    2011-07-01

    Nanomaterials have become a popular topic of research over the years because of their many important applications. It can be a challenge to stabilize the particles at a nanometer size, while having control over their surface features. Copper nanoparticles were synthesized photochemically using a photogenerated radical allowing spatial and temporal control over their formation. The synthesis was affected by the stabilizers used, which changed the size, dispersity, rate of formation, and oxidation rate. Copper nanoparticles suffer from their fast oxidation in air, so copper-silver bimetallic nanoparticles were synthesized in attempts to overcome the oxidation of copper nanoparticles. Bimetallic nanoparticles were synthesized, but preventing the oxidation of the copper nanoparticles proved difficult. One important application of nanoparticles that was explored here is in catalyzing organic reactions. Because of the fast oxidation of copper nanoparticles, silver nanoparticles were synthesized photochemically on different supports including TiO2 and hydrotalcite (HTC). Their catalytic efficiency was tested using alcohol oxidations. Different silver nanoparticle shapes (decahedra and plates) were compared with the spheres to see the different catalytic efficiencies.

  8. The molecular mechanism of photochemical internalization of cell penetrating peptide-cargo-photosensitizer conjugates

    PubMed Central

    Ohtsuki, Takashi; Miki, Shunya; Kobayashi, Shouhei; Haraguchi, Tokuko; Nakata, Eiji; Hirakawa, Kazutaka; Sumita, Kensuke; Watanabe, Kazunori; Okazaki, Shigetoshi

    2015-01-01

    In many drug delivery strategies, an inefficient transfer of macromolecules such as proteins and nucleic acids to the cytosol often occurs because of their endosomal entrapment. One of the methods to overcome this problem is photochemical internalization, which is achieved using a photosensitizer and light to facilitate the endosomal escape of the macromolecule. In this study, we examined the molecular mechanism of photochemical internalization of cell penetrating peptide-cargo (macromolecule)-photosensitizer conjugates. We measured the photophysical properties of eight dyes (photosensitizer candidates) and determined the respective endosomal escape efficiencies using these dyes. Correlation plots between these factors indicated that the photogenerated 1O2 molecules from photosensitizers were highly related to the endosomal escape efficiencies. The contribution of 1O2 was confirmed using 1O2 quenchers. In addition, time-lapse fluorescence imaging showed that the photoinduced endosomal escape occurred at a few seconds to a few minutes after irradiation (much longer than 1O2 lifetime), and that the pH increased in the endosome prior to the endosomal escape of the macromolecule. PMID:26686907

  9. Studies in photochemical smog chemistry. 1. Atmospheric chemistry of toulene. 2. Analysis of chemical reaction mechanisms for photochemical smog

    SciTech Connect

    Leone, J.A.

    1985-01-01

    This study focuses on two related topics in the gas phase organic chemistry of importance in urban air pollution. An experimental effort aimed at developing a new explicit reaction mechanism for the atmospheric photooxidation of toluene is described. This mechanism is tested using experimental data from both indoor and outdoor smog chamber facilities. The predictions of the new reaction mechanism are found to be in good agreement with both sets of experimental data. Additional simulations performed with the new mechanism are used to investigate various mechanistic paths. A theoretical analysis of lumped chemical reaction mechanisms for photochemical smog is presented. Included is a description of a new counter species analysis technique which can be used to analyze any complex chemical reaction mechanism. When applied to mechanisms for photochemical smog, this analysis is shown capable of providing answers to previously inaccessible questions such as the relative contributions of individual organics to photochemical ozone formation.

  10. Photochemical Transformation Processes in Sunlit Surface Waters

    NASA Astrophysics Data System (ADS)

    Vione, D.

    2012-12-01

    Photochemical reactions are major processes in the transformation of hardly biodegradable xenobiotics in surface waters. They are usually classified into direct photolysis and indirect or sensitised degradation. Direct photolysis requires xenobiotic compounds to absorb sunlight, and to get transformed as a consequence. Sensitised transformation involves reaction with transient species (e.g. °OH, CO3-°, 1O2 and triplet states of chromophoric dissolved organic matter, 3CDOM*), photogenerated by so-called photosensitisers (nitrate, nitrite and CDOM). CDOM is a major photosensitiser: is it on average the main source of °OH (and of CO3-° as a consequence, which is mainly produced upon oxidation by °OH of carbonate and bicarbonate) and the only important source of 1O2 and 3CDOM* [1, 2]. CDOM origin plays a key role in sensitised processes: allochthonous CDOM derived from soil runoff and rich in fulvic and humic substances is usually more photoactive than autochthonous CDOM (produced by in-water biological processes and mainly consisting of protein-like material) or of CDOM derived from atmospheric deposition. An interesting gradual evolution of CDOM origin and photochemistry can be found in mountain lakes across the treeline, which afford a gradual transition of allochthonous- autochtonous - atmopheric CDOM when passing from trees to alpine meadows to exposed rocks [3]. Another important issue is the sites of reactive species photoproduction in CDOM. While there is evidence that smaller molecular weight fractions are more photoactive, some studies have reported considerable 1O2 reactivity in CDOM hydrophobic sites and inside particles [4]. We have recently addressed the problem and found that dissolved species in standard humic acids (hydrodynamic diameter < 0.1 μm) account for the vast majority of 1O2 and triplet states photoproduction. In hydrophobic sites of particles, the formation rate of 1O2 is considerably lower than in the solution bulk [5], but the absence

  11. Mathematical Modeling of Photochemical Air Pollution.

    NASA Astrophysics Data System (ADS)

    McRae, Gregory John

    Air pollution is an environmental problem that is both pervasive and difficult to control. An important element of any rational control approach is a reliable means for evaluating the air quality impact of alternative abatement measures. This work presents such a capability, in the form of a mathematical description of the production and transport of photochemical oxidants within an urban airshed. The combined influences of advection, turbulent diffusion, chemical reaction, emissions and surface removal processes are all incorporated into a series of models that are based on the species continuity equations. A delineation of the essential assumptions underlying the formulation of a three-dimensional, a Lagrangian trajectory, a vertically integrated and single cell air quality model is presented. Since each model employs common components and input data the simpler forms can be used for rapid screening calculations and the more complex ones for detailed evaluations. The flow fields, needed for species transport, are constructed using inverse distance weighted polynomial interpolation techniques that map routine monitoring data onto a regular computational mesh. Variational analysis procedures are then employed to adjust the field so that mass is conserved. Initial concentration and mixing height distributions can be established with the same interpolation algorithms. Subgrid scale turbulent transport is characterized by a gradient diffusion hypothesis. Similarity solutions are used to model the surface layer fluxes. Above this layer different treatments of turbulent diffusivity are required to account for variations in atmospheric stability. Convective velocity scaling is utilized to develop eddy diffusivities for unstable conditions. The predicted mixing times are in accord with results obtained during sulfur hexafluoride (SF(,6)) tracer experiments. Conventional models are employed for neutral and stable conditions. A new formulation for gaseous deposition fluxes

  12. Non-photochemical Fluorescence Quenching in Photosystem II Antenna Complexes by the Reaction Center Cation Radical.

    PubMed

    Paschenko, V Z; Gorokhov, V V; Grishanova, N P; Korvatovskii, B N; Ivanov, M V; Maksimov, E G; Mamedov, M D

    2016-06-01

    In direct experiments, rate constants of photochemical (kP) and non-photochemical (kP(+)) fluorescence quenching were determined in membrane fragments of photosystem II (PSII), in oxygen-evolving PSII core particles, as well as in core particles deprived of the oxygen-evolving complex. For this purpose, a new approach to the pulse fluorometry method was implemented. In the "dark" reaction center (RC) state, antenna fluorescence decay kinetics were measured under low-intensity excitation (532 nm, pulse repetition rate 1 Hz), and the emission was registered by a streak camera. To create a "closed" [P680(+)QA(-)] RC state, a high-intensity pre-excitation pulse (pump pulse, 532 nm) of the sample was used. The time advance of the pump pulse against the measuring pulse was 8 ns. In this experimental configuration, under the pump pulse, the [P680(+)QA(-)] state was formed in RC, whereupon antenna fluorescence kinetics was measured using a weak testing picosecond pulsed excitation light applied to the sample 8 ns after the pump pulse. The data were fitted by a two-exponential approximation. Efficiency of antenna fluorescence quenching by the photoactive RC pigment in its oxidized (P680(+)) state was found to be ~1.5 times higher than that of the neutral (P680) RC state. To verify the data obtained with a streak camera, control measurements of PSII complex fluorescence decay kinetics by the single-photon counting technique were carried out. The results support the conclusions drawn from the measurements registered with the streak camera. In this case, the fitting of fluorescence kinetics was performed in three-exponential approximation, using the value of τ1 obtained by analyzing data registered by the streak camera. An additional third component obtained by modeling the data of single photon counting describes the P680(+)Pheo(-) charge recombination. Thus, for the first time the ratio of kP(+)/kP = 1.5 was determined in a direct experiment. The mechanisms of higher

  13. Studies on the photochemical and thermal dissociation synthesis of krypton difluoride

    SciTech Connect

    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.

  14. NOXIOUS TRACE GASES IN THE AIR. PART I. PHOTOCHEMICAL SMOG

    EPA Science Inventory

    An outline of the photochemical smog problem is presented, with emphasis on the chemical reactions taking place in the polluted air. The chemistry is discussed in terms of (1) the organic pollutants, such as hydrocarbons, (2) the nitrogen containing pollutants, such as nitrogen d...

  15. PHOTOCHEMICAL AIR POLLUTANT EFFECTS ON MIXED CONIFER ECOSYSTEMS

    EPA Science Inventory

    In 1972, a multi-disciplinary team of ecologists assembled to monitor and analyze some of the ecological consequences of photochemical oxidant air pollutants in California Mixed Conifer Forest ecosystems of the San Bernardino Mountains east of Los Angeles. The purposes included g...

  16. A Simple Photochemical Experiment for the Advanced Laboratory.

    ERIC Educational Resources Information Center

    Rosenfeld, Stuart M.

    1986-01-01

    Describes an experiment to provide students with: (1) an introduction to photochemical techniques and theory; (2) an experience with semimicro techniques; (3) an application of carbon-14 nuclear magnetic resonance; and (4) a laboratory with some qualities of a genuine experiment. These criteria are met in the photooxidation of 9,…

  17. Photochemical Copper Coating on 3D Printed Thermoplastics

    NASA Astrophysics Data System (ADS)

    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.

  18. Photochemical transformation of graphene oxide in sunlight (journal)

    EPA Science Inventory

    Graphene oxide (GO) is a graphene derivative that is more easily manufactured in large scale and used to synthesize reduced graphene oxide (rGO) with properties analogous to graphene. In this study, we investigate the photochemical fate of GO under sunlight conditions. The resu...

  19. Photochemical Copper Coating on 3D Printed Thermoplastics

    PubMed Central

    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

    2016-01-01

    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. PMID:27501761

  20. Surface retention and photochemical reactivity of the diphenylether herbicide oxyfluorfen.

    PubMed

    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. PMID:15074812

  1. Photochemical Copper Coating on 3D Printed Thermoplastics.

    PubMed

    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

    2016-01-01

    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. PMID:27501761

  2. Chemical kinetics and photochemical data for use in stratospheric modeling

    NASA Technical Reports Server (NTRS)

    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.

    1992-01-01

    As part of a series of evaluated sets, rate constants and photochemical cross sections compiled by the NASA Panel for Data Evaluation are provided. The primary application of the data is in the modeling of stratospheric processes, with particular emphasis on the ozone layer and its possible perturbation by anthropogenic and natural phenomena. Copies of this evaluation are available from the Jet Propulsion Laboratory.

  3. Photochemically induced emission tuning of conductive polumers used in OLEDs

    NASA Astrophysics Data System (ADS)

    Vasilopoulou, M.; Pistolis, G.; Argitis, P.

    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 (λmax = 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.

  4. PHOTOCHEMICAL OXIDANT FORMATION: OVERVIEW OF CURRENT KNOWLEDGE AND EMERGING ISSUES

    EPA Science Inventory

    Despite 1-1/2 decades of control effort, the photochemical ozone problem continues to plague human society and ecology in the U.S. One reason alleged for the difficulty in achieving the established ozone air quality standard is that current understanding of the science underlying...

  5. Packed bed reactor for photochemical .sup.196 Hg isotope separation

    DOEpatents

    Grossman, Mark W.; Speer, Richard

    1992-01-01

    Straight tubes and randomly oriented pieces of tubing having been employed in a photochemical mercury enrichment reactor and have been found to improve the enrichment factor (E) and utilization (U) compared to a non-packed reactor. One preferred embodiment of this system uses a moving bed (via gravity) for random packing.

  6. Chemical kinetic and photochemical data for use in stratospheric modelling

    NASA Technical Reports Server (NTRS)

    Demore, W. B.; Stief, L. J.; Kaufman, F.; Golden, D. M.; Hampton, R. F.; Kurylo, M. J.; Margitan, J. J.; Molina, M. J.; Watson, R. T.

    1979-01-01

    An evaluated set of rate constants and photochemical cross sections were compiled for use in modelling stratospheric processes. The data are primarily relevant to the ozone layer, and its possible perturbation by anthropogenic activities. The evaluation is current to, approximately, January, 1979.

  7. USER'S GUIDE FOR THE PHOTOCHEMICAL BOX MODEL (PBM)

    EPA Science Inventory

    The User's Guide for the Photochemical Box Model (PBM) attempts to describe the structure and operation of the model and its preprocessors as well as provide the potential user with guidance in setting up input data. The PBM is a simple stationary single-cell model with a variabl...

  8. EFFECTS OF PHOTOCHEMICAL KINETIC MECHANISMS ON OXIDANT MODEL PREDICTIONS

    EPA Science Inventory

    The comparative effects of kinetic mechanisms on oxidant model predictions have been tested using two different mechanisms (the Carbon-Bond Mechanism II (CBM-II) and the Demerjian Photochemical Box Model (DPBM) mechanism) in three air quality models (the OZIPM/EKMA, the Urban Air...

  9. AIR QUALITY CRITERIA FOR OZONE AND RELATED PHOTOCHEMICAL OXIDANTS

    EPA Science Inventory

    The Clean Air Act requires periodic (5-year) update revision of criteria and National Ambient Air Quality Standards (NAAQS) for Ozone. The previous revision of the criteria contained in the Air Quality Criteria Document (AQCD) for Ozone and Related Photochemical Oxidants was co...

  10. A review of iron and cobalt porphyrins, phthalocyanines, and related complexes for electrochemical and photochemical reduction of carbon dioxide

    DOE PAGESBeta

    Manbeck, Gerald F.; Fujita, Etsuko

    2015-03-30

    This review summarizes research on the electrochemical and photochemical reduction of CO₂ using a variety of iron and cobalt porphyrins, phthalocyanines, and related complexes. Metalloporphyrins and metallophthalocyanines are visible light absorbers with extremely large extinction coefficients. However, yields of photochemically-generated active catalysts for CO₂ reduction are typically low owing to the requirement of a second photoinduced electron. This requirement is not relevant to the case of electrochemical CO₂ reduction. Recent progress on efficient and stable electrochemical systems includes the use of FeTPP catalysts that have prepositioned phenyl OH groups in their second coordination spheres. This has led to remarkable progressmore » in carrying out coupled proton-electron transfer reactions for CO₂ reduction. Such ground-breaking research has to be continued in order to produce renewable fuels in an economically feasible manner.« less

  11. A review of iron and cobalt porphyrins, phthalocyanines, and related complexes for electrochemical and photochemical reduction of carbon dioxide

    SciTech Connect

    Manbeck, Gerald F.; Fujita, Etsuko

    2015-03-30

    This review summarizes research on the electrochemical and photochemical reduction of CO₂ using a variety of iron and cobalt porphyrins, phthalocyanines, and related complexes. Metalloporphyrins and metallophthalocyanines are visible light absorbers with extremely large extinction coefficients. However, yields of photochemically-generated active catalysts for CO₂ reduction are typically low owing to the requirement of a second photoinduced electron. This requirement is not relevant to the case of electrochemical CO₂ reduction. Recent progress on efficient and stable electrochemical systems includes the use of FeTPP catalysts that have prepositioned phenyl OH groups in their second coordination spheres. This has led to remarkable progress in carrying out coupled proton-electron transfer reactions for CO₂ reduction. Such ground-breaking research has to be continued in order to produce renewable fuels in an economically feasible manner.

  12. Effects of crystal orientation and ferroelastic domain structure on the photochemical reactivity of BiVO4 and related compounds

    NASA Astrophysics Data System (ADS)

    Munprom, Ratiporn

    Bismuth vanadate, BiVO4, has been recognized for its high efficiency as a photoanode for water splitting. However, its performance is limited by photogenerated electron--hole recombination. Thus, researchers have attempted to modify BiVO4 to improve its performance. One strategy to improve charge separation is to utilize an internal field arising from surface termination differences. Previous studies concentrated on polygonal single crystals of BiVO4, providing limited information about the orientation-reactivity relationship. The current research focuses on polycrystalline BiVO4, which makes it possible to study the photochemical reactivity of all possible orientations and determine the complete orientation dependence of the photochemical reactivity of BiVO4. (Abstract shortened by UMI.).

  13. Moral Reasoning in Hypothetical and Actual Situations.

    ERIC Educational Resources Information Center

    Sumprer, Gerard F.; Butter, Eliot J.

    1978-01-01

    Results of this investigation suggest that moral reasoning of college students, when assessed using the DIT format, is the same whether the dilemmas involve hypothetical or actual situations. Subjects, when presented with hypothetical situations, become deeply immersed in them and respond as if they were actual participants. (Author/BEF)

  14. Factors Related to Self-Actualization.

    ERIC Educational Resources Information Center

    Hogan, H. Wayne; McWilliams, Jettie M.

    1978-01-01

    Provides data to further support the notions that females score higher in self-actualization measures and that self-actualization scores correlate inversely to the degree of undesirability individuals assign to their heights and weights. Finds that, contrary to predictions, greater androgyny was related to lower, not higher, self-actualization…

  15. Mars atmospheric loss and isotopic fractionation by solar-wind-induced sputtering and photochemical escape

    NASA Technical Reports Server (NTRS)

    Jakosky, Bruce M.; Pepin, Robert O.; Johnson, Robert E.; Fox, J. L.

    1994-01-01

    We examine the effects of the loss of Mars atmospheric constituents by solar-wind-induced sputtering and by photochemical escape during the past 3.8 billion years. Sputtering is capable of efficiently removing species from the upper atmosphere, including the light noble gases; nitrogen and oxygen are removed by photochemical processes as well. Due to diffusive separation (by mass) above the homopause, removal from the top of the atmosphere will fractionate the isotopes of each species, with the lighter mass being preferentially lost. For carbon and oxygen, this allows us to determine the size of nonatmospheric reservoirs which mix with the atmosphere; these reservoirs can be CO2 adsorbed in the regolith and H2O in the polar ice caps. We have constructed both simple analytical models and time-dependent models of the loss of volatiles from and supply to the martian atmosphere. Both argon and neon require continued replenishment from outgassing over geologic time. For argon, sputtering loss explains the fractionation of (Ar-36)/(Ar-38) without requiring a distinct epoch of hydrodynamic escape (although fractionation of Xe isotopes still requires very early hydrodynamic loss). For neon, the current (Ne-22)/(Ne-20) ratio represents a balance between loss to space and continued resupply from the interior; the similarity of the ratio to the terrestrial value is coincidental. For nitrogen, the loss by both sputtering and photochemical escape would produce a fractionation of (N-15)/(N-14) larger than observed; an early, thicker carbon dioxide atmosphere could mitigate the nitrogen loss and produce the observed fractionation, as could continued outgassing of juvenile nitorgen. Based on the isotopic constraints, the total amount of carbon dioxide lost over geologic time is probably on the order of tens of millibars rather than a substantial fraction of a bar. The total loss from solar-wind-induced sputtering and photochemical escape, therefore, does not seem able to explain

  16. Photochemical degradation of a brominated flame retardant (tetrabromobisphenol A) in ice under field and laboratory conditions

    NASA Astrophysics Data System (ADS)

    Waligroski, G.; Grannas, A. M.

    2013-12-01

    Studies of brominated flame retardants have raised awareness of their potential environmental impact as toxic compounds. Because these compounds are now globally distributed, including in the Polar Regions, it is important to assess their potential fate in the environment. It has been shown that active photochemistry occurs in sunlit snow and ice, but there is little information regarding potential photochemical degradation of brominated flame retardants in snow and ice. The purpose of this research is to investigate the direct and indirect photochemical transformation pathways of a widely used brominated flame retardant, tetrabromobisphenol A (TBBPA). We have conducted field-based experiments in Barrow, Alaska to investigate the potential photochemical degradation of TBBPA in snow and ice under environmentally-relevant conditions. Field-based results show that TBBPA is efficiently degraded under direct photolysis conditions in frozen aqueous samples under natural Barrow sunlight. In aqueous solution the light absorption properties of TBBPA are pH dependent. Therefore, the photodegradation of TBBPA in snow and ice will be highly pH dependent. Reactions that are pH dependent may be affected by the nature of the liquid-like layers in snow/ice as well as the presence of other solutes that may indirectly affect the local pH experienced by TBBPA in snow and ice samples. In order to establish how the effective pH of liquid-like regions in ice might impact the degradation of TBBPA, various salts (sodium chloride, sodium fluoride, sodium bromide, ammonium chloride, ammonium acetate and ammonium sulfate) were added to aqueous solutions of TBBPA. Upon freezing, these different salts will induce pH differences in the liquid-like regions of the sample due to a phenomenon known as the freezing potential. Observed reactivity differences upon addition of these salts will be evaluated and discussed. Additionally, the presence of natural dissolved organic matter (DOM), an effective

  17. Fuel from water: the photochemical generation of hydrogen from water.

    PubMed

    Han, Zhiji; Eisenberg, Richard

    2014-08-19

    Hydrogen has been labeled the fuel of the future since it contains no carbon, has the highest specific enthalpy of combustion of any chemical fuel, yields only water upon complete oxidation, and is not limited by Carnot considerations in the amount of work obtained when used in a fuel cell. To be used on the scale needed for sustainable growth on a global scale, hydrogen must be produced by the light-driven splitting of water into its elements, as opposed to reforming of methane, as is currently done. The photochemical generation of H2, which is the reductive side of the water splitting reaction, is the focus of this Account, particularly with regard to work done in the senior author's laboratory over the last 5 years. Despite seminal work done more than 30 years ago and the extensive research conducted since then on all aspects of the process, no viable system has been developed for the efficient and robust photogeneration of H2 from water using only earth abundant elements. For the photogeneration of H2 from water, a system must contain a light absorber, a catalyst, and a source of electrons. In this Account, the discovery and study of new Co and Ni catalysts are described that suggest H2 forms via a heterocoupling mechanism from a metal-hydride and a ligand-bound proton. Several complexes with redox active dithiolene ligands are newly recognized to be effective in promoting the reaction. A major new development in the work described is the use of water-soluble CdSe quantum dots (QDs) as light absorbers for H2 generation in water. Both activity and robustness of the most successful systems are impressive with turnover numbers (TONs) approaching 10(6), activity maintained over 15 days, and a quantum yield for H2 of 36% with 520 nm light. The water solubilizing capping agent for the first system examined was dihydrolipoic acid (DHLA) anion, and the catalyst was determined to be a DHLA complex of Ni(II) formed in situ. Dissociation of DHLA from the QD surface proved

  18. Photochemical inactivation of pathogenic bacteria in human platelet concentrates.

    PubMed

    Lin, L; Londe, H; Janda, J M; Hanson, C V; Corash, L

    1994-05-01

    Platelet concentrates (PC) may be infrequently contaminated with low levels of bacteria that can cause septicemia and death in patients receiving transfusion therapy. We evaluated the efficacy of a photochemical decontamination (PCD) technique using 8-methoxypsoralen (8-MOP) and long wavelength UV light (UVA) to inactivate bacteria in standard therapeutic PC. Twelve phylogenetically distinct pathogenic bacteria, 5 gram-positive and 7 gram-negative organisms, were seeded into PC to a final challenge dose ranging from 10(5) to 10(7) colony-forming units (CFU)/mL. Contaminated PC were treated with 8-MOP (5 micrograms/mL) and 5 J/cm2 of UVA, a PCD treatment regimen found to adequately preserve in vitro platelet function. Greater than 10(5) CFU/mL of all 5 gram-positive (Staphylococcus aureus, Streptococcus epidermidis, Streptococcus pyogenes, Listeria monocytogenes, and Corynebacterium minutissimum) and 2 of the gram-negative (Escherichia coli and Yersinia enterocolitica) organisms were inactivated. The remaining 5 gram-negative organisms were more resistant, with less than 10(1) to 10(3.7) CFU/mL inactivated under these conditions. The inactivation efficiency for this resistant group of gram-negative organisms was improved when PC were resuspended in a synthetic storage medium with reduced plasma protein concentration (15%) and an increased 8-MOP concentration (23.4 micrograms/mL). Illumination with 3 J/cm2 of UVA in this system inactivated greater than 10(5) CFU/mL of 4 resistant gram-negative organisms (Salmonella choleraesuis, Enterobacter cloacae, Serratia marcescens, and Klebsiella pneumoniae) and 10(4.1) CFU/mL of the most resistant gram-negative organism (Pseudomonas aeruginosa). This level of PCD treatment did not adversely affect in vitro platelet function. These results demonstrate that PCD using 8-MOP (5 to 23.4 micrograms/mL) effectively inactivated high levels of pathogenic bacteria in PC with adequate preservation of in vitro platelet properties. PMID

  19. Mars atmospheric loss and isotopic fractionation by pick-up-ion sputtering and photochemical escape

    NASA Technical Reports Server (NTRS)

    Jakosky, B. M.; Pepin, R. O.; Johnson, R. E.; Fox, J. L.

    1994-01-01

    We examine the effects of loss of constituents of the Martian atmosphere due to sputtering by solar-wind pick-up ions and photochemical escape during the last 3.8 billion years. Sputtering is capable of efficiently removing species from the upper atmosphere to space, including the light noble gases; nitrogen and oxygen are removed by both sputtering ad photochemical processes. Due to diffusive separation (by mass) above the homopause, removal from the top of the atmosphere will fractionate the isotopes of each species, with the lighter isotope being preferentially lost. This allows current measurements of the isotopic ratios to be used as a measure of the atmospheric evolution as integrated over geologic time. For carbon and oxygen, isotopic fractionation is buffered by exchange of atmospheric species with non-atmospheric reservoirs of CO2 and H2O. This allows us to determine the size of the non-atmospheric reservoirs which are capable of mixing with the atmosphere; these reservoirs can be CO2 absorbed in the regolith and/or H2O in the polar ice caps. Such an exchangeable reservoir is required in order to keep the fractionation of the atmospheric gases as low as is observed.

  20. Adjoint sensitivity analysis for a three-dimensional photochemical model: implementation and method comparison.

    PubMed

    Martien, Philip T; Harley, Robert A; Cacuci, Dan G

    2006-04-15

    Photochemical air pollution forms when emissions of nitrogen oxides (NO(x)) and volatile organic compounds (VOC) react in the atmosphere in the presence of sunlight. The goal of applying three-dimensional photochemical air quality models is usually to conduct sensitivity analysis: for example, to predict changes in an ozone response due to changes in NO(x) and VOC emissions or other model data. Forward sensitivity analysis methods are best suited to investigating sensitivities of many model responses to changes in a few inputs or parameters. Here we develop a continuous adjoint model and demonstrate an adjoint sensitivity analysis procedure that is well-suited to the complementary case of determining sensitivity of a small number of model responses to many parameters. Sensitivities generated using the adjoint method agree with those generated using other methods. Compared to the forward method, the adjoint method had large disk storage requirements but was more efficient in terms of computer processor time for receptor-based investigations focused on a single response at a specified site and time. The adjoint method also generates sensitivity apportionment fields, which reveal when and where model data are important to the target response. PMID:16683606

  1. Wastewater remediation using a spiral shaped reactor for photochemical reduction of hexavalent chromium.

    PubMed

    Machado, Tiele Caprioli; Lansarin, Marla Azário; Ribeiro, Camila Silva

    2015-03-01

    The hexavalent chromium contained in wastewater of some industries is toxic to most microorganisms and potentially harmful to human health. The application of photochemical reduction of Cr(VI) in the treatment of wastewater from the electroplating industry was studied, and a continuous reactor in spiral shape made of borosilicate was designed and constructed (SSR). The statistical model of a circumscribed central composite design (CCCD) was used to investigate the influence of the amount of ethanol and the initial concentration of hexavalent chromium on total Cr(VI) reduction. A total Cr(VI) reduction of 46.0% was achieved under the optimal conditions established by the experimental design, using a synthetic Cr(VI) solution. In addition, the photochemical reduction of Cr(VI) follows pseudo first-order kinetics. The SSR exhibited similar behavior to that of the plug flow reactor (PFR), and presented higher photonic efficiency than the batch reactor. Finally, the designed reactor was effective when applied to real wastewater, showing a total Cr(VI) reduction of 51.8%, and its configuration is suitable for scale up. PMID:25355488

  2. Photochemical Conversion of Phenanthro[9,10-d]imidazoles into π-Expanded Heterocycles.

    PubMed

    Skonieczny, Kamil; Gryko, Daniel T

    2015-06-01

    We discovered that phenanthro[9,10-d]imidazoles bearing a 2-halogenoaryl substituent at position 2 undergo swift photochemically driven direct arylation, leading to barely known phenanthro[9',10':4,5]imidazo[1,2-f]phenanthridines. The reaction is high-yielding, and it does not require any sensitizer or base. The discovered process is tolerant of a variety of substituents present both at positions 1 and 2; i.e., strongly electron-donating and electron-withdrawing substituents are tolerated as well as various heterocyclic units. Steric hindrance does not affect this process. The evidence gathered here indicates that SRN1 mechanism is operating in this case with the formation of radical anion as a critical step, followed by heterolytic cleavage of a carbon-halogen bond. Also TfO groups were shown to undergo cyclization, which allows the use of salicylaldehydes in the construction of heterocyclic systems. Efficiency of this photochemically driven direct arylation has been demonstrated by the synthesis of two systems possessing 13 and 17 conjugated rings, respectively. Phenanthro[9',10':4,5]imidazo[1,2-f]phenanthridines are blue-emitters, and they exhibit strong fluorescence in solution and in the solid state in direct contrast to their precursors. PMID:25938658

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

    PubMed

    Koch, T; Jacobsen, N; Fensholdt, J; Boas, U; Fenger, M; Jakobsen, M H

    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, when the primers are immobilized prior to the PCR, a solid-phase PCR can be performed and the amplicons are thus produced directly on the solid support. PMID:10898568

  4. Photochemical predictive analysis of photodynamic therapy with non-homogeneous topical photosensitizer distribution in dermatological applications

    NASA Astrophysics Data System (ADS)

    Salas-García, I.; Fanjul-Vélez, F.; Ortega-Quijano, N.; López-Escobar, M.; Arce-Diego, J. L.

    2010-04-01

    Photodynamic Therapy (PDT) is a therapeutic technique widely used in dermatology to treat several skin pathologies. It is based in topical or systemic delivery of photosensitizing drugs followed by irradiation with visible light. The subsequent photochemical reactions generate reactive oxygen species which are considered the principal cytotoxic agents to induce cell necrosis. In this work we present a PDT model that tries to predict the photodynamic effect on the skin with a topically administered photosensitizer. The time dependent inhomogeneous distribution of the photoactive compound protoporphyrin IX (PpIX) is calculated after obtaining its precursor distribution (Methyl aminolevulinate, MAL) which depends on the drug permeability, diffusion properties of the skin, incubation time and conversion efficiency of MAL to PpIX. Once the optical energy is obtained by means of the Beer Lambert law, a photochemical model is employed to estimate the concentration of the different molecular compounds taking into account the electronic transitions between molecular levels and particles concentrations. The results obtained allow us to know the evolution of the cytotoxic agent in order to estimate the necrotic area adjusting parameters such as the optical power, the photosensitizer concentration, the incubation and exposition time or the diffusivity and permeability of the tissue.

  5. Photochemical Production Rates in Western Houston

    SciTech Connect

    Berkowitz, Carl M.; Spicer, C. W.; Doskey, Paul V.

    2004-01-01

    In this paper, we evaluate the instantaneous O3 chemical production rates, NOx (= NO + NO2) loss rates and ozone production efficiency within ozone plumes sampled on the west side of Houston, Texas, during the Texas 2000 Air Quality Study. We emphasize days during which rapid increases associated with plume passage were observed in the 15-minute average ozone mixing ratio, O3. The basis for this work will be observations of key nitrogen species and VOCs collected from the top of a sky scraper on the western edge of the city. These observations are used in a 0-dimensional model to quantify the chemical kinetics within parcels of air associated with ozone levels in excess of 100 ppb. We identify the key VOCs affecting ozone production and assess the relative role of anthropogenic versus biogenic VOCs to local ozone production. We also examine how the daily variations in ozone production and ozone production efficiencies are related to differences in VOC/NOx ratios.

  6. Advanced photochemical oxidation of emergent micropollutants: carbamazepine.

    PubMed

    Domínguez, Joaquín R; González, Teresa; Palo, Patricia; Cuerda-Correa, Eduardo M

    2014-01-01

    The combination of UV radiation with hydrogen peroxide has been widely used for the photodegradation of pollutants in aqueous solutions. Statistical design of experiments is a powerful tool to optimize this kind of process. Initial hydrogen peroxide concentration, pH and temperature were considered as the variables for the process optimization. The interactions existing between these three variables were analyzed. Initial concentration of hydrogen peroxide proved to be the most important variable conditioning the removal efficiency, followed by temperature, and pH shows a non-significant positive influence along the whole operation interval. The ANOVA test reported significance for five of the nine involved variables. The Response Surface Methodology technique was used to optimize carbamazepine degradation. Under optimal conditions (hydrogen peroxide concentration = 0.38·10(-3) mol L(-1), pH = 1 and temperature = 35.6°C) total carbamazepine degradation was achieved. PMID:24798897

  7. Influence of ferroelectric substrates on the photochemical reactivity of titanium dioxide thin films

    NASA Astrophysics Data System (ADS)

    Burbure, Nina

    The efficiency of particulate photocatalysts used to split water is limited by the recombination of photogenerated electrons and holes and the back reaction of intermediate species to reform water. This efficiency could be improved by better spatial separation of charge carriers and reaction sites. The primary goal of this work is to test the hypothesis that dipolar fields in ferroelectric substrates can drive photogenerated electrons and holes in opposite directions, thus creating spatially distinct locations for photochemical oxidation and reduction reactions on the surfaces of supported TiO2 thin films. To investigate this, thin films of TiO2 (10 to 100 nm) were grown on polycrystalline, ferroelectric BaTiO3 and BiFeO3 substrates by pulsed laser deposition. The films grown on BaTiO 3 were characterized by electron backscatter diffraction, which showed that some substrate orientations stabilize the anatase phase while others stabilize rutile. Specifically, orientations within about 25° of (100) BaTiO3 promote the growth of biaxially orientated anatase such that [001] BaTiO3 is parallel to [001] anatase and [110] BaTiO3 is parallel to [110] anatase. Orientations further from (100) stabilize the growth or rutile. While the rutile growth is epitaxial, there is no single orientation relationship. The photochemical properties of the surface were probed using the photochemical reduction of Ag+ to Ag0 and the photochemical oxidation of Pb2+ to Pb4+ These specific oxidation and reduction reactions were chosen because they leave behind insoluble reaction products (Ag and PbO2) on the surface that allow the location of the reaction to be determined. The same locations of the surface were imaged by atomic force microscopy before and after the reaction and the heights of the reaction product on the surface were used as a measure of the extent of the reactivity. In this study, we found that the ferroelectric substrate does influence reactivity on the surface of the thin film

  8. Ambient temperature ligation of diene functional polymer and peptide strands onto cellulose via photochemical and thermal protocols.

    PubMed

    Tischer, Thomas; Claus, Tanja K; Oehlenschlaeger, Kim K; Trouillet, Vanessa; Bruns, Michael; Welle, Alexander; Linkert, Katharina; Goldmann, Anja S; Börner, Hans G; Barner-Kowollik, Christopher

    2014-06-01

    In the present contribution, two novel ambient temperature avenues are introduced to functionalize solid cellulose substrates in a modular fashion with synthetic polymer strands (poly(trifluoro ethyl methacrylate), PTFEMA, Mn = 4400 g mol(-1) , Đ = 1.18) and an Arg-Gly-Asp (RGD) containing peptide sequence. Both protocols rely on a hetero Diels-Alder reaction between an activated thiocarbonyl functionality and a diene species. In the first-thermally activated-protocol, the cellulose features surface-expressed thiocarbonylthio compounds, which readily react with diene terminal macromolecules at ambient temperature. In the second protocol, the reactive ene species are photochemically generated based on a phenacyl sulfide-decorated cellulose surface, which upon irradiation expresses highly reactive thioaldehyde species. The generated functional hybrid surfaces are characterized in-depth via ToF-SIMS and XPS analysis, revealing the successful covalent attachment of the grafted materials, including the spatially resolved patterning of both synthetic polymers and peptide strands using the photochemical protocol. The study thus provides a versatile platform technology for solid cellulose substrate modification via efficient thermal and photochemical ligation strategies. PMID:24706565

  9. Contributions of biogenic and anthropogenic hydrocarbons to photochemical smog formation

    SciTech Connect

    Paulson, S.E.

    1991-01-01

    Photochemical oxidation of biogenic (Isoprene) and anthropogenic (1-octene) hydrocarbons are examined. Experiments studied the individual daylight reactions of both isoprene and 1-octene, including those of OH, O{sub 3}, O({sup 3}P), and NO{sub 2}. The O{sub 3} reactions are found to produce significant quantities of OH, O({sup 3}P), and carbonyl yields that total about 100%. Isomerization is found to be an important channel for both isoprene and 1-octene. O({sup 3}P) reactions are found to have relatively minor decomposition pathways, resulting instead in epoxide formation. Results from both the smog chamber experiments and computer kinetic modeling were then used to develop photochemical oxidation mechanisms for each hydrocarbon. Aerosol formed by isoprene and another biogenic, {beta}-pinene, are characterized.

  10. Intrinsic response of polymer liquid crystals in photochemical phase transition

    SciTech Connect

    Ikeda, Tomiki; Sasaki, Takeo; Kim, Haengboo )

    1991-01-24

    Time-resolved measurements were performed on the photochemically induced isothermal phase transition of polymer liquid crystals (PLC) with mesogenic side chains of phenyl benzoate (PAPB3) and cyanobiphenyl (PACB3) under conditions wherein the photochemical reaction of the doped photoresponsive molecule (4-butyl-4-{prime}-methoxyazobenzene, BMAB) was completed within {approximately} 10 ns, and the subsequent phase transition of the matrix PLC from nematic (N) to isotropic (I) state was followed by time-resolved measurements of the birefringence of the system. Formation of a sufficient amount of the cis isomer of BMAB with a single pulse of a laser lowered the N-I phase transition temperature of the mixture, inducing the N-I phase transition of PLCs isothermally in a time range of {approximately} 200 ms. This time range is comparable to that of low molecular weight liquid crystals, indicating that suppression in mobility of mesogens in PLCs does not affect significantly the thermodynamically controlled process.

  11. Photochemical mechanisms of light-triggered release from nanocarriers

    PubMed Central

    Fomina, Nadezda; Sankaranarayanan, Jagadis; Almutairi, Adah

    2012-01-01

    Over the last three decades, a handful of photochemical mechanisms have been applied to a large number of nanoscale assemblies that encapsulate a payload to afford spatio-temporal and remote control over activity of the encapsulated payload. Many of these systems are designed with an eye towards biomedical applications, as spatio-temporal and remote control of bioactivity would advance research and clinical practice. This review covers five underlying photochemical mechanisms that govern the activity of the majority of photoresponsive nanocarriers: 1. photo driven isomerization and oxidation, 2. surface plasmon absorption and photothermal effects, 3. photo driven hydrophobicity changes, 4. photo driven polymer backbone fragmentation and 5. photo driven de-crosslinking. The ways in which these mechanisms have been incorporated into nanocarriers and how they affect release is detailed, as well as the advantages and disadvantages of each system. PMID:22386560

  12. Composition/bandgap selective dry photochemical etching of semiconductor materials

    DOEpatents

    Ashby, C.I.H.; Dishman, J.L.

    1985-10-11

    Disclosed is a method of selectively photochemically dry etching a first semiconductor material of a given composition and direct bandgap Eg/sub 1/ in the presence of a second semiconductor material of a different composition and direct bandgap Eg/sub 2/, wherein Eg/sub 2/ > Eg/sub 1/, said second semiconductor material substantially not being etched during said method. The method comprises subjecting both materials to the same photon flux and to the same gaseous etchant under conditions where said etchant would be ineffective for chemical etching of either material were the photons not present, said photons being of an energy greater than Eg/sub 1/ but less than Eg/sub 2/, whereby said first semiconductor material is photochemically etched and said second material is substantially not etched.

  13. Composition/bandgap selective dry photochemical etching of semiconductor materials

    DOEpatents

    Ashby, Carol I. H.; Dishman, James L.

    1987-01-01

    A method of selectively photochemically dry etching a first semiconductor material of a given composition and direct bandgap Eg.sub.1 in the presence of a second semiconductor material of a different composition and direct bandgap Eg.sub.2, wherein Eg.sub.2 >Eg.sub.1, said second semiconductor material substantially not being etched during said method, comprises subjecting both materials to the same photon flux and to the same gaseous etchant under conditions where said etchant would be ineffective for chemical etching of either material were the photons not present, said photons being of an energy greater than Eg.sub.1 but less than Eg.sub.2, whereby said first semiconductor material is photochemically etched and said second material is substantially not etched.

  14. Photochemical reactions of biologically important quinoxaline n-oxides

    SciTech Connect

    Dvoryantseva, G.G.; Tetenchuk, K.P.; Pol'shakov, V.I.; Elina, A.S.

    1987-02-01

    The authors study the photochemical reactions of quinoxidine, dioxidine, and a number of related derivatives of quinoxaline 1,4-di-N-oxides containing methyl, halomethyl, and carboxamide groups in the pyrazine ring. Thin-layer chromatography, UV spectrophotometry, and NMR/sup 1/H and /sup 13/C spectroscopy were used as the main methods for monitoring the photolysis process and establishing the structure of the products formed. The investigation established that two types of photochemical reactions are observed in the series of compounds discussed: photoisomerization with migration of a substitutent to the nitrogen atom of the heterocycle, and photorearrangement with elimination of a substituent and the formation of the corresponding lactams.

  15. Explicit photochemical mechanism for atmospheric oxidation of n-butane

    SciTech Connect

    Wen, L.

    1992-01-01

    Alkanes, being an important component of atmosphere, serve as precursors to ozone formation in urban and rural air masses. An explicit photochemical oxidation mechanism for n-butane, which is the major hydrocarbon component of automobile exhaust, is created in this work. The yields of organic nitrates from n-butane, n-pentane, and methyl ethyl ketone photooxidations were studied in Teflon bag and smog chamber experiments. Comparing with the expression currently using the most atmospheric model studies, the total butyl nitrates yield obtained in this work is about 36% lower, and the ratio of primary to secondary butyl nitrates is slightly higher. It is shown in this work that the yields of hydroxyl and carbonyl butyl nitrates are very low, and can be ignored in the explicit photochemical mechanisms. The explicit photochemical oxidation mechanism for methyl ethyl ketone (MEK) was created first because it is the major product from photooxidation of n-butane. The explicit photochemical oxidation mechanism for n-butane, created later, draws on the MEK mechanism. The mechanisms were tested by comparing model predictions with experimental observations from smog chamber experiments. The comparisons were conducted for species which had experimental observation data, such as O[sub 3], NO, and NO[sub 2], n-butane, MEK, organic nitrates, and aldehydes species. The sixteen smog chamber experiments, used in model simulations, were conducted during 1978 to 1992. The mechanisms are mainly based on the available kinetic data in literature and the experimental result in this work. The rate constants for some reactions in the mechanisms were adjusted to make a better fit with the experimental observations. These reactions were: reaction of OH and n-butane to form secondary butyl peroxy radical, decomposition of secondary butoxy radical, and reaction of OH and MEK.

  16. Molecular-beam Studies of Primary Photochemical Processes

    DOE R&D Accomplishments Database

    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.

  17. Dispersion and photochemical evolution of reactive pollutants in street canyons

    NASA Astrophysics Data System (ADS)

    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.

  18. Photochemical fate of beta-blockers in NOM enriched waters.

    PubMed

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

    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 8.9h(-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. PMID:22503673

  19. Photochemical Reactions of Poly(4-vinylphenol) Thin Films

    SciTech Connect

    Uppalapati, Suji; Chada, Sailaja; Engelhard, Mark H.; Yan, Mingdi

    2010-02-15

    The mechanism involved in the photochemical immobilization of poly(4-vinylphenol) (PVP) thin films was investigated. The films were fabricated by a simple procedure of UV irradiation and solvent extraction. A combination of ellipsometry, IR, and high-resolution x-ray photoelectron spectroscopy (XPS) were used to provide detailed and quantitative analysis of the composition of the photochemical reaction products. Upon irradiation at 260 nm, benzyl and phenoxy radicals are generated in the polymer. In the absence of oxygen, PVP films crosslink via the combination of the benzyl radicals or phenoxy radicals. At lower irradiation doses, the photochemical process was dominated by crosslinking of the polymer backbone via the combination of benzyl radicals. At higher exposure doses, phenoxy radicals were generated producing crosslinked quinoid structures. The concentration increased 2 with the irradiation time and thus the percentage of the crosslinked quinoid structures. No oxidation or degradation products were observed. In the presence of oxygen, additional reactions of oxidation and degradation occurred. At lower doses, oxidation at the benzyl position produced the ketone structure evidenced by the drastic increase the O content in the irradiated films. As the irradiation doses increased, further oxidation at the methylene position occurred, and in addition, volatile and degradation products were also generated. This photochemical process was successfully employed to fabricate patterned PVP structures. Photolithography at lower doses followed by solvent development created negative-tone PVP patterns. Irradiating the film at higher doses generated “pseudo” positive-tone patterns after the volatile products in the irradiated areas left the film.

  20. Cloud pumping in a one-dimensional photochemical model

    NASA Technical Reports Server (NTRS)

    Costen, Robert C.; Tennille, Geoffrey M.; Levine, Joel S.

    1988-01-01

    Cloud pumping data based on tropical maritime updraft statistics are incorporated in a one-dimensional steady-state eddy diffusive photochemical model of the troposphere. It is suggested that regions with weaker convection, such as the midlatitudes, may also experience substantial effects from cloud pumping. The direct effects of cloud pumping on CO were found to be more significant than implied by sensitivity studies. The (CH3)2S profile computed with cloud pumping agrees well with previous data.

  1. Solar energy storage via endothermic photochemical reactions. Final technical report

    SciTech Connect

    Wamser, C.C.; Olmsted, J.A. III

    1983-12-26

    Research effort on this focused on two aspects of photochemical solar energy storage: the storage potential of photoisomerization reactions and studies of polymer-bound photosensitizers. The latter area has become the major focus of our research efforts, specifically the study of membrane-bound photosensitizers. The status of these studies at the termination of the grant are described below. Detailed results of the photoisomerization work have appeared in the literature, and a copy of that manuscript is included in this report.

  2. Photochemical Preparation of a Novel Low Molecular Weight Heparin

    PubMed Central

    Higashi, Kyohei; Hosoyama, Saori; Ohno, Asami; Masuko, Sayaka; Yang, Bo; Sterner, Eric; Wang, Zhenyu; Linhardt, Robert J.; Toida, Toshihiko

    2011-01-01

    Commercial low molecular weight heparins (LMWHs) are prepared by several methods including peroxidative cleavage, nitrous acid cleavage, chemical ß-elimination, and enzymatic β-elimination. The disadvantages of these methods are that strong reaction conditions or harsh chemicals are used and these can result in decomposition or modification of saccharide units within the polysaccharide backbone. These side-reactions reduce product quality and yield. Here we show the partial photolysis of unfractionated heparin can be performed in distillated water using titanium dioxide (TiO2). TiO2 is a catalyst that can be easily removed by centrifugation or filtration after the photochemical reaction takes place, resulting in highly pure products. The anticoagulant activity of photodegraded LMWH (pLMWH) is comparable to the most common commercially available LMWHs (i.e., Enoxaparin and Dalteparin). 1H NMR spectra obtained show that pLMWH maintains the same core structure as unfractionated heparin. This photochemical reaction was investigated using liquid chromatography/mass spectrometry (LC/MS) and unlike other processes commonly used to prepare LMWHs, photochemically preparation affords polysaccharide chains of reduced length having both odd and even of saccharide residues. PMID:22205826

  3. Photochemical Control of DNA Structure via Radical Disproportionation

    PubMed Central

    Pedro, Joanna Maria N. San; Greenberg, Marc M.

    2013-01-01

    Photolysis of an aryl sulfide containing 5,6-dihydropyrimidine (1) at 350 nm produces high yields of thymidine and products resulting from trapping of 5,6-dihydrothymidin-5-yl radical by O2 or thiols. Thymidine is believed to result from disproportionation of the radical pair originally generated from C-S bond homolysis in 1 on the microsecond timescale, which is significantly shorter than other photochemical transformations of modified nucleotides into their native forms. Duplex DNA containing 1 is destabilized, presumably due to disruption of π-stacking. Incorporation of 1 within the binding site of the restriction endonuclease EcoRV, provides a photochemical switch for turning on the enzyme's activity. In contrast, 1 is a substrate for endonuclease VIII and serves as a photochemical off switch for this base excision repair enzyme. Modification 1 also modulates the activity of the 10–23 DNAzyme despite its incorporation into a non-duplex region. Overall, dihydropyrimidine 1 shows promise as a tool that provides spatiotemporal control over DNA structure on the miscrosecond tiimescale. PMID:23940105

  4. Photochemical conversion of solar energy in the environment. Book chapter

    SciTech Connect

    Zepp, R.G.

    1991-01-01

    Past research on photochemistry in the environment has focused on gas phase reactions in the atmosphere. Recently, however, environmentally significant photoreactions have been discovered in natural waters (i.e., the sea, lakes, and rivers), on soil surfaces, and in atmospheric condensed phases. These new investigations have been stimulated in part by interest in developing a scientific understanding of the role of photochemical processes in the biogeochemical cycles of various elements. In addition, other studies have explored the role of natural photochemical processes in cleansing the environemnt of various waste materials or, in some cases, in converting the wastes to more toxic substances. In the paper, current research results on the photochemical conversion of solar energy in aquatic environments and on soil and metal oxide surfaces are presented. Rate equations and products for selected homogeneous and heterogeneous photoreactions that occur in these systems are described. Data are presented for direct and sensitized photoreactions and for sunlight-initiated free radical reactions. (Copyright (c) 1991 Kluwer Academic Publishers.)

  5. Numerical photochemical modeling over Madrid (Spain) mesoscale urban area

    NASA Astrophysics Data System (ADS)

    San Jose, Roberto; Ramirez-Montesinos, Arturo; Marcelo, Luis M.; Sanz, Miguel A.; Rodriguez, Luis M.

    1995-09-01

    Photochemical air quality models provide the most defensible method for relating future air quality to changes in emission, and hence are the foundation for determining the effectiveness of proposed control strategies. In this contribution, we will show results from different photochemical schemes under typical emission conditions for a summer day in the Madrid mesocsale urban area. We will show that complex numerical integrated urban mesoscale models are a powerful tool to predict the ozone levels on this area. The comparison of model simulations at different grid points show an acceptable preliminary behavior. The results presented in this paper are prepared for August 15th, 1991 and the predicted ozone values are compared with those measured at two stations of the Madrid city monitoring network. Results show that the shape is successfully predicted by using the NUFOMO (numerical photochemical model) model. Because of the computer limitations, we have limited the results to this case study. Further investigations will provide additional information to produce a statistical analysis of the results. However, preliminary results show that the NUFOMO model is able to reproduce the measured ozone values.

  6. The Photochemical Stability of Carbonates on Mars

    NASA Astrophysics Data System (ADS)

    Quinn, Richard; Zent, Aaron P.; McKay, Christopher P.

    2006-08-01

    Carbonates, predominately MgCO3, have been spectroscopically identified at a level of 2-5% in martian dust. However, in spite of this observation, and a large number of climate studies that suggest 1 to several bars of CO2 should be sequestered in carbonate rocks, no outcropscale exposures of carbonate have been detected anywhere on Mars to date. To address one hypothesis for this long-standing puzzle, the effect of ultraviolet (UV) light on the stability of calcium carbonate in a simulated martian atmosphere was experimentally investigated. Using 13C-labeled calcite, we found no experimental evidence of the UV photodecomposition of calcium carbonate in a simulated martian atmosphere. Extrapolating the lower limit of detection of our experimental system to an upper limit of carbonate decomposition on Mars yields a quantum efficiency of 3.5 × 10-8 molecules/photon over the wavelength interval of 190-390 nm and a maximum UV photodecomposition rate of 1.2 × 10-13 kg m-2 s-1 from a calcite surface. The maximum loss of bulk calcite due to this process would be 2.5 nm year-1 (Mars year). However, calcite is expected to be thermodynamically stable on the surface of Mars, and potential UV photodecomposition reaction mechanisms indicate that, though calcium carbonate may decompose under vacuum, it would be stable in a CO2 atmosphere. Given the expected stability of carbonate on Mars and our inability to detect carbonate decomposition, we conclude that it is unlikely that the apparent absence of extensive carbonate deposits on the martian surface is due to UV photodecomposition in the current environment.

  7. Mechanistic insights into chemical and photochemical transformations of bismuth vanadate photoanodes

    PubMed Central

    Toma, Francesca M.; Cooper, Jason K.; Kunzelmann, Viktoria; McDowell, Matthew T.; Yu, Jie; Larson, David M.; Borys, Nicholas J.; Abelyan, Christine; Beeman, Jeffrey W.; Yu, Kin Man; Yang, Jinhui; Chen, Le; Shaner, Matthew R.; Spurgeon, Joshua; Houle, Frances A.; Persson, Kristin A.; Sharp, Ian D.

    2016-01-01

    Artificial photosynthesis relies on the availability of semiconductors that are chemically stable and can efficiently capture solar energy. Although metal oxide semiconductors have been investigated for their promise to resist oxidative attack, materials in this class can suffer from chemical and photochemical instability. Here we present a methodology for evaluating corrosion mechanisms and apply it to bismuth vanadate, a state-of-the-art photoanode. Analysis of changing morphology and composition under solar water splitting conditions reveals chemical instabilities that are not predicted from thermodynamic considerations of stable solid oxide phases, as represented by the Pourbaix diagram for the system. Computational modelling indicates that photoexcited charge carriers accumulated at the surface destabilize the lattice, and that self-passivation by formation of a chemically stable surface phase is kinetically hindered. Although chemical stability of metal oxides cannot be assumed, insight into corrosion mechanisms aids development of protection strategies and discovery of semiconductors with improved stability. PMID:27377305

  8. Microfluidic integration of photonic crystal fibers for online photochemical reaction analysis.

    PubMed

    Unterkofler, S; McQuitty, R J; Euser, T G; Farrer, N J; Sadler, P J; Russell, P St J

    2012-06-01

    Liquid-filled hollow-core photonic crystal fibers (HC-PCFs) are perfect optofluidic channels, uniquely providing low-loss optical guidance in a liquid medium. As a result, the overlap of the dissolved specimen and the intense light field in the micronsized core is increased manyfold compared to conventional bioanalytical techniques, facilitating highly-efficient photoactivation processes. Here we introduce a novel integrated analytical technology for photochemistry by microfluidic coupling of a HC-PCF nanoflow reactor to supplementary detection devices. Applying a continuous flow through the fiber, we deliver photochemical reaction products to a mass spectrometer in an online and hence rapid fashion, which is highly advantageous over conventional cuvette-based approaches. PMID:22660084

  9. The use of the solar energy in photochemical and photocatalytic processes

    NASA Astrophysics Data System (ADS)

    Kuburovic, Natasha D.; Valent, Vladimir J.; Todorovic, Marija S.

    2003-06-01

    The increasing use of the Earth's natural resources has generated increasing disposal of waste products and contamination of the environment. Many of these products are organic chemicals. Characteristic examples of waste products in the atmosphere, hydrosphere and soil are insecticides, herbicides and pesticides used to protect crops, accidental leakages and spills, and the continual discharge of waste by products in effluent streams from petrochemical and essential industries. To purify these contaminated atmospheres, hydrosphere and soil a procedure and process has been developing with minimal specific consumption energy from a renewable energy source. This paper will provide a survey and analysis of the parameters, thermal efficiency and conversion energy in the use of solar energy in the photochemical and photocatalytic degradation processes of organic effluents. As a consequence of the use of solar energy in the degradation of these effluents, a conceptual solution of a technical-technological and photocatalytic process is given for effluents which are located in watercourses and soil in Yugoslavia.

  10. Mechanistic insights into chemical and photochemical transformations of bismuth vanadate photoanodes.

    PubMed

    Toma, Francesca M; Cooper, Jason K; Kunzelmann, Viktoria; McDowell, Matthew T; Yu, Jie; Larson, David M; Borys, Nicholas J; Abelyan, Christine; Beeman, Jeffrey W; Yu, Kin Man; Yang, Jinhui; Chen, Le; Shaner, Matthew R; Spurgeon, Joshua; Houle, Frances A; Persson, Kristin A; Sharp, Ian D

    2016-01-01

    Artificial photosynthesis relies on the availability of semiconductors that are chemically stable and can efficiently capture solar energy. Although metal oxide semiconductors have been investigated for their promise to resist oxidative attack, materials in this class can suffer from chemical and photochemical instability. Here we present a methodology for evaluating corrosion mechanisms and apply it to bismuth vanadate, a state-of-the-art photoanode. Analysis of changing morphology and composition under solar water splitting conditions reveals chemical instabilities that are not predicted from thermodynamic considerations of stable solid oxide phases, as represented by the Pourbaix diagram for the system. Computational modelling indicates that photoexcited charge carriers accumulated at the surface destabilize the lattice, and that self-passivation by formation of a chemically stable surface phase is kinetically hindered. Although chemical stability of metal oxides cannot be assumed, insight into corrosion mechanisms aids development of protection strategies and discovery of semiconductors with improved stability. PMID:27377305

  11. Hydrogen treatment of undoped ZnO thin film using photo-chemical vapor deposition

    SciTech Connect

    Baik, S.J.; Lim, K.S.; Song, J.

    1996-12-31

    To obtain high quality ZnO thin films for use as transparent electrodes of amorphous silicon solar cells, hydrogen treatment of the films using photo-chemical vapor deposition was performed for the first time. The as-deposited ZnO thin film was irradiated by UV light during the flow of hydrogen molecules in the presence of photo-sensitizers of mercury. As the treatment time increased, resistivity decreased from 1 {times} 10{sup {minus}2}{Omega}cm to 2 {times} 10{sup {minus}3}{Omega}cm. Moreover, haze ratio increased from 20% to 48%. Hydrogen radicals were thought to be playing various roles on the neighborhood of the surface region and the grain boundary region. This new trial gave us new understanding into the relation between hydrogen and ZnO. Moreover, these results could be applied to the process of amorphous silicon solar cells and a possible increase of efficiency is expected.

  12. Deposition and performance of CdS thin films on various substrates for photochemical cells

    NASA Astrophysics Data System (ADS)

    Bhardwaj, R. C.; Jadhav, C. M.; Taqui Khan, M. M.

    1984-09-01

    A photoelectrochemical study of CdS semiconductor electrodes with various metal substrates is presented. The current and voltage were measured by performing the experiments in a polysulphide electrolyte using a carbon counterelectrode. The electrodes were prepared by depositing a thin film of CdS by slurry painting, chemical-bath deposition, or electroplating in a non-aqueous solvent. The highest short-circuit current (0.9 mA) and open-circuit voltage (0.51 V) in a sun intensity of 70 mW/sq cm were obtained with slurry-painted electrodes after the films had been doped and etched. It appears that the efficiency of photochemical devices using polycrystal line CdS films can be improved to be comparable with that of single-crystal semiconductor material, with the advantages of low cost and simple technology.

  13. Accelerated gas-liquid visible light photoredox catalysis with continuous-flow photochemical microreactors.

    PubMed

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

    2016-01-01

    In this protocol, we describe the construction and use of an operationally simple photochemical microreactor for gas-liquid photoredox catalysis using visible light. The general procedure includes details on how to set up the microreactor appropriately with inlets for gaseous reagents and organic starting materials, and it includes examples of how to use it to achieve continuous-flow preparation of disulfides or trifluoromethylated heterocycles and thiols. The reported photomicroreactors are modular, inexpensive and can be prepared rapidly from commercially available parts within 1 h even by nonspecialists. Interestingly, typical reaction times of gas-liquid visible light photocatalytic reactions performed in microflow are lower (in the minute range) than comparable reactions performed as a batch process (in the hour range). This can be attributed to the improved irradiation efficiency of the reaction mixture and the enhanced gas-liquid mass transfer in the segmented gas-liquid flow regime. PMID:26633128

  14. Enhancing the efficacy of cytotoxic agents for cancer therapy using photochemical internalisation

    PubMed Central

    Moore, Caroline M.; Loizidou, Marilena; MacRobert, Alexander J.; Woodhams, Josephine H.

    2016-01-01

    Photochemical internalisation (PCI) is a technique for improving cellular delivery of certain bioactive agents which are prone to sequestration within endolysosomes. There is a wide range of agents suitable for PCI‐based delivery including toxins, oligonucleotides, genes and immunoconjugates which demonstrates the versatility of this technique. The basic mechanism of PCI involves triggering release of the agent from endolysosomes within the target cells using a photosensitiser which is selectively retained with the endolysosomal membranes. Excitation of the photosensitiser by visible light leads to disruption of the membranes via photooxidative damage thereby releasing the agent into the cytosol. This treatment enables the drugs to reach their intended subcellular target more efficiently and improves their efficacy. In this review we summarise the applications of this technique with the main emphasis placed on cancer chemotherapy. PMID:25758607

  15. Mechanistic insights into chemical and photochemical transformations of bismuth vanadate photoanodes

    NASA Astrophysics Data System (ADS)

    Toma, Francesca M.; Cooper, Jason K.; Kunzelmann, Viktoria; McDowell, Matthew T.; Yu, Jie; Larson, David M.; Borys, Nicholas J.; Abelyan, Christine; Beeman, Jeffrey W.; Yu, Kin Man; Yang, Jinhui; Chen, Le; Shaner, Matthew R.; Spurgeon, Joshua; Houle, Frances A.; Persson, Kristin A.; Sharp, Ian D.

    2016-07-01

    Artificial photosynthesis relies on the availability of semiconductors that are chemically stable and can efficiently capture solar energy. Although metal oxide semiconductors have been investigated for their promise to resist oxidative attack, materials in this class can suffer from chemical and photochemical instability. Here we present a methodology for evaluating corrosion mechanisms and apply it to bismuth vanadate, a state-of-the-art photoanode. Analysis of changing morphology and composition under solar water splitting conditions reveals chemical instabilities that are not predicted from thermodynamic considerations of stable solid oxide phases, as represented by the Pourbaix diagram for the system. Computational modelling indicates that photoexcited charge carriers accumulated at the surface destabilize the lattice, and that self-passivation by formation of a chemically stable surface phase is kinetically hindered. Although chemical stability of metal oxides cannot be assumed, insight into corrosion mechanisms aids development of protection strategies and discovery of semiconductors with improved stability.

  16. Photoclickable dendritic molecular glue: noncovalent-to-covalent photochemical transformation of protein hybrids.

    PubMed

    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". PMID:23477460

  17. Photophysical and photochemical properties of α-(8-quinolinoxy) zinc phthalocyanine for photodynamic therapy

    NASA Astrophysics Data System (ADS)

    Lv, Yuehui; Yu, Songlin; Lin, Huiyun; Li, Buhong; Xue, Jinping; Xie, Shusen

    2009-02-01

    The photophysical and photochemical properties of a newly developed photosensitizer α-(8-quinolinoxy) zinc phthalocyanine (α-(8-QLO)PcZn) were investigated for application in photodynamic therapy (PDT). The maximal Q band for α-(8-QLO)PcZn in dimethylformamide around 675 nm with the molar extinction coefficient of about 1.89×105 mol-1cm-1. The fluorescence quantum and singlet oxygen (1O2) yields were determined to be 0.18+/-0.02 and 0.62+/-0.03, respectively. α-(8-QLO) PcZn has a diffuse cytoplasmic distribution in nasopharyngeal carcinoma C666-1 cells, and the efficient photodynamic cytotoxicity was observed. Our findings of this study suggest that α-(8-QLO)PcZn is a promising second-generation photosensitizer for PDT.

  18. Metal-Free on-Surface Photochemical Homocoupling of Terminal Alkynes.

    PubMed

    Colazzo, Luciano; Sedona, Francesco; Moretto, Alessandro; Casarin, Maurizio; Sambi, Mauro

    2016-08-17

    On-surface synthesis involving the homocoupling of aryl-alkynes affords the buildup of bisacetylene derivatives directly at surfaces, which in turn may be further used as ingredients for the production of novel functional materials. Generally, homocoupling of terminal alkynes takes place by thermal activation of molecular precursors on metal surfaces. However, the interaction of alkynes with surface metal atoms often induces unwanted reaction pathways when thermal energy is provided to the system. In this contribution we report about light-induced metal-free homocoupling of terminal alkynes on highly oriented pyrolitic graphite (HOPG). The reaction occurred with high efficiency and selectivity within a self-assembled monolayer (SAM) of aryl-alkynes and led to the generation of large domains of ordered butadiynyl derivatives. Such a photochemical uncatalyzed pathway represents an original approach in the field of topological C-C coupling at the solid/liquid interface. PMID:27437555

  19. Dosimetry determines the initial OH radical concentration in fast photochemical oxidation of proteins (FPOP).

    PubMed

    Niu, Ben; Zhang, Hao; Giblin, Daryl; Rempel, Don L; Gross, Michael L

    2015-05-01

    Fast photochemical oxidation of proteins (FPOP) employs laser photolysis of hydrogen peroxide to give OH radicals that label amino acid side-chains of proteins on the microsecond time scale. A method for quantitation of hydroxyl radicals after laser photolysis is of importance to FPOP because it establishes a means to adjust the yield of •OH, offers the opportunity of tunable modifications, and provides a basis for kinetic measurements. The initial concentration of OH radicals has yet to be measured experimentally. We report here an approach using isotope dilution gas chromatography/mass spectrometry (GC/MS) to determine quantitatively the initial •OH concentration (we found ~0.95 mM from 15 mM H2O2) from laser photolysis and to investigate the quenching efficiencies for various •OH scavengers. PMID:25712620

  20. Aqueous-Phase Photochemical Production of Oxidants in Atmospheric Waters.

    NASA Astrophysics Data System (ADS)

    Allen, John Morrison

    1992-01-01

    The photochemical formation and subsequent reactions of oxidants plays an important role in the overall chemistry of the atmosphere. Much of the interest in atmospheric oxidation reactions has been fueled by the environmental consequences of the oxidation of sulfur dioxide (SO _2) forming sulfuric acid (H_2 SO_4). Oxidation reactions also play a crucial role in other atmospheric chemical transformations such as: (1) the destruction of tropospheric ozone, (2) redox cycling of transition metals, and (3) oxidation of organic compounds. Much of the research pertaining to atmospheric oxidant formation and the reactions that these oxidants undergo has centered upon gas-phase photochemical oxidant formation and: (1) subsequent reactions in the gas phase, or (2) partitioning of oxidants into cloud and fog drops and subsequent reactions in the aqueous phase. Only a very limited amount of data is available concerning aqueous -phase photochemical sources of oxidants in cloud and fog drops. The focus of one aspect of the work presented in this dissertation is upon the aqueous-phase sunlight photochemical formation of oxidants in authentic cloud and fog water samples from across the United States and Canada. It will be demonstrated that atmospheric waters typically absorb solar ultraviolet radiation at wavelengths ranging from 290 to 340 nm. This absorption is due to the presence of chemical constituents in the cloud and fog waters that contain chromophoric functional groups that give rise to the formation of: (1) singlet molecular oxygen O_2(^1Delta_ {rm g}), (2) peroxyl radicals (HO _2cdot and RO_2 cdot), (3) peroxides (HOOH, ROOH, and ROOR '), and (4) hydroxyl radical ( cdotOH). This work will demonstrate that aqueous-phase photochemical reactions are a significant and in some cases dominant source of these oxidants in cloud and fog drops. The transition metal catalyzed oxidation of SO _2 to H_2SO _4 by molecular oxygen has been extensively studied. This reaction is thought

  1. Iron in non-hydroxyl radical mediated photochemical processes for dye degradation: Catalyst or inhibitor?

    PubMed

    Wu, Bingdang; Zhang, Shujuan; Li, Xuchun; Liu, Xitong; Pan, Bingcai

    2015-07-01

    The acetylacetone (AA) mediated photochemical process has been proven as an efficient approach for decoloration. For azo dyes, the UV/AA process was several to more than ten times more efficient than the UV/H2O2 process. Iron is one of the most common elements on the earth. It is well known that iron can improve the UV/H2O2 process through thermal Fenton and photo-Fenton reactions. What will be the role of iron in the UV/AA process? Could iron-AA complexes act as photocatalysts in environmental remediation? To answer these questions, the photo-degradation of an azo dye, Acid Orange 7 (AO7), was conducted under the variant combinations of AA with iron species in both ionic (Fe2+, Fe3+) and complex (Fe(AA)3) forms. The pseudo-first-order decoloration rate constants of AO7 in these photochemical processes followed such an order: UV/Fe(II)/AA

  2. Realizing actual feedback control of complex network

    NASA Astrophysics Data System (ADS)

    Tu, Chengyi; Cheng, Yuhua

    2014-06-01

    In this paper, we present the concept of feedbackability and how to identify the Minimum Feedbackability Set of an arbitrary complex directed network. Furthermore, we design an estimator and a feedback controller accessing one MFS to realize actual feedback control, i.e. control the system to our desired state according to the estimated system internal state from the output of estimator. Last but not least, we perform numerical simulations of a small linear time-invariant dynamics network and a real simple food network to verify the theoretical results. The framework presented here could make an arbitrary complex directed network realize actual feedback control and deepen our understanding of complex systems.

  3. "Mitochondrial" photochemical drugs do not release toxic amounts of 1O(2) within the mitochondrial matrix space.

    PubMed

    Petrat, Frank; Pindiur, Stanislaw; Kirsch, Michael; de Groot, Herbert

    2003-04-15

    Previously, we demonstrated that mitochondrial NAD(P)H is the primary target of singlet oxygen (1O(2)) generated by photoactivation of mitochondria-selective rhodamine derivatives. Hence, local NAD(P)H oxidation/fluorescence decrease may be used to reveal the site of intracellular 1O(2) generation. Therefore, in addition to the previously used tetramethylrhodamine methylester (TMRM), 2('),4('),5('),7(')-tetrabromorhodamine 123 bromide (TBRB) and rhodamine 123 (Rho 123), we tested here whether mitochondrial NAD(P)H of cultured hepatocytes is directly oxidized upon irradiation of different "mitochondrial" photosensitizers (Photofrin; protoporphyrin IX; Al(III) phthalocyanine chloride tetrasulfonic acid; meso-tetra(4-sulfonatophenyl)porphine dihydrochloride; Visudyne). In contrast to TMRM and Rho 123, which directly oxidized NAD(P)H upon irradiation, irradiation of intracellular TBRB and the photochemical drugs only indirectly affected mitochondrial NAD(P)H due to loss of mitochondrial integrity. In line with this result only TMRM and Rho 123 exclusively localized within the mitochondrial matrix. Due to these results it is doubtful whether real mitochondrial photosensitizers actually exist among the photochemical drugs applicable/used for photodynamic therapy. PMID:12667484

  4. Photochemical reactions of cytochrome oxidase at low temperatures.

    PubMed

    Orii, Y

    1978-01-01

    that all CO-heme and CO-hemoprotein complexes are photodissociable, we observed little photodissociability with some CO-heme complexes, especially at very low temperatures, and presented a view that depending on the bond type between CO and heme iron the efficiency of photodissociation is so varied that under certain conditions practically no photodissociation occurs. According to this view a tilted arrangement of the ligated CO towards the heme plane accompanying a large extent of overlapping of the dpi(Fe) and the pi* antibonding orbital on the CO facilitates photodissociation. In addition to our own observations of photochemical properties of cytochrome oxidase and heme model compounds, recent photodynamic studies carried out by other investigator on CO-heme and CO-hemoproteins are summarized and the validity and limitation of their models are discussed. PMID:209671

  5. 50 CFR 253.16 - Actual cost.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 50 Wildlife and Fisheries 9 2011-10-01 2011-10-01 false Actual cost. 253.16 Section 253.16 Wildlife and Fisheries NATIONAL MARINE FISHERIES SERVICE, NATIONAL OCEANIC AND ATMOSPHERIC ADMINISTRATION, DEPARTMENT OF COMMERCE AID TO FISHERIES FISHERIES ASSISTANCE PROGRAMS Fisheries Finance Program §...

  6. 50 CFR 253.16 - Actual cost.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 50 Wildlife and Fisheries 11 2013-10-01 2013-10-01 false Actual cost. 253.16 Section 253.16 Wildlife and Fisheries NATIONAL MARINE FISHERIES SERVICE, NATIONAL OCEANIC AND ATMOSPHERIC ADMINISTRATION, DEPARTMENT OF COMMERCE AID TO FISHERIES FISHERIES ASSISTANCE PROGRAMS Fisheries Finance Program §...

  7. Humanistic Education and Self-Actualization Theory.

    ERIC Educational Resources Information Center

    Farmer, Rod

    1984-01-01

    Stresses the need for theoretical justification for the development of humanistic education programs in today's schools. Explores Abraham Maslow's hierarchy of needs and theory of self-actualization. Argues that Maslow's theory may be the best available for educators concerned with educating the whole child. (JHZ)

  8. Children's Rights and Self-Actualization Theory.

    ERIC Educational Resources Information Center

    Farmer, Rod

    1982-01-01

    Educators need to seriously reflect upon the concept of children's rights. Though the idea of children's rights has been debated numerous times, the idea remains vague and shapeless; however, Maslow's theory of self-actualization can provide the children's rights idea with a needed theoretical framework. (Author)

  9. Culture Studies and Self-Actualization Theory.

    ERIC Educational Resources Information Center

    Farmer, Rod

    1983-01-01

    True citizenship education is impossible unless students develop the habit of intelligently evaluating cultures. Abraham Maslow's theory of self-actualization, a theory of innate human needs and of human motivation, is a nonethnocentric tool which can be used by teachers and students to help them understand other cultures. (SR)

  10. Group Counseling for Self-Actualization.

    ERIC Educational Resources Information Center

    Streich, William H.; Keeler, Douglas J.

    Self-concept, creativity, growth orientation, an integrated value system, and receptiveness to new experiences are considered to be crucial variables to the self-actualization process. A regular, year-long group counseling program was conducted with 85 randomly selected gifted secondary students in the Farmington, Connecticut Public Schools. A…

  11. Racial Discrimination in Occupations: Perceived and Actual.

    ERIC Educational Resources Information Center

    Turner, Castellano B.; Turner, Barbara F.

    The relationship between the actual representation of Blacks in certain occupations and individual perceptions of the occupational opportunity structure were examined. A scale which rated the degree of perceived discrimination against Blacks in 21 occupations was administered to 75 black male, 70 black female, 1,429 white male and 1,457 white…

  12. Developing Human Resources through Actualizing Human Potential

    ERIC Educational Resources Information Center

    Clarken, Rodney H.

    2012-01-01

    The key to human resource development is in actualizing individual and collective thinking, feeling and choosing potentials related to our minds, hearts and wills respectively. These capacities and faculties must be balanced and regulated according to the standards of truth, love and justice for individual, community and institutional development,…

  13. [Effects of plastic film mulching and rain harvesting modes on chlorophyll fluorescence characteristics, yield and water use efficiency of dryland maize].

    PubMed

    Li, Shang-Zhong; Fan, Ting-Lu; Wang, Yong; Zhao, Gang; Wang, Lei; Tang, Xiao-Ming; Dang, Yi; Zhao, Hui

    2014-02-01

    The differences on chlorophyll fluorescence parameters, yield and water use efficiency of dryland maize were compared among full plastic film mulching on double ridges and planting in catchment furrows (FFDRF), half plastic film mulching on double ridges and planting in catchment furrows (HFDRF), plastic film mulching on ridge and planting in film-side (FS), and flat planting with no plastic film mulching (NM) under field conditions in dry highland of Loess Plateau in 2007-2012. The results showed that fluorescence yield (Fo), the maximum fluorescence yield (Fm), light-adapted fluorescence yield when PS II reaction centers were totally open (F), light-adapted fluorescence yield when PS II reaction centers closed (Fm'), the maximal photochemical efficiency of PS II (Fv/Fm), the actual photochemical efficiency of PS II in the light (Phi PS II), the relative electron transport rate (ETR), photochemical quenching (qP) and non-photochemical quenching (qN) in maize leaves of FFDRF were higher than that of control (NM), and the value of 1-qP was lower than that of control, at 13:00, chlorophyll fluorescence parameters values of FFDRF was significantly higher than control, which were increased by 5.3%, 56.8%, 10.7%, 36.3%, 23.6%, 56.7%, 64.4%, 45.5%, 23.6% and -55.6%, respectively, compared with the control. Yield and water use efficiency of FFDRF were the highest in every year no matter dry year, normal year, humid year and hail disaster year. Average yield and water use efficiency of FFDRF were 12,650 kg x hm(-2) and 40.4 kg x mm(-1) x hm(-2) during 2007-2012, increased by 57.8% and 61.6% compared with the control, respectively, and also significantly higher compared with HFDRF and PS. Therefore, it was concluded that FFDRF had significantly increased the efficiency of light energy conversion and improved the production capacity of dryland maize. PMID:24830246

  14. The Photochemical Isomerization of Maleic to Fumaric Acid: An Undergraduate Organic Chemistry Experiment.

    ERIC Educational Resources Information Center

    Castro, Albert J.; And Others

    1983-01-01

    Describes an undergraduate organic chemistry experiment on the photochemical isomerization of maleic to fumaric acid. Background information, chemical reactions involved, and experimental procedures are included. (JN)

  15. The photochemistry of daunomycin in solution and intercalated into DNA studied by photochemical hole burning

    NASA Astrophysics Data System (ADS)

    Flöser, Götz; Haarer, Dietrich

    1988-06-01

    We report photochemical hole-burning experiments on the antitumour drug daunomycin in solution and bound to two types of DNA oligonucleotides (d(AT) 5 and d(CG) 5). From the fact that hole-burning photochemistry is possible and from the width of the quasihomogeneous line we conclude that the DNA structure shows considerable inhomogeneous broadening and also provides an appropriate photochemical mechanism. A difference in the photochemical quantum yield by a factor of 60 between the two daunomycin-DNA complexes is observed; this reflects differences in the molecular environment of the intercalated dye. Evidence is presented that the photoprocess is a photophysical rather than a photochemical one.

  16. Whiteheadian Actual Entitities and String Theory

    NASA Astrophysics Data System (ADS)

    Bracken, Joseph A.

    2012-06-01

    In the philosophy of Alfred North Whitehead, the ultimate units of reality are actual entities, momentary self-constituting subjects of experience which are too small to be sensibly perceived. Their combination into "societies" with a "common element of form" produces the organisms and inanimate things of ordinary sense experience. According to the proponents of string theory, tiny vibrating strings are the ultimate constituents of physical reality which in harmonious combination yield perceptible entities at the macroscopic level of physical reality. Given that the number of Whiteheadian actual entities and of individual strings within string theory are beyond reckoning at any given moment, could they be two ways to describe the same non-verifiable foundational reality? For example, if one could establish that the "superject" or objective pattern of self- constitution of an actual entity vibrates at a specific frequency, its affinity with the individual strings of string theory would be striking. Likewise, if one were to claim that the size and complexity of Whiteheadian 'societies" require different space-time parameters for the dynamic interrelationship of constituent actual entities, would that at least partially account for the assumption of 10 or even 26 instead of just 3 dimensions within string theory? The overall conclusion of this article is that, if a suitably revised understanding of Whiteheadian metaphysics were seen as compatible with the philosophical implications of string theory, their combination into a single world view would strengthen the plausibility of both schemes taken separately. Key words: actual entities, subject/superjects, vibrating strings, structured fields of activity, multi-dimensional physical reality.

  17. Three-Dimensional Bimetal-Graphene-Semiconductor Coaxial Nanowire Arrays to Harness Charge Flow for the Photochemical Reduction of Carbon Dioxide.

    PubMed

    Hou, Jungang; Cheng, Huijie; Takeda, Osamu; Zhu, Hongmin

    2015-07-13

    The photochemical conversion of carbon dioxide provides a straightforward and effective strategy for the highly efficient production of solar fuels with high solar-light utilization efficiency. However, the high recombination rate of photoexcited electron-hole (e-h) pairs and the poor photostability have greatly limited their practical applications. Herein, a practical strategy is proposed to facilitate the separation of e-h pairs and enhance the photostability in a semiconductor by the use of a Schottky junction in a bimetal-graphene-semiconductor stack array. Importantly, Au-Cu nanoalloys (ca. 3 nm) supported on a 3D ultrathin graphene shell encapsulating a p-type Cu2O coaxial nanowire array promotes the stable photochemical reduction of CO2 to methanol by the synergetic catalytic effect of interfacial modulation and charge-transfer channel design. This work provides a promising lead for the development of practical catalysts for sustainable fuel synthesis. PMID:26068934

  18. Bis(subphthalocyanine)-azaBODIPY triad for ultrafast photochemical processes.

    PubMed

    Gobeze, Habtom B; Bandi, Venugopal; D'Souza, Francis

    2014-09-21

    Multi-modular supramolecular systems capable of undergoing photoinduced energy and electron transfer are of paramount importance to design light-to-energy and light-to-fuel converting devices. Often, this has been achieved by linking two or more photo-active or redox-active entities with complementary spectral and photochemical properties. In the present study, we report a new triad made out of two entities of subphthalocyanine covalently linked to BF2-chelated azadipyrromethene ((SubPc)2-azaBODIPY). The triad was fully characterized by spectral, computational, electrochemical and photochemical techniques. The B3LYP/6-31G* calculations revealed a structure wherein the donor, SubPc, and the acceptor, azaBODIPY, were well separated with no steric crowding. The different redox states were established from the differential pulse voltammetry studies and the data were used to estimate free-energy change associated with charge separation. Such calculations revealed the charge separation from either the (1)SubPc* or (1)azaBODIPY* to be thermodynamically feasible for yielding the (SubPc)SubPc˙(+)-azaBODIPY˙(-) radical ion-pair. Steady-state fluorescence studies revealed quantitative quenching of (1)SubPc* in the triad and solvent dependent quenching of (1)azaBODIPY* indicating participation of both fluorophores in promoting photochemical events. In nonpolar toluene, singlet-singlet energy transfer from the (1)SubPc* to azaBODIPY was observed, while in polar benzonitrile, evidence of energy transfer was feeble. Femtosecond laser flash photolysis studies provided concrete evidence for the occurrence of ultrafast photoinduced electron transfer by providing spectral proof for the formation of the (SubPc)SubPc˙(+)-azaBODIPY˙(-) charge separated state. The charge recombination followed populating the (3)azaBODIPY* prior to returning to the ground state. PMID:25076098

  19. Resin–Dentin Bonding Interface After Photochemical Surface Treatment

    PubMed Central

    Sano, Kazunobu; Ichinose, Shizuko; Araki, Kouji

    2015-01-01

    Abstract Objective The aim of this study is to elucidate the structure of the resin–dentin interface formed by photochemical dentin treatment using an argon fluoride (ArF) excimer laser. Background data The ArF excimer laser processes material by photochemical reaction without generating heat, while also providing surface conditioning that enhances material adhesion. In the case of bonding between resin and dentin, we demonstrated in a previous study that laser etching using an ArF excimer laser produced bonding strength comparable to that of the traditional bonding process; however, conditions of the bonding interface have not been fully investigated. Methods A dentin surface was irradiated in air with an ArF excimer laser followed by bonding treatment. Cross sections were observed under light microscope, transmission electron microscope (TEM), and scanning electron microscope, then analyzed using an energy dispersive X-ray spectroscope (EDS): EDS line profiles of the elements C, O, Si, Cl, P, and Ca at the resin–dentin interface were obtained. Results The density of C in resin decreased as it approached the interface, reaching its lowest level within the dentin at a depth of 2 μm from the resin–dentin interface on EDS. There was no hybrid layer observed at the interface on TEM. Therefore, it was suggested that the resin monomer infiltrated into the microspaces produced on the dentin surface by laser abrasion. Conclusions The monomer infiltration without hybrid layer is thought to be the adhesion mechanism after laser etching. Therefore, the photochemical processes at the bonding interface achieved using the ArF excimer laser has great potential to be developed into a new bonding system in dentistry. PMID:25555032

  20. Laboratory measurements of Photochemical Properties of Atmospheric Pollutants.

    NASA Astrophysics Data System (ADS)

    Orkin, V. L.

    2012-04-01

    One of the most important parameters in estimating the environmental impact due to emission of a compound is its residence time in the atmosphere, which is driven by the reaction of a compound with hydroxyl radicals (OH) for many atmospheric trace gases. The atmospheric lifetime is important for estimating ozone depletion potential (ODP) and global warming potential (GWP) of industrial compounds which are needed for evaluation of their environmental impact and regulatory purposes. The sources of critically evaluated photochemical data for atmospheric modeling, NASA/JPL Publications and IUPAC Publications, recommend uncertainties within 10%-60% for the majority of OH reaction rate constants with only a few cases where uncertainties lie at the low end of this range. These uncertainties can be somewhat conservative because evaluations are based on the data from various laboratories obtained during the last few decades. Nevertheless, even the authors of the original experimental works rarely estimate the total combined uncertainties of the published OH reaction rate constants to be less than ca. 10%. Thus, uncertainties in the photochemical properties of potential and current atmospheric trace gases obtained under controlled laboratory conditions still constitute a major source of uncertainty in estimating the compound's environmental impact. One of the purposes of the present work was to illustrate the potential for obtaining accurate laboratory measurements of the OH reaction rate constant over the temperature range of atmospheric interest. We provide a detailed inventory of accountable sources of instrumental uncertainties related to our FP-RF experiment to prove a total uncertainty of the OH reaction rate constant to be ca. 2%. The results of accurate measurements of photochemical properties of industrial and natural atmospheric pollutants will be presented.

  1. Do Photochemical Hazes Cloud the Atmosphere of 51 Eri b?

    NASA Astrophysics Data System (ADS)

    Marley, Mark; Zahnle, Kevin; Moses, Julianne; Morley, Caroline

    2015-12-01

    The first young giant planet to be discovered by the Gemini Planet Imager was the ~ 2MJ planet 51 Eri b. This ~20 Myr old young Jupiter is the first directly imaged planet to show unmistakable methane in H band. To constrain the planet’s mass, atmospheric temperature, and composition, the GPI J and H band spectra as well as some limited photometric points were compared to the predictions of substellar atmosphere models. The best fitting models reported in the discovery paper (Macintosh et al. 2015) relied upon a combination of clear and cloudy atmospheric columns to reproduce the data. In the atmosphere of an object as cool as 700 K the global silicate and iron clouds would be expected to be found well below the photosphere, although strong vertical mixing in the low gravity atmosphere is a possibility. Instead, clouds of Na2S, as have been detected in brown dwarf atmospheres, are a likely source of particle opacity. As a third explanation we have explored whether atmospheric photochemistry, driven by the UV flux from the primary star, may yield hazes that also influence the observed spectrum of the planet. To explore this possibility we have modeled the atmospheric photochemistry of 51 Eri b using two state-of-the-art photochemical models, both capable of predicting yields of complex hydrocarbons under various atmospheric conditions. We also have explored whether photochemical products can alter the equilibrium temperature profile of the atmosphere. In our presentation we will summarize the modeling approach employed to characterize 51 Eri b, explaining constraints on the planet’s effective temperature, gravity, and atmospheric composition and also present results of our studies of atmospheric photochemistry. We will discuss whether photochemical hazes could indeed be responsible for the particulate opacity that apparently sculpts the spectrum of the planet.

  2. Photochemical alkene formation in seawater from dissolved organic carbon: Results from laboratory experiments

    NASA Astrophysics Data System (ADS)

    Ratte, M.; Bujok, O.; Spitzy, A.; Rudolph, J.

    1998-03-01

    The production mechanism of light alkenes, alkanes, and isoprene was investigated in laboratory experiments by measuring their concentrations in natural seawater as a function of spectral range, exposure time and origin, and concentration of dissolved organic carbon (DOC). The production mechanism of alkanes and of isoprene could not be clarified. Ethene and propene are produced photochemically from DOC. The relevant spectral range is UV and short-wavelength visible light. Initial production rates (up to day 10 of exposure) were in the range of several pmol L-1 h-1 (mg DOC)-1; the corresponding mean quantum yields for the spectral range of 300-420 nm were about 10-8. Generally, the production rates and the quantum yields for ethene were about 2 times that of propene. The key factors in the total column integrated oceanic alkene production are the solar photon flux at sea surface, the penetration depth of the light into the ocean (especially the relation between different light absorbers, i.e., the extinction due to absorption of DOC), and the wavelength- and DOC-dependent quantum yields. As a result of the high variability of these parameters, actual local alkene production rates for a specific oceanic region may differ considerably from the globally averaged oceanic alkene production rates. The latter were estimated to be at most 5 Mt yr-1.

  3. The Role of Intersection Space Segments in Photochemical Reactions

    SciTech Connect

    Castano, Obis; Sancho, Unai; Garavelli, Marco; Olivucci, Massimo; Frutos, Luis Manuel

    2007-12-26

    We analyze here the role of the intersection space in the photochemistry of some organic compounds and how the topological properties of this space affect the mechanism of the photochemical reaction. This mechanism is related to the accessibility of different reaction paths in the relaxation in the ground state once the system reaches the intersection space (i.e. a conical intersection). It is proved that sometimes, even in the photochemistry of small organic molecules, the complete analysis of the intersection space is necessary for the correct computational prediction of the chemical mechanism and the formed photoproducts underlying the photoinduced reaction.

  4. Biological, chemical, electrochemical, and photochemical fractionation of Fe isotopes

    NASA Astrophysics Data System (ADS)

    John, S.; King, A.; Hutchins, D.; Adkins, J. F.; Fu, F.; Wasson, A.; Hodierne, C.

    2012-12-01

    Iron is an important nutrient for life in the ocean, where low Fe concentrations often limit the growth of marine phytoplankton. Fe stable isotope ratios (δ56Fe) are a potentially valuable new tool for studying the marine biological cycling of Fe. In order to effectively use Fe isotopes as a biological tracer, however, it is important to parameterize the isotope effect for biological uptake. We have therefore measured the biological fractionation of Fe isotopes by the marine diatoms Thalassiosira pseudonana, T. oceanica, and Phaeodactylum tricornutum in culture. During biological Fe acquisition, Fe(III) is often first reduced from Fe(III) to Fe(II), either in seawater or at the cell surface. Therefore, we have also measured the isotope effect for Fe(III) reduction by chemical, electrochemical, and photochemical processes. Diatoms were cultured in EDTA or NTA buffered media under varying Fe concentrations from Fe-sufficiency to Fe-limitation. Biological fractionation of Fe isotopes was determined by comparing δ56Fe of phytoplankton to the media. The use of a cell wash allows us to distinguish between isotopic fractionation during extracellular adsorption and intracellular uptake. The biological fractionation of Fe isotopes is highly dependent on culture conditions with Δδ56Fe ranging from +0.6 ‰ to -0.5 ‰ depending on ligand composition, species, and Fe-limitation status. Isotope effects for chemical, electrochemical, and photochemical reduction of Fe(III) to Fe(II) span an even larger range. For example, chemical reduction of Fe(III)-EDTA with hydroxylamine hydrochloride has an isotope effect of Δδ56Fe = -2.8 ‰. By contrast, photochemical reduction of Fe(III)-EDTA has an isotope effect of Δδ56Fe = +0.9 ‰. Isotope effects for electrochemical reduction of Fe(III) using a rotating disc electrode allow for greater control of experimental conditions, such as differentiating between the effects of electric potential (voltage) and mass transport (diffusion

  5. Photochemical production of formaldehyde in earth's primitive atmosphere

    NASA Astrophysics Data System (ADS)

    Pinto, J. P.; Gladstone, G. R.; Yung, Y. L.

    1980-10-01

    Formaldehyde could have been produced by photochemical reactions in the earth's primitive atmosphere, at a time when it consisted mainly of molecular nitrogen, water vapor, carbon dioxide, and trace amounts of molecular hydrogen and carbon monoxide. Removal of formaldehyde from the atmosphere by precipitation can provide a source of organic carbon to the oceans at the rate of 100 billion moles per year. Subsequent reactions of formaldehyde in primeval aquatic environments would have implications for the abiotic synthesis of complex organic molecules and the origin of life.

  6. Photochemical production of formaldehyde in earth's primitive atmosphere

    NASA Technical Reports Server (NTRS)

    Pinto, J. P.; Gladstone, G. R.; Yung, Y. L.

    1980-01-01

    Formaldehyde could have been produced by photochemical reactions in the earth's primitive atmosphere, at a time when it consisted mainly of molecular nitrogen, water vapor, carbon dioxide, and trace amounts of molecular hydrogen and carbon monoxide. Removal of formaldehyde from the atmosphere by precipitation can provide a source of organic carbon to the oceans at the rate of 100 billion moles per year. Subsequent reactions of formaldehyde in primeval aquatic environments would have implications for the abiotic synthesis of complex organic molecules and the origin of life.

  7. Laser machining of special designed photopolymers-photochemical ablation mechanism

    SciTech Connect

    Lippert, T.; Dickinson, J.T.; Langford, S.C.; Furutani, H.; Fukumura, H.; Masuhara, H.; Kunz, T.; Wokaun, A.

    1997-08-01

    Photopolymers based on the triazeno chromophore group (-N=N-N{lt}) have been developed. The absorption properties can be tailored for a specific irradiation wavelength. The photochemical exothermic decomposition yields high energetic gaseous products which are not contaminating the surface. The polymer can be structured with high resolution. No debris has been found around the etched corners. Maximum ablation rates of about 3 micrometer/pulse were achieved due to the dynamic absorption behavior (bleaching during the pulse). No physical or chemical modifications of the polymer surface could be detected after irradiation at the tailored absorption wavelength, whereas irradiation at different wavelengths resulted in modified (physical and chemical) surfaces.

  8. Photochemical vapor generation of lead for inductively coupled plasma mass spectrometric detection

    NASA Astrophysics Data System (ADS)

    Duan, Hualing; Zhang, Ningning; Gong, Zhenbin; Li, Weifeng; Hang, Wei

    2016-06-01

    Photochemical vapor generation (PCVG) of lead was successfully achieved with a simplified and convenient system, in which only low molecular weight organic acid and a high-efficiency photochemical reactor were needed. The reactor was used to generate lead volatile species when a solution of lead containing a small amount of low molecular weight organic acid was pumped through. Several factors, including the concentration of acetic acid, the concentration of hydrochloride acid, and the irradiation time of UV light were optimized. Under the optimal conditions, including the addition of 0.90% (v/v) acetic acid and 0.03% (v/v) hydrochloride acid, and irradiation time of 28 s, intense and repeatable signal of lead volatile species was successfully obtained and identified with inductively coupled plasma mass spectrometry (ICPMS). In addition, the effects from inorganic anions and transition metal ions, including Cl-, NO3-, SO42 -, Cu2 +, Fe3 +, Co2 + and Ni2 +, were investigated, which suggests that their suppression to the PCVG of lead was in the order of Cl- < SO42 - < NO3- for anions and Ni2 +, Co2 + < Fe3 + < Cu2 + for transition metal ions. Under optimized conditions, relative standard derivation (RSD) of 4.4% was achieved from replicate measurements (n = 5) of a standard solution of 0.1 μg L- 1 lead. And, the limit of quantitation (LOQ, 10σ) of 0.012 μg L- 1 lead was obtained using this method and the method blank could be easily controlled down to 0.023 μg L- 1. To validate applicability of this method, it was also employed for the determination of lead in tap water, rain water and lake water.

  9. Photochemical grid model implementation and application of VOC, NOx, and O3 source apportionment

    NASA Astrophysics Data System (ADS)

    Kwok, R. H. F.; Baker, K. R.; Napelenok, S. L.; Tonnesen, G. S.

    2015-01-01

    For the purposes of developing optimal emissions control strategies, efficient approaches are needed to identify the major sources or groups of sources that contribute to elevated ozone (O3) concentrations. Source-based apportionment techniques implemented in photochemical grid models track sources through the physical and chemical processes important to the formation and transport of air pollutants. Photochemical model source apportionment has been used to track source impacts of specific sources, groups of sources (sectors), sources in specific geographic areas, and stratospheric and lateral boundary inflow on O3. The implementation and application of a source apportionment technique for O3 and its precursors, nitrogen oxides (NOx) and volatile organic compounds (VOCs), for the Community Multiscale Air Quality (CMAQ) model are described here. The Integrated Source Apportionment Method (ISAM) O3 approach is a hybrid of source apportionment and source sensitivity in that O3 production is attributed to precursor sources based on O3 formation regime (e.g., for a NOx-sensitive regime, O3 is apportioned to participating NOx emissions). This implementation is illustrated by tracking multiple emissions source sectors and lateral boundary inflow. NOx, VOC, and O3 attribution to tracked sectors in the application are consistent with spatial and temporal patterns of precursor emissions. The O3 ISAM implementation is further evaluated through comparisons of apportioned ambient concentrations and deposition amounts with those derived from brute force zero-out scenarios, with correlation coefficients ranging between 0.58 and 0.99 depending on specific combination of target species and tracked precursor emissions. Low correlation coefficients occur for chemical regimes that have strong nonlinearity in O3 sensitivity, which demonstrates different functionalities between source apportionment and zero-out approaches, where appropriate use depends on whether source attribution or

  10. Photochemical grid model implementation of VOC, NOx, and O3 source apportionment

    NASA Astrophysics Data System (ADS)

    Kwok, R. H. F.; Baker, K. R.; Napelenok, S. L.; Tonnesen, G. S.

    2014-09-01

    For the purposes of developing optimal emissions control strategies, efficient approaches are needed to identify the major sources or groups of sources that contribute to elevated ozone (O3) concentrations. Source based apportionment techniques implemented in photochemical grid models track sources through the physical and chemical processes important to the formation and transport of air pollutants. Photochemical model source apportionment has been used to estimate impacts of specific sources, groups of sources (sectors), sources in specific geographic areas, and stratospheric and lateral boundary inflow on O3. The implementation and application of a source apportionment technique for O3 and its precursors, nitrogen oxides (NOx) and volatile organic compounds (VOC), for the Community Multiscale Air Quality (CMAQ) model are described here. The Integrated Source Apportionment Method (ISAM) O3 approach is a hybrid of source apportionment and source sensitivity in that O3 production is attributed to precursor sources based on O3 formation regime (e.g., for a NOx-sensitive regime, O3 is apportioned to participating NOx emissions). This implementation is illustrated by tracking multiple emissions source sectors and lateral boundary inflow. NOx, VOC, and O3 attribution to tracked sectors in the application are consistent with spatial and temporal patterns of precursor emissions. The O3 ISAM implementation is further evaluated through comparisons of apportioned ambient concentrations and deposition amounts with those derived from brute force zero-out scenarios, with correlation coefficients ranging between 0.58 and 0.99 depending on specific combination of target species and tracked precursor emissions. Low correlation coefficients occur for chemical regimes that have strong non-linearity in O3 sensitivity, which demonstrates different functionalities between source apportionment and zero-out approaches, depending on whether sources of interest are either to be accounted

  11. Lewis acid catalysis of photochemical reactions. 5. Selective isomerization of conjugated butenoic and dienoic esters

    SciTech Connect

    Lewis, F.D.; Howard, D.K.; Barancyk, S.V.; Oxman, J.D.

    1986-05-28

    The effects of Lewis and Broensted acids upon the photoisomerization reactions of several conjugated butenoic and dienoic esters have been investigated. Lewis acids inhibit the photochemical deconjugation of ..cap alpha..,..beta..- to ..beta..,..gamma..-unsaturated butenoic esters and shift the photoequilibrium between E and Z isomers toward the Z isomer. As such, irradiation of E ..cap alpha..,..beta..-unsaturated esters in the presence of EtAlCl/sub 2/ provides a convenient method for the preparation of the thermodynamically less stable Z isomer. Irradiation of methyl (E,E)-2,4-hexadienoate and methyl (E,E)-5-phenyl-2,4-pentadienoate in the absence of added catalysts results in nonselective E,Z isomerization to give mixtures of all four stereoisomers in roughly comparable yields. In the presence of the Broensted acid trifluoroacetic acid, quantitative conversion of methyl 2,4-hexadienoates to methyl 3,4-hexadienoate is observed. The acid serves as a catalyst for the thermal 1,3-hydrogen shift of an allenic enol ester formed via a photochemical 1,5-hydrogen shift of the conjugated esters. Irradiation of the ground-state complexes of the conjugated esters with the Lewis acids EtAlCl/sub 2/ or BF/sub 3/ results in selective E,Z isomerization about the ..cap alpha..,..beta..-double bond in methyl 2,4-hexadienoate and the ..gamma..,delta-double bond in methyl 5-phenyl-24-pentadienoate. The mechanistic bases for the observed effects of Lewis acids are selective excitation of the more strongly absorbing E complex and more efficient isomerization of the excited E vs. Z complex.

  12. Photochemical Production of Singlet Oxygen from Dissolved Organic Matter in Ice.

    PubMed

    Fede, Alexis; Grannas, Amanda M

    2015-11-01

    Dissolved natural organic matter (DOM) is a ubiquitous component of natural waters and an important photosensitizer. A variety of reactive oxygen species (ROS) are known to be produced from DOM photochemistry, including singlet oxygen, 1O2. Recently, it has been determined that humic-like substances and unknown organic chromophores are significant contributors to sunlight absorption in snowpack; however, DOM photochemistry in snow/ice has received little attention in the literature. We recently showed that DOM plays an important role in indirect photolysis processes in ice, producing ROS and leading to the efficient photodegradation of a probe hydrophobic organic pollutant, aldrin.1 ROS scavenger experiments indicated that 1O2 played a significant role in the indirect photodegradation of aldrin. Here we quantitatively examine 1O2 photochemically produced from DOM in frozen and liquid aqueous solutions. Steady-state 1O2 production is enhanced up to nearly 1000 times in frozen DOM samples compared to liquid samples. 1O2 production is dependent on the concentration of DOM, but the nature of the DOM source (terrestrial vs microbial) does not have a significant effect on 1O2 production in liquid or frozen samples, with different source types producing similar steady-state concentrations of 1O2. The temperature of frozen samples also has a significant effect on steady-state 1O2 production in the range of 228-262 K, with colder samples producing more steady-state 1O2. The large enhancement in 1O2 in frozen samples suggests that it may play a significant role in the photochemical processes that occur in snow and ice, and DOM could be a significant, but to date poorly understood, oxidant source in snow and ice. PMID:26460930

  13. The influence of photochemical fractionation on the evolution of the nitrogen isotope ratios - detailed analysis of current photochemical loss rates

    NASA Astrophysics Data System (ADS)

    Mandt, K. E.; Waite, J. H., Jr.; Westlake, J.; Magee, B.; Liang, M. C.; Bell, J.

    2012-04-01

    Tracking the evolution of molecular nitrogen over geologic time scales requires an understanding of the loss rates of both isotopologues (14N2 and 14N15N) as a function of time (e.g. Mandt et al., 2009). The relative loss rates, if different, “fractionate” the isotopes so that the ratios change as a function of time, and rate at which the ratio changes due to a loss process is determined by the “fractionation factor.” Photochemistry is known to fractionate the nitrogen isotopes in Titan’s atmosphere by preferentially removing the heavy isotope from the molecular nitrogen inventory and increasing the ratio (heavy/light) in one of the primary photochemical products, HCN. This fractionation occurs due to a selective shielding during photodissociation where the photons that dissociate 14N15N penetrate deeper into the atmosphere (Liang et al., 2007) than the photons that dissociate 14N14N. Two methods can be used to determine the photochemical fractionation factor, f. The first approach for calculating f is based on the isotopic ratios of the photochemical source and product, as measured by the Huygens Gas Chromatograph Mass Spectrometer (GCMS) (Niemann et al., 2010) and the Cassini Infrared Spectrometer (CIRS) (Vinatier et al., 2007), respectively. The second method uses the loss rates and the ratio of the source and requires detailed photochemical modeling to ensure that the loss rates are calculated accurately. We compare these two methods for calculating the photochemical fractionation factor for N2 by using measurements of the isotopic ratios of N2 and HCN combined with an updated coupled ion-neutral-thermal model (De la Haye et al., 2008). We find that accurate magnetospheric electron fluxes and a rotating model that accounts for diurnal variations are essential for accurate calculations of the HCN densities and for determination of the fractionation factor through photochemical modeling. References: De La Haye, V., J. H. Waite, Jr., T. E. Cravens, I. P

  14. Photochemical Synthesis of Shape-Controlled Nanostructured Gold on Zinc Oxide Nanorods as Photocatalytically Renewable Sensors.

    PubMed

    Xu, Jia-Quan; Duo, Huan-Huan; Zhang, Yu-Ge; Zhang, Xin-Wei; Fang, Wei; Liu, Yan-Ling; Shen, Ai-Guo; Hu, Ji-Ming; Huang, Wei-Hua

    2016-04-01

    Biosensors always suffer from passivation that prevents their reutilization. To address this issue, photocatalytically renewable sensors composed of semiconductor photocatalysts and sensing materials have emerged recently. In this work, we developed a robust and versatile method to construct different kinds of renewable biosensors consisting of ZnO nanorods and nanostructured Au. Via a facile and efficient photochemical reduction, various nanostructured Au was obtained successfully on ZnO nanorods. As-prepared sensors concurrently possess excellent sensing capability and desirable photocatalytic cleaning performance. Experimental results demonstrate that dendritic Au/ZnO composite has the strongest surface-enhanced Raman scattering (SERS) enhancement, and dense Au nanoparticles (NPs)/ZnO composite has the highest electrochemical activity, which was successfully used for electrochemical detection of NO release from cells. Furthermore, both of the SERS and electrochemical sensors can be regenerated efficiently for renewable applications via photodegrading adsorbed probe molecules and biomolecules. Our strategy provides an efficient and versatile method to construct various kinds of highly sensitive renewable sensors and might expand the application of the photocatalytically renewable sensor in the biosensing area. PMID:26928162

  15. The Actual Apollo 13 Prime Crew

    NASA Technical Reports Server (NTRS)

    1970-01-01

    The actual Apollo 13 lunar landing mission prime crew from left to right are: Commander, James A. Lovell Jr., Command Module pilot, John L. Swigert Jr.and Lunar Module pilot, Fred W. Haise Jr. The original Command Module pilot for this mission was Thomas 'Ken' Mattingly Jr. but due to exposure to German measles he was replaced by his backup, Command Module pilot, John L. 'Jack' Swigert Jr.

  16. Measurement of VOC reactivities using a photochemical flow reactor

    SciTech Connect

    Hurley, M.D.; Chang, T.Y.; Japar, S.M.; Wallington, T.J.

    1998-07-01

    A commercial ambient air monitoring instrument, the Airtrak 2000, has been modified for use as a photochemical flow reactor and used to measure the absolute and incremental reactivity of 18 single test VOCs and the incremental reactivity of six multicomponent VOC mixtures. A flow technique is a useful supplement to traditional static chamber experiments. The static chamber technique involves periodic sampling of an irradiated mixture in a photochemical chamber. Under these conditions, the irradiated mixture is always in transition. Using a flow system, a steady-state condition is established within the flow reactor that is representative, in this case, of the early stages of the smog forming process in the atmosphere. The measurement technique also allows changes in the background chamber reactivity to be monitored and taken into account. The incremental reactivity of 13 of the 18 test compounds measured is compared with previously reported results from a static chamber experiment, and the two data sets are generally in good agreement. The additivity of reactivity was tested by measuring the incremental reactivity of six multicomponent mixtures, the components being compounds measured individually in this study. The measured reactivity of a mixture was compared to that calculated from the sum of the measured reactivity of the mixture`s individual components. The results show that reactivity is additive for the concentration range studied.

  17. Morphological transformations of silver nanoparticles in seedless photochemical synthesis

    NASA Astrophysics Data System (ADS)

    Lu, Ya; Zhang, Congyun; Hao, Rui; Zhang, Dongjie; Fu, Yizheng; Moeendarbari, Sina; Pickering, Christopher S.; Hao, Yaowu; Liu, Yaqing

    2016-05-01

    Photochemical synthesis is an easily controlled and reliable method for the fabrication of silver (Ag) nanoparticles with various morphologies. In this work, we have systematically investigated the seedless photochemical synthesis of anisotropic Ag nanoparticles with and without PVP as surface capping agent. The time evolution of anisotropic Ag nanoparticles during the synthesis process are studied using UV–visible spectra, optical images and transmission electron microscopy. The results show that the light irradiation precisely controls the start and termination of the reaction, and the presence or absence of PVP greatly affects the morphology evolution of anisotropic Ag nanoparticles. With PVP as the surface capping agent, Ag nanoparticles grow into decahedra or prism by the deposition of Ag atoms on {111} or {110} facets through epitaxial growth. However, a different morphology evolution could happen when Ag nanoparticle is synthesized without PVP as surface capping agent. In this case, Ag nanoparticles can fuse into the decahedrons through an edge-selective particle fusion mechanism, which involves attachment, rotation and realignment of Ag nanoparticles. This process was evidenced with HRTEM images at the different stages of the transformation from Ag colloid to decahedra nanoparticles. Oriented attachment and Ostwald ripening also play important role in the transformation process.

  18. User's guide for the Photochemical Box Model (PBM)

    NASA Astrophysics Data System (ADS)

    Schere, K. L.; Demerjian, K. L.

    1984-11-01

    The user's guide for the photochemical box model (PBM) describes the structure and operation of the model and its preprocessors and provides the potential user with guidance in setting up input data. The PBM is a simple stationary single-cell model with a variable height lid designed to provide volume-integrated hour averages of O3 and other photochemical smog pollutants of interest for an urban area for a single day of simulation. The PBM is most appropriate for application in air stagnation conditions with light and variable winds. The PBM assumes that emission sources are homogeneously distributed across the surface face of the box volume and that the volume is well mixed at all times. The user must provide the PBM with initial species concentrations, hourly inputs of wind speed, source emission fluxes of CO, NC(x), THC, and hydrocarbon reactivity classes, and boundary species concentrations. Values of measured solar radiation and mixed layer depth may be specified at subhourly intervals throughout a simulation.

  19. An innovative photochemical facility at DAΦNE-L

    NASA Astrophysics Data System (ADS)

    Pace, E.; Cestelli Guidi, M.; De Sio, A.; Gambicorti, L.; Grilli, A.; Pietropaoli, M.; Raco, A.; Viviani, G.

    2013-03-01

    An on-going project for a photochemical facility at the DAFNE-L laboratory at the Frascati National Laboratories of INFN (National Institute of Nuclear Physics) is presented. Such a facility takes advantage from the combined capabilities of two different synchrotron radiation beam-lines. The first operates in the visible-UV and is used as a strong excitation and irradiation light-source in which both intensity and spectral range can be selected to fulfil the experiment requirements. The second is an infrared beamline equipped by FTIR micro-spectroscopy and imaging facility. An optical fiber allows UV irradiation of samples directly into the FTIR interferometer or the microscope. Thus, fast photo-chemical reactions can be analysed in real time, letting unveil inter-phases not normally observable by analysing the reagents and products of the reaction itself. Complex unstable systems can be irradiated and analysed without changing the sample condition (morphology, humidity, irradiation etc.). Preliminary experiments, validating most of the facility capability, will be presented.

  20. A photochemical box model for urban air quality study

    SciTech Connect

    Jin, Shengxin.

    1991-01-01

    The photochemical box model (PBM) is based on the principle of mass conservation. The concentration of any pollutant is determined by horizontal advection, vertical entrainment, source emissions, and chemical reactions. A one dimensional high resolution boundary layer model by Blackadar has been further developed by considering the effect of urban heat islands to simulate the variation of the mixed layer height and incorporated in the PBM. The model predicted mixed layer height is a significant improvement over the characteristic mixed layer growth curve used in the original PBM by Schere and Demerjian. The gas phase chemical kinetic mechanism used in the Regional Acid Deposition Study II (RADM2) and Demerjian chemical mechanism have been used to calculate the contributions of chemical reactions to the changes of pollutant concentrations. Detailed analysis and comparisons of the two chemical mechanisms have been made. The simulated pollutant concentration using both chemical mechanisms are in very good agreement with observations. A radiative transfer model developed by Madronich has been incorporated in the PBM for the calculation of actinic flux and photolytic rate constants. Height averaged and radiation corrected photolytic rate constant are used for the photochemical reactions. The simulated pollutant concentrations for CO, NO, NO[sub 2] and O[sub s] are in very good agreement with observations. Sensitivities of model results to the variation of photolytic rate constants, boundary conditions, hydrocarbon speciation factors, and thermal rate constant have been tested.

  1. Photochemical and biological degradation of water-soluble FWAs.

    PubMed

    Guglielmetti, L

    1975-01-01

    A study was made of the photochemical and biological degradation of two water-soluble fluorescent whitening agents (FWAs): the disodium 4,4'-bis(2-sulfostyryl)-biphenyl (1) and the disodium 4,4-bis ([4-anilino-6-(N-methyl-N-2-hydroxyethyl)amino 1,3,5-triazin-2-yl]amino)stilbene-2,2'-disulfonate (2). Each represents an important class of detergent fluorescent whitening agents. The photochemical degradation of (1) was studied by irradiating diluted aqueous solutions of this compound with a low intensity high pressure mercury vapor lamp. From the intermediate, as well as the ultimate photodegradation products isolated, it can be infered that photodegradation of (1) followed the proposed scheme. The biologica degradation of (1) and (2) by activated sludge under aerobic conditions was studied using equipment similar to that proposed by the OECD for determining the biodegradation of anionic synthetic surface active agents. Under the conditons applied, both FWAs were slowly biodegraded, within 30 days, whereas the photodegradation products of (1) were completely biodegraded within 14 days. PMID:6265

  2. Cancer treatment by photothermal, photochemical, and photobiological interactions

    NASA Astrophysics Data System (ADS)

    Chen, Wei R.; Korbelik, Mladen; Liu, Hong; Nordquist, Robert E.

    2005-01-01

    Laser tissue interactions hold great promise in cancer treatment. Photothermal interaction aims at the direct cell destruction through the increase of local tissue temperature, while photochemical interaction aims at the cell destruction using free radicals produced through the activation of photosensitizers in the target tissue. Photobiological interaction can target the immune host system to induce long-term control. Photothermal and photochemical interactions can be significantly enhanced by photobiological interaction through the use of immunoadjuvants. In our experiments, three different immunoadjuvants, complete Freund"s adjuvant (CF), incomplete Freund"s adjuvant (IF), and c-parvum (CP), were used in the treatment of metastatic mammary tumors in conjunction with photothermal interaction. In addition, a specific adjuvant, Glycated chitosan (GC), has been used in combination with photodynamic therapy (PDT) in the treatment of mouse tumors. In the treatment of rat tumors, CF, IF and CP raised the cure-rates from 0% to 18%, 7% and 9%, respectively. In comparison, GC resulted in a 29% long-term survival. In the treatment of EMT6 mammary sarcoma in mice, GC of 0.5% and 1.5% concentrations increased the cure rates of Photofrin-based PDT treatment from 38% to 63% and 75%, respectively. In the treatment of Line 1 lung adenocarcinoma in mice, a 1.67% GC solution enabled a non-curative mTHPC-based PDT to cure a 37% of the tumor bearing mice.

  3. Photochemical and Nonphotochemical Transformations of Cysteine with Dissolved Organic Matter.

    PubMed

    Chu, Chiheng; Erickson, Paul R; Lundeen, Rachel A; Stamatelatos, Dimitrios; Alaimo, Peter J; Latch, Douglas E; McNeill, Kristopher

    2016-06-21

    Cysteine (Cys) plays numerous key roles in the biogeochemistry of natural waters. Despite its importance, a full assessment of Cys abiotic transformation kinetics, products and pathways under environmental conditions has not been conducted. This study is a mechanistic evaluation of the photochemical and nonphotochemical (dark) transformations of Cys in solutions containing chromophoric dissolved organic matter (CDOM). The results show that Cys underwent abiotic transformations under both dark and irradiated conditions. Under dark conditions, the transformation rates of Cys were moderate and were highly pH- and temperature-dependent. Under UVA or natural sunlight irradiations, Cys transformation rates were enhanced by up to two orders of magnitude compared to rates under dark conditions. Product analysis indicated cystine and cysteine sulfinic acid were the major photooxidation products. In addition, this study provides an assessment of the contributions of singlet oxygen, hydroxyl radical, hydrogen peroxide, and triplet dissolved organic matter to the CDOM-sensitized photochemical oxidation of Cys. The results suggest that another unknown pathway was dominant in the CDOM-sensitized photodegradation of Cys, which will require further study to identify. PMID:27172378

  4. Global emissions and models of photochemically active compounds

    SciTech Connect

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

    1993-05-20

    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} {times} 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.

  5. Photochemical trajectory modelling studies of the 1987 Antarctic spring vortex

    NASA Technical Reports Server (NTRS)

    Austin, J.; Jones, R. L.; Mckenna, D. S.

    1988-01-01

    Simulations of Antarctic ozone photochemistry performed using a photochemical model integrated along air parcel trajectories are described. This type of model has a major advantage at high latitudes of being able to simulate correctly the complex interaction between photolysis and temperature fields, which, because of the polar night cannot be represented accurately in a zonally averaged framework. Isentropic air parcel trajectories were computed using Meteorological Office global model analyses and forecast fields from positions along the ER-2 flight paths during the Airborne Antarctic Ozone Experiment in Austral Spring 1987. A photochemical model is integrated along these trajectories using the aircraft observations to initialize constituent concentrations. The model includes additional reactions of the ClO dimer and also bromine reactions, which are thought to play a significant role in Antarctica. The model also includes heterogeneous reactions which are invoked when the air parcel passes through a polar stratospheric cloud (PSC). The existence of a PSC is determined throughout the course of the model integration from the parcel temperature and the saturated vapour pressure of water over an assumed H2O/HNO3 mixture. The air parcel temperature is used to determine the saturated vapor pressure of HNO3 over the same mixture. Mixing ratios which exceed saturation result in condensation of the excess in the model and hence lead to a reduction of the amount of gas phase NO2 available for chemical reaction.

  6. Upper limits of possible photochemical hazes on Pluto

    SciTech Connect

    Stansberry, J.A.; Lunine, J.I.; Tomasko, M.G. )

    1989-11-01

    Elliot et al. (1989) invoked a haze layer near the surface of Pluto to explain certain features of a stellar occultation by that planet in June, 1988. The primary requirements for this haze layer were that it achieve unity tangential optical depth at a radius of 1174 km and be essentially transparent above 1189 km. The authors explore here the possibility that aerosols generated through methane photolysis could be responsible for such a haze layer. A comprehensive model of aerosol production, particle growth, sedimentation and condensation is applied to the atmosphere of Pluto using pressures, temperatures and composition derived from the stellar occultation and other data. They test two atmosphere models proposed in the literature, one from Elliot et al. (1989), and one from Hubbard et al. (1989), as well as a range of optical properties for the particles. In order to produce a haze with unity tangential optical depth at 1174 km, they had to use an aerosol mass production rate equal to twice the total methane dissociation rate due to solar UV expected for Pluto and assume that the particles produced were 10 times more absorbing than those in other hazes in the outer solar system. The possibility of condensation in the atmosphere was considered but did not result in distinctly different haze optical depths. If a photochemical haze on Pluto was responsible for the occultation lightcurve measured by Elliot et al., operation of a photochemical system different from those on Titan, Uranus or Neptune is indicated.

  7. Dual-Templated Cobalt Oxide for Photochemical Water Oxidation.

    PubMed

    Deng, Xiaohui; Bongard, Hans-Josef; Chan, Candace K; Tüysüz, Harun

    2016-02-01

    Mesoporous Co3 O4 was prepared using a dual templating approach whereby mesopores inside SiO2 nanospheres, as well as the void spaces between the nanospheres, were used as templates. The effect of calcination temperature on the crystallinity, morphology, and textural parameters of the Co3 O4 replica was investigated. The catalytic activity of Co3 O4 for photochemical water oxidation in a [Ru(bpy)3 ](2+) [S2 O8 ](2-) system was evaluated. The Co3 O4 replica calcined at the lowest temperature (150 °C) exhibited the best performance as a result of the unique nanostructure and high surface area arising from the dual templating. The performance of Co3 O4 with highest surface area was further examined in electrochemical water oxidation. Superior activity over high temperature counterpart and decent stability was observed. Furthermore, CoO with identical morphology was prepared from Co3 O4 using an ethanol reduction method and a higher turnover-frequency number for photochemical water oxidation was obtained. PMID:26404798

  8. Evaluation of leaf energy dissipation by the Photochemical Reflectance

    NASA Astrophysics Data System (ADS)

    Raddi, S.; Magnani, F.

    Starting from the early paper by Heber (1969), several studies have demonstrated a subtle shift in leaf spectroscopic characteristics (both absorbance and reflectance) in response to rapid changes in environmental conditions. More recent work, briefly reviewed here, has also demonstrated the existence of two components in the maked peak centered at 505-540 nm: an irreversible component, attributed to the interconversion of leaf xanthophylls, and a reversible component at slightly longer wavelengths, resulting from conformational changes induced by the buildup of a pH gradient across the thylakoid membrane associated with photosynthetic electron transport. Both processes (xanthophyll de-epoxidation and conformational changes) are known to contribute to the dissipation of excess energy in Photosystem II (PSII). Leaf spectroscopy could therefore provide a powerful non-invasive tool for the determination of leaf photosynthetic processes. This led to the development of the normalized spectral index PRI (Photochemical Reflectance Index; Gamon, Penuelas &Field 1992; Gamon, Serrano &Surfus 1997), which relates the functional signal at 531 nm to a reference signal at 570 nm. The index has been found to track diurnal changes in xanthophyll de-epoxidation state, radiation use efficiency and fluorescence in response to light, both at the leaf and more recently at the canopy level. A common relationship has also beenreported across species and functional types, although such a generality has not always been confirmed. Recent reports (Stylinski et al. 2000) have also hinted of a possible link between PRI and leaf photosynthetic potential, possibly through the correlation between xanthophyll content and electron transport machinery in the chloroplast. Such a link, if confirmed, could prove very useful for the remote sensing and modelling ofvegetation. Some of these open questions were addressed in the present study. The correlation between leaf function and reflectance was

  9. INVESTIGATION OF PHOTOCHEMICAL MODELING OF POINT SOURCE POLLUTANTS WITH EULERIAN GRID AND LAGRANGIAN PLUME APPROACHES

    EPA Science Inventory

    In this paper, results of Eulerian grid and Lagrangian photochemical model simulations of emissions from a major elevated point source are presented. eries of simulations with grid sizes varying from 30 km to 2 km were performed with the Urban Airshed Model, a photochemical grid ...

  10. 40 CFR 52.2035 - Photochemical Assessment Monitoring Stations (PAMS) Program.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...) Pennsylvania § 52.2035 Photochemical Assessment Monitoring Stations (PAMS) Program. On September 23, 1994... Clean Air Act. EPA approved the Photochemical Assessment Monitoring Stations (PAMS) Program on September 11, 1995 and made it part of Pennsylvania SIP. As with all components of the SIP, Pennsylvania...

  11. 40 CFR 52.2035 - Photochemical Assessment Monitoring Stations (PAMS) Program.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ...) Pennsylvania § 52.2035 Photochemical Assessment Monitoring Stations (PAMS) Program. On September 23, 1994... Clean Air Act. EPA approved the Photochemical Assessment Monitoring Stations (PAMS) Program on September 11, 1995 and made it part of Pennsylvania SIP. As with all components of the SIP, Pennsylvania...

  12. Studies in photochemical smog chemistry. I. Atmospheric chemistry of toluene. II. Analysis of chemical reaction mechanisms for photochemical smog

    SciTech Connect

    Leone, J.A.

    1985-01-01

    This study focuses on two related topics in the gas phase organic chemistry of importance in urban air pollution. Part I describes an experimental and modeling effort aimed at developing a new explicit reaction mechanism for the atmospheric photooxidation of toluene. This mechanism is tested using experimental data from both indoor and outdoor smog chamber facilities. The predictions of the new reaction mechanism are found to be in good agreement with both sets of experimental data. Additional simulations performed with the new mechanism are used to investigate various mechanistic paths, and to gain insight into areas where the understanding is not complete. The outdoor experimental facility, which was built to provide the second set of experimental data, consists of a 65 cubic meter teflon smog chamber together with full instrumentation capable of measuring ozone, nitrogen dioxide, nitric oxide, peroxyacetyl nitrate (PAN), carbon monoxide, relative humidity, temperature, aerosol size distributions, and of course toluene and its photooxidation products. In Part II, a theoretical analysis of lumped chemical reaction mechanisms for photochemical smog is presented. Included is a description of a new counter species analysis technique which can be used to analyze any complex chemical reaction mechanism. Finally, a new lumped mechanism for photochemical smog is developed and tested against experimental data from two smog chamber facilities. Advantages of this mechanism relative to the existing lumped mechanisms are discussed.

  13. INTERACTIONS BETWEEN PHOTOCHEMICAL AND MICROBIAL DECOMPOSITION IN MODIFYING THE BIOLOGICAL AVAILABILITY AND OPTICAL PROPERTIES OF ESTUARINE DISSOLVED ORGANIC MATTER

    EPA Science Inventory

    Direct photodecomposition and photochemically-mediated bacterial degradation (via photochemical modification of otherwise refractory DOM into biologically labile forms) provide
    important pathways for the loss of dissolved organic matter in coastal waters. Here we report
    lab...

  14. Air resistance measurements on actual airplane parts

    NASA Technical Reports Server (NTRS)

    Weiselsberger, C

    1923-01-01

    For the calculation of the parasite resistance of an airplane, a knowledge of the resistance of the individual structural and accessory parts is necessary. The most reliable basis for this is given by tests with actual airplane parts at airspeeds which occur in practice. The data given here relate to the landing gear of a Siemanms-Schuckert DI airplane; the landing gear of a 'Luftfahrzeug-Gesellschaft' airplane (type Roland Dlla); landing gear of a 'Flugzeugbau Friedrichshafen' G airplane; a machine gun, and the exhaust manifold of a 269 HP engine.

  15. Photochemical free radical production rates in the eastern Caribbean

    NASA Astrophysics Data System (ADS)

    Dister, Brian; Zafiriou, Oliver C.

    1993-02-01

    Potential photochemical production rates of total (NO-scavengeable) free radicals were surveyed underway (> 900 points) in the eastern Caribbean and Orinoco delta in spring and fall 1988. These data document seasonal trends and large-scale (˜ 10-1000 km) variability in the pools of sunlight-generated reactive transients, which probably mediate a major portion of marine photoredox transformations. Radical production potential was detectable in all waters and was reasonably quantifiable at rates above 0.25 nmol L-1 min-1 sun-1. Radical production rates varied from ˜ 0.1-0.5 nmol L-1 min-1 of full-sun illumination in "blue water" to > 60 nmol L-1 min-1 in some estuarine waters in the high-flow season. Qualitatively, spatiotemporal potential rate distributions strikingly resembled that of "chlorophyll" (a riverine-influence tracer of uncertain specificity) in 1979-1981 CZCS images of the region [Müller-Karger et al., 1988] at all scales. Basin-scale occurrence of greatly enhanced rates in fall compared to spring is attributed to terrestrial chromophore inputs, primarily from the Orinoco River, any contributions from Amazon water and nutrient-stimulus effects could not be resolved. A major part of the functionally photoreactive colored organic matter (COM) involved in radical formation clearly mixes without massive loss out into high-salinity waters, although humic acids may flocculate in estuaries. A similar conclusion applies over smaller scales for COM as measured optically [Blough et al., this issue]. Furthermore, optical absorption and radical production rates were positively correlated in the estuarine region in fall. These cruises demonstrated that photochemical techniques are now adequate to treat terrestrial photochemical chromophore inputs as an estuarine mixing problem on a large scale, though the ancillary data base does not currently support such an analysis in this region. Eastern Caribbean waters are not markedly more reactive at comparable salinities

  16. Photochemical Strategies for the Synthesis of Advanced Materials

    NASA Astrophysics Data System (ADS)

    Billone, Paul S.

    This thesis describes the study of a variety of nanoscale materials and the development of novel synthetic strategies for their production. While the focus and bulk of this study have been directed specifically at subwavelength lithography, a significant portion of this thesis research involves nanoparticle synthesis, characterization, and functionalization. Put in very simple terms, optical lithography is a process where a beam of light, focused in a specific pattern, is used to generate a physical pattern on a solid substrate. This technology forms the basis for almost all microchip production in the world at the present time. As demand for faster and more powerful chips increases, the need to further miniaturize the patterns while minimizing cost has become very important. Multiple photochemical systems were developed in the search for non-reciprocal photochemistry at 193 nm to increase the resolution of lithographic processes at that wavelength. One approach, based on anthracene sensitization of sulfonium salts for acid generation, used photochemically reversible 4+4 aromatic cycloaddition reactions to introduce the non-linear photochemistry. A second approach took advantage of the photochemistry of N-methylphenothiazine and provided the first true example of a lithographically-relevant multi-photon acid generating process. Since all of the systems we studied used sulfonium salts as the acid generating species, we also looked at the photochemistry of the salts themselves. We evaluated the structural effects of the salts on their direct photochemistry and the implications for sensitized multi-photon photochemistry. We found that the identity of the anion plays a significant role in both processes and propose a new photochemical mechanism for acid generation that involves a charge transfer excitation process. We also describe the synthesis and characterization of novel fluorescent silver nanoparticles, both in solution and polymer films. We show that the

  17. Photochemical internalization-mediated nonviral gene transfection: polyamine core-shell nanoparticles as gene carrier

    PubMed Central

    Zamora, Genesis; Wang, Frederick; Sun, Chung-Ho; Trinidad, Anthony; Kwon, Young Jik; Cho, Soo Kyung; Berg, Kristian; Madsen, Steen J.; Hirschberg, Henry

    2014-01-01

    Abstract. The overall objective of the research was to investigate the utility of photochemical internalization (PCI) for the enhanced nonviral transfection of genes into glioma cells. The PCI-mediated introduction of the tumor suppressor gene phosphatase and tensin homolog (PTEN) or the cytosine deaminase (CD) pro-drug activating gene into U87 or U251 glioma cell monolayers and multicell tumor spheroids were evaluated. In the study reported here, polyamine-DNA gene polyplexes were encapsulated in a nanoparticle (NP) with an acid degradable polyketal outer shell. These NP synthetically mimic the roles of viral capsid and envelope, which transport and release the gene, respectively. The effects of PCI-mediated suppressor and suicide genes transfection efficiency employing either “naked” polyplex cores alone or as NP-shelled cores were compared. PCI was performed with the photosensitizer AlPcS2a and λ=670-nm laser irradiance. The results clearly demonstrated that the PCI can enhance the delivery of both the PTEN or CD genes in human glioma cell monolayers and multicell tumor spheroids. The transfection efficiency, as measured by cell survival and inhibition of spheroid growth, was found to be significantly greater at suboptimal light and DNA levels for shelled NPs compared with polyamine-DNA polyplexes alone. PMID:25341069

  18. Increased biomass productivity in green algae by tuning non-photochemical quenching.

    PubMed

    Berteotti, Silvia; Ballottari, Matteo; Bassi, Roberto

    2016-01-01

    Photosynthetic microalgae have a high potential for the production of biofuels and highly valued metabolites. However, their current industrial exploitation is limited by a productivity in photobioreactors that is low compared to potential productivity. The high cell density and pigment content of the surface layers of photosynthetic microalgae result in absorption of excess photons and energy dissipation through non-photochemical quenching (NPQ). NPQ prevents photoinhibition, but its activation reduces the efficiency of photosynthetic energy conversion. In Chlamydomonas reinhardtii, NPQ is catalyzed by protein subunits encoded by three lhcsr (light harvesting complex stress related) genes. Here, we show that heat dissipation and biomass productivity depends on LHCSR protein accumulation. Indeed, algal strains lacking two lhcsr genes can grow in a wide range of light growth conditions without suffering from photoinhibition and are more productive than wild-type. Thus, the down-regulation of NPQ appears to be a suitable strategy for improving light use efficiency for biomass and biofuel production in microalgae. PMID:26888481

  19. Photochemical internalization-mediated nonviral gene transfection: polyamine core-shell nanoparticles as gene carrier

    NASA Astrophysics Data System (ADS)

    Zamora, Genesis; Wang, Frederick; Sun, Chung-Ho; Trinidad, Anthony; Kwon, Young Jik; Cho, Soo Kyung; Berg, Kristian; Madsen, Steen J.; Hirschberg, Henry

    2014-10-01

    The overall objective of the research was to investigate the utility of photochemical internalization (PCI) for the enhanced nonviral transfection of genes into glioma cells. The PCI-mediated introduction of the tumor suppressor gene phosphatase and tensin homolog (PTEN) or the cytosine deaminase (CD) pro-drug activating gene into U87 or U251 glioma cell monolayers and multicell tumor spheroids were evaluated. In the study reported here, polyamine-DNA gene polyplexes were encapsulated in a nanoparticle (NP) with an acid degradable polyketal outer shell. These NP synthetically mimic the roles of viral capsid and envelope, which transport and release the gene, respectively. The effects of PCI-mediated suppressor and suicide genes transfection efficiency employing either "naked" polyplex cores alone or as NP-shelled cores were compared. PCI was performed with the photosensitizer AlPcS2a and λ=670-nm laser irradiance. The results clearly demonstrated that the PCI can enhance the delivery of both the PTEN or CD genes in human glioma cell monolayers and multicell tumor spheroids. The transfection efficiency, as measured by cell survival and inhibition of spheroid growth, was found to be significantly greater at suboptimal light and DNA levels for shelled NPs compared with polyamine-DNA polyplexes alone.

  20. Detection of bromine by ICP-oa-ToF-MS following photochemical vapor generation.

    PubMed

    Sturgeon, Ralph E

    2015-03-01

    A unique flow-through photochemical reactor is utilized for the generation of volatile methyl bromide from aqueous solutions of bromide and bromate ions in a medium of 2% acetic acid containing 3000 μg/mL NH4Cl. The volatile product is transported to a thin-film gas-liquid phase separator and directed to an inductively coupled plasma (ICP) tine-of-flight mass spectrometer for detection and quantitation using either of the (79)Br or (81)Br isotopes. Utilizing a sample flow rate of 3.3 mL/min and a 13 s irradiation time, a detection limit of 0.14 ng/mL is achieved, yielding a 17-fold enhancement over conventional solution nebulization. The estimated generation efficiency of 95% provides for a significant increase in analyte transport efficiency to the ICP. Precision of replicate measurement is 2.5% (RSD) at 20 ng/mL. The methodology was validated by successful determination of bromine in reference materials, including IRMM (BCR-611) low level bromide in groundwater, NIST SRM 1568b Rice Flour, and SRM 1632 bituminous coal. PMID:25649253

  1. Photochemical charges separation and photoelectric properties of flexible solar cells with two types of heterostructures

    NASA Astrophysics Data System (ADS)

    Liu, Xiangyang; Wang, Shun; Zheng, Haiwu; Cheng, Xiuying; Gu, Yuzong

    2015-12-01

    Photochemical charges generation, separation, and transport at nanocrystal interfaces are central to energy conversion for solar cells. Here, Zn2SnO4 nanowires/Cu4Bi4S9 (ZTO/CBS), ZTO nanowires/CBS-reduced graphene oxide (ZTO/CBS-RGO), and bulk heterojunction (BHJ) solar cells were measured. The signals of steady state and electric field-induced surface photovoltage indicate that RGO with high electron mobility can evidently improve the photovoltaic response. Besides, ZTO/CBS and ZTO/CBS-RGO cells exhibit the excellent performance and the highest efficiencies of 1.2% and 2.8%, respectively. The internal relations of photoelectric properties to some factors, such as film thickness, direct paths, RGO conductive network, energy level matching, etc., were discussed in detail. Qualitative and quantitative analyses further verified the comprehensive effect of RGO and other factors. Importantly, the fine bendable characteristic of BHJ solar cells with excellent efficiency and facile, scalable production gives the as-made flexible solar cells device potential for practical application in future.

  2. Increased biomass productivity in green algae by tuning non-photochemical quenching

    PubMed Central

    Berteotti, Silvia; Ballottari, Matteo; Bassi, Roberto

    2016-01-01

    Photosynthetic microalgae have a high potential for the production of biofuels and highly valued metabolites. However, their current industrial exploitation is limited by a productivity in photobioreactors that is low compared to potential productivity. The high cell density and pigment content of the surface layers of photosynthetic microalgae result in absorption of excess photons and energy dissipation through non-photochemical quenching (NPQ). NPQ prevents photoinhibition, but its activation reduces the efficiency of photosynthetic energy conversion. In Chlamydomonas reinhardtii, NPQ is catalyzed by protein subunits encoded by three lhcsr (light harvesting complex stress related) genes. Here, we show that heat dissipation and biomass productivity depends on LHCSR protein accumulation. Indeed, algal strains lacking two lhcsr genes can grow in a wide range of light growth conditions without suffering from photoinhibition and are more productive than wild-type. Thus, the down-regulation of NPQ appears to be a suitable strategy for improving light use efficiency for biomass and biofuel production in microalgae. PMID:26888481

  3. Photochemical charges separation and photoelectric properties of flexible solar cells with two types of heterostructures

    SciTech Connect

    Liu, Xiangyang E-mail: yzgu@henu.edu.cn; Wang, Shun; Zheng, Haiwu; Cheng, Xiuying; Gu, Yuzong E-mail: yzgu@henu.edu.cn

    2015-12-14

    Photochemical charges generation, separation, and transport at nanocrystal interfaces are central to energy conversion for solar cells. Here, Zn{sub 2}SnO{sub 4} nanowires/Cu{sub 4}Bi{sub 4}S{sub 9} (ZTO/CBS), ZTO nanowires/CBS-reduced graphene oxide (ZTO/CBS-RGO), and bulk heterojunction (BHJ) solar cells were measured. The signals of steady state and electric field-induced surface photovoltage indicate that RGO with high electron mobility can evidently improve the photovoltaic response. Besides, ZTO/CBS and ZTO/CBS-RGO cells exhibit the excellent performance and the highest efficiencies of 1.2% and 2.8%, respectively. The internal relations of photoelectric properties to some factors, such as film thickness, direct paths, RGO conductive network, energy level matching, etc., were discussed in detail. Qualitative and quantitative analyses further verified the comprehensive effect of RGO and other factors. Importantly, the fine bendable characteristic of BHJ solar cells with excellent efficiency and facile, scalable production gives the as-made flexible solar cells device potential for practical application in future.

  4. Influence of speciation on the response from selenium to UV-photochemical vapor generation.

    PubMed

    Suzuki, Toshihiro; Sturgeon, Ralph E; Zheng, Chengbin; Hioki, Akiharu; Nakazato, Tetsuya; Tao, Hiroaki

    2012-01-01

    By exposure to appropriate UV intensities, rapid and quantitative oxidation/reduction of inorganic selenite, selenate and several organoselenium compounds representative of those of biochemical/metabolic interest, including selenomethionine, selenobetaine, L-selenocystine, selenomethylselenocysteine, γ-glutamyl-seleno-methylselenocysteine and selenocystamine, is achieved. In the presence of acetic acid, quantitative conversion to volatile SeH(2) and SeCO occurs using a flow-through system comprising a highly efficient 40 W UV lamp for oxidation in tandem with a lower power 8 W UV photocatalytic reactor utilizing a thin-film coating of titania. The volatile reduced species are detected by atomic absorption spectrometry using a heated quartz tube atomizer. Direct photochemical conversion of selenite, selenomethionine, L-selenocystine, γ-glutamyl-Se-methylselenocysteine and selenocystamine occurs in the presence of 5% acetic acid, following exposure to an 8 W UV field, to yield volatile detectable species, whereas selenobetaine and selenate are unresponsive unless the latter is first subjected to oxidation by exposure to a highly efficient 40 W UV lamp and the selenate reduced in the presence of titania. PMID:22878637

  5. An overview of photochemical smog studies in Australian cities

    SciTech Connect

    Physick, W.L.

    1996-12-31

    The problem of photochemical smog is being addressed by authorities in the five major cities of Australia. Detrimental levels of smog are exceeded occasionally in the larger cities of Sydney and Melbourne, while the geographic features and meteorology of Brisbane, Perth and Adelaide suggest potentially unacceptable levels as those cities continue to grow. Motor vehicles are the dominant source of precursor emissions for smog and this is reflected in the comparison by Ahmet and van Dijk (1994) of hourly-averaged ozone exceedences for Australia`s major cities, i.e., the number of exceedences is roughly proportional to the population. Although statistics such as these can be strongly influenced by the distribution of monitors within a network, the relatively low exceedence threshold (0.08 ppm) probably ensures that the results are a realistic indicator of the relative extent of the problem in each city.

  6. A photochemically resistant component in riverine dissolved black carbon

    NASA Astrophysics Data System (ADS)

    Dittmar, Thorsten; Riedel, Thomas; Niggemann, Jutta; Vähätalo, Anssi

    2015-04-01

    Rivers transport combustion-derived dissolved black carbon (DBC) to the oceans at an annual flux that is much higher than required to balance the oceanic inventory of DBC. To resolve this mismatch we studied the long-term stability of DBC in ten major world rivers that together account for approximately 1/3 of the global freshwater discharge to the oceans. Riverine DBC was remarkably resistant against microbial degradation, but decomposition of nearly all chromophoric dissolved organic matter under extensive irradiation with simulated sunlight removed almost 80% of DBC. Photochemically transformed DBC was further microbially decomposed by more than 10% in a subsequent one-year long bioassay. Based on these findings, on a global scale, the estimated riverine flux of microbially degraded and photo-resistant DBC is sufficient to replenish the oceans with DBC and likely contributes to the dissolved organic matter pool that persists in the oceans and sequesters carbon for centuries to millennia.

  7. NMR Studies on the Aqueous Phase Photochemical Degradation of TNT

    SciTech Connect

    Thorn, Kevin A.; Cox, Larry G.

    2008-04-06

    Aqueous phase photochemical degradation of 2,4,6-trinitrotoluene (TNT) is an important pathway in several environments, including washout lagoon soils, impact craters from partially detonated munitions that fill with rain or groundwater, and shallow marine environments containing unexploded munitions that have corroded. Knowledge of the degradation products is necessary for compliance issues on military firing ranges and formerly used defense sites. Previous laboratory studies have indicated that UV irradiation of aqueous TNT solutions results in a multicomponent product mixture, including polymerization compounds, that has been only partially resolved by mass spectrometric analyses. This study illustrates how a combination of solid and liquid state 1H, 13C, and 15N NMR spectroscopy, including two dimensional analyses, provides complementary information on the total product mixture from aqueous photolysis of TNT, and the effect of reaction conditions. Among the degradation products detected were amine, amide, azoxy, azo, and carboxylic acid compounds.

  8. Photochemical aerosols on Titan and the giant planets

    NASA Astrophysics Data System (ADS)

    West, R.

    2015-10-01

    Our ideas about the nature of photochemical aerosols on Titan and the giant planets is evolving thanks to new data coming in from the Cassini spacecraft, ground-based and space-based telescopes, and theory and modeling. Aerosol formation begins at altitudes around 1000 km on Titan and around 800 km above the 1-bar pressure level in the polar thermospheres of Jupiter and Saturn where auroral energy is available to form ions and radicals. We have evidence that hydrocarbon chemistry is important in aerosol formation for all of these bodies and we believe that hydrazine on Jupiter and phosphine on Saturn may lead to aerosol production. Aeroso ls have a fractal aggregate structure on Titan and in the polar regions of Jupiter and Saturn. Their vertical and horizontal distributions reflect a balance between local production and horizontal and vertical transport governed by eddies and jets. They are important for radiative energy balance in ways that have only recently come to light.

  9. Evaluated kinetic and photochemical data for atmospheric chemistry

    NASA Technical Reports Server (NTRS)

    Baulch, D. L.; Cox, R. A.; Hampson, R. F., Jr.; Kerr, J. A.; Troe, J.; Watson, R. T.

    1980-01-01

    This paper contains a critical evaluation of the kinetics and photochemistry of gas phase chemical reactions of neutral species involved in middle atmosphere chemistry (10-55 km altitude). Data sheets have been prepared for 148 thermal and photochemical reactions, containing summaries of the available experimental data with notes giving details of the experimental procedures. For each reaction a preferred value of the rate coefficient at 298 K is given together with a temperature dependency 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. The data sheets are intended to provide the basic physical chemical data needed as input for calculations which model atmospheric chemistry. A table summarizing the preferred rate data is provided, together with an appendix listing the available data on enthalpies of formation of the reactant and product species.

  10. Applying green chemistry to the photochemical route to artemisinin

    NASA Astrophysics Data System (ADS)

    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.

  11. Revisions to Photochemical Data for Use in Atmospheric Modeling

    NASA Technical Reports Server (NTRS)

    Shutter, Joshua D.; Willacy, Karen; Allen, Mark

    2012-01-01

    Solar and stellar flux incident on an atmosphere can cause molecules to dissociate into highly reactive species and allows for photochemical processes to play a fundamental role in atmospheric chemistry. While models have tried to simulate such processes, they are extremely sensitive to photoabsorption cross-sections and quantum yields: two parameters that are important in determining the photodissociation rate, and hence the lifetime, of atmospheric compounds. Obtaining high-resolution and current data for these parameters is therefore highly desirable. Due to this, database and literature searches for high-quality cross-sections and quantum yields were performed and compiled for KINETICS, a Caltech/JPL Chemical Transport Model that can be used in modeling planetary atmospheres. Furthermore, photodissociation rates determined by running a Titan 1-D model were used to verify the completeness of these latest revisions.

  12. Photochemical and thermal evolution of interstellar/precometary ice analogs

    NASA Technical Reports Server (NTRS)

    Allamandola, L. J.; Sandford, S. A.; Valero, G. J.

    1988-01-01

    The photochemical and thermal evolution of H2O-, CH3OH-, NH3-, and CO-containing ices whose relative proportions in mixture are consistent with those of interstellar ice are presently studied experimentally. The UV photolysis of these ice analogs invariably generates H2CO, CO2, CO, CH4, and HCO, largely through the photofragmentation of CH3OH. CO and CH4 leave the samples as warmup proceeds to 100 K; most of the parent ice molecules are found to have sublimed upon the reaching of 200 K, with only a mixture of more refractory substances remaining. A residue of CH2 groups remains even after warmup to 300 K.

  13. Applying green chemistry to the photochemical route to artemisinin.

    PubMed

    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. PMID:25991527

  14. Photochemical activation of TRPA1 channels in neurons and animals

    PubMed Central

    Kokel, David; Cheung, Chung Yan J.; Mills, Robert; Coutinho-Budd, Jaeda; Huang, Liyi; Setola, Vincent; Sprague, Jared; Jin, Shan; Jin, Youngnam N.; Huang, Xi-Ping; Bruni, Giancarlo; Woolf, Clifford; Roth, Bryan L.; Hamblin, Michael R; Zylka, Mark J.; Milan, David J.; Peterson, Randall T.

    2013-01-01

    Optogenetics is a powerful research tool because it enables high-resolution optical control of neuronal activity. However, current optogenetic approaches are limited to transgenic systems expressing microbial opsins and other exogenous photoreceptors. Here, we identify optovin, a small molecule that enables repeated photoactivation of motor behaviors in wild type animals. Surprisingly, optovin's behavioral effects are not visually mediated. Rather, photodetection is performed by sensory neurons expressing the cation channel TRPA1. TRPA1 is both necessary and sufficient for the optovin response. Optovin activates human TRPA1 via structure-dependent photochemical reactions with redox-sensitive cysteine residues. In animals with severed spinal cords, optovin treatment enables control of motor activity in the paralyzed extremities by localized illumination. These studies identify a light-based strategy for controlling endogenous TRPA1 receptors in vivo, with potential clinical and research applications in non-transgenic animals, including humans. PMID:23396078

  15. Rethinking organic aerosols: semivolatile emissions and photochemical aging.

    PubMed

    Robinson, Allen L; Donahue, Neil M; Shrivastava, Manish K; Weitkamp, Emily A; Sage, Amy M; Grieshop, Andrew P; Lane, Timothy E; Pierce, Jeffrey R; Pandis, Spyros N

    2007-03-01

    Most primary organic-particulate emissions are semivolatile; thus, they partially evaporate with atmospheric dilution, creating substantial amounts of low-volatility gas-phase material. Laboratory experiments show that photo-oxidation of diesel emissions rapidly generates organic aerosol, greatly exceeding the contribution from known secondary organic-aerosol precursors. We attribute this unexplained secondary organic-aerosol production to the oxidation of low-volatility gas-phase species. Accounting for partitioning and photochemical processing of primary emissions creates a more regionally distributed aerosol and brings model predictions into better agreement with observations. Controlling organic particulate-matter concentrations will require substantial changes in the approaches that are currently used to measure and regulate emissions. PMID:17332409

  16. Photochemical route for synthesizing atomically dispersed palladium catalysts.

    PubMed

    Liu, Pengxin; Zhao, Yun; Qin, Ruixuan; Mo, Shiguang; Chen, Guangxu; Gu, Lin; Chevrier, Daniel M; Zhang, Peng; Guo, Qing; Zang, Dandan; Wu, Binghui; Fu, Gang; Zheng, Nanfeng

    2016-05-13

    Atomically dispersed noble metal catalysts often exhibit high catalytic performances, but the metal loading density must be kept low (usually below 0.5%) to avoid the formation of metal nanoparticles through sintering. We report a photochemical strategy to fabricate a stable atomically dispersed palladium-titanium oxide catalyst (Pd1/TiO2) on ethylene glycolate (EG)-stabilized ultrathin TiO2 nanosheets containing Pd up to 1.5%. The Pd1/TiO2 catalyst exhibited high catalytic activity in hydrogenation of C=C bonds, exceeding that of surface Pd atoms on commercial Pd catalysts by a factor of 9. No decay in the activity was observed for 20 cycles. More important, the Pd1/TiO2-EG system could activate H2 in a heterolytic pathway, leading to a catalytic enhancement in hydrogenation of aldehydes by a factor of more than 55. PMID:27174982

  17. Appearance of photochemical function in prothylakoids during plastid development.

    PubMed

    Wellburn, A R; Hampp, R

    1979-08-14

    1. A method to separate the vesicles of prothylakoids from prolamellar body preparations obtained from etiolated and rapidly greening Avena laminae (0.25--4 h illumination ) is described. The prothylakoid preparations were found to be free from contaminating prolamellar bodies but enriched prolamellar body preparations (enriched prolamellar body preparations) still contained some adhering prothylakoid material. 2. Only existing beta-carotene appears to be transferred from the prolamellar bodies to the prothylakoids during early development and this ceases when freshly synthesized beta-carotene becomes available. 3. Prolamellar body structures proper show no positive association of existing or developing photochemical activities; these are only to be found in the developing prothylakoids. 4. Using methylviologen-linked electron transport-dependent oxygen consumption, Photosystem I activities may be detected with added diaminodurene within 15 min of illumination and within 30 min and 1 h with added tetramethylphenylenediamine and dichlorophenolindophenol, respectively. 5. During the 2nd, and 3rd. h of greening, proton-pumping capability and later ATP formation increased in prothylakoids in the presence of diaminodurene. 6. The first indications of Photosystem II activity using diphenylcarbazide as electron donor are shown at a similar time (2 h) with prothylakoids. The last photochemical activity to appear is the capacity to split water (3 h) and consequently the diphenylcarbazide activity diminished to zero before 8 h of illumination have passed. 7. The lack of effect of uncouplers such as NH4+ prior to 2 h suggests that in spite of some proton-pumping ability there is the possibility of proton-leaky areas existing within prothylakoids. This lack of a persistent proton gradient before 2 h of illumination may explain the different starting times of phenazine methosulfate- and diaminodurene-dependent photophosphorylation (0.25 and 2 h, respectively). PMID:37909

  18. PHOTOCHEMICAL CO2 REDUCTION BY RHENUIM AND RUTHENIUM COMPLEXES.

    SciTech Connect

    FUJITA,E.; MUCKERMAN, J.T.; TANAKA, K.

    2007-11-30

    Photochemical conversion of CO{sub 2} to fuels or useful chemicals using renewable solar energy is an attractive solution to both the world's need for fuels and the reduction of greenhouse gases. Rhenium(I) and ruthenium(II) diimine complexes have been shown to act as photocatalysts and/or electrocatalysts for CO{sub 2} reduction to CO. We have studied these photochemical systems focusing on the identification of intermediates and the bond formation/cleavage reactions between the metal center and CO{sub 2}. For example, we have produced the one-electron-reduced monomer (i.e. Re(dmb)(CO){sub 3}S where dmb = 4,4'-dimethy-2,2'-bipyridine and S = solvent) either by reductive quenching of the excited states of fac-[Re(dmb)(CO){sub 3}(CH{sub 3}CN)]PF{sub 6} or by photo-induced homolysis of [Re(dmb)(CO){sub 3}]{sub 2}. We previously found that: (1) the remarkably slow dimerization of Re(dmb)(CO){sub 3}S is due to the absence of a vacant coordination site for Re-Re bond formation, and the extra electron is located on the dmb ligand; (2) the reaction of Re(dmb)(CO){sub 3}S with CO{sub 2} forms a CO{sub 2}-bridged binuclear species (CO){sub 3}(dmb)Re-CO(O)-Re(dmb)(CO){sub 3} as an intermediate in CO formation; and (3) the kinetics and mechanism of reactions are consistent with the interaction of the CO{sub 2}-bridged binuclear species with CO{sub 2} to form CO and CO{sub 3}{sup 2-}.

  19. Photochemical production of singlet oxygen from particulate organic matter.

    PubMed

    Appiani, Elena; McNeill, Kristopher

    2015-03-17

    Dissolved organic matter is established as one of the most relevant photosensitizers in aquatic environments, producing singlet oxygen (1O2) alongside other photochemically produced reactive intermediates. While the production of 1O2 from DOM has been well studied, the relative importance of particulate organic matter (POM) to the overall 1O2 production is less well understood. POM is known to play an important role in pollutant fate through the sorption and transport of hydrophobic pollutants. If POM is directly involved in 1O2 production, sorbed molecules would be expected to undergo enhanced photodegradation. In this work, synthetic POM was prepared by coating silica particles with commercial humic acid. The photochemical behavior of these POM samples was compared to dissolved commercial humic acids (DOM). Suspended natural sediment was also studied to test the environmental relevance of the synthetic POM model. Synthetic POM particles appear to simulate well the 1O2-production of suspended sediment. The 1O2 concentrations experienced by POM-sorbed probe molecules was up to 30% higher than experienced by DOM-sorbed ones, even though the aqueous concentration of 1O2 in irradiated POM suspensions was much lower than the analogous DOM solutions. These results were interpreted with a reaction-diffusion model, which suggested that the production rate of 1O2 by POM is lower than DOM, but the loss of 1O2 from the POM-phase is also lower than DOM. Based on the experimental results of this study, calculations were conducted to estimate the impact of removing POM on 1O2-mediated processes. These calculations indicate that compounds with a log Koc value near 4 will be most affected by removal of POM and that the magnitude of the effect is proportional to the fraction of the total organic matter represented by POM. This study demonstrates that particles can play an important role in the degradation of organic compounds via aquatic photochemistry. PMID:25674663

  20. Photochemical hazes in planetary atmospheres: solar system bodies and beyond

    NASA Astrophysics Data System (ADS)

    Imanaka, Hiroshi; Cruikshank, Dale P.; McKay, Christopher P.

    2015-11-01

    Recent transit observations of exoplanets have demonstrated the possibility of a wide prevalence of haze/cloud layers at high altitudes. Hydrocarbon photochemical haze could be the candidate for such haze particles on warm sub-Neptunes, but the lack of evidence for methane poses a puzzle for such hydrocarbon photochemical haze. The CH4/CO ratios in planetary atmospheres vary substantially from their temperature and dynamics. An understanding of haze formation rates and plausible optical properties in a wide diversity of planetary atmospheres is required to interpret the current and future observations.Here, we focus on how atmospheric compositions, specifically CH4/CO ratios, affect the haze production rates and their optical properties. We have conducted a series of cold plasma experiments to constrain the haze mass production rates from gas mixtures of various CH4/CO ratios diluted either in H2 or N2 atmosphere. The mass production rates in the N2-CH4-CO system are much greater than those in the H2-CH4-CO system. They are rather insensitive to the CH4/CO ratios larger than at 0.3. Significant formation of solid material is observed both in H2-CO and N2-CO systems without CH4 in the initial gas mixtures. The complex refractive indices were derived for haze samples from N2-CH4, H2-CH4, and H2-CO gas mixtures. These are the model atmospheres for Titan, Saturn, and exoplanets, respectively. The imaginary part of the complex refractive indices in the UV-Vis region are distinct among these samples, which can be utilized for modeling these planetary atmospheres.

  1. A photochemical source of peroxypropionic and peroxyisobutanoic nitric anhydride

    NASA Astrophysics Data System (ADS)

    Furgeson, Amanda; Mielke, Levi H.; Paul, Dipayan; Osthoff, Hans D.

    2011-09-01

    A method to photochemically generate stable outputs of peroxyacetic, peroxypropionic, or peroxyisobutanoic nitric anhydride (PAN, PPN, or PiBN) in dilute gas streams is described. The PANs are generated by photolysis of excess acetone, diethyl ketone, or diisopropyl ketone in the presence of oxygen and either nitric oxide or nitrogen dioxide. The source output was characterized using a commercial NO y monitor, an in-house constructed thermal dissociation cavity ring-down spectrometer (TD-CRDS) equipped with a heated inlet for quantification of NO 2, total peroxyacyl nitrates (∑PAN), and total alkyl nitrates (∑AN), and a thermal dissociation chemical ionization mass spectrometer (TD-CIMS) operated with iodide reagent ion. The TD-CIMS was calibrated (against TD-CRDS) using diffusion sources containing synthetic PAN standards. Response factors of 21, 19, and 5 counts per pptv, normalized to 1 million counts of iodide reagent ion, were found for PAN (monitored at m/z 59), PPN ( m/z 73), and PiBN ( m/z 87), respectively. The photo source was found to generate the three PANs in high yield. CIMS response factors derived using the photo source and TD-CRDS were identical to those derived from synthetic standards for PAN and PPN; hence, the photochemical PAN and PPN sources may be used to calibrate TD-CIMS (against TD-CRDS). For PiBN, the response factor derived using the photo source was 60% larger than that derived using the synthetic standard, limiting its use to deliver a calibrated stream of PiBN.

  2. 7 CFR 1437.101 - Actual production history.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 7 Agriculture 10 2012-01-01 2012-01-01 false Actual production history. 1437.101 Section 1437.101... Determining Yield Coverage Using Actual Production History § 1437.101 Actual production history. Actual production history (APH) is the unit's record of crop yield by crop year for the APH base period. The...

  3. 7 CFR 1437.101 - Actual production history.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 7 Agriculture 10 2014-01-01 2014-01-01 false Actual production history. 1437.101 Section 1437.101... Determining Yield Coverage Using Actual Production History § 1437.101 Actual production history. Actual production history (APH) is the unit's record of crop yield by crop year for the APH base period. The...

  4. 7 CFR 1437.101 - Actual production history.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 7 Agriculture 10 2013-01-01 2013-01-01 false Actual production history. 1437.101 Section 1437.101... Determining Yield Coverage Using Actual Production History § 1437.101 Actual production history. Actual production history (APH) is the unit's record of crop yield by crop year for the APH base period. The...

  5. 7 CFR 1437.101 - Actual production history.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 7 Agriculture 10 2011-01-01 2011-01-01 false Actual production history. 1437.101 Section 1437.101... Determining Yield Coverage Using Actual Production History § 1437.101 Actual production history. Actual production history (APH) is the unit's record of crop yield by crop year for the APH base period. The...

  6. 7 CFR 1437.101 - Actual production history.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 7 Agriculture 10 2010-01-01 2010-01-01 false Actual production history. 1437.101 Section 1437.101... Determining Yield Coverage Using Actual Production History § 1437.101 Actual production history. Actual production history (APH) is the unit's record of crop yield by crop year for the APH base period. The...

  7. The actual status of Astronomy in Moldova

    NASA Astrophysics Data System (ADS)

    Gaina, A.

    The astronomical research in the Republic of Moldova after Nicolae Donitch (Donici)(1874-1956(?)) were renewed in 1957, when a satellites observations station was open in Chisinau. Fotometric observations and rotations of first Soviet artificial satellites were investigated under a program SPIN put in action by the Academy of Sciences of former Socialist Countries. The works were conducted by Assoc. prof. Dr. V. Grigorevskij, which conducted also research in variable stars. Later, at the beginning of 60-th, an astronomical Observatory at the Chisinau State University named after Lenin (actually: the State University of Moldova), placed in Lozovo-Ciuciuleni villages was open, which were coordinated by Odessa State University (Prof. V.P. Tsesevich) and the Astrosovet of the USSR. Two main groups worked in this area: first conducted by V. Grigorevskij (till 1971) and second conducted by L.I. Shakun (till 1988), both graduated from Odessa State University. Besides this research areas another astronomical observations were made: Comets observations, astroclimate and atmospheric optics in collaboration with the Institute of the Atmospheric optics of the Siberian branch of the USSR (V. Chernobai, I. Nacu, C. Usov and A.F. Poiata). Comets observations were also made since 1988 by D. I. Gorodetskij which came to Chisinau from Alma-Ata and collaborated with Ukrainean astronomers conducted by K.I. Churyumov. Another part of space research was made at the State University of Tiraspol since the beggining of 70-th by a group of teaching staff of the Tiraspol State Pedagogical University: M.D. Polanuer, V.S. Sholokhov. No a collaboration between Moldovan astronomers and Transdniestrian ones actually exist due to War in Transdniestria in 1992. An important area of research concerned the Radiophysics of the Ionosphere, which was conducted in Beltsy at the Beltsy State Pedagogical Institute by a group of teaching staff of the University since the beginning of 70-th: N. D. Filip, E

  8. What Galvanic Vestibular Stimulation Actually Activates

    PubMed Central

    Curthoys, Ian S.; MacDougall, Hamish Gavin

    2012-01-01

    In a recent paper in Frontiers Cohen et al. (2012) asked “What does galvanic vestibular stimulation actually activate?” and concluded that galvanic vestibular stimulation (GVS) causes predominantly otolithic behavioral responses. In this Perspective paper we show that such a conclusion does not follow from the evidence. The evidence from neurophysiology is very clear: galvanic stimulation activates primary otolithic neurons as well as primary semicircular canal neurons (Kim and Curthoys, 2004). Irregular neurons are activated at lower currents. The answer to what behavior is activated depends on what is measured and how it is measured, including not just technical details, such as the frame rate of video, but the exact experimental context in which the measurement took place (visual fixation vs total darkness). Both canal and otolith dependent responses are activated by GVS. PMID:22833733

  9. MODIS Solar Diffuser: Modelled and Actual Performance

    NASA Technical Reports Server (NTRS)

    Waluschka, Eugene; Xiong, Xiao-Xiong; Esposito, Joe; Wang, Xin-Dong; Krebs, Carolyn (Technical Monitor)

    2001-01-01

    The Moderate Resolution Imaging Spectroradiometer (MODIS) instrument's solar diffuser is used in its radiometric calibration for the reflective solar bands (VIS, NTR, and SWIR) ranging from 0.41 to 2.1 micron. The sun illuminates the solar diffuser either directly or through a attenuation screen. The attenuation screen consists of a regular array of pin holes. The attenuated illumination pattern on the solar diffuser is not uniform, but consists of a multitude of pin-hole images of the sun. This non-uniform illumination produces small, but noticeable radiometric effects. A description of the computer model used to simulate the effects of the attenuation screen is given and the predictions of the model are compared with actual, on-orbit, calibration measurements.

  10. Metal-polypyridyl catalysts for electro- and photochemical reduction of water to hydrogen.

    PubMed

    Zee, David Z; Chantarojsiri, Teera; Long, Jeffrey R; Chang, Christopher J

    2015-07-21

    Climate change, rising global energy demand, and energy security concerns motivate research into alternative, sustainable energy sources. In principle, solar energy can meet the world's energy needs, but the intermittent nature of solar illumination means that it is temporally and spatially separated from its consumption. Developing systems that promote solar-to-fuel conversion, such as via reduction of protons to hydrogen, could bridge this production-consumption gap, but this effort requires invention of catalysts that are cheap, robust, and efficient and that use earth-abundant elements. In this context, catalysts that utilize water as both an earth-abundant, environmentally benign substrate and a solvent for proton reduction are highly desirable. This Account summarizes our studies of molecular metal-polypyridyl catalysts for electrochemical and photochemical reduction of protons to hydrogen. Inspired by concept transfer from biological and materials catalysts, these scaffolds are remarkably resistant to decomposition in water, with fast and selective electrocatalytic and photocatalytic conversions that are sustainable for several days. Their modular nature offers a broad range of opportunities for tuning reactivity by molecular design, including altering ancillary ligand electronics, denticity, and/or incorporating redox-active elements. Our first-generation complex, [(PY4)Co(CH3CN)2](2+), catalyzes the reduction of protons from a strong organic acid to hydrogen in 50% water. Subsequent investigations with the pentapyridyl ligand PY5Me2 furnished molybdenum and cobalt complexes capable of catalyzing the reduction of water in fully aqueous electrolyte with 100% Faradaic efficiency. Of particular note, the complex [(PY5Me2)MoO](2+) possesses extremely high activity and durability in neutral water, with turnover frequencies at least 8500 mol of H2 per mole of catalyst per hour and turnover numbers over 600 000 mol of H2 per mole of catalyst over 3 days at an

  11. Photochemically triggered cytosolic drug delivery using pH-responsive hyaluronic acid nanoparticles for light-induced cancer therapy.

    PubMed

    Lee, Chung-Sung; Na, Kun

    2014-11-10

    A photochemically triggered cytosolic drug delivery system based on combining tumor-targeting pH-responsive hyaluronic acid (HA) nanoparticles (PHANs) with anticancer therapeutics (doxorubicin; DOX) was successfully developed for light-induced cancer therapy. PHANs were prepared through the self-assembly of a photosensitizer (PS), chlorin e6, and a pH-responsive moiety, poly(diisopropylaminoethyl) aspartamide (PDIPASP),conjugated to HA. DOX encapsulating PHANs (DOX@PHANs) have a uniform spherical shape,a sub-100 nm size distribution and a negative surface charge. The pH-responsiveness of PHANs leads to their disassembly due to the protonation of PDIPASP, which triggers DOX release. Competitive cellular uptake and confocal microscopy studies revealed CD44 receptor-mediated endocytosis, endosomal escape capability and efficient drug targeting. Compared to treatment with free DOX or PHANs, the combined treatment with DOX@PHANs and spatiotemporally defined irradiation remarkably improved the anticancer efficacy both in vitro and in vivo studies. Therefore, this strategy shows promise for the photochemically triggered cytosolic drug delivery of therapeutic agents for light-induced cancer therapy. PMID:25251731

  12. Light-induced dissociation of an antenna hetero-oligomer is needed for non-photochemical quenching induction.

    PubMed

    Betterle, Nico; Ballottari, Matteo; Zorzan, Simone; de Bianchi, Silvia; Cazzaniga, Stefano; Dall'osto, Luca; Morosinotto, Tomas; Bassi, Roberto

    2009-05-29

    PsbS plays a major role in activating the photoprotection mechanism known as "non-photochemical quenching," which dissipates chlorophyll excited states exceeding the capacity for photosynthetic electron transport. PsbS activity is known to be triggered by low lumenal pH. However, the molecular mechanism by which this subunit regulates light harvesting efficiency is still unknown. Here we show that PsbS controls the association/dissociation of a five-subunit membrane complex, composed of two monomeric Lhcb proteins (CP29 and CP24) and the trimeric LHCII-M. Dissociation of this supercomplex is indispensable for the onset of non-photochemical fluorescence quenching in high light, strongly suggesting that protein subunits catalyzing the reaction of heat dissipation are buried into the complex and thus not available for interaction with PsbS. Consistently, we showed that knock-out mutants on two subunits participating to the B4C complex were strongly affected in heat dissipation. Direct observation by electron microscopy and image analysis showed that B4C dissociation leads to the redistribution of PSII within grana membranes. We interpreted these results to mean that the dissociation of B4C makes quenching sites, possibly CP29 and CP24, available for the switch to an energy-quenching conformation. These changes are reversible and do not require protein synthesis/degradation, thus allowing for changes in PSII antenna size and adaptation to rapidly changing environmental conditions. PMID:19307183

  13. Light-induced Dissociation of an Antenna Hetero-oligomer Is Needed for Non-photochemical Quenching InductionS⃞

    PubMed Central

    Betterle, Nico; Ballottari, Matteo; Zorzan, Simone; de Bianchi, Silvia; Cazzaniga, Stefano; Dall'Osto, Luca; Morosinotto, Tomas; Bassi, Roberto

    2009-01-01

    PsbS plays a major role in activating the photoprotection mechanism known as “non-photochemical quenching,” which dissipates chlorophyll excited states exceeding the capacity for photosynthetic electron transport. PsbS activity is known to be triggered by low lumenal pH. However, the molecular mechanism by which this subunit regulates light harvesting efficiency is still unknown. Here we show that PsbS controls the association/dissociation of a five-subunit membrane complex, composed of two monomeric Lhcb proteins (CP29 and CP24) and the trimeric LHCII-M. Dissociation of this supercomplex is indispensable for the onset of non-photochemical fluorescence quenching in high light, strongly suggesting that protein subunits catalyzing the reaction of heat dissipation are buried into the complex and thus not available for interaction with PsbS. Consistently, we showed that knock-out mutants on two subunits participating to the B4C complex were strongly affected in heat dissipation. Direct observation by electron microscopy and image analysis showed that B4C dissociation leads to the redistribution of PSII within grana membranes. We interpreted these results to mean that the dissociation of B4C makes quenching sites, possibly CP29 and CP24, available for the switch to an energy-quenching conformation. These changes are reversible and do not require protein synthesis/degradation, thus allowing for changes in PSII antenna size and adaptation to rapidly changing environmental conditions. PMID:19307183

  14. Atmospheric photochemical transformations enhance 1,3-butadiene-induced inflammatory responses in human epithelial cells: The role of ozone and other photochemical degradation products.

    PubMed

    Doyle, Melanie; Sexton, Kenneth G; Jeffries, Harvey; Jaspers, Ilona

    2007-03-20

    Chemistry of hazardous air pollutants has been studied for many years, yet little is known about how these chemicals, once reacted within urban atmospheres, affect healthy and susceptible individuals. Once released into the atmosphere, 1,3-butadiene (BD) reacts with hydroxyl radicals and ozone (created by photochemical processes), to produce many identified and unidentified products. Once this transformation has occurred, the toxic potential of atmospheric pollutants such as BD in the ambient environment is currently unclear. During this study, environmental irradiation chambers (also called smog chambers), utilizing natural sunlight, were used to create photochemical transformations of BD. The smog chamber/in vitro exposure system was designed to investigate the toxicity of chemicals before and after photochemical reactions and to investigate interactions with the urban atmosphere using representative in vitro samples. In this study, we determined the relative toxicity and inflammatory gene expression induced by coupling smog chamber atmospheres with an in vitro system to expose human respiratory epithelial cells to BD, BDs photochemical degradation products, or the equivalent ozone generated within the photochemical mixture. Exposure to the photochemically generated products of BD (primarily acrolein, acetaldehyde, formaldehyde, furan and ozone) induced significant increases in cytotoxicity, IL-8, and IL-6 gene expression compared to a synthetic mixture of primary products that was created by injecting the correct concentrations of the detected products from the irradiation experiments. Interestingly, exposure to the equivalent levels of ozone generated during the photochemical transformation of BD did not induce the same level of inflammatory cytokine release for either exposure protocol, suggesting that the effects from ozone alone do not account for the entire response in the irradiation experiments. These results indicate that BDs full photochemical product

  15. Photochemical coal dissolution. Quarterly technical progress report, October 1, 1995--December 31, 1995

    SciTech Connect

    Doetschman, D.C.

    1996-05-01

    The remaining types of photochemical extraction experiments originally proposed have now been examined. Experiments in which benzophenone (BP) in solution was employed as a photochemical extraction reagent on pre-extracted coals were performed with Hg arc light through a quartz light filter at a concentration permitting light absorption primarily by the coal. Experiments were done on pre-extracted coals in which tetralin was employed as the photochemical extraction reagent. Finally experiments were performed in which the pre-extracted coal was swelled with BP above its melting point, irradiated through a quartz filter and extracted. The solvent was acetonitrile in all cases.

  16. On the interpretation of in situ HONO observations via photochemical steady state.

    PubMed

    Crilley, Leigh R; Kramer, Louisa; Pope, Francis D; Whalley, Lisa K; Cryer, Danny R; Heard, Dwayne E; Lee, James D; Reed, Christopher; Bloss, William J

    2016-07-18

    A substantial body of recent literature has shown that boundary layer HONO levels are higher than can be explained by simple, established gas-phase chemistry, to an extent that implies that additional HONO sources represent a major, or the dominant, precursor to OH radicals in such environments. This conclusion may be reached by analysis of point observations of (for example) OH, NO and HONO, alongside photochemical parameters; however both NO and HONO have non-negligible atmospheric lifetimes, so these approaches may be problematic if substantial spatial heterogeneity exists. We report a new dataset of HONO, NOx and HOx observations recorded at an urban background location, which support the existence of additional HONO sources as determined elsewhere. We qualitatively evaluate the possible impacts of local heterogeneity using a series of idealised numerical model simulations, building upon the work of Lee et al. (J. Geophys. Res., 2013, DOI: 10.1002/2013JD020341). The simulations illustrate the time required for photostationary state approaches to yield accurate results following substantial perturbations in the HOx/NOx/NOy chemistry, and the scope for bias to an inferred HONO source from NOx and VOC emissions in either a positive or negative sense, depending upon the air mass age following emission. To assess the extent to which these impacts may be present in actual measurements, we present exploratory spatially resolved measurements of HONO and NOx abundance obtained using a mobile instrumented laboratory. Measurements of the spatial variability of HONO in urban, suburban and rural environments show pronounced changes in abundance are found in proximity to major roads within urban areas, indicating that photo-stationary steady state (PSS) analyses in such areas are likely to be problematic. The measurements also show areas of very homogeneous HONO and NOx abundance in rural, and some suburban, regions, where the PSS approach is likely to be valid. Implications

  17. Catalytic combustion of actual low and medium heating value gases

    NASA Technical Reports Server (NTRS)

    Bulzan, D. L.

    1982-01-01

    Catalytic combustion of both low and medium heating value gases using actual coal derived gases obtained from operating gasifiers was demonstrated. A fixed bed gasifier with a complete product gas cleanup system was operated in an air blown mode to produce low heating value gas. A fluidized bed gasifier with a water quench product gas cleanup system was operated in both an air enriched and an oxygen blown mode to produce low and medium, heating value gas. Noble metal catalytic reactors were evaluated in 12 cm flow diameter test rigs on both low and medium heating value gases. Combustion efficiencies greater than 99.5% were obtained with all coal derived gaseous fuels. The NOx emissions ranged from 0.2 to 4 g NO2 kg fuel.

  18. Tracking Actual Usage: The Attention Metadata Approach

    ERIC Educational Resources Information Center

    Wolpers, Martin; Najjar, Jehad; Verbert, Katrien; Duval, Erik

    2007-01-01

    The information overload in learning and teaching scenarios is a main hindering factor for efficient and effective learning. New methods are needed to help teachers and students in dealing with the vast amount of available information and learning material. Our approach aims to utilize contextualized attention metadata to capture behavioural…

  19. Caustic-Side Solvent Extraction: Prediction of Cesium Extraction for Actual Wastes and Actual Waste Simulants

    SciTech Connect

    Delmau, L.H.; Haverlock, T.J.; Sloop, F.V., Jr.; Moyer, B.A.

    2003-02-01

    This report presents the work that followed the CSSX model development completed in FY2002. The developed cesium and potassium extraction model was based on extraction data obtained from simple aqueous media. It was tested to ensure the validity of the prediction for the cesium extraction from actual waste. Compositions of the actual tank waste were obtained from the Savannah River Site personnel and were used to prepare defined simulants and to predict cesium distribution ratios using the model. It was therefore possible to compare the cesium distribution ratios obtained from the actual waste, the simulant, and the predicted values. It was determined that the predicted values agree with the measured values for the simulants. Predicted values also agreed, with three exceptions, with measured values for the tank wastes. Discrepancies were attributed in part to the uncertainty in the cation/anion balance in the actual waste composition, but likely more so to the uncertainty in the potassium concentration in the waste, given the demonstrated large competing effect of this metal on cesium extraction. It was demonstrated that the upper limit for the potassium concentration in the feed ought to not exceed 0.05 M in order to maintain suitable cesium distribution ratios.

  20. Photochemical oxidation of arsenic(III) to arsenic(V) using peroxydisulfate ions as an oxidizing agent.

    PubMed

    Neppolian, Bernaurdshaw; Celik, Evrim; Choi, Heechul

    2008-08-15

    The photochemical oxidation of arsenic, As(III), to the less toxic As(V) using peroxydisulfate ions (S2O8(2-)) as the oxidizing agent under UV light irradiation was investigated. The photochemical oxidation of As(III) to As(V) assisted using peroxydisulfate ions (KPS) proved to be a simple and efficient method, and the rate of oxidation for As(III) was exceptionally high in accordance with the concentration of KPS. In this study, the UV light intensity was of primary importance for the dissociation of the KPS in generating sulfate anion radicals (SO4(-*)). Upon intense UV light irradiation, very efficient oxidation was achieved due to the complete decomposition of KPS into SO4(-*) radicals which favor a higher reaction rate. Subsequent pH variation from 3 to 9 was seen to have no influence on the photolytic cleavage of KPS, and hence, the reaction was unaltered. There was also no significant effect from the continuous purging of oxygen or dissolved oxygen before the reaction as the air-equilibrated condition was found to be sufficient for efficient oxidation. However, the continuous purging of nitrogen substantially reduced the reaction rate (20%), confirming that the dissolved oxygen plays a role in this reaction, although at high concentrations of KPS, this situation was overcome. Humic acid was also found to have no detrimental effect on the reaction rate, even at 20 ppm concentration. The resultant SO4(2-) obtained in this studywas,thus, not considered a pollutant. Moreover, there was no need for a sensitizer or other metals with highly alkaline conditions that are normally used in conjunction with KPS. Natural solar light could also effectively oxidize As(III) at room temperature. This simple technique was, thus, considered a cost-effective and safe method for the oxidation of As(III) to As(V). PMID:18767684

  1. Potential biosignatures in super-Earth atmospheres II. Photochemical responses.

    PubMed

    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

  2. Potential Biosignatures in Super-Earth Atmospheres II. Photochemical Responses

    PubMed Central

    Gebauer, S.; Godolt, M.; Palczynski, K.; Rauer, H.; Stock, J.; von Paris, P.; Lehmann, R.; Selsis, F.

    2013-01-01

    Abstract 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

  3. Fine control on the photochemical and photobiological properties of Ru(II) arene complexes.

    PubMed

    Chen, Yongjie; Lei, Wanhua; Hou, Yuanjun; Li, Chao; Jiang, Guoyu; Zhang, Baowen; Zhou, Qianxiong; Wang, Xuesong

    2015-04-28

    A series of six Ru(arene) complexes, [(η(6)-p-cymene)Ru(dpb)(py-R)](2+) (1-6, dpb = 2,3-bis(2-pyridyl)benzoquinoxaline, py-R = 4-substituted pyridine, R = N(CH3)2, NH2, OCH3, H, COOCH3 and NO2), were synthesized and their photochemical and photobiological properties were compared in detail. The electron push/pull character of the R groups has a significant impact on both ligand photodissociation and (1)O2 generation of the complexes. The photoinduced DNA covalent binding capabilities increase from 1 to 6 under both aerobic and anaerobic conditions, and DNA photocleavage occurs simultaneously in aerobic environments. 4 has the most potent phototoxicity against human lung carcinoma A549 cells among the examined complexes. The substituent effect may be ascribed to the influences of the R groups on the energy levels of (3)MC and (3)MLCT states as well as the energy gaps between (3)MC, (3)MLCT and dpb-based (3)IL states. Similar chemical modification on bidentate and arene ligands or other sites of the pyridine ligand may lead to more efficient agents with PDT and/or PACT activities. PMID:25797273

  4. Determination of total mercury in biological tissue by isotope dilution ICPMS after UV photochemical vapor generation.

    PubMed

    Liu, Rui; Xu, Mo; Shi, Zeming; Zhang, Jiayun; Gao, Ying; Yang, Lu

    2013-12-15

    A method is developed for the determination of trace mercury in biological samples using photo chemical vapor generation (PVG) and isotope dilution inductively coupled plasma mass spectrometry (ID ICPMS) detection. Biological tissues were solubilized in formic acid. Subsequently, the sample solutions were exposed to an ultraviolet (UV) source for the reduction of mercury into vapor species prior to ICPMS measurements. The formic acid served not only as a tissue solubilizer in the sample preparation procedure, but also as a photochemical reductant for mercury in the PVG process. The problem arising from the opaque formic acid digested solution was efficiently solved by using ID method. The optimum conditions for sample treatment and PVG were investigated. A limit of detection (LOD) of 0.5 pg g(-1), based on an external calibration, provided 350-fold improvement over that obtained by utilizing conventional pneumatic nebulization sample introduction. Method validation was demonstrated by the determination of total mercury in several biological tissue certified reference materials (CRMs). The results were in good agreement with the certified values. PMID:24209355

  5. Photochemical tissue penetration via photosensitizer for effective drug penetration in a non-vascular tumor.

    PubMed

    Min, Daehong; Jeong, Dooyong; Choi, Myung Gyu; Na, Kun

    2015-06-01

    To improve the tissue penetration efficiency (PE%) of hydrophilic-drugs in non-vascular drug eluting stents (DES), we designed photochemical tissue penetration (PTP) invested DES (PTP-DES). The PTP technology was applied to the stent as a covering membrane to generate singlet oxygen. Singlet oxygen damages the epithelial layer, so the PE% of released drugs could be improved. To prepare the PTP-DES membrane, chlorin e6 (Ce6, photosensitizer) was incorporated in a gemcitabine (GEM) eluting polyurethane (PU) membrane (Ce6-GEM-PU). Ce6-GEM-PU has smooth surface that is ∼40 μm thick. The photoactivity of Ce6 was maintained for 2 weeks (in vitro GEM releasing period). In a separate cell culture system, both 1.5 folds higher PE% and an improved tumor cell growth inhibition effect were shown after light exposure. Additionally, in tissue penetration experimental system, 2 folds increased in the PE% of GEM was induced by laser exposure at 80 J/cm2. Additionally, improved PE% of hydrophilic molecules (Fluorescein and GEM) was confirmed in colon tumor bearing mice. Consequentially, tumor growth, when implanted with Ce6-GEM-PU, was effectively inhibited without significant side effects. Based on these results, we believe that the PTP-DES system has great potential for improving the therapeutic effect of conventional DES. PMID:25818454

  6. The photochemical reflectance index provides an optical indicator of spring photosynthetic activation in evergreen conifers.

    PubMed

    Wong, Christopher Y S; Gamon, John A

    2015-04-01

    In evergreens, the seasonal down-regulation and reactivation of photosynthesis is largely invisible and difficult to assess with remote sensing. This invisible phenology may be changing as a result of climate change. To better understand the mechanism and timing of these hidden physiological transitions, we explored several assays and optical indicators of spring photosynthetic activation in conifers exposed to a boreal climate. The photochemical reflectance index (PRI), chlorophyll fluorescence, and leaf pigments for evergreen conifer seedlings were monitored over 1 yr of a boreal climate with the addition of gas exchange during the spring. PRI, electron transport rate, pigment levels, light-use efficiency and photosynthesis all exhibited striking seasonal changes, with varying kinetics and strengths of correlation, which were used to evaluate the mechanisms and timing of spring activation. PRI and pigment pools were closely timed with photosynthetic reactivation measured by gas exchange. The PRI provided a clear optical indicator of spring photosynthetic activation that was detectable at leaf and stand scales in conifers. We propose that PRI might provide a useful metric of effective growing season length amenable to remote sensing and could improve remote-sensing-driven models of carbon uptake in evergreen ecosystems. PMID:25641209

  7. Photochemical vapor deposition of undoped and n-type amorphous silicon films produced from disilane

    SciTech Connect

    Inoue, T.; Konagai, M.; Takahashi, K.

    1983-10-15

    Hydrogenated amorphous silicon films have been deposited by mercury photosensitized decomposition (photochemical vapor deposition: photo-CVD) of disilane at a substrate temperature below 300 /sup 0/C. The structural and optical properties of undoped films are very similar to those of films deposited by rf glow discharge decomposition. The electronic property measurement shows that the conductivity strongly depends on the substrate temperature during deposition. The photoconductivity reaches 5.7 x 10/sup -3/ (..cap omega.. cm)/sup -1/ (AM1,100 mW/cm/sup 2/) at a substrate temperature of 200 /sup 0/C. The dark conductivity is 10/sup -6/--10/sup -8/ (..cap omega.. cm)/sup -1/ and the Fermi level is located near the middle of the gap. n-type doping has been also achieved by adding phosphine as an impurity to disilane. Furthermore, a p-i-n a-Si solar cell was fabricated using photo-CVD undoped and P-doped films. The initial cell showed a conversion efficiency of 4.39% under AM1 insolation.

  8. Investigation of the Coupled Effects of Molecular Weight and Charge-Transfer Interactions on the Optical and Photochemical Properties of Dissolved Organic Matter.

    PubMed

    McKay, Garrett; Couch, Kylie D; Mezyk, Stephen P; Rosario-Ortiz, Fernando L

    2016-08-01

    We studied the formation of photochemically produced reactive intermediates (RI) from dissolved organic matter (DOM). Specifically, we focused on the effects of variable molecular weight and chemical reduction on the optical properties of DOM (absorbance and fluorescence) and the formation of singlet oxygen ((1)O2), DOM triplet excited states ((3)DOM*), and the hydroxyl radical ((•)OH). The data are largely evaluated in terms of a charge-transfer (CT) model, but deficiencies in the model to explain the data are pointed out when evident. A total of two sets of samples were studied that were subjected to different treatments; the first set included secondary-treated wastewaters and a wastewater-impacted stream, and the second was a DOM isolate. Treatments included size fractionation and chemical reduction using sodium borohydride. Taken as a whole, the results demonstrate that decreasing molecular weight and borohydride reduction work in opposition regarding quantum efficiencies for (1)O2 and (3)DOM* production but in concert for fluorescence and (•)OH production. The optical and photochemical data provide evidence for a limited role of CT interactions occurring in lower-molecular-weight DOM molecules. In addition, the data suggest that the observed optical and photochemical properties of DOM are a result of multiple populations of chromophores and that their relative contribution is changed by molecular-weight fractionation and borohydride reduction. PMID:27377760

  9. Chemical kinetics and photochemical data for use in stratospheric modeling. Evaluation number 6

    NASA Technical Reports Server (NTRS)

    Demore, W. B.; Molina, M. J.; Watson, R. T.; Golden, D. M.; Hampson, R. F.; Kurylo, M. J.; Howard, C. J.; Ravishankara, A. R.

    1983-01-01

    Evaluated sets of rate constants and photochemical cross sections are presented. The primary application of the data is in the modeling of stratospheric processes, with particular emphasis on the ozone layer and its possible perturbation by anthropogenic and natural phenomena.

  10. Chemical kinetics and photochemical data for use in stratospheric modeling: Evaluation number 5

    NASA Technical Reports Server (NTRS)

    Demore, W. B.

    1982-01-01

    Sets of rate constants and photochemical cross sections compiled which were evaluated. The primary application of the data is in the modeling of stratospheric processes on the ozone layer and its possible perturbation by anthropogenic and natural phenomena are emphasized.

  11. AIR QUALITY CRITERIA FOR OZONE AND OTHER PHOTOCHEMICAL OXIDANTS. VOLUME 3.

    EPA Science Inventory

    Selected scientific information through early 1985 is presented and evaluated relative to the health and welfare effects associated with exposure to ozone and other photochemical oxidants. Data on health and welfare effects are emphasized; additional information is provided for u...

  12. A Photochemical Reactor for the Study of Kinetics and Adsorption Phenomena

    ERIC Educational Resources Information Center

    Poce-Fatou, J. A.; Gil, M. L. A.; Alcantara, R.; Botella, C.; Martin, J.

    2004-01-01

    The interaction between light and matter is examined with the help of a photochemical experiment. This experiment is useful for the investigation of heterogeneous catalysis, semiconductor properties and adsorption phenomena.

  13. Electronic-carrier-controlled photochemical etching process in semiconductor device fabrication

    DOEpatents

    Ashby, Carol I. H.; Myers, David R.; Vook, Frederick L.

    1989-01-01

    An electronic-carrier-controlled photochemical etching process for carrying out patterning and selective removing of material in semiconductor device fabrication includes the steps of selective ion implanting, photochemical dry etching, and thermal annealing, in that order. In the selective ion implanting step, regions of the semiconductor material in a desired pattern are damaged and the remainder of the regions of the material not implanted are left undamaged. The rate of recombination of electrons and holes is increased in the damaged regions of the pattern compared to undamaged regions. In the photochemical dry etching step which follows ion implanting step, the material in the undamaged regions of the semiconductor are removed substantially faster than in the damaged regions representing the pattern, leaving the ion-implanted, damaged regions as raised surface structures on the semiconductor material. After completion of photochemical dry etching step, the thermal annealing step is used to restore the electrical conductivity of the damaged regions of the semiconductor material.

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

    DOEpatents

    Ashby, Carol I. H.; Myers, David R.

    1992-01-01

    The minority carrier lifetime is significantly much shorter in semiconductor materials with very high impurity concentrations than it is in semiconductor materials with lower impurity concentration levels. This phenomenon of reduced minority carrier lifetime in semiconductor materials having high impurity concentration is utilized to advantage for permitting highly selective semiconductor material etching to be achieved using a carrier-driven photochemical etching reaction. Various means may be employed for increasing the local impurity concentration level in specific near-surface regions of a semiconductor prior to subjecting the semiconductor material to a carrier-driven photochemical etching reaction. The regions having the localized increased impurity concentration form a self-aligned mask inhibiting photochemical etching at such localized regions while the adjacent regions not having increased impurity concentrations are selectively photochemically etched. Liquid- or gas-phase etching may be performed.

  15. On-line method of determining utilization factor in Hg-196 photochemical separation process

    DOEpatents

    Grossman, Mark W.; Moskowitz, Philip E.

    1992-01-01

    The present invention is directed to a method for determining the utilization factor [U] in a photochemical mercury enrichment process (.sup.196 Hg) by measuring relative .sup.196 Hg densities using absorption spectroscopy.

  16. CHANGES IN SPECTRAL AND PHOTOCHEMICAL PROPERTIES OF COLORED DISSOLVED ORGANIC MATTER IN A COASTAL ESTUARY

    EPA Science Inventory

    Colored dissolved organic matter (CDOM) is the primary determinant of UV penetration and exposure in freshwater and coastal environments. CDOM is photochemically reactive and its photoreactions can lead to reductions in UV absorbance and increased UV exposure in aquatic ecosystem...

  17. PHOTOCHEMICAL OXIDANT AIR POLLUTION EFFECTS ON A MIXED CONIFER FOREST FOREST ECOSYSTEM - A PROGRESS REPORT

    EPA Science Inventory

    Since 1972, twelve scientists representing several research disciplines have collaborated in integrated studies to determine the chronic effects of photochemical oxidant air pollutants on a western mixed conifer forest ecosystem. An enormous amount of data has been collected, des...

  18. Inhalation of Photochemically Altered Urban Mixtures Depresses Cardiac Function in Mice

    EPA Science Inventory

    Rationale: Epidemiological studies have indicated an association between urban air pollution exposure and cardiovascular morbidity and mortality. The present study was designed to evaluate the cardiac effects of inhaled photochemical products in urban mixtures in a murine model. ...

  19. Electronic-carrier-controlled photochemical etching process in semiconductor device fabrication

    DOEpatents

    Ashby, C.I.H.; Myers, D.R.; Vook, F.L.

    1988-06-16

    An electronic-carrier-controlled photochemical etching process for carrying out patterning and selective removing of material in semiconductor device fabrication includes the steps of selective ion implanting, photochemical dry etching, and thermal annealing, in that order. In the selective ion implanting step, regions of the semiconductor material in a desired pattern are damaged and the remainder of the regions of the material not implanted are left undamaged. The rate of recombination of electrons and holes is increased in the damaged regions of the pattern compared to undamaged regions. In the photochemical dry etching step which follows ion implanting step, the material in the undamaged regions of the semiconductor are removed substantially faster than in the damaged regions representing the pattern, leaving the ion-implanted, damaged regions as raised surface structures on the semiconductor material. After completion of photochemical dry etching step, the thermal annealing step is used to restore the electrical conductivity of the damaged regions of the semiconductor material.

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

    EPA Science Inventory

    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 ...

  1. Axi-symmetrical flow reactor for [sup 196]Hg photochemical enrichment

    DOEpatents

    Grossman, M.W.

    1991-04-30

    The present invention is directed to an improved photochemical reactor useful for the isotopic enrichment of a predetermined isotope of mercury, especially, [sup 196]Hg. Specifically, two axi-symmetrical flow reactors were constructed according to the teachings of the present invention. These reactors improve the mixing of the reactants during the photochemical enrichment process, affording higher yields of the desired [sup 196]Hg product. Measurements of the variation of yield (Y) and enrichment factor (E) along the flow axis of these reactors indicates very substantial improvement in process uniformity compared to previously used photochemical reactor systems. In one preferred embodiment of the present invention, the photoreactor system was built such that the reactor chamber was removable from the system without disturbing the location of either the photochemical lamp or the filter employed therewith. 10 figures.

  2. IRON-INDUCED CHANGES IN LIGHT HARVESTING AND PHOTOCHEMICAL ENERGY CONVERSION IN EUKARYOTIC MARINE ALGAE

    EPA Science Inventory

    The role of iron in regulating light harvesting and photochemical energy conversion process was examined in the marine unicellular chlorophyte Dunaliella tertiolecta and the marine diatom Phaeodactylum tricornutum. In both species, iron limitation led to a reduction in cellular c...

  3. Examining ruthenium chromophores for the photochemical reduction of CO2 to methanol

    NASA Astrophysics Data System (ADS)

    Boston, David J.

    Our consumption of energy for transportation and electricity has been growing as quickly as our population. As this demand for energy increases we increase our production of carbon dioxide by the burning of fossil fuels to try and meet this increasing demand. A sustainable method to convert carbon dioxide (CO2) to a viable liquid fuel is one potential way in which both the increasing energy demand and increasing CO2 concentration issues can both be helped. Currently such methods being investigated include thermal, electrochemical, and photochemical processes. Because thermal conversion is not an ideal situation because of the requirement of strong reducing agents or extreme conditions such as steam reformation reactions, we need to find better alternatives such as electrochemical and photochemical methods. Both electrochemical and photochemical methods have the ability to be sustainable, however, the vast majority of these systems are limited to producing CO and/or formic acid, with only a few performing deeper reduction to products such formaldehyde, methanol and methane. All of the systems capable of reducing CO2 past two electrons involve either a heterogeneous catalyst (e.g. TiO2) or an electrode. In recent times Bocarsly and coworkers have shown that pyridine was capable of reducing CO2 to methanol through a sequential process of proton and electron transfers. This process seems to start with the formation of a CO2-pyridine adduct in solution that is reduced one more time to form formate/formic acid. The next reduction is a slow process and allows for a buildup of formate in solution leading to a higher formate concentration in solution. The subsequent reductions seem to occur very rapidly and form methanol at good efficiencies. Theoretical work done recently has argued for the necessity of the Pt, Pd, or GaP surface in the electrochemistry. Carter and coworkers have claimed that the surface of the electrode is a necessary part of the catalysis with the

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

    NASA Astrophysics Data System (ADS)

    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

  5. Consequences of Predicted or Actual Asteroid Impacts

    NASA Astrophysics Data System (ADS)

    Chapman, C. R.

    2003-12-01

    Earth impact by an asteroid could have enormous physical and environmental consequences. Impactors larger than 2 km diameter could be so destructive as to threaten civilization. Since such events greatly exceed any other natural or man-made catastrophe, much extrapolation is necessary just to understand environmental implications (e.g. sudden global cooling, tsunami magnitude, toxic effects). Responses of vital elements of the ecosystem (e.g. agriculture) and of human society to such an impact are conjectural. For instance, response to the Blackout of 2003 was restrained, but response to 9/11 terrorism was arguably exaggerated and dysfunctional; would society be fragile or robust in the face of global catastrophe? Even small impacts, or predictions of impacts (accurate or faulty), could generate disproportionate responses, especially if news media reports are hyped or inaccurate or if responsible entities (e.g. military organizations in regions of conflict) are inadequately aware of the phenomenology of small impacts. Asteroid impact is the one geophysical hazard of high potential consequence with which we, fortunately, have essentially no historical experience. It is thus important that decision makers familiarize themselves with the hazard and that society (perhaps using a formal procedure, like a National Academy of Sciences study) evaluate the priority of addressing the hazard by (a) further telescopic searches for dangerous but still-undiscovered asteroids and (b) development of mitigation strategies (including deflection of an oncoming asteroid and on- Earth civil defense). I exemplify these issues by discussing several representative cases that span the range of parameters. Many of the specific physical consequences of impact involve effects like those of other geophysical disasters (flood, fire, earthquake, etc.), but the psychological and sociological aspects of predicted and actual impacts are distinctive. Standard economic cost/benefit analyses may not

  6. The carbon-bond mechanism: a condensed kinetic mechanism for photochemical smog

    SciTech Connect

    Whitten, G.Z.; Hog, H.; Killus, J.P.

    1980-06-01

    Efforts to develop a model that can simulate photochemical smog with kinetic mechanisms are discussed. The carbon-bond mechanism is a set of generalized reactions that can be used to model photochemical oxidant formation. The theoretical framework of carbon-bond mechanism is outlined. Chemical variables that are incorporated into the carbon-bond mechanism model are described. Further work that is needed on the carbon-bond mechanism model is considered. (1 diagram, 13 graphs, 30 references, 2 tables)

  7. Seasonal Photochemical Transformations of Nitrogen Species in a Forest Stream and Lake

    PubMed Central

    Porcal, Petr; Kopáček, Jiří; Tomková, Iva

    2014-01-01

    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. PMID:25551441

  8. Kinetic and photochemical data for atmospheric chemistry reactions of the nitrogen oxides

    NASA Technical Reports Server (NTRS)

    Hampson, R. F., Jr.

    1980-01-01

    Data sheets for thermal and photochemical reactions of importance in the atmospheric chemistry of the nitrogen oxides are presented. For each reaction the available experimental data are summarized and critically evaluated, and a preferred value of the rate coefficient is given. The selection of the preferred value is discussed and an estimate of its accuracy is given. For the photochemical process, the data are summarized, and preferred for the photoabsorption cross section and primary quantum yields are given.

  9. Nickel complex with internal bases as efficient molecular catalyst for photochemical H2 production.

    PubMed

    Yang, Yong; Wang, Mei; Xue, Liqin; Zhang, Fengbo; Chen, Lin; Ahlquist, Mårten S G; Sun, Licheng

    2014-10-01

    A Ni complex with internal bases that contain bipyridine-derived ligands, [Ni(L)2 (H2 O)2 ](BF4 )2 ([1](BF4 )2 , L=2-(2-pyridyl)-1,8-naphthyridine), and a reference complex that bears analogous bipyridine-derived ligands but without an internal base, [Ni(L')3 ](BF4 )2 ([2](BF4 )2 , L'=2-(2-pyridyl)quinoline), were synthesized and characterized. The electrochemical properties of these complexes were studied in CH3 CN, H2 O, and a mixture of EtOH/H2 O. The fluorescence spectroscopic studies suggest that both dynamic and the sphere-of-action static quenching exist in the fluorescein Fl(2-) /[1](2+) and Fl(2-) /[2](2+) systems. These noble-metal-free molecular systems were studied for photocatalytic H2 generation. Under optimal conditions, the turnover number of H2 evolution reaches 3230 based on [1](2+) , whereas [2](2+) displays only approximately one third of the turnover of [1](2+) . A plausible mechanism for the catalytic H2 generation by [1](2+) is presented based on DFT calculations. PMID:25179906

  10. Photochemical pollution at two southern California smog receptor sites

    SciTech Connect

    Grosjean, D.; Williams, E.L. II. )

    1992-06-01

    A one-year survey of air quality has been carried out at two southern California inland locations, Perris and Palm Springs to evaluate transport of photochemical smog from the Los Angeles area and to assess population exposure to toxic air pollutants in the Coachella Valley and eastern Riverside County. Air pollutants measured included formaldehyde, acetaldehyde, nitric acid, and peroxyacetyl nitrate (PAN). Acetic acid was also measured as part of the time-integrated method employed to measure PAN. In addition, intensive studies were carried out at both locations and included measurements of aldehydes, nitric acid, PAN, peroxypropionyl nitrate (PPN), methylchloroform and tetrachloroethylene. Maximum concentrations of HCHO, CH{sub 3}CHO, HNO{sub 3}, PAN, PPN, CH{sub 3}COOH and C{sub 2}Cl{sub 4} were 26, 21, 4.5, 7.6, 0.42, 6.6 and 0.29 ppb in Palm Springs and 15, 30, 6.3, 9.1, 0.73, 7.8 and 0.43 ppb in Perris. Pollutant concentrations measured in Palm Springs and Perris are compared to those measured in the Los Angeles area, and are discussed in terms of formation and removal during transport.

  11. Atmospheric photochemical degradation of 1,4-unsaturated dicarbonyls

    SciTech Connect

    Liu, X.; Jeffries, H.E.; Sexton, K.G.

    1999-12-01

    To better understand fates of aromatics hydrocarbon species in the atmosphere, the authors have investigated the transformation chemistry of butenedial (CHOCH{double{underscore}bond}CHCHO), 4-oxo-2-pentenal (CH{sub 3}COCH{double{underscore}bond}CHCHO), and 3-hexene-2, 5-dione (CH{sub 3}COCH{double{underscore}bond}CHCOCH{sub 3}). These 1,4-unsaturated dicarbonyls are known to be products of aromatic photochemical oxidation. Both hydroxyl radical (OH) and ozone (O{sub 3}) initiated smog chamber experiments under atmospheric conditions were conducted in the University of North Carolina outdoor smog chamber. Carbonyl intermediates and products were measured using the O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine derivatization method followed by gas chromatography/ion trap mass spectrometry analysis. Carbonyl products detected and identified by comparison with standards in the OH-initiated photooxidation of butenedial include formaldehyde, acrolein, glycolaldehyde, glyoxal, and malonaldehyde (CHOCH{sub 2}CHO). For 4-oxo-2-pentenal, the carbonyl products were formaldehyde, methyl vinyl ketone, glycolaldehyde, hydroxyacetone, glyoxal, methylglyoxal, and malonaldehyde. for 3-hexene-2,5-dione the products were formaldehyde, acetaldehyde, acetone, hydroxyacetone, and methylglyoxal. Carbonyl products detected in the P{sub 3}-initiated experiments with cyclohexane as the OH scavenger were formaldehyde and glyoxal in butenedial; formaldehyde, glyoxal, methyl-glyoxal, and malonaldehyde in 4-oxo-2-pentenal; and formaldehyde and methylglyoxal in 3-hexene-2,5-dione.

  12. Photochemical aging of light-absorbing secondary organic aerosol material.

    PubMed

    Sareen, Neha; Moussa, Samar G; McNeill, V Faye

    2013-04-11

    Dark reactions of methylglyoxal with NH4(+) in aqueous aerosols yield light-absorbing and surface-active products that can influence the physical properties of the particles. Little is known about how the product mixture and its optical properties will change due to photolysis as well as oxidative aging by O3 and OH in the atmosphere. Here, we report the results of kinetics and product studies of the photochemical aging of aerosols formed by atomizing aqueous solutions of methylglyoxal and ammonium sulfate. Experiments were performed using aerosol flow tube reactors coupled with an aerosol chemical ionization mass spectrometer (Aerosol-CIMS) for monitoring gas- and particle-phase compositions. Particles were also impacted onto quartz windows in order to assess changes in their UV-visible absorption upon oxidation. Photooxidation of the aerosols leads to the formation of small, volatile organic acids including formic acid, acetic acid, and glyoxylic acid. The atmospheric lifetime of these species during the daytime is predicted to be on the order of minutes, with photolysis being an important mechanism of degradation. The lifetime with respect to O3 oxidation was observed to be on the order of hours. O3 oxidation also leads to a net increase in light absorption by the particles due to the formation of additional carbonyl compounds. Our results are consistent with field observations of high brown carbon absorption in the early morning. PMID:23506538

  13. Spectrofluorimetric determination of tetrabenazine after photochemical derivatization in basic medium

    NASA Astrophysics Data System (ADS)

    Osório, Ana C. P.; da Cunha, Alessandra L. M. C.; Khan, Sarzamin; Ponciano, Cássia R.; Aucélio, Ricardo Q.

    Photochemical derivatization is proposed for the spectrofluorimetric determination of tetrabenazine (TBZ). A central composite design was used to adjust experimental conditions (60 min of UV in a 0.45 mol L-1 NaOH solution) enabling the improvement of the analyte signal-to-blank ratio of one order of magnitude, when compared to the TBZ original fluorescence. Limit of quantification was 4.7 × 10-8 mol L-1 but the detection power can be improved at least 10 times using solid phase extraction that also allows the separation of the analyte from matrix components, enabling the analysis of biologic fluids. Linear range covered at least three orders of magnitude. The combined uncertainty of the determination (at a 5 × 10-6 mol L-1) was 16%. Recoveries of TBZ in the analyses of a pharmaceutical formulation were in agreement with the ones obtained using a HPLC method. Recovery in saliva (5 × 10-7 mol L-1 of TBZ) was 90 ± 3% (n = 3). The procedure minimizes the use of toxic chemical derivatization reagents and the generation of hazardous waste.

  14. Photochemical predictive analysis of photodynamic therapy in dermatology

    NASA Astrophysics Data System (ADS)

    Fanjul-Vélez, F.; Salas-García, I.; López-Escobar, M.; Ortega-Quijano, N.; Arce-Diego, J. L.

    2010-02-01

    Photodynamic Therapy is a recent treatment modality that allows malignant tissue destruction. The technique provides a localized effect and good cosmetic results. The application of Photodynamic Therapy is based on the inoculation of a photosensitizer and the posterior irradiation by an optical source. This radiation chemically activates the drug and provokes reactions that lead to tissue necrosis. Nowadays there are fixed clinical Photodynamic Therapy protocols that make use of a particular optical dose and photosensitizer amount. These parameters are independent of the patient and the lesion. In this work we present a Photodynamic Therapy model that tries to predict the effect of the treatment on the skin. First the results of a clinical study in the Dermatology Department of the Marqués de Valdecilla University Hospital are presented. The most common lesions and some unsuccessful cases are stated. The predictive model proposed is based on a 3D optical propagation of radiation by a Monte Carlo approach. Once the optical energy is obtained, a complex photochemical model is employed. This model takes into account the electronic transitions between molecular levels and particles concentrations. As the process of generation of photosensitizer is not homogeneous, the photosensitizer distribution is also taken into account. The optical power of the source, the exposition time and the optochemical characteristics of the tissue can be varied. This implies that these parameters could be adjusted to the particular pathology we are dealing with, so the unsuccessful cases could be better treated.

  15. van Hove Singularity Enhanced Photochemical Reactivity of Twisted Bilayer Graphene.

    PubMed

    Liao, Lei; Wang, Huan; Peng, Han; Yin, Jianbo; Koh, Ai Leen; Chen, Yulin; Xie, Qin; Peng, Hailin; Liu, Zhongfan

    2015-08-12

    Twisted bilayer graphene (tBLG) exhibits van Hove singularities (VHSs) in the density of states that can be tuned by changing the twist angle (θ), sparking various novel physical phenomena. Much effort has been devoted to investigate the θ-dependent physical properties of tBLG. Yet, the chemical properties of tBLG with VHSs, especially the chemical reactivity, remain unexplored. Here we report the first systematic study on the chemistry of tBLG through the photochemical reaction between graphene and benzoyl peroxide. Twisted bilayer graphene exhibits θ-dependent reactivity, and remarkably enhanced reactivity is obtained when the energy of incident laser matches with the energy interval of the VHSs of tBLG. This work provides an insight on the chemistry of tBLG, and the successful enhancement of chemical reactivity derived from VHS is highly beneficial for the controllable chemical modification of tBLG as well as the development of tBLG based devices. PMID:26151687

  16. Photochemical Microscale Electrophoresis Allows Fast Quantification of Biomolecule Binding.

    PubMed

    Möller, Friederike M; Kieß, Michael; Braun, Dieter

    2016-04-27

    Intricate spatiotemporal patterns emerge when chemical reactions couple to physical transport. We induce electrophoretic transport by a confined photochemical reaction and use it to infer the binding strength of a second, biomolecular binding reaction under physiological conditions. To this end, we use the photoactive compound 2-nitrobenzaldehyde, which releases a proton upon 375 nm irradiation. The charged photoproducts locally perturb electroneutrality due to differential diffusion, giving rise to an electric potential Φ in the 100 μV range on the micrometer scale. Electrophoresis of biomolecules in this field is counterbalanced by back-diffusion within seconds. The biomolecule concentration is measured by fluorescence and settles proportionally to exp(-μ/D Φ). Typically, binding alters either the diffusion coefficient D or the electrophoretic mobility μ. Hence, the local biomolecule fluorescence directly reflects the binding state. A fit to the law of mass action reveals the dissociation constant of the binding reaction. We apply this approach to quantify the binding of the aptamer TBA15 to its protein target human-α-thrombin and to probe the hybridization of DNA. Dissociation constants in the nanomolar regime were determined and match both results in literature and in control experiments using microscale thermophoresis. As our approach is all-optical, isothermal and requires only nanoliter volumes at nanomolar concentrations, it will allow for the fast screening of biomolecule binding in low volume multiwell formats. PMID:27042755

  17. Photochemically driven redox chemistry induces protocell membrane pearling and division.

    PubMed

    Zhu, Ting F; Adamala, Katarzyna; Zhang, Na; Szostak, Jack W

    2012-06-19

    Prior to the evolution of complex biochemical machinery, the growth and division of simple primitive cells (protocells) must have been driven by environmental factors. We have previously demonstrated two pathways for fatty acid vesicle growth in which initially spherical vesicles grow into long filamentous vesicles; division is then mediated by fluid shear forces. Here we describe a different pathway for division that is independent of external mechanical forces. We show that the illumination of filamentous fatty acid vesicles containing either a fluorescent dye in the encapsulated aqueous phase, or hydroxypyrene in the membrane, rapidly induces pearling and subsequent division in the presence of thiols. The mechanism of this photochemically driven pathway most likely involves the generation of reactive oxygen species, which oxidize thiols to disulfide-containing compounds that associate with fatty acid membranes, inducing a change in surface tension and causing pearling and subsequent division. This vesicle division pathway provides an alternative route for the emergence of early self-replicating cell-like structures, particularly in thiol-rich surface environments where UV-absorbing polycyclic aromatic hydrocarbons (PAHs) could have facilitated protocell division. The subsequent evolution of cellular metabolic processes controlling the thiol:disulfide redox state would have enabled autonomous cellular control of the timing of cell division, a major step in the origin of cellular life. PMID:22665773

  18. Photochemical chlorine and bromine activation from artificial saline snow

    NASA Astrophysics Data System (ADS)

    Wren, S. N.; Donaldson, D. J.; Abbatt, J. P. D.

    2013-05-01

    The activation of reactive halogen species - particularly Cl2 - from sea ice and snow surfaces is not well understood. In this study, we used a photochemical snow reactor coupled to a chemical ionization mass spectrometer to investigate the production of Br2, BrCl and Cl2 from NaCl/NaBr-doped artificial snow samples. At temperatures above the NaCl-water eutectic, illumination of samples (λ > 310 nm) in the presence of gas phase O3 led to the accelerated release of Br2, BrCl and the release of Cl2 in a process that was significantly enhanced by acidity, high surface area and additional gas phase Br2. Cl2 production was only observed when both light and ozone were present. The total halogen release depended on [O3] and pre-freezing [NaCl]. Our observations support a "halogen explosion" mechanism occurring within the snowpack which is initiated by heterogeneous oxidation, and propagated by Br2 or BrCl photolysis and by recycling of HOBr and HOCl into the snowpack. Our study implicates an important role for active chemistry occurring within the interstitial air of aged (i.e., acidic) snow for halogen activation at polar sunrise.

  19. Photochemical chlorine and bromine activation from artificial saline snow

    NASA Astrophysics Data System (ADS)

    Wren, S. N.; Donaldson, D. J.; Abbatt, J. P. D.

    2013-10-01

    The activation of reactive halogen species - particularly Cl2 - from sea ice and snow surfaces is not well understood. In this study, we used a photochemical snow reactor coupled to a chemical ionization mass spectrometer to investigate the production of Br2, BrCl and Cl2 from NaCl/NaBr-doped artificial snow samples. At temperatures above the NaCl-water eutectic, illumination of samples (λ > 310 nm) in the presence of gas phase O3 led to the accelerated release of Br2, BrCl and the release of Cl2 in a process that was significantly enhanced by acidity, high surface area and additional gas phase Br2. Cl2 production was only observed when both light and ozone were present. The total halogen release depended on [ozone] and pre-freezing [NaCl]. Our observations support a "halogen explosion" mechanism occurring within the snowpack, which is initiated by heterogeneous oxidation and propagated by Br2 or BrCl photolysis and by recycling of HOBr and HOCl into the snowpack. Our study implicates this important role of active chemistry occurring within the interstitial air of aged (i.e. acidic) snow for halogen activation at polar sunrise.

  20. Transport and photochemical modeling. Studies of atmospheric species

    NASA Technical Reports Server (NTRS)

    Natarajan, M.

    1987-01-01

    A program of research studies related to the photochemistry, radiative transfer, and dynamics of the stratosphere is described. Investigations were conducted in two broad areas: (1) studies of the stratospheric processes and their response to external perturbations, and (2) analysis of satellite measurements in conjunction with theoretical models. Contemporary one dimensional photochemical, radiative-convective model was used to assess the impact of perturbations such as solar flux variability, increases in atmospheric carbon dioxide, chlorofluoromethanes and other greenhouse gases. Data from satellite experiments such as LIMS and SBUV, were used along with theoretical models to develop a climatology of trace species in the stratosphere. The consistency of contemporary ozone photochemistry was examined in the light of LIMS data. Research work also includes analysis of stratospheric nitrogen dioxide distributions from different satellite experiments, investigation of the wintertime latitudinal gradients in NO2, estimation of the stratospheric odd nitrogen level and its variability, and studies related to the changes in ozone in the Antarctic, and mid latitude Southern Hemisphere.

  1. Transport and photochemical modeling. Studies of atmospheric species

    SciTech Connect

    Natarajan, M.

    1987-03-01

    A program of research studies related to the photochemistry, radiative transfer, and dynamics of the stratosphere is described. Investigations were conducted in two broad areas: (1) studies of the stratospheric processes and their response to external perturbations, and (2) analysis of satellite measurements in conjunction with theoretical models. Contemporary one dimensional photochemical, radiative-convective model was used to assess the impact of perturbations such as solar flux variability, increases in atmospheric carbon dioxide, chlorofluoromethanes and other greenhouse gases. Data from satellite experiments such as LIMS and SBUV, were used along with theoretical models to develop a climatology of trace species in the stratosphere. The consistency of contemporary ozone photochemistry was examined in the light of LIMS data. Research work also includes analysis of stratospheric nitrogen dioxide distributions from different satellite experiments, investigation of the wintertime latitudinal gradients in NO/sub 2/, estimation of the stratospheric odd nitrogen level and its variability, and studies related to the changes in ozone in the Antarctic, and midlatitude Southern Hemisphere.

  2. A photochemical reactor for studies of atmospheric chemistry

    NASA Astrophysics Data System (ADS)

    Nilsson, E. J. K.; Eskebjerg, C.; Johnson, M. S.

    A photochemical reactor for studies of atmospheric kinetics and spectroscopy has been built at the Copenhagen Center for Atmospheric Research. The reactor consists of a vacuum FTIR spectrometer coupled to a 100 L quartz cylinder by multipass optics mounted on electropolished stainless steel end flanges, surrounded by UV-A, UV-C and broadband sun lamps in a temperature-controlled housing. The combination of a quartz vessel and UV-C lamps allows higher concentrations of O( 1D) and OH than can be generated by similar chambers. The reactor is able to produce radical concentrations of ca. 8 × 10 11 cm -3 for OH, 3 × 10 6 cm -3 for O( 1D), 3.3 × 10 10 cm -3 for O( 3P) and 1.6 × 10 12 cm -3 for Cl. The reactor can be operated at pressures from 10 -3 to 10 3 mbar and temperatures from 240 to 330 K. As a test of the system we have studied the reaction CHCl 3 + Cl using the relative rate technique and find k CHCl3+Cl/k CH4+Cl = 1.03 ± 0.11, in good agreement with the accepted value.

  3. G-Quadruplex Supramolecular Assemblies in Photochemical Upconversion.

    PubMed

    Mutsamwira, Saymore; Ainscough, Eric W; Partridge, Ashton C; Derrick, Peter J; Filichev, Vyacheslav V

    2016-07-18

    Parallel, tetramolecular G-quadruplex (G4) DNA possessing TINA monomer, (R)-1-O-[4-(1-pyrenylethynyl)phenylmethyl]glycerol, were synthesised and evaluated in complexes with tris(2,2'-bipyridine)ruthenium(II), [Ru(bpy)3 ](2+) , and the Zn(2+) derivative of 5,10,15,20-tetrakis-(1-methyl-4-pyridyl)-21 H,23H-porphine, ZnTMpyP4. UV/Vis, fluorescence, and circular dichroism (CD) spectroscopy showed that the use of G4-DNA as a template resulted in the effective communication between the ligands and the TINA molecule that was covalently attached to the 5'-end and between T and dG at the 5'-end of the dTG4 T sequence. Only one G4-DNA possessing the TINA molecule at the 5'-end of the dTG4 T sequence was able to yield a green-to-blue photochemical upconversion (PUC, λem =420 nm) in the presence of [Ru(bpy)3 ](2+) upon excitation at 500 nm. Different DNA secondary structures can thus be used in DNA-based assemblies for PUC and the way of attachment of chromophores to DNA plays a pivotal role for the creation of a photosynthetic centre. PMID:27172273

  4. Synergistic chemotherapy by combined moderate hyperthermia and photochemical internalization

    PubMed Central

    Christie, Catherine; Molina, Stephanie; Gonzales, Jonathan; Berg, Kristian; Nair, Rohit Kumar; Huynh, Khoi; Madsen, Steen J.; Hirschberg, Henry

    2016-01-01

    Combination therapies of photochemical internalization (PCI) and moderate hyperthermia (MHT) were investigated in an in vitro system consisting of human and rat glioma spheroids. PCI using the amphiphilic photosensitizer, AlPcS2a and two anti cancer agents BLM or 5-FU were used. Spheroids were irradiated with λ = 670 nm laser light in an incubator at temperatures ranging from 37 to 44°C. For each temperature investigated, spheroids were divided into 4 groups: control, drug-only, photodynamic therapy (PDT), and PCI. PDT and PCI spheroids were exposed to radiant exposures ranging from 0.3 to 2.5 J cm−2 using an irradiance of 5 mW cm−2. Toxicity was evaluated from spheroid growth kinetics. The combination of PCI and MHT resulted in significant increases in BLM efficacy at 44°C for both cell line derived spheroids compared to controls at 37°C over the range of radiant exposures examined. 5-FU PCI was ineffective for the human cell line at both 37 and 44°C. PMID:27446650

  5. Animal cryptochromes mediate magnetoreception by an unconventional photochemical mechanism.

    PubMed

    Gegear, Robert J; Foley, Lauren E; Casselman, Amy; Reppert, Steven M

    2010-02-11

    Understanding the biophysical basis of animal magnetoreception has been one of the greatest challenges in sensory biology. Recently it was discovered that the light-dependent magnetic sense of Drosophila melanogaster is mediated by the ultraviolet (UV)-A/blue light photoreceptor cryptochrome (Cry). Here we show, using a transgenic approach, that the photoreceptive, Drosophila-like type 1 Cry and the transcriptionally repressive, vertebrate-like type 2 Cry of the monarch butterfly (Danaus plexippus) can both function in the magnetoreception system of Drosophila and require UV-A/blue light (wavelength below 420 nm) to do so. The lack of magnetic responses for both Cry types at wavelengths above 420 nm does not fit the widely held view that tryptophan triad-generated radical pairs mediate the ability of Cry to sense a magnetic field. We bolster this assessment by using a mutant form of Drosophila and monarch type 1 Cry and confirm that the tryptophan triad pathway is not crucial in magnetic transduction. Together, these results suggest that animal Crys mediate light-dependent magnetoreception through an unconventional photochemical mechanism. This work emphasizes the utility of Drosophila transgenesis for elucidating the precise mechanisms of Cry-mediated magnetosensitivity in insects and also in vertebrates such as migrating birds. PMID:20098414

  6. Isotope Fractionation Associated with the Photochemical Dechlorination of Chloroanilines.

    PubMed

    Ratti, Marco; Canonica, Silvio; McNeill, Kristopher; Bolotin, Jakov; Hofstetter, Thomas B

    2015-08-18

    Isotope fractionation associated with the photochemical transformation of organic contaminants is not well understood and can arise not only from bond cleavage reactions but also from photophysical processes. In this work, we investigated the photolytic dechlorination of 2-Cl- and 3-Cl-aniline to aminophenols to obtain insights into the impact of the substituent position on the apparent (13)C and (15)N kinetic isotope effects (AKIEs). Laboratory experiments were performed in aerated aqueous solutions at an irradiation wavelength of 254 nm over the pH range 2.0 to 7.0 in the absence and presence of Cs(+) used as an excited singlet state quencher. Photolysis of 2-Cl-anilinium cations exhibits normal C and inverse N isotope fractionation, while neutral 2-Cl-aniline species shows inverse C and normal N isotope fractionation. In contrast, the photolysis of 3-Cl-aniline was almost insensitive to C isotope composition and the moderate N isotope fractionation points to rate-limiting photophysical processes. (13)C- and (15)N-AKIE-values of 2-Cl-aniline decreased in the presence of Cs(+), whereas those for 3-Cl-aniline were not systematically affected by Cs(+). Our current and previous work illustrates that photolytic dechlorinations of 2-Cl-, 3-Cl-, and 4-Cl-aniline isomers are each accompanied by distinctly different and highly variable C and N isotope fractionation due to spin selective isotope effects. PMID:26196498

  7. Synergistic chemotherapy by combined moderate hyperthermia and photochemical internalization.

    PubMed

    Christie, Catherine; Molina, Stephanie; Gonzales, Jonathan; Berg, Kristian; Nair, Rohit Kumar; Huynh, Khoi; Madsen, Steen J; Hirschberg, Henry

    2016-04-01

    Combination therapies of photochemical internalization (PCI) and moderate hyperthermia (MHT) were investigated in an in vitro system consisting of human and rat glioma spheroids. PCI using the amphiphilic photosensitizer, AlPcS2a and two anti cancer agents BLM or 5-FU were used. Spheroids were irradiated with λ = 670 nm laser light in an incubator at temperatures ranging from 37 to 44°C. For each temperature investigated, spheroids were divided into 4 groups: control, drug-only, photodynamic therapy (PDT), and PCI. PDT and PCI spheroids were exposed to radiant exposures ranging from 0.3 to 2.5 J cm(-2) using an irradiance of 5 mW cm(-2). Toxicity was evaluated from spheroid growth kinetics. The combination of PCI and MHT resulted in significant increases in BLM efficacy at 44°C for both cell line derived spheroids compared to controls at 37°C over the range of radiant exposures examined. 5-FU PCI was ineffective for the human cell line at both 37 and 44°C. PMID:27446650

  8. Methane on Mars: Thermodynamic Equilibrium and Photochemical Calculations

    NASA Technical Reports Server (NTRS)

    Levine, J. S.; Summers, M. E.; Ewell, M.

    2010-01-01

    The detection of methane (CH4) in the atmosphere of Mars by Mars Express and Earth-based spectroscopy is very surprising, very puzzling, and very intriguing. On Earth, about 90% of atmospheric ozone is produced by living systems. A major question concerning methane on Mars is its origin - biological or geological. Thermodynamic equilibrium calculations indicated that methane cannot be produced by atmospheric chemical/photochemical reactions. Thermodynamic equilibrium calculations for three gases, methane, ammonia (NH3) and nitrous oxide (N2O) in the Earth s atmosphere are summarized in Table 1. The calculations indicate that these three gases should not exist in the Earth s atmosphere. Yet they do, with methane, ammonia and nitrous oxide enhanced 139, 50 and 12 orders of magnitude above their calculated thermodynamic equilibrium concentration due to the impact of life! Thermodynamic equilibrium calculations have been performed for the same three gases in the atmosphere of Mars based on the assumed composition of the Mars atmosphere shown in Table 2. The calculated thermodynamic equilibrium concentrations of the same three gases in the atmosphere of Mars is shown in Table 3. Clearly, based on thermodynamic equilibrium calculations, methane should not be present in the atmosphere of Mars, but it is in concentrations approaching 30 ppbv from three distinct regions on Mars.

  9. Photochemical degradation of Corexit components in ocean water.

    PubMed

    Glover, Caitlin M; Mezyk, Stephen P; Linden, Karl G; Rosario-Ortiz, Fernando L

    2014-09-01

    Due to the large quantities of dispersants used during the Deepwater Horizon spill in 2010, there were immediate concerns with regards to the fate and transport of the mixture in ocean waters. Direct and sensitized photolysis experiments were carried out for two compounds chosen as surrogates for the Corexit mixture (9500 and 9527) that were applied to surface waters during the oil spill in the Gulf of Mexico. The results showed that direct photolysis did not contribute significantly to the overall degradation (max ∼30%), therefore the focus shifted to sensitized photolysis, specifically the degradation stemming from the reaction rate with hydroxyl radical (HO). The direct photochemical degradation rates for two of the compounds, dioctyl sulfosuccinate (DOSS) and dipropylene glycol butyl ether (DGBE) were measured as 4.29×10(-6)s(-1) and 5.95×10(-6)s(-1), respectively; whereas the overall degradation rate in ocean water was 1.56×10(-5)s(-1) and 2.23×10(-5)s(-1). The formation rates and apparent quantum yields for HO formation were determined for six ocean water samples. The values ranged from 1.81×10(-5) near shore to 0.061×10(-5) for the open ocean. These degradation rates suggest the possibility for photolysis to play a role in the overall fate of Corexit. PMID:24997971

  10. Dispersion of an urban photochemical plume in Phoenix metropolitan area

    NASA Astrophysics Data System (ADS)

    Lee, Sang-Mi; Fernando, H. J. S.

    2013-12-01

    Air quality simulations were conducted using MM5/CMAQ modeling platform to study the intricacies introduced by photochemical reactions during the dispersion of urban pollution plume of Phoenix metropolis. The simulation days included the sole ozone episode recorded during 1996-2005, which violated the previous 1-h ozone standard (0.12 ppm). The modeling results suggest that the Phoenix urban plume can be described in terms of “inert passive dispersion” and “chemically active dispersion”. The former is exemplified by the CO distribution and takes the form of a Gaussian-like plume, for which the source is located at the ground level of the urban core or a freeway. The passive dispersion, nevertheless, is directly subjected to heterogeneities of topography and flow patterns, and hence cannot be strictly Gaussian. The case of active dispersion is much more complicated, and leads to a different plume shape, depending on the chemical reactivity of pollutant species. Secondary pollutants such as ozone and its precursors cause the plume core to have its maximum concentration far downwind of the urban area. Chemical species such as VOCs, which are directly emitted from a source as well as transformed by other primary pollutants, form a plume that qualitatively resembles a transition from an inert plume (CO) to a highly reactive plume (NOx).

  11. Photochemically and Thermally Cross-Linkable Polyconjugated Systems

    NASA Technical Reports Server (NTRS)

    2000-01-01

    This project focused on the synthesis and characterization of water soluble and/or water-borne electrically conducting polymer systems that could be cross-linked thermally or photochemically. The development of these materials was carried out so that they could be applied as metal and fabric coatings. Polyaniline and polypyrrole were the polymers under investigation. The main impediment preventing commercial development of these polymers is their inherent insolubility. Methods employed to enhance polymer solubility were monomer or polymer modifications. Some post-polymerization modifications were attempted to derivatize the parent polymers, These involved attachment of suitable pendant groups that would enhance polar solvent solubility. The pendant groups of these derivatized polymers were then further reacted to cross-link, rendering the polymer insoluble. The other modifications involved polymerization of monomers in the presence of polyelectrolytic polymers. The acid functionalities of the electrolyte served as a template/dopant for monomer alignment/complexation before polymerization, resulting in a water-borne composite or complex.

  12. Photochemical coal dissolution. Quarterly technical progress report, July 1--September 30, 1995

    SciTech Connect

    Doetschman, D.C.

    1995-12-31

    Examination of the photochemical extractions of the four Argonne Premium Coal Residues has been under way in a routine manner during this last quarter. An unexpectedly great effort last quarter had been necessary to find extraction solvents and photochemical reagents that were photochemically stable and inert. While it is a rather poor thermal extraction solvent, acetonitrile has proven to be the best solvent the authors have examined. In addition to runs with only the acetonitrile solvent present, experiments were performed with the photochemical reagents, benzophenone and pyridine. Both ketone and pyridine triplet states are well-known for their hydrogen abstraction and electron transfer capabilities. The photochemical reagents were used at concentrations resulting in 50% transmission of the light across the reactor pathlength at 320 nm. Experiments with the quartz cutoff filter remain to be completed at concentrations resulting in 50% transmittance at lower wavelengths. Changes in the transmission of light by the column effluent were monitored continuously and the extraction yield by weight was measured by evaporation of the solvent and subtraction of reagent weight. Thermal extraction yields without light under otherwise identical conditions were measured for comparison. As a check on undesirable effects, such as solvent photochemical degradation, otherwise identical light and dark experiments were also done without the coal on the column.

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

    NASA Astrophysics Data System (ADS)

    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.

  14. Diels-Alder Trapping of Photochemically Generated Dienes with Acrylic Esters: A Novel Approach to Photocured Polymer Film Development

    NASA Technical Reports Server (NTRS)

    Ilhan, Faysal; Tyson, Daniel S.; Smith, Deedee; Meador, Mary Ann; Meador, Michael A.

    2004-01-01

    Diels-Alder cycloadditions have often been utilized in polymer synthesis as an alternative to condensation reactions. In our earlier efforts, we developed a new method for the preparation of linear aromatic polyimides, which employs o-quionodimethanes (o-QDMs), generated by a well-known photochemical reaction: the photoenolization of o-methylphenyl ketones. Photolysis of o-methylbenzophenone 1 produces hydroxy-o-quino- diemthane 2, which can be trapped with dienophiles, such as dimethyl acetylenedicarboxylate, to efficiently yield the corresponding cycloadduct (Scheme 1). Here we extend this approach to a novel photocuring process for development of polymer films. We synthesized a series of molecules with multi o-mehtylphenyl ketone functionalities. We further investigated these molecules as photoreactive monomers to obtain polyester films through Diels-Alder cycloadditions.

  15. In vivo photochemical skin micronucleus test using a sunlight simulator: detection of 8-methoxypsoralen and benzo[a]pyrene in hairless mice.

    PubMed

    Hara, Takumi; Nishikawa, Takashi; Sui, Hajime; Kawakami, Kumiko; Matsumoto, Hirotaka; Tanaka, Noriho

    2007-07-10

    Evaluating in vivo photochemical genotoxicity (photogenotoxicity) or photochemical carcinogenicity (photocarcinogenicity) in the skin that is actually exposed to light is important for estimating the risk of human exposure to chemicals under sunlight. With regard to the skin micronucleus test, Nishikawa et al. developed a reliable technique that is simple and in which the negative control has a stable background. In the present study, we applied 8-methoxypsoralen (8-MOP) and benzo[a]pyrene (B[a]P) to the backs of hairless mice and subjected the mice to irradiation by a sunlight simulator in order to investigate whether this test can detect photogenotoxicity of these chemicals. In the treatment with 8-MOP [0.00075% and 0.0015% (w/v)], a significant increase was observed in the frequency of micronucleated cells only under light irradiation using the sunlight simulator. At a high chemical dose, the frequency of micronucleated cells increased from 48h after the treatment, peaked at 96h, and then decreased at 168h. Furthermore, at 96h with the high dose under light irradiation, we frequently observed cells with nuclear buds. In the treatment with B[a]P [first experiment: 0.025% and 0.05% (w/v); second experiment: 0.005%, 0.01%, and 0.02% (w/v)], a significant increase was observed in the frequency of micronucleated cells at skin-irritating doses [0.01%, 0.02%, 0.025%, and 0.05% (w/v)] at 72 or 96h after the treatment only under light irradiation using the sunlight simulator. In conclusion, photogenotoxicity of 8-MOP and B[a]P was detected in the in vivo photochemical skin micronucleus study. PMID:17512241

  16. Aluminosilicates as controlled molecular environments for selective photochemical and catalytic reactions

    SciTech Connect

    Carrado, K.A.

    1986-01-01

    This dissertation concerns research that involves photochemical, catalytic and spectroscopic studies of clays, pillared clays and zeolites. Incorporation of uranyl ions into hectorite, montmorillonite, bentonite and vermiculite clays was monitored by XRD and luminescence methods. Excitation and emission characteristics were studied in order to understand the behavior of uranyl ions in clays after various thermal treatments. Luminescence lifetime measurements elucidated the number of uranyl sites. Uranyl-exchanged clays were found to absorb light at lower energies (445-455nm) than analogous uranyl-exchanged zeolites (425nm). Each uranyl-exchanged clay was tested as a catalyst for the photoassisted oxidation of isopropyl alcohol. Energy transfer (ET) between uranyl and Eu(III) ions in different zeolite framework systems was examined. The efficiency of ET (eta/sub t/) was found to be affected by the type of framework present. Pillared bentonites were examined in the hydrocracking of decane. A catalytically and spectroscopically active dopant ion, Cr(III), was introduced into the clays in both pillared and unpillared forms depending upon synthetic conditions. EPR and DRS were employed to monitor the environment of Cr(III) for determination of its location - whether in the micropore structure or associated with alumina pillars. Catalytic behavior based upon this variability of location was examined. Incorporation of Cr(III) ions into an alumina pillar was found to increase the stability and activity with respect to an alumina PILC catalyst. The results of these studies suggest that selective, efficient catalysts can be designed around inorganic ions in aluminosilicate supports.

  17. Differential characteristics of photochemical acclimation to cold in two contrasting sweet sorghum hybrids.

    PubMed

    Zegada-Lizarazu, Walter; Fernando Luna, Dario; Monti, Andrea

    2016-08-01

    Sweet sorghum has a photosynthetic system which is highly sensitive to cold stress and hence strongly limits its development in temperate environments; therefore, the identification of key exploitable cold tolerance traits is imperative. From a preliminary field trial, two dissimilar sweet sorghum hybrids (ICSSH31 and Bulldozer), in terms of early vigor and productivity, were selected for a controlled-environment trial aiming at identifying useful traits related to acclimation mechanisms to cold stress. The higher cold tolerance of Bulldozer was partially related to a more efficient photochemical regulation mechanism of the incoming light energy: the higher tolerance of photosystem II (PSII) to photo-inactivation was because of a more effective dissipation capacity of the excess of energy and to a more balanced diversion of the absorbed energy into alternative energy sinks. ICSSH31 increased the dissipation and accumulation of a large amount of xanthophylls, as in Bulldozer, but, at the same time, inactivated the oxygen evolving complex and the re-synthesis of chlorophyll (Chl) a and b, thus, leading to an overproduction of CO2 fixation enzymes after re-warming. In summary, in Bulldozer, the acclimation adjustments of the photosynthetic apparatus occurred through an efficient control of energy transfer toward the reaction centers, and this likely allowed a more successful seedling establishment; ICSSH31, conversely, exhibited a fast re-synthesis of Chl pigments, which appears to divert photosynthates from dry matter accumulation. Such broad acclimation traits may constitute a source for selecting higher genetic gain traits relevant for enlarging the growing season of promising biomass sorghum ideotypes in temperate climates. PMID:26867791

  18. THERMOCHEMICAL AND PHOTOCHEMICAL KINETICS IN COOLER HYDROGEN-DOMINATED EXTRASOLAR PLANETS: A METHANE-POOR GJ436b?

    SciTech Connect

    Line, Michael R.; Yung, Yuk L.; Vasisht, Gautam; Chen, Pin; Angerhausen, D. E-mail: gv@s383.jpl.nasa.gov

    2011-09-01

    We introduce a thermochemical kinetics and photochemical model. We use high-temperature bidirectional reaction rates for important H, C, O, and N reactions (most importantly for CH{sub 4} to CO interconversion), allowing us to attain thermochemical equilibrium, deep in an atmosphere, purely kinetically. This allows the chemical modeling of an entire atmosphere, from deep-atmosphere thermochemical equilibrium to the photochemically dominated regime. We use our model to explore the atmospheric chemistry of cooler (T{sub eff} < 10{sup 3} K) extrasolar giant planets. In particular, we choose to model the nearby hot-Neptune GJ436b, the only planet in this temperature regime for which spectroscopic measurements and estimates of chemical abundances now exist. Recent Spitzer measurements with retrieval have shown that methane is driven strongly out of equilibrium and is deeply depleted on the day side of GJ436b, whereas quenched carbon monoxide is abundant. This is surprising because GJ436b is cooler than many of the heavily irradiated hot Jovians and thermally favorable for CH{sub 4}, and thus requires an efficient mechanism for destroying it. We include realistic estimates of ultraviolet flux from the parent dM star GJ436, to bound the direct photolysis and photosensitized depletion of CH{sub 4}. While our models indicate fairly rich disequilibrium conditions are likely in cooler exoplanets over a range of planetary metallicities, we are unable to generate the conditions for substantial CH{sub 4} destruction. One possibility is an anomalous source of abundant H atoms between 0.01 and 1 bars (which attack CH{sub 4}), but we cannot as yet identify an efficient means to produce these hot atoms.

  19. Rapid photochemical equilibration of isotope bond ordering in O2

    NASA Astrophysics Data System (ADS)

    Yeung, Laurence Y.; Ash, Jeanine L.; Young, Edward D.

    2014-09-01

    The abundances of 18O18O and 17O18O in the atmosphere were recently found to be enriched relative to the stochastic distribution of isotopes in O2. The enrichment is believed to arise from O(3P) + O2 isotope exchange reactions, which reorder the isotopes in O2 to a distribution that favors bonds between heavy isotopes. Theoretical predictions and laboratory experiments suggest that the reordered distribution of isotopes should reflect internal isotopic equilibrium, but a laboratory test of this hypothesis for the complete O2 isotopologue system has not yet been realized. Here we use a simple photochemical experiment that reorders the isotopes in O2 at temperatures between 200 K and 350 K. Using simultaneous measurements of five O2 isotopologues, we show that O(3P) + O2 reorders the isotopes in O2 to isotopic equilibrium. Furthermore, we use this scheme to calibrate measurements of isotopic ordering in samples of O2, obtaining Δ36 and Δ35 values within ±0.1‰. Measurements of atmospheric O2 sampled at the University of California, Los Angeles, from 2012 to 2014 have mean values of Δ36 = 1.97 ± 0.07‰ and Δ35 = 1.0 ± 0.1‰ (2 SE; n = 23), with no detectable long-term trend. These measurements are consistent with values for air reported earlier, but with a threefold to fourfold improvement in precision. Together, the experiments and observations support the case that isotopic ordering in tropospheric O2 is altered by O(3P) + O2; however, they also suggest that tropospheric Δ36 and Δ35 values do not reflect complete isotopic equilibration in the troposphere. Isotopic ordering in atmospheric O2 likely reflects the decadal-scale balance of stratospheric and tropospheric air masses modulated by variations in tropospheric photochemistry and convection.

  20. Sensitivity of Urban Photochemical Models to Upper Wind Measurements

    NASA Astrophysics Data System (ADS)

    Al-Wali, Khalid Ibrahim

    1995-01-01

    The 1992 Atlanta Field Intensive of the Southern Oxidants Research Program on Ozone Non-Attainment (SORP -ONA) provided a unique data set of urban meteorological measurements. The data were used to investigate the sensitivity of photochemical model results to the spatial and temporal resolution of upper-air meteorological measurements. Root Mean Square Differences (RMSD) and average absolute deviations for winds and model calculated rm NO_ {y} and rm O_3 values were computed for a variety of measurement strategies which differed in the spatial and temporal resolution of the upper-air data. A Lagrangian particle dispersion model (LPDM) was used to study the movement of the plumes from the Atlanta urban core and an elevated power plant located northwest of Atlanta. Scenarios with different sets of wind measurements were performed. The results show that placement of upper-air measurements at or near the center of emissions density should be highest priority of field measurements campaigns. A prognostic model, the Regional Atmospheric Modeling System (RAMS), was used to generate the three dimensional winds to run the UAM. Results from the UAM runs also support the conclusion that upper-air measurements at or near the center of emissions density should be highest priority of field measurements campaigns. A number of Large Eddy Simulations (LES) were performed for urban forested and unforested areas with different soil moisture to examine the extent of the thermals that represent the height of the mixed layer. Results from the LES runs show that simulations with dry soil produce higher sensible heat flux and stronger thermals with a deeper mixed layer than simulations with moister soil. LES runs also showed that sensible heat fluxes, vertical motion, and mixing is weaker over forested areas compared to over urban areas. Three methods were used to calculate the height of the convective mixed layer. Differences of up to 200 m were found between the three methods.

  1. Photochemical Activation of Chlorine by Iron and Iron Oxide Aerosol

    NASA Astrophysics Data System (ADS)

    Wittmer, J.; Zetzsch, C.

    2015-12-01

    The photochemical activation of chlorine by dissolved iron in sea-salt aerosol droplets and by highly dispersed Fe2O3 aerosol particles (mainly hematite, specific surface > 100 m2/g), exposed to gaseous HCl, was investigated in humidified air in a Teflon simulation chamber. Employing the radical-clock technique, we quantified the production of gaseous atomic Cl. When the artificial sea salt aerosols contained suspended Fe2O3 alone at pH 6, no significant Cl production could be observed, even if the dissolution of iron was forced by "weathering" (repeatedly freezing and thawing for five times). Adjusting the pH in the stock suspension to 2.6, 2.2, and 1.9 and equilibrating for one week resulted in a quantifiable amount of dissolved iron (0.03, 0.2, and 0.6 mmol/L, respectively) and in gaseous Cl production rates of ~1.6, 6, and 8 × 1021 atoms cm-2 h-1, respectively. Exposing the pure Fe2O3 aerosol in the absence of salt to various gaseous HCl concentrations resulted in rates ranging from 8 × 1020 Cl atoms cm-2 h-1 (at ~4 ppb HCl) to 5 × 1022 Cl atoms cm-2 h-1 (at ~350 ppb HCl) and confirmed the uptake and conversion of HCl to atomic Cl (at HCl to Cl conversion yields of 2-5 % mol/mol, depending on the relative humidity). The relevance for environmental processes in the atmosphere will be discussed.

  2. Pluto Photochemical Models for the New Horizons Flyby

    NASA Astrophysics Data System (ADS)

    Gladstone, R.; Wong, M. L.; Yung, Y. L.

    2014-12-01

    During the New Horizons flyby of the Pluto system on July 14, 2015 a number of observations will be made to determine the structure, composition, and variability of Pluto's atmosphere. A key observation of this type is the Alice solar occultation, which will measure the full disk ultraviolet (52-187 nm) spectral flux from the Sun through ingress and egress behind Pluto, about one hour after closest approach. This observation will be used to determine the temperature and vertical density profiles of N2, CH4, and various minor species above two regions of very different surface albedo. Nearly simultaneous Earth ingress and egress occultations observed in X-band uplink will provide profiles of temperature and pressure in Pluto's lower atmosphere, and electron densities in the ionosphere. Wave structures in both the solar and radio occultation data will provide constraints on atmospheric dynamics. In order to interpret and understand these data sets, we have modified a 1-D Titan photochemical model to Pluto, for the epoch of the New Horizons flyby. The model uses a similar, but updated reaction list to that of Krasnopolsky and Cruikshank [1999] and Wong et al. [2014], and adopts the results of Zhu et al. [2014] for the background atmosphere. We present here initial results for several assumed eddy diffusion profiles. Krasnopolsky, V. A., and D. P. Cruikshank, J. Geophys. Res., 104, 21,979, 1999. Wong, M. L., Y. L. Yung, and G. R. Gladstone, Icarus, in press, 2014. Zhu, X., D F. Strobel, and J. T. Erwin, Icarus, 228, 301, 2014.

  3. Photochemical Thrombosis Of Retinal And Choroidal Vessels Using Rose Bengal

    NASA Astrophysics Data System (ADS)

    Lewis, Mary Lou; Winward, Kirk; Watson, Brant D.; Hernandez, Eleut

    1989-09-01

    Rose bengal is an effective photosensitizing agent which interacts with argon green light to induce photochemical thrombosis of irradiated vessels. We used focal, low energy irradiation to occlude retinal and choroidal vessels in both albino and pigmented rabbits. Immediately after intravenous injection of rose bengal at concentrations of 10 and 20 mg/kg, irradiation was performed via a slit lamp-delivered argon green laser (514.5 nm) with the aid of fundus contact lens. In 11 eyes, arteries were treated with 50-100 interrupted bursts of 75u spot size at 0.2 sec and 40-100 mW (9

  4. Photochemical internalization for the treatment of malignant gliomas

    NASA Astrophysics Data System (ADS)

    Madsen, Steen J.; Kharkhuu, Khishigzaya; Berg, Kristian; Hirschberg, Henry

    2007-02-01

    Photochemical internalization (PCI) is a technique to improve the utilization of macromolecules (e.g. chemotherapeutic agents) in cancer therapy in a site-specific manner. The concept is based on the use of specially designed photosensitizers which localize preferentially in the membranes of endocytic vesicles. Upon exposure to light the photosensitizers induce the formation of reactive oxygen species such as singlet molecular oxygen. The photooxidation of the endocytic membranes leads to the release of the contents of the vesicles into the cytosol. In this way, macromolecules encapsulated by the vesicles will reach the cytosol and exert their biological activity instead of being degraded by lysosomal hydrolases. The utility of PCI for the treatment of malignant gliomas was investigated in vitro using an F98 rat glioma cell line. The cytotoxicity of 5-aminolevulinic acid (ALA) based PCI of bleomycin was compared to: (1) ALA-PDT, and (2) bleomycin. In all cases, monolayers were incubated in ALA, bleomycin, or ALA + bleomycin for 4 hours and were subsequently exposed to 635 nm light. Toxicity was evaluated using colony formation assays. F98 rat glioma cells in monolayer were found to be susceptible to the effects of both ALA-PDT and bleomycin. ALA-PDT was found to be particularly effective when light was delivered at a low irradiance of 5 mW cm -2. In this case, a radiant exposure of 20 J cm -2 resulted in only 4% survival. Bleomycin was found to be toxic at relatively low concentrations, incubation of F98 cells in 10 μg ml -1 for 4 hours resulted in 1% survival. The PCI effect was found to be negligible for the parameters investigated in the F98 cell line suggesting that: (1) the incubation time was sub-optimal and/or (2) ALA was inappropriate for this application.

  5. Synthesis, Photochemical and Photoinduced Antibacterial Activity Studies of meso-Tetra(pyren-1-yl)porphyrin and its Ni, Cu and Zn Complexes

    PubMed Central

    Zoltan, Tamara; Vargas, Franklin; Rivas, Carlos; López, Verónica; Perez, Jhackelym; Biasutto, Antonio

    2010-01-01

    The synthesis of the meso-tetra(pyren-1-yl)porphyrin (1) was successfully accomplished by means of the pyrrole condensation with pyrene-1-carb-aldehyde in acidic media. Its metallization was carried out in an almost quantitative yield to obtain the corresponding complexes of Ni(II) (2), Cu(II) (3) and Zn (4). Their photophysical properties such as fluorescence quantum yield and energy transfer to oxygen for an efficient generation of singlet oxygen were determined. Their photophysical and photochemical properties were compared with those of other similar porphyrin derivatives such as tetraphenylporphyrin and tetranaphthylporphyrin. Photochemical studies on their effectiveness as photosensitizer were carried out by means of the photoinduced oxidation of aromatic alcohols like α-naphthol to naphthoquinone. The antibacterial photoactivity assay for compounds 1–4 was testeted against Escherichia coli (ATCC 8739) and its proliferation and viability were measured by chemiluminescence. An efficient inactivation of E. coli was observed. This was more efficient for compounds 2 and 3, following the direct relationship to high generation of singlet oxygen by these compounds. PMID:21179316

  6. A Systematic Evaluation of the Extent of Photochemical Processing in Different Types of Secondary Organic Aerosols in the Aqueous Phase

    NASA Astrophysics Data System (ADS)

    Romonosky, D.; Lee, H.; Epstein, S. A.; Nizkorodov, S.; Laskin, J.; Laskin, A.

    2013-12-01

    A significant fraction of atmospheric organic compounds are predominantly found in condensed phases, such as organic phase in aerosol particles or aqueous phase in cloud droplets. The oxidation of VOCs followed by the condensation of products into particles was thought to be the main mechanism of organic aerosol (OA) formation. However, in the last several years, scientists have realized that a large fraction, if not the majority of organic particles, is produced through cloud and fog photochemical processes. Many of these organic compounds are photolabile, and can degrade through direct photolysis or indirect photooxidation processes on time scales that are comparable to the typical lifetimes of droplets (hours) and particles (days). We previously reported that compounds in secondary organic aerosol (SOA) from ozonolysis of d-limonene efficiently photodegrade in both organic (Walser et al., 2007) and aqueous phases (Bateman et al., 2011). Significant photolysis was also observed in an aqueous extract of SOA from high-NOx photooxidation of isoprene (Nguyen et al., 2012). More recent experiments studying the response to irradiation of complex aqueous mixtures (as opposed to solutions of isolated compounds) found surprising resilience to photodegradation in aqueous extracts of SOA prepared by photooxidation of alpha-pinene (Romonosky et al., unpublished). We present a systematic investigation of the extent of photochemical processing in different types of SOA from various biogenic and anthropogenic precursors. Chamber- or flowtube-generated SOA is collected on an inert substrate, extracted in a methanol/water solution (70:30), photolyzed in the aqueous solution, and the extent of change in the molecular level composition of the material is assessed with high-resolution mass spectrometry (HR-MS). The outcome of this study will be improved understanding of the role of condensed-phase photochemistry in chemical aging of aerosol particles and cloud droplets. Bateman et

  7. Photochemical products in urban mixtures enhance inflammatory responses in lung cells.

    PubMed

    Sexton, Kenneth G; Jeffries, Harvey E; Jang, Myoseon; Kamens, Richard M; Doyle, Melanie; Voicu, Iuliana; Jaspers, Ilona

    2004-01-01

    Complex urban air mixtures that realistically mimic urban smog can be generated for investigating adverse health effects. "Smog chambers" have been used for over 30 yr to conduct experiments for developing and testing photochemical models that predict ambient ozone (O(3)) concentrations and aerosol chemistry. These chambers were used to generate photochemical and nonirradiated systems, which were interfaced with an in vitro exposure system to compare the inflammatory effects of complex air pollutant mixtures with and without sunlight-driven chemistry. These are preliminary experiments in a new project to study the health effects of particulate matter and associated gaseous copollutants. Briefly, two matched outdoor chambers capable of using real sunlight were utilized to generate two test atmospheres for simultaneous exposures to cultured lung cells. One chamber was used to produce a photochemically active system, which ran from sunrise to sunset, producing O(3) and the associated secondary products. A few hours after sunset, NO was added to titrate and remove completely the O(3), forming NO(2). In the second chamber, an equal amount of NO(2) and the same amount of the 55-component hydrocarbon mixture used to setup the photochemical system in the first side were injected. A549 cells, from an alveolar type II-like cell line grown on membranous support, were exposed to the photochemical mixture or the "original" NO(2)/hydrocarbon mixture for 5 h and analyzed for inflammatory response (IL-8 mRNA levels) 4 h postexposure. In addition, a variation of this experiment was conducted to compare the photochemical system producing O(3) and NO(2), with a simple mixture of only the O(3) and NO(2). Our data suggest that the photochemically altered mixtures that produced secondary products induced about two- to threefold more IL-8 mRNA than the mixture of NO(2) and hydrocarbons or O(3). These results indicate that secondary products generated through the photochemical reactions

  8. Gauging triple stores with actual biological data

    PubMed Central

    2012-01-01

    Background Semantic Web technologies have been developed to overcome the limitations of the current Web and conventional data integration solutions. The Semantic Web is expected to link all the data present on the Internet instead of linking just documents. One of the foundations of the Semantic Web technologies is the knowledge representation language Resource Description Framework (RDF). Knowledge expressed in RDF is typically stored in so-called triple stores (also known as RDF stores), from which it can be retrieved with SPARQL, a language designed for querying RDF-based models. The Semantic Web technologies should allow federated queries over multiple triple stores. In this paper we compare the efficiency of a set of biologically relevant queries as applied to a number of different triple store implementations. Results Previously we developed a library of queries to guide the use of our knowledge base Cell Cycle Ontology implemented as a triple store. We have now compared the performance of these queries on five non-commercial triple stores: OpenLink Virtuoso (Open-Source Edition), Jena SDB, Jena TDB, SwiftOWLIM and 4Store. We examined three performance aspects: the data uploading time, the query execution time and the scalability. The queries we had chosen addressed diverse ontological or biological questions, and we found that individual store performance was quite query-specific. We identified three groups of queries displaying similar behaviour across the different stores: 1) relatively short response time queries, 2) moderate response time queries and 3) relatively long response time queries. SwiftOWLIM proved to be a winner in the first group, 4Store in the second one and Virtuoso in the third one. Conclusions Our analysis showed that some queries behaved idiosyncratically, in a triple store specific manner, mainly with SwiftOWLIM and 4Store. Virtuoso, as expected, displayed a very balanced performance - its load time and its response time for all the

  9. Characteristics of atmospheric particles over urban city Osaka occasionally covered with photochemical smog

    NASA Astrophysics Data System (ADS)

    Sano, Itaru

    The photochemical smog events, which are affected by transported air pollutants, become to be more frequent and heavier in Japan. Thereby the photochemical smog is observed not only at urban areas but also at remote islands. The long range transported pollutant influences on the local atmospheric condition mixed with the locally emitted gases and particulates. It is known that intensive solar radiation in summer seasons changes the nitrogen oxide gases into oxidant through photochemical processes. This work intends to investigate what are the aerosol characteristics in photochemical smog events at Osaka. Osaka is a part of Kansai industrial area, which is the second megalopolis in Japan and surrounded by the backside mountains. Therefore lots of anthropogenic emissions often remain in the atmosphere over the cities. The radiometric observations with Cimel CE-318 sun/sky and the measurements of PM1, PM2.5 and PM10 mass concentration at Kinki University in Osaka provide us with effective information of atmospheric particles. The other in-situ measurements such as SOx, NOx, Ox, HC and weather conditions taken by local governmental office are available for analysis of photochemical smog events. Further a backward trajectory based on NOAA HYSPLIT looks promising to help us with our comprehensive investigation of long range transported pollutants.

  10. Does free-air carbon dioxide enrichment affect photochemical energy use by evergreen trees in different seasons? A chlorophyll fluorescence study of mature loblolly pine

    SciTech Connect

    Hymus, G.J.; Ellsworth, D.S.; Baker, N.R.; Long, S.P.

    1999-08-01

    Previous studies of the effects of growth at elevated CO{sup 2} on energy partitioning in the photosynthetic apparatus have produced conflicting results. The hypothesis was developed and tested that elevated CO{sub 2} increases photochemical energy use when there is a high demand for assimilates and decreases usage when demand is low. Modulated chlorophyll a fluorescence and leaf gas exchange were measured on needles at the tope of a mature, 12-m loblolly pine (Pinus taeda L.l) forest. Trees were exposed to ambient CO{sub 2} or ambient plus 20 Pa CO{sub 2} using free-air CO{sub 2} enrichment. During April and August, periods of shoot growth, light-saturated photo-synthesis and linear electron transport were increased by elevated CO{sub 2}. In November, when growth had ceased but temperatures were still moderate, CO{sub 2} treatment had no significant effect on linear electron transport. In February, when low temperatures were likely to inhibit translocation, CO{sub 2} treatment caused a significant decrease in linear electron transport. This coincided with a slower recovery of the maximum photosystem II efficiency on transfer of needles to the shade, indicating that growth in elevated CO{sub 2} induced a more persistent photoinhibition. Both the summer increase and the winter decrease in linear electron transport in elevated CO{sub 2} resulted from a change in photochemical quenching, not in the efficiency of energy transfer within the photosystem II antenna. There was no evidence of any effect of CO{sub 2} on photochemical energy sinks other than carbon metabolism. Their results suggest that elevated CO{sub 2} may increase the effects of winter stress on evergreen foliage.

  11. 2-Diazo-1-(4-hydroxyphenyl)ethanone: A Versatile Photochemical and Synthetic Reagenta

    PubMed Central

    Senadheera, Sanjeewa N.; Evans, Anthony S.; Toscano, John P.; Givens, Richard S.

    2014-01-01

    α-Diazo arylketones are well-known substrates for Wolff rearrangement to phenylacetic acids through a ketene intermediate by either thermal or photochemical activation. Likewise, α-substituted p-hydroxyphenacyl (pHP) esters are substrates for photo-Favorskii rerrangements to phenylacetic acids by a different pathway that purportedly involves a cyclopropanone intermediate. In this paper, we show that the photolysis of a series of α-diazo-p-hydroxyacetophenones and p-hydroxyphenacyl (pHP) α-esters both generate the identical rearranged phenylacetates as major products. Since α-diazo-p-hydroxyacetophenone (1a, pHP N2) contains all the necessary functionalities for either Wolff or Favorskii rearrangement, we were prompted to probe this intriguing mechanistic dichotomy under conditions favorable to the photo-Favorskii reangement, i.e., photolysis in hydroxylic media. An investigation of the mechanism for conversion of 1a to p-hydroxyphenyl acetic acid (4a) using time-resolved infrared (TRIR) spectroscopy clearly demonstrates the formation of a ketene intermediate that is subsequently trapped by solvent or nucleophiles. The photoreaction of 1a is quenched by oxygen and sensitized by triplet sensitizers and the quantum yields for 1a–c range from 0.19 to a robust 0.25. The lifetime of the triplet, determined by Stern-Volmer quenching, is 15 ns with a rate for appearance of 4a of k = 7,1 × 106 s−1 in aq. acetonitrile (1:1 v:v). These studies establish that the primary rearrangement pathway for 1a involves ketene formation in accordance with the photo-Wolff rearrangement. Furthermore we have also demonstrated the synthetic utility of 1a as an esterification and etherification reagent with a variety of substituted α-diazo-p-hydroxyacetophenones, using them as synthons for efficiently coupling it to acids and phenols to produce pHP protect substrates. PMID:24305682

  12. Management of Spent Organic Ion-Exchange Resins by Photochemical Oxidation

    SciTech Connect

    Srinivas, C.; Sugilal, S.; Wattal, P. K.

    2003-02-26

    Management of spent ion-exchange resin waste arising from nuclear reactor operations by traditional practice of encapsulation in cement is associated with problems such as swelling and disintegration. Complete oxidation (mineralization) is an attractive alternative option. This paper reports the development of photochemical mineralization process for organic ion-exchange resins of poly (styrene-divinyl benzene) type with sulfonic acid and quaternary ammonium functional groups. It is a two-step process consisting of dissolution (conversion of solid resin into water-soluble reaction products) and photo-Fenton mineralization of the dissolved resin. Cation and anion resin dissolution was effected by reaction of the resin with H2O2 at 50-60 C in the presence of ferrous/copper sulphate catalyst. Direct dissolution of mixed resin was not efficient. However, the cation resin portion in the mixed resin could be selectively dissolved without affecting the anion portion. The solid anion resin after separation from the cation resin solution could be dissolved. About 0.5 liters of 50% H2O2 was required for dissolution of one kg of wet resin. The reaction time was 4-5 hours. Dissolution experiments were conducted on up to 8 liters of wet resin. The second step, viz., photo-Fenton mineralization of the dissolved resin was effected at ambient temperature(25-35 C). Kinetic results of laboratory scale experiments in immersion type photo-reactor and pilot scale experiments in tubular flow photo-reactor were presented. These results clearly demonstrated the photo-Fenton mineralization of dissolved resin at ambient temperature with stoichiometric quantity of H2O2 as against 70-200% excess H2O2 requirement in chemical mineralization experiments under Fenton oxidation conditions at 90-95 C. Based on these studies, a treatment scheme was developed and presented in this paper.

  13. Selective disruption of the blood-brain barrier by photochemical internalization

    NASA Astrophysics Data System (ADS)

    Hirschberg, Henry; Zhang, Michelle J.; Gach, Michael H.; Uzal, Francisco A.; Chighvinadze, David; Madsen, Steen J.

    2009-02-01

    Introduction: Failure to eradicate infiltrating glioma cells using conventional treatment regimens results in tumor recurrence and is responsible for the dismal prognosis of patients with glioblastoma multiforme (GBM). This is due to the fact that these migratory cells are protected by the blood-brain barrier (BBB) which prevents the delivery of most anti-cancer agents. We have evaluated the ability of photochemical internalization (PCI) to selectively disrupt the BBB in rats. This will permit access of anti-cancer drugs to effectively target the infiltrating tumor cells, and potentially improve the treatment effectiveness for malignant gliomas. Materials and Methods: PCI treatment, coupling a macromolecule therapy of Clostridium perfringens (Cl p) epsilon prototoxin with AlPcS2a-PDT, was performed on non-tumor bearing inbred Fisher rats. T1-weighted post-contrast magnetic resonance imaging (MRI) scans were used to evaluate the extent of BBB disruption which can be inferred from the volume contrast enhancement. Results: The synergistic effect of PCI to disrupt the BBB was observed at a fluence level of 1 J with an intraperitoneal injection of Cl p prototoxin. At the fluence level of 2.5J, the extent of BBB opening induced by PCI was similar to the result of PDT suggesting no synergistic effect evoked under these conditions. Conclusion: PCI was found to be highly effective and efficient for inducing selective and localized disruption of the BBB. The extent of BBB opening peaked on day 3 and the BBB was completed restored by day 18 post treatment.

  14. Sensitivity analysis of photochemical ozone to its precursor emissions over East Asia by CMAQ-DDM

    NASA Astrophysics Data System (ADS)

    Itahashi, S.; Uno, I.; Kim, S.

    2011-12-01

    In the past three decades, anthropogenic emissions in East Asia have increased dramatically in parallel with the economic growth, and the trans-boundary air pollution arose as a concerning issue. For instance, high photochemical oxidant (over 120 ppbv) was observed at the remote clean island in Japan during 2007 springtime. In this event, many studies concluded that the high possibility of the impact of Asian-scale trans-boundary pollutants. To investigate the source-receptor relationships, modeling study is useful, however, if the chemical reaction involves the nonlinear response (e.g., ozone), to estimate its S-R relationships is quite difficult. The decoupled direct method (DDM) which was implemented in CMAQ ver. 4.7.1 is an efficient and accurate way of performing sensitivity analysis to model inputs. CMAQ-DDM has been extended to higher-order (HDDM) for gas-phase, and calculates first and second-order sensitivity coefficients representing the responsiveness of atmospheric chemical concentrations to perturbations in a model input or parameter (e.g., emission, reaction rate, initical condition, or boundary condition). This applications are well conducted in the U.S., whereas it is not fully examined in East Asia. In this study, we apply CMAQ-DDM technique for ozone and its precursor pollutants in East Asia. In the case of trans-boundary air pollution episode occurred on 7-9 May, 2007, the 1st order ozone sensitivity to the anthropogenic NOx emissions from China show the positive value in almost part over East Asia, namely represent the NOx-sensitive region, whereas in the large-point sources in China (e.g., Beijing and Shanghai), it shows the negative value due to the ozone titration by NO. We will also report more detailed region specified S-R analysis and cross-sensitivity analysis between NOx and VOC over China, Korea and Japan.

  15. Experimental Results on the Destruction of PCE using a Photo-Chemical Remediation Reactor

    NASA Astrophysics Data System (ADS)

    Lee, J. J.; Lee, K. Y.; Stencel, J. R.; Khinast, J.

    2001-12-01

    A vapor-phase tetrachloroethylene (PCE) destruction experiment using a newly constructed photo-chemical remediation (PCR) reactor is performed. One of the applications for the PCR reactor is subsurface remediation of volatile organic compounds (VOCs). Ultraviolet (UV) light, when emitted at an effective absorption frequency (primary wavelengths of 185 and 254 nm), cleaves a VOC's carbon-chlorine bond thus reducing harmful contaminants to harmless products. The PCR reactor consists of a stainless steel tubular vessel with internal dimensions 0.32 m in diameter and 1.05 m in length. Sixteen Suprasil glass sleeves (Heraeus Inc.) with external dimensions of 25 mm in diameter and 1.1 m in length are inserted along the length of the reactor. The Suprasil sleeves are positioned in a geometrical pattern to provide maximum UV exposure. An amalgam UV lamp (Heraeus Inc. NIQ 200/110) is placed inside every Suprasil sleeve. Each UV lamp has its own igniter and ballast for versatile power control. The Suprasil sleeves provide barrier protection between the UV lamps and the vapor-phase contaminant, and at the same time allow transmission of UV light to the interior of the PCR reactor. A gas heater is installed to increase the influent vapor-phase temperature and the PCR reactor is insulated to minimize heat loss. However, the PCE destruction experiment is presently being performed without the aid of the gas heater. During the experiment, the PCR reactor temperature reached in excess of 200 degrees Celsius from heat generated from the UV lamps. Vapor-phase samples are collected at the influent and effluent reactor sampling ports prior and after UV lamp ignitions. Preliminary results show good PCE destruction efficiency for the range of influent PCE concentrations considered in this study.

  16. Testing the early Mars H2-CO2 greenhouse hypothesis with a 1-D photochemical model

    NASA Astrophysics Data System (ADS)

    Batalha, Natasha; Domagal-Goldman, Shawn D.; Ramirez, Ramses; Kasting, James F.

    2015-09-01

    A recent study by Ramirez et al. (Ramirez, R.M. et al. [2014]. Nat. Geosci. 7(1), 59-63.) demonstrated that an atmosphere with 1.3-4 bar of CO2 and H2O, in addition to 5-20% H2, could have raised the mean annual and global surface temperature of early Mars above the freezing point of water. Such warm temperatures appear necessary to generate the rainfall (or snowfall) amounts required to carve the ancient martian valleys. Here, we use our best estimates for early martian outgassing rates, along with a 1-D photochemical model, to assess the conversion efficiency of CO, CH4, and H2S to CO2, SO2, and H2. Our outgassing estimates assume that Mars was actively recycling volatiles between its crust and interior, as Earth does today. H2 production from serpentinization and deposition of banded iron-formations is also considered. Under these assumptions, maintaining an H2 concentration of ˜1-2% by volume is achievable, but reaching 5% H2 requires additional H2 sources or a slowing of the hydrogen escape rate below the diffusion limit. If the early martian atmosphere was indeed H2-rich, we might be able to see evidence of this in the rock record. The hypothesis proposed here is consistent with new data from the Curiosity Rover, which show evidence for a long-lived lake in Gale Crater near Mt. Sharp. It is also consistent with measured oxygen fugacities of martian meteorites, which show evidence for progressive mantle oxidation over time.

  17. Factors controlling the redox potential of ZnCe6 in an engineered bacterioferritin photochemical 'reaction centre'.

    PubMed

    Mahboob, Abdullah; Vassiliev, Serguei; Poddutoori, Prashanth K; van der Est, Art; Bruce, Doug

    2013-01-01

    Photosystem II (PSII) of photosynthesis has the unique ability to photochemically oxidize water. Recently an engineered bacterioferritin photochemical 'reaction centre' (BFR-RC) using a zinc chlorin pigment (ZnCe6) in place of its native heme has been shown to photo-oxidize bound manganese ions through a tyrosine residue, thus mimicking two of the key reactions on the electron donor side of PSII. To understand the mechanism of tyrosine oxidation in BFR-RCs, and explore the possibility of water oxidation in such a system we have built an atomic-level model of the BFR-RC using ONIOM methodology. We studied the influence of axial ligands and carboxyl groups on the oxidation potential of ZnCe6 using DFT theory, and finally calculated the shift of the redox potential of ZnCe6 in the BFR-RC protein using the multi-conformational molecular mechanics-Poisson-Boltzmann approach. According to our calculations, the redox potential for the first oxidation of ZnCe6 in the BRF-RC protein is only 0.57 V, too low to oxidize tyrosine. We suggest that the observed tyrosine oxidation in BRF-RC could be driven by the ZnCe6 di-cation. In order to increase the efficiency of tyrosine oxidation, and ultimately oxidize water, the first potential of ZnCe6 would have to attain a value in excess of 0.8 V. We discuss the possibilities for modifying the BFR-RC to achieve this goal. PMID:23935866

  18. Photochemical modification of polymeric materials and the polarization of light in ionomeric guest/host systems

    NASA Astrophysics Data System (ADS)

    Pan, Bo

    Photochemical methods were introduced to develop important extrusion processes, through which polymers can either be functionalized or modified by altering molecular weight characteristics. Therefore, poly(methyl methacrylate) (PMMA) incorporated with a small amount of light-reactive functional groups was synthesized. These functional groups can be activated by UV irradiation in a post extrusion process to produce high molecular weight polymer and/or crosslinked polymer. Environmental stress cracking resistance of these polymers was examined and correlated to damping using dynamic mechanic analysis. To improve industrial reactive extrusion process of preparing maleic anhydride grafted polypropylene (MAR-g-PP), photografting was proposed and studied. Using benzophenone (BP) as the initiator, grafting efficiency was significantly improved compared to peroxide initiated grafting. Moreover, nearly constant conversion of maleic anhydride was observed in photografting. The high efficiency of benzophenone initiated photografting was attributed to the formation of the excited triplet state maleic anhydride. A rate constant of 6.0*109 M-1*sec-1 for the quenching of triplet state BP with MAH was obtained using laser photolysis spectroscopy. In a comparison, the hydrogen abstraction process from polypropylene by the triplet state BP molecules has a rate constant of 4.1*105 M-1*sec-1. In solution grafting with the use of benzene as the solvent, a facile triplet state energy transfer process may also occur leading to the formation of the excited triplet state MAH. Spectroscopic methods involving light were also used for the study of the guest-host interactions in polymer systems. The use of ionomers as the matrix for the oriented guest/host systems, cationic dye systems in particular, was shown to enhance polarization efficiency as well as dye uptake as comparing to conventional polymers, such as poly(vinyl alcohol). It was found that the dye molecules in carboxylated EVOH

  19. Photochemical dynamics of surface oriented molecules. Progress report, August 1, 1991--July 31, 1992

    SciTech Connect

    Ho, W.

    1992-09-01

    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.

  20. Photochemical reduction of CO{sub 2} to fuels and chemicals

    SciTech Connect

    DuBois, D.; Eisenberg, R.; Fujita, E.

    1996-09-01

    Photochemical reduction of CO{sub 2} represents a potentially useful approach to developing a sustainable source of carbon-based chemicals, fuels, and materials. In this report the present status of photochemical CO{sub 2} reduction is assessed, areas that need to be better understood for advancement are identified, and approaches to overcoming barriers are suggested. Because of the interdisciplinary nature of this field, assessments of three closely interrelated areas are given including integrated photochemical systems for catalytic CO{sub 2} reduction, thermal catalytic CO{sub 2} reactions, and electrochemical CO{sub 2} reduction. The report concludes with a summary and assessment of potential impacts of this area on chemical and energy technologies.

  1. Photochemical carbon dioxide reduction with metal complexes: Differences between cobalt and nickel macrocycles

    SciTech Connect

    Fujita, Etsuko; Brunschwig, B.S.; Cabelli, D.; Renner, M.W.; Furenlid, L.R.; Ogata, Tomoyuki |; Wada, Yuji; Yanagida, Shozo

    1997-12-31

    Problems related to increases of green house gases in the atmosphere and the depletion of fossil fuels have made the conversion of CO{sub 2} into useful chemicals and fuels an important area of research. However, CO{sub 2} reduction poses many scientific challenges. Despite intense interest in photochemical and electrochemical CO{sub 2} reduction, the kinetics and mechanism of the reduction remain unclear in many systems. This research focuses on mechanistic and kinetic studies of photochemical and electrochemical CO{sub 2} reduction that involves metal complexes as catalysts. This work makes use of UV-vis, NMR, and FTIR spectroscopy, flash photolysis, pulse radiolysis, X-ray diffraction, XANES (X-ray absorption near-edge spectroscopy) and EXAFS (extended X-ray absorption fine structure). Here the authors summarize their research on photochemical carbon dioxide reduction with metal macrocycles.

  2. The impact of aerosols on solar ultraviolet radiation an photochemical smog

    SciTech Connect

    Dickerson, R.R.; Kondragunta, S.; Stenchikov, G.

    1997-10-31

    Photochemical smog, or ground-level ozone, has been the most recalcitrant of air pollution problems, but reductions in emissions of sulfur and hydrocarbons may yield unanticipated benefits in air quality. While sulfate and some organic aerosol particles scatter solar radiation back into space and can cool Earth`s surface, they also change the actinic flux of ultraviolet (UV) radiation. Observations and numerical models show that UV-scattering particles in the boundary layer accelerate photochemical reactions and smog production, but UV-absorbing aerosols such as mineral dust and soot inhibit smog production. Results could have major implications for the control of air pollution. 19 refs., 4 figs.

  3. Utilization of UARS Data in Validation of Photochemical and Dynamical Mechanisms in Stratospheric Models

    NASA Technical Reports Server (NTRS)

    Ko, Malcolm K. W.; Rodriquez, Jose M.; Hu, Wenjie; Danilin, Michael Y.; Shia, Run-Li

    1998-01-01

    The proposed work utilized Upper Atmosphere Research Satellite (UARS) measurements of short-lived and long-lived species, in conjunction with existing photochemical "box" models, trajectory models, and two-dimensional global models, to elucidate outstanding questions in our understanding of photochemical and dynamical mechanisms in the stratosphere. Particular emphasis was given to arriving at the best possible understanding of the chemical and dynamical contribution to the stratospheric ozone budget. Such understanding will increase confidence in the simulations carried out by assessment models.

  4. Highly sensitive and simple SERS substrate based on photochemically generated carbon nanotubes-gold nanorods hybrids.

    PubMed

    Caires, A J; Vaz, R P; Fantini, C; Ladeira, L O

    2015-10-01

    We report a simple and easy formation of hybrids between multi-wall carbon nanotubes and gold nanorods by one-pot in situ photochemical synthesis. Measurements of surface-enhanced Raman scattering (SERS) through the effect "coffee ring" in visible and near infrared (NIR) show high sensitivity with detection of nanomolar concentrations of aromatic dyes. The formation of nanocomposites between carbon nanotubes and gold nanorods without chemical binders simplifies the preparation. Photochemical synthesis is an advance over the techniques previously published. PMID:26057106

  5. Photochemical functionalization of diamond films using a short carbon chain acid

    NASA Astrophysics Data System (ADS)

    Wang, Chun; Huang, Nan; Zhuang, Hao; Yang, Bing; Zhai, Zhaofeng; Jiang, Xin

    2016-02-01

    Diamond is recognized as a promising semiconductor material for biological applications, because of its high chemical stability and biocompatibility. Here, we report an acid with only three carbon chain, acrylic acid (AA), for the functionalization of H-terminated diamond film via photochemical method. The successfully modified surfaces were characterized by X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FTIR) spectroscopy and contact angle analyzer. Our functionalization approach was proven to be simple and facile, which shows a new potential opportunity for the photochemical modification of diamond surface with short carbon chain acid.

  6. Spectral luminescence and photochemical properties of chlorophyll a in solution containing carbon tetrachloride

    SciTech Connect

    Gruzinskii, V.V.; Gurinovich, V.V.; Sagun, E.I.; Tsvirko, M.P.

    1987-08-01

    Studies were conducted on photophysical and photochemical processes in chlorophyll a in carbon tetrachloride and ether by means of flash photolysis, electron spin resonance, and fluorescence spectroscopy. Lifetimes and quenching of triplet states were analyzed and absorption spectra and fluorescence decay times are given. The kinetics of triplet-triplet absorption and hyperfine structure were determined. An absolute quantum yield of the photochemical reaction was measured within the range of linear dependence of the optical density on the time of chlorophyll a irradiation by a krypton laser and the excitation wavelength of 647.1 nm.

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

    NASA Technical Reports Server (NTRS)

    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.

  8. (Study of flow properties of wet solids using laser induced photochemical anemometry)

    SciTech Connect

    Falco, B.

    1990-07-23

    A new diagnostic measurement technique is being developed that will enable the investigation of the dynamics of flowing wet solids. The technique involves that use of Laser Induced Photochemical Anemometry (LIPA), enhanced to enable two photochemical species to be excited. It uses laser induced photochromic and photo luminescent molecules to separately tag the two phases for times long enough for them to distort the tagging. Recording the distortions of the tagging caused by the movement of each phase enables us to obtain local characterization of flow properties of both phases of the wet solids at many positions simultaneously across a pipe.

  9. (Study of flow properties of wet solids using laser induced photochemical anemometry)

    SciTech Connect

    Falco, B.

    1990-04-03

    A new diagnostic measurement technique is being developed that will enable the investigation of the dynamics of flowing wet solids. The technique involves the use of Laser Induced Photochemical Anemometry (LIPA), enhanced to enable two photochemical species to be excited. It uses laser induced photochromic and photo luminescent molecules to separately tag the two phases for times long enough for them to distort the tagging. Recording the distortions of the tagging caused by the movement of each phase enables us to obtain local characterization of flow properties of both phases of the wet solids at many positions simultaneously across a pipe.

  10. (Study of flow properties of wet solids using laser induced photochemical anemometry)

    SciTech Connect

    Falco, B.; Nocera, D.

    1990-01-23

    A new diagnostic measurement technique is being developed that will enable the investigation of the dynamics of flowing wet solids. The technique involves the use of Laser Induced Photochemical Anemometry (LIPA), enhanced to enable two photochemical species to be excited. It uses laser induced photochromic and photo luminescent molecules to separately tag the two phases for times long enough for them to distort the tagging. Recording the distortions of the tagging caused by the movement of each phase enables us to obtain local characterization of flow properties of both phases of the wet solids at many positions simultaneously across a pipe.

  11. Enantioselective Organocatalytic Diels–Alder Trapping of Photochemically Generated Hydroxy‐o‐Quinodimethanes

    PubMed Central

    Dell'Amico, Luca; Vega‐Peñaloza, Alberto; Cuadros, Sara

    2016-01-01

    Abstract The photoenolization/Diels–Alder strategy offers straightforward access to synthetically valuable benzannulated carbocyclic products. This historical light‐triggered process has never before succumbed to efforts to develop an enantioselective catalytic approach. Herein, we demonstrate how asymmetric organocatalysis provides simple yet effective catalytic tools to intercept photochemically generated hydroxy‐o‐quinodimethanes with high stereoselectivity. We used a chiral organic catalyst, derived from natural cinchona alkaloids, to activate maleimides toward highly stereoselective Diels–Alder reactions. An unconventional mechanism of stereocontrol is operative, wherein the organocatalyst is actively involved in both the photochemical pathway, by leveraging the formation of the reactive photoenol, and the stereoselectivity‐defining event. PMID:26797768

  12. Comparison of measured ozone in southeastern Virginia with computer predictions from a photochemical model

    NASA Technical Reports Server (NTRS)

    Wakelyn, N. T.; Gregory, G. L.

    1980-01-01

    Data for one day of the 1977 southeastern Virginia urban plume study are compared with computer predictions from a traveling air parcel model using a contemporary photochemical mechanism with a minimal description of nonmethane hydrocarbon (NMHC) constitution and chemistry. With measured initial NOx and O3 concentrations and a current separate estimate of urban source loading input to the model, and for a variation of initial NMHC over a reasonable range, an ozone increase over the day is predicted from the photochemical simulation which is consistent with the flight path averaged airborne data.

  13. 26 CFR 1.953-2 - Actual United States risks.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ..., and water damage risks incurred when property is actually located in the United States and marine... 26 Internal Revenue 10 2014-04-01 2013-04-01 true Actual United States risks. 1.953-2 Section 1... coverage as “.825% plus .3% fire, etc. risks plus .12% water risks = 1.245%”, a reasonable basis exists...

  14. Self-actualization: Its Use and Misuse in Teacher Education.

    ERIC Educational Resources Information Center

    Ivie, Stanley D.

    1982-01-01

    The writings of Abraham Maslow are analyzed to determine the meaning of the psychological term "self-actualization." After pointing out that self-actualization is a rare quality and that it has little to do with formal education, the author concludes that the concept has little practical relevance for teacher education. (PP)

  15. The Self-Actualization of Polk Community College Students.

    ERIC Educational Resources Information Center

    Pearsall, Howard E.; Thompson, Paul V., Jr.

    This article investigates the concept of self-actualization introduced by Abraham Maslow (1954). A summary of Maslow's Needs Hierarchy, along with a description of the characteristics of the self-actualized person, is presented. An analysis of humanistic education reveals it has much to offer as a means of promoting the principles of…

  16. From Self-Awareness to Self-Actualization

    ERIC Educational Resources Information Center

    Cangemi, Joseph P.; Englander, Meryl R.

    1974-01-01

    Highest priority of education is to help students utilize as much of their talent as is possible. Third Force psychologists would interpret this as becoming self-actualized. Self-awareness is required for psychological growth. Without self-awareness there can be no growth, no mental hygiene, and no self-actualization. (Author)

  17. 12 CFR 1806.203 - Selection Process, actual award amounts.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 12 Banks and Banking 7 2010-01-01 2010-01-01 false Selection Process, actual award amounts. 1806... OF THE TREASURY BANK ENTERPRISE AWARD PROGRAM Awards § 1806.203 Selection Process, actual award... round: (1) To select Applicants not previously selected, using the calculation and selection...

  18. Self-Actualization and the Effective Social Studies Teacher.

    ERIC Educational Resources Information Center

    Farmer, Rodney B.

    1980-01-01

    Discusses a study undertaken to investigate the relationship between social studies teachers' degrees of self-actualization and their teacher effectiveness. Investigates validity of using Maslow's theory of self-actualization as a way of identifying the effective social studies teacher personality. (Author/DB)

  19. Facebook as a Library Tool: Perceived vs. Actual Use

    ERIC Educational Resources Information Center

    Jacobson, Terra B.

    2011-01-01

    As Facebook has come to dominate the social networking site arena, more libraries have created their own library pages on Facebook to create library awareness and to function as a marketing tool. This paper examines reported versus actual use of Facebook in libraries to identify discrepancies between intended goals and actual use. The results of a…

  20. Perceived and Actual Student Support Needs in Distance Education.

    ERIC Educational Resources Information Center

    Visser, Lya; Visser, Yusra Laila

    2000-01-01

    This study sought to determine the academic, affective, and administrative support expectations of distance education students, and to compare actual expectations of distance education students with the instructor's perceptions of such expectations. Results demonstrated divergence between perceived and actual expectations of student support in…

  1. Gebrauchstexte im Fremdsprachenunterricht ("Actual" Texts in Foreign Language Teaching)

    ERIC Educational Resources Information Center

    Ziegesar, Detlef von

    1976-01-01

    Presents for analysis actual texts and texts specially written for teaching, arriving at a basis for a typology of actual texts. Defines teaching aims using such texts, and develops, from a TV program, a teaching unit used in a Karlsruhe school. (Text is in German.) (IFS/WGA)

  2. Self-Actualizing Men and Women: A Comparison Study.

    ERIC Educational Resources Information Center

    Hall, Eleanor G.; Hansen, Jan B.

    1997-01-01

    The self-actualization of 167 women who lived in the Martha Cook (MC) dormitory of the University of Michigan (1950-1970) was compared to that of a group of Ivy League men researched in another study. In addition, two groups of MC women were compared to each other to identify differences which might explain why some self-actualized while other did…

  3. SELF-ACTUALIZATION AND THE UTILIZATION OF TALENT.

    ERIC Educational Resources Information Center

    FRENCH, JOHN R.P.; MILLER, DANIEL R.

    THIS STUDY ATTEMPTED (1) TO DEVELOP A THEORY OF THE CAUSES AND CONSEQUENCES OF SELF-ACTUALIZATION AS RELATED TO THE UTILIZATION OF TALENT, (2) TO FIT THE THEORY TO EXISTING DATA, AND (3) TO PLAN ONE OR MORE RESEARCH PROJECTS TO TEST THE THEORY. TWO ARTICLES ON IDENTITY AND MOTIVATION AND SELF-ACTUALIZATION AND SELF-IDENTITY THEORY REPORTED THE…

  4. Self-Actualization Effects Of A Marathon Growth Group

    ERIC Educational Resources Information Center

    Jones, Dorothy S.; Medvene, Arnold M.

    1975-01-01

    This study examined the effects of a marathon group experience on university student's level of self-actualization two days and six weeks after the experience. Gains in self-actualization as a result of marathon group participation depended upon an individual's level of ego strength upon entering the group. (Author)

  5. 26 CFR 1.962-3 - Treatment of actual distributions.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 26 Internal Revenue 10 2013-04-01 2013-04-01 false Treatment of actual distributions. 1.962-3... TAX (CONTINUED) INCOME TAXES (CONTINUED) Controlled Foreign Corporations § 1.962-3 Treatment of actual... a foreign corporation. (ii) Treatment of section 962 earnings and profits under § 1.959-3....

  6. School Guidance Counselors' Perceptions of Actual and Preferred Job Duties

    ERIC Educational Resources Information Center

    Edwards, John Dexter

    2010-01-01

    The purpose of this study was to provide process data for school counselors, administrators, and the public, regarding school counselors' actual roles within the guidance counselor preferred job duties and actual job duties. In addition, factors including National Certification or no National Certification, years of counseling experience, and…

  7. Photochemical Dimerization of Dibenzylideneacetone: A Convenient Exercise in [2+2] Cycloaddition Using Chemical Ionization Mass Spectrometry

    ERIC Educational Resources Information Center

    Rao, G. Nageswara; Janardhana, Chelli; Ramanathan, V.; Rajesh, T.; Kumar, P. Harish

    2006-01-01

    Chemical reactions induced by light have been utilized for synthesizing highly strained, thermodynamically unstable compounds, which are inaccessible through non-photochemical methods. Photochemical cycloaddition reactions, especially those leading to the formation of four-membered rings, constitute a convenient route to compounds that are…

  8. Photochemical Control of Organic Carbon Availability to Coastal Microbial Communities

    NASA Astrophysics Data System (ADS)

    Miller, W. L.; Reader, H. E.; Powers, L. C.

    2010-12-01

    using a three-stage filtration process to remove larger detritus and biological particles before collecting the bacterial population on a 0.2um filter, for re-suspension in a small volume of filter-sterilized seawater. To ensure eventual carbon limitation in microbial incubations, the samples were spiked with inorganic nitrogen and phosphorus. Oxygen measurements were made as a proxy for community carbon uptake with an Ocean Optics FOXY-R fluorescence probe. Post irradiation, 15 samples were immediately sacrificed to take t=0 oxygen measurements, and the remainder were incubated in the dark for 10-12 days. Seasonal biolabile carbon photoproduction values ranged from -1.8E-2 to 9.2E-2 mol C produced/mol photons absorbed. To compare seasonal and spatial variations over this large data set, irradiations were set at a photon dose of 3.2 mol photons/m^2. Progressive photon dose experiments shows that irradiation length strongly influences the total biolabile product as assayed with microbial measurements. A conceptual model is presented to explain this dependence on photon dose. This varying dependence on photon dose is different from other photochemical products such as CO, and further complicates attempts to quantify the effect of photochemistry on the bioavailability of carbon in marine environments.

  9. Photochemical Transformation Processes in Sunlit Surface Waters (Invited)

    NASA Astrophysics Data System (ADS)

    Vione, D.

    2013-12-01

    Photochemical reactions are major processes in the transformation of hardly biodegradable xenobiotics in surface waters. They are usually classified into direct photolysis and indirect or sensitised degradation. Direct photolysis requires xenobiotic compounds to absorb sunlight, and to get transformed as a consequence. Sensitised transformation involves reaction with transient species (e.g. °OH, CO3-°, 1O2 and triplet states of chromophoric dissolved organic matter, 3CDOM*), photogenerated by so-called photosensitisers (nitrate, nitrite and CDOM). CDOM is a major photosensitiser: is it on average the main source of °OH (and of CO3-° as a consequence, which is mainly produced upon oxidation by °OH of carbonate and bicarbonate) and the only important source of 1O2 and 3CDOM* [1, 2]. CDOM origin plays a key role in sensitised processes: allochthonous CDOM derived from soil runoff and rich in fulvic and humic substances is usually more photoactive than autochthonous CDOM (produced by in-water biological processes and mainly consisting of protein-like material) or of CDOM derived from atmospheric deposition. An interesting gradual evolution of CDOM origin and photochemistry can be found in mountain lakes across the treeline, which afford a gradual transition of allochthonous- autochtonous - atmopheric CDOM when passing from trees to alpine meadows to exposed rocks [3]. Another important issue is the sites of reactive species photoproduction in CDOM. While there is evidence that smaller molecular weight fractions are more photoactive, some studies have reported considerable 1O2 reactivity in CDOM hydrophobic sites and inside particles [4]. We have recently addressed the problem and found that dissolved species in standard humic acids (hydrodynamic diameter < 0.1 μm) account for the vast majority of 1O2 and triplet states photoproduction. In hydrophobic sites of particles, the formation rate of 1O2 is considerably lower than in the solution bulk [5], but the absence

  10. Photochemical Aging of Organic Aerosols: A Laboratory Study

    NASA Astrophysics Data System (ADS)

    Papanastasiou, Dimitrios K.; Kostenidou, Evangelia; Gkatzelis, Georgios I.; Psichoudaki, Magdalini; Louvaris, Evangelos; Pandis, Spyros N.

    2014-05-01

    Organic aerosols (OA) are either emitted directly (primary OA) or formed (secondary OA) in the atmosphere and consist of an extremely complex mixture of thousands of organic compounds. Although the scientific community has put significant effort, in the past few decades, to understand organic aerosol (OA) formation, evolution and fate in the atmosphere, traditional models often fail to reproduce the ambient OA levels. Secondary organic aerosol (SOA) formed, in traditional laboratory chamber experiments, from the gas phase oxidation of known precursors, such as α-pinene, is semi-volatile and with an O:C ratio of around 0.4. In contrast, OA found in the atmosphere is significantly less volatile, while the O:C ratio often ranges from 0.5 to 1. In conclusion, there is a significant gap of knowledge in our understanding of OA formation and photochemical transformation in the atmosphere. There is increased evidence that homogeneous gas phase aging by OH radicals might be able to explain, at least in part, the significantly higher OA mass loadings observed and also the oxidation state and volatility of OA in the atmosphere. In this study, laboratory chamber experiments were performed to study the role of the continued oxidation of first generation volatile and semi-volatile species by OH radicals in the evolution of the SOA characteristics (mass concentration, volatility, and oxidation state). Ambient air mixtures or freshly formed SOA from α-pinene ozonolysis were used as the source of organic aerosols and semi-volatile species. The initial mixture of organic aerosols and gas phase species (volatile and semi-volatile) was then exposed to atmospheric concentrations of OH radicals to study the aging of aerosols. Experiments were performed with various OH radical sources (H2O2 or HONO) and under various NOx conditions. A suite of instruments was employed to characterize both the gas and the aerosol phase. A Scanning Mobility Particle Sizer (SMPS) and a High

  11. 43 CFR 418.35 - Efficiencies.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... Distribution System Efficiency table (§ 418.13 (a)(4)). The efficiency of the Project will vary with the amount of entitlement water actually delivered at the headgates. Since most of the distribution system... irrigation season based on actual measured amounts. The application of any adjustments to Lahontan...

  12. NAD binding site of diphtheria toxin: identification of a residue within the nicotinamide subsite by photochemical modification with NAD.

    PubMed Central

    Carroll, S F; Collier, R J

    1984-01-01

    We showed earlier that exposing mixtures of NAD and diphtheria toxin fragment A to ultraviolet radiation (253.7 nm) induced the formation of covalently linked protein-ligand photoproducts. Here we report that when [carbonyl-14C]NAD was employed in such procedures, the efficiency of labeling of the protein approached 1 mol/mol, and at least 94% of the incorporated label was associated with a single residue, glutamic acid at position 148. Fragment A photolabeled in this manner was enzymically inactive. The efficiency of photolabeling was much lower (less than 0.2 mol/mol) when NAD radiolabeled in either the adenine moiety or the adenylate phosphate was used, and the label was attached to different site(s) within fragment A. Efficient photochemical transfer of label from [carbonyl-14C]NAD occurred under identical conditions with the nucleotide-free form of whole diphtheria toxin, CRM-45, or activated exotoxin A from Pseudomonas aeruginosa, but not with nucleotide-bound diphtheria toxin, CRM-197, native exotoxin A, or any of several NAD-linked dehydrogenases. On the basis of these and other results we suggest that part or all of the nicotinamide moiety of NAD is efficiently transferred to glutamate-148 of fragment A under the influence of ultraviolet irradiation and that this residue is located within the nicotinamide subsite. This location implies that glutamate-148 is at or near the catalytic center of the toxin. Our data provide direct evidence for the location of the NAD site in an ADP-ribosylating toxin and demonstrate highly efficient and specific photolabeling by [carbonyl-14C]NAD. Images PMID:6145155

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

    NASA Astrophysics Data System (ADS)

    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.

  14. Oxidative capacity and radical chemistry in the polluted atmosphere of Hong Kong and Pearl River Delta region: analysis of a severe photochemical smog episode

    NASA Astrophysics Data System (ADS)

    Xue, Likun; Gu, Rongrong; Wang, Tao; Wang, Xinfeng; Saunders, Sandra; Blake, Donald; Louie, Peter K. K.; Luk, Connie W. Y.; Simpson, Isobel; Xu, Zheng; Wang, Zhe; Gao, Yuan; Lee, Shuncheng; Mellouki, Abdelwahid; Wang, Wenxing

    2016-08-01

    We analyze a photochemical smog episode to understand the oxidative capacity and radical chemistry of the polluted atmosphere in Hong Kong and the Pearl River Delta (PRD) region. A photochemical box model based on the Master Chemical Mechanism (MCM v3.2) is constrained by an intensive set of field observations to elucidate the budgets of ROx (ROx = OH+HO2+RO2) and NO3 radicals. Highly abundant radical precursors (i.e. O3, HONO and carbonyls), nitrogen oxides (NOx) and volatile organic compounds (VOCs) facilitate strong production and efficient recycling of ROx radicals. The OH reactivity is dominated by oxygenated VOCs (OVOCs), followed by aromatics, alkenes and alkanes. Photolysis of OVOCs (except for formaldehyde) is the dominant primary source of ROx with average daytime contributions of 34-47 %. HONO photolysis is the largest contributor to OH and the second-most significant source (19-22 %) of ROx. Other considerable ROx sources include O3 photolysis (11-20 %), formaldehyde photolysis (10-16 %), and ozonolysis reactions of unsaturated VOCs (3.9-6.2 %). In one case when solar irradiation was attenuated, possibly by the high aerosol loadings, NO3 became an important oxidant and the NO3-initiated VOC oxidation presented another significant ROx source (6.2 %) even during daytime. This study suggests the possible impacts of daytime NO3 chemistry in the polluted atmospheres under conditions with the co-existence of abundant O3, NO2, VOCs and aerosols, and also provides new insights into the radical chemistry that essentially drives the formation of photochemical smog in the high-NOx environment of Hong Kong and the PRD region.

  15. Stepwise Two-Photon-Gated Photochemical Reaction in Photochromic [2.2]Paracyclophane-Bridged Bis(imidazole dimer).

    PubMed

    Mutoh, Katsuya; Nakagawa, Yuki; Sakamoto, Akira; Kobayashi, Yoichi; Abe, Jiro

    2015-05-01

    Stepwise two-photon processes not only have great potential for efficient light harvesting but also can provide valuable insights into novel photochemical sciences. Here we have designed a [2.2]paracyclophane-bridged bis(imidazole dimer), a molecule that is composed of two photochromic units and absorbs two photons in a stepwise manner. The absorption of the first photon leads to the formation of a short-lived biradical species (half-life = 88 ms at 298 K), while the absorption of the additional photon by the biradical species triggers a subsequent photochromic reaction to afford a long-lived quinoid species. The short-lived biradical species and the long-lived quinoid species display significantly different absorption spectra and rates of the thermal back-reaction. The stepwise two-photon excitation process in this photochromic system can be initiated even by incoherent continuous-wave light irradiation, indicating that this two-photon reaction is highly efficient. Our molecule based on the bridged bis(imidazole dimer) unit should be a good candidate for multiphoton-gated optical materials. PMID:25909469

  16. Effects of pH on photochemical decomposition of perfluorooctanoic acid in different atmospheres by 185nm vacuum ultraviolet.

    PubMed

    Wang, Yuan; Zhang, Pengyi

    2014-11-01

    Perfluorooctanoic acid (PFOA), a persistent organic pollutant, receives increasing concerns due to its worldwide occurrence and resistance to most conventional treatment processes. The photochemical decomposition by 185nm vacuum ultraviolet (VUV) is one of the efficient methods for PFOA decomposition. The effects of pH on PFOA decomposition in nitrogen atmosphere or oxygen atmosphere were investigated. At its original pH (4.5) of PFOA aqueous solution, PFOA decomposed efficiently both in nitrogen and in oxygen atmosphere. However, when the pH increased to 12.0, PFOA decomposition was greatly inhibited in oxygen atmosphere, while it was greatly accelerated in nitrogen atmosphere with a very short half-life time (9min). Furthermore, fluorine atoms originally contained in PFOA molecules were almost completely transformed into fluoride ions. Two decomposition pathways have been proposed to explain the PFOA decomposition under different conditions. In acidic and neutral solutions, PFOA predominantly decomposes via the direct photolysis in both atmospheres; while in the alkaline solution and in the absence of oxygen, the decomposition of PFOA is mainly induced by hydrated electrons. PMID:25458674

  17. The inhibition of photochemical smog. VIII. Disperion of the chemical inhibitor

    SciTech Connect

    Heicklen, J.

    1980-03-01

    In laboratory and simulated atmospheric chemical studies, it has been shown that diethylhydroxylamine can effectively inhibit photochemical smog formation. The chemical prevents the long-chain free radical oxidation of nitric oxide. Gradients for the introduction of diethylhydroxylamine from point sources are determined. (17 references, 2 tables)

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

    EPA Science Inventory

    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...

  19. REGIONAL SCALE (1000 KM) MODEL OF PHOTOCHEMICAL AIR POLLUTION. PART 1. THEORETICAL FORMULATION

    EPA Science Inventory

    A theoretical framework for a multi-day 1000 km scale simulation model of photochemical oxidant is developed. It is structured in a highly modular form so that eventually the model can be applied through straightforward modifications to simulations of particulates, visibility and...

  20. 40 CFR 52.229 - Control strategy and regulations: Photochemical oxidants (hydrocarbons), Metropolitan Los Angeles...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 CFR 52.223 is retained. (ii) Rule 1115, Automotive Coatings, adopted on March 16, 1984 by the...: Photochemical oxidants (hydrocarbons), Metropolitan Los Angeles Intrastate Region. 52.229 Section 52.229... oxidants (hydrocarbons), Metropolitan Los Angeles Intrastate Region. (a) (b) The following rules...

  1. 40 CFR 52.229 - Control strategy and regulations: Photochemical oxidants (hydrocarbons), Metropolitan Los Angeles...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 CFR 52.223 is retained. (ii) Rule 1115, Automotive Coatings, adopted on March 16, 1984 by the...: Photochemical oxidants (hydrocarbons), Metropolitan Los Angeles Intrastate Region. 52.229 Section 52.229... oxidants (hydrocarbons), Metropolitan Los Angeles Intrastate Region. (a) (b) The following rules...

  2. 40 CFR 52.229 - Control strategy and regulations: Photochemical oxidants (hydrocarbons), Metropolitan Los Angeles...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 CFR 52.223 is retained. (ii) Rule 1115, Automotive Coatings, adopted on March 16, 1984 by the...: Photochemical oxidants (hydrocarbons), Metropolitan Los Angeles Intrastate Region. 52.229 Section 52.229... oxidants (hydrocarbons), Metropolitan Los Angeles Intrastate Region. (a) (b) The following rules...

  3. 40 CFR 52.229 - Control strategy and regulations: Photochemical oxidants (hydrocarbons), Metropolitan Los Angeles...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 CFR 52.223 is retained. (ii) Rule 1115, Automotive Coatings, adopted on March 16, 1984 by the...: Photochemical oxidants (hydrocarbons), Metropolitan Los Angeles Intrastate Region. 52.229 Section 52.229... oxidants (hydrocarbons), Metropolitan Los Angeles Intrastate Region. (a) (b) The following rules...

  4. 40 CFR 52.229 - Control strategy and regulations: Photochemical oxidants (hydrocarbons), Metropolitan Los Angeles...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 CFR 52.223 is retained. (ii) Rule 1115, Automotive Coatings, adopted on March 16, 1984 by the...: Photochemical oxidants (hydrocarbons), Metropolitan Los Angeles Intrastate Region. 52.229 Section 52.229... oxidants (hydrocarbons), Metropolitan Los Angeles Intrastate Region. (a) (b) The following rules...

  5. Energy transduction inside of amphiphilic vesicles: encapsulation of photochemically active semiconducting particles.

    PubMed

    Summers, David P; Noveron, Juan; Basa, Ranor C B

    2009-04-01

    Amphiphilic bilayer membrane structures (vesicles) have been postulated to have been abiotically formed and spontaneously assemble on the prebiotic Earth, providing compartmentalization for the origin of life. These vesicles are similar to modern cellular membranes and can serve to contain water-soluble species, concentrate species, and have the potential to catalyze reactions. The origin of the use of photochemical energy in metabolism (i.e. energy transduction) is one of the central issues in the origin of life. This includes such questions as how energy transduction may have occurred before complex enzymatic systems, such as required by contemporary photosynthesis, had developed and how simple a photochemical system is possible. It has been postulated that vesicle structures developed the ability to capture and transduce light, providing energy for reactions. It has also been shown that pH gradients across the membrane surface can be photochemically created, but coupling these to drive chemical reactions has been difficult. Colloidal semiconducting mineral particles are known to photochemically drive redox chemistry. We propose that encapsulation of these particles has the potential to provide a source of energy transduction inside vesicles, and thereby drive protocellular chemistry, and represents a model system for early photosynthesis. In our experiments we show that TiO2 particles, in the approximately 20 nm size range, can be incorporated into vesicles and retain their photoactivity through the dehydration/rehydration cycles that have been shown to concentrate species inside a vesicle. PMID:19259781

  6. Has the Performance of Regional-Scale Photochemical Modelling Systems Changed over the Past Decade?

    EPA Science Inventory

    This study analyzed summertime ozone concentrations that have been simulated by various regional-scale photochemical modelling systems over the Eastern U.S. as part of more than ten independent studies. Results indicate that there has been a reduction of root mean square errors ...

  7. 2013 Final Report: Integrated Science Assessment of Ozone and Related Photochemical Oxidants

    EPA Science Inventory

    Cover of the Integrated Science Assessment (ISA) for Ozone and Related <span class=Photochemical Oxidants" vspace = "5" hspace="5" align="right" border="1" /> EPA is announcing the availability of the <...

  8. 76 FR 17121 - Draft Integrated Science Assessment for Ozone and Related Photochemical Oxidants

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-03-28

    ... published on February 28, 2011 (76 FR 10893). This assessment document was developed by the National Center... provided in the SUPPLEMENTARY INFORMATION section of Federal Register Notice (76 FR 10893). For information... AGENCY Draft Integrated Science Assessment for Ozone and Related Photochemical Oxidants...

  9. The photochemical reflectance index from directional cornfield reflectances: Observations and simulations

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The two-layer Markov chain Analytical Canopy Reflectance Model (ACRM) was linked with in situ hyperspectral leaf optical properties to simulate the Photochemical Reflectance Index (PRI) for a corn crop canopy at three different growth stages. This is an extended study after a successful demonstratio...

  10. PHOTOCHEMICAL OXIDANT AIR POLLUTION EFFECTS ON A MIXED CONIFER FOREST ECOSYSTEM

    EPA Science Inventory

    EPA contract 68-03-2442 provided support for three years of the studies to determine the chronic effects of photochemical oxidant air pollutants on a western mixed conifer forest ecosystem. This report deals with the year 1976-77 and is the final publication on EPA contract 68-03...

  11. Energy Transduction Inside of Amphiphilic Vesicles: Encapsulation of Photochemically Active Semiconducting Particles

    NASA Astrophysics Data System (ADS)

    Summers, David P.; Noveron, Juan; Basa, Ranor C. B.

    2009-04-01

    Amphiphilic bilayer membrane structures (vesicles) have been postulated to have been abiotically formed and spontaneously assemble on the prebiotic Earth, providing compartmentalization for the origin of life. These vesicles are similar to modern cellular membranes and can serve to contain water-soluble species, concentrate species, and have the potential to catalyze reactions. The origin of the use of photochemical energy in metabolism (i.e. energy transduction) is one of the central issues in the origin of life. This includes such questions as how energy transduction may have occurred before complex enzymatic systems, such as required by contemporary photosynthesis, had developed and how simple a photochemical system is possible. It has been postulated that vesicle structures developed the ability to capture and transduce light, providing energy for reactions. It has also been shown that pH gradients across the membrane surface can be photochemically created, but coupling these to drive chemical reactions has been difficult. Colloidal semiconducting mineral particles are known to photochemically drive redox chemistry. We propose that encapsulation of these particles has the potential to provide a source of energy transduction inside vesicles, and thereby drive protocellular chemistry, and represents a model system for early photosynthesis. In our experiments we show that TiO2 particles, in the ~20 nm size range, can be incorporated into vesicles and retain their photoactivity through the dehydration/rehydration cycles that have been shown to concentrate species inside a vesicle.

  12. COMPARISON OF PHOTOCHEMICAL BEHAVIOR OF VARIOUS HUMIC SUBSTANCES IN WATER: II. PHOTOSENSITIZED OXYGENATIONS

    EPA Science Inventory

    The photochemical oxygenation of 2, 5-dimethylfuran (DMF) in water was studied under a variety of reaction conditions employing various humic substances as photosensitizers. As predicted by theory, the reactions at low DMF concentrations were first order with respect to DMF, and ...

  13. Functional, photochemically active, and chemically asymmetric membranes by interfacial polymerization of derivatized multifunctional prepolymers

    DOEpatents

    Lonsdale, Harold K.; Wamser, Carl C.

    1988-01-01

    The preparation of a novel class of thin film membranes by interfacial polymerization is disclosed, said membanes incorporating as part of their polymeric structure the functionality of monomeric or oligomeric precursors. Specific embodiments include porphyrin and phthalocyanime derivatives that are photochemically or electrochemically active, as well as chemically asymmetric membranes.

  14. Functional, photochemically active, and chemically asymmetric membranes by interfacial polymerization of derivatized multifunctional prepolymers

    DOEpatents

    Lonsdale, H.K.; Wamser, C.C.

    1990-04-17

    The preparation of a novel class of thin film membranes by interfacial polymerization is disclosed, said membranes incorporating as part of their polymeric structure the functionality of monomeric or oligomeric precursors. Specific embodiments include porphyrin and phthalocyanine derivatives that are photochemically or electrochemically active, as well as chemically asymmetric membranes.

  15. Functional, photochemically active, and chemically asymmetric membranes by interfacial polymerization of derivatized multifunctional prepolymers

    DOEpatents

    Lonsdale, Harold K.; Wamser, Carl C.

    1990-01-01

    The preparation of a novel class of thin film membranes by interfacial polymerization is disclosed, said membranes incorporating as part of their polymeric structure the functionality of monomeric or oligomeric precursors. Specific embodiments include porphyrin and phthalocyanine derivatives that are photochemically or electrochemically active, as well as chemically asymmetric membranes.

  16. 40 CFR 52.2426 - Photochemical Assessment Monitoring Stations (PAMS) Program.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... (CONTINUED) AIR PROGRAMS (CONTINUED) APPROVAL AND PROMULGATION OF IMPLEMENTATION PLANS (CONTINUED) Virginia § 52.2426 Photochemical Assessment Monitoring Stations (PAMS) Program. On November 23, 1994 Virginia's... Stations (PAMS) Program on September 11, 1995 and made it part of the Virginia SIP. As with all...

  17. 40 CFR 52.2426 - Photochemical Assessment Monitoring Stations (PAMS) Program.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... (CONTINUED) AIR PROGRAMS (CONTINUED) APPROVAL AND PROMULGATION OF IMPLEMENTATION PLANS (CONTINUED) Virginia § 52.2426 Photochemical Assessment Monitoring Stations (PAMS) Program. On November 23, 1994 Virginia's... Stations (PAMS) Program on September 11, 1995 and made it part of the Virginia SIP. As with all...

  18. 40 CFR 52.2426 - Photochemical Assessment Monitoring Stations (PAMS) Program.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... (CONTINUED) AIR PROGRAMS (CONTINUED) APPROVAL AND PROMULGATION OF IMPLEMENTATION PLANS (CONTINUED) Virginia § 52.2426 Photochemical Assessment Monitoring Stations (PAMS) Program. On November 23, 1994 Virginia's... Stations (PAMS) Program on September 11, 1995 and made it part of the Virginia SIP. As with all...

  19. 40 CFR 52.2426 - Photochemical Assessment Monitoring Stations (PAMS) Program.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... (CONTINUED) AIR PROGRAMS (CONTINUED) APPROVAL AND PROMULGATION OF IMPLEMENTATION PLANS (CONTINUED) Virginia § 52.2426 Photochemical Assessment Monitoring Stations (PAMS) Program. On November 23, 1994 Virginia's... Stations (PAMS) Program on September 11, 1995 and made it part of the Virginia SIP. As with all...

  20. 40 CFR 52.2426 - Photochemical Assessment Monitoring Stations (PAMS) Program.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... (CONTINUED) AIR PROGRAMS (CONTINUED) APPROVAL AND PROMULGATION OF IMPLEMENTATION PLANS (CONTINUED) Virginia § 52.2426 Photochemical Assessment Monitoring Stations (PAMS) Program. On November 23, 1994 Virginia's... Stations (PAMS) Program on September 11, 1995 and made it part of the Virginia SIP. As with all...

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

    NASA Technical Reports Server (NTRS)

    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.

  2. MODELING OF SIMULATED PHOTOCHEMICAL SMOG WITH KINETIC MECHANISMS. VOLUME 1. INTERIM REPORT

    EPA Science Inventory

    Computer modeling of smog chamber data is discussed in three parts. First, a series of detailed chemical mechanisms were developed to describe the photochemical formation of ozone from nitrogen oxides and the following organic compounds (alone and in various combinations): formal...

  3. MODELING OF SIMULATED PHOTOCHEMICAL SMOG WITH KINETIC MECHANISMS. VOLUME 2. INTERIM REPORT APPENDIX

    EPA Science Inventory

    Computer modeling of smog chamber data is discussed in three parts. First, a series of detailed chemical mechanisms were developed to describe the photochemical formation of ozone from nitrogen oxides and the following organic compounds (alone and in various combinations): formal...

  4. OZONE AND OTHER PHOTOCHEMICAL OXIDANTS. VOLUME 1 (CHAPTERS 1-7)

    EPA Science Inventory

    The report deals primarily with the origins and effects of ozone and other photochemical oxidants. It is limited, more or less, to the problem of urban pollution and to such closely related topics as natural background in the earth's boundary layer. No consideration is given to t...

  5. OZONE AND OTHER PHOTOCHEMICAL OXIDANTS. VOLUME 2 (CHAPTERS 8-15)

    EPA Science Inventory

    The report deals primarily with the origins and effects of ozone and other photochemical oxidants. It is limited, more or less, to the problem of urban pollution and to such closely related topics as natural background in the earth's boundary layer. No consideration is given to t...

  6. PHOTOCHEMICAL MINERALIZATION OF DISSOLVED ORGANIC NITROGEN TO AMMONIUM IN THE BALTIC SEA

    EPA Science Inventory

    Solar radiation-induced photochemistry can be considered as a new source of nutrients when photochemical reactions release bioavailable nitrogen from biologically non-reactive dissolved organic nitrogen (DON). Pretreatments of Baltic Sea waters in the dark indicated that >72% of ...

  7. PHOTOCHEMICAL PRODUCTS IN URBAN MIXTURES ENHANCE INFLAMMATORY RESPONSES IN LUNG CELLS

    EPA Science Inventory

    Complex urban air mixtures that realistically mimic urban smog can be generated for investigating adverse health effects. "Smog chambers" have been used for over 30 yr to conduct experiments for developing and testing photochemical models that predict ambient ozone (O(3)) concent...

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

    EPA Science Inventory

    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)...

  9. Air Quality Criteria for Ozone and Related Photochemical Oxidants (First External Review Draft)

    EPA Science Inventory

    This first external review draft of the Air Quality Criteria for Ozone and Related Photochemical Oxidants (Ozone Criteria Document) is being released in January 2005 for public comment and for review by EPA's Clean A...

  10. Air Quality Criteria for Ozone and Related Photochemical Oxidants (Second External Review Draft)

    EPA Science Inventory

    This second external review draft of the Air Quality Criteria for Ozone and Related Photochemical Oxidants, Volumes I-III (Ozone Criteria Document) is being released for public comment and for review by EPA's Clean Air Scientific Advisory Committee (CASAC) r...

  11. FINAL EVALUATION OF URBAN-SCALE PHOTOCHEMICAL AIR QUALITY SIMULATION MODELS

    EPA Science Inventory

    The research study discussed here is a continuation of previous work whose goal was to determine the accuracy of several selected urban photochemical air quality simulation models using data from the Regional Air Pollution Study in St. Louis. This work reports on the testing of t...

  12. 40 CFR 52.430 - Photochemical Assessment Monitoring Stations (PAMS) Program.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... Photochemical Assessment Monitoring Stations (PAMS) Program as a state implementation plan (SIP) revision, as... Stations (PAMS) Program on September 11, 1995 and made it part of the Delaware SIP. As with all components of the SIP, Delaware must implement the program as submitted and approved by EPA....

  13. Integrated Science Assessment of Ozone and Related Photochemical Oxidants (First External Review Draft)

    EPA Science Inventory

    EPA announced that the First External Review Draft of the Integrated Science Assessment for Ozone and Related Photochemical Oxidants has been made available for independent peer review and public review. This draft document represents a concise synthesis and evaluation of ...

  14. THE ROLE OF PHOTOCHEMICAL PROCESSES FOR PATHOGEN INACTIVATION IN NON-CONVENTIONAL WASTEWATER TREATMENT SYSTEMS

    EPA Science Inventory

    This research will lead to a better understanding of sunlight-mediated photochemical processes within NC-WWT systems, their relation to the NOM/EfOM found within such systems and their role in pathogen inactivation. Such results should lead to better estimations on systems...

  15. In situ photochemical synthesis of fluorescent carbon dots for optical sensing of hydrogen peroxide and antioxidants.

    PubMed

    Costas-Mora, Isabel; Romero, Vanesa; Lavilla, Isela; Bendicho, Carlos

    2015-11-01

    A new synthesis approach for obtaining fluorescent carbon dots (CDs) based on UV irradiation of carbohydrates was developed. The photochemical synthesis pathway allows the formation of water soluble CDs of analytical usefulness within one min. CDs obtained by photochemical treatment from the sucrose/NaOH/poly(ethylene glycol) system are monodisperse with an average size of 8 nm as determined by transmission electron microscopy. A dramatic increase in the CDs fluorescence (turn on) is observed when H2O2 is added. The decrease in CDs size occurring by the action of highly oxidant OH radicals gives rise to confinement of emissive energy traps and, in turn, to fluorescence enhancement. Antioxidants such as ascorbic acid and glutathione inhibit the photochemical reaction giving rise to a decrease in fluorescence of the CDs/H2O2 system (turn on-off). The detection limit was 5 µM H2O2 and the repeatability expressed as the relative standard deviation was 3.8% (N=7). The photochemical synthesis of CDs allows building a green, low-cost, safe and fast assay for the detection of H2O2 and antioxidants. An application of the novel fluorescent nanoprobe to H2O2 detection in contact lens cleaning solutions is performed. PMID:26452963

  16. The Photochemical Synthesis, Kinetics, and Reactions of Nitrosomethane Dimer: A Physical-Organic Experiment.

    ERIC Educational Resources Information Center

    Kozubek, H.; And Others

    1982-01-01

    Provides background information procedures, and results for the photochemical synthesis and reactions of nitrosomethane dimer. The experiments described have shown a high degree of reliability with student use and are suggested to illustrate some problems of physical and organic photochemistry. (Author/JN)

  17. A Framework for Evaluating Regional-Scale Numerical Photochemical Modeling Systems

    EPA Science Inventory

    This paper discusses the need for critically evaluating regional-scale (~ 200-2000 km) three dimensional numerical photochemical air quality modeling systems to establish a model's credibility in simulating the spatio-temporal features embedded in the observations. Because of li...

  18. The determination and role of peroxyacetil nitrate in photochemical processes in atmosphere

    PubMed Central

    2012-01-01

    Peroxyacetilnitrates (PAN) is the most characteristic photoxidant of a range of secondary pollutants formed by the photochemical reaction of hydrocarbons with nitrogen oxides in the atmosphere: it is phytotoxic and shows an increasing role in human health effects due to ambient air exposure, especially in presence of high ozone concentrations. Because of the similarity of the conditions required for their photochemical production PAN is observed in conjunction with elevated ozone concentrations. PAN has very low natural background concentrations so it is the very specific indicator of anthropogenic photochemical air pollution. In this paper we report PAN concentrations determined in Rome urban area during winter- and summer-period. PAN measurements were carried out by means of a gas-chromatograph equipped with an Electron Capture Detector (ECD) detector. For identifying the acute episodes of atmospheric photochemical pollutants the relationship between PAN and the variable Ox (=NO2+O3) which describes the oxidation process evolution is investigated. The role of Volatile Organic Compounds and PAN in the ozone formation is investigated as well the issue of taking in account the autovehicular emissions for checking the NOx fraction in fuel. PMID:22594443

  19. Integrated Science Assessment of Ozone and Related Photochemical Oxidants (Second External Review Draft)

    EPA Science Inventory

    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...

  20. Integrated Science Assessment of Ozone and Related Photochemical Oxidants (Third External Review Draft)

    EPA Science Inventory

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