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Sample records for psii photochemical efficiency

  1. Effect of leaf dehydration duration and dehydration degree on PSII photochemical activity of papaya leaves.

    Science.gov (United States)

    Liu, Meijun; Zhang, Zishan; Gao, Huiyuan; Yang, Cheng; Fan, Xingli; Cheng, Dandan

    2014-09-01

    Although the effect of dehydration on photosynthetic apparatus has been widely studied, the respective effect of dehydration duration and dehydration degree was neglected. This study showed that, when leaves dehydrated in air, the PSII activities of leaves decreased with the decline of leaf relative water content (RWC). Unexpectedly, when leaves dehydrated to same RWC, the decreases in Fv/Fm, Ψo and RC/CSm were lower in leaves dehydrating at 43 °C than those at 25 °C. However, to reach the same RWC, leaves dehydrating at 43 °C experienced 1/6 of the dehydration duration for leaves dehydrating at 25 °C. To distinguish the respective effect of dehydration degree and dehydration duration on photosynthetic apparatus, we studied the PSII activities of leaves treated with different concentration of PEG solutions. Increasing dehydration degree aggravated the decline of Fv/Fm, Ψo and RC/CSm in leaves with the same dehydration duration, while prolonging the dehydration duration also exacerbated the decline of Fv/Fm, Ψo and RC/CSm in leaves with identical dehydration degree. With the same dehydration degree and duration, high temperature enhanced the decrease of Fv/Fm, Ψo and RC/CSm in the leaves. When leaves dehydrated in air, the effect of high temperature was underestimated due to reduction of dehydration duration. The results demonstrated that, dehydration degree and duration both play important roles in damage to photosynthetic apparatus. We suggest that, under combined stresses, the effects of dehydration degree and duration on plants should be considered comprehensively, otherwise, partial or incorrect results may be obtained. Copyright © 2014 Elsevier Masson SAS. All rights reserved.

  2. Altered gene expression by sedaxane increases PSII efficiency, photosynthesis and growth and improves tolerance to drought in wheat seedlings.

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    Ajigboye, Olubukola O; Lu, Chungui; Murchie, Erik H; Schlatter, Christian; Swart, Gina; Ray, Rumiana V

    2017-04-01

    Succinate dehydrogenase inhibitor (SDHI) fungicides have been shown to increase PSII efficiency and photosynthesis under drought stress in the absence of disease to enhance the biomass and yield of winter wheat. However, the molecular mechanism of improved photosynthetic efficiency observed in SDHI-treated wheat has not been previously elucidated. Here we used a combination of chlorophyll fluorescence, gas exchange and gene expression analysis, to aid our understanding of the basis of the physiological responses of wheat seedlings under drought conditions to sedaxane, a novel SDHI seed treatment. We show that sedaxane increased the efficiency of PSII photochemistry, reduced non-photochemical quenching and improved the photosynthesis and biomass in wheat correlating with systemic changes in the expression of genes involved in defense, chlorophyll synthesis and cell wall modification. We applied a coexpression network-based approach using differentially expressed genes of leaves, roots and pregerminated seeds from our wheat array datasets to identify the most important hub genes, with top ranked correlation (higher gene association value and z-score) involved in cell wall expansion and strengthening, wax and pigment biosynthesis and defense. The results indicate that sedaxane confers tolerant responses of wheat plants grown under drought conditions by redirecting metabolites from defense/stress responses towards growth and adaptive development. Copyright © 2016 Elsevier Inc. All rights reserved.

  3. Seasonal fluctuations in photochemical efficiency of Symbiodinium ...

    African Journals Online (AJOL)

    A. formosa and P. verucosa responded significantly to seasonal fluctuation in both solar radiation and sea surface temperature by regulating their Symbiodinium cells densities and photochemical efficiencies except P. cylindrica. However, such seasonal fluctuations in these environmental parameters are not accompanied ...

  4. Increased Photochemical Efficiency in Cyanobacteria via an Engineered Sucrose Sink.

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    Abramson, Bradley W; Kachel, Benjamin; Kramer, David M; Ducat, Daniel C

    2016-12-01

    In plants, a limited capacity to utilize or export the end-products of the Calvin-Benson cycle (CB) from photosynthetically active source cells to non-photosynthetic sink cells can result in reduced carbon capture and photosynthetic electron transport (PET), and lowered photochemical efficiency. The down-regulation of photosynthesis caused by reduced capacity to utilize photosynthate has been termed 'sink limitation'. Recently, several cyanobacterial and algal strains engineered to overproduce target metabolites have exhibited increased photochemistry, suggesting that possible source-sink regulatory mechanisms may be involved. We directly examined photochemical properties following induction of a heterologous sucrose 'sink' in the unicellular cyanobacterium Synechococcus elongatus PCC 7942. We show that total photochemistry increases proportionally to the experimentally controlled rate of sucrose export. Importantly, the quantum yield of PSII (ΦII) increases in response to sucrose export while the PET chain becomes more oxidized from less PSI acceptor-side limitation, suggesting increased CB activity and a decrease in sink limitation. Enhanced photosynthetic activity and linear electron flow are detectable within hours of induction of the heterologous sink and are independent of pigmentation alterations or the ionic/osmotic effects of the induction system. These observations provide direct evidence that secretion of heterologous carbon bioproducts can be used as an alternative approach to improve photosynthetic efficiency, presumably by by-passing sink limitation. Our results also suggest that engineered microalgal production strains are valuable alternative models for examining photosynthetic sink limitation because they enable greater control and monitoring of metabolite fluxes relative to plants. © The Author 2016. Published by Oxford University Press on behalf of Japanese Society of Plant Physiologists. All rights reserved. For permissions, please email

  5. Estimating chlorophyll content and photochemical yield of photosystem II (ΦPSII) using solar-induced chlorophyll fluorescence measurements at different growing stages of attached leaves.

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    Tubuxin, Bayaer; Rahimzadeh-Bajgiran, Parinaz; Ginnan, Yusaku; Hosoi, Fumiki; Omasa, Kenji

    2015-09-01

    This paper illustrates the possibility of measuring chlorophyll (Chl) content and Chl fluorescence parameters by the solar-induced Chl fluorescence (SIF) method using the Fraunhofer line depth (FLD) principle, and compares the results with the standard measurement methods. A high-spectral resolution HR2000+ and an ordinary USB4000 spectrometer were used to measure leaf reflectance under solar and artificial light, respectively, to estimate Chl fluorescence. Using leaves of Capsicum annuum cv. 'Sven' (paprika), the relationships between the Chl content and the steady-state Chl fluorescence near oxygen absorption bands of O2B (686nm) and O2A (760nm), measured under artificial and solar light at different growing stages of leaves, were evaluated. The Chl fluorescence yields of ΦF 686nm/ΦF 760nm ratios obtained from both methods correlated well with the Chl content (steady-state solar light: R(2) = 0.73; artificial light: R(2) = 0.94). The SIF method was less accurate for Chl content estimation when Chl content was high. The steady-state solar-induced Chl fluorescence yield ratio correlated very well with the artificial-light-induced one (R(2) = 0.84). A new methodology is then presented to estimate photochemical yield of photosystem II (ΦPSII) from the SIF measurements, which was verified against the standard Chl fluorescence measurement method (pulse-amplitude modulated method). The high coefficient of determination (R(2) = 0.74) between the ΦPSII of the two methods shows that photosynthesis process parameters can be successfully estimated using the presented methodology. © The Author 2015. Published by Oxford University Press on behalf of the Society for Experimental Biology.

  6. [Effects of NO3- stress on photosynthetic rate, photochemical efficiency of PS II and light energy allocation in cucumber seedling leaves].

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    Su, Xiu-Rong; Wang, Xiu-Feng; Yang, Feng-Juan; Wei, Min

    2007-07-01

    This paper studied the effects of different NO3- concentration on the photosynthetic rate, photochemical efficiency, and absorbed light energy allocation in cucumber seedling leaves. The results indicated that when the available NO3- concentration in the medium was low (14-98 mmol NO3- x L(-1)), an appropriate supplement of NO3- could enhance the capability of cucumber leaves in capturing light energy, and promote the photosynthesis. However, with further increase of NO3-, the photochemical efficiency of PS II decreased, electron transfer restrained, and net photosynthetic rate as well as the absorbed light energy used in photochemical reaction of PS II decreased. At the same time, the light energy used in antenna heat dissipation increased, while the photochemical efficiency decreased. After treated with 140 and 182 mmol NO3- x L(-1) for 6 days, the photosynthetic rate (P(n)) was decreased by 35% and 78%, respectively, maximal PS II efficiency at open centers in the absence of NPQ (F(v)/F(m)), antenna efficiency at open centers in the presence of NPQ (F(v)'/F(m)'), actual PS II efficiency (phi (PSII ) and photochemical quenching (q(P)) were lower, non-photochemical quenching (NPQ) was higher, and the deviation from full balance between PS I and PS II (beta/alpha - 1) was improved significantly, compared with the control. The fluctuant ranges of these chlorophyll fluorescence parameters were increased at higher NO3- concentration, compared with those at lower NO3- concentration. The absorbed light energy allocated to the photochemical reaction of PS II (P) was reduced by high light intensity and high NO3- concentration. Meanwhile, the proportion allocated in antenna heat dissipation (D) increased significantly. Antenna heat dissipation was the main way for excessive energy dissipation.

  7. Cold-acclimation limits low temperature induced photoinhibition by promoting a higher photochemical quantum yield and a more effective PSII restoration in darkness in the Antarctic rather than the Andean ecotype of Colobanthus quitensis Kunt Bartl (Cariophyllaceae

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    Bascuñán-Godoy Luisa

    2012-07-01

    Full Text Available Abstract Background Ecotypes of Colobanthus quitensis Kunt Bartl (Cariophyllaceae from Andes Mountains and Maritime Antarctic grow under contrasting photoinhibitory conditions, reaching differential cold tolerance upon cold acclimation. Photoinhibition depends on the extent of photodamage and recovery capability. We propose that cold acclimation increases resistance to low-temperature-induced photoinhibition, limiting photodamage and promoting recovery under cold. Therefore, the Antarctic ecotype (cold hardiest should be less photoinhibited and have better recovery from low-temperature-induced photoinhibition than the Andean ecotype. Both ecotypes were exposed to cold induced photoinhibitory treatment (PhT. Photoinhibition and recovery of photosystem II (PSII was followed by fluorescence, CO2 exchange, and immunoblotting analyses. Results The same reduction (25% in maximum PSII efficiency (Fv/Fm was observed in both cold-acclimated (CA and non-acclimated (NA plants under PhT. A full recovery was observed in CA plants of both ecotypes under dark conditions, but CA Antarctic plants recover faster than the Andean ecotype. Under PhT, CA plants maintain their quantum yield of PSII, while NA plants reduced it strongly (50% and 73% for Andean and Antarctic plants respectively. Cold acclimation induced the maintenance of PsaA and Cyt b6/f and reduced a 41% the excitation pressure in Antarctic plants, exhibiting the lowest level under PhT. xCold acclimation decreased significantly NPQs in both ecotypes, and reduced chlorophylls and D1 degradation in Andean plants under PhT. NA and CA plants were able to fully restore their normal photosynthesis, while CA Antarctic plants reached 50% higher photosynthetic rates after recovery, which was associated to electron fluxes maintenance under photoinhibitory conditions. Conclusions Cold acclimation has a greater importance on the recovery process than on limiting photodamage. Cold acclimation determined the

  8. on the growth and photochemical efficiency of Acropora cervicornis

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    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.

  9. Lead induced changes in phosphorylation of PSII proteins in low light grown pea plants.

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    Wioleta, Wasilewska; Anna, Drożak; Ilona, Bacławska; Kamila, Kąkol; Elżbieta, Romanowska

    2015-02-01

    Light-intensity and redox-state induced thylakoid proteins phosphorylation involved in structural changes and in regulation of protein turnover. The presence of heavy metal ions triggers a wide range of cellular responses including changes in plant growth and photosynthesis. Plants have evolved a number of mechanisms to protect photosynthetic apparatus. We have characterized the effect of lead on PSII protein phosphorylation in pea (Pisum sativum L.) plants grown in low light conditions. Pb ions affected only slightly photochemical efficiency of PSII and had no effect on organization of thylakoid complexes. Lead activated strongly phosphorylation of PSII core D1 protein and dephosphorylation of this protein did not proceed in far red light. D1 protein was also not degraded in this conditions. However, phosphorylation of LHCII proteins was not affected by lead. These results indicate that Pb(2+) stimulate the phosphorylation of PSII core proteins and by disturbing the disassembly of supercomplexes play a role in PSII repair mechanism. LHCII phosphorylation could control the distribution of energy between the photosystems in low light conditions. This demonstrates that plants may respond to heavy metals by induction different pathways responsible for protein protection under stress conditions.

  10. 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

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    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

  11. Photobiological hydrogen production : photochemical efficiency and bioreactor design

    NARCIS (Netherlands)

    Akkerman, I.; Janssen, M.; Rocha, J.; Wijffels, R.H.

    2002-01-01

    Biological production of hydrogen can be carried out by photoautotrophic or photoheterotrophic organisms. Here, the photosystems of both processes are described. The main drawback of the photoautotrophic hydrogen production process is oxygen inhibition. The few efficiencies reported on the

  12. WATER DEFICIT ENSURES THE PHOTOCHEMICAL EFFICIENCY OF Copaifera langsdorffii Desf1

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    Angélica Lino Rodrigues

    2017-02-01

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

  13. Plant photosystem I--the most efficient nano-photochemical machine.

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    Nelson, Nathan

    2009-03-01

    Hydrogen is one of the most promising energy carriers among environmentally friendly and clean energy sources for the future. If the extremely effective photosynthetic energy conversion could be efficiently combined with a biological process of hydrogen production, it will represent a significant step toward this goal. The best candidate to do the job is photosystem I (PSI) of oxygenic photosynthesis. Despite its enormous complexity, the plant PSI is arguably the most efficient nano-photochemical machine in Nature. It emerged as a homodimeric structure containing several chlorophyll molecules over 3.5 billion years ago, and has perfected its photoelectric properties ever since. The recently determined structure of plant PSI, which is at the top of the evolutionary tree of this kind of complexes, provided the first relatively high-resolution structural model of the supercomplex containing a reaction center (RC) and a peripheral antenna (LHCI) complexes. The structure should provide a template for designing artificial systems amenable for utilizable energy production.

  14. Detection of herbicide effects on pigment composition and PSII photochemistry in Helianthus annuus by Raman spectroscopy and chlorophyll a fluorescence

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    Vítek, Petr; Novotná, Kateřina; Hodaňová, Petra; Rapantová, Barbora; Klem, Karel

    2017-01-01

    The effects of herbicides from three mode-of-action groups - inhibitors of protoporphyrinogen oxidase (carfentrazone-ethyl), inhibitors of carotenoid biosynthesis (mesotrione, clomazone, and diflufenican), and inhibitors of acetolactate synthase (amidosulfuron) - were studied in sunflower plants (Helianthus annuus). Raman spectroscopy, chlorophyll fluorescence (ChlF) imaging, and UV screening of ChlF were combined to evaluate changes in pigment composition, photosystem II (PSII) photochemistry, and non-photochemical quenching in plant leaves 6 d after herbicide application. The Raman signals of phenolic compounds, carotenoids, and chlorophyll were evaluated and differences in their intensity ratios were observed. Strongly augmented relative content of phenolic compounds was observed in the case of amidosulfuron-treated plants, with a simultaneous decrease in the chlorophyll/carotenoid intensity ratio. The results were confirmed by in vivo measurement of flavonols using UV screening of ChlF. Herbicides from the group of carotenoid biosynthesis inhibitors significantly decreased both the maximum quantum efficiency of PSII and non-photochemical quenching as determined by ChlF. Resonance Raman imaging (mapping) data with high resolution (150,000-200,000 spectra) are presented, showing the distribution of carotenoids in H. annuus leaves treated by two of the herbicides acting as inhibitors of carotenoid biosynthesis (clomazone or diflufenican). Clear signs were observed that the treatment induced carotenoid depletion within sunflower leaves. The depletion spatial pattern registered differed depending on the type of herbicide applied.

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

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    Matthew R. Nitschke

    2018-02-01

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

  16. Physiology of the seasonal relationship between the photochemical reflectance index and photosynthetic light use efficiency.

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    Porcar-Castell, Albert; Garcia-Plazaola, José Ignacio; Nichol, Caroline J; Kolari, Pasi; Olascoaga, Beñat; Kuusinen, Nea; Fernández-Marín, Beatriz; Pulkkinen, Minna; Juurola, Eija; Nikinmaa, Eero

    2012-10-01

    The photochemical reflectance index (PRI) is regarded as a promising proxy to track the dynamics of photosynthetic light use efficiency (LUE) via remote sensing. The implementation of this approach requires the relationship between PRI and LUE to scale not only in space but also in time. The short-term relationship between PRI and LUE is well known and is based on the regulative process of non-photochemical quenching (NPQ), but at the seasonal timescale the mechanisms behind the relationship remain unclear. We examined to what extent sustained forms of NPQ, photoinhibition of reaction centres, seasonal changes in leaf pigment concentrations, or adjustments in the capacity of alternative energy sinks affect the seasonal relationship between PRI and LUE during the year in needles of boreal Scots pine. PRI and NPQ were highly correlated during most of the year but decoupled in early spring when the foliage was deeply downregulated. This phenomenon was attributed to differences in the physiological mechanisms controlling the seasonal dynamics of PRI and NPQ. Seasonal adjustments in the pool size of the xanthophyll cycle pigments, on a chlorophyll basis, controlled the dynamics of PRI, whereas the xanthophyll de-epoxidation status and other xanthophyll-independent mechanisms controlled the dynamics of NPQ at the seasonal timescale. We conclude that the PRI leads to an underestimation of NPQ, and consequently overestimation of LUE, under conditions of severe stress in overwintering Scots pine, and most likely also in species experiencing severe drought. This severe stress-induced decoupling may challenge the implementation of the PRI approach.

  17. High-Efficiency Photochemical Water Splitting of CdZnS/CdZnSe Nanostructures

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    Chen-I Wang

    2013-01-01

    Full Text Available We have prepared and employed TiO2/CdZnS/CdZnSe electrodes for photochemical water splitting. The TiO2/CdZnS/CdZnSe electrodes consisting of sheet-like CdZnS/CdZnSe nanostructures (8–10 μm in length and 5–8 nm in width were prepared through chemical bath deposition on TiO2 substrates. The TiO2/CdZnS/CdZnSe electrodes have light absorption over the wavelength 400–700 nm and a band gap of 1.87 eV. Upon one sun illumination of 100 mW cm−2, the TiO2/CdZnS/CdZnSe electrodes provide a significant photocurrent density of 9.7 mA cm−2 at −0.9 V versus a saturated calomel electrode (SCE. Incident photon-to-current conversion efficiency (IPCE spectrum of the electrodes displays a maximum IPCE value of 80% at 500 nm. Moreover, the TiO2/CdZnS/CdZnSe electrodes prepared from three different batches provide a remarkable photon-to-hydrogen efficiency of 7.3 ± 0.1% (the rate of the photocatalytically produced H2 by water splitting is about 172.8 mmol·h−1·g−1, which is the most efficient quantum-dots-based photocatalysts used in solar water splitting.

  18. Photochemical reflectance ratio for tracking light use efficiency for sunlit leaves in two forest types

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    Zheng, Ting; Chen, Jing M.

    2017-01-01

    The estimation of maximum carboxylation rate (Vcmax)-a critical determinant of the terrestrial carbon simulation-over space remains a challenging task. Inverting the Vcmax through the sunlit gross primary productivity (GPP) is a possible solution if the key parameter sunlit light use efficiency (ɛsun) could be acquired through remote sensing approaches. Previous studies have shown that the reflectance centered at 531 nm (R531) is very sensitive to variations of ɛsun and the photochemical reflectance index (PRI, the normalized difference index using R531 and R570) can be used as an indicator of ɛsun at the leaf level though little is known about the PRI-ɛsun relationship at the canopy level due to the mixing of sunlit and shaded leaves. In this study, the photochemical reflectance ratio (PRR, defined as the ratio between R531 and R570) is proposed to enable the sunlit-shaded separation of the canopy reflectance observations acquired from a tower based multi-angular platform. The canopy PRR can be expressed as the algebraic sum of sunlit PRR and shaded PRR weighted by the visible portions of the sunlit canopy and the shaded canopy respectively. The visible portions from different angles were simulated using the 4-Scale model and the sunlit (/shaded) PRR was acquired through solving a set of equations describing the canopy PRR obtained from different angles. The relationships between the sunlit PRR (PRRsun) and ɛsun were studied for a white pine stand (TP39) and a sugar maple stand (HA). At both sites, significant correlations between PRRsun and ɛsun were obtained (R2 = 0.57 (TP39), 0.585 (HA), p < 0.001), showing the ability of PRRsun to track the variation of ɛsun. Nevertheless, differences existed in the expressions of the PRRsun-ɛsun relationship between TP39 and HA, a general expression could not be found. Further studies have shown that introducing the normalized difference vegetation index (NDVI) to correct PRRsun (NDVI × PRRsun) largely removed such

  19. Modulation of photosynthetic energy conversion efficiency in nature: from seconds to seasons.

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    Demmig-Adams, Barbara; Cohu, Christopher M; Muller, Onno; Adams, William W

    2012-09-01

    Modulation of the efficiency with which leaves convert absorbed light to photochemical energy [intrinsic efficiency of open photosystem II (PSII) centers, as the ratio of variable to maximal chlorophyll fluorescence] as well as leaf xanthophyll composition (interconversions of the xanthophyll cycle pigments violaxanthin and zeaxanthin) were characterized throughout single days and nights to entire seasons in plants growing naturally in contrasting light and temperature environments. All pronounced decreases of intrinsic PSII efficiency took place in the presence of zeaxanthin. The reversibility of these PSII efficiency changes varied widely, ranging from reversible-within-seconds (in a vine experiencing multiple sunflecks under a eucalypt canopy) to apparently permanently locked-in for entire seasons (throughout the whole winter in a subalpine conifer forest at 3,000 m). While close association between low intrinsic PSII efficiency and zeaxanthin accumulation was ubiquitous, accompanying features (such as trans-thylakoid pH gradient, thylakoid protein composition, and phosphorylation) differed among contrasting conditions. The strongest and longest-lasting depressions in intrinsic PSII efficiency were seen in the most stress-tolerant species. Evergreens, in particular, showed the most pronounced modulation of PSII efficiency and thermal dissipation, and are therefore suggested as model species for the study of photoprotection. Implications of the responses of field-grown plants in nature for mechanistic models are discussed.

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

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    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

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

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    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.

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

    Science.gov (United States)

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

    2015-08-01

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

  3. In vivo assessment of effect of phytotoxin tenuazonic acid on PSII reaction centers.

    Science.gov (United States)

    Chen, Shiguo; Strasser, Reto Jörg; Qiang, Sheng

    2014-11-01

    Tenuazonic acid (TeA), a phytotoxin produced by the fungus Alternaria alternata isolated from diseased croftonweed (Ageratina adenophora), exhibits a strong inhibition in photosystem II (PSII) activity. In vivo chlorophyll fluorescence transients of the host plant croftonweed, show that the dominant effect of TeA is not on the primary photochemical reaction but on the biochemical reaction after QA. The most important action site of TeA is the QB site on the PSII electron-acceptor side, blocking electron transport beyond QA(-) by occupying the QB site in the D1 protein. However, TeA does not affect the antenna pigments, the energy transfer from antenna pigment molecules to reaction centers (RCs), and the oxygen-evolving complex (OEC) at the donor side of PSII. TeA severely inactivated PSII RCs. The fraction of non-QA reducing centers and non-QB reducing centers show a time- and concentration-dependent linear increase. Conversely, the amount of active QA or QB reducing centers declined sharply in a linear way. The fraction of non-QB reducing centers calculated from data of fluorescence transients is close to the number of PSII RCs with their QB site filled by TeA. An increase of the step-J level (VJ) in the OJIP fluorescence transients attributed to QA(-) accumulation due to TeA bound to the QB site is a typical characteristic response of the plants leaf with respect to TeA penetration. Copyright © 2014 Elsevier Masson SAS. All rights reserved.

  4. Overexpressed Superoxide Dismutase and Catalase Act Synergistically to Protect the Repair of PSII during Photoinhibition in Synechococcus elongatus PCC 7942.

    Science.gov (United States)

    Sae-Tang, Penporn; Hihara, Yukako; Yumoto, Isao; Orikasa, Yoshitake; Okuyama, Hidetoshi; Nishiyama, Yoshitaka

    2016-09-01

    The repair of PSII under strong light is particularly sensitive to reactive oxygen species (ROS), such as the superoxide radical and hydrogen peroxide, and these ROS are efficiently scavenged by superoxide dismutase (SOD) and catalase. In the present study, we generated transformants of the cyanobacterium Synechococcus elongatus PCC 7942 that overexpressed an iron superoxide dismutase (Fe-SOD) from Synechocystis sp. PCC 6803; a highly active catalase (VktA) from Vibrio rumoiensis; and both enzymes together. Then we examined the sensitivity of PSII to photoinhibition in the three strains. In cells that overexpressed either Fe-SOD or VktA, PSII was more tolerant to strong light than it was in wild-type cells. Moreover, in cells that overexpressed both Fe-SOD and VktA, PSII was even more tolerant to strong light. However, the rate of photodamage to PSII, as monitored in the presence of chloramphenicol, was similar in all three transformant strains and in wild-type cells, suggesting that the overexpression of these ROS-scavenging enzymes might not protect PSII from photodamage but might protect the repair of PSII. Under strong light, intracellular levels of ROS fell significantly, and the synthesis de novo of proteins that are required for the repair of PSII, such as the D1 protein, was enhanced. Our observations suggest that overexpressed Fe-SOD and VktA might act synergistically to alleviate the photoinhibition of PSII by reducing intracellular levels of ROS, with resultant protection of the repair of PSII from oxidative inhibition. © The Author 2016. Published by Oxford University Press on behalf of Japanese Society of Plant Physiologists. All rights reserved. For permissions, please email: journals.permissions@oup.com.

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

    Science.gov (United States)

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

    2014-09-01

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

  6. Photochemical Reflectance Index (PRI) as a proxy of Light Use Efficiency (LUE) and transpiration in Mediterranean crop sites

    Science.gov (United States)

    LE Dantec, V.; Chebbi, W.; Boulet, G.; Merlin, O.; Lili-Chabaane, Z.; Er Raki, S.; Ceschia, E.; Khabba, S.; Fanise, P.; Zawilski, B.; Simonneaux, V.; Jarlan, L.

    2016-12-01

    The Photochemical Reflectance Index (PRI) is based on the short term reversible xanthophyll pigment changes accompanying plant stress and therefore of the associated photosynthetic activities. Strong relationships between PRI and Light Use Efficiency (LUE) were shown at leaf and canopy scales and over a wide range of species (Garbulsky et al., 2011). But very few previous works have explored the potential link with plant water status. In this study, we have first analyzed the link between PRI and LUE at canopy scale on two different crops in terms of canopy structure and crop management: olive grove (Tunisia) and wheat grown under different water regimes (irrigated or rainfed) and climate zones (France, Morocco). We have investigated the daily and seasonal dynamics of PRI; linking its variations to meteorological factors (global radiation and sun angle effects, soil water content, relative air humidity …) and plant processes. The highest correlations were mainly observed in clear skies conditions. We have found, whatever site, linear negative relationships between PRI and LUE using data acquired in midday (i.e. in solar zenithal angle condition). Linear link between PRI and sapflow measurements was also revealed. This correlation was obtained over periods characterized by a moderate soil water deficit, i.e. by when transpiration rate was mainly control by Vapor Pressure Deficit. We will then briefly presented alternative and complementary approaches to this index, to detect different level of water stress using thermal infrared emissions.

  7. Chloroplast movement provides photoprotection to plants by redistributing PSII damage within leaves.

    Science.gov (United States)

    Davis, Phillip A; Hangarter, Roger P

    2012-09-01

    Plants use light to fix carbon through the process of photosynthesis but light also causes photoinhibition, by damaging photosystem II (PSII). Plants can usually adjust their rate of PSII repair to equal the rate of damage, but under stress conditions or supersaturating light-intensities damage may exceed the rate of repair. Light-induced chloroplast movements are one of the many mechanisms plants have evolved to minimize photoinhibition. We found that chloroplast movements achieve a measure of photoprotection to PSII by altering the distribution of photoinhibition through depth in leaves. When chloroplasts are in the low-light accumulation arrangement a greater proportion of PSII damage occurs near the illuminated surface than for leaves where the chloroplasts are in the high-light avoidance arrangement. According to our findings chloroplast movements can increase the overall efficiency of leaf photosynthesis in at least two ways. The movements alter light profiles within leaves to maximize photosynthetic output and at the same time redistribute PSII damage throughout the leaf to reduce the amount of inhibition received by individual chloroplasts and prevent a decrease in photosynthetic potential.

  8. Oxyradicals and PSII activity in maize leaves in the absence of UV ...

    Indian Academy of Sciences (India)

    ... oxyradicals invoked higher activity of antioxidant enzymes like superoxide dismutase and peroxidase under ambient UV, they also imposed limitation on the photosynthetic efficiency of PSII. Exclusion of UV components (UV-B 280–315 nm; UV-A 315–400 nm) translated to enhanced photosynthesis, growth and biomass.

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

    Science.gov (United States)

    Zhen, Shuyang; van Iersel, Marc W

    2017-02-01

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

  10. UV-photochemical vapor generation of selenium for atomic absorption spectrometry: Optimization and 75Se radiotracer efficiency study

    Czech Academy of Sciences Publication Activity Database

    Rybínová, M.; Musil, Stanislav; Červený, J.; Vobecký, Miloslav; Rychlovský, P.

    2016-01-01

    Roč. 123, SEP (2016), s. 134-142 ISSN 0584-8547 R&D Projects: GA ČR GA14-23532S Institutional support: RVO:68081715 Keywords : UV-photochemical vapor generation * Selenium * 75Se radiotracer Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 3.241, year: 2016

  11. Disentangling two non-photochemical quenching processes in Cyclotella meneghiniana by spectrally-resolved picosecond fluorescence at 77K.

    Science.gov (United States)

    Chukhutsina, Volha U; Büchel, Claudia; van Amerongen, Herbert

    2014-06-01

    Diatoms, which are primary producers in the oceans, can rapidly switch on/off efficient photoprotection to respond to fast light-intensity changes in moving waters. The corresponding thermal dissipation of excess-absorbed-light energy can be observed as non-photochemical quenching (NPQ) of chlorophyll a fluorescence. Fluorescence-induction measurements on Cyclotella meneghiniana diatoms show two NPQ processes: qE1 relaxes rapidly in the dark while qE2 remains present upon switching to darkness and is related to the presence of the xanthophyll-cycle pigment diatoxanthin (Dtx). We performed picosecond fluorescence measurements on cells locked in different (quenching) states, revealing the following sequence of events during full development of NPQ. At first, trimers of light-harvesting complexes (fucoxanthin-chlorophyll a/c proteins), or FCPa, become quenched, while being part of photosystem II (PSII), due to the induced pH gradient across the thylakoid membrane. This is followed by (partial) detachment of FCPa from PSII after which quenching persists. The pH gradient also causes the formation of Dtx which leads to further quenching of isolated PSII cores and some aggregated FCPa. In subsequent darkness, the pH gradient disappears but Dtx remains present and quenching partly pertains. Only in the presence of some light the system completely recovers to the unquenched state. Copyright © 2014 Elsevier B.V. All rights reserved.

  12. Effects of severe dehydration on leaf photosynthesis in Quercus petraea (Matt.) Liebl.: photosystem II efficiency, photochemical and nonphotochemical fluorescence quenching and electrolyte leakage.

    Science.gov (United States)

    Epron, D; Dreyer, E

    1992-04-01

    Leaf disks of oak (Quercus petraea (Matt.) Liebl.) trees were subjected to rapid dehydration in air in the dark. Optimal photochemical efficiency of PS II (F(v)/F(M)), photochemical (q(P)) and nonphotochemical (q(NP)) quenchings of chlorophyll a fluorescence, and relative conductivity (C(r)) of leaf disk diffusate were measured in leaf disks with different water deficits (D). No effect of dehydration was detected before D reached values above 0.30. When D increased from 0.30 to 0.50, q(NP) increased without any change in q(P), which may indicate that thermal deexcitation of PS II increased, allowing reduced photochemical activity and maintenance of a large pool of oxidized primary acceptors (QA), although carbon reduction was impaired. Large changes in electron transport chain activity, leading to decreases in both q(P) and q(NP), appeared only in leaf disks subjected to severe water deficits (D > 0.60) and were correlated with a modification of membrane structure. However, stability of F(v)/F(M) indicated that the functional integrity of PS II was not altered until D reached values above 0.75. We conclude that the photosynthetic apparatus of Q. petraea is rather insensitive to leaf dehydration per se during drought under natural conditions.

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

    Science.gov (United States)

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

    2016-03-01

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

  14. [Growth and photochemical efficiency of photosystem ii in seedlings of two varieties of Capsicum annuum L. inoculated with rhizobacteria and arbuscular mycorrhizal fungi].

    Science.gov (United States)

    Angulo-Castro, Azareel; Ferrera-Cerrato, Ronald; Alarcón, Alejandro; Almaraz-Suárez, Juan José; Delgadillo-Martínez, Julián; Jiménez-Fernández, Maribel; García-Barradas, Oscar

    2017-10-17

    Plant growth promoting rhizobacteria (PGPR) and arbuscular mycorrhizal fungi (AMF) are a biological alternative for the sustainable management of Capsicum annuum L. This research work evaluated the effects of both PGPR and AMF on bell pepper and jalapeno pepper plants. Five bacterial strains isolated from several locations in Estado de Mexico were used: [P61 (Pseudomonas tolaasii), A46 (P. tolaasii), R44 (Bacillus pumilus), BSP1.1 (Paenibacillus sp.), and OLs-Sf5 (Pseudomonas sp.)], and three treatments with AMF [H1 (consortium isolated from pepper crops in the State of Puebla), H2 (Rhizophagus intraradices), and H3 (consortium isolated from the rhizosphere of lemon trees, State of Tabasco)]. In addition, a fertilized treatment (Steiner nutrient solution at 25%) and an unfertilized control were included. Seedlings of "Caloro" jalapeno pepper and "California Wonder" bell pepper were inoculated with AMF at seed sowing, and PGPR were inoculated after 15 days of seedling emergence; seedlings were grown under plant growth chamber conditions. P61 bacterium and H1 AMF consortia were the most effective microorganisms for jalapeno pepper whereas R44 bacterium and AMF H3 and H1 were the most effective for bell peppers, when compared to the unfertilized control. Furthermore, P61 and R44 bacteria showed beneficial effects on PSII efficiency. Copyright © 2017 Asociación Argentina de Microbiología. Publicado por Elsevier España, S.L.U. All rights reserved.

  15. Ascorbic Acid Alleviates Damage from Heat Stress in the Photosystem II of Tall Fescue in Both the Photochemical and Thermal Phases

    Directory of Open Access Journals (Sweden)

    Ke Chen

    2017-08-01

    Full Text Available L-Ascorbate (Asc plays important roles in plant development, hormone signaling, the cell cycle and cellular redox system, etc. The higher content of Asc in plant chloroplasts indicates its important role in the photosystem. The objective of this study was to study the roles of Asc in tall fescue leaves against heat stress. After a heat stress treatment, we observed a lower value of the maximum quantum yield for primary photochemistry (φPo, which reflects the inhibited activity of the photochemical phase of photosystem II (PSII. Moreover, we observed a higher value of efficiency of electron transfer from QB to photosystem I acceptors (δR0, which reflects elevated activity of the thermal phase of the photosystem of the tall fescue. The addition of Asc facilitate the behavior of the photochemical phase of the PSII by lowering the ROS content as well as that of the alternative electron donor to provide electron to the tyrosine residue of the D1 protein. Additionally, exogenous Asc reduces the activity of the thermal phase of the photosystem, which could contribute to the limitation of energy input into the photosystem in tall fescue against heat stress. Synthesis of the Asc increased under heat stress treatment. However, under heat stress this regulation does not occur at the transcription level and requires further study.

  16. Catalysis of Photochemical Reactions.

    Science.gov (United States)

    Albini, A.

    1986-01-01

    Offers a classification system of catalytic effects in photochemical reactions, contrasting characteristic properties of photochemical and thermal reactions. Discusses catalysis and sensitization, examples of catalyzed reactions of excepted states, complexing ground state substrates, and catalysis of primary photoproducts. (JM)

  17. Photochemical efficiency of adult and young leaves of the neotropical understory shrub Psychotria limonensis (Rubiaceaein response to changes in the light environment

    Directory of Open Access Journals (Sweden)

    Gerardo Avalos

    2004-12-01

    Full Text Available We explored the short-term adjustment in photochemical efficiency (Fv /Fm in adult and young leaves of the understory neotropical shrub Psychotria limonensis Krause (Rubiaceaein response to rapid changes in the light environment.Leaves were collected from 20 individual plants growing under sun and shade conditions on Gigante Peninsula,Barro Colorado Natural Monument (Republic of Panama,during the wet season of 1996. Leaves were distributed in four sequences of light treatments (AB leaves were expanded under sun and were transferred to shade,BA leaves experienced the opposite transfer,and the controls AA and BB leaves that were expanded and maintained under sun or shade conditions.Adult and young leaves did not differ in overall photochemical efficiency.Instead,differences were found among light environments,for which leaves transferred from shade to sun showed the lowest F v /F m ratios.There was no relationship between photochemical efficiency and leaf temperature.In P.limonensis,understory plants are susceptible of photoinhibition independently of the leaf ontogenetic stage.The approach utilized in this experiment allowed the rapid exploration of this capacity, and could be applied to poorly studied understory species. Rev.Biol.Trop.52(4:839-844.Epub 2005 Jun 24.Se exploró el ajuste a corto plazo en la eficiencia fotosintética (Fv /Fm en hojas jovenes y adultas del arbusto del sotobosque neotropical Psychotria limonensis Krause (Rubiaceaeen respuesta a cambios rápidos de luz ambiental. Las hojas fueron recolectadas de 20 plantas individuales bajo condiciones de sol y sombra en Peninsula Gigante, Monumento Natural Barro Colorado (Panamá,durante la estación lluviosa de 1996.Las hojas fueron distribuidas en una secuencia cuatro tratamientos de luz (AB las hojas fueron expandidas bajo el sol y fueron transferidas a la sombra,BA las hojas experimentaron la transferencia contraria,y las hojas controles AA y BB que fueron expandidas y mantenidas

  18. Rice Photosynthetic Productivity and PSII Photochemistry under Nonflooded Irrigation

    Directory of Open Access Journals (Sweden)

    Haibing He

    2014-01-01

    Full Text Available Nonflooded irrigation is an important water-saving rice cultivation technology, but little is known on its photosynthetic mechanism. The aims of this work were to investigate photosynthetic characteristics of rice during grain filling stage under three nonflooded irrigation treatments: furrow irrigation with plastic mulching (FIM, furrow irrigation with nonmulching (FIN, and drip irrigation with plastic mulching (DI. Compared with the conventional flooding (CF treatment, those grown in the nonflooded irrigation treatments showed lower net photosynthetic rate (PN, lower maximum quantum yield (Fv/Fm, and lower effective quantum yield of PSII photochemistry (ΦPSII. And the poor photosynthetic characteristics in the nonflooded irrigation treatments were mainly attributed to the low total nitrogen content (TNC. Under non-flooded irrigation, the PN, Fv/Fm, and ΦPSII significantly decreased with a reduction in the soil water potential, but these parameters were rapidly recovered in the DI and FIM treatments when supplementary irrigation was applied. Moreover, The DI treatment always had higher photosynthetic productivity than the FIM and FIN treatments. Grain yield, matter translocation, and dry matter post-anthesis (DMPA were the highest in the CF treatment, followed by the DI, FIM, and FIN treatments in turn. In conclusion, increasing nitrogen content in leaf of rice plants could be a key factor to improve photosynthetic capacity in nonflooded irrigation.

  19. Relative contribution of Na+/K+homeostasis, photochemical efficiency and antioxidant defense system to differential salt tolerance in cotton (Gossypium hirsutum L.) cultivars.

    Science.gov (United States)

    Wang, Ning; Qiao, Wenqing; Liu, Xiaohong; Shi, Jianbin; Xu, Qinghua; Zhou, Hong; Yan, Gentu; Huang, Qun

    2017-10-01

    In this study, the role of specific components of different coping strategies to salt load were identified. A pot experiment was conducted with four cotton (Gossypium hirsutum L.) cultivars (differing in salt-sensitivity) under salinity stress. Based on observed responses in growth performance and physiological characteristics, CZ91 was the most tolerant of the four cultivars, followed by cultivars CCRI44 and CCRI49, with Z571 being much more sensitive to salt stress. To perform this tolerant response, they implement different adaptative mechanisms to cope with salt-stress. The superior salt tolerance of CZ91 was conferred by at least three complementary physiological mechanisms: its ability to regulate K + and Na + transport more effectively, its higher photochemical efficiency and better antioxidant defense capacity. However, only one or a few specific components of these defense systems play crucial roles in moderately salt tolerant CCRI44 and CCRI49. Lower ROS load in CCRI44 may be attributed to simultaneous induction of antioxidant defenses by maintaining an unusually high level of SOD, and higher activities of CAT, APX, and POD during salt stress. CCRI49 could reduce the excess generation of ROS not only by maintaining a higher selective absorption of K + over Na + in roots across the membranes through SOS1, AKT1, and HAK5, but also by displaying higher excess-energy dissipation (e.g., higher ETR, P R and qN) during salt stress. Overall, our data provide a mechanistic explanation for differential salt stress tolerance among these cultivars and shed light on the different strategies employed by cotton cultivars to minimize the ill effects of stress. Copyright © 2017. Published by Elsevier Masson SAS.

  20. Photochemical and antioxidant responses in the leaves of Xerophyta viscosa Baker and Digitaria sanguinalis L. under water deficit.

    Science.gov (United States)

    Ekmekci, Yasemin; Bohms, Andreas; Thomson, Jennifer A; Mundree, Sagadevan G

    2005-01-01

    In this study, photochemical and antioxidant responses of the monocotyledonous resurrection plant Xerophyta viscosa Baker and the crab grass Digitaria sanguinalis L. under water deficit were investigated as a function of time. Water deficit was imposed by withholding irrigation for 21 d. Gas exchange and chlorophyll a fluorescence analyses indicated that the dehydration treatment caused photoinhibition in both species. The reduction in the photosynthesis rate in both species during water deficit probably contributed to the decline in the photochemical efficiency of PSII and electron transport rate. However, the stomatal conductance of both species did not change during treatment whereas the intercellular CO2 pressure increased after 10 d of water deficit treatment. These observations could be related to nonstomatal limitations. The increasing net transpiration rate of both species may have contributed to leaf cooling because of water limitations. Prolonged water deficit resulted in photosynthetic pigment chlorophyll (a + b) and carotenoids content loss in only D. sanguinalis. Both species especially D. sanguinalis had increased the level of anthocyanin after 15 d of treatment, possibly to prevent the damaging effect of photooxidation. The total SOD activity of D. sanguinalis was significantly different from X. viscosa during the treatment. The total peroxidase activity in D. sanguinalis was significantly higher than in X. viscosa. X. viscosa acclimated to water deficit with no ultimate apparent oxidative damage due to endogenous protective mechanisms of resurrection. In case of D. sanguinalis, water deficit induced considerable stress and possibly caused some oxidative damage, despite the upregulation of protection mechanisms.

  1. Regional Inversion of the Maximum Carboxylation Rate (Vcmax) through the Sunlit Light Use Efficiency Estimated Using the Corrected Photochemical Reflectance Ratio Derived from MODIS Data

    Science.gov (United States)

    Zheng, T.; Chen, J. M.

    2016-12-01

    The maximum carboxylation rate (Vcmax), despite its importance in terrestrial carbon cycle modelling, remains challenging to obtain for large scales. In this study, an attempt has been made to invert the Vcmax using the gross primary productivity from sunlit leaves (GPPsun) with the physiological basis that the photosynthesis rate for leaves exposed to high solar radiation is mainly determined by the Vcmax. Since the GPPsun can be calculated through the sunlit light use efficiency (ɛsun), the main focus becomes the acquisition of ɛsun. Previous studies using site level reflectance observations have shown the ability of the photochemical reflectance ratio (PRR, defined as the ratio between the reflectance from an effective band centered around 531nm and a reference band) in tracking the variation of ɛsun for an evergreen coniferous stand and a deciduous broadleaf stand separately and the potential of a NDVI corrected PRR (NPRR, defined as the product of NDVI and PRR) in producing a general expression to describe the NPRR-ɛsun relationship across different plant function types. In this study, a significant correlation (R2 = 0.67, p<0.001) between the MODIS derived NPRR and the site level ɛsun calculated using flux data for four Canadian flux sites has been found for the year 2010. For validation purpose, the ɛsun in 2009 for the same sites are calculated using the MODIS NPRR and the expression from 2010. The MODIS derived ɛsun matches well with the flux calculated ɛsun (R2 = 0.57, p<0.001). Same expression has then been applied over a 217 × 193 km area in Saskatchewan, Canada to obtain the ɛsun and thus GPPsun for the region during the growing season in 2008 (day 150 to day 260). The Vcmax for the region is inverted using the GPPsun and the result is validated at three flux sites inside the area. The results show that the approach is able to obtain good estimations of Vcmax values with R2 = 0.68 and RMSE = 8.8 μmol m-2 s-1.

  2. Photochemical Energy Conversion.

    Science.gov (United States)

    Batschelet, William H.; George, Arnold

    1986-01-01

    Describes procedures for two demonstrations: (1) photochemical energy conversion using ferric oxalate actinometry and (2) liquification of gases using Freon 114. Safety precautions are given for both demonstrations, as are procedures and material specifications. (JM)

  3. Temperature-sensitive PSII: a novel approach for sustained photosynthetic hydrogen production.

    Science.gov (United States)

    Bayro-Kaiser, Vinzenz; Nelson, Nathan

    2016-12-01

    The need for energy and the associated burden are ever growing. It is crucial to develop new technologies for generating clean and efficient energy for society to avoid upcoming energetic and environmental crises. Sunlight is the most abundant source of energy on the planet. Consequently, it has captured our interest. Certain microalgae possess the ability to capture solar energy and transfer it to the energy carrier, H2. H2 is a valuable fuel, because its combustion produces only one by-product: water. However, the establishment of an efficient biophotolytic H2 production system is hindered by three main obstacles: (1) the hydrogen-evolving enzyme, [FeFe]-hydrogenase, is highly sensitive to oxygen; (2) energy conversion efficiencies are not economically viable; and (3) hydrogen-producing organisms are sensitive to stressful conditions in large-scale production systems. This study aimed to circumvent the oxygen sensitivity of this process with a cyclic hydrogen production system. This approach required a mutant that responded to high temperatures by reducing oxygen evolution. To that end, we randomly mutagenized the green microalgae, Chlamydomonas reinhardtii, to generate mutants that exhibited temperature-sensitive photoautotrophic growth. The selected mutants were further characterized by their ability to evolve oxygen and hydrogen at 25 and 37 °C. We identified four candidate mutants for this project. We characterized these mutants with PSII fluorescence, P700 absorbance, and immunoblotting analyses. Finally, we demonstrated that these mutants could function in a prototype hydrogen-producing bioreactor. These mutant microalgae represent a novel approach for sustained hydrogen production.

  4. Exogenous Melatonin Mitigates Photoinhibition by Accelerating Non-photochemical Quenching in Tomato Seedlings Exposed to Moderate Light during Chilling

    Science.gov (United States)

    Ding, Fei; Wang, Meiling; Liu, Bin; Zhang, Shuoxin

    2017-01-01

    Melatonin plays an important role in tolerance to multiple stresses in plants. Recent studies have shown that melatonin relieves photoinhibition in plants under cold stress; however, the mechanisms are not fully understood. Non-photochemical quenching (NPQ) is a key process thermally dissipating excess light energy that plants employ as a protective mechanism to prevent the over reduction of photosystem II. Here, we report the effects of exogenous melatonin on NPQ and mitigation of photoinhibition in tomato seedlings exposed to moderate light during chilling. In response to moderate light during chilling, the maximum quantum yield (Fv/Fm) and the effective photochemical efficiency (F′v/F′m) of PSII were both substantially reduced, showing severe photoinhibition in tomato seedlings, whereas exogenous application of melatonin effectively alleviated the photoinhibition. Further experiment showed that melatonin accelerated the induction of NPQ in response to moderate light and maintained higher level of NPQ upon longer exposure to light during chilling. Consistent with the increased NPQ was the elevated de-epoxidation state of xanthophyll pigments in melatonin-pretreated seedlings exposed to light during chilling. Enzyme activity assay showed that violaxanthin de-epoxidase (VDE), which catalyzes the de-epoxidation reaction in the xanthophyll cycle, was activated by light and the activity was further enhanced by application of melatonin. Further analysis revealed that melatonin induced the expression of VDE gene in tomato seedlings under moderate light and chilling conditions. Ascorbic acid is an essential cofactor of VDE and the level of it was found to be increased in melatonin-pretreated seedlings. Feeding tomato seedlings with dithiothreitol, an inhibitor of VDE, blocked the effects of melatonin on the de-epoxidation state of xanthophyll pigments and the induction of NPQ. Collectively, these results suggest that exogenous melatonin mitigates photoinhibition by

  5. Efeitos da aplicação de herbicidas sobre a eficiência fotoquímica em plantas de soja convencional e geneticamente modificada Effects of herbicides application on photochemical efficiency in conventional and genetically modified soybeans

    Directory of Open Access Journals (Sweden)

    Maria José Pinheiro Corrêa

    2010-10-01

    , chlorimuron-ethyl + bentazon, glyphosate + imazethapyr, lactofen + chlorimuron-ethyl + imazethapyr, lactofen + chlorimuron-ethyl + imazethapyr / haloxyfop-methyl. The tests included two control. The evaluations were taken after the application of herbicides at 4; 11; 18; 25 and 32 in the first crop and at 6, 14, 21, 28 and 35 DAA in the second crop. The M-SOY 8001 was susceptible the herbicides application mostly the herbicide mixture lactofen + chlorimuron-ethyl and lactofen + chlorimuron-ethyl + imazethapyr + haloxifop-methyl the herbicides caused reduction in maximum quantum efficiency of PSII (Fv/Fm. However, both varieties were susceptible to the treatments lactofen alone applied and the mixtures lactofen + chlorimuron-ethyl, chlorimuron-ethyl + imazethapyr, lactofen + chlorimuron-ethyl + imazethapyr and lactofen + chlorimuron-ethyl + imazethapyr + haloxifop-methyl with reduction in chlorophyll relative content by portable chlorophyll meter. However, these damages were reversible, disappearing gradually with plant growth.

  6. Photochemical Assessment Monitoring Stations (PAMS)

    Data.gov (United States)

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

  7. Photochemical cutting of fabrics

    Science.gov (United States)

    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.

  8. Relationships between PSII-independent hydrogen bioproduction and starch metabolism as evidenced from isolation of starch catabolism mutants in the green alga Chlamydomonas reinhardtii

    Energy Technology Data Exchange (ETDEWEB)

    Chochois, Vincent; Constans, Laure; Beyly, Audrey; Soliveres, Melanie; Peltier, Gilles; Cournac, Laurent [CEA, DSV, IBEB, Laboratoire de Bioenergetique et Biotechnologie des Bacteries and Microalgues, Saint Paul Lez Durance, F-13108 (France); CNRS, UMR Biologie Vegetale and Microbiologie Environnementales, Saint Paul lez Durance, F-13108 (France); Aix-Marseille Universite, Saint Paul lez Durance, F-13108 (France); Dauvillee, David; Ball, Steven [Univ Lille Nord de France, F-59000 Lille (France); USTL, UGSF, F-59650 Villeneuve d' Ascq (France); CNRS, UMR 8576, F-59650 Villeneuve d' Ascq (France)

    2010-10-15

    Sulfur deprivation, which is considered as an efficient way to trigger long-term hydrogen photoproduction in unicellular green algae has two major effects: a decrease in PSII which allows anaerobiosis to be reached and carbohydrate (starch) storage. Starch metabolism has been proposed as one of the major factors of hydrogen production, particularly during the PSII-independent (or indirect) pathway. While starch biosynthesis has been characterized in the green alga Chlamydomonas reinhardtii, little remains known concerning starch degradation. In order to gain a better understanding of starch catabolism pathways and identify those steps likely to limit the starch-dependent hydrogen production, we have designed a genetic screening procedure aimed at isolating mutants of the green alga C. reinhardtii affected in starch mobilization. Using two different screening protocols, the first one based on aerobic starch degradation in the dark and the second one on anaerobic starch degradation in the light, eighteen mutants were isolated among a library of 15,000 insertion mutants, eight (std1-8) with the first screen and ten (sda1-10) with the second. Most of the mutant strains isolated in this study showed a reduction or a delay in the PSII-independent hydrogen production. Further characterization of these mutants should allow the identification of molecular determinants of starch-dependent hydrogen production and supply targets for future biotechnological improvements. (author)

  9. Light dependence of quantum yields for PSII charge separation and oxygen evolution in eucaryotic algae

    NARCIS (Netherlands)

    Flameling, I.A.; Kromkamp, J.C.

    1998-01-01

    Quantum yields of photosystem II (PSII) charge separation (Phi(P)) and oxygen production (Phi(O2)) were determined by simultaneous measurements of oxygen production and variable fluorescence in four different aquatic microalgae representing three different taxonomic groups: the freshwater alga

  10. The response of Hordeum spontaneum desert ecotype to drought and excessive light intensity is characterized by induction of O2 dependent photochemical activity and anthocyanin accumulation.

    Science.gov (United States)

    Eppel, Amir; Keren, Nir; Salomon, Eitan; Volis, Sergei; Rachmilevitch, Shimon

    2013-03-01

    The goal of the current research was to study the role of anthocyanin accumulation, O(2)-related photochemical processes and non-photochemical quenching (NPQ) in the response of desert and Mediterranean plants to drought and excessive light. Plants of Hordeum spontaneum were collected from Mediterranean and desert environments and were subjected to terminal drought for 25 days and then measured for PSII yield at 2 and 21% O(2), NPQ, net carbon assimilation, stomatal conductance, leaf relative water content (LRWC), anthocyanin concentration and leaf absorbance. Under terminal drought, LRWC, carbon assimilation and stomatal conductance decreased similarly and significantly in both the Mediterranean and the desert ecotypes. Anthocyanin accumulated more in the desert ecotype than in the Mediterranean ecotype. NPQ increased more in the Mediterranean ecotype as compared with the desert ecotype. PSII yield decreased significantly in the Mediterranean ecotype under drought and was much lower than in the desert ecotype under drought. The relatively high PSII yield under drought in the desert ecotype was O(2) dependent. The response of the H. spontaneum ecotype from a desert environment to drought stress was characterized by anthocyanin accumulation and induction of O(2) dependent photochemical activity, while the response of the Mediterranean ecotype was based on a higher induction of NPQ. Copyright © 2012 Elsevier Ireland Ltd. All rights reserved.

  11. Effects of Pb 2+ on energy distribution and photochemical activity of spinach chloroplast

    Science.gov (United States)

    Wu, Xiao; Hong, Fashui; Liu, Chao; Su, Mingyu; Zheng, Lei; Gao, Fengqing; Yang, Fan

    2008-03-01

    Lead (Pb 2+) is a well-known highly toxic element. The mechanisms of the Pb 2+ toxicity are not well understood for photosynthesis. In this paper, we reported the effect of Pb 2+ on light absorption, distribution and conversion of spinach chloroplast by spectroscopy, and photochemical reaction activities. Several effects of Pb 2+ were observed: (1) the absorption peak intensity of chloroplast obviously decreased in red and blue region and produced optical flattering; (2) fluorescence quantum yield nearby 680 nm of chloroplast greatly declined; (3) the excitation band nearby 440 nm of chloroplast significantly descended; (4) Pb 2+ treatments reduced of the rate of whole chain electron transport, photochemical activities of PSII DCPIP photoreduction and oxygen evolution, but the photoreduction activities of PSI were little changed. Together, the studies of the experiments showed that Pb 2+ decreased absorption of light on spinach chloroplast and inhibited excitation energy to be absorbed by LHCII and transferred to PSII, then reduced the conversion from light energy to electron energy, and decelerated electron transport, water photolysis and oxygen evolution.

  12. Assessing the additive risks of PSII herbicide exposure to the Great Barrier Reef.

    Science.gov (United States)

    Lewis, Stephen E; Schaffelke, Britta; Shaw, Melanie; Bainbridge, Zoë T; Rohde, Ken W; Kennedy, Karen; Davis, Aaron M; Masters, Bronwyn L; Devlin, Michelle J; Mueller, Jochen F; Brodie, Jon E

    2012-01-01

    Herbicide residues have been measured in the Great Barrier Reef lagoon at concentrations which have the potential to harm marine plant communities. Monitoring on the Great Barrier Reef lagoon following wet season discharge show that 80% of the time when herbicides are detected, more than one are present. These herbicides have been shown to act in an additive manner with regards to photosystem-II inhibition. In this study, the area of the Great Barrier Reef considered to be at risk from herbicides is compared when exposures are considered for each herbicide individually and also for herbicide mixtures. Two normalisation indices for herbicide mixtures were calculated based on current guidelines and PSII inhibition thresholds. The results show that the area of risk for most regions is greatly increased under the proposed additive PSII inhibition threshold and that the resilience of this important ecosystem could be reduced by exposure to these herbicides. Copyright © 2011 Elsevier Ltd. All rights reserved.

  13. Trocas gasosas e eficiência fotoquímica potencial em mamoeiro do grupo 'Formosa' cultivado em condição de campo Leaf gas exchange and potential photochemical efficiency of field-grown papaya plants

    Directory of Open Access Journals (Sweden)

    Fabrício de Oliveira Reis

    2008-12-01

    gas exchange is extremely important for the optimization of CO2 photosynthetic assimilation and water loss control. In order to contribute to this, in two seasons, October 2002 and January 2003, the gas exchange and the potential photochemical efficiency in 'Formosa' papaya plants cultivated under field condition in São Francisco do Itabapoana, Rio de Janeiro State, were studied. The CO2 photosynthetic assimilation (A, stomatal conductance (gS, photosynthetic photon flux density (PPFD were evaluated daily, four days per month, each every hour, from 8 a.m. to 5 p.m. In addition, the potential photochemical efficiency was measured from the same leaves and at the same conditions as before. The CO2 photosynthetic assimilation was higher in January. This result was due to a greater stomatal aperture on leaves of plants cultivated during this season. The lower A value observed in October, caused by the reduction of gS, was due to a higher photosynthetic photon flux density (Cloudless days occurred in this month. Under the experimental conditions, measuring the potential photochemical efficiency, the photoinhibitory chronic type effect was not verified. Possibly the non-detection of damage to the photosynthetic apparatus has been due to the paraheliotropic movement of leaves, observed at warmer periods of the day. These results can contribute significantly for the papaya tree management grown under field condition, since any management strategy that optimizes the stomatal aperture will help the CO2 photosynthetic assimilation, and may result in an increase of productivity.

  14. Deletion of CGLD1 Impairs PSII and Increases Singlet Oxygen Tolerance of Green Alga Chlamydomonas reinhardtii

    Directory of Open Access Journals (Sweden)

    Jiale Xing

    2017-12-01

    Full Text Available The green alga Chlamydomonas reinhardtii is a key model organism for studying photosynthesis and oxidative stress in unicellular eukaryotes. Using a forward genetics approach, we have identified and characterized a mutant x32, which lacks a predicted protein named CGLD1 (Conserved in Green Lineage and Diatom 1 in GreenCut2, under normal and stress conditions. We show that loss of CGLD1 resulted in minimal photoautotrophic growth and PSII activity in the organism. We observed reduced amount of PSII complex and core subunits in the x32 mutant based on blue-native (BN/PAGE and immunoblot analysis. Moreover, x32 exhibited increased sensitivity to high-light stress and altered tolerance to different reactive oxygenic species (ROS stress treatments, i.e., decreased resistance to H2O2/or tert-Butyl hydroperoxide (t-BOOH and increased tolerance to neutral red (NR and rose bengal (RB that induce the formation of singlet oxygen, respectively. Further analysis via quantitative real-time PCR (qRT-PCR indicated that the increased singlet-oxygen tolerance of x32 was largely correlated with up-regulated gene expression of glutathione-S-transferases (GST. The phenotypical and physiological implications revealed from our experiments highlight the important roles of CGLD1 in maintaining structure and function of PSII as well as in protection of Chlamydomonas under photo-oxidative stress conditions.

  15. Determination of microphytobenthos PSII quantum efficiency and photosynthetic activity by means of variable chlorophyll fluorescence

    NARCIS (Netherlands)

    Kromkamp, J.C.; Barranguet, C.; Peene, J.

    1998-01-01

    A pulse amplitude modulated fluorometer (PAM) was used to investigate photosynthetic activity of microphytobenthos on an intertidal mudflat. Spectral irradiance measurements indicate that 75% of the signal detectable by the PAM originates in the upper 150 mu m of the sediment. From the

  16. Phytoplankton growth and PSII efficiency sensitivity to a glyphosate-based herbicide (Factor 540®).

    Science.gov (United States)

    Smedbol, Élise; Lucotte, Marc; Labrecque, Michel; Lepage, Laurent; Juneau, Philippe

    2017-11-01

    The use of glyphosate-based herbicides in agriculture has increased steadily since the mid 90's and there is now evidence of glyphosate leaching and contamination of aquatic ecosystems. The aim of this study was to evaluate the effects of a glyphosate-based herbicide (Factor 540 ® ) on growth and photosynthetic capacity of algae and cyanobacteria. Six algal and three cyanobacterial species/strains, of three different taxonomic groups, were exposed to five glyphosate concentrations (10, 50, 100, 500 and 1000μgl -1 ) during 48h. All species have significant growth inhibition at concentrations varying between 50 and 500μgl -1 . The photosynthetic response, after glyphosate exposure, varied among species, but a general pattern has emerged. There was an increase in the amount of photons absorbed (ABS/RC), in dissipated (DI O /RC) and trapped (TR O /RC) energy in the photosystem II reaction centers, along with a decreased of the maximum photosystem II quantum yield (F V /F M ) and electron transport per reaction center (ET O /RC). The EC 50 and LOEC values for growth and photosynthesis were calculated and established that growth was the most affected parameter by glyphosate-based herbicide, while parameter TR O /RC was the least affected. All species showed reduced growth at glyphosate concentrations lower than the Canadian standard for the protection of aquatic life, set at 800μgl -1 or the American aquatic life benchmark for acute toxicity in non vascular plants of 12 100μgl -1 questioning the validity of these thresholds in assessing the risks related to the presence of glyphosate and glyphosate-based herbicides in aquatic systems. Crown Copyright © 2017. Published by Elsevier B.V. All rights reserved.

  17. Evaluation of leaf energy dissipation by the Photochemical Reflectance

    Science.gov (United States)

    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

  18. Effects of acute O3 stress on PSII and PSI photochemistry of sensitive and resistant snap bean genotypes (Phaseolus vulgaris L.), probed by prompt chlorophyll "a" fluorescence and 820 nm modulated reflectance.

    Science.gov (United States)

    Salvatori, Elisabetta; Fusaro, Lina; Strasser, Reto J; Bussotti, Filippo; Manes, Fausto

    2015-12-01

    The response of PSII and PSI photochemistry to acute ozone (O3) stress was tested in a "model plant system", namely the O3 sensitive (S156) and O3 resistant (R123) genotype pairs of Phaseolus vulgaris L., during a phenological phase of higher O3 sensitivity (pod formation). The modulation of the photosynthetic activity during O3 stress was analysed by measuring gas exchanges, Prompt Fluorescence (PF, JIP-test) and 820 nm Modulated Reflectance (MR), a novel techniques which specifically detects the changes in the redox state of P700 and plastocyanin. The results showed that, coherently with genotypic-specific O3 sensitivity, the response of the two snap bean genotypes differed for the intensity and time of onset of the considered physiological changes. In fact, despite leaf injury and gas exchanges reduction appeared concurrently in both genotypes, S156 showed a PSII down regulation already after the first day of fumigation (DOF), and an enhancement of Cyclic Electron Flow of PSI after the second DOF, whereas R123 showed only slight adjustments until the third DOF, when the activity of both photosystems was down-regulated. Despite these differences, it is possible to distinguish in both genotypes an early O3 response of the photochemical apparatus, involving PSII only, and a following response, in which PSI activity and content are also modulated. The measurement of the MR signal, performed simultaneously with the PF measurements and the JIP-test analysis, has allowed a better understanding of the role that PSI plays in the O3 stress response of the S156/R123 model plant system. Copyright © 2015 Elsevier Masson SAS. All rights reserved.

  19. Stoichiometric relationship between the (Mn){sub 4}-cluster and PSII Ca{sup 2+} necessary for O{sub 2}-evolution. Final report

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1998-11-01

    This report focuses on the following research accomplishments: Stoichiometric relationship between the (Mn){sub 4}-cluster and PSII Ca{sup 2+} necessary for O{sub 2}-evolution; Photodamage of Mn-depleted PSII membranes: Sites and mechanisms of photoinactivation of primary reactions; The photoassembly of the PSII (Mn){sub 4}cluster is modulated by Ca{sup 2+} and DCIP; The natural product sorgoleone inhibits electron transfer at the Q{sub A}/Q{sub B} site of PSII; and Photodamages of Ca{sup 2+}-depleted PSII membranes: Sites and mechanisms of inactivation of donor side reactions.

  20. Photochemical cooperativity in photosystem II. Characterization of oxygen evolution discontinuities in the light-response curves.

    Science.gov (United States)

    Viruvuru, V; Fragata, M

    2008-11-28

    In two previous papers (Fragata et al., J. Phys. Chem. B, 2005, 109, 14707-14714; Fragata et al., J. Phys. Chem. B, 2007, 111, 3315-3320), it was shown that the variation of oxygen evolution with the light intensity (I) in photosystem II (PSII) in steady state conditions can be formulated according to the Langmuir adsorption isotherm for heterogeneous catalysis. This yielded the expression OEth = OEth(max) I/(L1/2 + I), where OEth is the theoretical oxygen evolution, OEth(max) the maximum oxygen evolution, and L1/2 the irradiance giving OEth(max)/2. In this approximation, the photons interaction with the chlorophylls in the PSII reaction center is assumed to be a heterogeneous reaction in which the light is represented as a stream of particles instead of an electromagnetic wave. That is, the chlorophyll molecules are the adsorption surfaces (or heterogeneous catalysts), and the incident (or exciting) photons are the substrate, or the reagent. Recently, the examination of new experimental data obtained with 2,6-dichloro-p-benzoquinone (DCBQ) and p-benzoquinone (pBQ) as exogenous electron acceptors, disclosed the presence of oxygen evolution discontinuities (or transitions) in the light-response curves. The new data were fitted with a mathematical summation of hyperbola of order n(i) > 1, OEth = Sigma(i) [OEth(max)]iIn(i)/[(L1/2)i(n(i)) + I(n(i))], where the n(i)'s are the number of sites used by the incident photons in their interaction with the photosynthetic pigments in each population i of PSII centers open for photochemistry. The mathematical simulations yielded only three distinct n(i)'s, that is, 1.8, 4.8, 8.5 and 1.8, 4.2, 8.4 for isolated PSII particles incubated with DCBQ and pBQ, respectively. Implicitly, this means the simultaneous excitation of each PSII reaction center with more than one photon, that is, the excitation of more than one pigment molecule. It is suggested that these transitions have their origin in the cooperative interaction of the

  1. Photosystem II Water Oxidation: Mechanism, Efficiency and Flux in Diverse Oxygenic Phototrophs

    Energy Technology Data Exchange (ETDEWEB)

    Dismukes, Gerard Charles [Rutgers Univ., Piscataway, NJ (United States); Ananyev, Gennady [Rutgers Univ., Piscataway, NJ (United States); Gates, Colin [Rutgers Univ., Piscataway, NJ (United States)

    2018-01-09

    In one year, we pursued four aims: 1) extend the VZAD model to allow analysis of PSII chlorophyll fluorescence emission as modulated by interaction with the WOC (partial success); 2) compare the solar energy conversion efficiencies of PSII-WOCs from intact cells, isolated thylakoid membranes and PSII core complexes and crystals from cyanobacterium Thermosynechococcus elongatus (collaboration with Lawrence Berkeley National Laboratory; some success after changing collaborator); 3) determine whether PSIIs can store light energy by pumping protons across the thylakoid membrane (PSII-cyclic electron flow) and how it is regulated within the green alga Chlorella ohadii (collaboration with the Hebrew University of Jerusalem; some success); and 4) genetically replace the native PSII-D1 protein subunit from a higher plant with two cyanobacterial D1 isoforms to test whether their functional advantages in growth and photoprotection can be transferred (collaboration with Rutgers University; success).

  2. Isolation of novel PSII-LHCII megacomplexes from pea plants characterized by a combination of proteomics and electron microscopy.

    Science.gov (United States)

    Albanese, Pascal; Nield, Jon; Tabares, Jose Alejandro Muñoz; Chiodoni, Angelica; Manfredi, Marcello; Gosetti, Fabio; Marengo, Emilio; Saracco, Guido; Barber, James; Pagliano, Cristina

    2016-12-01

    In higher plants, photosystem II (PSII) is a multi-subunit pigment-protein complex embedded in the thylakoid membranes of chloroplasts, where it is present mostly in dimeric form within the grana. Its light-harvesting antenna system, LHCII, is composed of trimeric and monomeric complexes, which can associate in variable number with the dimeric PSII core complex in order to form different types of PSII-LHCII supercomplexes. Moreover, PSII-LHCII supercomplexes can laterally associate within the thylakoid membrane plane, thus forming higher molecular mass complexes, termed PSII-LHCII megacomplexes (Boekema et al. 1999a, in Biochemistry 38:2233-2239; Boekema et al. 1999b, in Eur J Biochem 266:444-452). In this study, pure PSII-LHCII megacomplexes were directly isolated from stacked pea thylakoid membranes by a rapid single-step solubilization, using the detergent n-dodecyl-α-D-maltoside, followed by sucrose gradient ultracentrifugation. The megacomplexes were subjected to biochemical and structural analyses. Transmission electron microscopy on negatively stained samples, followed by single-particle analyses, revealed a novel form of PSII-LHCII megacomplexes, as compared to previous studies (Boekema et al.1999a, in Biochemistry 38:2233-2239; Boekema et al. 1999b, in Eur J Biochem 266:444-452), consisting of two PSII-LHCII supercomplexes sitting side-by-side in the membrane plane, sandwiched together with a second copy. This second copy of the megacomplex is most likely derived from the opposite membrane of a granal stack. Two predominant forms of intact sandwiched megacomplexes were observed and termed, according to (Dekker and Boekema 2005 Biochim Biophys Acta 1706:12-39), as (C2S2)4 and (C2S2 + C2S2M2)2 megacomplexes. By applying a gel-based proteomic approach, the protein composition of the isolated megacomplexes was fully characterized. In summary, the new structural forms of isolated megacomplexes and the related modeling performed provide novel insights into

  3. Solar UV-B effects on PSII performance in Betula nana are influenced by PAR level and reduced by EDU

    DEFF Research Database (Denmark)

    Albert, Kristian Rost; Mikkelsen, Teis Nørgaard; Ro-Poulsen, Helge

    2012-01-01

    The long-term and diurnal responses of photosystem II (PSII) performance to near-ambient UV-B radiation were investigated in High Arctic Betula nana. We conducted an UV exclusion experiment with five replicated blocks consisting of open control (no filter), photosynthetic active radiation and UV...... the effects of UV-B. Chlorophyll-a fluorescence induction curves were used for analysis of OJIP test parameters. Near-ambient UV-B radiation reduced across season maximum quantum yield (TRo /ABS = Fv /Fm ), approximated number of active PSII reaction center (RC/ABS) and the performance index (PIABS ), despite...... in reduced UV-B compared to near-ambient UV-B. This demonstrates current solar UV-B to reduce the PSII performance both on a daily as well as a seasonal basis in this High Arctic species....

  4. Antagonism between elevated CO2, nighttime warming, and summer drought reduces the robustness of PSII performance to freezing events

    DEFF Research Database (Denmark)

    Albert, Kristian Rost; Boesgaard, Kristine Stove; Ro-Poulsen, Helge

    2013-01-01

    out in the CLIMAITE multifactor experiment, which includes the combined impact of elevated CO2 (free air carbon enrichment; CO2), warming (passive nighttime warming; T) and summer drought (rain-excluding curtains; D) in a temperate heath ecosystem. PSII performance was probed by the effective quantum...... in the wavy hair-grass, Deschampsia flexuosa, and in the evergreen dwarf shrub common heather, Calluna vulgaris, and following freezing events the PItotal and Fv′/Fm′ were reduced even more. Contrary to expected, indirect effects of the previous summer drought reduced PSII performance before freezing events......, particularly in Calluna. In combinations with elevated CO2 interactive effects with drought, D×CO2 and warming, T×D×CO2, were negatively skewed and caused the reduction of PSII performance in both species after occurrence of freezing events. Neither passive nighttime warming nor elevated CO2 as single factors...

  5. Estimating chlorophyll content and photochemical yield of photosystem II (ΦPSII) using solar-induced chlorophyll fluorescence measurements at different growing stages of attached leaves

    OpenAIRE

    Tubuxin, Bayaer; Rahimzadeh-Bajgiran, Parinaz; Ginnan, Yusaku; Hosoi, Fumiki; Omasa, Kenji

    2015-01-01

    This paper illustrates the possibility of measuring chlorophyll (Chl) content and Chl fluorescence parameters by the solar-induced Chl fluorescence (SIF) method using the Fraunhofer line depth (FLD) principle, and compares the results with the standard measurement methods. A high-spectral resolution HR2000+ and an ordinary USB4000 spectrometer were used to measure leaf reflectance under solar and artificial light, respectively, to estimate Chl fluorescence. Using leaves of Capsicum annuum cv....

  6. Variations in morphology and PSII photosynthetic capabilities during the early development of tetraspores of Gracilaria vermiculophylla (Ohmi) Papenfuss (Gracilariales, Rhodophyta).

    Science.gov (United States)

    Xie, Xiujun; Wang, Guangce; Pan, Guanghua; Gao, Shan; Xu, Pu; Zhu, Jianyi

    2010-04-28

    Red algae are primitive photosynthetic eukaryotes, whose spores are ideal subjects for studies of photosynthesis and development. Although the development of red alga spores has received considerable research attention, few studies have focused on the detailed morphological and photosynthetic changes that occur during the early development of tetraspores of Gracilaria vermiculophylla (Ohmi) Papenfuss (Gracilariales, Rhodophyta). Herein, we documented these changes in this species of red algae. In the tetraspores, we observed two types of division, cruciate and zonate, and both could develop into multicellular bodies (disks). During the first 84 hours, tetraspores divided several times, but the diameter of the disks changed very little; thereafter, the diameter increased significantly. Scanning electron microscopy observations and analysis of histological sections revealed that the natural shape of the disk remains tapered over time, and the erect frond grows from the central protrusion of the disk. Cultivation of tissue from excised disks demonstrated that the central protrusion of the disk is essential for initiation of the erect frond. Photosynthetic (i.e., PSII) activities were measured using chlorophyll fluorescence analysis. The results indicated that freshly released tetraspores retained limited PSII photosynthetic capabilities; when the tetraspores attached to a substrate, those capabilities increased significantly. In the disk, the PSII activity of both marginal and central cells was similar, although some degree of morphological polarity was present; the PSII photosynthetic capabilities in young germling exhibited an apico-basal gradient. Attachment of tetraspores to a substrate significantly enhanced their PSII photosynthetic capabilities, and triggered further development. The central protrusion of the disk is the growth point, may have transfer of nutritive material with the marginal cells. Within the young germling, the hetero-distribution of PSII

  7. Variations in morphology and PSII photosynthetic capabilities during the early development of tetraspores of Gracilaria vermiculophylla (Ohmi Papenfuss (Gracilariales, Rhodophyta

    Directory of Open Access Journals (Sweden)

    Gao Shan

    2010-04-01

    Full Text Available Abstract Background Red algae are primitive photosynthetic eukaryotes, whose spores are ideal subjects for studies of photosynthesis and development. Although the development of red alga spores has received considerable research attention, few studies have focused on the detailed morphological and photosynthetic changes that occur during the early development of tetraspores of Gracilaria vermiculophylla (Ohmi Papenfuss (Gracilariales, Rhodophyta. Herein, we documented these changes in this species of red algae. Results In the tetraspores, we observed two types of division, cruciate and zonate, and both could develop into multicellular bodies (disks. During the first 84 hours, tetraspores divided several times, but the diameter of the disks changed very little; thereafter, the diameter increased significantly. Scanning electron microscopy observations and analysis of histological sections revealed that the natural shape of the disk remains tapered over time, and the erect frond grows from the central protrusion of the disk. Cultivation of tissue from excised disks demonstrated that the central protrusion of the disk is essential for initiation of the erect frond. Photosynthetic (i.e., PSII activities were measured using chlorophyll fluorescence analysis. The results indicated that freshly released tetraspores retained limited PSII photosynthetic capabilities; when the tetraspores attached to a substrate, those capabilities increased significantly. In the disk, the PSII activity of both marginal and central cells was similar, although some degree of morphological polarity was present; the PSII photosynthetic capabilities in young germling exhibited an apico-basal gradient. Conclusions Attachment of tetraspores to a substrate significantly enhanced their PSII photosynthetic capabilities, and triggered further development. The central protrusion of the disk is the growth point, may have transfer of nutritive material with the marginal cells. Within

  8. Structure of PSI, PSII and antennae complexes from yellow-green alga Xanthonema debile.

    Science.gov (United States)

    Gardian, Zdenko; Tichý, Josef; Vácha, František

    2011-05-01

    Photosynthetic carbon fixation by Chromophytes is one of the significant components of a carbon cycle on the Earth. Their photosynthetic apparatus is different in pigment composition from that of green plants and algae. In this work we report structural maps of photosystem I, photosystem II and light harvesting antenna complexes isolated from a soil chromophytic alga Xanthonema debile (class Xanthophyceae). Electron microscopy of negatively stained preparations followed by single particle analysis revealed that the overall structure of Xanthophytes' PSI and PSII complexes is similar to that known from higher plants or algae. Averaged top-view projections of Xanthophytes' light harvesting antenna complexes (XLH) showed two groups of particles. Smaller ones that correspond to a trimeric form of XLH, bigger particles resemble higher oligomeric form of XLH.

  9. Ambient UV-B radiation reduces PSII performance and net photosynthesis in high Arctic Salix arctica

    DEFF Research Database (Denmark)

    Albert, Kristian Rost; Mikkelsen, Teis Nørgaard; Ro-Poulsen, H.

    2011-01-01

    Ambient ultraviolet-B (UV-B) radiation potentially impacts the photosynthetic performance of high Arctic plants. We conducted an UV-B exclusion experiment in a dwarf shrub heath in NE Greenland (74°N), with open control, filter control, UV-B filtering and UV-AB filtering, all in combination...... was characterized by simultaneous gas exchange and chlorophyll fluorescence measurements and the PSII performance through the growing season was investigated with fluorescence measurements. Leaf harvest towards the end of the growing season was done to determine the specific leaf area and the content of carbon......, nitrogen and UV-B absorbing compounds. Compared to a 60% reduced UV-B irradiance, the ambient solar UV-B reduced net photosynthesis in Salix arctica leaves fixed in the 45° position which exposed leaves to maximum natural irradiance. Also a reduced Calvin Cycle capacity was found, i.e. the maximum rate...

  10. Photochemical processes and ozone production in Finnish conditions

    Energy Technology Data Exchange (ETDEWEB)

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

    1996-12-31

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

  11. Influence of humidity on photochemical ozone generation with 172nm xenon excimer lamps

    Science.gov (United States)

    Salvermoser, M. J.; Kogelschatz, U.; Murnick, D. E.

    2009-08-01

    The reaction kinetics of photochemical ozone (O{3}) generation in humid air and oxygen (O{2}) using efficient, narrow band vacuum ultra violet (VUV) 172 nm xenon excimer lamps is discussed. Trace amounts of water (H{2}O) vapor in the process gas leads to hydroxyl (OH) and hydroperoxy (HO{2}) radical formation. These radicals drive a catalytic O{3} destruction cycle limiting O{3} saturation concentration. This catalytic O{3} destruction cycle was included into a quantitative kinetic model describing photochemical O{3} production. Experimental O{3} saturation concentrations obtained with coaxial VUV driven photochemical O{3} generators compare satisfactorily with the models predictions.

  12. Engineering photochemical smog through convection towers

    Energy Technology Data Exchange (ETDEWEB)

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

    1995-02-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Fedorowski, Jennifer [Department of Chemistry and Biochemistry, University of Maryland, Baltimore County, 1000 Hilltop Circle, Baltimore, MD 21250 (United States); LaCourse, William R., E-mail: lacourse@umbc.edu [Department of Chemistry and Biochemistry, University of Maryland, Baltimore County, 1000 Hilltop Circle, Baltimore, MD 21250 (United States)

    2010-01-04

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

  14. Proteomic characterization and three-dimensional electron microscopy study of PSII-LHCII supercomplexes from higher plants.

    Science.gov (United States)

    Pagliano, Cristina; Nield, Jon; Marsano, Francesco; Pape, Tillmann; Barera, Simone; Saracco, Guido; Barber, James

    2014-09-01

    In higher plants a variable number of peripheral LHCII trimers can strongly (S), moderately (M) or loosely (L) associate with the dimeric PSII core (C2) complex via monomeric Lhcb proteins to form PSII-LHCII supercomplexes with different structural organizations. By solubilizing isolated stacked pea thylakoid membranes either with the α or β isomeric forms of the detergent n-dodecyl-D-maltoside, followed by sucrose density ultracentrifugation, we previously showed that PSII-LHCII supercomplexes of types C2S2M2 and C2S2, respectively, can be isolated [S. Barera et al., Phil. Trans. R Soc. B 67 (2012) 3389-3399]. Here we analysed their protein composition by applying extensive bottom-up and top-down mass spectrometry on the two forms of the isolated supercomplexes. In this way, we revealed the presence of the antenna proteins Lhcb3 and Lhcb6 and of the extrinsic polypeptides PsbP, PsbQ and PsbR exclusively in the C2S2M2 supercomplex. Other proteins of the PSII core complex, common to the C2S2M2 and C2S2 supercomplexes, including the low molecular mass subunits, were also detected and characterized. To complement the proteomic study with structural information, we performed negative stain transmission electron microscopy and single particle analysis on the PSII-LHCII supercomplexes isolated from pea thylakoid membranes solubilized with n-dodecyl-α-D-maltoside. We observed the C2S2M2 supercomplex in its intact form as the largest PSII complex in our preparations. Its dataset was further analysed in silico, together with that of the second largest identified sub-population, corresponding to its C2S2 subcomplex. In this way, we calculated 3D electron density maps for the C2S2M2 and C2S2 supercomplexes, approaching respectively 30 and 28Å resolution, extended by molecular modelling towards the atomic level. This article is part of a special issue entitled: photosynthesis research for sustainability: keys to produce clean energy. Copyright © 2013. Published by

  15. Tropospheric Ozone and Photochemical Smog

    Science.gov (United States)

    Sillman, S.

    2003-12-01

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

  16. Ecophysiological responses of the salt marsh grass Spartina ...

    African Journals Online (AJOL)

    At the inland site, soil water potential (ø), electrical conductivity of the soil, total cations, and the concentrations of Na+, Ca2+, Mg2+ and P, were significantly higher than those of the streamside site, while CO2 exchange, quantum yield of PSII, ETR through PSII, and intrinsic photochemical efficiency of PSII were significantly ...

  17. A four state parametric model for the kinetics of the non-photochemical quenching in Photosystem II.

    Science.gov (United States)

    Snellenburg, Joris J; Johnson, Matthew P; Ruban, Alexander V; van Grondelle, Rienk; van Stokkum, Ivo H M

    2017-10-01

    The phenomenon of non-photochemical quenching (NPQ) was studied in spinach chloroplasts using pulse amplitude modulated (PAM) fluorometry. We present a new analysis method which describes the observed fluorescence quantum yield as the sum of the product of four different states of PSII and their corresponding quantum yields. These four distinct states are PSII in the quenched or unquenched state, and with its reaction center either open or closed depending upon the reduction of the QA site. With this method we can describe the dynamics of the NPQ induction and recovery as well as quantify the percentage of photoinactivated RC throughout the measurement. We show that after one cycle of quenching followed by a period of recovery, approximately 8-9% of the RC are photoinactivated, after two cycles of illumination this number becomes 15-17%. The recovery from the quenching appeared with rates of (50s)-1 and (1h)-1. The new analysis method presented here is flexible, allowing it to be applied to any type of PAM fluorometry protocol. The method allows to quantitatively compare qualitatively different PAM curves on the basis of statistically relevant fitting parameters and to quantify quenching dynamics and photoinactivation. Moreover, the results presented here demonstrate that the analysis of a single PAM fluorometry quenching experiment can already provide information on the relative quantum yield of the four different states of PSII for the intact chloroplasts - something no other form of spectroscopy could provide in a single measurement. Copyright © 2017 Elsevier B.V. All rights reserved.

  18. Brassica rapa plants adapted to microgravity with reduced photosystem I and its photochemical activity

    Science.gov (United States)

    Jiao, Shunxing; Hilaire, Emmanuel; Paulsen, Avelina Q.; Guikema, James A.

    2004-01-01

    The photosynthetic apparatus contains several protein complexes, many of which are regulated by environmental conditions. In this study, the influences of microgravity on PSI and PSII in Brassica rapa plants grown aboard the space shuttle were examined. We found that Brassica plants grown in space had a normal level of growth relative to controls under similar conditions on Earth. Upon return to Earth, cotyledons were harvested and thylakoid membranes were isolated. Analysis of chlorophyll contents showed that the Chl a/b ratio (3.5) in flight cotyledons was much higher than a ratio of 2.42 in the ground controls. The flight samples also had a reduction of PSI complexes and a corresponding 30% decrease of PSI photochemical activity. Immunoblotting showed that the reaction centre polypeptides of PSI were more apparently decreased (e.g. by 24-33% for PsaA and PsaB, and 57% for PsaC) than the light-harvesting complexes. In comparison, the accumulation of PSII complex was less affected in microgravity, thus only a slight reduction in D1, D2 and LHCII was observed in protein blots. However, there was a 32% decrease of OEC1 in the flight samples, indicating a defective OEC subcomplex. In addition, an average 54% increase of the 54 kDa CF1-beta isoform was found in the flight samples, suggesting that space-grown plants suffered from certain stresses, consistent with implications of the increased Chl a/b ratio. Taken together, the results demonstrated that Brassica plants can adapt to spaceflight microgravity, but with significant alterations in chloroplast structures and photosynthetic complexes, and especially reduction of PSI and its activity.

  19. Predawn and high intensity application of supplemental blue light decreases the quantum yield of PSII and enhances the amount of phenolic acids, flavonoids, and pigments in Lactuca sativa.

    Science.gov (United States)

    Ouzounis, Theoharis; Razi Parjikolaei, Behnaz; Fretté, Xavier; Rosenqvist, Eva; Ottosen, Carl-Otto

    2015-01-01

    To evaluate the effect of blue light intensity and timing, two cultivars of lettuce [Lactuca sativa cv. "Batavia" (green) and cv. "Lollo Rossa" (red)] were grown in a greenhouse compartment in late winter under natural light and supplemental high pressure sodium (SON-T) lamps yielding 90 (±10) μmol m(-2) s(-1) for up to 20 h, but never between 17:00 and 21:00. The temperature in the greenhouse compartments was 22/11°C day/night, respectively. The five light-emitting diode (LED) light treatments were Control (no blue addition), 1B 06-08 (Blue light at 45 μmol m(-2) s(-1) from 06:00 to 08:00), 1B 21-08 (Blue light at 45 μmol m(-2) s(-1) from 21:00 to 08:00), 2B 17-19 (Blue at 80 μmol m(-2) s(-1) from 17:00 to 19:00), and 1B 17-19 (Blue at 45 μmol m(-2) s(-1) from 17:00 to 19:00). Total fresh and dry weight was not affected with additional blue light; however, plants treated with additional blue light were more compact. The stomatal conductance in the green lettuce cultivar was higher for all treatments with blue light compared to the Control. Photosynthetic yields measured with chlorophyll fluorescence showed different response between the cultivars; in red lettuce, the quantum yield of PSII decreased and the yield of non-photochemical quenching increased with increasing blue light, whereas in green lettuce no difference was observed. Quantification of secondary metabolites showed that all four treatments with additional blue light had higher amount of pigments, phenolic acids, and flavonoids compared to the Control. The effect was more prominent in red lettuce, highlighting that the results vary among treatments and compounds. Our results indicate that not only high light level triggers photoprotective heat dissipation in the plant, but also the specific spectral composition of the light itself at low intensities. However, these plant responses to light are cultivar dependent.

  20. Predawn and high intensity application of supplemental blue light decreases the quantum yield of PSII and enhances the amount of phenolic acids, flavonoids, and pigments in Lactuca sativa.

    Directory of Open Access Journals (Sweden)

    Theoharis eOuzounis

    2015-02-01

    Full Text Available To evaluate the effect of blue light intensity and timing, two cultivars of lettuce [Lactuca sativa cv. ’Batavia’ (green and cv. ‘Lollo Rossa’ (red] were grown in a greenhouse compartment in late winter under natural light and supplemental high pressure sodium (SON-T lamps yielding 90 (±10 µmol m-2 s-1 for up to 20 hr, but never between 17:00 and 21:00. The temperature in the greenhouse compartments was 22/11°C day/night, respectively. The five light-emitting diode (LED light treatments were Control (no blue addition, 1B 06-08 (Blue light at 45 µmol m-2 s-1 from 06:00 to 08:00, 1B 21-08 (Blue light at 45 µmol m-2 s-1 from 21:00 to 08:00, 2B 17-19 (Blue at 80 µmol m-2 s-1 from 17:00 to 19:00, and (1B 17-19 Blue at 45 µmol m-2 s-1from 17:00 to 19:00. Total fresh and dry weight was not affected with additional blue light; however, plants treated with additional blue light were more compact. The stomatal conductance in the green lettuce cultivar was higher for all treatments with blue light compared to the Control. Photosynthetic yields measured with chlorophyll fluorescence showed different response between the cultivars; in red lettuce, the quantum yield of PSII decreased and the yield of non-photochemical quenching increased with increasing blue light, whereas in green lettuce no difference was observed. Quantification of secondary metabolites showed that all four treatments with additional blue light had higher amount of pigments, phenolic acids, and flavonoids compared to the Control. The effect was more prominent in red lettuce, highlighting that the results vary among treatments and compounds. Our results indicate that not only high light level triggers photoprotective heat dissipation in the plant, but also the specific spectral composition of the light itself at low intensities. However, these plant responses to light are cultivar dependent.

  1. Predawn and high intensity application of supplemental blue light decreases the quantum yield of PSII and enhances the amount of phenolic acids, flavonoids, and pigments in Lactuca sativa

    Science.gov (United States)

    Ouzounis, Theoharis; Razi Parjikolaei, Behnaz; Fretté, Xavier; Rosenqvist, Eva; Ottosen, Carl-Otto

    2015-01-01

    To evaluate the effect of blue light intensity and timing, two cultivars of lettuce [Lactuca sativa cv. “Batavia” (green) and cv. “Lollo Rossa” (red)] were grown in a greenhouse compartment in late winter under natural light and supplemental high pressure sodium (SON-T) lamps yielding 90 (±10) μmol m−2 s−1 for up to 20 h, but never between 17:00 and 21:00. The temperature in the greenhouse compartments was 22/11°C day/night, respectively. The five light-emitting diode (LED) light treatments were Control (no blue addition), 1B 06-08 (Blue light at 45 μmol m−2 s−1 from 06:00 to 08:00), 1B 21-08 (Blue light at 45 μmol m−2 s−1 from 21:00 to 08:00), 2B 17-19 (Blue at 80 μmol m−2 s−1 from 17:00 to 19:00), and 1B 17-19 (Blue at 45 μmol m−2 s−1 from 17:00 to 19:00). Total fresh and dry weight was not affected with additional blue light; however, plants treated with additional blue light were more compact. The stomatal conductance in the green lettuce cultivar was higher for all treatments with blue light compared to the Control. Photosynthetic yields measured with chlorophyll fluorescence showed different response between the cultivars; in red lettuce, the quantum yield of PSII decreased and the yield of non-photochemical quenching increased with increasing blue light, whereas in green lettuce no difference was observed. Quantification of secondary metabolites showed that all four treatments with additional blue light had higher amount of pigments, phenolic acids, and flavonoids compared to the Control. The effect was more prominent in red lettuce, highlighting that the results vary among treatments and compounds. Our results indicate that not only high light level triggers photoprotective heat dissipation in the plant, but also the specific spectral composition of the light itself at low intensities. However, these plant responses to light are cultivar dependent. PMID:25767473

  2. Stratospheric Ozone: Transport, Photochemical Production and Loss

    Science.gov (United States)

    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.

  3. Development of Thermal and Photochemical Strategies for Thiol−Ene Click Polymer Functionalization

    NARCIS (Netherlands)

    Campos, Luis M.; Killops, Kato L.; Sakai, Ryosuke; Paulusse, Jos Marie Johannes; Damiron, Denis; Drockenmuller, Eric; Messmore, Benjamin W.; Hawker, Craig J.

    2008-01-01

    A series of alkene-functional polymers were synthesized by controlled polymerization techniques in order to investigate and compare the efficiency and orthogonality of both photochemically and thermally initiated thiol−ene click coupling reactions. The copolymers were designed to have single or

  4. 40 CFR 52.1877 - Control strategy: Photochemical oxidants (hydrocarbons).

    Science.gov (United States)

    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 interstate...

  5. Photochemical Transformation of Graphene Oxide in Sunlight

    Science.gov (United States)

    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...

  6. Southern Africa - a giant natural photochemical reactor

    CSIR Research Space (South Africa)

    Diab, RD

    2006-04-01

    Full Text Available The analogy of a ‘giant natural photochemical reactor’ is extended in this paper to the central and southern African tropics, where tropospheric ozone enhancement occurs over a vast geographical area from the Congo to South Africa, and over a long...

  7. Additive and Photochemical Manufacturing of Copper

    Science.gov (United States)

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

    2016-12-01

    In recent years, 3D printing technologies have been extensively developed, enabling rapid prototyping from a conceptual design to an actual product. However, additive manufacturing of metals in the existing technologies is still cost-intensive and time-consuming. Herein a novel platform for low-cost additive manufacturing is introduced by simultaneously combining the laser-induced forward transfer (LIFT) method with photochemical reaction. Using acrylonitrile butadiene styrene (ABS) polymer as the sacrificial layer, sufficient ejection momentum can be generated in the LIFT method. A low-cost continuous wave (CW) laser diode at 405 nm was utilized and proved to be able to transfer the photochemically synthesized copper onto the target substrate. The wavelength-dependent photochemical behaviour in the LIFT method was verified and characterized by both theoretical and experimental studies compared to 1064 nm fiber laser. The conductivity of the synthesized copper patterns could be enhanced using post electroless plating while retaining the designed pattern shapes. Prototypes of electronic circuits were accordingly built and demonstrated for powering up LEDs. Apart from pristine PDMS materials with low surface energies, the proposed method can simultaneously perform laser-induced forward transfer and photochemical synthesis of metals, starting from their metal oxide forms, onto various target substrates such as polyimide, glass and thermoplastics.

  8. A rapid and clean synthetic approach to cyclic peptides via micro-flow peptide chain elongation and photochemical cyclization: synthesis of a cyclic RGD peptide.

    Science.gov (United States)

    Mifune, Yuto; Nakamura, Hiroyuki; Fuse, Shinichiro

    2016-11-29

    A cyclic RGD peptide was efficiently synthesized based on micro-flow, triphosgene-mediated peptide chain elongation and micro-flow photochemical macrolactamization. Our approach enabled a rapid (amidation for peptide chain elongation peptide.

  9. Cyclic electron flow may provide some protection against PSII photoinhibition in rice (Oryza sativa L.) leaves under heat stress.

    Science.gov (United States)

    Essemine, Jemaa; Xiao, Yi; Qu, Mingnan; Mi, Hualing; Zhu, Xin-Guang

    2017-04-01

    Previously we have shown that a quick down-regulation in PSI activity compares to that of PSII following short-term heat stress for two rice groups including C4023 and Q4149, studied herein. These accessions were identified to have different natural capacities in driving cyclic electron flow (CEF) around PSI; i.e., low CEF (lcef) and high CEF (hcef) for C4023 and Q4149, respectively. The aim of this study was to investigate whether these two lines have different mechanisms of protecting photosystem II from photodamage under heat stress. We observed a stepwise alteration in the shape of Chl a fluorescence induction (OJIP) with increasing temperature treatment. The effect of 44°C treatment on the damping in Chl a fluorescence was more pronounced in C4023 than in Q4149. Likewise, we noted a disruption in the I-step, a decline in the Fv due to a strong damping in the Fm, and a slight increase in the F0. Normalized data demonstrated that the I-step seems more susceptible to 44°C in C4023 than in Q4149. We also measured the redox states of plastocyanin (PC) and P700 by monitoring the transmission changes at 820nm (I820), and observed a disturbance in the oxidation/reduction kinetics of PC and P700. The decline in the amplitude of their oxidation was shown to be about 29% and 13% for C4023 and Q4149, respectively. The electropotential component (Δφ) of ms-DLE appeared more sensitive to temperature stress than the chemical component (ΔpH), and the impact of heat was more evident and drastic in C4023 than in Q4149. Under heat stress, we noticed a concomitant decline in the primary photochemistry of PSII as well as in both the membrane energization process and the lumen protonation for both accessions, and it is evident that heat affects these parameters more in C4023 than in Q4149. All these data suggest that higher CET can confer higher photoprotection to PSII in rice lines, which can be a desirable trait during rice breeding, especially in the context of a "warming

  10. Culture density influence on the photosynthetic efficiency of microalgae growing under different spectral compositions of light.

    Science.gov (United States)

    Kula, M; Kalaji, H M; Skoczowski, A

    2017-02-01

    A density in algal suspension causes a significant change in the intensity and spectral composition of light reaching individual cells. Measurements of chlorophyll fluorescence allow us to observe any general changes in the bioenergetic status of photosynthesis. The aim of the study was to determine the effect of cultivation density on the PSII photochemical efficiency of three species of algae (Chlorella vulgaris, Botryococcus braunii and Chlorella emersonii), each with a different rate of growth - high, medium and low - respectively. The cell density of algae in suspension differentiated through the cultivation time (2, 4, and 8days) and the spectral composition of light. The results showed that the density of cultivation led to change in the photosynthetic apparatus of algae. The differences described between each day of cultivation (2, 4, and 8) in the kinetics of chlorophyll a fluorescence intensity in cells of the algal strains under study probably resulted from the different phases of growth of these cultures. In addition the results showed the beneficial effect of far red light on the photosynthetic apparatus and the growth of biomass in investigated algal strains. Copyright © 2017 Elsevier B.V. All rights reserved.

  11. Photochemical stability of electrochromic polymers and devices

    DEFF Research Database (Denmark)

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

    2013-01-01

    , AM 1.5G) under ambient conditions the majority of the polymers degraded within 4-5 hours. Three polymers showed increased stability with degradation rates from 0.44 to 1.58% per hour measured as loss of absorption. Application of oxygen and UV barrier foils was found to drastically slow......The stability of fully printed flexible organic electrochromics based on 11 different conjugated polymers is explored from the fundamental chemical degradation level to the operational device level. The photochemical stability of the electrochromic polymers (ECPs) is studied enabling an analysis...... of the influence that the chemical constitution of the conjugated polymer backbone has on the photochemical stability. Based on changes in the UV-visible absorption and IR spectra, the polymers were categorized into two distinct groups, each with a separate degradation mechanism. During irradiation (1000 W m -2...

  12. Photochemical Phenomenology Model for the New Millennium

    Science.gov (United States)

    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.

  13. Application of photochemical technologies for treatment of landfill leachate

    Energy Technology Data Exchange (ETDEWEB)

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

    2012-03-30

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

  14. Merging Structural Information from X-ray Crystallography, Quantum Chemistry, and EXAFS Spectra: The Oxygen-Evolving Complex in PSII.

    Science.gov (United States)

    Chernev, Petko; Zaharieva, Ivelina; Rossini, Emanuele; Galstyan, Artur; Dau, Holger; Knapp, Ernst-Walter

    2016-10-12

    Structural data of the oxygen-evolving complex (OEC) in photosystem II (PSII) determined by X-ray crystallography, quantum chemistry (QC), and extended X-ray absorption fine structure (EXAFS) analyses are presently inconsistent. Therefore, a detailed study of what information can be gained about the OEC through a comparison of QC and crystallographic structure information combined with the information from range-extended EXAFS spectra was undertaken. An analysis for determining the precision of the atomic coordinates of the OEC by QC is carried out. OEC model structures based on crystallographic data that are obtained by QC from different research groups are compared with one another and with structures obtained by high-resolution crystallography. The theory of EXAFS spectra is summarized, and the application of EXAFS spectra to the experimental determination of the structure of the OEC is detailed. We discriminate three types of parameters entering the formula for the EXAFS spectrum: (1) model-independent, predefined, and fixed; (2) model-dependent that can be computed or adjusted; and (3) model-dependent that must be adjusted. The information content of EXAFS spectra is estimated and is related to the precision of atomic coordinates and resolution power to discriminate different atom-pair distances of the OEC. It is demonstrated how a precise adjustment of atomic coordinates can yield a nearly perfect representation of the experimental OEC EXAFS spectrum, but at the expense of overfitting and losing the knowledge of the initial OEC model structure. Introducing a novel type of penalty function, it is shown that moderate adjustment of atomic coordinates to the EXAFS spectrum limited by constraints avoids overfitting and can be used to validate different OEC model structures. This technique is used to identify the OEC model structures whose computed OEC EXAFS spectra agree best with the measured spectrum. In this way, the most likely S-state and protonation pattern

  15. Thermo-cleavable polymers: Materials with enhanced photochemical stability

    DEFF Research Database (Denmark)

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

    2010-01-01

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

  16. Singlet Oxygen Sensor Green: Photochemical Behavior in Solution and in a Mammalian Cell

    DEFF Research Database (Denmark)

    Gollmer, Anita; Arnbjerg, Jacob; Blaikie, Frances Helen

    2011-01-01

    The development of efficient and selective luminescent probes for reactive oxygen species, particularly for singlet molecular oxygen, is currently of great importance. In this study, the photochemical behavior of Singlet Oxygen Sensor Green® (SOSG), a commercially available fluorescent probe...... of the reaction between SOSG and singlet oxygen is, itself, an efficient singlet oxygen photosensitizer. Second, SOSG appears to efficiently bind to proteins which, in turn, can influence uptake by a cell as well as behavior in the cell. As such, incorrect use of SOSG can yield misleading data on yields...

  17. Photochemical and antioxidative responses of the glume and flag leaf to seasonal senescence in wheat

    Directory of Open Access Journals (Sweden)

    Lingan eKong

    2015-05-01

    Full Text Available The non-leaf photosynthetic organs have recently attracted much attention for the breeding and screening of varieties of cereal crops to achieve a high grain yield. However, the glume photosynthetic characteristics and responses to high temperature at the late stages of grain filling are not well known in winter wheat (Triticum aestivum L.. In the present study, an experiment was conducted to investigate the anatomy, chloroplast temporal changes, chlorophyll fluorescence, xanthophyll cycle and antioxidative defense system in glumes of field-grown wheat during grain filling compared with flag leaves. Observations using a light microscope revealed that the glumes developed a solid structural base for performing photosynthesis. Compared with the flag leaves, the glumes preserved a more integral ultrastructure, as observed under transmission electron microscopy, and had higher values of Fv/Fm and ΦPSII at the maturity stage. Further analysis of the chlorophyll fluorescence demonstrated that the glumes experienced high non-photochemical quenching (NPQ at the late stages. Determination of the pool size of the xanthophyll cycle suggested that the (A+Z/(V+A+Z ratio was consistently higher in glumes than in flag leaves and that the V+A+Z content was considerably higher in glumes at the maturity stage. In addition, the glumes exhibited a higher antioxidant enzyme activity and a lower accumulation of reactive oxygen species. These results suggest that the glumes are photosynthetically active and senesce later than the flag leaves; the advantages may have been achieved by coordinated contributions of the structural features, higher NPQ levels, greater de-epoxidation of the xanthophyll cycle components and antioxidative defense metabolism.

  18. Chemistry of Aliphatic Unconjugated Nitramines. Part 7. Interrelations between the Thermal, Photochemical and Mass Spectral Fragmentation of RDX,

    Science.gov (United States)

    The mass spectral fragmentation of RDX and HMX has been described in terms of their metastable transitions, mass measurements and ionization...efficiency curves. The ring migration of an NO2 group is noted. The known interrelation between the thermal, photochemical and mass spectral fragmentation of

  19. 40 CFR 52.777 - Control strategy: photochemical oxidants (hydrocarbons).

    Science.gov (United States)

    2010-07-01

    ... oxidants (hydrocarbons). 52.777 Section 52.777 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Control strategy: photochemical oxidants (hydrocarbons). (a) The requirements of subpart G of this chapter... for photochemical oxidants (hydrocarbons) in the Metropolitan Indianapolis Intrastate Region by May 31...

  20. Evaluation of the photochemical production of hydrogen from solar energy

    Energy Technology Data Exchange (ETDEWEB)

    Heppert, J. A.

    1977-08-09

    The potential for utilizing solar energy through photochemical storage were investigated. Both water and nitrosyl chloride systems are examined. A comprehensive review of the literature led to the conclusion that many major questions must be answered before photochemical energy storage becomes a viable alternate means of exploiting solar energy.

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

    Science.gov (United States)

    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.

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

    African Journals Online (AJOL)

    Because of deficiencies in the monitoring equipment, information on trends in photochemical smog levels over the past decade is limited. Trends in oxides of nitrogen, one of the main precursors of photochemical smog, and therefore an indicator of the potential for its formation, were examined for the period 1984 - 1993.

  3. [Photochemical degradation of landfill leachate facilitated by combined schwertmannite and H2O2].

    Science.gov (United States)

    Wang, He-Ru; Song, Yong-Wei; Xu, Zhi-Hui; Cui, Chun-Hong; Zhou, Li-Xiang

    2014-04-01

    It is practically important that high concentrations of organic pollutants in landfill leachate were degraded by a rapid and efficient approach. The influence of operating conditions such as schwertmannite dosage, V(H2O2)/m (schwertmannite) ratio on the degradation efficiency of color, TOC and COD contents of landfill leachate, was investigated by using the schwertmannite/H2O2/UV process. It was demonstrated that the color, TOC and COD removal efficiencies increased significantly with the increase in schwertmannite dosage, and then were approximately stable. However, COD removal efficiency declined because of the presence of the residual H2O2 when V (H2O2)/m (schwertmannite) was greater than 2, and the best removal efficiency of COD was 44.9%. Furthermore, high-intensity ultraviolet was more conducive to eliminate pollutants through photochemical oxidation with schwertmannite/H2O2. The color, TOC and COD removal efficiencies were 90.0%, 78.8% and 52.6% respectively after 2.5 hours of photochemical degradation, with UV-500 W under optimal initial pH = 2.5; meanwhile, this study found that it was beneficial to the photochemical degradation of leachate at room temperature via the schwertmannite/H2O2/UV process, and COD removal efficiency declined gradually when the temperature was higher than 25 degrees C. Controlled trials showed that the schwertmannite/H2O2 method was conducive to the removal of color compared with the traditional homogeneous Fenton reaction.

  4. Natural isoforms of the Photosystem II D1 subunit differ in photoassembly efficiency of the water-oxidizing complex.

    Science.gov (United States)

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

    2016-05-01

    Oxygenic photosynthesis efficiency at increasing solar flux is limited by light-induced damage (photoinhibition) of Photosystem II (PSII), primarily targeting the D1 reaction center subunit. Some cyanobacteria contain two natural isoforms of D1 that function better under low light (D1:1) or high light (D1:2). Herein, rates and yields of photoassembly of the Mn4CaO5 water-oxidizing complex (WOC) from the free inorganic cofactors (Mn(2+), Ca(2+), water, electron acceptor) and apo-WOC-PSII are shown to differ significantly: D1:1 apo-WOC-PSII exhibits a 2.3-fold faster rate-limiting step of photoassembly and up to seven-fold faster rate to the first light-stable Mn(3+) intermediate, IM1*, but with a much higher rate of photoinhibition than D1:2. Conversely, D1:2 apo-WOC-PSII assembles slower but has up to seven-fold higher yield, achieved by a higher quantum yield of charge separation and slower photoinhibition rate. These results confirm and extend previous observations of the two holoenzymes: D1:2-PSII has a greater quantum yield of primary charge separation, faster [P680 (+) Q A (-) ] charge recombination and less photoinhibition that results in a slower rate and higher yield of photoassembly of its apo-WOC-PSII complex. In contrast, D1:1-PSII has a lower quantum yield of primary charge separation, a slower [P680 (+) Q A (-) ] charge recombination rate, and faster photoinhibition that together result in higher rate but lower yield of photoassembly at higher light intensities. Cyanobacterial PSII reaction centers that contain the high- and low-light D1 isoforms can tailor performance to optimize photosynthesis at varying light conditions, with similar consequences on their photoassembly kinetics and yield. These different efficiencies of photoassembly versus photoinhibition impose differential costs for biosynthesis as a function of light intensity.

  5. Photochemically induced oscillations of aromatic pentazadienes

    Energy Technology Data Exchange (ETDEWEB)

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

    1997-06-01

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

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

    Science.gov (United States)

    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.

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

    DEFF Research Database (Denmark)

    Koch, T; Jacobsen, N; Fensholdt, J

    2000-01-01

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

  8. Photochemical processing of aqueous atmospheric brown carbon

    Directory of Open Access Journals (Sweden)

    R. Zhao

    2015-06-01

    Full Text Available 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.

  9. A photochemical source of methyl chloride in saline waters.

    Science.gov (United States)

    Moore, Robert M

    2008-03-15

    It is shown experimentallythatthe methoxy group in simple lignin-like molecules can be the source of the methyl group in CH3Cl produced by a photochemical reaction in an aqueous solution of chloride. Terrestrially derived colored dissolved organic matter (CDOM) in river water also yields CH3Cl through a photochemical process in a chloride solution. CDOM extracted from subsurface ocean waters showed some ability to enhance photochemical production of CH3Cl while CDOM from surface water showed no effect. Reactions of the kind described in this paper may be contributors to the marine source of methyl chloride and possibly other alkyl halides.

  10. Natural Genetic Variation for Acclimation of Photosynthetic Light Use Efficiency to Growth Irradiance in Arabidopsis1[OPEN

    Science.gov (United States)

    Harbinson, Jeremy

    2015-01-01

    Plants are known to be able to acclimate their photosynthesis to the level of irradiance. Here, we present the analysis of natural genetic variation for photosynthetic light use efficiencyPSII) in response to five light environments among 12 genetically diverse Arabidopsis (Arabidopsis thaliana) accessions. We measured the acclimation of ΦPSII to constant growth irradiances of four different levels (100, 200, 400, and 600 µmol m−2 s−1) by imaging chlorophyll fluorescence after 24 d of growth and compared these results with acclimation of ΦPSII to a step-wise change in irradiance where the growth irradiance was increased from 100 to 600 µmol m−2 s−1 after 24 d of growth. Genotypic variation for ΦPSII is shown by calculating heritability for the short-term ΦPSII response to different irradiance levels as well as for the relation of ΦPSII measured at light saturation (a measure of photosynthetic capacity) to growth irradiance level and for the kinetics of the response to a step-wise increase in irradiance from 100 to 600 µmol m−2 s−1. A genome-wide association study for ΦPSII measured 1 h after a step-wise increase in irradiance identified several new candidate genes controlling this trait. In conclusion, the different photosynthetic responses to a changing light environment displayed by different Arabidopsis accessions are due to genetic differences, and we have identified candidate genes for the photosynthetic response to an irradiance change. The genetic variation for photosynthetic acclimation to irradiance found in this study will allow future identification and analysis of the causal genes for the regulation of ΦPSII in plants. PMID:25670817

  11. Homogeneous photochemical water oxidation by biuret-modified Fe-TAML: evidence of Fe(V)(O) intermediate.

    Science.gov (United States)

    Panda, Chakadola; Debgupta, Joyashish; Díaz Díaz, David; Singh, Kundan K; Sen Gupta, Sayam; Dhar, Basab B

    2014-09-03

    Water splitting, leading to hydrogen and oxygen in a process that mimics natural photosynthesis, is extremely important for devising a sustainable solar energy conversion system. Development of earth-abundant, transition metal-based catalysts that mimic the oxygen-evolving complex of photosystem II, which is involved in oxidation of water to O2 during natural photosynthesis, represents a major challenge. Further, understanding the exact mechanism, including elucidation of the role of active metal-oxo intermediates during water oxidation (WO), is critical to the development of more efficient catalysts. Herein, we report Fe(III) complexes of biuret-modified tetra-amidomacrocyclic ligands (Fe-TAML; 1a and 1b) that catalyze fast, homogeneous, photochemical WO to give O2, with moderate efficiency (maximum TON = 220, TOF = 0.76 s(-1)). Previous studies on photochemical WO using iron complexes resulted in demetalation of the iron complexes with concomitant formation of iron oxide nanoparticles (NPs) that were responsible for WO. Herein, we show for the first time that a high valent Fe(V)(O) intermediate species is photochemically generated as the active intermediate for the oxidation of water to O2. To the best of our knowledge, this represents the first example of a molecular iron complex catalyzing photochemical WO through a Fe(V)(O) intermediate.

  12. Surface and Interface Control on Photochemically Initiated Immobilization

    Energy Technology Data Exchange (ETDEWEB)

    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.

  13. Application of photochemical technologies for treatment of landfill leachate.

    Science.gov (United States)

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

    2012-03-30

    Because of widely varying practices in solid waste management, an all-inclusive solution to long-term management of landfill leachate is currently not available. There is a major technological need for sustainable, economical options for safe discharge of leachate to the environment. Two potential on-site pretreatment technologies, photochemical iron-mediated aeration (PIMA) and TiO(2) photocatalysis were compared for treatment of landfill leachate at laboratory scale. Results of bench scale testing of real landfill leachate with PIMA and TiO(2) photocatalysis showed up to 86% conversion of refractory COD to complete mineralization, up to 91% removal of lead, up to 71% removal of ammonia without pH adjustment, and up to 90% effective color removal with detention times between 4 and 6h, in field samples. The estimated contact times for 90% removal of COD, ammonia, lead, and color were found to be on the order of 10-200 h for PIMA and 3-37 h for TiO(2) photocatalysis. Testing with actual leachate samples showed 85% TiO(2) photocatalyst recovery efficiency with no loss in performance after multiple (n>4 uses). Pre-filtration was not found to be necessary for effective treatment using either process. Copyright © 2012 Elsevier B.V. All rights reserved.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1995-12-31

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

  15. A comprehensive approach to the photochemical synthesis of ...

    Indian Academy of Sciences (India)

    isoxazolone, 2-thiazoline-2-thiol, 1-phenyl-3-methyl-5-pyrazolone under photochemical conditions have been described. The UV light-induced irradiation mainly produced benzazepine and quinoline carboxylic acid derivatives. The products have been ...

  16. Method of making gold thiolate and photochemically functionalized microcantilevers

    Science.gov (United States)

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

    2009-08-25

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

  17. Photochemical organonitrate formation in wet aerosols

    Directory of Open Access Journals (Sweden)

    Y. B. Lim

    2016-10-01

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

  18. Photochemical oxidants: state of the science.

    Science.gov (United States)

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

    1999-01-01

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

  19. Remotely Sensing the Photochemical Reflectance Index (PRI)

    Science.gov (United States)

    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.

  20. Photochemical Phenomenology Model for the New Millenium

    Science.gov (United States)

    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.

  1. Photochemical Patterning of Ionically Cross-Linked Hydrogels

    Directory of Open Access Journals (Sweden)

    Marion Bruchet

    2013-08-01

    Full Text Available Iron(III cross-linked alginate hydrogel incorporating sodium lactate undergoes photoinduced degradation, thus serving as a biocompatible positive photoresist suitable for photochemical patterning. Alternatively, surface etching of iron(III cross-linked hydrogel contacting lactic acid solution can be used for controlling the thickness of the photochemical pattering. Due to biocompatibility, both of these approaches appear potentially useful for advanced manipulation with cell cultures including growing cells on the surface or entrapping them within the hydrogel.

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

    Science.gov (United States)

    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.

  3. Photochemical Formation of Sulfur-Containing Aerosols

    Science.gov (United States)

    Kroll, Jay A.; Vaida, Veronica

    2017-06-01

    In order to understand planetary climate systems, modeling the properties of atmospheric aerosols is vital. Aerosol formation plays an important role in planetary climates and is tied to feedback loops that can either warm or cool a planet. Sulfur compounds are known to play an important role in new particle aerosol formation and have been observed in a number of planetary atmospheres throughout our solar system. Our current understanding of sulfur chemistry explains much of what we observe in Earth's atmosphere; however, several discrepancies arise when comparing observations of the Venusian atmosphere with model predictions. This suggests that there are still problems in our fundamental understanding of sulfur chemistry. This is concerning given recent renewed interest in sulfate injections in the stratosphere for solar radiation management geo-engineering schemes. We investigate the role of sunlight as a potential driver of the formation of sulfur-containing aerosols. I will present recent work investigating the generation of large quantities of aerosol from the irradiation of mixtures of SO_2 with water and organic species, using a solar simulator that mimics the light that is available in the Earth's troposphere and the Venusian middle atmosphere. I will present on recent work done in our lab suggesting the formation of sulfurous acid, H_2SO_3, and describe experimental work that supports this proposed mechanism. Additionally I will present on new work showing the highly reactive nature of electronically excited SO_2 with saturated alkane species. The implications of this photochemically induced sulfur aerosol formation in the atmosphere of Earth and other planetary atmospheres will be discussed.

  4. Topography of photochemical initiation in molecular materials.

    Science.gov (United States)

    Aluker, Edward D; Krechetov, Alexander G; Mitrofanov, Anatoly Y; Zverev, Anton S; Kuklja, Maija M

    2013-11-15

    We propose a fluctuation model of the photochemical initiation of an explosive chain reaction in energetic materials. In accordance with the developed model, density fluctuations of photo-excited molecules serve as reaction nucleation sites due to the stochastic character of interactions between photons and energetic molecules. A further development of the reaction is determined by a competition of two processes. The first process is growth in size of the isolated reaction cell, leading to a micro-explosion and release of the material from the cell towards the sample surface. The second process is the overlap of reaction cells due to an increase in their size, leading to the formation of a continuous reaction zone and culminating in a macro-explosion, i.e., explosion of the entire area, covering a large part of the volume of the sample. Within the proposed analytical model, we derived expressions of the explosion probability and the duration of the induction period as a function of the initiation energy (exposure). An experimental verification of the model was performed by exploring the initiation of pentaerythritol tetranitrate (PETN) with the first harmonic of YAG: Nd laser excitation (1,064 nm, 10 ns), which has confirmed the adequacy of the model. This validation allowed us to make a few quantitative assessments and predictions. For example, there must be a few dozen optically excited molecules produced by the initial fluctuations for the explosive decomposition reaction to occur and the life-time of an isolated cell before the micro-explosion must be of the order of microseconds.

  5. Topography of Photochemical Initiation in Molecular Materials

    Directory of Open Access Journals (Sweden)

    Edward D. Aluker

    2013-11-01

    Full Text Available We propose a fluctuation model of the photochemical initiation of an explosive chain reaction in energetic materials. In accordance with the developed model, density fluctuations of photo-excited molecules serve as reaction nucleation sites due to the stochastic character of interactions between photons and energetic molecules. A further development of the reaction is determined by a competition of two processes. The first process is growth in size of the isolated reaction cell, leading to a micro-explosion and release of the material from the cell towards the sample surface. The second process is the overlap of reaction cells due to an increase in their size, leading to the formation of a continuous reaction zone and culminating in a macro-explosion, i.e., explosion of the entire area, covering a large part of the volume of the sample. Within the proposed analytical model, we derived expressions of the explosion probability and the duration of the induction period as a function of the initiation energy (exposure. An experimental verification of the model was performed by exploring the initiation of pentaerythritol tetranitrate (PETN with the first harmonic of YAG: Nd laser excitation (1,064 nm, 10 ns, which has confirmed the adequacy of the model. This validation allowed us to make a few quantitative assessments and predictions. For example, there must be a few dozen optically excited molecules produced by the initial fluctuations for the explosive decomposition reaction to occur and the life-time of an isolated cell before the micro-explosion must be of the order of microseconds.

  6. C lostridium difficile surface proteins are anchored to the cell wall using CWB2 motifs that recognise the anionic polymer PSII

    Science.gov (United States)

    Willing, Stephanie E.; Candela, Thomas; Shaw, Helen Alexandra; Seager, Zoe; Mesnage, Stéphane; Fagan, Robert P.

    2015-01-01

    Summary Gram‐positive surface proteins can be covalently or non‐covalently anchored to the cell wall and can impart important properties on the bacterium in respect of cell envelope organisation and interaction with the environment. We describe here a mechanism of protein anchoring involving tandem CWB2 motifs found in a large number of cell wall proteins in the Firmicutes. In the Clostridium difficile cell wall protein family, we show the three tandem repeats of the CWB2 motif are essential for correct anchoring to the cell wall. CWB2 repeats are non‐identical and cannot substitute for each other, as shown by the secretion into the culture supernatant of proteins containing variations in the patterns of repeats. A conserved Ile Leu Leu sequence within the CWB2 repeats is essential for correct anchoring, although a preceding proline residue is dispensable. We propose a likely genetic locus encoding synthesis of the anionic polymer PSII and, using RNA knock‐down of key genes, reveal subtle effects on cell wall composition. We show that the anionic polymer PSII binds two cell wall proteins, SlpA and Cwp2, and these interactions require the CWB2 repeats, defining a new mechanism of protein anchoring in Gram‐positive bacteria. PMID:25649385

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

    Science.gov (United States)

    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).

  8. [Photochemical oxidants in Novi Sad 1992-1995].

    Science.gov (United States)

    Kristoforović-Ilić, M

    1996-01-01

    Nowadays photochemical oxidants present the most important problem of air pollution in the world, and due to this a leading cause of destroying quality of environmental health. Higher concentrations of ozone in urban areas of Europe are evident (about 1-2%) from the North to the South especially. During 1992-1995, from June to September, photochemical oxidants concentrations were studied (ozone at 4 a.m. and 4 p.m.; nitrogen dioxide at 8 a.m.; formaldehyde at 8 a.m. and total carbon dioxide at 8 a.m.) all factors of "Summer photochemical smog", with records on the number of vehicles on highways and climate data. Gathered results show that the health of the population is not endangered by Summer smog. Linear correlation data of certain pollutants with climate (temperature, atmospheric pressure and relative air humidity) are in accordance with data in the world.

  9. Iminium and enamine catalysis in enantioselective photochemical reactions

    Science.gov (United States)

    Hörmann, Fabian M.

    2018-01-01

    Although enantioselective catalysis under thermal conditions has been well established over the last few decades, the enantioselective catalysis of photochemical reactions is still a challenging task resulting from the complex enantiotopic face differentiation in the photoexcited state. Recently, remarkable achievements have been reported by a synergistic combination of organocatalysis and photocatalysis, which have led to the expedient construction of a diverse range of enantioenriched molecules which are generally not easily accessible under thermal conditions. In this tutorial review, we summarize and highlight the most significant advances in iminium and enamine catalysis of enantioselective photochemical reactions, with an emphasis on catalytic modes and reaction types. PMID:29155908

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

    Science.gov (United States)

    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.

  11. Photochemical Activation of Electrospun In2O3 Nanofibers for High-Performance Electronic Devices.

    Science.gov (United States)

    Meng, You; Liu, Guoxia; Liu, Ao; Guo, Zidong; Sun, Wenjia; Shan, Fukai

    2017-03-29

    Electrospun metal oxide nanofibers have been regarded as promising blocks for large-area, low-cost, and one-dimensional electronic devices. However, the electronic devices based on electrospun nanofibers usually suffer from poor performance and inferior viability. Here, we report an efficient photochemical process using UV light generated by a high-pressure mercury lamp to promote the electrical performance of the nanofiber-based electronic devices. Such UV treatment can lead to strong photochemical activation of electrospun nanofibers, and therefore, a stable adherent nanofiber network and electronic-clean interface were formed. By use of UV treatment, high-performance indium oxide (In2O3) nanofiber based field-effect transistors (FETs) with highly efficient modulation of electrical characteristics have been successfully fabricated. To reduce the operating voltage and further improve the device performance, the In2O3 nanofiber FETs based on solution-processed high-k AlOx dielectrics were integrated and investigated. The as-fabricated In2O3/AlOx FETs exhibit superior electrical performance, including a high mobility of 19.8 cm2 V-1 s-1, a large on/off current ratio of 106, and high stability over time and cycling. The improved performance of the UV-treated FETs was further confirmed by the integration of the electrospun In2O3/AlOx FETs into inverters. This work presents an important advance toward the practical applications of electrospun nanofibers for functional electronic devices.

  12. Mathematical Modeling of Photochemical Air Pollution.

    Science.gov (United States)

    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

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

    DEFF Research Database (Denmark)

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

    2008-01-01

    The photochemical and electrochemical properties of self-assembled monolayers (SAM) of three structurally distinct hexahydro- and hexafluoro-dithienylcyclopentene-based photochromic switches on gold electrodes are reported. The photochemical and electrochemical switching between the open and clos...

  14. 78 FR 11172 - Integrated Science Assessment for Ozone and Related Photochemical Oxidants

    Science.gov (United States)

    2013-02-15

    ... Committee (CASAC), an independent science advisory committee whose existence and whose review and advisory... AGENCY Integrated Science Assessment for Ozone and Related Photochemical Oxidants AGENCY: Environmental... final document titled, ``Integrated Science Assessment for Ozone and Related Photochemical Oxidants...

  15. Multiple LHCII antennae can transfer energy efficiently to a single Photosystem I

    NARCIS (Netherlands)

    Bos, Inge; Bland, Kaitlyn M.; Tian, Lijin; Croce, Roberta; Frankel, Laurie K.; van Amerongen, Herbert; Bricker, Terry M.; Wientjes, Emilie

    2017-01-01

    Photosystems I and II (PSI and PSII) work in series to drive oxygenic photosynthesis. The two photosystems have different absorption spectra, therefore changes in light quality can lead to imbalanced excitation of the photosystems and a loss in photosynthetic efficiency. In a short-term adaptation

  16. Kinetic and degradation efficiency of trichloroethylene (TCE) via ...

    African Journals Online (AJOL)

    Kinetic and degradation efficiency of trichloroethylene (TCE) via photochemical process from contaminated water. S Dobaradaran, R Nabizadeh, AH Mahvi, A Noroozi, M Yunesian, N Rastkari, S Nazmara, S Zarei ...

  17. Sucrose and Starch Content Negatively Correlates with PSII Maximum Quantum Efficiency in Tomato (Solanum lycopersicum) Exposed to Abnormal Light/Dark Cycles and Continuous Light"

    NARCIS (Netherlands)

    Velez Ramirez, A.I.; Carreno Quintero, N.; Vreugdenhil, D.; Millenaar, Frank F.; Ieperen, van W.

    2017-01-01

    Light is most important to plants as it fuels photosynthesis and provides clues about the environment. If provided in unnatural long photoperiods, however, it can be harmful and even lethal. Tomato (Solanum lycopersicum), for example, develops mottled chlorosis and necrosis when exposed to

  18. Influence of temperature on properties of nitrogen plasma source ion implantation (N-PSII) of Ti6A14V alloy

    CERN Document Server

    Geng Man; Zhao Qing

    2001-01-01

    Specimens of Ti6Al4V alloy were implanted with nitrogen plasma source ion implantation (N-PSII) at temperatures between 100 degree C and 600 degree C to a ion dose of 4 x 10 sup 1 sup 7 cm sup - sup 2. Auger Electron Spectroscopy (AES) was used to determine the nitrogen concentration depth profiles. Microhardness measurements and pin-on-disk wear test were performed to evaluate the improvements of the surface modification. Glancing angle X-ray diffraction (XRD) was employed to determine the phases presented in the surface modified layer. The thickness of implanted layer increased by about an order of magnitude when the temperature was elevated from 100 degree C to 600 degree C. Higher surface hardness and wear resistance was also obtained at higher temperature. Scanning electron microscopy (SEM) showed distinct microstructural changes and the presence of titanium nitrides in the implanted surface

  19. Photochemical Copper Coating on 3D Printed Thermoplastics

    Science.gov (United States)

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

    2016-08-01

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

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

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

    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.

  2. Photochemical Generation and Reactivity of Naphthyl Cations: cine Substitution

    NARCIS (Netherlands)

    Slegt, M.; Minne, F.; Zuilhof, H.; Overkleeft, H.S.; Lodder, G.

    2007-01-01

    The photochemical solvolyses of naphthalen-1-yl(phenyl)iodonium tetrafluoroborate and naphthalen-2-yl(phenyl)iodonium tetrafluoroborate in methanol regiospecifically yield the naphthalen-1- and -2-yl ethers but afford scrambled 1- and 2-phenylnaphthalene Friedel-Crafts products. It is demonstrated

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

    Science.gov (United States)

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

    African Journals Online (AJOL)

    precursors of photochemical smog, notably nitrogen dioxide, and some of its components, notably ozone, have been shown to be detrimental to respiratory health at levels close to, or below, current recommended guidelines. A continuing increase in these pollutants will therefore result in more respiratory illness, particularly ...

  5. A photochemical reactor for studies of atmospheric chemistry

    DEFF Research Database (Denmark)

    Nilsson, Elna Johanna Kristina; Eskebjerg, Carsten; Johnson, Matthew Stanley

    2009-01-01

    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...

  6. 40 CFR 52.269 - Control strategy and regulations: Photochemical oxidants (hydrocarbons) and carbon monoxide.

    Science.gov (United States)

    2010-07-01

    ...: Photochemical oxidants (hydrocarbons) and carbon monoxide. 52.269 Section 52.269 Protection of Environment... PLANS California § 52.269 Control strategy and regulations: Photochemical oxidants (hydrocarbons) and... provide for attainment and maintenance of the national standards for photochemical oxidants (hydrocarbons...

  7. Tracking of photochemical Ostwald ripening of nanoparticles through voltammetric atom counting.

    Science.gov (United States)

    Bartlett, Thomas R; Sokolov, Stanislav V; Plowman, Blake J; Young, Neil P; Compton, Richard G

    2016-09-15

    We report the tracking of atom count in individual nanoparticles during photochemical Ostwald ripening. The nano-impact technique, in conjunction with UV-Vis and TEM analysis, is used to follow the photochemical formation of silver nano-prisms from spherical seed particles. A mechanism of photochemical Ostwald ripening is deduced and key growth stages are identified.

  8. Feedbacks between microphysics and photochemical aging in viscous aerosol

    Science.gov (United States)

    Dou, Jing; Corral Arroyo, Pablo; Alpert, Peter A.; Ammann, Markus; Peter, Thomas; Krieger, Ulrich K.

    2017-04-01

    Fe(III)-citrate complex photochemistry, which plays an important role in aerosol aging, especially in lower troposphere, has been widely recognized in both solution and solid states. It can get excited by light below about 500 nm, inducing the oxidation of carboxylate ligands and the production of peroxides (e.g., OH•, HO2•), which have a significant impact on the climate, air quality and health. Recently, there is literature reporting that aqueous aerosol particles may attain highly viscous, semi-solid or even glassy physical states under a wide range of atmospheric conditions. However, systematic studies on the effect of high viscosity on photochemical processes are scarce. In this research, mass and size changes of a single, aqueous Fe(III)-citrate/citric acid particle levitated in an electrodynamic balance (EDB) are tracked during photochemical processing. We observe an overall mass loss during photochemical processing due to evaporation of volatile (e.g., CO2) and semi-volatile (e.g., ketones) compounds. It is known that relative humidity and temperature strongly effects the viscosity of citric acid. Hence, under light intensities large enough not limiting photochemical processing (at a wavelength of either 375 nm or 473 nm), the quasi-steady state evaporation rate in our experiments depends on relative humidity and temperature. The same holds true for the characteristic time scale for reaching thermodynamic equilibrium after switching off the light source. We are focusing on the high viscosity case (i.e., reduced molecular mobility and low water content), which slows down the transport of products but can also affect chemical reaction rates (e.g., initial absorption process, charge and energy transfer). Data are compared to kinetic modeling and diffusivities for semi-volatile compounds are estimated aiming at a more detailed understanding of the feedbacks between microphysics and photochemical aging.

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

    Directory of Open Access Journals (Sweden)

    Z. Hosaynali Beygi

    2011-08-01

    Full Text Available 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

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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

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

    Science.gov (United States)

    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.

  13. Viscosity and medium effects on the fluorescence and photochemical behaviour of some aryl chalcones

    Science.gov (United States)

    Ebeid, El-Zeiny M.; Abdel-Kader, Mahmood H.; Issa, Raafat M.; El-Daly, Samy A.

    1988-05-01

    The emission, excitation and absorption spectra toghether with the fluorescence and photochemical quantum yields of some chalcone derivatives have been studied in organic solvents and micellar and microemulsion media. Both 4-[2-(2-pyridyl)ethenyl] ( I) and 4-[2-(4-pyridyl)ethenyl ( II) chalcones show large positive solvatochromic effects. The fluorescence quantum yields increase substantially as the medium viscosity increases with a subsequent decrease in the photochemical quatum yield. Compounds I and II undergo excited-state molecular aggregation in concentrated solutions giving excimer-like emission that coincides with emission from crystalline samples. The enthalpies of photoassociation have been estimated. The chalcone derivative I acts as an efficient quencher of the fluorescence of the laser dye 1,4-bis (β-pyridyl-2-vinyl)benzene via a long-range mechanism. The excited-state lifetimes of both I and II are short and at 20°C their τ values are less than 800 ps.

  14. Ferric ion mediated photochemical decomposition of perfluorooctanoic acid (PFOA) by 254 nm UV light

    Energy Technology Data Exchange (ETDEWEB)

    Wang Yuan [State Key Laboratory of Environmental Aquatic Chemistry, Research Center for Eco-Environmental Science, Chinese Academy of Science, Beijing 100085 (China); Department of Environmental Science and Engineering, Tsinghua University, Beijing 100084 (China); Zhang Pengyi [Department of Environmental Science and Engineering, Tsinghua University, Beijing 100084 (China)], E-mail: zpy@tsinghua.edu.cn; Pan Gang; Chen Hao [State Key Laboratory of Environmental Aquatic Chemistry, Research Center for Eco-Environmental Science, Chinese Academy of Science, Beijing 100085 (China)

    2008-12-15

    The great enhancement of ferric ion on the photochemical decomposition of environmentally persistent perfluorooctanoic acid (PFOA) under 254 nm UV light was reported. In the presence of 10 {mu}M ferric ion, 47.3% of initial PFOA (48 {mu}M) was decomposed and the defluorination ratio reached 15.4% within 4 h reaction time. While the degradation and defluorination ratio greatly increased to 80.2% and 47.8%, respectively, when ferric ion concentration increased to 80 {mu}M, and the corresponding half-life was shortened to 103 min. Though the decomposition rate was significantly lowered under nitrogen atmosphere, PFOA was efficiently decomposed too. Other metal ions like Cu{sup 2+} and Zn{sup 2+} also slightly improved the photochemical decomposition of PFOA under irradiation of 254 nm UV light. Besides fluoride ion, other intermediates during PFOA decomposition including formic acid and five shorter-chain perfluorinated carboxylic acids (PFCAs) with C7, C6, C5, C4 and C3, respectively, were identified and quantified by IC or LC/MS. The mixture of PFOA and ferric ion had strong absorption around 280 nm. It is proposed that PFOA coordinates with ferric ion to form a complex, and its excitation by 254 nm UV light leads to the decomposition of PFOA in a stepwise way.

  15. Studies in Photochemical Smog Chemistry: I. Atmospheric Chemistry of Toluene. I. Analysis of Chemical Reaction Mechanisms for Photochemical Smog

    Science.gov (United States)

    Leone, Joseph Anthony

    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 our 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, we present a theoretical analysis of lumped chemical reaction mechanisms for photochemical smog. 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. The counter species analysis is applied to six existing mechanisms for photochemical smog to determine why they predict substantially different degrees of emission controls to achieve the same desired air quality under identical conditions. For each mechanism critical areas are identified that when altered bring the predictions of the various mechanisms into much closer agreement. Finally, a new lumped mechanism for photochemical smog is

  16. Arabidopsis plants lacking PsbQ and PsbR subunits of the oxygen-evolving complex show altered PSII super-complex organization and short-term adaptive mechanisms.

    Science.gov (United States)

    Allahverdiyeva, Yagut; Suorsa, Marjaana; Rossi, Fabio; Pavesi, Andrea; Kater, Martin M; Antonacci, Alessia; Tadini, Luca; Pribil, Mathias; Schneider, Anja; Wanner, Gerhard; Leister, Dario; Aro, Eva-Mari; Barbato, Roberto; Pesaresi, Paolo

    2013-08-01

    The oxygen-evolving complex of eukaryotic photosystem II (PSII) consists of four extrinsic subunits, PsbO (33 kDa), PsbP (23 kDa), PsbQ (17 kDa) and PsbR (10 kDa), encoded by seven nuclear genes, PsbO1 (At5g66570), PsbO2 (At3g50820), PsbP1 (At1g06680), PsbP2 (At2g30790), PsbQ1 (At4g21280), PsbQ2 (At4g05180) and PsbR (At1g79040). Using Arabidopsis insertion mutant lines, we show that PsbP1, but not PsbP2, is essential for photoautotrophic growth, whereas plants lacking both forms of PsbQ and/or PsbR show normal growth rates. Complete elimination of PsbQ has a minor effect on PSII function, but plants lacking PsbR or both PsbR and PsbQ are characterized by more pronounced defects in PSII activity. Gene expression and immunoblot analyses indicate that accumulation of each of these proteins is highly dependent on the presence of the others, and is controlled at the post-transcriptional level, whereas PsbO stability appears to be less sensitive to depletion of other subunits of the oxygen-evolving complex. In addition, comparison of levels of the PSII super-complex in wild-type and mutant leaves reveals the importance of the individual subunits of the oxygen-evolving complex for the supramolecular organization of PSII and their influence on the rate of state transitions. © 2013 The Authors The Plant Journal © 2013 John Wiley & Sons Ltd.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1987-03-10

    A method is described of selectively photochemically dry etching a first semiconductor material of a given composition and direct bandgap E/sub g1/ in the presence of a second semiconductor material of a different composition and direct bandgap E/sub g2/, wherein E/sub g2/>E/sub g1/. The second semiconductor material is not substantially etched during the method, comprising subjecting both materials to the same photon flux and to the same gaseous etchant under conditions where the etchant would be ineffective for chemical etching of either material where the photons are not present, the photons being of an energy greater than E/sub g1/ but less than E/sub g2/, whereby the first semiconductor material is photochemically etched and the second material is substantially not etched.

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

    Energy Technology Data Exchange (ETDEWEB)

    Ashby, Carol I. H. (Edgewood, NM); Dishman, James L. (Albuquerque, NM)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  20. Photochemical Dynamics of Intramolecular Singlet Fission

    Science.gov (United States)

    Lin, Zhou; Iwasaki, Hikari; Van Voorhis, Troy

    2017-06-01

    Singlet fission (SF) converts a singlet exciton (S_1) into a pair of triplet ones (T_1) via a ``multi-exciton'' (ME) intermediate: S_1 \\longleftrightarrow ^1ME \\longleftrightarrow ^1(T_1T_1) \\longrightarrow 2T_1. In exothermic cases, e.g., crystalline pentacene or its derivatives, the quantum yield of SF can reach 200%. With SF doubling the electric current generated by an incident high-energy photon, the solar conversion efficiency in pentacene-based organic photovoltaics (OPVs) can exceed the Shockley-Queisser limit of 33.7%. The ME state is popularly considered to be a dimeric state with significant charge transfer (CT) character that is strongly coupled to both S_1 and ^1(T_1T_1), while this local model lacks strong support from full quantum dynamics studies. Intramolecular SF (ISF) occurring to covalently-bound dimers in the solution phase is an excellent model for a straightforward dynamics simulation of local excitons. In the present study, we investigate the ISF mechanisms for three covalently-bound dimers of pentacene derivatives, including ortho-, meta-, and para-bis(6,13-bis(triisopropylsilylethynyl)pentacene)benzene, in non-protic solvents. Specifically, we propagate the real-time, non-adiabatic quantum mechanical/molecular mechanical (QM/MM) dynamics on the potential energy surfaces associated with the states of S_1, ^1(T_1T_1) and CT. We explore how the energies of these ISF-relevant states and the non-adiabatic couplings between each other fluctuate with time and the instantaneous molecular configuration (e.g., intermonomer distance and orientation). We also quantitatively compare Condon and non-Condon ISF dynamics with solution-phase spectroscopic data. Our results allow us to understand the roles of CT energy levels in the ISF mechanism and propose a design strategy to maximize ISF efficiency. M. B. Smith and J. Michl, Chem. Rev. 110, 6891 (2010). W. Shockley and H. J. Queisser, J. Appl. Phys. 32, 510 (1961). T. C. Berkelbach, M. S. Hybertsen

  1. Contrasting Photophysiological Characteristics of Phytoplankton Assemblages in the Northern South China Sea.

    Science.gov (United States)

    Jin, Peng; Gao, Guang; Liu, Xin; Li, Futian; Tong, Shanying; Ding, Jiancheng; Zhong, Zhihai; Liu, Nana; Gao, Kunshan

    2016-01-01

    The growth of phytoplankton and thus marine primary productivity depend on photophysiological performance of phytoplankton cells that respond to changing environmental conditions. The South China Sea (SCS) is the largest marginal sea of the western Pacific and plays important roles in modulating regional climate and carbon budget. However, little has been documented on photophysiological characteristics of phytoplankton in the SCS. For the first time, we investigated photophysiological characteristics of phytoplankton assemblages in the northern South China Sea (NSCS) using a real-time in-situ active chlorophyll a fluorometry, covering 4.0 × 105 km2. The functional absorption cross section of photosystem II (PSII) in darkness (σPSII) or under ambient light (σPSII') (A2 quanta-1) increased from the surface to deeper waters at all the stations during the survey period (29 July to 23 August 2012). While the maximum (Fv/Fm, measured in darkness) or effective (Fq'/Fm', measured under ambient light) photochemical efficiency of PSII appeared to increase with increasing depth at most stations, it showed inverse relationship with depth in river plume areas. The functional absorption cross section of PSII changes could be attributed to light-adapted genotypic feature due to niche-partition and the alteration of photochemical efficiency of PSII could be attributed to photo-acclimation. The chlorophyll a fluorometry can be taken as an analog to estimate primary productivity, since areas of higher photochemical efficiency of PSII coincided with those of higher primary productivity reported previously in the NSCS.

  2. Integrated photochemical and biological treatment of a commercial textile surfactant: Process optimization, process kinetics and COD fractionation

    Energy Technology Data Exchange (ETDEWEB)

    Arslan-Alaton, Idil [Istanbul Technical University, Faculty of Civil Engineering, Department of Environmental Engineering, 34469 Maslak, Istanbul (Turkey)]. E-mail: arslanid@itu.edu.tr; Cokgor, Emine Ubay [Istanbul Technical University, Faculty of Civil Engineering, Department of Environmental Engineering, 34469 Maslak, Istanbul (Turkey); Koban, Baris [Istanbul Technical University, Faculty of Civil Engineering, Department of Environmental Engineering, 34469 Maslak, Istanbul (Turkey)

    2007-07-31

    The biodegradability of surfactants is a frequent and complex issue arising both at domestic as well as industrial treatment facilities. In the present experimental study, the integrated photochemical (H{sub 2}O{sub 2}/UV-C) and biochemical (activated sludge) treatment of a commercial grade nonionic/anionic textile surfactant formulation was investigated. Photochemical baseline experiments have shown that once the initial pH and H{sub 2}O{sub 2} dose were optimized, practically complete COD removal (COD{sub o} = 500 {+-} 30 mg L{sup -1}) could be achieved. Once the COD was elevated to values being typical for the textile fabric preparation stage, treatment efficiency was seriously retarded provided that the photochemical treatment conditions remained constant. Moreover, a definite relationship existed between H{sub 2}O{sub 2} consumption and COD removal for H{sub 2}O{sub 2}/UV-C advanced oxidation of the textile surfactant. In the second part of the study, COD abatement was modeled for the biodegradation of untreated and photochemically pretreated textile surfactant formulation according to their COD fractions. Results have indicated that the readily biodegradable and rapidly hydrolysable COD fractions of the textile surfactant solution could be appreciably increased upon exposure to an optimum H{sub 2}O{sub 2} concentration (60 mM; i.e. 2.1 g H{sub 2}O{sub 2} (g COD{sub o}){sup -1}) and extended UV-C irradiation times (i.e. 90 and 120 min)

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

    Science.gov (United States)

    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. Copyright © 2012 Elsevier B.V. All rights reserved.

  4. Photochemical micropatterning of carbohydrates on a surface.

    Science.gov (United States)

    Carroll, Gregory T; Wang, Denong; Turro, Nicholas J; Koberstein, Jeffrey T

    2006-03-14

    In this report, we demonstrate a versatile method for the immobilization and patterning of unmodified carbohydrates onto glass substrates. The method employs a novel self-assembled monolayer to present photoactive phthalimide chromophores at the air-monolayer interface. Upon exposure to UV radiation, the phthalimide end-groups graft to surface-adsorbed carbohydrates, presumably by a hydrogen abstraction mechanism followed by radical recombination to form a covalent bond. Immobilized carbohydrate thin films are evidenced by fluorescence, ellipsometry and contact-angle measurements. Surface micropatterns of mono-, oligo-, and polysaccharides are generated by exposure through a contact photomask and are visualized by condensing water onto the surface. The efficiency of covalent coupling is dependent on the thermodynamic state of the surface. The amount of surface-grafted carbohydrate is enhanced when carbohydrate surface interactions are increased by the incorporation of amine-terminated molecules into the monolayer. Glass substrates modified with mixed monolayers of this nature are used to construct carbohydrate microarrays by spotting the carbohydrates with a robot and subsequently illuminating them with UV light to covalently link the carbohydrates. Surface-immobilized polysaccharides display well-defined antigenic determinants for antibody recognition. We demonstrate, therefore, that this novel technology combines the ability to create carbohydrate microarrays using the current state-of-the-art technology of robotic microspotting and the ability to control the shape of immobilized carbohydrate patterns with a spatial resolution defined by the UV wavelength and a shape defined by a photomask.

  5. PSII as an in vivo molecular catalyst for the production of energy rich hydroquinones - A new approach in renewable energy.

    Science.gov (United States)

    Das, Sai; Maiti, Soumen K

    2018-02-03

    One of the pertinent issues in the field of energy science today is the quest for an abundant source of hydrogen or hydrogen equivalents. In this study, phenyl-p-benzoquinone (pPBQ) has been used to generate a molecular store of hydrogen equivalents (phenyl-p-hydroquinone; pPBQH 2 ) from thein vivo splitting of water by photosystem II of the marine cyanobacterium Synechococcus elongatus BDU 70542. Using this technique, 10.8 μmol of pPBQH 2 per mg chlorophyll a can be extracted per minute, an efficiency that is orders of magnitude higher when compared to the techniques present in the current literature. Moreover, the photo-reduction process was stable when tested over longer periods of time. Addition of phenyl-p-benzoquinone on an intermittent basis resulted in the precipitation of phenyl-p-hydroquinone, obviating the need for costly downstream processing units for product recovery. Phenyl-p-hydroquinone so obtained is a molecular store of free energy preserved through the light driven photolysis of water and can be used as a cheap and a renewable source of hydrogen equivalents by employing transition metal catalysts or fuel cells with the concomitant regeneration of phenyl-p-benzoquinone. The cyclic nature of this technique makes it an ideal candidate to be utilized in mankind's transition from fossil fuels to solar fuels. Copyright © 2018 Elsevier B.V. All rights reserved.

  6. Graphene Charge Transfer, Spectroscopy, and Photochemical Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Brus, Louis [Columbia Univ., New York, NY (United States)

    2017-01-31

    This project focused on the special electronic and optical properties of graphene and adsorbed molecular species. Graphene makes an excellent substrate for current collection in nanostructured photovoltaic designs. Graphene is almost transparent, and can be used as a solar cell window. It also has no surface states, and thus current is efficiently transported over long distances. Progress in graphene synthesis indicates that there will soon be practical methods for making large pieces of graphene for devices. We now need to understand exactly what happens to both ground state and electronically excited molecules and Qdots near graphene, if we are going to use them to absorb light in a nano-structured photovoltaic device using graphene to collect photocurrent. We also need to understand how to shift the graphene Fermi level, to optimize the kinetics of electron transfer to graphene. And we need to learn how to convert local graphene areas to semiconductor structure, to make useful spatially patterned graphenes. In this final report, we describe how we addressed these goals. We explored the question of possible Surface Enhanced Raman spectroscopy from molecular Charge Transfer onto Graphene substrates. We observed strong hole doping of graphene by adsorbed halogens as indicated by the shift of the graphene G Raman band. In the case of iodine adsorption, we also observed the anionic species made by hole doping. At low frequency in the Raman spectrum, we saw quite intense lines from I3- and I5- , suggesting possible SERS. We reported on Fresnel calculations on this thin film system, which did not show any net electromagnetic field enhancement.

  7. Modeling the kinetics of a photochemical water treatment process by means of artificial neural networks

    Energy Technology Data Exchange (ETDEWEB)

    Goeb, S.; Oliveros, E.; Bossmann, S.H.; Braun, A.M. [Lehrstuhl fuer Umweltmesstechnik, Engler-Bunte-Institut, Universitaet Karlsruhe, Karlsruhe (Germany); Guardani, R.; Nascimento, C.A.O. [Process Control and Simulation Laboratory, Chemical Engineering Department, University of Sao Paulo, Sao Paulo (Brazil)

    1999-07-01

    We have investigated the kinetics of the degradation of 2,4-dimethyl aniline (2,4-xylidine), chosen as a model pollutant, by the photochemically enhanced Fenton reaction. This process, which may be efficiently applied to the treatment of industrial waste waters, involves a series of complex reactions leading eventually to the mineralization of the organic pollutant. A model based on artificial neural networks has been developed for fitting the experimental data obtained in a laboratory batch reactor. The model can describe the evolution of the pollutant concentration during irradiation time under various conditions. It has been used for simulating the behaviour of the reaction system in sensitivity studies aimed at optimizing the amounts of reactants employed in the process - an iron(II) salt and hydrogen peroxide. The results show that the process is much more sensitive to the iron(II) salt concentration than to the hydrogen peroxide concentration, a favorable condition in terms of economic feasibility. (author)

  8. Optimal experimental design and artificial neural networks applied to the photochemically enhanced Fenton reaction.

    Science.gov (United States)

    Göb, S; Oliveros, E; Bossmann, S H; Braun, A M; Nascimento, C A; Guardani, R

    2001-01-01

    Among advanced oxidation processes (AOPs), the photochemically enhanced Fenton reaction may be considered as one of the most efficient for the degradation of contaminants in industrial wastewater. This process involves a series of complex reactions. Therefore, an empirical model based on artificial neural networks has been developed for fitting the experimental data obtained in a laboratory batch reactor for the degradation of 2,4-dimethyl aniline (2,4-xylidine), chosen as a model pollutant. The model describes the evolution of the pollutant concentration during irradiation time as a function of the process conditions. It has been used for simulating the behavior of the reaction system in sensitivity studies aimed at optimizing the amounts of reactants employed in the process, an iron(III) salt and hydrogen peroxide, as well as the temperature. The results show that the process is most sensitive to the concentration of iron(III) salt and temperature, whereas the concentration of hydrogen peroxide has a minor effect.

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

    Science.gov (United States)

    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. Dosimetry Determines the Initial OH Radical Concentration in Fast Photochemical Oxidation of Proteins (FPOP)

    Science.gov (United States)

    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.

  11. The effect of fuel composition on the formation of photochemical smog

    Energy Technology Data Exchange (ETDEWEB)

    Dutkiewicz, R.K. [Cape Town Univ. (South Africa). Energy Research Inst.

    1995-12-31

    The high level of solar radiation, moderate to high ambient temperatures and increasing vehicle density have resulted in an increasing number of incidents of photochemical smog in Cape Town. Whilst the situation has not reached levels reported from many cities around the world there is concern that photochemical smog may become a serious pollution problem. Work has started on a characterization of the photochemical smog and to determine what measures will be required to limit photochemical smog. The work has consisted of the monitoring of ambient levels of photochemical precursors such as hydrocarbons and oxides of nitrogen, and measurement of ozone. In addition to continuous monitoring by the Cape Town City Council some measurements have been made of PAN and other components of photochemical smog. In addition a study is being carried out of the composition of a brown haze which envelopes CaPe Town during spring and autumn under strong inversion episodes. In addition to ambient monitoring, work is being carried out on the effect of vehicle emissions and fuel evaporation on the formation of photochemical smog. This work involves the formation of photochemical smog in an indoor smog chamber in which exhaust emissions and volatile organic compounds are tested in terms of their photochemical smog tendency. This work is aimed at estimating the effect of increasing precursor levels on the potential photochemical smog situation in Cape Town

  12. Discerning the effects of photoinhibition and photoprotection on the rate of oxygen evolution in Arabidopsis leaves.

    Science.gov (United States)

    Giovagnetti, Vasco; Ruban, Alexander V

    2015-11-01

    Higher plants possess a set of interconnected processes to regulate light harvesting. Non-photochemical quenching of chlorophyll a fluorescence (NPQ) is the fastest process activated to protect the photosystem (PS) II from the absorption of excess light energy. However, damage of PSII reaction centers (RCIIs) is often inevitable, a phenomenon known as photoinhibition. Both NPQ and photoinhibition undermine PSII quantum yield (ΦPSII). Recently, we devised a fluorescence-based methodology that uses the coefficient of photochemical quenching measured in the dark following illumination (qPd) to assess the intactness of RCIIs. This procedure enables to express ΦPSII as a function (ƒ) of NPQ and qPd, ΦPSII=ƒ(NPQ,qPd), thus allowing to efficiently discern between the effects of protective NPQ and photoinhibition upon the efficiency of electron transport. In this study, we addressed the relationship between qPd and ΦPSII measured by photosynthetic oxygen evolution in intact leaves of Arabidopsis. We found a linear correlation between qPd and ΦPSII of oxygen evolution (as well as Fv/Fm). This relates to the fact that qPd reflects the onset of photoinhibition. These results further demonstrate the validity of the qPd parameter and underlying theory in quantitatively assessing PSII efficiency solely by using this effective and simple fluorescence technique. Copyright © 2015 Elsevier B.V. All rights reserved.

  13. On the in vivo photochemical rate parameters for PDT reactive oxygen species modeling

    Science.gov (United States)

    Kim, Michele M.; Ghogare, Ashwini A.; Greer, Alexander; Zhu, Timothy C.

    2017-03-01

    Photosensitizer photochemical parameters are crucial data in accurate dosimetry for photodynamic therapy (PDT) based on photochemical modeling. Progress has been made in the last few decades in determining the photochemical properties of commonly used photosensitizers (PS), but mostly in solution or in vitro. Recent developments allow for the estimation of some of these photochemical parameters in vivo. This review will cover the currently available in vivo photochemical properties of photosensitizers as well as the techniques for measuring those parameters. Furthermore, photochemical parameters that are independent of environmental factors or are universal for different photosensitizers will be examined. Most photosensitizers discussed in this review are of the type II (singlet oxygen) photooxidation category, although type I photosensitizers that involve other reactive oxygen species (ROS) will be discussed as well. The compilation of these parameters will be essential for ROS modeling of PDT.

  14. Correlated behavior of the EPR signal of cytochrome b-559 heme Fe(III) ligated by OH- and the multiline signal of the Mn cluster in PS-II membrane fragments.

    Science.gov (United States)

    Fiege, R; Shuvalov, V A

    1996-05-27

    EPR signals of Cyt b-559 heme Fe(III) ligated by OH- and the multiline signal of the Mn cluster in PS-II membrane fragments have been investigated. In 2,3-dicyano-5,6-dichloro-p-benzoquinone-oxidized PS-II membrane fragments the light-induced decrease of the EPR signal of the heme Fe(III)-OH- is accompanied by the appearance of the EPR multiline signal of the Mn cluster. Addition of F- ions, which act as a stronger ligand for heme Fe(III) than OH-, decreases to the same extent the dark- and light-induced signal of the heme Fe(III)-OH- and the light-induced multiline signal of the Mn cluster. These results are discussed in terms of the light-induced formation of a bound OH' radical shared between the Cyt b-559 heme Fe and the Mn cluster as a first step of water oxidation.

  15. Improved UV-B screening capacity does not prevent negative effects of ambient UV irradiance on PSII performance in High Arctic plants. Results from a six year UV exclusion study

    DEFF Research Database (Denmark)

    Albert, Kristian Rost; Mikkelsen, Teis Nørgaard; Ro-Poulsen, H.

    2010-01-01

    Long-term responses of ambient solar ultraviolet (UV) radiation were investigated on Salix arctica and Vaccinium uliginosum in a High Arctic heath ecosystem in Zackenberg, northeast Greenland. Over a period of six years, UV exclusion was conducted in the growing season by means of filters: 60% UV......-B reduction, 90% UV-B + UV-A reduction, UV transparent filter control, and an open control without filter. Plant responses were evaluated using specific leaf area, leaf content of UV-B absorbing compounds and PSII performance parameters derived from chlorophyll-a fluorescence induction curves. Based...... increased TRo/ABS = FV/FM and REo/ETo. These results demonstrate the current level of ambient UV-B to decrease PSII performance significantly in these High Arctic plants. It appears that the two plant species both have improved their UV-screening capacity, but through different strategies, although this did...

  16. Photochemical Cyclopolymerization of Polyimides in Ultraviolet Ridgidizing Composites for Use in Inflatable Structures Project

    Data.gov (United States)

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

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

    Science.gov (United States)

    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.

  18. The local and observed photochemical reaction rates revisited.

    Science.gov (United States)

    Alfano, Orlando M; Irazoqui, Horacio A; Cassano, Alberto E

    2009-07-01

    In a broad sense, photochemical reactions proceed through pathways involving several reaction steps. The initiation step is the absorption of energy both by the reactant or sensitizer molecules and in some cases, by the catalyst, leading to intermediate products that ultimately give rise to stable end products. Preferably, the reaction rate expression is derived from a proposed mechanism together with sound simplifying assumptions; otherwise, it may be adopted on an empirical basis. Under a kinetic control regime, the rate expression thus obtained depends on the local rate of photon absorption according to a power law whose exponent very often ranges from one half to unity. The kinetic expression should be valid at every point of the reactor volume. However, due to radiation attenuation in an absorbing and/or scattering medium, the value of the photon absorption rate is always a function of the spatial position. Therefore, the overall photochemical reaction rate will not be uniform throughout the entire reaction zone, and the distinction between local and volume average photochemical reaction rates becomes mandatory. Experimental values of reaction rates obtained from concentration measurements performed in well-mixed reaction cells are, necessarily, average values. Consequently, for validation purposes, experimental results from these cells must be compared with volume averages of the mechanistically or empirically derived local reaction rate expressions. In this work it is shown that unless the rate is first order with respect to the photon absorption rate or the attenuation in the absorbing and/or scattering medium is kept very low, when the averaging operation is not performed, significant errors may be expected.

  19. Apertureless cantilever-free pen arrays for scanning photochemical printing.

    Science.gov (United States)

    Zhou, Yu; Xie, Zhuang; Brown, Keith A; Park, Daniel J; Zhou, Xiaozhu; Chen, Peng-Cheng; Hirtz, Michael; Lin, Qing-Yuan; Dravid, Vinayak P; Schatz, George C; Zheng, Zijian; Mirkin, Chad A

    2015-02-25

    A novel, apertureless, cantilever-free pen array can be used for dual scanning photochemical and molecular printing. Serial writing with light is enabled by combining self-focusing pyramidal pens with an opaque backing between pens. The elastomeric pens also afford force-tuned illumination and simultaneous delivery of materials and optical energy. These attributes make the technique a promising candidate for maskless high-resolution photopatterning and combinatorial chemistry. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. The kinetics of photochemical processes in polymer-salt systems

    Science.gov (United States)

    Ostroushko, A. A.; Sennikov, M. Yu.

    2009-01-01

    The kinetics of photochemical reactions in aqueous polymer-salt systems containing ammonium heptamolybdate, dodecatungstate, or metavanadate and polyvinyl alcohol or polyvinylpyrrolidone was studied by measurements of photoinduced electrode potential difference. The rate of primary accumulation of reduced d metal forms was evaluated for different systems. Possible reasons for complex oscillatory processes in the systems were analyzed. Comparative data were obtained for compositions containing polyoxometallate shaped like buckyball:(NH4)42[Mo{72/VI}Mo{60/V}O372(HCOO)30(H2O)72] · 30HCOONH4 · 250H2O. UV irradiation of this system caused the oxidation of molybdenum(V).

  1. Formation of fatty acids in photochemical conversions of saturated hydrocarbons

    Science.gov (United States)

    Telegina, T. A.; Pavlovskaya, T. Y.; Ladyzhenskaya, A. I.

    1977-01-01

    Abiogenic synthesis of fatty acids was studied in photochemical conversions of saturated hydrocarbons. It was shown that, in a hydrocarbon water CaCO3 suspension, the action of 254 nm UV rays caused the formation of fatty acids with a maximum number of carbon atoms in the chain not exceeding that in the initial hydrocarbon. Synthesis of acetic, propionic, butyric, valeric, caproic, enanthic and caprylic (in the case of octane) acids occurs in heptane water CaCO3 and octane water CaCO3 systems.

  2. Photochemical and photocatalytic evaluation of 1D titanate/TiO{sub 2} based nanomaterials

    Energy Technology Data Exchange (ETDEWEB)

    Conceição, D.S.; Ferreira, D.P. [Centro de Química-Física Molecular and IN-Institute of Nanoscience and Nanotechnology Instituto Superior Técnico, Universidade de Lisboa Av. Rovisco Pais, 1049-001 Lisboa (Portugal); Graça, C.A.L. [Universidade de São Paulo, Avenida Prof. Luciano Gualberto, tr. 3, 380 São Paulo (Brazil); Júlio, M.F.; Ilharco, L.M. [Centro de Química-Física Molecular and IN-Institute of Nanoscience and Nanotechnology Instituto Superior Técnico, Universidade de Lisboa Av. Rovisco Pais, 1049-001 Lisboa (Portugal); Velosa, A.C. [Instituto Nacional de Tecnologia, Av. Venezuela 82, Rio de Janeiro (Brazil); Santos, P.F. [Centro de Química, Vila Real Universidade de Trás-os-Montes e Alto Douro, 5001-801 Vila Real (Portugal); Vieira Ferreira, L.F., E-mail: lfvieiraferreira@tecnico.ulisboa.pt [Centro de Química-Física Molecular and IN-Institute of Nanoscience and Nanotechnology Instituto Superior Técnico, Universidade de Lisboa Av. Rovisco Pais, 1049-001 Lisboa (Portugal)

    2017-01-15

    Highlights: • 1D titanate based nanomaterials were prepared via a hydrothermal approach. • The structural and photochemical evaluation of the nanomaterials was performed. • A fluorescent dye was used as a surface probe in visible excitation conditions. • Amicarbazone was used as the model contaminant for photodegradation studies. - Abstract: One-dimensional (1D) titanate based nanomaterials were synthesized following an alkaline hydrothermal approach of commercial TiO{sub 2} nanopowder. The morphological features of all materials were monitored by means of scanning electron microscopy (SEM), transmission electron microscopy (TEM), and also Brunauer-Emmett-Teller (BET) technique. In addition the photochemical behaviour of these nanostructured materials were evaluated with the use of laser induced luminescence (LIL), ground-state diffuse reflectance (GSDR), and laser-flash photolysis in diffuse reflectance mode (DRLFP). The mixed titanate/TiO{sub 2} nanowires presented the least intense fluorescence spectra, suggesting the presence of surficial defects that can extend the lifetime of the excited charge carriers. A fluorescent ‘rhodamine-like’ dye was adsorbed onto different materials and examined via photoexcitation in the visible range to study the self-photosensitization mechanism. The presence of the radical cation of the dye and the degradation kinetics, when compared with a neutral substrate—cellulose, provided significant evidences regarding the photoactivity of the different materials. Regarding all the materials under study, the nanowires exhibited a strong photocatalytic efficiency, for the adsorbed fluorescent probe. The photocatalytic mechanism was also considered by studying the photodegradation capability of the titanate based materials in the presence of an herbicide, Amicarbazone, after ultraviolet (UVA) photoexcitation.

  3. Photochemical migration of liquid column in a glass tube

    Science.gov (United States)

    Muto, M.; Ayako, Y.; Yamamoto, K.; Yamamoto, M.; Kondo, Y.; Motosuke, M.

    2017-04-01

    A light-induced migration of liquid columns in a 2.5-mm glass capillary by photochemical isomerization was demonstrated. The isomerization of a surfactant AZTMA, which was added into ultrapure water, occurred by irradiating UV or visible light and results in the surface tension of the liquid. By utilizing this effect, the column manipulation was performed by irradiating the UV light to a half portion of the liquid column so that liquid-gas interface at two column ends had different surface tension dye to the photochemical isomerization. As a result, the migration of the columns generated by a difference in the Laplace pressure at two ends was observed. The columns firstly advanced at constant speeds depending on their lengths and then decelerated by mixing of isomers in the columns. Moreover, it was found that shorter the column length, higher the mobility. This characteristic was explained by the viscous friction, which counteracted the driving force, and the Marangoni convection in the vicinity of the interface.

  4. TEMPO Specific Photochemical Reflectance Index for Monitoring Crop Productivity

    Science.gov (United States)

    Wulamu, A.; Fishman, J.; Maimaitiyiming, M.

    2016-12-01

    Chlorophyll fluorescence and Photochemical Reflectance Index (PRI) are two key indicators of plant functional status used for early stress detection. With its less than one nanometer hyperspectral resolution and hourly revisit capabilities, NASA's Tropospheric Emissions: Monitoring of Pollution (TEMPO) sensor provides new opportunities for monitoring regional food security. Chlorophyll fluorescence can be retrieved by TEMPO using Oxygen B (O2-B) absorption region at 687 nm. The Photochemical Reflectance Index (PRI) is calculated from spectral reflectance at 531 and 570. However, TEMPO spectral range covers from 290 mm - 490 nm and 540 nm -740 nm, does not provide the 531 nm measurement band for PRI. It is imperative to develop alternate wavelengths within the TEMPO spectral range for these early stress indicators so that regional crop health can be observed by TEMPO with unparalleled spectral and temporal resolutions to address food security. Combining field and airborne remote sensing experiments and radiative transfer simulations, this work proposes a TEMPO specific PRI and demonstrates that TEMPO offers a new set of high-resolution spectral data for crop monitoring.

  5. Global aspects of photochemical air pollution: A kinetic study

    Energy Technology Data Exchange (ETDEWEB)

    Parmar, S.S. [Atmospheric Analysis and Consulting, Ventura, CA (United States); Fernandez, C.; Guyton, J.; Lee, C.P. [Arizona Department of Environmental Quality, Phoenix, AZ (United States)

    1994-12-31

    One of the most serious effects of increasing photochemical air pollution on a global basis is the production of high concentration of submicron aerosol in the atmosphere, resulting in unfavorable changes in weather patterns and world climate. The probability that these changes may occur with an unchecked increase in photochemical air pollution justifies a comprehensive control of pollutant emission as well as a detailed study into their atmospheric chemistry. Structure-reactivity relationships (SRR) and linear free energy relationships (LFER) are presented for environmentally important chemical reactions of unsaturated aliphatic contaminants in air and water. SRR of the form log k (k = rate constant for reaction with O{sub 3}, OH, and NO{sub 3}) vs ionization potential, and tortional frequency as well as LFER of the form log k (A) vs. log k (B) where A and B = O{sub 3}, OH, and NO{sub 3} are presented and can be used to estimate reaction rate constants and environmental persistence (in air and water) for many unsaturated compounds for which no data exist. As examples of application, rate constants for reactions of OH (gas phase), OH (water) and NO{sub 3} (gas phase) are estimated for many unsaturated compounds.

  6. The influence of aerosols on photochemical smog in Mexico City

    Energy Technology Data Exchange (ETDEWEB)

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

    2001-04-01

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

  7. Photochemical and other air pollutions in the Netherlands

    Energy Technology Data Exchange (ETDEWEB)

    Floor, H.

    1975-01-01

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

  8. Photochemically promoted degradation of poly(ε-caprolactone) film

    Energy Technology Data Exchange (ETDEWEB)

    Mosnáček, Jaroslav, E-mail: jaroslav.mosnacek@savba.sk [Polymer Institute, Centre of Excellence FUN-MAT, Slovak Academy of Sciences, Dúbravská cesta 9, 845 41 Bratislava (Slovakia); Borská, Katarína, E-mail: katarina.borska@gmail.com [Polymer Institute, Slovak Academy of Sciences, Dúbravská cesta 9, 845 41 Bratislava (Slovakia); Danko, Martin, E-mail: martin.danko@savba.sk [Polymer Institute, Slovak Academy of Sciences, Dúbravská cesta 9, 845 41 Bratislava (Slovakia); Janigová, Ivica, E-mail: ivica.janigova@savba.sk [Polymer Institute, Slovak Academy of Sciences, Dúbravská cesta 9, 845 41 Bratislava (Slovakia)

    2013-06-15

    Poly(ε-caprolactone) (PCL) films were doped with photoactive 1,2-diphenylethane-1,2-dione (benzil, BZ), and the effect of the photochemical transformation of benzil on the molecular characteristics of the PCL films and the rate of PCL hydrolysis was studied. Both crosslinking and degradation of the PCL film were observed during irradiation of the PCL/BZ films. Irradiation of a PCL/BZ film at λ > 400 nm under an air atmosphere resulted in a decrease of the average molecular weight (M{sub n}) of PCL to approximately one half, while formation of polar groups and an increase in the hydrophilicity of the PCL film were observed. Moreover, a subsequent hydrolytic test showed a significant increase in the hydrolytic degradation rate of the PCL/BZ film in comparison with non-irradiated or irradiated PCL films without doped benzil. Using benzil as a dopant in the PCL matrix can allow adjusting the degradation rate of PCL, what can be very important from both environmental and biomedical perspectives. - Highlights: • Photochemical transformation of doped benzil affected molar characteristics of PCL. • Crosslinking/degradation of PCL was observed depending on irradiation conditions. • Promoted hydrolytic degradation of PCL was achieved.

  9. 40 CFR 52.229 - Control strategy and regulations: Photochemical oxidants (hydrocarbons), Metropolitan Los Angeles...

    Science.gov (United States)

    2010-07-01

    ...: 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 are... not interfere with the attainment and maintenance of NAAQS for photochemical oxidants (hydrocarbons...

  10. Structural studies of supramolecular photochemical beta-cyclodextrin inclusion complexes

    Science.gov (United States)

    Brett, Thomas John

    X-ray crystallography has played an essential role in our understanding of the factors controlling the outcomes of solid-state photochemical reactions. The detailed and systematic study of supramolecular photochemical systems is not very common. The dissertation research described here was designed to help fill this deficit. beta-cyclodextrin (beta-CD) is an example of a host molecule which has been used as a host to photochemical reactions. An important influence on the outcome of the solid state reaction is the surrounding crystalline environment. Structural studies of beta-CD inclusion complexes with derivatized biphenyl molecules, biphenyl and p-amino-p '-nitrobiphenyl, characterize the beta-CD dimer environment as non-constraining. Both molecules exhibit twisted conformations within the beta-CD dimer, identical to their conformations displayed in the gas phase. The photodimerization of various coumarins in crystalline beta-CD complexes was studied in detail. The beta-CD/coumarin complex was found to be a 2:3 host:guest (H:G) complex in contradiction to previous literature reports. The beta-CD dimers stack in long channels with the coumarin molecules stacked one on top of another inside creating a reaction nano-tube in which the theoretical yield is limited to 67%. The photodimerization of 7-hydroxy-4-methylcoumarin in its crystalline beta-CD inclusion complex was directly observed by X-ray diffraction. Examination of the structure of an unreacted crystal and one that was irradiated for 6 days revealed that the reaction proceeds in a topochemical fashion within the beta-CD dimer cavity. The beta-CD dimers arrange in a manner which creates isolated reaction nano-vessels throughout the crystal. The structure of the beta-CD/7-hydroxycoumarin complex shows that this complex is nearly identical the beta-CD/7-hydroxy-4-methylcoumarin complex despite the looser spatial fit of the guest to the cavity. The studies of the beta-CD/4,7-dimethylcoumarin complex produced

  11. Flexible metal-oxide devices made by room-temperature photochemical activation of sol-gel films.

    Science.gov (United States)

    Kim, Yong-Hoon; Heo, Jae-Sang; Kim, Tae-Hyeong; Park, Sungjun; Yoon, Myung-Han; Kim, Jiwan; Oh, Min Suk; Yi, Gi-Ra; Noh, Yong-Young; Park, Sung Kyu

    2012-09-06

    Amorphous metal-oxide semiconductors have emerged as potential replacements for organic and silicon materials in thin-film electronics. The high carrier mobility in the amorphous state, and excellent large-area uniformity, have extended their applications to active-matrix electronics, including displays, sensor arrays and X-ray detectors. Moreover, their solution processability and optical transparency have opened new horizons for low-cost printable and transparent electronics on plastic substrates. But metal-oxide formation by the sol-gel route requires an annealing step at relatively high temperature, which has prevented the incorporation of these materials with the polymer substrates used in high-performance flexible electronics. Here we report a general method for forming high-performance and operationally stable metal-oxide semiconductors at room temperature, by deep-ultraviolet photochemical activation of sol-gel films. Deep-ultraviolet irradiation induces efficient condensation and densification of oxide semiconducting films by photochemical activation at low temperature. This photochemical activation is applicable to numerous metal-oxide semiconductors, and the performance (in terms of transistor mobility and operational stability) of thin-film transistors fabricated by this route compares favourably with that of thin-film transistors based on thermally annealed materials. The field-effect mobilities of the photo-activated metal-oxide semiconductors are as high as 14 and 7 cm(2) V(-1) s(-1) (with an Al(2)O(3) gate insulator) on glass and polymer substrates, respectively; and seven-stage ring oscillators fabricated on polymer substrates operate with an oscillation frequency of more than 340 kHz, corresponding to a propagation delay of less than 210 nanoseconds per stage.

  12. Disentangling the photochemical salinity tolerance in Aster tripolium L.: connecting biophysical traits with changes in fatty acid composition.

    Science.gov (United States)

    Duarte, B; Cabrita, M T; Gameiro, C; Matos, A R; Godinho, R; Marques, J C; Caçador, I

    2017-03-01

    A profound analysis of A. tripolium photochemical traits under salinity exposure is lacking in the literature, with very few references focusing on its fatty acid profile role in photophysiology. To address this, the deep photochemical processes were evaluated by Pulse Amplitude Modulated (PAM) Fluorometry coupled with a discrimination of its leaf fatty acid profile. Plants exposed to 125-250 mm NaCl showed higher photochemical light harvesting efficiencies and lower energy dissipation rates. under higher NaCl exposure, there is evident damage of the oxygen evolving complexes (OECs). On the other hand, Reaction Centre (RC) closure net rate and density increased, improving the energy fluxes entering the PS II, in spite of the high amounts of energy dissipated and the loss of PS II antennae connectivity. Energy dissipation was mainly achieved through the auroxanthin pathway. Total fatty acid content displayed a similar trend, being also higher under 125-250 mm NaCl with high levels of omega-3 and omega-6 fatty acids. The increase in oleic acid and palmitic acid allows the maintenance of the good functioning of the PS II. Also relevant was the high concentration of chloroplastic C16:1t in the individuals subjected to 125-250 mm NaCl, related with a higher electron transport activity and with the organization of the Light Harvesting Complexes (LHC) and thus reducing the activation of energy dissipation mechanisms. All these new insights shed some light not only on the photophysiology of this potential cash-crop, but also highlight its important saline agriculture applications of this species as forage and potential source of essential fatty acids. © 2016 German Botanical Society and The Royal Botanical Society of the Netherlands.

  13. Development and in Vitro Characterization of Photochemically Crosslinked Polyvinylpyrrolidone Coatings for Drug-Coated Balloons

    Directory of Open Access Journals (Sweden)

    Svea Petersen

    2013-12-01

    Full Text Available Polyvinylpyrrolidone (PVP is a conventionally applied hydrophilic lubricious coating on catheter-based cardiovascular devices, used in order to ease movement through the vasculature. Its use as drug reservoir and transfer agent on drug-coated balloons (DCB is therefore extremely promising with regard to the simplification of its approval as a medical device. Here, we developed a PVP-based coating for DCB, containing paclitaxel (PTX as a model drug, and studied the impact of crosslinking via UV radiation on drug stability, wash off, and transfer during simulated use in an in vitro vessel model. We showed that crosslinking was essential for coating stability and needed to be performed prior to PTX incorporation due to decreased drug bioavailability as a result of photodecomposition and/or involvement in vinylic polymerization with PVP under UV radiation. Moreover, the crosslinking time needed to be carefully controlled. While short radiation times did not provide enough coating stability, associated with high wash off rates during DCB insertion, long radiation times lowered drug transfer efficiency upon balloon expansion. A ten minutes radiation of PVP, however, combined a minimized drug wash off rate of 34% with an efficient drug transfer of 49%, underlining the high potential of photochemically crosslinked PVP as a coating matrix for DCB.

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

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Xiangyang, E-mail: lxy081276@126.com, E-mail: yzgu@henu.edu.cn; Wang, Shun; Zheng, Haiwu; Cheng, Xiuying; Gu, Yuzong, E-mail: lxy081276@126.com, E-mail: yzgu@henu.edu.cn [Institute of Microsystems Physics and School of Physics and Electronics, Henan University, Kaifeng 475004 (China)

    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.

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

    Science.gov (United States)

    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.

  16. Energy and Molecules from Photochemical/Photocatalytic Reactions. An Overview

    Directory of Open Access Journals (Sweden)

    Davide Ravelli

    2015-01-01

    Full Text Available Photocatalytic reactions have been defined as those processes that require both a (not consumed catalyst and light. A previous definition was whether such reactions brought a system towards or away from the (thermal equilibrium. This consideration brings in the question whether a part of the photon energy is incorporated into the photochemical reaction products. Data are provided for representative organic reactions involving or not molecular catalysts and show that energy storage occurs only when a heavily strained structure is generated, and in that case only a minor part of photon energy is actually stored (ΔG up to 25 kcal·mol−1. The green role of photochemistry/photocatalysis is rather that of forming highly reactive intermediates under mild conditions.

  17. Photochemical water splitting mediated by a C1 shuttle

    KAUST Repository

    Alderman, N. P.

    2016-10-31

    The possibility of performing photochemical water splitting in a two-stage system, separately releasing the H and O components, has been probed with two separate catalysts and in combination with a formaldehyde/formate shuttling redox couple. In the first stage, formaldehyde releases hydrogen vigorously in the presence of an Na[Fe(CN)]·10HO catalyst, selectively affording the formate anion. In the second stage, the formate anion is hydro-genated back to formaldehyde by water and in the presence of a BiWO photocatalyst whilst releasing oxygen. Both stages operate at room temperature and under visible light irradiation. The two separate photocatalysts are compatible since water splitting can also be obtained in one-pot experiments with simultaneous H/O evolution.

  18. Applying green chemistry to the photochemical route to artemisinin

    Science.gov (United States)

    Amara, Zacharias; Bellamy, Jessica F. B.; Horvath, Raphael; Miller, Samuel J.; Beeby, Andrew; Burgard, Andreas; Rossen, Kai; Poliakoff, Martyn; George, Michael W.

    2015-06-01

    Artemisinin is an important antimalarial drug, but, at present, the environmental and economic costs of its semi-synthetic production are relatively high. Most of these costs lie in the final chemical steps, which follow a complex acid- and photo-catalysed route with oxygenation by both singlet and triplet oxygen. We demonstrate that applying the principles of green chemistry can lead to innovative strategies that avoid many of the problems in current photochemical processes. The first strategy combines the use of liquid CO2 as solvent and a dual-function solid acid/photocatalyst. The second strategy is an ambient-temperature reaction in aqueous mixtures of organic solvents, where the only inputs are dihydroartemisinic acid, O2 and light, and the output is pure, crystalline artemisinin. Everything else—solvents, photocatalyst and aqueous acid—can be recycled. Some aspects developed here through green chemistry are likely to have wider application in photochemistry and other reactions.

  19. Investigation on Surface Roughness of Inconel 718 in Photochemical Machining

    Directory of Open Access Journals (Sweden)

    Nitin D. Misal

    2017-01-01

    Full Text Available The present work is focused on estimating the optimal machining parameters required for photochemical machining (PCM of an Inconel 718 and effects of these parameters on surface topology. An experimental analysis was carried out to identify optimal values of parameters using ferric chloride (FeCl3 as an etchant. The parameters considered in this analysis are concentration of etchant, etching time, and etchant temperature. The experimental analysis shows that etching performance as well as surface topology improved by appropriate selection of etching process parameters. Temperature of the etchant found to be dominant parameter in the PCM of Inconel 718 for surface roughness. At optimal etching conditions, surface roughness was found to be 0.201 μm.

  20. Effect of fulvic acid on the photochemical degradation of methylparathion.

    Science.gov (United States)

    Manzanilla-Cano, José A; Barceló-Quintal, Manuel H; Alcocer-Can, Ligia Del C; Coral-Martínez, Tania I

    2010-05-01

    Photochemical degradation of methylparathion (O,O,-dimethyl O-4 nitrophenylphosphorothioate) in the presence of fulvic acid (FA) between pH 2 and 7 was studied by differential pulse polarography (DPP). Fulvic acid and its photoproducts were not electro-active under the experimental conditions used in this study, and only the pesticide exhibited polarographic signals. Photolysis of methylparathion in acid media was sensitized by fulvic acid since the pesticide did not degrade in the absence of this compound. Methylparathion degradation was observed at each of the studied pHs. The reaction was first-order with rate constant values ranging from 3.3 x 10(-3) to 8.8 x 10(-3)min(-1).

  1. Versatile and nondestructive photochemical process for biomolecule immobilization.

    Science.gov (United States)

    Viel, Pascal; Walter, Justine; Bellon, Sophie; Berthelot, Thomas

    2013-02-12

    Covalent immobilization of unmodified biological materials as proteins has been performed through a one-step and soft method. This process is based on a polyazidophenylene layer derived from the electroreduction of the parent salt 4-azidobenzenediazonium tetrafluoborate on gold substrates. The wavelength used (365 nm) for the photochemical grafting of a large variety of molecules as biomolecules is a key point to this nondestructive immobilization method. This simple process is also versatile and could be used for covalently binding a wide range of molecules such as polyethylene glycol moieties, for example. To validate this approach for biochip or microarray fabrication, a surface plasmon resonance imaging (SPRi) platform for immobilization of various antibody families was created by grafting G-protein through this process. This SPRi antibodies platform was tested with several consecutive cycles of antigen injections/regeneration steps without loss of activity.

  2. Photochemical oxidation of persistent cyanide-related compounds

    Science.gov (United States)

    Budaev, S. L.; Batoeva, A. A.; Khandarkhaeva, M. S.; Aseev, D. G.

    2017-03-01

    Kinetic regularities of the photolysis of thiocyanate solutions using of mono- and polychromatic UV radiation sources with different spectral ranges are studied. Comparative experiments aimed at investigating the role of photochemical action during the oxidation of thiocyanates with persulfates and additional catalytic activation with iron(III) ions are performed. The rate of conversion and the initial rate of thiocyanate oxidation are found to change in the order UV < UV/S2O 8 2- < S2O 8 2- /Fe3+ < UV/S2O 8 2- /Fe3+. A synergistic effect is detected when using the combined catalytic method for the destruction of thiocyanates by the UV/S2O 8 2- /Fe3+ oxidation system. This effect is due to the formation of reactive oxygen species, as a result of both the decomposition of persulfate and the reduction of inactive Fe3+ intermediates into Fe3+.

  3. Evaluated kinetic and photochemical data for atmospheric chemistry

    Science.gov (United States)

    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.

  4. Photochemical versus Thermal Synthesis of Cobalt Oxyhydroxide Nanocrystals

    Energy Technology Data Exchange (ETDEWEB)

    Alvarado, Samuel R.; Guo, Yijun; Ruberu, T. Purnima A.; Bakac, Andreja; Vela, Javier

    2012-04-18

    Photochemical methods facilitate the generation, isolation, and study of metastable nanomaterials having unusual size, composition, and morphology. These harder-to-isolate and highly reactive phases, inaccessible using conventional high-temperature pyrolysis, are likely to possess enhanced and unprecedented chemical, electromagnetic, and catalytic properties. We report a fast, low-temperature and scalable photochemical route to synthesize very small (3 nm) monodisperse cobalt oxyhydroxide (Co(O)OH) nanocrystals. This method uses readily and commercially available pentaamminechlorocobalt(III) chloride, [Co(NH3)5Cl]Cl2, under acidic or neutral pH and proceeds under either near-UV (350 nm) or Vis (575 nm) illumination. Control experiments showed that the reaction proceeds at competent rates only in the presence of light, does not involve a free radical mechanism, is insensitive to O2, and proceeds in two steps: (1) Aquation of [Co(NH3)5Cl]2+ to yield [Co(NH3)5(H2O)]3+, followed by (2) slow photoinduced release of NH3 from the aqua complex. This reaction is slow enough for Co(O)OH to form but fast enough so that nanocrystals are small (ca. 3 nm). The alternative dark thermal reaction proceeds much more slowly and produces much larger (250 nm) polydisperse Co(O)OH aggregates. UV–Vis absorption measurements and ab initio calculations yield a Co(O)OH band gap of 1.7 eV. Fast thermal annealing of Co(O)OH nanocrystals leads to Co3O4 nanocrystals with overall retention of nanoparticle size and morphology. Thermogravimetric analysis shows that oxyhydroxide to mixed-oxide phase transition occurs at significantly lower temperatures (up to ΔT = 64 °C) for small nanocrystals compared with the bulk.

  5. [Responses of primary photochemical reactions in apple fruit peel to the changes of incident PFD and air temperature in sunny days].

    Science.gov (United States)

    Sun, Shan; Zhang, Li-Tao; Gao, Hui-Yuan; Shu, Huai-Rui; Wang, Lai-Ping

    2009-10-01

    Taking Malus domestica Borkh as test object, this paper studied the primary photochemical reactions and xanthophyll cycle in its fruit peel in response to the diurnal changes of incident photon flux density (PFD) and air temperature in sunny days. With the increase of PFD and air temperature in a daily cycle, a severe photo-inhibition of the primary photochemical reactions in M. domestica fruit peel occurred from 12:00 to 14:00. The relative variable fluorescence at 300 micros of chlorophyll a fluorescence transient (Wk) did not change significantly through the day, which indicated that the activity of oxygen evolving complex (OEC) was not damaged by strong light and high temperature. However, the efficiency that a trapped exciton moved an electron into the electron transport chain beyond QA(-) (Psio) was reduced from 12:00 to 14:00, indicating that the acceptor side of PS II in apple fruit peel was damaged. Strong light decreased the density of PS II reaction centers per excited cross-section (RC/CS), which induced the increase of the energy absorption per active reaction center (ABS/RC). However, the excited energy was not able to be efficiently used via photochemical reaction (TRo/RC), resulting in an increase in non-photochemical energy dissipation per active reaction center (DIo/RC). Along with the appearance of photo-inhibition, the de-epoxidation level of xanthophyll pigment pool (PRI) increased markedly, showing that the xanthophyll cycle in fruit peel was enhanced by strong light to dissipate excess excitation energy to prevent photosynthetic apparatus from further damage. Both strong light and high temperature enhanced the photo-inhibition in apple fruit peel, and the effect of strong light was significantly more prominent than that of high temperature during a day.

  6. Effects of photochemical smog from a flow reactor on bacteria. II. Determination of bactericidal components in photochemical smog

    Energy Technology Data Exchange (ETDEWEB)

    Nover, H.; Botzenhart, K.

    1983-04-01

    The mixture of substances in the photochemical smog could be detected by different reduction rates of exposed bacteria. Beside ozone other products of the ozone/olefine-reaction could reduce the survival of exposed bacteria. For Staph. epidermidis a toxic influence from the reaction products could be found only after UV-irradiation. The main components were aldehydes, hydrocarbons, radicals, peroxiradicals and radicaloxides. For peroxiacetylnitrate (PAN) no bactericidal effect could be found for bacteria adsorbed on membrane filters in concentrations of 300 ppb in the smog (UV-irradiation was put off for two hours) and even in concentrations of 1000 ppb prepared by gaschromatography. The influence on lipopolysaccharide (lps) defective mutants of Salmonella minnesota showed the protection of the lps-layer against e.g. relative humidity and ozone (500 ppb), but no specific protection against smog components.

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

    Science.gov (United States)

    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

  8. Photochemical solution processing of films of metastable phases for flexible devices: the β-Bi2O3 polymorph

    Science.gov (United States)

    Pérez-Mezcua, Dulce; Bretos, Iñigo; Jiménez, Ricardo; Ricote, Jesús; Jiménez-Rioboó, Rafael J.; da Silva, Cosmelina Gonçalves; Chateigner, Daniel; Fuentes-Cobas, Luis; Sirera, Rafael; Calzada, M. Lourdes

    2016-12-01

    The potential of UV-light for the photochemical synthesis and stabilization of non-equilibrium crystalline phases in thin films is demonstrated for the β-Bi2O3 polymorph. The pure β-Bi2O3 phase is thermodynamically stable at high temperature (450-667 °C), which limits its applications in devices. Here, a tailored UV-absorbing bismuth(III)-N-methyldiethanolamine complex is selected as an ideal precursor for this phase, in order to induce under UV-light the formation of a -Bi-O-Bi- continuous network in the deposited layers and the further conversion into the β-Bi2O3 polymorph at a temperature as low as 250 °C. The stabilization of the β-Bi2O3 films is confirmed by their conductivity behavior and a thorough characterization of their crystal structure. This is also supported by their remarkable photocatalytic activity. Besides, this processing method has allowed us for the first time the preparation of β-Bi2O3 films on flexible plastic substrates, which opens new opportunities for using these materials in potential applications not available until now (e.g., flexible photocatalytic reactors, self-cleaning surfaces or wearable antimicrobial fabrics). Therefore, photochemical solution deposition (PCSD) demonstrates to be not only an efficient approach for the low temperature processing of oxide films, but also an excellent alternative for the stabilization of metastable phases.

  9. Model estimates of enhanced photochemical production of ozone resulting from convective transport of precursors

    Science.gov (United States)

    Pickering, Kenneth E.; Thompson, Anne M.; Dickerson, Russell R.

    1989-01-01

    Vertical profiles of net photochemical ozone production rates and total tropospheric column production rates were estimated using two models, a simple photochemical box model and a time-dependent one-dimensional transport/kinetics model. Photochemical production of ozone is found to dominate over destruction throughout the vertical extent of the troposphere over the central United States during typical summertime convective conditions. The column net production can be enhanced by the transport of the ozone precursors NO and NMHC from the boundary layer to the free troposphere by convective activity.

  10. A photochemical box model for urban air quality study

    Science.gov (United States)

    Jin, Shengxin; Demerjian, Kenneth

    The photochemical box model (PBM) developed in the present study is based on the principle of mass conservation. It has a horizontal domain of the size of a typical city and a vertical dimension defined by the mixed-layer height. 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 ( Preprints, Third Symp. on Atmospheric Turbulence, Diffusion, and Air Quality, Raleigh, Am. Met. Soc., pp. 443-447, 1976; Advances in Environmental Sciences and Engineering, Vol. 1, No. 1 (edited by Pfafflin J. and Ziegler E.), pp. 50-85. Gordon and Breach, New York, 1979) has been incorporated in the PBM and further developed to consider the effect of urban heat islands in the simulation of mixed layer height. The predicted mixed-layer heights compare very well with observations. The gas phase chemical kinetic mechanism used in the Regional Acid Deposition Model II (RADM2) and that of an earlier version of PBM 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 concentrations using both chemical mechanisms are in very good agreement with available observations for CO, NO, NO 2 and O 3. A radiative transfer model developed by Madronich ( J. geophys. Res.92, 9740-9752, 1987) has been incorporated in the PBM for the calculation of actinic flux and photolytic rate constants. Height-averaged and radiation-corrected photolytic rate constants are used for the photochemical reactions. Budget analyses conducted for CO, NO, NO 2 and O 3 have enhanced our understanding of the relative contributions of horizontal advection, vertical entrainment, source emissions and chemical reactions to the overall rate of change of their concentrations. Model predictions are not sensitive to the large

  11. Photochemical ionogenesis in solutions of zinc octaethyl porphyrin

    Science.gov (United States)

    Ballard, S. G.; Mauzerall, D. C.

    1980-01-01

    Absolute ion yields and the kinetic parameters of ion formation and decay have been determined by transient conductimetry for two photochemical ionogenic reactions of zinc octaethyl porphyrin in a variety of inert organic solvents. One reaction (T-P) involves electron transfer in the encounter complex of the porphyrin triplet state (T) and ground state (P); it is relatively slow (kTP˜108M-1s-1, and solvent insensitive). The second (T-T reaction) involves reactive collision between two triplets; it occurs at the encounter limit (kTT˜1010M-1s-1). Neither rate constant depends on solvent dielectric constant. Reaction yields are very dielectric-dependent, however, and provide unusually straightforward experimental access to the problem of geminate ion-pair decorrelation. A two-parameter model is presented in which the initial photochemically-formed ion pair is created by electron tunneling in a specific spin state at nontrivial separation. The electron transfer radii for the two reactions are determined by completely independent analysis of the kinetic and yield data to be ˜21 Å, some 7 Å greater than twice the radius of the porphyrin π-electron system. Following e- transfer, the solvent-separated components of the geminate pair diffuse in their Coulomb field, undergoing both coherent and incoherent changes in their combined spin state as they do so. They either escape beyond the Coulomb radius to give uncorrelated and conductimetrically active doublet ions, or approach to the critical radius for reverse electron transfer to the ground state (2P) and, subject to a spin selection rule, are annihilated. The dominant mechanism of spin interconversion appears to be spin-orbit coupling to the molecular rotations rather than nuclear hyperfine interactions. The coupled diffusion and spin relaxation equations are solved numerically by the method of finite differences; theoretical yields of free ions show good fit to the data over five orders of magnitude. Recombination

  12. Hybrid functional studies of InGaN alloys and oxides for photochemical watersplitting

    Science.gov (United States)

    Moses, Poul Georg

    2011-03-01

    Photochemical watersplitting can potentially be a future sustainable energy source, converting sunlight and water into hydrogen. However, in order to have highly efficient devices materials are needed that absorb a large proportion of the solar spectrum while at the same time having valence and conduction bands that straddle the hydrogen and oxygen evolution redox potentials. It is well known that DFT consistently underestimates the band gap (the so-called ``band-gap problem''). As a consequence, the positions of the valence and conduction bands (and hence the band offsets) also suffer from uncertainties. To address these deficiencies of the local density approximation (LDA) and generalized gradient approximation (GGA) we use the HSE exchange correlation functional in order to accurately calculate the electronic band structure. We will discuss bowing effects in InGaN alloys based on accurate calculation of band gaps of InGaN alloys and on an analysis of experimental results using our calculated deformation potentials to disentangle the effect of strain and alloying on the band gap. We will also discuss calculations of the absolute position of the valence band maximum and the conduction band minimum. Including a discussion and comparison with generalized gradient and local density approximations results. Finally we show that HSE may be used to understand the nature of surface defects. Acknowledgment is made to the Donors of the American Chemical Society Petroleum Research Fund for support of this research and CNSI Computing Facility, the Teragrid TACC and NCSA supercomputer facilities.

  13. Photochemical production of hydrogen from water using microporous porphyrin coordination lattices.

    Science.gov (United States)

    Sato, Konomi; Kataoka, Yusuke; Mori, Wasuke

    2012-01-01

    In this study, we investigated the photochemical production of hydrogen from water using bio-inspired heterogeneous microporous porphyrin coordination lattices (PCLs), [Ru2(MTCPP)BF4] (M = H2 (PCL-1), Zn (PCL-2); TCPP = Tetrakis(4-carboxyphenyl)porphyrin), under visible (380 nm photocatalytic activity for hydrogen evolution; the maximum amounts of turnover numbers (TONs) of PCL-1 and PCL-2 at 24 h irradiation were 20.8 and 29.9, respectively. In the catalytic reactions, the relation between PCLs and MV2+ was similar to the relation between a [cytochrome c3 hydrogenase] pair and lysine residues in enzymatic reactions. By using the hydrogen production rate and the MV+ (methyl-vilologen radical-cation) concentration, kinetic parameters such as affinities between MV+ and PCLs, maximum reaction rate, and total efficiency of the reaction are introduced using the Michaelis-Menten equation. These parameters indicated that PCLs are good artificial enzyme model catalysts. The stability of the PCLs after the catalytic reactions was confirmed by X-ray photoelectron spectroscopy and Fourier transform-infrared spectra. These results indicated that the frameworks of PCLs are stable for this catalytic reaction.

  14. Novel Naphthalene Based Lariat-Type Crown Ethers Using Direct Single Electron Transfer Photochemical Strategy

    Energy Technology Data Exchange (ETDEWEB)

    Park, Hea Jung; Sung, Nam Kyung; Kim, Su Rhan; Kim, Su Rhan; Ahn, So Hyun; Yoon, Ung Chan [Pusan National Univ., Busan (Korea, Republic of); Cho, Dae Won [Yeungnam Univ., Geoungsan (Korea, Republic of); Mariano, Patrick S. [Univ. of New Mexico, Albuquerque (United States)

    2013-12-15

    This study explored a direct SET-photochemical strategy to construct a new family of thioene conjugated-naphthalamide fluorophore based lariat-crown ethers which show strong binding properties towards heavy metal ions. Irradiations of designed nitrogen branched (trimethylsilyl)methylthio-terminated polyethylenoxy-tethered naphthalimides in acidic methanol solutions have led to highly efficient photocyclization reactions to generate naphthalamide based lariat type thiadiazacrown ethers directly in chemo- and regio-selective manners which undergo very facile secondary dehydration reactions during separation processes to produce their corresponding amidoenethio ether cyclic products tethered with electron donating diethyleneoxy- and diethyenethio-side arm chains. Fluorescence and metal cation binding properties of the lariat type enamidothio products were examined. The photocyclized amidoenethio products, thioene conjugated naphthalamide fluorophore containing lariat-thiadiazacrowns exhibited strong fluorescence emissions in region of 330-450 nm along with intramolecular exciplex emissions in region of 450-560 nm with their maxima at 508 nm. Divalent cation Hg{sup 2+} and Pb{sup 2+} showed strong binding to sulfur atom(s) in side arm chain and atoms in enethiadiazacrown ether rings which led to significant enhancement of fluorescence from its chromophore singlet excited state and concomitant quenching of exciplex emission. The dual fluorescence emission responses towards divalent cations might provide a new guide for design and development of fluorescence sensors for detecting those metals.

  15. Femtosecond Laser Irradiation of Plasmonic Nanoparticles in Polymer Matrix: Implications for Photothermal and Photochemical Material Alteration

    Directory of Open Access Journals (Sweden)

    Anton A. Smirnov

    2014-11-01

    Full Text Available We analyze the opportunities provided by the plasmonic nanoparticles inserted into the bulk of a transparent medium to modify the material by laser light irradiation. This study is provoked by the advent of photo-induced nano-composites consisting of a typical polymer matrix and metal nanoparticles located in the light-irradiated domains of the initially homogeneous material. The subsequent irradiation of these domains by femtosecond laser pulses promotes a further alteration of the material properties. We separately consider two different mechanisms of material alteration. First, we analyze a photochemical reaction initiated by the two-photon absorption of light near the plasmonic nanoparticle within the matrix. We show that the spatial distribution of the products of such a reaction changes the symmetry of the material, resulting in the appearance of anisotropy in the initially isotropic material or even in the loss of the center of symmetry. Second, we analyze the efficiency of a thermally-activated chemical reaction at the surface of a plasmonic particle and the distribution of the product of such a reaction just near the metal nanoparticle irradiated by an ultrashort laser pulse.

  16. PHENOL DEGRADATION VIA PHOTO-FENTON USING A ANNULAR PHOTOCHEMICAL REACTOR

    Directory of Open Access Journals (Sweden)

    Léa Elias Mendes Carneiro Zaidan

    2015-07-01

    Full Text Available The water pollution is one of the main threats and challenges facing humanity today. Everyday human activities introduce contaminants considered refractory in various water matrices. Within these contaminants, phenol and its derivatives represent a significant threat to the environment because of their toxicity, bioaccumulation stability and permanence in the environment for long periods. These compounds are highly toxic, carcinogenic and allergenic, causing considerable damage to human health, besides causing threats to the ecosystem. Therefore, determination and elimination of environment are of great importance to ensure better water quality. Advanced oxidation processes (AOP have been extensively studied due to their potential for degradation, as alternatives or supplements to conventional treatment processes of wastewater. Hydroxyl radicals generated during the process are highly reactive and unselective, may act in the chemical oxidation of a wide range of substances. For experimental development phenol samples were used in aqueous solution at a concentration of 200 mg L-1. Assays were performed using a photochemical reactor, operating with artificial UV radiation source (80W lamp. The analysis of the concentrations of phenol was performed using High Efficiency Liquid Chromatography (HPLC. The results of the degradation of phenol by Photo-Fenton process were satisfactory, succeeding in reducing the same to 98,82 %.

  17. Photochemical decomposition of perfluorooctanoic acid in aqueous periodate with VUV and UV light irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Cao, M.H.; Wang, B.B.; Yu, H.S.; Wang, L.L.; Yuan, S.H. [Environmental Science Research Institution, College of Environment Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074 (China); Chen, J., E-mail: chenjing@mail.hust.edu.cn [Environmental Science Research Institution, College of Environment Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074 (China)

    2010-07-15

    The photochemical decomposition of perfluorooctanoic acid (PFOA) in aqueous periodate (IO{sub 4}{sup -}) was investigated under two types of low-pressure mercury lamps: one emits at 254 nm light (UV light) and the other emits both 254 nm and 185 nm light (VUV light). PFOA decomposed efficiently under VUV light irradiation while it decomposed poorly under UV light irradiation. The addition of IO{sub 4}{sup -} significantly increased the rate of decomposition and defluorination of PFOA irradiated with UV light whereas it decreased both processes under VUV irradiation. Reactive radical (IO{sub 3}{center_dot}) generated by photolysis of IO{sub 4}{sup -} initiated the oxidation of PFOA in UV process. Aquated electrons (e{sub aq}{sup -}), generated from water homolysis, scavenged IO{sub 4}{sup -} resulting in decrease of reactive radical species production and PFOA decomposition. The shorter-chain perfluorocarboxylic acids (PFCAs) formed in a stepwise manner from long-chain PFCAs.

  18. Triplet Tuning - a New ``BLACK-BOX'' Computational Scheme for Photochemically Active Molecules

    Science.gov (United States)

    Lin, Zhou; Van Voorhis, Troy

    2017-06-01

    Density functional theory (DFT) is an efficient computational tool that plays an indispensable role in the design and screening of π-conjugated organic molecules with photochemical significance. However, due to intrinsic problems in DFT such as self-interaction error, the accurate prediction of energy levels is still a challenging task. Functionals can be parameterized to correct these problems, but the parameters that make a well-behaved functional are system-dependent rather than universal in most cases. To alleviate both problems, optimally tuned range-separated hybrid functionals were introduced, in which the range-separation parameter, ω, can be adjusted to impose Koopman's theorem, ɛ_{HOMO} = -I. These functionals turned out to be good estimators for asymptotic properties like ɛ_{HOMO} and ɛ_{LUMO}. In the present study, we propose a ``black-box'' procedure that allows an automatic construction of molecule-specific range-separated hybrid functionals following the idea of such optimal tuning. However, instead of focusing on ɛ_{HOMO} and ɛ_{LUMO}, we target more local, photochemistry-relevant energy levels such as the lowest triplet state, T_1. In practice, we minimize the difference between two E_{{T}_1}'s that are obtained from two DFT-based approaches, Δ-SCF and linear-response TDDFT. We achieve this minimization using a non-empirical adjustment of two parameters in the range-separated hybrid functional - ω, and the percentage of Hartree-Fock contribution in the short-range exchange, c_{HF}. We apply this triplet tuning scheme to a variety of organic molecules with important photochemical applications, including laser dyes, photovoltaics, and light-emitting diodes, and achieved good agreements with the spectroscopic measurements for E_{{T}_1}'s and related local properties. A. Dreuw and M. Head-Gordon, Chem. Rev. 105, 4009 (2015). O. A. Vydrov and G. E. Scuseria, J. Chem. Phys. 125, 234109 (2006). L. Kronik, T. Stein, S. Refaely-Abramson, and R

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

    Science.gov (United States)

    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

  20. Tree size and light availability increase photochemical instead of non-photochemical capacities of Nothofagus nitida trees growing in an evergreen temperate rain forest.

    Science.gov (United States)

    Coopman, Rafael E; Briceño, Verónica F; Corcuera, Luis J; Reyes-Díaz, Marjorie; Alvarez, Daniela; Sáez, Katherine; García-Plazaola, José I; Alberdi, Miren; Bravo, León A

    2011-10-01

    Nothofagus nitida (Phil.) Krasser (Nothofagaceae) regenerates under the canopy in microsites protected from high light. Nonetheless, it is common to find older saplings in clear areas and adults as emergent trees of the Chilean evergreen forest. We hypothesized that this shade to sun transition in N. nitida is supported by an increase in photochemical and non-photochemical energy dissipation capacities of both photosystems in parallel with the increase in plant size and light availability. To dissect the relative contribution of light environment and plant developmental stage to these physiological responses, the photosynthetic performance of both photosystems was studied from the morpho-anatomical to the biochemical level in current-year leaves of N. nitida plants of different heights (ranging from 0.1 to 7 m) growing under contrasting light environments (integrated quantum flux (IQF) 5-40 mol m(-2). Tree height (TH) and light environment (IQF) independently increased the saturated electron transport rates of both photosystems, as well as leaf and palisade thickness, but non-photochemical energy flux, photoinhibition susceptibility, state transition capacity, and the contents of D1 and PsbS proteins were not affected by IQF and TH. Spongy mesophyll thickness and palisade cell diameter decreased with IQF and TH. A(max), light compensation and saturation points, Rubisco and nitrogen content (area basis) only increased with light environment (IQF), whereas dark respiration (R(d)) decreased slightly and relative chlorophyll content was higher in taller trees. Overall, the independent effects of more illuminated environment and tree height mainly increased the photochemical instead of the non-photochemical energy flux. Regardless of the photochemical increase with TH, carbon assimilation only significantly improved with higher IQF. Therefore it seems that mainly acclimation to the light environment supports the phenotypic transition of N. nitida from shade to

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  3. Photochemical Activity of Aldrin and Dieldrin in Liquid and Frozen Aqueous Systems: Field and Laboratory Studies

    Science.gov (United States)

    Bausch, A. R.; Rowland, G. A.; Grannas, A. M.

    2008-12-01

    The phenomenon of global distillation generates significant accumulation of volatile, anthropogenic persistent organic pollutants (POPs) in polar regions. Bioaccumulation presents serious concerns for human health within Arctic subsistence communities. In the recent past, the photochemical processes of POPs have been observed in the laboratory. Despite some established knowledge regarding photochemical processes in reactive frozen media, little published literature exists regarding the chemical transformations and fate of POPs in the Arctic. Here, we consider the photochemical transformations of aldrin and dieldrin, two structurally similar organochlorine pollutants whose presence has been confirmed in the Arctic. Their photochemical transformation, resulting from ultraviolet exposure, was investigated by both field studies in Barrow, AK and controlled laboratory experiments. Pollutant degradation and photoproduct formation were monitored by GC-ECD analysis. Based on kinetic studies of liquid and frozen samples and identification of photoproducts, we will propose potential reaction mechanisms for the transformations of aldrin and dieldrin. Further implications for environmental processes will be discussed.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

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

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

    Science.gov (United States)

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

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

    Science.gov (United States)

    Lu, Haifei

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

  8. Long-term Low Radiation Decreases Leaf Photosynthesis, Photochemical Efficiency and Grain Yield in Winter Wheat

    DEFF Research Database (Denmark)

    Mu, H; Jiang, D; Wollenweber, Bernd

    2010-01-01

    the impact of low radiation on crop growth, photosynthesis and yield. Grain yield losses and leaf area index (LAI) reduction were less than the reduction in solar radiation under both shading treatment in both cultivars. Compared with the control (S0), grain yield only reduced 6.4 % and 9.9 % under 22.......0-22.9 % (S1) and 29.5-49.6 % (S2), which was consistent with the reduction in radiation. The reduction in LAI was partially compensated by increases in the fraction of the top and bottom leaf area to the total leaf area, which facilitated to intercept more solar radiation by the canopy. The decrease......Low radiation reduces wheat grain yield in tree-crop intercropping systems in the major wheat planting area of China. Here, two winter wheat (Triticum aestivum L) cultivars, Yangmai 158 (shading tolerant) and Yangmai 11 (shading sensitive), were shaded from jointing to maturity to evaluate...

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

    NARCIS (Netherlands)

    Toh, K.C.; Stojkovic, E.A; van Stokkum, I.H.M.; Moffat, K.; Kennis, J.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. Thephytochrome light activation mechanism involves isomerization around the C15-C16 double bond of an open-chain tetrapyrrole chromophore, resulting in a flip

  10. Photochemical double 5-exo cyclization of alkenyl-substituted dithienylacetylenes: efficient synthesis of diarylated dithienofulvalenes.

    Science.gov (United States)

    Fukazawa, Aiko; Karasawa, Takashi; Zhang, Hongyu; Minemura, Kazumitsu; Camacho, Cristopher; Wang, Jian; Irle, Stephan; Yamaguchi, Shigehiro

    2013-09-27

    Smooth and selective: Upon photoirradiation, bis(3-alkenyl-2-thienyl)acetylenes smoothly and selectively undergo double 5-exo-dig cyclization to produce a series of thiophene-fused pentafulvalenes with various aryl substituents. In this fused π-conjugated skeleton, the fused thiophene rings and the aryl substituents significantly modulate the electronic structure of the pentafulvalene skeleton. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Prevention of vein graft intimal hyperplasia with photochemical tissue passivation.

    Science.gov (United States)

    Salinas, Harry M; Khan, Saiqa I; McCormack, Michael C; Fernandes, Justin R; Gfrerer, Lisa; Watkins, Michael T; Redmond, Robert W; Austen, William G

    2017-01-01

    Saphenous vein is the conduit of choice for bypass grafting. Saphenous vein grafts have poor long-term patency rates because of intimal hyperplasia (IH) and subsequent accelerated atherosclerosis. One of the primary triggers of IH is endothelial injury resulting from excessive dilation of the vein after exposure to arterial pressures. Photochemical tissue passivation (PTP) is a technology that cross-links adventitial collagen by a light-activated process, which limits dilation by improving vessel compliance. The objective of this study was to investigate whether PTP limits the development of IH in a rodent venous interposition graft model. PTP is accomplished by coating venous adventitia with a photosensitizing dye and exposing it to light. To assess the degree of collagen cross-linking after PTP treatment, a biodegradation assay was performed. Venous interposition grafts were placed in the femoral artery of Sprague-Dawley rats. Rats were euthanized after 4 weeks, and intimal thickness was measured histologically. Vein dilation at the time of the initial procedure was also measured. Time to digestion was 63 ± 7 minutes for controls, 101 ± 2.4 minutes for rose bengal (RB), and 300 ± 0 minutes for PTP (P collagen cross-linking, decreased vessel compliance, and significant reduction in IH. Copyright © 2015 Society for Vascular Surgery. Published by Elsevier Inc. All rights reserved.

  12. Spectroscopic and photochemical properties of the lichen compound lobaric acid.

    Science.gov (United States)

    Hidalgo, María Eliana; Bascuñan, Luis; Quilhot, Wanda; Fernández, Ernesto; Rubio, Cecilia

    2005-01-01

    Lichens synthesize and accumulate photoprotective compounds against possible damage induced by UV radiation in the photobiont. A biological model has been recently formulated that allows the use of lichens to evaluate changes at different UV radiation levels. The thermodynamics, photophysical and photochemical properties of lobaric acid were studied in acetonitrile, ethanol and Brij 35(3%) micelles at different pH values. Also the sun protector factor (SPF) was determined by in vitro methods. Lobaric acid was extracted from Stereoculon alpinum Laur. and characterized by means of standard procedures. Solutions were irradiated in oxygen and under nitrogen conditions with a UV medium pressure lamp. Lobaric acid absorbs at 287, 303 nm, and no fluorescence emission was observed. The maximum value of the molar extinction coefficient (5479.6 M(-1) cm(-1)) was obtained in Brij 35 at pH 12. Solubility is pH dependant and is highest in Brij 35 at pH 12 (4.45 x 10(-4) M). Photoconsumption quantum yields ranged between 10(-4) and 10(-5) in aerobic and anaerobic experimental conditions. Lobaric acid SPF was very low (0.5) compared with homosalate (4.0), (reference solar filter). Two pKa values, 5.05 (carboxylic acid group deprotonation) and 9.75 (phenolic OH deprotonation), were determined.

  13. Macrophages as drug delivery vehicles for photochemical internalization (Conference Presentation)

    Science.gov (United States)

    Madsen, Steen J.; Gonzalez, Jonathan; Molina, Stephanie; Kumar Nair, Rohit; Hirschberg, Henry

    2017-02-01

    Targeted delivery of chemotherapeutic drugs to tumor sites is a major challenge in cancer chemotherapy. Cell-based vectorization of therapeutic agents has great potential for cancer therapy in that it can target and maintain an elevated concentration of therapeutic agents at the tumor site and prevent their spread into healthy tissue. The use of circulating cells such as monocytes/macrophages (Ma) offers several advantages compared to nanoparticles as targeted drug delivery vehicles. Ma can be easily obtained from the patient, loaded in vitro with drugs and reinjected into the blood stream. Ma can selectively cross the partially compromised blood-brain barrier surrounding brain tumors and are known to actively migrate to tumors, drawn by chemotactic factors, including hypoxic regions where conventional chemo and radiation therapy are least effective. The utility of Ma as targeted drug delivery vehicles for photochemical internalization (PCI) of tumors was investigated in this study. In vitro studies were conducted using a mixture of F98 rat glioma cells and rat macrophages loaded with a variety of chemotherapeutic agents including bleomycin and 5-fluorouracil. Preliminary data show that macrophages are resistant to both chemotherapeutics while significant toxicity is observed for F98 cells exposed to both drugs. Co-incubation of F98 cells with loaded Ma results in significant F98 toxicity suggesting that Ma are releasing the drugs and, hence providing the rationale for their use as delivery vectors for cancer therapies such as PCI.

  14. Methane on Mars: Thermodynamic Equilibrium and Photochemical Calculations

    Science.gov (United States)

    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.

  15. Photochemical trajectory modeling of ozone concentrations in Hong Kong.

    Science.gov (United States)

    Cheng, H R; Saunders, S M; Guo, H; Louie, P K K; Jiang, F

    2013-09-01

    In this study, tropical cyclones over the East and South China Seas were found to be the most predominant weather conditions associated with the occurrence of high ozone (O3) episodes in Hong Kong in 2005-2009. A photochemical trajectory model coupled with Master Chemical Mechanism (MCM) was adapted to simulate the O3 concentrations during two O3 pollution episodes. The results agreed well with the observed data. A representative backward air mass trajectory was used to determine the contribution of each volatile organic compound (VOC) to the O3 levels. After taking into account both reactivity and mass emission of each VOC, 10 species were found to be the key O3 precursors in Hong Kong. Further analysis identified solvent related products accounting for 70% of the modeled O3 concentration in Hong Kong. The results highlight the importance of considering together reactivity and source sector emissions in developing targeted VOC reduction for O3 abatement strategies. Copyright © 2013 Elsevier Ltd. All rights reserved.

  16. Disequilibrium Chemistry and Photochemical Hazes in Temperate Jupiter Atmospheres

    Science.gov (United States)

    Gao, Peter; Zahnle, Kevin; Marley, Mark; Morley, Caroline

    2018-01-01

    Probing the chemical composition and aerosol content of "temperate Jupiters" - young, Jupiter-like worlds with effective temperatures between 400 and 800 K with no direct analogues in our own Solar System - may be possible with the James Webb Space Telescope and its direct imaging capabilities. The relatively low temperatures of these exoplanets, as compared to hot Jupiters, means that disequilibrium processes such as eddy mixing and photochemistry could play a dominant role in determining the composition of their atmospheres. In this work we use a photochemical model and a cloud microphysics model to investigate the impact of disequilibrium processes. We find that the resulting model atmospheres may be significantly different from one predicted by equilibrium chemistry. For example, upward transport of CO from depth leads to the formation of large amounts of CO2, such that observed CO2 abundances may not scale with metallicity the same way as in equilibrium models. In addition, formation of sulfur hazes from H2S loss could lead to UV heating of the atmosphere, and increased albedos at red-optical wavelengths. Our results show that disequilibrium models may be necessary to interpret future observations of these cool objects.

  17. Metal assisted photochemical etching of 4H silicon carbide

    Science.gov (United States)

    Leitgeb, Markus; Zellner, Christopher; Schneider, Michael; Schwab, Stefan; Hutter, Herbert; Schmid, Ulrich

    2017-11-01

    Metal assisted photochemical etching (MAPCE) of 4H-silicon carbide (SiC) in Na2S2O8/HF and H2O2/HF aqueous solutions is investigated with platinum as metallic cathode. The formation process of the resulting porous layer is studied with respect to etching time, concentration and type of oxidizing agent. From the experiments it is concluded that the porous layer formation is due to electron hole pairs generated in the semiconductor, which stem from UV light irradiation. The generated holes are consumed during the oxidation of 4H-SiC and the formed oxide is dissolved by HF. To maintain charge balance, the oxidizing agent has to take up electrons at the Pt/etching solution interface. Total dissolution of the porous layers is achieved when the oxidizing agent concentration decreases during MAPCE. In combination with standard photolithography, the definition of porous regions is possible. Furthermore chemical micromachining of 4 H-SiC at room temperature is possible.

  18. Photochemical chlorine and bromine activation from artificial saline snow

    Directory of Open Access Journals (Sweden)

    S. N. Wren

    2013-10-01

    Full Text Available 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.

  19. Photochemical ozone budget during the BIBLE A and B campaigns

    Science.gov (United States)

    Ko, Malcolm; Hu, Wenjie; Rodríguez, José M.; Kondo, Yutaka; Koike, Makoto; Kita, Kazuyuki; Kawakami, Shuji; Blake, Donald; Liu, Shaw; Ogawa, Toshihiro

    2003-02-01

    Using the measured concentrations of NO, O3, H2O, CO, CH4, and NMHCs along the flight tracks, a photochemical box model is used to calculate the concentrations of the Ox radicals, the HOx radicals, and the nitrogen species at the sampling points. The calculations make use of the measurements from radiometers to scale clear sky photolysis rates to account for cloud cover and ground albedo at the sampling time/point. The concentrations of the nitrogen species in each of the sampled air parcels are computed assuming they are in instantaneous equilibrium with the measured NO and O3. The diurnally varying species concentrations are next calculated using the box model and used to estimate the diurnally averaged production and removal rates of ozone for the sampled air parcels. Clear sky photolysis rates are used in the diurnal calculations. The campaign also provided measured concentration of NOy. The observed NO/NOy ratio is usually larger than the model calculated equilibrium value. There are several possible explanations. It could be a result of recent injection of NO into the air parcel, recent removal of HNO3 from the parcel, recent rapid transport of an air parcel from another location, or a combination of all processes. Our analyses suggest that the local production rate of O3 can be used as another indicator of recent NO injection. However, more direct studies using air trajectory analyses and other collaborative evidences are needed to ascertain the roles played by individual process.

  20. CO2 Reduction: From the Electrochemical to Photochemical Approach.

    Science.gov (United States)

    Wu, Jinghua; Huang, Yang; Ye, Wen; Li, Yanguang

    2017-11-01

    Increasing CO2 concentration in the atmosphere is believed to have a profound impact on the global climate. To reverse the impact would necessitate not only curbing the reliance on fossil fuels but also developing effective strategies capture and utilize CO2 from the atmosphere. Among several available strategies, CO2 reduction via the electrochemical or photochemical approach is particularly attractive since the required energy input can be potentially supplied from renewable sources such as solar energy. In this Review, an overview on these two different but inherently connected approaches is provided and recent progress on the development, engineering, and understanding of CO2 reduction electrocatalysts and photocatalysts is summarized. First, the basic principles that govern electrocatalytic or photocatalytic CO2 reduction and their important performance metrics are discussed. Then, a detailed discussion on different CO2 reduction electrocatalysts and photocatalysts as well as their generally designing strategies is provided. At the end of this Review, perspectives on the opportunities and possible directions for future development of this field are presented.

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

    Science.gov (United States)

    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.

  2. International conference on the photochemical conversion and storage of solar energy

    Energy Technology Data Exchange (ETDEWEB)

    Hofman, M.Z.

    1977-01-31

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1998-11-01

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

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

    Science.gov (United States)

    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.

  5. Photochemical reactions of aromatic compounds and the concept of the photon as a traceless reagent.

    Science.gov (United States)

    Hoffmann, Norbert

    2012-11-01

    Electronic excitation significantly changes the reactivity of chemical compounds. Compared to ground state reactions, photochemical reactions considerably enlarge the application spectrum of a particular functional group in organic synthesis. Multistep syntheses may be simplified and perspectives for target oriented synthesis (TOS) and diversity oriented synthesis (DOS) are developed. New compound families become available or may be obtained more easily. In contrast to common chemical reagents, photons don't generate side products resulting from the transformation of a chemical reagent. Therefore, they are considered as a traceless reagent. Consequently, photochemical reactions play a central role in the methodology of sustainable chemistry. This aspect has been recognized since the beginning of the 20th century. As with many other photochemical transformations, photochemical reactions of aromatic, benzene-like compounds illustrate well the advantages in this context. Photochemical cycloadditions of aromatic compounds have been investigated for a long time. Currently, they are applied in various fields of organic synthesis. They are also studied in supramolecular structures. The phenomena of reactivity and stereoselectivity are investigated. During recent years, photochemical electron transfer mediated reactions are particularly focused. Such transformations have likewise been performed with aromatic compounds. Reactivity and selectivity as well as application to organic synthesis are studied.

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

    Science.gov (United States)

    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.

  7. Photochemical cleavage of individual stereoisomers of coumarin-5-fluorouracil crossdimers via single- and two-photon-absorption

    Science.gov (United States)

    Behrendt, Philipp J.; Kim, Hee-Cheol; Hampp, Norbert

    2013-11-01

    Coumarin-5-fluorouracil crossdimers were photochemically synthesized. Three different isomers were isolated and their photo-cycloreversion, induced by single- and two-photon-absorption, was studied. The single-photon absorption quantum yields strongly correlate with the dipole moments and the absorption behavior of the stereoisomers. Between the stereoisomers a maximal factor of 6.5 in cyclobutane cleavage efficiency is observed. The two-photon-absorption cross-sections were determined for all three stereoisomers. A good correlation between the single and two-photon-absorption cross-sections was found. The isomer with the highest light sensitivity is the syn-head-to-head isomer. For most applications, isomer pure preparations seem advisable as the required light intensities may be reduced significantly.

  8. A photochemical kinetic model for solid dosage forms.

    Science.gov (United States)

    Carvalho, Thiago C; La Cruz, Thomas E; Tábora, Jose E

    2017-11-01

    Photochemical kinetic models to describe the solution phase degradation of pharmaceutical compounds have been extensively reported, but formalisms applicable to the solid phase under polychromatic light have not received as much attention. The objective of this study was to develop a mathematical model to describe the solid state photodegradation of pharmaceutical powder materials under different area/volumetric scales and light exposure conditions. The model considered the previous formalism presented for photodegradation kinetics in solution phase with important elements applied to static powder material being irradiated with a polychromatic light source. The model also included the influence of optical phenomena (i.e. reflectance, scattering factors, etc.) by applying Beer-Lambert law to light attenuation, including effects of powder density. Drug substance and drug product intermediates (blends and tablet cores) were exposed to different light sources and intensities. The model reasonably predicted the photodegradation levels of powder beds of drug substance and drug product intermediates under white and yellow lights with intensities around 5-11kLux. Importantly, the model estimates demonstrated that the reciprocity law for photoreactions was held. Further model evaluation showed that, due to light attenuation, the powder bed is in virtual darkness at cake depths greater than 500μm. At 100μm, the photodegradation of the investigated compound is expected to be close to 100% in 10days under white fluorescent halophosphate light at 9.5kLux. For tablets, defining the volume over exposed surface area ratio is more challenging. Nevertheless, the model can consider a bracket between worst and best cases to provide a reasonable photodegradation estimate. This tool can be significantly leveraged to simulate different light exposure scenarios while assessing photostability risk in order to define appropriate control strategy in manufacturing. Copyright © 2017

  9. Photochemical Thrombosis Of Retinal And Choroidal Vessels Using Rose Bengal

    Science.gov (United States)

    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

  10. Coupled Photochemical and Condensation Model for the Venus Atmosphere

    Science.gov (United States)

    Bierson, Carver; Zhang, Xi; Mendonca, Joao; Liang, Mao-Chang

    2017-10-01

    Ground based and Venus Express observations have provided a wealth of information on the vertical and latitudinal distribution of many chemical species in the Venus atmosphere [1,2]. Previous 1D models have focused on the chemistry of either the lower [3] or middle atmosphere [4,5]. Photochemical models focusing on the sulfur gas chemistry have also been independent from models of the sulfuric acid haze and cloud formation [6,7]. In recent years sulfur-bearing particles have become important candidates for the observed SO2 inversion above 80 km [5]. To test this hypothesis it is import to create a self-consistent model that includes photochemistry, transport, and cloud condensation.In this work we extend the domain of the 1D chemistry model of Zhang et al. (2012) [5] to encompass the region between the surface to 110 km. This model includes a simple sulfuric acid condensation scheme with gravitational settling. It simultaneously solves for the chemistry and condensation allowing for self-consistent cloud formation. We compare the resulting chemical distributions to observations at all altitudes. We have also validated our model cloud mass against pioneer Venus observations [8]. This updated full atmosphere chemistry model is also being applied in our 2D solver (altitude and altitude). With this 2D model we can model how the latitudinal distribution of chemical species depends on the meridional circulation. This allows us to use the existing chemical observations to place constraints on Venus GCMs [9-11].References: [1] Arney et al., JGR:Planets, 2014 [2] Vandaele et al., Icarus 2017 (pt. 1 & 2) [3] Krasnopolsky, Icarus, 2007 [4] Krasnopolsky, Icarus, 2012 [5] Zhang et al., Icarus 2012 [6] Gao et al., Icarus, 2014 [7] Krasnopolsky, Icarus, 2015 [8] Knollenberg and Hunten, JGR:Space Physics, 1980 [9] Lee et al., JGR:Planets, 2007 [10] Lebonnois et al., Towards Understanding the Climate of Venus, 2013 [11] Mendoncca and Read, Planetary and Space Science, 2016

  11. Photochemical and other air pollutants in South Holland

    Energy Technology Data Exchange (ETDEWEB)

    Posthumus, A.C.

    1975-01-01

    This year at fifteen places, regularly distributed over the industrial area west of Rotterdam, indicator plants for air pollution were again set out in the open. Tulip, gladiolus and freesia, indicators for HF, all demonstrated the same two sites to have maximum HF concentration. Spinach, an indicator for O/sub 3//SO/sub 2/, showed maximum injury in April and May and more south of the New Waterway than north of it. Medicago sativa, a plant species rather sensitive for SO/sub 2/ and O/sub 3/, showed little damage, and the reaction of petunia indicated a possible effect of ethylene only in a few cases. The photochemical air pollutant PAN caused in a few cases as well a slight injury to the indicator plants Urtica urens and Poa annua. The frequency of the injury to tobacco Bel W3 by O/sub 3//SO/sub 2/ was maximum during some periods in summer and autumn. This year again the effect of air pollution on growth and yield of tulips, tobacco and tomato plants was studied at six sites at the mouth of the Rhine with filtered and unfiltered greenhouses. The climatic conditions in these greenhouses were completely alike. Tulips in all the unfiltered greenhouses showed twice as heavy leaf injury as those in the filtered greenhouses. Tobacco plants had a higher average fresh and dry weight in the filtered greenhouses than in the unfiltered ones. The same usually held for tomato plants and also for the number of fruits and the average fresh and dry weight of tomato fruits.

  12. Photo-chemical transport modelling of tropospheric ozone: A review

    Science.gov (United States)

    Sharma, Sumit; Sharma, Prateek; Khare, Mukesh

    2017-06-01

    Ground level ozone (GLO), a secondary pollutant having adverse impact on human health, ecology, and agricultural productivity, apart from being a major contributor to global warming, has been a subject matter of several studies. In order to identify appropriate strategies to control GLO levels, accurate assessment and prediction is essential, for which elaborate simulation and modelling is required. Several studies have been undertaken in the past to simulate GLO levels at different scales and for various applications. It is important to evaluate these studies, widely spread over in literature. This paper aims to critically review various studies that have been undertaken, especially in the past 15 years (2000-15) to model GLO. The review has been done of the studies that range over different spatial scales - urban to regional and continental to global. It also includes a review of performance evaluation and sensitivity analysis of photo-chemical transport models in order to assess the extent of application of these models and their predictive capability. The review indicates following major findings: (a) models tend to over-estimate the night-time GLO concentrations due to limited titration of GLO with NO within the model; (b) dominance of contribution from far-off regional sources to average ozone concentration in the urban region and higher contribution of local sources during days of high ozone episodes; requiring strategies for controlling precursor emissions at both regional and local scales; (c) greater influence of NOx over VOC in export of ozone from urban regions due to shifting of urban plumes from VOC-sensitive regime to NOx-sensitive as they move out from city centres to neighbouring rural regions; (d) models with finer resolution inputs perform better to a certain extent, however, further improvement in resolutions (beyond 10 km) did not show improvement always; (e) future projections show an increase in GLO concentrations mainly due to rise in

  13. Photochemical green synthesis of calcium-alginate-stabilized Ag and Au nanoparticles and their catalytic application to 4-nitrophenol reduction.

    Science.gov (United States)

    Saha, Sandip; Pal, Anjali; Kundu, Subrata; Basu, Soumen; Pal, Tarasankar

    2010-02-16

    Silver and gold nanoparticles have been grown on calcium alginate gel beads using a green photochemical approach. The gel served as both a reductant and a stabilizer. The nanoparticles were characterized using UV-visible spectroscopy, X-ray diffraction (XRD), scanning and transmission electron microscopy (SEM and TEM), energy dispersive X-ray (EDS), and selected area electron diffraction (SAED) analyses. The particles are spherical, crystalline, and the size ranges for both Ag and Au nanoparticles are Ag. The effectiveness of the as-prepared dried alginate-stabilized Ag and Au nanoparticles as a solid phase heterogeneous catalyst has been evaluated, for the first time, on the well-known 4-nitrophenol (4-NP) reduction to 4-aminophenol (4-AP) in the presence of excess borohydride. The reduction was very efficient and followed zero-order kinetics for both Ag and Au nanocomposites. The effects of borohydride, initial 4-NP concentration, and catalyst dose were evaluated. The catalyst efficiency was examined on the basis of turnover frequency (TOF) and recyclability. The catalytic efficiency of alginate-based Ag catalyst was much more compared to that of the Au catalyst. The as-prepared new solid-phase biopolymer-based catalysts are very efficient, stable, easy to prepare, eco-friendly, and cost-effective, and they have the potential for industrial applications.

  14. Seasonal changes in photochemical properties of dissolved organic matter in small boreal streams

    Directory of Open Access Journals (Sweden)

    P. Porcal

    2013-08-01

    Full Text Available The fate of dissolved organic matter (DOM in lakes and streams is significantly affected by photochemical transformation of DOM. A series of laboratory photochemical experiments was conducted to describe seasonal changes in photochemical properties of DOM. The stream samples used in this study originated from three different catchments in the southernmost part of the Boreal ecozone near Dorset, Ontario, Canada. A first-order kinetics equation was used to model photochemical degradation of DOM and the kinetic rate constant, K, was used as an indicator of photochemical properties of DOM. Kinetic rate constants from all three catchments showed a sinusoidal pattern during the hydrological year. K increased steadily during autumn and winter and decreased during spring and summer with a more than 3-fold range in each stream. The highest values were observed during spring melt events when DOM was flushed from terrestrial sources by high flows. The minimum rate constants were found in summer when discharge was lowest. K was strongly correlated with pH and iron. DOM molecular weight and specific absorbance at 254 nm also exhibited annual cycles corresponding to the seasonal cycles of terrestrial organic matter, but the relationships between these properties and K differed between seasons and may have been affected by previous exposure to solar radiation during transit from the catchment.

  15. Characteristics of atmospheric particles over urban city Osaka occasionally covered with photochemical smog

    Science.gov (United States)

    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.

  16. Assessment of diphenylcyclopropenone for photochemically induced mutagenicity in the Ames assay

    Energy Technology Data Exchange (ETDEWEB)

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

    1987-10-01

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

  17. Isotope fractionation of mercury during its photochemical reduction by low-molecular-weight organic compounds.

    Science.gov (United States)

    Zheng, Wang; Hintelmann, Holger

    2010-04-01

    Photochemical reduction of Hg(II) by various low-molecular-weight organic compounds (LMWOC) was investigated to evaluate the effect of specific functional groups that are typically encountered in natural dissolved organic matters (DOM) on the photoreactivity and isotope fractionation of Hg. LMWOC with reduced sulfur functional groups (e.g., cysteine, glutathione) resulted in slower photochemical reduction of Hg(II) than those without reduced sulfur groups (e.g., serine, oxalic acid). Reduction rate constants were specifically determined for two contrasting LMWOC: dl-serine (0.640 h(-1)) and l-cysteine (0.047 h(-1)). Different mass independent isotope effects of Hg were induced by the two types of LMWOC. S-containing ligands specifically enriched magnetic isotopes ((199)Hg and (201)Hg) in the product (Hg(0)) while sulfurless ligands enriched (199)Hg and (201)Hg in the reactant (Hg(II)), suggesting that opposite magnetic isotope effects were produced by different types of ligands. The nuclear field shift effect was also observed in the photochemical reduction by serine. These isotope effects are related to specific functional groups and reduction mechanisms, and may be used to distinguish between primary and secondary photochemical reduction mechanisms of Hg(II) and to explain isotope fractionation during the photochemical reduction of Hg(II) by natural DOM, which provides mixed bonding conditions.

  18. The time course of non-photochemical quenching in phycobilisomes of Synechocystis sp. PCC6803 as revealed by picosecond time-resolved fluorimetry.

    Science.gov (United States)

    Maksimov, E G; Schmitt, F-J; Shirshin, E A; Svirin, M D; Elanskaya, I V; Friedrich, T; Fadeev, V V; Paschenko, V Z; Rubin, A B

    2014-09-01

    As high-intensity solar radiation can lead to extensive damage of the photosynthetic apparatus, cyanobacteria have developed various protection mechanisms to reduce the effective excitation energy transfer (EET) from the antenna complexes to the reaction center. One of them is non-photochemical quenching (NPQ) of the phycobilisome (PB) fluorescence. In Synechocystis sp. PCC6803 this role is carried by the orange carotenoid protein (OCP), which reacts to high-intensity light by a series of conformational changes, enabling the binding of OCP to the PBs reducing the flow of energy into the photosystems. In this paper the mechanisms of energy migration in two mutant PB complexes of Synechocystis sp. were investigated and compared. The mutant CK is lacking phycocyanin in the PBs while the mutant ΔPSI/PSII does not contain both photosystems. Fluorescence decay spectra with picosecond time resolution were registered using a single photon counting technique. The studies were performed in a wide range of temperatures - from 4 to 300 K. The time course of NPQ and fluorescence recovery in darkness was studied at room temperature using both steady-state and time-resolved fluorescence measurements. The OCP induced NPQ has been shown to be due to EET from PB cores to the red form of OCP under photon flux densities up to 1000 μmolphotonsm⁻²s⁻¹. The gradual changes of the energy transfer rate from allophycocyanin to OCP were observed during the irradiation of the sample with blue light and consequent adaptation to darkness. This fact was interpreted as the revelation of intermolecular interaction between OCP and PB binding site. At low temperatures a significantly enhanced EET from allophycocyanin to terminal emitters has been shown, due to the decreased back transfer from terminal emitter to APC. The activation of OCP not only leads to fluorescence quenching, but also affects the rate constants of energy transfer as shown by model based analysis of the decay associated

  19. Photochemical approach to high-barrier films for the encapsulation of flexible laminary electronic devices

    Energy Technology Data Exchange (ETDEWEB)

    Prager, L., E-mail: lutz.prager@iom-leipzig.de [Leibniz-Institut für Oberflächenmodifizierung e.V., Permoserstr. 15, 04318 Leipzig (Germany); Helmstedt, U. [Leibniz-Institut für Oberflächenmodifizierung e.V., Permoserstr. 15, 04318 Leipzig (Germany); Herrnberger, H. [Solarion AG, Pereser Höhe 1, Breitscheidstraße 45, 04442 Zwenkau (Germany); Kahle, O. [Fraunhofer-Einrichtung für Polymermaterialien und Composite PYCO, Kantstraße 55, 14513 Teltow (Germany); Kita, F. [AZ Electronic Materials Germany GmbH, Rheingaustraße 190-196, 65203 Wiesbaden (Germany); Münch, M. [Solarion AG, Pereser Höhe 1, Breitscheidstraße 45, 04442 Zwenkau (Germany); Pender, A.; Prager, A.; Gerlach, J.W. [Leibniz-Institut für Oberflächenmodifizierung e.V., Permoserstr. 15, 04318 Leipzig (Germany); Stasiak, M. [Fraunhofer-Einrichtung für Polymermaterialien und Composite PYCO, Kantstraße 55, 14513 Teltow (Germany)

    2014-11-03

    Based on results of preceding research and development, thin gas barriers were made by wet application of perhydropolysilazane solution onto polymer films and its subsequent photo-initiated conversion to dense silica layers applying vacuum ultraviolet irradiation. Compared to the state of the art, these layers were sufficiently improved and characterized by spectroscopic methods, by scanning electron microscopy and by gas permeation measurements. Water vapor transmission rates (WVTR) below 10{sup −2} g m{sup −2} d{sup −1} were achieved. In this way, single barrier films were developed and produced on a pilot plant from roll to roll, 250 mm wide, at speeds up to 10 m min{sup −1}. Two films were laminated using adhesives curable with ultraviolet (UV) light and evaluated by peel tests, gas permeation measurement and climate testing. It could be shown that the described high-barrier laminates which exhibit WVTR ≈ 5 × 10{sup −4} g m{sup −2} d{sup −1}, determined by the calcium mirror method, are suitable for encapsulation of flexible thin-film photovoltaic modules. Durability of the encapsulated modules could be verified in several climate tests including damp-heat, thermo-cycle (heating, freezing, wetting) and UV exposures which are equivalent to more than 20 years of endurance at outdoor conditions in temperate climate. In the frame of further research and technical development it seems to be possible to design a cost efficient industrial scale process for the production of encapsulation films for photovoltaic applications. - Highlights: • Dense silica barrier layers were developed by a photochemical approach. • Polymer based barrier films were laminated yielding flexible high-barrier films. • Using these laminates photovoltaic test modules were encapsulated and tested. • A durability of more than 20 years at outdoor conditions could be proved.

  20. Combining Sun-Induced Chlorophyll Fluorescence and Photochemical Reflectance Index Improves Diurnal Modeling of Gross Primary Productivity

    Directory of Open Access Journals (Sweden)

    Anke Schickling

    2016-07-01

    Full Text Available Sun-induced chlorophyll fluorescence (F is a novel remote sensing parameter providing an estimate of actual photosynthetic rates. A combination of this new observable and Monteith’s light use efficiency (LUE concept was suggested for an advanced modeling of gross primary productivity (GPP. In this demonstration study, we evaluate the potential of both F and the more commonly used photochemical reflectance index (PRI to approximate the LUE term in Monteith’s equation and eventually improve the forward modeling of GPP diurnals. Both F and the PRI were derived from ground and airborne based spectrometer measurements over two different crops. We demonstrate that approximating dynamic changes of LUE using F and PRI significantly improves the forward modeling of GPP diurnals. Especially in sugar beet, a changing photosynthetic efficiency during the day was traceable with F and incorporating F in the forward modeling significantly improved the estimation of GPP. Airborne data were projected to produce F and PRI maps for winter wheat and sugar beet fields over the course of one day. We detected a significant variability of both, F and the PRI within one field and particularly between fields. The variability of F and PRI was higher in sugar beet, which also showed a physiological down-regulation of leaf photosynthesis. Our results underline the potential of F to serve as a superior indicator for the actual efficiency of the photosynthetic machinery, which is linked to physiological responses of vegetation.

  1. Dopant type and/or concentration selective dry photochemical etching of semiconductor materials

    Energy Technology Data Exchange (ETDEWEB)

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

    1987-03-10

    A method is described of selectively photochemically dry etching a first semiconductor material of a given composition in the presence of a second semiconductor material which is of a composition different from the first material. The second material is not substantially etched during the method which comprises: subjecting both materials to the same photon flux of an energy greater than their respective direct bandgaps and to the same gaseous chemical etchant under conditions where the etchant would be ineffective for chemical etching of either material where the photons not present, the conditions also being such that the resultant electronic structure of the first semiconductor material under the photon flux is sufficient for the first material to undergo substantial photochemical etching under the conditions. The conditions also are such that the resultant electronic structure of the second semiconductor material under the photon flux is not sufficient for the second material to undergo substantial photochemical etching under the conditions.

  2. Effect of chemical kinetics uncertainties on calculated constituents in a tropospheric photochemical model

    Science.gov (United States)

    Thompson, Anne M.; Stewart, Richard W.

    1991-01-01

    Random photochemical reaction rates are employed in a 1D photochemical model to examine uncertainties in tropospheric concentrations and thereby determine critical kinetic processes and significant correlations. Monte Carlo computations are used to simulate different chemical environments and their related imprecisions. The most critical processes are the primary photodissociation of O3 (which initiates ozone destruction) and NO2 (which initiates ozone formation), and the OH/methane reaction is significant. Several correlations and anticorrelations between species are discussed, and the ozone/transient OH correlation is examined in detail. One important result of the modeling is that estimates of global OH are generally about 25 percent uncertain, limiting the precision of photochemical models. Techniques for reducing the imprecision are discussed which emphasize the use of species and radical species measurements.

  3. Photochemical carbon dioxide reduction with metal complexes: Differences between cobalt and nickel macrocycles

    Energy Technology Data Exchange (ETDEWEB)

    Fujita, Etsuko; Brunschwig, B.S.; Cabelli, D.; Renner, M.W.; Furenlid, L.R. [Brookhaven National Lab., Upton, NY (United States); Ogata, Tomoyuki [Brookhaven National Lab., Upton, NY (United States)]|[Osaka Univ., Suita, Osaka (Japan); Wada, Yuji; Yanagida, Shozo [Osaka Univ., Suita, Osaka (Japan)

    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.

  4. Photochemical reactivity of perfluorooctanoic acid (PFOA) in conditions representing surface water

    Energy Technology Data Exchange (ETDEWEB)

    Vaalgamaa, Sanna, E-mail: sanna.vaalgamaa@helsinki.fi [Department of Environmental Sciences, P.O. Box 65, FI-00014 University of Helsinki (Finland); Vaehaetalo, Anssi V. [Department of Environmental Sciences, P.O. Box 65, FI-00014 University of Helsinki (Finland); Coastal Zone Research Team, Aronia Research and Development Institute, Novia University of Applied Sciences and Abo Akademi University, Raseborgsvaegen 9, FI-10600 Ekenaes (Finland); Perkola, Noora; Huhtala, Sami [Finnish Environment Institute, Research and Innovation Laboratory, Hakuninmaantie 6 (P.O. Box 149), FI-00251 Helsinki (Finland)

    2011-07-15

    Potential of perfluorooctanoic acid (PFOA) to degrade via indirect photolysis in aquatic solution under conditions representing surface water was studied. Globally distributed and bioaccumulative PFOA does not absorb solar radiation by itself, but may be potentially photochemically transformed by the natural sensitizers such as dissolved organic matter (DOM), nitrate or ferric iron. Reaction solutions containing purified water, fulvic acid (representing DOM), nitrate, ferric iron or sea water from the Baltic Sea were spiked with PFOA and irradiated with an artificial sun (290-800 nm). In comparison similar samples were also irradiated under UV radiation at 254 nm in order to study the direct photolysis. UV radiation at 254 nm decomposed PFOA to perfluoroheptanoic-, perfluorohexanoic- and perfluoropentanoic acids. The samples irradiated with an artificial sun contained no decomposition products and no decrease in PFOA concentration was observed. According to the detection limit of the products and typical solar radiation at the surface of ocean, the photochemical half-life for PFOA was estimated to be at least 256 years at the depth of 0 m, > 5000 years in the mixing layer of open ocean and > 25,000 years in coastal ocean. This is significantly more than the previously reported photochemical half-life of PFOA (> 0.96 years). - Research highlights: {yields} UV-vis irradiation (290-800 nm) with natural sensitizers did not promote decomposition of PFOA. {yields} The photochemical half-life of PFOA is at least 256 years at the depth of 0 m. {yields} In the mixing layer of open ocean the photochemical half-life is > 5000 years. {yields} In coastal ocean PFOA photochemical half-life is more than 25,000 years.

  5. A universal protocol for photochemical covalent immobilization of intact carbohydrates for the preparation of carbohydrate microarrays.

    Science.gov (United States)

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

    2011-01-19

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

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

    Directory of Open Access Journals (Sweden)

    Anshu Bhati

    2016-01-01

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

  7. [Detection of damaged myocardial cells in histological sections by photochemical fluorochroming].

    Science.gov (United States)

    Tsimmerman, V G; Tsellarius, Iu G

    1976-01-01

    The effect of photochemical fluorochromizing used in the method suggested consists in the following: after the exposure of sections to short-wave ultraviolet irradiation the preparations start to fluorescence intensively in the visible region with the long-wave the myocardium of mice, dogs and section materials showed that following photochemical fluorochroming the intensity of lumenescence of damaged cells of the myocardium increased markedly as compared with that of intact cells. The authors recommend to use the described method in diagnosis of early stages of ischemic lesions of the myocardium.

  8. Graphene oxide interface enhances the photochemical synthesis, stability and photothermal effect of plasmonic gold nanostructures

    Science.gov (United States)

    Rady, Hossam S.; Emam, Ahmed N.; Mohamed, Mona B.; El-Shall, M. Samy

    2017-12-01

    A novel photochemical approach is presented for the synthesis of shape-controlled plasmonic gold nanostructures supported on reduced graphene oxide. Graphene oxide (GO) interface enhances the rate of photochemical reduction of gold ions in water and influnces the growth rate of the initial gold nuclei leading the the formation of different shapes and assembiles depeding on the light source. The size, shape and morphology of the Au nanocrystals could be tailored by varying the light source and the exposure time. The resulting hybrid Au@RGO plasmonic nanostructures show signficantly enhanced photostability and photothermal response as compared to free gold nanostructures.

  9. Fabrication of fin field-effect transistor silicon nanocrystal floating gate memory using photochemical vapor deposition

    Science.gov (United States)

    Kim, Sang Soo; Cho, Won-Ju; Ahn, Chang-Geun; Im, Kiju; Yang, Jong-Heon; Baek, In-Bok; Lee, Seongjae; Lim, Koeng Su

    2006-05-01

    The fin field-effect transistor (FET) silicon nanocrystal floating gate memory using the photochemical vapor deposition and the plasma doping processes was proposed. The silicon nanocrystals with a uniform size were formed on a vertical sidewall surface of the fin channel by the photochemical vapor deposition. The plasma doping was applied to form the junctions at the sidewall of the fin source-drain extension regions with a high aspect ratio. The FinFET silicon nanocrystal floating gate memory with a gate length of 100nm was successfully fabricated and it revealed a memory effect as well as a suppressed short-channel effect.

  10. Ammonia removal from leachate by photochemical process using H2O2

    Directory of Open Access Journals (Sweden)

    Giovani Archanjo Brota

    2010-08-01

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

  11. Photochemical reduction of uranyl ion with some alkyl amides and N-alkyl derivatives of formamide

    Energy Technology Data Exchange (ETDEWEB)

    Brar, A.S.; Chander, R.; Kohli, K.B.; Sandhu, S.S. (Guru Nanak Dev Univ., Amritsar (India). Dept. of Chemistry)

    1982-03-01

    The photochemical reduction of uranyl ion by formamide, acetamide, propionamide, n-butylramide, isobutylramide, N-methylformamide, N,N-dimethylformamide and N,N-diethylformamide has been investigated in aqueous acidic medium using radiations in the visible region. The plots of reciprocal of quantum yield versus reciprocal of the initial amide concentration are linear with intercepts on the ordinate axis. The Stern-Volmer quenching constants have been calculated from luminescence measurements. Absorption spectra reveal that there is no ground state interaction between the uranyl ion and the amides. A mechanism of photochemical reduction of uranyl ion with amides has been suggested.

  12. The impact of aerosols on solar ultraviolet radiation and photochemical smog.

    Science.gov (United States)

    Dickerson, R R; Kondragunta, S; Stenchikov, G; Civerolo, K L; Doddridge, B G; Holben, B N

    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.

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

    Science.gov (United States)

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

    2010-01-01

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

  14. Photochemical Stability of π-Conjugated Polymers for Polymer Solar Cells: a Rule of Thumb

    DEFF Research Database (Denmark)

    Manceau, Matthieu

    2010-01-01

    of the moieties commonly used in the PSCs field are thus included in this study. The behavior of each material has been carefully investigated under simulated sunlight (1 sun, 1000 W m-2, AM 1.5G) and ambient atmosphere. Degradation was monitored all along ageing combining UV-visible and Infra-red spectroscopies...... of different points on photochemical stability is discussed (donor and acceptor group nature, side-chain type). This screening finally allowed for the description of general rules for π-conjugated polymer photochemical stability. Our results thus provide a better description of the structure – stability...

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

    Science.gov (United States)

    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. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Photochemical Control of Organic Carbon Availability to Coastal Microbial Communities

    Science.gov (United States)

    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.

  17. Oxidative capacity and radical chemistry in the polluted atmosphere of Hong Kong and Pearl River Delta region: analysis of a severe photochemical smog episode

    Science.gov (United States)

    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.

  18. Oxidative capacity and radical chemistry in the polluted atmosphere of Hong Kong and Pearl River Delta region: analysis of a severe photochemical smog episode

    Directory of Open Access Journals (Sweden)

    L. Xue

    2016-08-01

    Full Text Available 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.

  19. Power conversion efficiency of non-equilibrium light absorption

    Directory of Open Access Journals (Sweden)

    I. Santamaría-Holek

    2017-04-01

    Full Text Available We deduce a novel expression for the non-equilibrium photochemical potential and the power conversion efficiency of non-equilibrium light absorption by a thermostated material. Application of our results for the case of electron migration from valence to conduction bands in photovoltaic cells allows us to accurately interpolate experimental results for the maximal efficiencies of Ge-, Si-, GaAs-based cells and the like.

  20. Effects of pH on photochemical decomposition of perfluorooctanoic acid in different atmospheres by 185nm vacuum ultraviolet.

    Science.gov (United States)

    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. Copyright © 2014. Published by Elsevier B.V.

  1. Photochemical of Polychlorinated biphenyl by the photolysis and ...

    African Journals Online (AJOL)

    Michael Horsfall

    Concentration of acetone that acted as a sensitizer was used to ensure the enhancement of PCBs photodegradation. The reaction mixture inside the cell was continuously ... photolysis rate was very high during the first one or two time point ... Table 2: Effect of UV intensity on PCBs degradation efficiency (%) of photolysis.

  2. Photochemical source of biological substrates in sea water: implications for carbon cycling

    Science.gov (United States)

    Kieber, David J.; McDaniel, Julie; Mopper, Kenneth

    1989-10-01

    DISSOLVED organic carbon (DOC) in sea water represents one of the largest reservoirs of carbon on the earth1. The main fraction of this DOC is generally believed to be composed of old2, biologi-cally refractory material3 such as humic substances, for which the removal mechanisms remain largely unknown. One potentially important removal process in the ocean that has not been investi-gated is the photochemical breakdown of this DOC in the photic zone to form biologically labile organic products. Here we show that biological uptake of pyruvate is highly correlated to its rate of photochemical production in sea water (r = 0.964), and that the photochemical precursor(s) of pyruvate is from the fraction of DOC having a nominal molecular weight of 500. This is the first evidence that photochemical breakdown of high-molecular-weight marine DOC, which is presumably biologically refractory, results in the production of a compound that is used by plankton as a substrate. Our results have important implications for the oceanic carbon cycle, particularly with respect to planktonic-food-web dynamics and the global carbon budget.

  3. Influence of processing and intrinsic polymer parameters on photochemical stability of polythiophene thin films

    DEFF Research Database (Denmark)

    Vesterager Madsen, Morten; Tromholt, Thomas; Böttiger, Arvid P.L.

    2012-01-01

    shielding effects were shown to have a negligible effect on the photochemical degradation rate. The results obtained in this work advance the understanding of polymer stability and will help improve the design of materials used for polymer solar cells resulting in longer lifetimes, which will push...

  4. Interfacial electrochemistry of colloidal ruthenium dioxide and catalysis of the photochemical generation of hydrogen from water

    NARCIS (Netherlands)

    Kleijn, J.M.

    1987-01-01

    The formation of hydrogen from water using solar energy is a very attractive research topic, because of the potential use of hydrogen as an alternative, clean fuel. It has been shown by many workers in the field that photochemical hydrogen generation can be achieved in an aqueous system,

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

    Science.gov (United States)

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

    1997-01-01

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

  6. Chemical kinetics and photochemical data for use in stratospheric modeling: Evaluation number 11

    Science.gov (United States)

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

    1994-01-01

    This is the eleventh 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.

  7. Water Treatment Process Intensification by Combination of Electrochemical and Photochemical Methods

    Czech Academy of Sciences Publication Activity Database

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

    2015-01-01

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

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

    Science.gov (United States)

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

    2014-08-18

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

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

    DEFF Research Database (Denmark)

    Skov, H.; Egeløv, A.H.; Granby, K.

    1997-01-01

    The representativeness of the monitoring station at L1. Valby, Denmark, has been tested. Furthermore, the relation of gaseous NOy and O-3 is investigated. From the linear orthogonal regression analyses of Ox (sum of O-3+NO2) and other photochemical products measured at L1. Valby Denmark and from...

  10. Photochemical Upconversion: A Physical or Inorganic Chemistry Experiment for Undergraduates Using a Conventional Fluorimeter

    Science.gov (United States)

    Wilke, Bryn M.; Castellano, Felix N.

    2013-01-01

    Photochemical upconversion is a regenerative process that transforms lower-energy photons into higher-energy light through two sequential bimolecular reactions, triplet sensitization of an appropriate acceptor followed by singlet fluorescence producing triplet-triplet annihilation derived from two energized acceptors. This laboratory directly…

  11. Photochemical Generation of Six- and Five-Membered Cyclic Vinyl Cations

    NARCIS (Netherlands)

    Slegt, M.; Gronheid, R.; Vlugt, van der D.; Ochiai, M.; Okuyama, T.; Zuilhof, H.; Overkleeft, H.S.; Lodder, G.

    2006-01-01

    [GRAPHICS] The photochemical solvolyses of 4-tert-butylcyclohex-1-enyl(phenyl)iodonium tetrafluoroborate (1) and cyclopent-1-enyl(phenyl)iodonium tetrafluoroborate (2) in methanol yield vinylic ethers and vinylic cycloalkenyliodoberizenes and cycloalkenylbenzene, which are the trapping products of

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

    DEFF Research Database (Denmark)

    Shiraishi, Takehiko; Nielsen, Peter E

    2011-01-01

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

  13. One-Step Photochemical Attachment of NHS-Terminated Monolayers onto Silicon Surfaces and Subsequent Functionalization

    NARCIS (Netherlands)

    Yang, M.; Teeuwen, R.L.M.; Giesbers, M.; Baggerman, J.; Arafat, A.; Wolf, de F.A.; Hest, van J.C.M.; Zuilhof, H.

    2008-01-01

    N-Hydroxysuccinimide (NHS)-ester-terminated monolayers were covalently attached in one step onto silicon using visible light. This mild photochemical attachment, starting from ¿-NHS-functionalized 1-alkenes, yields a clean and flat monolayer-modified silicon surface and allows a mild and rapid

  14. High-temperature photochemical destruction of toxic organic wastes using concentrated solar radiation

    Energy Technology Data Exchange (ETDEWEB)

    Dellinger, B.; Graham, J.L.; Berman, J.M.; Taylor, P.H. [Dayton Univ., OH (United States)

    1994-05-01

    Application of concentrated solar energy has been proposed to be a viable waste disposal option. Specifically, this concept of solar induced high-temperature photochemistry is based on the synergistic contribution of concentrated infrared (IR) radiation, which acts as an intense heating source, and near ultraviolet and visible (UV-VIS) radiation, which can induce destructive photochemical processes. Some significant advances have been made in the theoretical framework of high-temperature photochemical processes (Section 2) and development of experimental techniques for their study (Section 3). Basic thermal/photolytic studies have addressed the effect of temperature on the photochemical destruction of pure compounds (Section 4). Detailed studies of the destruction of reaction by-products have been conducted on selected waste molecules (Section 5). Some very limited results are available on the destruction of mixtures (Section 6). Fundamental spectroscopic studies have been recently initiated (Section 7). The results to date have been used to conduct some relatively simple scale-up studies of the solar detoxification process. More recent work has focused on destruction of compounds that do not directly absorb solar radiation. Research efforts have focused on homogeneous as well as heterogeneous methods of initiating destructive reaction pathways (Section 9). Although many conclusions at this point must be considered tentative due to lack of basic research, a clearer picture of the overall process is emerging (Section 10). However, much research remains to be performed and most follow several veins, including photochemical, spectroscopic, combustion kinetic, and engineering scale-up (Section 11).

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

    Czech Academy of Sciences Publication Activity Database

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

    2014-01-01

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

  16. Photochemical Grafting and Patterning of Organic Monolayers on Indium Tin Oxide Substrates

    NARCIS (Netherlands)

    Li, Y.; Zuilhof, H.

    2012-01-01

    Covalently attached organic layers on indium tin oxide (ITO) surfaces were prepared by the photochemical grafting with 1-alkenes. The surface modification was monitored with static water contact angle, X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM) measurements.

  17. Photosystem Trap Energies and Spectrally-Dependent Energy-Storage Efficiencies in the Chl d-Utilizing Cyanobacterium, Acaryochloris Marina

    Science.gov (United States)

    Mielke, Steven P.; Kiang, Nancy Y.; Blankenship, Robert E.; Mauzerall, David

    2012-01-01

    Acaryochloris marina is the only species known to utilize chlorophyll (Chl) d as a principal photopigment. The peak absorption wavelength of Chl d is redshifted approx. 40 nm in vivo relative to Chl a, enabling this cyanobacterium to perform oxygenic phototrophy in niche environments enhanced in far-red light. We present measurements of the in vivo energy-storage (E-S) efficiency of photosynthesis in A. marina, obtained using pulsed photoacoustics (PA) over a 90-nm range of excitation wavelengths in the red and far-red. Together with modeling results, these measurements provide the first direct observation of the trap energies of PSI and PSII, and also the photosystem-specific contributions to the total E-S efficiency. We find the maximum observed efficiency in A. marina (40+/-1% at 735 nm) is higher than in the Chl a cyanobacterium Synechococcus leopoliensis (35+/-1% at 690 nm). The efficiency at peak absorption wavelength is also higher in A. marina (36+/-1% at 710 nm vs. 31+/-1% at 670 nm). In both species, the trap efficiencies are approx. 40% (PSI) and approx. 30% (PSII). The PSI trap in A. marina is found to lie at 740+/-5 nm, in agreement with the value inferred from spectroscopic methods. The best fit of the model to the PA data identifies the PSII trap at 723+/-3 nm, supporting the view that the primary electron-donor is Chl d, probably at the accessory (ChlD1) site. A decrease in efficiency beyond the trap wavelength, consistent with uphill energy transfer, is clearly observed and fit by the model. These results demonstrate that the E-S efficiency in A. marina is not thermodynamically limited, suggesting that oxygenic photosynthesis is viable in even redder light environments.

  18. Using Temperature of IR Sources for Assessing Photochemical and Aphakic Retinal Hazard

    Directory of Open Access Journals (Sweden)

    Faramarz Madjidi

    2016-03-01

    Full Text Available Introduction Blue light is a part of the spectrum with the highest energy content, which can reach the retina. The damage that it can cause to the retina is called photochemical or blue-light retinal injury. For the retinal injury assessment of the photochemical and aphakic retinal hazards in the wavelength range of 300-700 nm, use of effective spectral radiance limits (W.m-2.sr-1 seems to be slightly perplexing for ophthalmologists. However, in this study, the temperature (OC that can emit the same effective spectral radiance limit was detected using a computer code; this method could help prevent blue-light retinal injury. Materials and Methods The limits proposed by International Commission on Non-Ionizing Radiation Protection for blue-light induced photochemical and aphakic eye hazards were expressed in terms of temperature by a computer code for 13 Planckian sources that produce the same radiance. The calculated temperature by the computer code, here known as threshold temperature, is the maximum source temperature that for a specified viewing distance and source diameter does not cause the exposure at the receptor position to exceed the exposure limit. Results In terms of threshold temperature, the exposure limits for aphakia or infant retinal injury are much lower than retinal photochemical damage. For light sources with more effective radiances, these differences reach 800 K. Conclusion This method allows evaluation of photochemical and aphakic retinal hazard only by comparing the calculated threshold temperature by a computer code with the temperature of the radiant source, which may be beneficial for hygienist and ophthalmic clinicians.

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

    Directory of Open Access Journals (Sweden)

    C. Chou

    2013-01-01

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

  20. Unexpected effect of catalyst concentration on photochemical CO2reduction bytrans(Cl)-Ru(bpy)(CO)2Cl2: new mechanistic insight into the CO/HCOO-selectivity.

    Science.gov (United States)

    Kuramochi, Yusuke; Itabashi, Jun; Fukaya, Kyohei; Enomoto, Akito; Yoshida, Makoto; Ishida, Hitoshi

    2015-05-01

    Photochemical CO 2 reduction catalysed by trans (Cl)-Ru(bpy)(CO) 2 Cl 2 (bpy = 2,2'-bipyridine) efficiently produces carbon monoxide (CO) and formate (HCOO - ) in N , N -dimethylacetamide (DMA)/water containing [Ru(bpy) 3 ] 2+ as a photosensitizer and 1-benzyl-1,4-dihydronicotinamide (BNAH) as an electron donor. We have unexpectedly found catalyst concentration dependence of the product ratio (CO/HCOO - ) in the photochemical CO 2 reduction: the ratio of CO/HCOO - decreases with increasing catalyst concentration. The result has led us to propose a new mechanism in which HCOO - is selectively produced by the formation of a Ru(i)-Ru(i) dimer as the catalyst intermediate. This reaction mechanism predicts that the Ru-Ru bond dissociates in the reaction of the dimer with CO 2 , and that the insufficient electron supply to the catalyst results in the dominant formation of HCOO - . The proposed mechanism is supported by the result that the time-course profiles of CO and HCOO - in the photochemical CO 2 reduction catalysed by [Ru(bpy)(CO) 2 Cl] 2 (0.05 mM) are very similar to those of the reduction catalysed by trans (Cl)-Ru(bpy)(CO) 2 Cl 2 (0.10 mM), and that HCOO - formation becomes dominant under low-intensity light. The kinetic analyses based on the proposed mechanism could excellently reproduce the unusual catalyst concentration effect on the product ratio. The catalyst concentration effect observed in the photochemical CO 2 reduction using [Ru(4dmbpy) 3 ] 2+ (4dmbpy = 4,4'-dimethyl-2,2'-bipyridine) instead of [Ru(bpy) 3 ] 2+ as the photosensitizer is also explained with the kinetic analyses, reflecting the smaller quenching rate constant of excited [Ru(4dmbpy) 3 ] 2+ by BNAH than that of excited [Ru(bpy) 3 ] 2+ . We have further synthesized trans (Cl)-Ru(6Mes-bpy)(CO) 2 Cl 2 (6Mes-bpy = 6,6'-dimesityl-2,2'-bipyridine), which bears bulky substituents at the 6,6'-positions in the 2,2'-bipyridyl ligand, so that the ruthenium complex cannot form the dimer due to the

  1. Photochemical transformation of anionic 2-nitro-4-chlorophenol in surface waters: Laboratory and model assessment of the degradation kinetics, and comparison with field data

    Energy Technology Data Exchange (ETDEWEB)

    Sur, Babita [Dipartimento di Chimica, Universita di Torino, Via P. Giuria 5, 10125 Torino (Italy); Department of Chemical Engineering, Calcutta University, 92 Acharya P. C. Road, Kolkata 700009 (India); De Laurentiis, Elisa; Minella, Marco; Maurino, Valter; Minero, Claudio [Dipartimento di Chimica, Universita di Torino, Via P. Giuria 5, 10125 Torino (Italy); Vione, Davide [Dipartimento di Chimica, Universita di Torino, Via P. Giuria 5, 10125 Torino (Italy); Centro Interdipartimentale NatRisk, Universita di Torino, Via Leonardo da Vinci 44, 10095 Grugliasco (Italy)

    2012-06-01

    Anionic 2-nitro-4-chlorophenol (NCP) may occur in surface waters as a nitroderivative of 4-chlorophenol, which is a transformation intermediate of the herbicide dichlorprop. Here we show that NCP would undergo efficient photochemical transformation in environmental waters, mainly by direct photolysis and reaction with {center_dot}OH. NCP has a polychromatic photolysis quantum yield {Phi}{sub NCP} = (1.27 {+-} 0.22) {center_dot} 10{sup -5}, a rate constant with {center_dot}OH k{sub NCP,}{center_dot}{sub OH} = (1.09 {+-} 0.09) {center_dot} 10{sup 10} M{sup -1} s{sup -1}, a rate constant with {sup 1}O{sub 2}k{sub NCP,1O2} = (2.15 {+-} 0.38) {center_dot} 10{sup 7} M{sup -1} s{sup -1}, a rate constant with the triplet state of anthraquinone-2-sulphonate k{sub NCP,3AQ2S*} = (5.90 {+-} 0.43) {center_dot} 10{sup 8} M{sup -1} s{sup -1}, and is poorly reactive toward CO{sub 3}{sup -}{center_dot}. The k{sub NCP,3AQ2S*} value is representative of reaction with the triplet states of chromophoric dissolved organic matter. The inclusion of photochemical reactivity data into a model of surface-water photochemistry allowed the NCP transformation kinetics to be predicted as a function of water chemical composition and column depth. Very good agreement between model predictions and field data was obtained for the shallow lagoons of the Rhone delta (Southern France). Highlights: Black-Right-Pointing-Pointer Phototransformation kinetics of 2-nitro-4-chlorophenol, relevant to surface waters. Black-Right-Pointing-Pointer Determination of photochemical reactivity data in the laboratory. Black-Right-Pointing-Pointer Model approach to combine photochemical reactivity with environmental variables. Black-Right-Pointing-Pointer Good agreement with field data in lagoon water (Rhone delta, Southern France). Black-Right-Pointing-Pointer Direct photolysis and reaction with {center_dot}OH as main photoprocesses in the environment.

  2. Direct impact of the sustained decline in the photosystem II efficiency upon plant productivity at different developmental stages.

    Science.gov (United States)

    Tian, Yonglan; Ungerer, Petra; Zhang, Huayong; Ruban, Alexander V

    2017-05-01

    The impact of chronic photoinhibition of photosystem II (PSII) on the productivity of plants remains unknown. The present study investigated the influences of persistent decline in the PSII yield on morphology and productivity of Arabidopsis plants that were exposed to lincomycin at two different developmental stages (seedling and rosette stage). The results indicated that, although retarded, the lincomycin treated plants were able to accomplish the entire growth period with only 50% of the maximum quantum yield of primary photochemistry (Fv/Fm) of the control plants. The decline in quantum yield limited the electron transport rate (ETR). The impact of lincomycin on NPQ was not significant in seedlings, but was pronounced in mature plants. The treated plants produced an above ground biomass of 50% compared to control plants. Moreover, a linear relationship was found between the above ground biomass and total rosette leaf area, and the slope was decreased due to photoinhibition. The starch accumulation was highly inhibited by lincomycin treatment. Lincomycin induced a significant decrease in seed yield with plants treated from the rosette state showing higher yield than those treated from the seedling stage. Our data suggest that the sustained decline of PSII efficiency decreases plant productivity by constraining the ETR, leaf development and starch production. Copyright © 2017 Elsevier GmbH. All rights reserved.

  3. Mutations of photosystem II D1 protein that empower efficient phenotypes of Chlamydomonas reinhardtii under extreme environment in space.

    Directory of Open Access Journals (Sweden)

    Maria Teresa Giardi

    Full Text Available Space missions have enabled testing how microorganisms, animals and plants respond to extra-terrestrial, complex and hazardous environment in space. Photosynthetic organisms are thought to be relatively more prone to microgravity, weak magnetic field and cosmic radiation because oxygenic photosynthesis is intimately associated with capture and conversion of light energy into chemical energy, a process that has adapted to relatively less complex and contained environment on Earth. To study the direct effect of the space environment on the fundamental process of photosynthesis, we sent into low Earth orbit space engineered and mutated strains of the unicellular green alga, Chlamydomonas reinhardtii, which has been widely used as a model of photosynthetic organisms. The algal mutants contained specific amino acid substitutions in the functionally important regions of the pivotal Photosystem II (PSII reaction centre D1 protein near the QB binding pocket and in the environment surrounding Tyr-161 (YZ electron acceptor of the oxygen-evolving complex. Using real-time measurements of PSII photochemistry, here we show that during the space flight while the control strain and two D1 mutants (A250L and V160A were inefficient in carrying out PSII activity, two other D1 mutants, I163N and A251C, performed efficient photosynthesis, and actively re-grew upon return to Earth. Mimicking the neutron irradiation component of cosmic rays on Earth yielded similar results. Experiments with I163N and A251C D1 mutants performed on ground showed that they are better able to modulate PSII excitation pressure and have higher capacity to reoxidize the QA (- state of the primary electron acceptor. These results highlight the contribution of D1 conformation in relation to photosynthesis and oxygen production in space.

  4. Mutations of photosystem II D1 protein that empower efficient phenotypes of Chlamydomonas reinhardtii under extreme environment in space.

    Science.gov (United States)

    Giardi, Maria Teresa; Rea, Giuseppina; Lambreva, Maya D; Antonacci, Amina; Pastorelli, Sandro; Bertalan, Ivo; Johanningmeier, Udo; Mattoo, Autar K

    2013-01-01

    Space missions have enabled testing how microorganisms, animals and plants respond to extra-terrestrial, complex and hazardous environment in space. Photosynthetic organisms are thought to be relatively more prone to microgravity, weak magnetic field and cosmic radiation because oxygenic photosynthesis is intimately associated with capture and conversion of light energy into chemical energy, a process that has adapted to relatively less complex and contained environment on Earth. To study the direct effect of the space environment on the fundamental process of photosynthesis, we sent into low Earth orbit space engineered and mutated strains of the unicellular green alga, Chlamydomonas reinhardtii, which has been widely used as a model of photosynthetic organisms. The algal mutants contained specific amino acid substitutions in the functionally important regions of the pivotal Photosystem II (PSII) reaction centre D1 protein near the QB binding pocket and in the environment surrounding Tyr-161 (YZ) electron acceptor of the oxygen-evolving complex. Using real-time measurements of PSII photochemistry, here we show that during the space flight while the control strain and two D1 mutants (A250L and V160A) were inefficient in carrying out PSII activity, two other D1 mutants, I163N and A251C, performed efficient photosynthesis, and actively re-grew upon return to Earth. Mimicking the neutron irradiation component of cosmic rays on Earth yielded similar results. Experiments with I163N and A251C D1 mutants performed on ground showed that they are better able to modulate PSII excitation pressure and have higher capacity to reoxidize the QA (-) state of the primary electron acceptor. These results highlight the contribution of D1 conformation in relation to photosynthesis and oxygen production in space.

  5. Photochemical transformation of anionic 2-nitro-4-chlorophenol in surface waters: laboratory and model assessment of the degradation kinetics, and comparison with field data.

    Science.gov (United States)

    Sur, Babita; De Laurentiis, Elisa; Minella, Marco; Maurino, Valter; Minero, Claudio; Vione, Davide

    2012-06-01

    Anionic 2-nitro-4-chlorophenol (NCP) may occur in surface waters as a nitroderivative of 4-chlorophenol, which is a transformation intermediate of the herbicide dichlorprop. Here we show that NCP would undergo efficient photochemical transformation in environmental waters, mainly by direct photolysis and reaction with OH. NCP has a polychromatic photolysis quantum yield Φ(NCP)=(1.27±0.22)·10(-5), a rate constant with OH k(NCP,)(OH)=(1.09±0.09)·10(10) M(-1) s(-1), a rate constant with (1)O(2)k(NCP,1O2)=(2.15±0.38)·10(7) M(-1) s(-1), a rate constant with the triplet state of anthraquinone-2-sulphonate k(NCP,3AQ2S*)=(5.90±0.43)·10(8) M(-1) s(-1), and is poorly reactive toward CO(3)(-). The k(NCP,3AQ2S*) value is representative of reaction with the triplet states of chromophoric dissolved organic matter. The inclusion of photochemical reactivity data into a model of surface-water photochemistry allowed the NCP transformation kinetics to be predicted as a function of water chemical composition and column depth. Very good agreement between model predictions and field data was obtained for the shallow lagoons of the Rhône delta (Southern France). Copyright © 2012 Elsevier B.V. All rights reserved.

  6. Pt nanoparticles supported over Ce-Ti-O: the solvothermal and photochemical approaches for the preparation of catalytic materials

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Adrian M. T., E-mail: adrian@fe.up.pt; Machado, Bruno F.; Gomes, Helder T.; Figueiredo, Jose L. [Universidade do Porto, Laboratorio de Catalise e Materiais (LCM), Laboratorio Associado LSRE/LCM, Departamento de Engenharia Quimica, Faculdade de Engenharia (Portugal); Drazic, Goran, E-mail: goran.drazic@ijs.s [Jozef Stefan Institute, Department of Nanostructured Materials (Slovenia); Faria, Joaquim L. [Universidade do Porto, Laboratorio de Catalise e Materiais (LCM), Laboratorio Associado LSRE/LCM, Departamento de Engenharia Quimica, Faculdade de Engenharia (Portugal)

    2010-01-15

    Ce-Ti-O supports with different Ce/Ti molar ratios were synthesized by the solvothermal method using hexadecyltrimethylammonium bromide. Pt nanoparticles were then supported by photochemical deposition. The shape, size, and structure of these materials were analyzed by high-resolution transmission electron microscopy. The single CeO{sub 2} support was also prepared, consisting of agglomerated cubic particles ranging from {approx}3 to 8 nm. When titania was combined with ceria, a nanostructured architecture was produced, evidencing the strong influence of Ti in the support structure. Photodeposition of Pt nanoparticles is more efficient on Ce-Ti-O supports than in pristine CeO{sub 2}. Crystalline Pt nanoparticles (mainly of {approx}2 to 4 nm) were detected. The catalytic properties of the materials were tested in the selective hydrogenation of cinnamaldehyde to cinnamyl alcohol. It was observed that Pt supported on Ce-Ti-O is more active and selective than Pt on CeO{sub 2} or TiO{sub 2} separately. The catalyst with 40 mol% Ce leads to total conversion of cinnamaldehyde in a few minutes; however, higher selectivity toward the desired product (cinnamyl alcohol) was obtained with higher amounts of Ce (50 mol%).

  7. Deconvolution of pigment and physiologically related photochemical reflectance index variability at the canopy scale over an entire growing season.

    Science.gov (United States)

    Hmimina, G; Merlier, E; Dufrêne, E; Soudani, K

    2015-08-01

    The sensitivity of the photochemical reflectance index (PRI) to leaf pigmentation and its impacts on its potential as a proxy for light-use efficiency (LUE) have recently been shown to be problematic at the leaf scale. Most leaf-to-leaf and seasonal variability can be explained by such a confounding effect. This study relies on the analysis of PRI light curves that were generated at the canopy scale under natural conditions to derive a precise deconvolution of pigment-related and physiologically related variability in the PRI. These sources of variability were explained by measured or estimated physiologically relevant variables, such as soil water content, that can be used as indicators of water availability and canopy chlorophyll content. The PRI mainly reflected the variability in the pigment content of the canopy. However, the corrected PRI, which was obtained by subtracting the pigment-related seasonal variability from the PRI measurement, was highly correlated with the upscaled LUE measurements. Moreover, the sensitivity of the PRI to the leaf pigment content may mask the PRI versus LUE relationship or result in an artificial relationship that reflects the relationship of chlorophyll versus LUE, depending on the species phenology. © 2015 John Wiley & Sons Ltd.

  8. Toward Photochemical Water Splitting Using Band-Gap-Narrowed Semiconductors and Transition-Metal Based Molecular Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Muckerman,J.T.; Rodriguez, J.A.; Fujita, E.

    2009-06-07

    We are carrying out coordinated theoretical and experimental studies of toward photochemical water splitting using band-gap-narrowed semiconductors (BGNSCs) with attached multi-electron molecular water oxidation and hydrogen production catalysts. We focus on the coupling between the materials properties and the H{sub 2}O redox chemistry, with an emphasis on attaining a fundamental understanding of the individual elementary steps in the following four processes: (1) Light-harvesting and charge-separation of stable oxide or oxide-derived semiconductors for solar-driven water splitting, including the discovery and characterization of the behavior of such materials at the aqueous interface; (2) The catalysis of the four-electron water oxidation by dinuclear hydroxo transition-metal complexes with quinonoid ligands, and the rational search for improved catalysts; (3) Transfer of the design principles learned from the elucidation of the DuBois-type hydrogenase model catalysts in acetonitrile to the rational design of two-electron hydrogen production catalysts for aqueous solution; (4) Combining these three elements to examine the function of oxidation catalysts on BGNSC photoanode surfaces and hydrogen production catalysts on cathode surfaces at the aqueous interface to understand the challenges to the efficient coupling of the materials functions.

  9. Linking Load, Fuel, and Emission Controls to Photochemical Production of Secondary Organic Aerosol from a Diesel Engine.

    Science.gov (United States)

    Jathar, Shantanu H; Friedman, Beth; Galang, Abril A; Link, Michael F; Brophy, Patrick; Volckens, John; Eluri, Sailaja; Farmer, Delphine K

    2017-02-07

    Diesel engines are important sources of fine particle pollution in urban environments, but their contribution to the atmospheric formation of secondary organic aerosol (SOA) is not well constrained. We investigated direct emissions of primary organic aerosol (POA) and photochemical production of SOA from a diesel engine using an oxidation flow reactor (OFR). In less than a day of simulated atmospheric aging, SOA production exceeded POA emissions by an order of magnitude or more. Efficient combustion at higher engine loads coupled to the removal of SOA precursors and particle emissions by aftertreatment systems reduced POA emission factors by an order of magnitude and SOA production factors by factors of 2-10. The only exception was that the retrofitted aftertreatment did not reduce SOA production at idle loads where exhaust temperatures were low enough to limit removal of SOA precursors in the oxidation catalyst. Use of biodiesel resulted in nearly identical POA and SOA compared to diesel. The effective SOA yield of diesel exhaust was similar to that of unburned diesel fuel. While OFRs can help study the multiday evolution, at low particle concentrations OFRs may not allow for complete gas/particle partitioning and bias the potential of precursors to form SOA.

  10. Photochemical defluorination of aqueous perfluorooctanoic acid (PFOA) by Fe(0)/GAC micro-electrolysis and VUV-Fenton photolysis.

    Science.gov (United States)

    Zhang, Li-Hong; Cheng, Jian-Hua; You, Xia; Liang, Xiao-Yan; Hu, Yong-You

    2016-07-01

    Perfluorooctanoic acid (PFOA) is extremely persistent and bioaccumulative in the environment; thus, it is very urgent to investigate an effective and moderate technology to treat the pollution of PFOA. In this study, a process combined iron and granular activated carbon (Fe(0)/GAC) micro-electrolysis with VUV-Fenton system is employed for the remediation of PFOA. Approximately 50 % PFOA (10 mg L(-1)) could be efficiently defluorinated under the following conditions: pH 3.0, dosage of Fe 7.5 g L(-1), dosage of GAC 12.5 g L(-1), and concentration of H2O2 22.8 mmol L(-1). Meanwhile, during the process, evident defluorination was observed and the concentration of fluoride ion was eventually 3.23 mg L(-1). The intermediates including five shorter-chain perfluorinated carboxylic acids (PFCAs), i.e., C7, C6, C5, C4, and C3, were also analyzed by high-performance liquid chromatography tandem mass spectrometry (HPLC/MS/MS) and defluorination mechanisms of PFOA was proposed, which involved photochemical of OH·, direct photolysis (185-nm VUV), and photocatalytic degradation of PFOA in the presence of Fe(3+) (254-nm UV).

  11. Equilibrium, photophysical, photochemical, and quantum chemical examination of anionic mercury(II) mono- and bisporphyrins.

    Science.gov (United States)

    Valicsek, Zsolt; Lendvay, György; Horváth, Ottó

    2008-11-20

    increased efficiency of the indirect photoinduced LMCT, not the redox potential, but the position of the metal center is responsible. The two orders of magnitude higher photoredux quantum yield for the 3:2 complex, compared to that of the 2:2 species, can be explained by the repulsive effect of the inner mercury(II) ion pushing the other two farther out of the ligand cavity. In bisporphyrins the second excited states are photochemically more reactive than the first ones, while most of the photochemical processes of HgP(4-) originate from the first excited state. According to our quantum chemical calculations, the mercury(II) ion causes the expansion of the porphyrin-cavity; therefore its out-of-plane position is smaller than the value expected based on its ionic radius. In the hitherto unknown 2:2 dimer two 1:1 saucer-shaped monomers are kept together by secondary forces, mostly by pi-pi interaction, but their relative arrangement was not unequivocally determined by the two DFT functionals used. The arrangements with a symmetry axis or plane perpendicular to both rings are not favored; instead, the two monomers are shifted along the porphyrin planes, either in a Hg-P-Hg-P or a Hg-P-P-Hg order. Our time-dependent density functional theory (TD-DFT) calculations indicate that the electronic spectra are not very sensitive to the structure of the dimer, even though the environment of the porphyrin rings is quite different if one of the metal ions is between or outside of both macrocycles. The calculated spectral shifts agree only partially with the experimental data. The TD-DFT calculations suggest that the chromophores are not fully independent in the bisporphyrins and that the observed spectral shift cannot be uniquely assigned to the geometrical distortion of the porphyrin macrocyle.

  12. Implications of imprecision in kinetic rate data for photochemical model calculations

    Energy Technology Data Exchange (ETDEWEB)

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

    1997-12-31

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

  13. Photochemical neutralization of HIV-1 and inhibition of HIV-1 induced syncytium formation

    Energy Technology Data Exchange (ETDEWEB)

    Lewis, D.E.; Utecht, R.E. [South Dakota State Univ., Brookings, SD (United States); Chanh, T.C.; Allan, J.S. [Southwest Foundation for Biomedical Research, San Antonio, TX (United States); Sogandares-Bernal, F.; Judy, M.M.; Matthews J.L. [Baylor Research Foundation, Dallas, TX (United States)

    1993-12-31

    The authors have prepared a new class of photochemically activatable antiviral compounds based on the 1,8-naphthalimide skeleton which are excited by visible (420 nm) light, and which are highly effective in causing neutralization of enveloped viruses including HIV-1, HSV-1, and VSV. One such photoactive compound, 1,14-bis-(N-hexyl-3-bromo-1,8-naphthalimid-4-yl)-1,4,11,14-tetrazatetradecane-5,10-dione (diED66Br) effectively neutralized HIV-1 in vitro at concentrations below .1{mu}M; similar results are obtained for HSV-1 and VSV. DiED66Br also effectively inhibits syncytium formation induced by cells infected with HIV-1 at doses which had no effect on normal human blood peripheral mononuclear cells. The synthesis of the photochemically active compounds and the mode of antiviral action will be discussed.

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

    Directory of Open Access Journals (Sweden)

    Gülşah Gümrükçü

    2014-01-01

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

  15. COPD prevalence in nonsmokers in high and low photochemical air pollution areas.

    Science.gov (United States)

    Hodgkin, J E; Abbey, D E; Euler, G L; Magie, A R

    1984-12-01

    The prevalence of respiratory symptoms, as ascertained by questionnaire, was evaluated in 6,666 nonsmokers who had lived for at least 11 years in either a high photochemical pollution area (4,379 individuals) or a low photochemical pollution area (2,287 individuals). Of these, 5,178 had never smoked, and none was currently smoking. The risk estimate for "definite" COPD, as defined in this study, was 15 percent higher in the high pollution area (p = 0.03), after adjusting for sex, age, race, education, occupational exposure, and past smoking history. Past smokers had a risk estimate 22 percent higher than never smokers (p = 0.01). Multivariate analysis showed a significant effect of air pollution on the prevalence of "definite" COPD which univariate analysis failed to demonstrate.

  16. Fused thiophene/quinoxaline low band gap polymers for photovoltaic's with increased photochemical stability

    DEFF Research Database (Denmark)

    Carlé, Jon Eggert; Jørgensen, Mikkel; Manceau, Matthieu

    2011-01-01

    We investigate a family of low band-gap polymers based on the common acceptor moiety 2,3-bis-(3-octyloxyphenyl)quinoxaline (Q) combined with thiophene (T) or the fused thiophene systems: benzo[2,1-b:3,4-b′]-dithiophene (BDT) or dithieno[3,2-b,2′,3′-d]-thiophene (DTT). The photochemical stability...... of the three polymers was examined and compared to P3HT. They were found to be substantially more robust than P3HT with a ranking of DTTQ>BDTQ>TQ1P3HT, indicating that the fused ring systems of DTT and BDT impart a large degree of photochemical stability than thiophene. Furthermore devices with normal...

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

    Science.gov (United States)

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

    2014-01-01

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

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

    Directory of Open Access Journals (Sweden)

    Maria del Pilar Rodríguez-Torres

    2014-10-01

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

  19. Enantioselective Organocatalytic Diels-Alder Trapping of Photochemically Generated Hydroxy-o-Quinodimethanes.

    Science.gov (United States)

    Dell'Amico, Luca; Vega-Peñaloza, Alberto; Cuadros, Sara; Melchiorre, Paolo

    2016-03-01

    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. © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  20. Analysis of protein-nucleic acid interactions by photochemical cross-linking and mass spectrometry

    DEFF Research Database (Denmark)

    Steen, Hanno; Jensen, Ole Nørregaard

    2002-01-01

    and for sequencing of peptide-nucleic acid heteroconjugates. The combination of photochemical cross-linking and MS provides a fast screening method to gain insights into the overall structure and formation of protein-oligonucleotide complexes. Because the analytical methods are continuously refined and protein...... structural data are rapidly accumulating in databases, we envision that many protein-nucleic acid assemblies will be initially characterized by combinations of cross-linking methods, MS, and computational molecular modeling....

  1. Production of hydrogen by electron transfer catalysis using conventional and photochemical means

    Science.gov (United States)

    Rillema, D. P.

    1981-01-01

    Alternate methods of generating hydrogen from the sulfuric acid thermal or electrochemical cycles are presented. A number of processes requiring chemical, electrochemical or photochemical methods are also presented. These include the design of potential photoelectrodes and photocatalytic membranes using Ru impregnated nafion tubing, and the design of experiments to study the catalyzed electrolytic formation of hydrogen and sulfuric acid from sulfur dioxide and water using quinones as catalysts. Experiments are carried out to determine the value of these approaches to energy conversion.

  2. Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies: Evaluation Number 18

    Science.gov (United States)

    Burkholder, J. B.; Sander, S. P.; Abbatt, J. P. D.; Barker, J. R.; Huie, R. E.; Kolb, C. E.; Kurylo, M. J.; Orkin, V. L.; Wilmouth, D. M.; Wine, P. H.

    2015-01-01

    This is the eighteenth in a series of evaluated sets of rate constants, photochemical cross sections, heterogeneous parameters, and thermochemical parameters compiled by the NASA Panel for Data Evaluation. The data are used primarily to model stratospheric and upper tropospheric processes, with particular emphasis on the ozone layer and its possible perturbation by anthropogenic and natural phenomena. The evaluation is available in electronic form from the following Internet URL: http://jpldataeval.jpl.nasa.gov/

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

    Science.gov (United States)

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

    2014-09-01

    The aerosol number concentration and size distribution as well as size-resolved particle chemical composition were measured during haze and photochemical smog episodes in Shanghai in 2009. The number of haze days accounted for 43%, of which 30% was severe (visibilitydistributed in winter and spring. The mean particle number concentration was about 17,000/cm(3) in haze, more than 2 times that in clean days. The greatest increase of particle number concentration was in 0.5-1μm and 1-10μm size fractions during haze events, about 17.78 times and 8.78 times those of clean days. The largest increase of particle number concentration was within 50-100nm and 100-200nm fractions during photochemical smog episodes, about 5.89 times and 4.29 times those of clean days. The particle volume concentration and surface concentration in haze, photochemical smog and clean days were 102, 49, 15μm(3)/cm(3) and 949, 649, 206μm(2)/cm(3), respectively. As haze events got more severe, the number concentration of particles smaller than 50nm decreased, but the particles of 50-200nm and 0.5-1μm increased. The diurnal variation of particle number concentration showed a bimodal pattern in haze days. All soluble ions were increased during haze events, of which NH4(+), SO4(2-) and NO3(-) increased greatly, followed by Na(+), K(+), Ca(2+) and Cl(-). These ions were very different in size-resolved particles during haze and photochemical smog episodes. Copyright © 2014. Published by Elsevier B.V.

  4. Rapid photochemical surface patterning of proteins in thiol-ene based microfluidic devices

    DEFF Research Database (Denmark)

    Lafleur, Josiane P.; Kwapiszewski, Radoslaw; Jensen, Thomas G.

    2012-01-01

    The ability to immobilize biomolecules at specific locations on the surface of solid supports is central to many biochip applications. This paper reports the rapid one-step photochemical surface patterning of biomolecules in thiol-ene microfluidic chips. Adjusting the stoichiometric ratio of "thi...... photolithography. We also present quantitative data on the number of functional groups available for surface modification on thiol-ene substrates and their stability....

  5. Effects of C60 on the Photochemical Formation of Reactive Oxygen Species from Natural Organic Matter.

    Science.gov (United States)

    Yin, Lijuan; Zhou, Huaxi; Lian, Lushi; Yan, Shuwen; Song, Weihua

    2016-11-01

    Buckminsterfullerenes (C60) are widely used nanomaterials that are present in surface water. The combination of C60 and humic acid (HA) generates reactive oxygen species (ROS) under solar irradiation, but this process is not well understood. Thus, the present study focused on the photochemical formation of singlet oxygen (1O2), hydroxyl radical (HO•)-like species, superoxide radicals (O2•-), hydrogen peroxide (H2O2), and triplet excited states (3C60*/3HA*) in solutions containing both C60 and HA. The quantum yield coefficients of excited triplet states (fTMP) and apparent quantum yields of ROS were measured and compared to the calculated values, which were based on the conservative mixing model. Although C60 proved to have only a slight impact on the 1O2 formation from HA, C60 played a key role in the inhibition of O2•-. The photochemical formation of H2O2 followed the conservative mixing model due to the reaction of C60•- with HO2•/O2•-, and the biomolecular reaction rate constant has been measured as (7.4 ± 0.6) × 106 M-1 s-1. The apparent fTMP was significantly lower than the calculated value, indicating that the steric effect of HA was significant in the reaction of 3C60* with the TMP probe. In contrast, C60 did not have an effect on the photochemical formation of HO• from HA, suggesting that HO• is elevated from the hydrophilic surface of HA. The aforementioned results may be useful for predicting the photochemical influence of C60 on aqueous environments.

  6. Enhancing the mechanical properties of collagen by photo-chemical cross-linking

    OpenAIRE

    Shahban, S. A.; Brown, R. A.; Bozec, L.; Cheema, U.

    2009-01-01

    Cell survival within mechanically strong scaffolds is critical in the design of tissue engineered constructs. Collagen type I gels tend to be mechanically weak due to the low percentage of collagen with limited orientation and crosslinking. To enhance the properties of collagen type I gels we used the following approaches: a) plastically compress the collagen gel to increase the density and b) photochemically crosslink the gel using riboflavin as a photoinitiator and high intensity blue light...

  7. Chemical kinetics and photochemical data for use in stratospheric modeling evaluation Number 8

    Science.gov (United States)

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

    1987-01-01

    This is the eighth 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 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, Documentation Section, 111-116B, California Institute of Technology, Pasadena, California, 91109.

  8. Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies Evaluation Number 15

    Science.gov (United States)

    Sander, S. P.; Friedl, R. R.; Golden, D. M.; Kurylo, M. J.; Moortgat, G. K.; Wine, P. H.; Ravishankara, A. R.; Kolb, C. E.; Molina, M. J.; Finlayson-Pitts, B. J.; hide

    2006-01-01

    This is the fifteenth in a series of evaluated sets of rate constants and photochemical cross sections compiled by the NASA Panel for Data Evaluation. The data are used primarily to model stratospheric and upper tropospheric processes, with particular emphasis on the ozone layer and its possible perturbation by anthropogenic and natural phenomena. Copies of this evaluation are available in electronic form and may be printed from the following Internet URL: http://jpldataeval.jpl.nasa.gov/.

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

    Science.gov (United States)

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

    2018-01-01

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

  10. Photochemical injury to the foveomacula of the monkey eye following argon blue-green panretinal photocoagulation.

    OpenAIRE

    Parver, L M

    2000-01-01

    PURPOSE: Visual loss following panretinal photocoagulation was found in the Diabetic Retinopathy and the Early Treatment Diabetic Retinopathy Studies. This study was designed to test the hypothesis that light scattered in the monkey eye during a procedure designed to mimic a clinical panretinal photocoagulation (PRP) can produce a photochemical injury to the foveomacula. METHODS: Ten eyes of 5 adult cynomologous monkeys underwent a PRP using an argon blue-green laser. Three eyes in 2 monkeys ...

  11. Photochemical generation, isomerization, and oxygenation of stilbene cation radicals

    Energy Technology Data Exchange (ETDEWEB)

    Lewis, F.D.; Bedell, A.M.; Dykstra, R.E.; Elbert, J.E. (Northwestern Univ., Evanston, IL (USA)); Gould, I.R.; Farid, S. (Eastman Kodak Co., Rochester, NY (USA))

    1990-10-24

    The cation radicals of cis- and trans-stilbene and several of their ring-substituted derivatives have been generated in solution directly by means of pulsed-laser-induced electron transfer to singlet cyanoanthracenes or indirectly via electron transfer from biphenyl to the singlet cyanoanthracene followed by secondary electron transfer from the stilbenes to the biphenyl cation radical. Transient absorption spectra of the cis- and trans-stilbene cation radicals generated by secondary electron transfer are similar to those previously obtained in 77 K matrices. Quantum yields for radical ion-pair cage escape have been measured for direct electron transfer from the stilbenes to three neutral and one charged singlet acceptor. These values increase as the ion-pair energy increases due to decreased rate constants for radical ion-pair return electron transfer, in accord with the predictions of Marcus theory for highly exergonic electron transfer. Cage-escape efficiencies are larger for trans- vs cis-stilbene cation radicals, possibly due to the greater extent of charge delocalization in the planar trans vs nonpolar cis cation radicals. Cage-escape stilbene cation radicals can initiate a concentration-dependent one way cis- {yields} trans-stilbene isomerization reaction.

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

    Directory of Open Access Journals (Sweden)

    Yi Yang

    2017-10-01

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

  13. Dopant type and/or concentration selective dry photochemical etching of semiconductor materials

    Energy Technology Data Exchange (ETDEWEB)

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

    1985-10-11

    Disclosed is a method of selectively photochemically dry etching a first semiconductor material of a given composition in the presence of a second semiconductor material which is of a composition different from said first material, said second material substantially not being etched during said method. The method comprises subjecting both materials to the same photon flux of an energy greater than their respective direct bandgaps and to the same gaseous chemical etchant under conditions where said etchant would be ineffective for chemical etching of either material were the photons not present, said conditions also being such that the resultant electronic structure of the first semiconductor material under said photon flux is sufficient for the first material to undergo substantial photochemical etching under said conditions and being such that the resultant electronic structure of the second semiconductor material under said photon flux is not sufficient for the second material to undergo substantial photochemical etching under said conditions. In a preferred mode, the materials are subjected to a bias voltage which suppresses etching in n- or p-type material but not in p- or n-type material, respectively; or suppresses etching in the more heavily doped of two n-type or two p-type materials.

  14. Dopant type and/or concentration selective dry photochemical etching of semiconductor materials

    Energy Technology Data Exchange (ETDEWEB)

    Ashby, Carol I. H. (Edgewood, NM); Dishman, James L. (Albuquerque, NM)

    1987-01-01

    A method of selectively photochemically dry etching a first semiconductor material of a given composition in the presence of a second semiconductor material which is of a composition different from said first material, said second material substantially not being etched during said method, comprises subjecting both materials to the same photon flux of an energy greater than their respective direct bandgaps and to the same gaseous chemical etchant under conditions where said etchant would be ineffective for chemical etching of either material were the photons not present, said conditions also being such that the resultant electronic structure of the first semiconductor material under said photon flux is sufficient for the first material to undergo substantial photochemical etching under said conditions and being such that the resultant electronic structure of the second semiconductor material under said photon flux is not sufficient for the second material to undergo substantial photochemical etching under said conditions. In a preferred mode, the materials are subjected to a bias voltage which suppresses etching in n- or p- type material but not in p- or n-type material, respectively; or suppresses etching in the more heavily doped of two n-type or two p-type materials.

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

    Science.gov (United States)

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

    2018-01-15

    Quantum defects are an emerging class of synthetic single-photon emitters that hold vast potential for near-infrared imaging, chemical sensing, materials engineering, and quantum information processing. Herein, we show that it is possible to optically direct the synthetic creation of molecularly tunable fluorescent quantum defects in semiconducting single-walled carbon nanotube hosts through photochemical reactions. By exciting the host semiconductor with light that resonates with its electronic transition, we find that halide-containing aryl groups can covalently bond to the sp2 carbon lattice. The introduced quantum defects generate bright photoluminescence that allows tracking of the reaction progress in situ. We show that the reaction is independent of temperature but correlates strongly with the photon energy used to drive the reaction, suggesting a photochemical mechanism rather than photothermal effects. This type of photochemical reactions opens the possibility to control the synthesis of fluorescent quantum defects using light and may enable lithographic patterning of quantum emitters with electronic and molecular precision. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Partial Photochemical Oxidation Was a Dominant Fate of Deepwater Horizon Surface Oil.

    Science.gov (United States)

    Ward, Collin P; Sharpless, Charles M; Valentine, David L; French-McCay, Deborah P; Aeppli, Christoph; White, Helen K; Rodgers, Ryan P; Gosselin, Kelsey M; Nelson, Robert K; Reddy, Christopher M

    2018-02-20

    Following the Deepwater Horizon (DWH) blowout in 2010, oil floated on the Gulf of Mexico for over 100 days. In the aftermath of the blowout, substantial accumulation of partially oxidized surface oil was reported, but the pathways that formed these oxidized residues are poorly constrained. Here we provide five quantitative lines of evidence demonstrating that oxidation by sunlight largely accounts for the partially oxidized surface oil. First, residence time on the sunlit sea surface, where photochemical reactions occur, was the strongest predictor of partial oxidation. Second, two-thirds of the partial oxidation from 2010 to 2016 occurred in less than 10 days on the sunlit sea surface, prior to coastal deposition. Third, multiple diagnostic biodegradation indices, including octadecane to phytane, suggest that partial oxidation of oil on the sunlit sea surface was largely driven by an abiotic process. Fourth, in the laboratory, the dominant photochemical oxidation pathway of DWH oil was partial oxidation to oxygenated residues rather than complete oxidation to CO 2 . Fifth, estimates of partial photo-oxidation calculated with photochemical rate modeling overlap with observed oxidation. We suggest that photo-oxidation of surface oil has fundamental implications for the response approach, damage assessment, and ecosystem restoration in the aftermath of an oil spill, and that oil fate models for the DWH spill should be modified to accurately reflect the role of sunlight.

  17. Photochemical coating of Kapton® with hydrophilic polymers for the improvement of neural implants.

    Science.gov (United States)

    Hadler, Christoph; Wissel, Kirsten; Brandes, Gudrun; Dempwolf, Wibke; Reuter, Günter; Lenarz, Thomas; Menzel, Henning

    2017-06-01

    The polyimide Kapton® was coated photochemically with hydrophilic polymers to prevent undesirable cell growth on the polyimide surface. The polymer coatings were generated using photochemically reactive polymers synthesized by a simple and modular strategy. Suitable polymers or previously synthesized copolymer precursors were functionalized with photoactive arylazide groups by a polymer analogous amide coupling reaction with 4-azidobenzoic acid. A photoactive chitosan derivative (chitosan-Az) and photochemically reactive copolymers containing DMAA, DEAA or MTA as primary monomers were synthesized using this method. The amount of arylazide groups in the polymers was adjusted to approximately 5%, 10% and 20%. As coating on Kapton® all polymers effect a significantly reduced water contact angle (WCA) and consequently a rise of the surface hydrophilicity compared to the untreated Kapton®. The presence of the polymer coatings was also proven by ATR-IR spectroscopy. Coatings with chitosan-Az and the DEAA copolymer cause a distinct inhibition of the growth of fibroblasts. In the case of the DMAA copolymer even a strong anti-adhesive behavior towards fibroblasts was verified. Biocompatibility of the polymer coatings was proven which enables their utilization in biomedical applications. Copyright © 2017 Elsevier B.V. All rights reserved.

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

    Science.gov (United States)

    Yang, Yi; Pignatello, Joseph J

    2017-10-13

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

  19. Absorptivity of brown carbon in fresh and photo-chemically aged biomass-burning emissions

    Directory of Open Access Journals (Sweden)

    R. Saleh

    2013-08-01

    Full Text Available Experiments were conducted to investigate light absorption of organic aerosol (OA in fresh and photo-chemically aged biomass-burning emissions. The experiments considered residential hardwood fuel (oak and fuels commonly consumed in wild-land and prescribed fires in the United States (pocosin pine and gallberry. Photo-chemical aging was performed in an environmental chamber. We constrained the effective light-absorption properties of the OA using conservative limiting assumptions, and found that both primary organic aerosol (POA in the fresh emissions and secondary organic aerosol (SOA produced by photo-chemical aging contain brown carbon, and absorb light to a significant extent. This work presents the first direct evidence that SOA produced in aged biomass-burning emissions is absorptive. For the investigated fuels, SOA is less absorptive than POA in the long visible, but exhibits stronger wavelength-dependence and is more absorptive in the short visible and near-UV. Light absorption by SOA in biomass-burning emissions might be an important contributor to the global radiative forcing budget.

  20. Structured near-infrared Magnetic Circular Dichroism spectra of the Mn4CaO5 cluster of PSII in T. vulcanus are dominated by Mn(IV) d-d 'spin-flip' transitions.

    Science.gov (United States)

    Morton, Jennifer; Chrysina, Maria; Craig, Vincent S J; Akita, Fusamichi; Nakajima, Yoshiki; Lubitz, Wolfgang; Cox, Nicholas; Shen, Jian-Ren; Krausz, Elmars

    2018-02-01

    Photosystem II passes through four metastable S-states in catalysing light-driven water oxidation. Variable temperature variable field (VTVH) Magnetic Circular Dichroism (MCD) spectra in PSII of Thermosynochococcus (T.) vulcanus for each S-state are reported. These spectra, along with assignments, provide a new window into the electronic and magnetic structure of Mn4CaO5. VTVH MCD spectra taken in the S2 state provide a clear g=2, S=1/2 paramagnetic characteristic, which is entirely consistent with that known by EPR. The three features, seen as positive (+) at 749nm, negative (-) at 773nm and (+) at 808nm are assigned as 4A→2E spin-flips within the d3 configuration of the Mn(IV) centres present. This assignment is supported by comparison(s) to spin-flips seen in a range of Mn(IV) materials. S3 exhibits a more intense (-) MCD peak at 764nm and has a stronger MCD saturation characteristic. This S3 MCD saturation behaviour can be accurately modelled using parameters taken directly from analyses of EPR spectra. We see no evidence for Mn(III) d-d absorption in the near-IR of any S-state. We suggest that Mn(IV)-based absorption may be responsible for the well-known near-IR induced changes induced in S2 EPR spectra of T. vulcanus and not Mn(III)-based, as has been commonly assumed. Through an analysis of the nephelauxetic effect, the excitation energy of S-state dependent spin-flips seen may help identify coordination characteristics and changes at each Mn(IV). A prospectus as to what more detailed S-state dependent MCD studies promise to achieve is outlined. Copyright © 2017 Elsevier B.V. All rights reserved.

  1. Photochemical-biological treatment of a real industrial biorecalcitrant wastewater containing 5-amino-6-methyl-2-benzimidazolone.

    Science.gov (United States)

    Sarria, V; Parra, S; Invernizzi, M; Peringer, P; Pulgarin, C

    2001-01-01

    5-amino-6-methyl-2-benzimidazolone (AMBI), used in the manufacture of dyes, was characterised as a biorecalcitrant compound by means of different biodegradability tests. In order to enhance the biodegradability of this important pollutant, the application of Advanced Oxidation Process (AOPs) as a pretreatment was explored. Some experiments were addressed to find the most efficient AOP. The systems H2O2/hv, TiO2/H2O2/hv, Fe3+/hv, Fe3+/H2O2 and Fe3+/H2O2/hv were compared. The photo-Fenton system was the most efficient and the optimal conditions (AMBI, Fe3+, H2O2 concentrations) for the degradation of AMBI were found. During the photo-Fenton degradation, experiments were also made to obtain information concerning the evolution of: (a) organic carbon and initial compound concentration; (b) the oxidation state; (c) the toxicity; (d) the biodegradability; and (e) the chemical nature of the intermediates. These analyses show that the solution resulting from the treatment of AMBI is biologically compatible and complete mineralisation can be performed by biological means. A combined photochemical (Fenton) and biological flow reactor for the degradation of AMBI was successfully operated in continuous mode at laboratory scale. 100% of the initial concentration of AMBI and 80.3% of Dissolved Organic Carbon (DOC) were removed in 3.5 hours of total residence time. Finally, some field experiments under direct sunlight carried out at the Plataforma Solar de Almeria, Spain, demonstrated that this solar catalytic system is an effective treatment for this kind of industrial wastewater.

  2. Design of an EGFR-targeting toxin for photochemical delivery: in vitro and in vivo selectivity and efficacy.

    Science.gov (United States)

    Berstad, M B; Cheung, L H; Berg, K; Peng, Q; Fremstedal, A S V; Patzke, S; Rosenblum, M G; Weyergang, A

    2015-10-29

    The number of epidermal growth factor receptor (EGFR)-targeting drugs in the development for cancer treatment is continuously increasing. Currently used EGFR-targeted monoclonal antibodies and tyrosine kinase inhibitors have specific limitations related to toxicity and development of resistance, and there is a need for alternative treatment strategies to maximize the clinical potential of EGFR as a molecular target. This study describes the design and production of a novel EGFR-targeted fusion protein, rGel/EGF, composed of the recombinant plant toxin gelonin and EGF. rGel/EGF was custom-made for administration by photochemical internalization (PCI), a clinically tested modality for cytosolic release of macromolecular therapeutics. rGel/EGF lacks efficient mechanisms for endosomal escape and is therefore minimally toxic as monotherapy. However, PCI induces selective and efficient cytosolic release of rGel/EGF in EGFR-expressing target cells by light-directed activation of photosensitizers accumulated selectively in tumor tissue. PCI of rGel/EGF was shown to be highly effective against EGFR-expressing cell lines, including head and neck squamous cell carcinoma (HNSCC) cell lines resistant to cetuximab (Erbitux). Apoptosis, necrosis and autophagy were identified as mechanisms of action following PCI of rGel/EGF in vitro. PCI of rGel/EGF was further shown as a highly tumor-specific and potent modality in vivo, with growth inhibitory effects demonstrated on A-431 squamous cell carcinoma (SCC) xenografts and reduction of tumor perfusion and necrosis induction in SCC-026 HNSCC tumors. Considering the small amount of rGel/EGF injected per animal (0.1 mg/kg), the presented in vivo results are highly promising and warrant optimization and production of rGel/EGF for further preclinical evaluation with PCI.

  3. [Effects of water depth on the growth of Vallisneria natans and photosynthetic system II photochemical characteristics of the leaves].

    Science.gov (United States)

    Yang, Xin; Zhang, Qi-Chao; Sun, Shu-Yun; Chen, Kai-Ning

    2014-06-01

    The effects of water depth on the growth of Vallisneria natans and photosynthetic system II photochemical characteristics of the leaves were investigated at three depths of 0.6, 1.3 and 2.0 m. The rapid fluorescence induction kinetics curves (OJIP) of the leaves were measured with Plant Efficiency Analyzer and analyzed with JIP-test. The results indicated that the light intensities at water depths of 0.6, 1.3 and 2.0 m were obviously different and the growth of V. natans was restricted under water depth of 2.0 m. Biomass, number of ramets, number of leaves, total root length, root surface area and other morphological indices decreased significantly with the increasing water depth, and the maximum leaf length, average leaf length, maximum leaf width changed insignificantly with the water depth. With the increasing water depth, absorption flux per reaction center (ABS/RC), trapped energy flux per RC (TR0/RC), electron transport flux per RC (ET0/RC), reduction of end acceptors at photosynthetic system I (PS I ) electron acceptor side per RC (RE0/ RC) decreased significantly. The dissipated energy flux per RC (DI0/RC) also decreased significantly, which led to no obvious difference in quantum yield for the reduction of end acceptors of PS I per photon absorbed (phiR0) and the efficiency for the trapped exciton to move an electron into the electron transport chain from QA- to the PS I end electron acceptors (deltaR0). Because the amount of active PS II RCs per CS increased significantly, photosynthesis per area of V. natans grown at 2.0 m was significantly greater than that of V. natans grown at 0.6 m. The performance index PIs, Ples, Plabs,.otal photochemistry efficiency of leaves of V. natans grown at 2.0 m was significantly in- creased, suggesting that light stress may promote a more efficient conversion of light energy to active chemical energy. V. natans leaves accommodate the low light intensity environment through activating inactive reaction centers but not

  4. Investigating the pathway for the photochemical formation of VOCs in presence of an organic monolayer at the air/water interface.

    Science.gov (United States)

    Tinel, Liselotte; Rossignol, Stéphanie; Ciuraru, Raluca; George, Christian

    2015-04-01

    Investigating the pathway for the photochemical formation of VOCs in presence of an organic monolayer at the air/water interface. Liselotte Tinel, Stéphanie Rossignol, Raluca Ciuraru and Christian George Université de Lyon, Université Lyon 1, CNRS, UMR5256, IRCELYON, Institut de recherches sur la catalyse et l'environnement de Lyon, Villeurbanne, F-69626, France Recently the surface microlayer (SML) has received growing attention for its role in the deposition and emission of trace gases. This SML is presumably a highly efficient environment for photochemical reactions thanks to its physical and chemical properties, showing enrichment in chromophores [1]. Still, little is known about the possible photochemical processes that could influence the emission and deposition of volatile organic compounds (VOCs) in the SML. A recent study underlines the particularity of the presence of an organic microlayer, showing enhanced formation of peptide bonds at the air-water interface, although this reaction is thermodynamically disfavoured in bulk water [2]. Also, emissions of small gas phase carbonyl compounds formed photochemically by dissolved organic matter have been measured above natural water and glyoxal, for example, measured above the open ocean is thought to be photochemically produced [3, 4]. This study presents the results of a set of laboratory studies set up in order to better understand the role of the SML in the photochemical production of VOCs. Recently, our group has shown the formation of VOCs by light driven reactions in a small quartz reactor (14mL) containing aqueous solutions of humic acids (HA) in the presence of an organic (artificial or natural) microlayer [5]. The main VOCs produced were oxidized species, such as aldehydes, ketones and alcohols, as classically can be expected by the oxidation of the organics present at the interface initiated by triplet excited chromophores present in the HA. But also alkenes, dienes, including isoprene and

  5. Supramolecular tetrad featuring covalently linked bis(porphyrin)-phthalocyanine coordinated to fullerene: construction and photochemical studies.

    Science.gov (United States)

    K C, Chandra B; Lim, Gary N; Karr, Paul A; D'Souza, Francis

    2014-06-16

    A multimodular donor-acceptor tetrad featuring a bis(zinc porphyrin)-(zinc phthalocyanine) ((ZnP-ZnP)-ZnPc) triad and bis-pyridine-functionalized fullerene was assembled by a "two-point" binding strategy, and investigated as a charge-separating photosynthetic antenna-reaction center mimic. The spectral and computational studies suggested that the mode of binding of the bis-pyridine-functionalized fullerene involves either one of the zinc porphyrin and zinc phthalocyanine (Pc) entities of the triad or both zinc porphyrin entities leaving ZnPc unbound. The binding constant evaluated by constructing a Benesi-Hildebrand plot by using the optical data was found to be 1.17×10(5) M(-1), whereas a plot of "mole-ratio" method revealed a 1:1 stoichiometry for the supramolecular tetrad. The mode of binding was further supported by differential pulse voltammetry studies, in which redox modulation of both zinc porphyrin and zinc phthalocyanine entities was observed. The geometry of the tetrad was deduced by B3LYP/6-31G* optimization, whereas the energy levels for different photochemical events was established by using data from the optical absorption and emission, and electrochemical studies. Excitation of the zinc porphyrin entity of the triad and tetrad revealed ultrafast singlet-singlet energy transfer to the appended zinc phthalocyanine. The estimated rate of energy transfer (k(ENT)) in the case of the triad was found to be 7.5×10(11) s(-1) in toluene and 6.3×10(11) s(-1) in o-dichlorobenzene, respectively. As was predicted from the energy levels, photoinduced electron transfer from the energy-transfer product, that is, singlet-excited zinc phthalocyanine to fullerene was verified from the femtosecond-transient spectral studies, both in o-dichlorobenzene and toluene. Transient bands corresponding to ZnPc(⋅+) in the 850 nm range and C60(⋅-) in the 1020 nm range were clearly observed. The rate of charge separation, k(CS), and rate of charge recombination, k

  6. Judicious Design of Cationic, Cyclometalated Ir(III) Complexes for Photochemical Energy Conversion and Optoelectronics.

    Science.gov (United States)

    Mills, Isaac N; Porras, Jonathan A; Bernhard, Stefan

    2018-02-20

    The exponential growth in published studies on phosphorescent metal complexes has been triggered by their utilization in optoelectronics, solar energy conversion, and biological labeling applications. Very recent breakthroughs in organic photoredox transformations have further increased the research efforts dedicated to discerning the inner workings and structure-property relationships of these chromophores. Initially, the principal focus was on the Ru(II)-tris-diimine complex family. However, the limited photostability and lack of luminescence tunability discovered in these complexes prompted a broadening of the research to include 5d transition metal ions. The resulting increase in ligand field splitting prevents the population of antibonding e g * orbitals and widens the energy range available for color tuning. Particular attention was given to Ir(III), and its cyclometalated, cationic complexes have now replaced Ru(II) in the vast majority of applications. At the start, this Account documents the initial efforts dedicated to the color tuning of these complexes for their application in light emitting electrochemical cells, an easy to fabricate single-layer organic light emitting device (OLED). Systematic modifications of the ligand sphere of [Ir(ppy) 2 bpy] + (ppy: 2-phenylpyridine, bpy: 2,2'-bipyridine) with electron withdrawing and donating substituents allowed access to complexes with luminescence emission maxima throughout the visible spectrum exhibiting room temperature excited state lifetimes ranging from nanoseconds to dozens of microseconds and quantum yields up to 15 times that of [Ru(bpy) 3 ] 2+ . The diverse photophysical properties were also beneficial when using these Ir(III) complexes for driving solar fuel-producing reactions. For instance, photocatalytic water-reduction systems were explored to gain access to efficient water splitting systems. For this purpose, a variety of water reduction catalysts were paired with libraries of Ir

  7. Photosystem II recovery in the presence and absence of chloroplast protein repair in the symbionts of corals exposed to bleaching conditions

    Science.gov (United States)

    Hill, R.; Takahashi, S.

    2014-12-01

    Increased seawater temperature causes photoinhibition due to accumulation of photodamaged photosystem II (PSII) in symbiotic algae (genus Symbiodinium) within corals, and it is assumed to be associated with coral bleaching. To avoid photoinhibition, photosynthetic organisms repair the photodamaged PSII through replacing the PSII proteins, primarily the D1 protein, with newly synthesised proteins. However, in experiments using cultured Symbiodinium strains, the PSII repair of Symbiodinium has been suggested not to be related to the synthesis of the D1 protein. In this study, we examined the relationship between the recovery of PSII photochemical efficiency ( F V/ F M) and the content of D1 protein after high-light and high-temperature treatments using the bleaching-sensitive coral species, Pocillopora damicornis and Acropora millepora, and the bleaching-tolerant coral species, Montipora digitata and Pavona decussata. When corals were exposed to strong light (600 µmol photons m-2 s-1) at elevated temperature (32 °C) for 8 h, significant bleaching occurred in bleaching-sensitive coral species although an almost similar extent of reduced PSII function was found across all coral species tested. During a subsequent 15-h recovery under low light (10 µmol photons m-2 s-1) at optimal temperature (22 °C), the reduced F V/ F M recovered close to initial levels in all coral species, but the reduced D1 content recovered only in one coral species ( Pavona decussata). D1 content was therefore not strongly linked to chloroplast protein synthesis-dependent PSII repair. These results demonstrate that the recovery of photodamaged PSII does not always correspond with the recovery of D1 protein content in Symbiodinium within corals, suggesting that photodamaged PSII can be repaired by a unique mechanism in Symbiodinium within corals.

  8. ENERGETICS TRANSFER IN THE PHOTODYNAMIC REACTIONS. I. PHOTODYNAMIC SENSITIVITY OF THE RETINA. II. PHOTODYNAMIC ACTION AND CANCER. III. PHOTOCHEMICAL SYNTHESIS OF AMINO ACIDS IN ABIOGENIC CONDITIONS.

    Science.gov (United States)

    PHOTOSENSITIVITY(BIOLOGICAL), *CANCER, * AMINO ACIDS , RETINA, PHOTOCHEMICAL REACTIONS, RETINA, PATHOLOGY, RESPIRATION, GLYCOLYSIS, FISHES, ELECTROPHYSIOLOGY, FORMALDEHYDE, CATALYSTS, LIGHT, STIMULATION(PHYSIOLOGY), CHEMORECEPTORS, OXYGEN, ULTRAVIOLET RADIATION, MICE, ITALY.

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

    National Research Council Canada - National Science Library

    Lavaud, Johann; Materna, Arne C; Sturm, Sabine; Vugrinec, Sascha; Kroth, Peter G

    2012-01-01

    .... The xanthophyll cycle (XC) dependent non-photochemical chlorophyll fluorescence quenching (NPQ) is one of the most important photoprotective processes that rapidly regulate photosynthesis in diatoms...

  10. FIGAERO ToF CIMS measurements of chlorine photochemical activation by nitryl chloride chemistry at a semi-rural site in Beijing

    Science.gov (United States)

    Le Breton, Michael; Hallquist, Åsa M.; Kant Pathak, Ravi; Simpson, David; Wang, Yujue; Zheng, Jing; Yang, Yudong; Shang, Dongjie; Wang, Haichao; Lu, Keding; Guo, Song; Hu, Min; Hallquist, Mattias

    2017-04-01

    Severe pollution events across China pose a major threat to air quality and climate through the direct emission of pollutants, but also via the production of photochemically induced secondary pollutants. Nitryl chloride (ClNO2), produced from heterogeneous reactions of dinitrogen pentoxide (N2O5) and aerosols containing chloride, is photolysed rapidly in sunlight and activates chlorine. Subsequent daytime oxidation via the chlorine atom can proceed orders of magnitude faster than that of the hydroxyl radical and therefore significantly perturb radical budgets and concentrations of ozone and secondary pollutants. Knowledge of the formation pathways, abundance and fate of these secondary pollutants, which can depend on ClNO2 abundance, is not fully understood but is necessary to support abatement strategies which will efficiently account for both primary and secondary pollutants. A Time of Flight Chemical Ionisation Mass Spectrometer (ToF CIMS) utilising the Filter Inlet for Gases and AEROsols (FIGAERO) was deployed in Changping, Beijing, during June and July, 2016 as part of an intercollaborative project to assess the photochemical smog in China. Concentrations of ClNO2 regularly exceeded 500 ppt throughout the campaign and reached a maximum concentration of 2.8 ppb, whereas relatively low N2O5 concentrations were observed, indicating a rapid heterogeneous production of ClNO2. Correlation of particulate chloride and carbon monoxide during the campaign suggests an anthropogenic chlorine source, also supported by high daytime Cl2 concentrations. Observations of ClNO2 desorptions using the FIGAERO suggest a possible unaccounted particulate reservoir of active chlorine in highly polluted regions. The persistence of ClNO2 several hours passed sunrise significantly increases the atomic chlorine production rate throughout the day further perturbing standard daytime oxidation processes. Simultaneous ToF CIMS measurements of Cl2, ClNO2, HCl, HOCl, OClO and ClONO2 were

  11. Modeling perchloroethylene degradation under ultrasonic irradiation and photochemical oxidation in aqueous solution.

    Science.gov (United States)

    Kargar, Mahdi; Nabizadeh, Ramin; Naddafi, Kazem; Nasseri, Simin; Mesdaghinia, Alireza; Mahvi, Amir Hossein; Alimohammadi, Mahmood; Nazmara, Shahrokh; Pahlevanzadeh, Bagher

    2012-12-23

    Sonolysis and photochemical degradation of different compounds such as chlorinated aliphatic hydrocarbons are among the recent advanced oxidation processes. Perchloroethylene is one of these compounds that has been mainly used as a solvent and degreaser. In this work, elimination of perchloroethylene in aqueous solution by ultrasonic irradiation, andphotochemical oxidation by ultra violet ray and hydrogen peroxide were investigated. Three different initial concentrations of perchloroethylene at different pH values, detention periods, and concentrations of hydrogen peroxide were investigated. Head space gas chromatography with FID detector was used for analyses of perchloroethylene. This research was performed in 9 months from April through December 2011.Results showed that perchloroethylene could be effectively and rapidly degraded by ultrasonic irradiation, photochemical oxidation by ultra violet ray, hydrogen peroxide and a combination of these methods. Kinetics of perchloroethylene was strongly influenced by time, initial concentration and pH value. Degradation of Perchloroethylene increased with decrease in the initial concentration of perchloroethylene from 0.3 to 10 mg/L at all initial pH. The results showed an optimum degradation condition achieved at pH = 5 but did not affect significantly the perchloroethylene destruction in the various pH values. Kinetic modeling applied for the obtained results showed that the degradation of perchloroethylene by ultrasound and photo-oxidation followed first order and second order model. The percentage of removal in the hybrids reactor was higher than each of the reactors alone, the reason being the role of hydroxyl radical induced by ultrasound and photochemical reaction.

  12. Modeling Perchloroethylene Degradation Under Ultrasonic Irradiation and Photochemical Oxidation in Aqueous Solution

    Directory of Open Access Journals (Sweden)

    Mahmood Alimohammadi

    2012-12-01

    Full Text Available Sonolysis and photochemical degradation of different compounds such as chlorinated aliphatic hydrocarbons are among the recent advanced oxidation processes.Perchloroethylene is one of these compounds that has been mainly used as a solvent and degreaser. In this work, elimination of perchloroethylene in aqueous solution by ultrasonic irradiation, andphotochemical oxidation by ultra violet ray and hydrogen peroxide were investigated. Three different initial concentrations of perchloroethylene at different pH values, detention periods , and concentrations of hydrogen peroxide were investigated. Headspace gas chromatography with FID detector was used for analyses of perchloroethylene.This research was performed in 9 months from April through December 2011.Results showed that perchloroethylene could be effectively and rapidly degraded by ultrasonic irradiation, photochemical oxidation by ultra violet ray, hydrogen peroxide and acombination of these methods. Kinetics of perchloroethylene was strongly influenced by time, initial concentration and pH value. Degradation of Perchloroethylene increased withdecrease in the initial concentration of perchloroethylene from 0.3 to 10 mg/L at all initial pH. The results showed an optimum degradation condition achieved at pH = 5 but did notaffect significantly the perchloroethylene destruction in the various pH values. Kinetic modeling applied for the obtained results showed that the degradation of perchloroethyleneby ultrasound and photo-oxidation followed first order and second order model. The percentage of removal in the hybrids reactor was higher than each of the reactors alone, the reason being the role of hydroxyl radical induced by ultrasound and photochemical reaction.

  13. Impact of Anthropogenic Emissions on Isoprene Photochemical Oxidation Pathways in Central Amazonia

    Science.gov (United States)

    Thayer, M. P.; Dorris, M. R.; Keutsch, F. N.; Goldstein, A. H.; Guenther, A. B.; Isaacman-VanWertz, G. A.; Jimenez, J. L.; Kim, S.; Liu, Y.; Martin, S. T.; Palm, B. B.; Park, J. H.; Seco, R.; Sjostedt, S. J.; Springston, S. R.; Wernis, R. A.; Yee, L.

    2016-12-01

    The atmosphere over the Amazon rainforest is characterized by high concentrations of biogenic volatile organic compounds (BVOCs) - most notably isoprene, which is the most abundant non-methane VOC both locally and globally. These BVOCs are photochemically oxidized, forming oVOCs, especially via reaction with the hydroxyl radical (OH). This photochemical processing can result in formation of secondary pollutants such as ozone (O3) and secondary organic aerosol (SOA). During the Green Ocean Amazon campaign (GoAmazon2014/5), we obtained formaldehyde and glyoxal measurements together with OH, peroxy radicals (RO2+HO2), nitrogen oxides (NOx), CO, CO2, O3, (o)VOCs, and aerosol particle size distribution. Here we present data collected during 2014 at the T3 field site, 60 km to the west of Manaus, Brazil (3°12'47.82"S, 60°35'55.32"W). The T3 GoAmazon site varies between sampling strictly pristine (biogenic) emissions and influence from anthropogenic emissions from Manaus, depending on meteorological conditions. The day-to-day oscillation provides an ideal setting for evaluating the impact of pollution from biomass burning and urban emissions on VOC oxidation and resultant secondary pollutant production. Anthropogenic plumes contain not only additional VOC precursors, but also enhanced NOx, which drastically alters the relative importance of various isoprene oxidation pathways. We utilize a 0-D photochemical box model to examine how these factors impact reactivity and pollutant formation. Due to ongoing expansion of human influence and emissions in previously-pristine areas, understanding the sensitivity of biogenic oxidation to anthropogenic influence has significant impacts for tropospheric air quality, both in the rapidly-developing Amazon Basin and other BVOC-dominated regions.

  14. One-step surface selective modification of UV-curable hard coatings with photochemical metal organics

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Yoon Kwang; Park, Chang-Sun; Park, Hyung-Ho, E-mail: hhpark@yonsei.ac.kr

    2016-12-15

    Graphical abstract: This study demonstrates suitable for exceptional hybrid film under UV exposure. A small quantity of the dispersive photochemical precursor Sr 2-ethylhexanoate was mixed and the composition altered from the surface to the bottom, forming an organic layer and a densely concentrated SrO surface layer. The surface-selective SrO strongly enhanced the surface flatness and hardness of the UV-curable organic coating film. - Highlights: • Hybrid bi-layer coating was synthesized through one-pot UV exposure chemical route. • The influence of additive and different reactivity formed densely concentrated SrO surface layer. • Chemical composition and continuous interface between organic and inorganic were analyzed. • Surface flatness and mechanical property were improved by inorganic material. - Abstract: An organic–inorganic hybrid bi-layer film with a selective distribution of inorganic components was synthesized from a one-pot process of UV irradiation. A photochemical metal oxide precursor (Sr 2-ethylhexanoate) varying from 0 to 4 wt% was dispersed in UV-curable coating materials. Under UV exposure, the bi-layer started reacting simultaneously but at different rates due to differences in the two UV-condensable components’ reactivity. The effects of the dispersed inorganic component on the surface morphology and mechanical properties were investigated by atomic force microscopy and nanoindentation, respectively. The reaction process and rates were studied from linkage change using Fourier transform infrared spectroscopy at various UV exposure times (0–30 min). The elemental distribution and the interface on the coating layer were characterized by X-ray photoelectron spectroscopy from Ar etching, revealing continuous and gradual composition changes in depth. The results showed that a flattened and surface-selectively hardened SrO containing the coating film could be obtained by this simple process. Consequently, a small ratio of photochemical

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

    Science.gov (United States)

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

    2016-03-01

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

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

    DEFF Research Database (Denmark)

    Konhauser, Kurt O.; Amskold, Larry; Lalonde, Stefan V.

    2007-01-01

    to the rise of atmospheric oxygen and the development of a protective ozone layer, the Earth's surface was subjected to high levels of ultraviolet radiation. Bulk ocean waters that were anoxic at this time could have supported high concentrations of dissolved Fe(II). Under such conditions, dissolved ferrous...... for biology [Fran??ois, L.M., 1986, Extensive deposition of banded iron formations was possible without photosynthesis. Nature 320, 352-354]. Here, we evaluate the potential importance of photochemical oxidation using a combination of experiments and thermodynamic models. The experiments simulate...

  17. Rapid photochemical surface patterning of proteins in thiol-ene based microfluidic devices

    DEFF Research Database (Denmark)

    Lafleur, Josiane P.; Kwapiszewski, Radoslaw; Jensen, Thomas Glasdam

    2013-01-01

    The suitable optical properties of thiol–ene polymers combined with the ease of modifying their surface for the attachment of recognition molecules make them ideal candidates in many biochip applications. This paper reports the rapid one-step photochemical surface patterning of biomolecules...... ! 17 SH nm"2. Biotin alkyne was patterned directly inside thiol–ene microchannels prior to conjugation with fluorescently labelled streptavidin. The surface bound conjugates were detected by evanescent waveinduced fluorescence (EWIF), demonstrating the success of the grafting procedure and its...... potential for biochip applications....

  18. Halogen-Bond-Promoted Photoactivation of Perfluoroalkyl Iodides: A Photochemical Protocol for Perfluoroalkylation Reactions.

    Science.gov (United States)

    Wang, Yaxin; Wang, Junhua; Li, Guo-Xing; He, Gang; Chen, Gong

    2017-03-17

    A new protocol for photochemical perfluoroalkylation reactions using perfluoroalkyl iodide, amine additive, and THF solvent is reported. This protocol does not require a photoredox catalyst and proceeds at ambient temperature with irradiation from a compact fluorescent lamp, low-intensity UV lamp, or sunlight. This protocol can be applied to the synthesis of perfluoroalkyl-substituted phenanthridines as well as effect the iodo-perfluoroalkylation of alkenes/alkynes and the C-H perfluoroalkylation of electron-rich arenes and heteroarenes. This C-H perfluoroalkylation reaction offers a unique method for site-selective labeling of oligopeptides at the tryptophan residue.

  19. Evaluating simple oxidant prediction methods using complex photochemical models: cluster analysis applied to urban ozone characteristics

    Energy Technology Data Exchange (ETDEWEB)

    Hillyer, M.S.

    1981-08-01

    This report describes efforts to classify cities observing ozone levels greater than 0.12 ppm into distinct subgroups. Cluster analysis, using such factors as mixing height, wind speed, temperature, NMOC/NOx ratio and type of precursor sources, is used to identify subgroups of cities. Identification of a limited number of such subgroups could provide a means for more convincingly demonstrating the general applicability of complex photochemical models by conducting validation exercises in cities representative of each subgroup. The report indicates that the technique shows promise but, nevertheless, requires some further refinement before it can be used to identify most appropriate subgroups.

  20. Photochemical oxidants potentiate yield losses in snap beans attributable to sulfur dioxide.

    Science.gov (United States)

    Heggestad, H E; Bennett, J H

    1981-08-28

    Field-grown snap beans (Phaseolus vulgaris) were given recurring midday exposures to sulfur dioxide in open-top field chambers containing ambient photochemical oxidants. There was a linear correlation (correlation coefficient = -.99) between increasing concentrations of sulfur dioxide and the yields of snap beans. Synergism was indicated for the mixtures of ambient ozone plus sulfur dioxide, leading to threefold greater yield losses in nonfiltered air than in charcoal-filtered air (to remove the ozone). Even the lowest sulfur dioxide dose in nonfiltered air reduced the yields of Astro, a cultivar that exhibited no visible pollutant-induced foliar injury.

  1. Photochemical Oxidative Cyclisation of Stilbenes and Stilbenoids—The Mallory-Reaction

    Directory of Open Access Journals (Sweden)

    Kåre B. Jørgensen

    2010-06-01

    Full Text Available After Mallory described in 1964 the use of iodine as catalyst for the photochemical cyclisation of stilbenes, this reaction has proven its effectiveness in the synthesis of phenanthrenes, other PAHs and phenacenes with a surprisingly large selection of substituents. The “early age” of the reaction was reviewed by Mallory in 1984in a huge chapter in the Organic Reactions series, but the development has continued. Alternative conditions accommodate more sensitive substituents, and isomers can be favoured by sacrificial substituents. Herein the further developments and applications of this reaction after 1984 are discussed and summarized.

  2. Photochemical reactions of poly(3-butoxythiophene-2,5-diyl) with chloroform

    OpenAIRE

    Imit, Mokhtar; Yamamoto, Takakazu; Imin, Patigul

    2005-01-01

    Photochemical reactions of poly(3-butoxythiophene-2,5-diyl) with chloroform under irradiation with light were studied. The reactions were separately carried out under air, oxygen, and nitrogen. The obtained results showed that this reaction belongs to the pseudo-first-order reaction with a rate constant k obs of 1.4×10−5 s−1 at room temperature. The presence or absence of air, oxygen, and nitrogen did not have obvious effects on the reaction rate under irradiation with light.

  3. Tuning the photochemical properties of the fulvalene-tetracarbonyl-diruthenium system.

    Science.gov (United States)

    Lennartson, Anders; Lundin, Angelica; Börjesson, Karl; Gray, Victor; Moth-Poulsen, Kasper

    2016-06-07

    In a Molecular Solar-Thermal Energy Storage (MOST) system, solar energy is converted to chemical energy using a compound that undergoes reversible endothermic photoisomerization. The high-energy photoisomer can later be converted back to the parent compound and the excess energy is released as heat. One of the most studied MOST systems is based on fulvalene-tetracarbonyl-diruthenium, and this paper demonstrates, for the first time, the possibility to tune the photochemical properties of this system by positive steric hindrance working on the fulvalene unit.

  4. Electro-optical properties of photochemically stable polymer-stabilized blue-phase material

    Energy Technology Data Exchange (ETDEWEB)

    Chojnowska, O., E-mail: ochojnowska@wat.edu.pl; Dąbrowski, R. [Institute of Chemistry, Military University of Technology, Warsaw 00-908 (Poland); Yan, J.; Chen, Y.; Wu, S. T. [College of Optics and Photonics, University of Central Florida, Orlando, Florida 32816 (United States)

    2014-12-07

    Polymer-stabilized blue-phase liquid crystal (BPLC) comprising fluorinated compounds with high resistivity and photochemical stability is demonstrated. The Kerr constant, driving voltage, and response time of this BPLC are measured using an in-plane switching liquid crystal cell. At 20 °C, the measured total response time is faster than 0.7 ms and Kerr constant is 2 nm/V{sup 2}. This fluorinated BPLC material is a promising candidate for next-generation photonic and display devices, because it can be used in active matrix addressed devices.

  5. Construction of a photochemical reactor combining a CCD spectrophotometer and a LED radiation source.

    Science.gov (United States)

    Gombár, Melinda; Józsa, Éva; Braun, Mihály; Ősz, Katalin

    2012-10-01

    An inexpensive photoreactor using LED light sources and a fibre-optic CCD spectrophotometer as a detector was built by designing a special cell holder for standard 1.000 cm cuvettes. The use of this device was demonstrated by studying the aqueous photochemical reaction of 2,5-dichloro-1,4-benzoquinone. The developed method combines the highly quantitative data collection of CCD spectrophotometers with the possibility of illuminating the sample independently of the detecting light beam, which is a substantial improvement of the method using diode array spectrophotometers as photoreactors.

  6. Electro-optical properties of photochemically stable polymer-stabilized blue-phase material

    Science.gov (United States)

    Chojnowska, O.; Dąbrowski, R.; Yan, J.; Chen, Y.; Wu, S. T.

    2014-12-01

    Polymer-stabilized blue-phase liquid crystal (BPLC) comprising fluorinated compounds with high resistivity and photochemical stability is demonstrated. The Kerr constant, driving voltage, and response time of this BPLC are measured using an in-plane switching liquid crystal cell. At 20 °C, the measured total response time is faster than 0.7 ms and Kerr constant is 2 nm/V2. This fluorinated BPLC material is a promising candidate for next-generation photonic and display devices, because it can be used in active matrix addressed devices.

  7. Photo-mediated bromate--1,4-benzoquinone reaction: A novel photochemical oscillator

    Science.gov (United States)

    Zhao, Bei; Wang, Jichang

    2006-10-01

    1,4-Benzoquinone is uncovered to react with acidic bromate in the presence of illumination, in which temporal oscillations are observed in the stirred batch system. This new photochemical oscillator shows subtle dependence on compositions of the reaction mixture, in which oscillations could be revived immediately upon the addition of fresh 1,4-benzoquinone solution. A proposed mechanism on the basis of light-induced conversion of 1,4-benzoquinone to 1,4-hydroquinone qualitatively reproduces the oscillatory phenomena as well as the long induction time seen in experiments.

  8. Synthesis of fluorescent metal nanoparticles in aqueous solution by photochemical reduction

    KAUST Repository

    Kshirsagar, Prakash

    2014-01-06

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

  9. Photochemical stability of π-conjugated polymers for polymer solar cells: a rule of thumb

    DEFF Research Database (Denmark)

    Manceau, Matthieu; Bundgaard, Eva; Carlé, Jon Eggert

    2011-01-01

    A comparative photochemical stability study of a wide range of π-conjugated polymers relevant to polymer solar cells is presented. The behavior of each material has been investigated under simulated sunlight (1 sun, 1000 W m−2, AM 1.5G) and ambient atmosphere. Degradation was monitored during...... ageing combining UV-visible and infrared spectroscopies. From the comparison of the collected data, the influence of the polymer chemical structure on its stability has been discussed. General rules relative to the polymer structure–stability relationship are proposed....

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

    Directory of Open Access Journals (Sweden)

    Ulrich C. Fischer

    2014-09-01

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

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

    Science.gov (United States)

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

    2015-10-27

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

  12. Chrysanthemum morphology, photosynthetic efficiency and antioxidant capacity are differentially modified by light quality.

    Science.gov (United States)

    Zheng, Liang; Van Labeke, Marie-Christine

    2017-06-01

    The effect of light quality on leaf morphology, photosynthetic efficiency and antioxidant capacity of leaves that fully developed under a specific spectrum was investigated in Chrysanthemum cv. Four light treatments were applied at 100μmolm-2s-1 and a photoperiod of 14h using light-emitting diodes, which were 100% red (R), 100% blue (B), 75% red with 25% blue (RB) and white (W), respectively. Intraspecific variation was investigated by studying the response of eight cultivars. Overall, red light significantly decreased the leaf area while the thinnest leaves were observed for W. Chlorophyll content and Chl a/b ratio was highest for W and lowest under R. B and RB resulted in the highest maximum quantum yield (Fv/Fm) and quantum efficiencyPSII). A negative correlation between heat dissipation (NPQ) and ΦPSII was found. Blue light induced the highest hydrogen peroxide content, which is a proxy for total ROS generation, followed by W and RB while low contents were found under R. The antioxidative response was not always correlated with hydrogen content and differed depending on the light quality treatment. Blue light enhanced the proline levels, while carotenoids, total flavonoid and phenolic compounds were higher under W. Intraspecific variation in the responses were observed for most parameters with exception of leaf thickness; this intraspecific variation was most pronounced for total phenolic and flavonoid compounds. Copyright © 2017 Elsevier GmbH. All rights reserved.

  13. Degradation of polyvinyl alcohol (PVA) by homogeneous and heterogeneous photocatalysis applied to the photochemically enhanced Fenton reaction.

    Science.gov (United States)

    Bossmann, S H; Oliveros, E; Göb, S; Kantor, M; Göppert, A; Lei, L; Yue, P L; Braun, A M

    2001-01-01

    The reaction mechanism of the oxidative degradation of polyvinyl alcohol (PVA) by the photochemically enhanced Fenton reaction was studied using a homogeneous (Fe2+(aq) + H2O2) and a heterogeneous reaction system (iron(III)-exchanged zeolite Y+ H2O2). In the homogeneous Fenton system, efficient degradation was observed in a batch reactor, equipped with a medium pressure mercury arc in a Pyrex envelope and employing 80% of the stoichiometric amount of H2O2 required for the total oxidation of PVA and a concentration ratio as low as I mole of iron(II) sulfate per 20 moles of PVA sub-units (C2H40). Model PVA polymers of three different molecular weights (15,000, 49,000 and 100,000 g mol(-1)) were found to follow identical degradation patterns. Strong experimental evidence supports the formation of supermacromolecules (MW: 1-5 x 10(6) g/mol) consisting of oxidized PVA and trapped iron(III) at an early reaction stage. Low molecular weight intermediates, such as oxalic acid, formic acid or formaldehyde were not found during PVA degradation in the homogeneous Fenton system, and we may deduce that the manifold of degradation reactions is mainly taking place within the super-macromolecules from which CO2 is directly released. However, in the heterogeneous Fenton system, the reaction behavior was found to be distinctly different: a decrease of the molecular weights of all three tested monodisperse PVA samples was observed by the broadening of the GPC-traces during irradiation, and oxalic acid was formed. The results lead to the mechanistic hypothesis that during the heterogeneous Fenton process, the cleavage of the PVA-chains may occur at random positions, the reactive centres being located inside the iron(III)-doped zeolite Y photocatalysts.

  14. Photochemical data assimilation and tropospheric pollution forecast; Assimilation de donnees photochimiques et prevision de la pollution tropospherique

    Energy Technology Data Exchange (ETDEWEB)

    Blond, N.

    2002-12-15

    The Chemistry-Transport Models (CTM) are now sufficiently efficient to simulate realistic photochemical pollutant concentrations. Nevertheless, the complexity of involved processes and the temporal and spatial variability of the emission sources make it impossible to perfectly reproduce pollutant concentrations. If an intrinsic parameter or an input is not well described, A huge error results. CHIMERE is a CTM which covers the major part of Europe with a resolution of about fifty kilometers. It offers the possibility to zoom and simulate pollutant concentrations in a more detailed way over some key regions, such as Ile-de-France and the Berre and Marseille regions. We present results of a comparison of the continental and regional simulations with surface observations and aircraft measurements from the ESQUIF campaign (Etude et Simulation de la QUalite de l'Air en Ile-de-France). This comparison allows us to quantify the total error made in ozone and nitrogen dioxide concentrations. We also present different methods (e.g. Statistical Interpolation and Kriging) we have tested and adapted to the pollution case in order to correct this error. We compare the methods and show in an objective way that it is possible to obtain more realistic three-dimensional maps of pollutants (e.g. analyses) by combining both simulations and surface observations. A series of real time experiments realized in the PIONEER project show that the forecast error may propagate from one region to another. The european scale ozone analyses are thus used to re-initialize the forecast model. The aim is then to answer the question of whether it possible to improve short time forecasts by using better initial values instead of the forecasts for the day before. (author)

  15. Characterization of Photochemical Processes for H2 Production by CdS Nanorod-[FeFe] Hydrogenase Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Brown, K. A.; Wilker, M. B.; Boehm, M.; Dukovic, G.; King, P. W.

    2012-03-28

    We have developed complexes of CdS nanorods capped with 3-mercaptopropionic acid (MPA) and Clostridium acetobutylicum [FeFe]-hydrogenase I (CaI) that photocatalyze reduction of H{sup +} to H{sub 2} at a CaI turnover frequency of 380-900 s{sup -1} and photon conversion efficiencies of up to 20% under illumination at 405 nm. In this paper, we focus on the compositional and mechanistic aspects of CdS:CaI complexes that control the photochemical conversion of solar energy into H{sub 2}. Self-assembly of CdS with CaI was driven by electrostatics, demonstrated as the inhibition of ferredoxin-mediated H{sub 2} evolution by CaI. Production of H{sub 2} by CdS:CaI was observed only under illumination and only in the presence of a sacrificial donor. We explored the effects of the CdS:CaI molar ratio, sacrificial donor concentration, and light intensity on photocatalytic H{sub 2} production, which were interpreted on the basis of contributions to electron transfer, hole transfer, or rate of photon absorption, respectively. Each parameter was found to have pronounced effects on the CdS:CaI photocatalytic activity. Specifically, we found that under 405 nm light at an intensity equivalent to total AM 1.5 solar flux, H{sub 2} production was limited by the rate of photon absorption ({approx}1 ms{sup -1}) and not by the turnover of CaI. Complexes were capable of H{sub 2} production for up to 4 h with a total turnover number of 106 before photocatalytic activity was lost. This loss correlated with inactivation of CaI, resulting from the photo-oxidation of the CdS capping ligand MPA.

  16. Characterization of photochemical processes for H2 production by CdS nanorod-[FeFe] hydrogenase complexes.

    Science.gov (United States)

    Brown, Katherine A; Wilker, Molly B; Boehm, Marko; Dukovic, Gordana; King, Paul W

    2012-03-28

    We have developed complexes of CdS nanorods capped with 3-mercaptopropionic acid (MPA) and Clostridium acetobutylicum [FeFe]-hydrogenase I (CaI) that photocatalyze reduction of H(+) to H(2) at a CaI turnover frequency of 380-900 s(-1) and photon conversion efficiencies of up to 20% under illumination at 405 nm. In this paper, we focus on the compositional and mechanistic aspects of CdS:CaI complexes that control the photochemical conversion of solar energy into H(2). Self-assembly of CdS with CaI was driven by electrostatics, demonstrated as the inhibition of ferredoxin-mediated H(2) evolution by CaI. Production of H(2) by CdS:CaI was observed only under illumination and only in the presence of a sacrificial donor. We explored the effects of the CdS:CaI molar ratio, sacrificial donor concentration, and light intensity on photocatalytic H(2) production, which were interpreted on the basis of contributions to electron transfer, hole transfer, or rate of photon absorption, respectively. Each parameter was found to have pronounced effects on the CdS:CaI photocatalytic activity. Specifically, we found that under 405 nm light at an intensity equivalent to total AM 1.5 solar flux, H(2) production was limited by the rate of photon absorption (~1 ms(-1)) and not by the turnover of CaI. Complexes were capable of H(2) production for up to 4 h with a total turnover number of 10(6) before photocatalytic activity was lost. This loss correlated with inactivation of CaI, resulting from the photo-oxidation of the CdS capping ligand MPA.

  17. Recent Advances in Modeling the Near-Source Chemistry of Biomass-Burning Plumes in Photochemical Transport Models

    Science.gov (United States)

    Lonsdale, Chantelle; Brodowski, Christopher; Alvarado, Matthew; Henderson, John; Pierce, Jeffrey; Ramnarine, Emily; Lin, John; Kochanski, Adam

    2017-04-01

    Aerosol and gases freshly emitted from biomass-burning events are a complex mixture of organic species, black carbon, and inorganic salts, with their size, number, and chemical composition dependent on the type of vegetation that is burning, the size and combustion efficiency of the fire event, and the ambient conditions. These mixtures evolve quickly in the atmosphere due to coagulation, evaporation, and chemistry, including trace gases, ozone and secondary organic aerosol formation. Understanding and simulating this complex evolution is critical to assessing and quantifying the impact of biomass-burning plumes on air quality and climate. Since 3D Eulerian models take estimates of the primary emissions from biomass burning and unphysically mix them across large-scale grid boxes, this leads to inaccurate chemical modeling and incorrect estimates of the impact of biomass burning on air quality and climate. Plume-scale process models like the newly developed System for Atmospheric Modeling integrated with AER's Aerosol Simulation Program (SAM-ASP) allow an advanced representation of the near-source biomass-burning plume evolution, with the ability to develop parameterizations for use in air quality and climate models. We present results from a model study of a shrub land fire in California, as well as the development of a parameterization that improves upon the ASP-based parameterization of Lonsdale et al. (2015) that accounted for the formation of trace gases and secondary organic aerosols in biomass burning plumes for various fire conditions and fuel types. The newly improved parameterization additionally includes the complex processes of dispersion, advection, deposition and plume concentrations. We show results of the integration of this parameterization into a plume-in-grid sub-model within a larger-scale photochemical transport model for the first time.

  18. Uncovering Structural Diversity of Unsaturated Fatty Acyls in Cholesteryl Esters via Photochemical Reaction and Tandem Mass Spectrometry

    Science.gov (United States)

    Ren, Jia; Franklin, Elissia T.; Xia, Yu

    2017-07-01

    Mass spectrometry analysis of cholesteryl esters (CEs) faces several challenges, with one of them being the determination of the carbon-carbon double bond (C=C) locations within unsaturated fatty acyl chains. Paternὸ-Büchi (PB) reaction, a photochemical reaction based on the addition of acetone to C=C, is capable of C=C location determination when coupled with tandem mass spectrometry (MS/MS). In this study, the PB reaction conditions were tailored for CEs and subsequent nanoelectrospray ionization (nanoESI). A solvent system containing acetone/methanol/dichloromethane/water (40/30/20/10, volume ratios) and 100 μM LiOH was determined to be optimal, resulting in reasonable PB reaction yield ( 30%) and good ionization efficiency (forming lithium adduct of CEs). Collision-induced dissociation (CID) of the PB reaction products produced characteristic fragment ions of CE together with those modified by the PB reactions, such as lithiated fatty acyl ([FA + Li]+) and its PB product ([FA - PB + Li]+). MS3 CID of [FA - PB + Li]+ led to abundant C=C diagnostic ion formation, which was used for C=C location determination and isomer quantitation. A PB-MS3 CID approach was developed and applied for CE analysis from human plasma. A series of unsaturated CEs was identified with specific C=C locations within fatty acyl chains. Absolute quantitation for each CE species was achieved including coexisting C=C location isomers, such as Δ9 and Δ11 isomers of CE 18:1 and ω-6 and ω-3 isomers of CE 18:3. These results show that PB-MS/MS is useful in uncovering structural diversity of CEs due to unsaturation in fatty acyls, which is often undetected from current lipid analysis approach.

  19. Photochemical behavior of carbon nanotubes in natural waters: reactive oxygen species production and effects on •OH generation by Suwannee River fulvic acid, nitrate, and Fe (III).

    Science.gov (United States)

    Zhou, Lei; Zhang, Ya; Wang, Qi; Ferronato, Corinne; Yang, Xi; Chovelon, Jean-Marc

    2016-10-01

    The photochemical activities of three kinds of carbon nanotubes (CNTs) were investigated in the present study. Efficient procedures of dispersing the three kinds of carbon nanotubes in water were established, and the quantitative analysis methods were also developed by TOC-absorbance method. High pH value or low ionic strength of the colloidal solutions facilitated the dispersion of CNTs. The suspensions of three kinds of CNTs could generate singlet oxygen ((1)O2) and hydroxyl radical (•OH) under irradiation of simulated sunlight, while superoxide radical (O2 (•-)) was not detected. The steady-state concentrations of (1)O2 and •OH generated by these CNTs were also determined. The presence of CNTs in natural waters can affect the photochemical behavior of water constituents, such as nitrate, dissolved organic matter, and Fe(3+). Specifically, in nitrate solution, the presence of CNTs could inhibit the generation of •OH by nitrate through light screening effect, while the quenching effect of hydroxyl radicals by CNTs was not observed. Besides light screening effect, the three kinds of CNTs used in the experiments also have a strong inhibiting effect on the ability of DOM to produce •OH by binding to the active sites. Moreover, the adsorption of Fe(3+) on MWCNT-OH and MWCNT-COOH could lead to its inactivation of formation of •OH in acidic conditions. However, the presence of the three kinds of CNTs did not affect the ligand-to-metal charge transfer (LMCT) reaction of DOM-Fe (III) complex.

  20. Photochemical decomposition of 1H,1H,2H,2H-perfluorooctane sulfonate (6:2FTS) induced by ferric ions.

    Science.gov (United States)

    Jin, Ling; Jiang, Chuanjia; Zhang, Pengyi

    2017-01-01

    Perfluorooctane sulfonate (PFOS) had wide applications, such as in the electroplating industry, but its use was restricted in 2009 by the Stockholm Convention, due to its environmental persistence and potential hazards. As the most common PFOS alternative, 1H,1H,2H,2H-perfluorooctane sulfonic acid (6:2FTS) and its salts have been increasingly used. However, little is known about its photochemical decomposition. This paper reports the ferric ion-induced efficient decomposition and defluorination of 6:2FTS under 254nm ultraviolet (UV) irradiation; the underlying mechanisms were also investigated. In the presence of 100μmol/L ferric ion and at pH3.0, the first-order decomposition rate constant of 6:2FTS (10mg/L) was 1.59/hr, which was 6 times higher than for direct UV photolysis. The effects of the ferric ion concentration and the solution pH on the 6:2FTS photodecomposition were investigated and the optimal reaction conditions were determined. In addition to fluoride and sulfate ions, shorter-chain PFCAs (C2-C7) were detected as major intermediates. The addition of hydrogen peroxide or oxalic acid accelerated the decomposition of 6:2FTS under UV irradiation, but not its defluorination, indicating that hydroxyl radicals can directly react with 6:2FTS but not with the shorter-chain PFCAs. Accordingly, a mechanism for 6:2FTS photochemical decomposition in the presence of ferric ion was proposed, which comprises two reaction pathways. First, hydroxyl radicals can directly attack 6:2FTS, leading to CC bond cleavage. Alternatively, 6:2FTS coordinates with ferric ion to form Fe(III)-6:2FTS complexes, which can undergo ligand-to-metal charge transfer under UV irradiation, causing CS bond cleavage. Copyright © 2016. Published by Elsevier B.V.

  1. High photochemical trapping efficiency in Photosystem I from the red Glade algae Chromera velia and Phaeodactylum tricornuturn

    Czech Academy of Sciences Publication Activity Database

    Belgio, Erica; Santabarbara, S.; Bína, David; Trsková, Eliška; Herbstová, Miroslava; Kaňa, Radek; Zucchelli, G.; Prášil, Ondřej

    2017-01-01

    Roč. 1858, č. 1 (2017), s. 56-63 ISSN 0005-2728 R&D Projects: GA ČR(CZ) GA14-15728S; GA MŠk(CZ) LO1416; GA MŠk(CZ) ED2.1.00/19.0392; GA ČR GBP501/12/G055; GA ČR(CZ) GA16-10088S Institutional support: RVO:61388971 ; RVO:60077344 Keywords : Chromera velia * Phaeodactylum tricornutum * Red Glade algae Subject RIV: EE - Microbiology, Virology; BO - Biophysics (BC-A) Impact factor: 4.932, year: 2016

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1989-03-25

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

  3. The photochemical origins of life and photoreaction of ferrous ion in the archaean oceans

    Science.gov (United States)

    Mauzerall, David C.

    1990-01-01

    A general argument is made for the photochemical origins of life. A constant flux of free energy is required to maintain the organized state of matter called life. Solar photons are the unique source of the large amounts of energy probably required to initiate this organization and certainly required for the evolution of life to occur. The completion of this argument will require the experimental determination of suitable photochemical reactions. It is shown that biogenetic porphyrins readily photooxidize substrates and emit hydrogen in the presence of a catalyst. These results are consistent with the Granick hypothesis, which relates a biosynthetic pathway to its evolutionary origin. It has been shown that photoexcitation of ferrous ion at neutral pH with near ultraviolet light produces hydrogen with high quantum yield. This same simple system may reduce carbon dioxide to formaldehyde and further products. These reactions offer a solution to the dilemma confronting the Oparin-Urey-Miller model of the chemical origin of life. If carbon dioxide is the main form of carbon on the primitive earth, the ferrous photoreaction may provide the reduced carbon necessary for the formation of amino acids and other biogenic molecules. These results suggest that this progenitor of modern photosynthesis may have contributed to the chemical origins of life.

  4. The mechanism of non-linear photochemical oscillations in the mesopause region

    Directory of Open Access Journals (Sweden)

    M. Yu. Kulikov

    2012-09-01

    Full Text Available The mechanism of generation of 2-day photochemical oscillations in the mesopause region (80–90 km has been studied analytically. The initial system of equations of chemical kinetics describing the temporal evolution of O, O3, H, OH and HO2 concentrations with allowance for diurnal variations of solar radiation has been simplified successively to a system of two nonlinear first-order time equations with sinusoidal external forcing. The obtained system has a minimum number of terms needed for generation of 2-day oscillations. Linearization of this system near the period-doubling threshold permits separating explicitly a particular case of the Mathieu equation + α · sin ω t · x = 0, in which the first sub-harmonic (ω/2 of the exciting force starts to grow exponentially when the amplitude of external forcing (α exceeds its threshold value. Finally, a system of two simplest differential equations with power-law nonlinearity has been derived that allows analytical investigation of the effect of arising of reaction-diffusion waves in the mesospheric photochemical system.

  5. Photochemical Transformation of Four Ionic Liquid Cation Structures in Aqueous Solution.

    Science.gov (United States)

    Pati, Sarah G; Arnold, William A

    2017-10-17

    Ionic liquids (ILs) are a new class of solvents expected to be used increasingly by the chemical industry in the coming years. Given their slow biodegradation and limited sorption affinities, IL cations have a high potential to reach aquatic environments. We investigated the fate of ILs in sunlit surface water by determining direct and indirect photochemical transformation rates of imidazolium, pyridinium, pyrrolidinium, and piperidinium cations. The photodegradation of all investigated IL cations was faster in solutions containing dissolved organic matter (DOM) than in ultrapure water, illustrating the importance of indirect photochemical processes. Experiments with model sensitizers and DOM isolates revealed that reactions with hydroxyl radicals dominated the transformation of tested IL cations. Bimolecular reaction rate constants with hydroxyl radicals ranged from (2.04 ± 0.37) × 10(9) to (8.47 ± 0.97) × 10(9) M(-1) s(-1) and showed an increase in rate constants with increasing carbon side-chain length. Consequently, average estimated half-lives of IL cations in sunlit surface water ranged from 32 ± 4 to 135 ± 25 days, highlighting the potential of IL cations to become persistent aquatic contaminants.

  6. Radiochemical synthesis and photochemical properites of the uncoupler 2-azido-4-nitrophenol, a versatile photoaffinity labeling

    Energy Technology Data Exchange (ETDEWEB)

    Hanstein, W.G.; Hatefi, Y.; Kiefer, H.

    1979-03-20

    2-Amino-4-nitrophenol was tritiated in an acid catalyzed hydrogen exchange reaction. Radioactive 2-azido-4-nitrophenol with a specific radioactivity up to 21 mCi/mmol was synthesized from 2-amino-4-nitrophenol by diazotization and azide coupling. The photochemical properties of the uncoupler, 2-azido-4-nitrophenol, were studied as free solute and as ligand bound to uncoupler binding sites in bovine serum albumin and mitochondria. Based on product analyses, irradiation of free or bound 2-azido-4-nitrophenolate with visible light results in the formation of nitrene intermediates with a singlet to triplet ratio of 6:1 to 9:1. 2-Azido-4-nitrophenolate and bovine serum albumin form a strong 1:1 complex (K/sub D/ = 0.7 ..mu..M) which can be converted into a photoproduct with a covalent bond between the label and the protein. The acid dissociation constant of the protein-bound 2-amino-4-nitrophenol moiely is strongly pH dependent. Photoaffinity labeling of mitochondria by 2-azido-4-nitrophenolate follows a pattern expected from equilibrium binding studies using normal and lipid-depleted particles: polypeptides were found to bear 90 to 95% of the radioactive label, and 5 to 10% of the latter was bound to phospholipids. Two polypeptides (approximately 56,000 and 31,000 daltons) were associated with 60% of the label, indicating a high degree of specific photochemical labeling.

  7. Synthesis and photochemical properties of a photochromic iron(II) complex of hexaarylbiimidazole.

    Science.gov (United States)

    Miyamoto, Yuki; Kikuchi, Azusa; Iwahori, Fumiyasu; Abe, Jiro

    2005-11-17

    The photochromic ligand bis(terpyridyl)hexaarylbiimidazole (bistpy-HABI) and the Fe(II) complex of bistpy-HABI with formula [{Fe(tpy)}2.bistpy-HABI](PF6)4.4H2O were synthesized and characterized. Bistpy-HABI is readily cleaved into a pair of terpyridyltriphenylimidazolyl radicals (tpy-TPI*) on irradiation with UV light. This photochemical reaction is completely reversible, and the light-induced radicals can thermally recombine to form bistpy-HABI in the dark. [{Fe(tpy)}2.bistpy-HABI]4+ is the first example of a transition-metal complex of an HABI derivative and was found to show photochromic reaction in solution. The spin state of the light-induced radical pair in a frozen matrix was investigated by ESR spectroscopy. The triplet state of the light-induced radical pair from [{Fe(tpy)}2.bistpy-HABI]4+, as well as that from bistpy-HABI, was confirmed to be a ground state or nearly degenerated with a singlet state. Kinetic studies on the radical recombination reaction in solution elucidated the decrease in the activation energy by forming the Fe(II) complex. This is the first observation of a decrease in the activation energy of the radical recombination reaction by the formation of a metal-coordinated radical complex. The syntheses, photochemical properties, and spin states of bistpy-HABI and [{Fe(tpy)}2.bistpy-HABI](PF6)4 are discussed.

  8. Experimental Study of Nonequilibrium Electrodeposition of Nanostructures on Copper and Nickel for Photochemical Fuel Cell Application

    Directory of Open Access Journals (Sweden)

    Rajesh K. Shanmugam

    2011-01-01

    Full Text Available To increase the performance of photochemical fuel cells, nonequilibrium electrodeposition has been performed on Cu and Ni to make photosensitive anodes. Processing parameters including electrolyte concentration, and electrode potential were studied using cyclic voltammetry. Scanning electron microscopy (SEM and X-ray Spectroscopy (EDS were performed to understand the formation of the nanostructures during the nonequilibrium deposition of copper fractals. An increase in the deposition rate was observed with the increase in electrolyte concentration (from 0.05 M to 1.0 M. Similar trend was found when the cathode potential was decreased from −0.5 V to −4.5 V. The effect of substrate material was also examined. Porous fractal structures on copper were achieved, while the deposited material showed high density of surface cracks on nickel. The fractal structures deposited on copper electrode with the increased surface area were converted into copper oxide by oxidation in air. Such oxide samples were made into anodes for photochemical fuel cell application. We demonstrated that an increase in the magnitude of open circuit output voltage is associated with the increase in the fractal surface area under the ultraviolet irradiation test conditions. However, the electrodeposited fractals on nickel showed very limited increase in the magnitude of open circuit voltage.

  9. Sunlight-induced photochemical decay of oxidants in natural waters: implications in ballast water treatment.

    Science.gov (United States)

    Cooper, William J; Jones, Adam C; Whitehead, Robert F; Zika, Rod G

    2007-05-15

    The transport and discharge of ship ballast water has been recognized as a major vector for the introduction of invasive species. Chemical oxidants, long used in drinking water and wastewater treatment, are alternative treatment methods for the control of invasive species currently being tested for use on ships. One concern when a ballasted vessel arrives in port is the adverse effects of residual oxidant in the treated water. The most common oxidants include chlorine (HOCl/OCl-), bromine (HOBr/OBr-), ozone (03), hydrogen peroxide (H2O2), chlorine dioxide (ClO2), and monochloramine (NH2Cl). The present study was undertaken to evaluate the sunlight-mediated photochemical decomposition of these oxidants. Sunlight photodecomposition was measured at various pH using either distilled water or oligotrophic Gulf Stream water for specific oxidants. For selected oxidants, quantum yields at specific wavelengths were obtained. An environmental photochemical model, GCSOLAR, also provided predictions of the fate (sunlight photolysis half-lives) of HOCI/OCl-, HOBr/OBr-, ClO2, and NH2Cl for two different seasons at latitude 40 degrees and in water with two different concentrations of chromophoric dissolved organic matter. These data are useful in assessing the environmental fate of ballast water treatment oxidants if they were to be discharged in port.

  10. The photochemical origins of life and photoreaction of ferrous ion in the archaean oceans

    Science.gov (United States)

    Mauzerall, David C.

    1990-05-01

    A general argument is made for the photochemical origins of life. A constant flux of free energy is required to maintain the organized state of matter called life. Solar photons are the unique source of the large amounts of energy probably require to initiate this organization and certainly required for the evolution of life to occur. The completion of this argument will require the experimental determination of suitable photochemical reactions. Our work shows that biogenetic porphyrins readily photooxidize substrates and emit hydrogen in the presence of a catalyst. These results are consistent with the Granick hypothesis, which relates a biosynthetic pathway to its evolutionary origin. We have shown that photoexcitation of ferrous ion at neutral pH with near ultraviolet light produces hydrogen with high quantum yield. This same simple system may reduce carbon dioxide to formaldehyde and further products. These reactions offer a solution to the dilemma confronting the Oparin-Urey-Miller model of the chemical origin of life. If carbon dioxide is the main form of carbon on the primitive earth, the ferrous photoreaction may provide the reduced carbon necessary for the formation of amino acids and other biogenic molecules. These results suggest that this progenitor of modern photosynthesis may have contributed to the chemical origins of life.

  11. Small gold nanoparticles formed by rapid photochemical flow-through synthesis using microfluid segment technique

    Energy Technology Data Exchange (ETDEWEB)

    Hafermann, Lars, E-mail: lars.hafermann@tu-ilmenau.de; Michael Köhler, J. [Technische Universität Ilmenau, Department for Physical Chemistry/Microreaction Technology, Faculty of Mathematics and Natural Science, Institute for Chemistry and Biotechnology (Germany)

    2015-02-15

    The photochemical synthesis of gold nanoparticles was transferred into a three-step micro-continuous flow process. A solution of tetrachloroaurate and a solution of a photoinitiator and polyvinylpyrrolidone were mixed within micro-fluid segments using a cross-injector. The segments (0.5 mm inner diameter) pass a focused UV ray after a short mixing by means of segment-internal convection. The nucleation of nanoparticles was initiated by this exposure, which lasted 30–300 ms depending on the applied flow rate. The growth of nanoparticles was completed by the passage of a residence loop of a length of 0.5 m. The obtained colloidal product solution was characterized by UV/VIS spectrophotometry, centrifugal sedimentation spectroscopy, dynamic light scattering, and SEM/TEM. In result, small gold nanoparticles with enhanced quality, compared to photochemical batch experiments, were obtained. The particle size can be tuned by variation of the composition of reactant solutions or flow rate between 2.5 and 4 nm. The small gold nanoparticles are suitable for use as seed particles for the formation of larger particles with an adjustable diameter.

  12. Temporal Changes in Photochemically Labile DOM and Implications for Carbon Budgets in Peatland Aquatic Systems

    Science.gov (United States)

    Pickard, A.

    2015-12-01

    Aquatic systems in peatland catchments are subject to high loading of dissolved organic matter (DOM) from surrounding terrestrial environments. However the significance of photochemical transformation of DOM in peatland carbon budgets remains poorly constrained. In this study UV irradiation experiments were conducted on water samples collected over one year from two contrasting systems in Scotland: a stream draining a peatland with high levels of DOM and a reservoir draining a peat catchment with low levels of DOM. Further samples were collected from the high DOM system during two storm events. After experimental exposure, optical and chemical analyses were employed to determine photochemical lability of the DOM pool. At both sites irradiation-induced decreases in dissolved organic carbon (DOC) as a percentage of the total carbon pool were greatest in winter, suggesting that DOM was depleted in photo-reactive molecules in summer. Seasonal variability in DOC was high at the stream site and was positively correlated with CO₂ and CO photoproduction (r2 = 0.81 and 0.83, respectively; plabile DOM in headwater streams. Conservative estimates using data from this study suggest that up to 7% of the DOM pool of peatland streams can be lost (primarily as CO₂ and CO) upon exposure to 8 hours of environmentally representative UV irradiation. Further investigation in field campaigns under natural UV exposure are underway to assess the importance of photodegradation of DOM as a loss pathway of carbon based gases from aquatic systems.

  13. Photochemical decoration of silver nanoparticles on graphene oxide nanosheets and their optical characterization

    Energy Technology Data Exchange (ETDEWEB)

    Lan, Nguyen Thi; Chi, Do Thi; Dinh, Ngo Xuan; Hung, Nguyen Duy; Lan, Hoang [Department of Nanoscience and Nanotechnology, Advanced Institute for Science and Technology (AIST), Hanoi University of Science and Technology (HUST), No. 1 Dai Co Viet Street, Hai Ba Trung District, Hanoi (Viet Nam); Tuan, Pham Anh [Vietnam Metrology Institute, 08 Hoang Quoc Viet Road, Cau Giay District, Hanoi (Viet Nam); Thang, Le Hong [School of Materials Science and Engineering, Hanoi University of Science and Technology (HUST), 01 Dai Co Viet Street, Hai Ba Trung District, Hanoi (Viet Nam); Trung, Nguyen Ngoc [School of Engineering Physics, Hanoi University of Science and Technology (HUST), 01 Dai Co Viet Street, Hai Ba Trung District, Hanoi (Viet Nam); Hoa, Nguyen Quang [Department of Physics, Hanoi University of Science, 334 Nguyen Trai, Thanh Xuan, Hanoi (Viet Nam); Huy, Tran Quang [Laboratory for Ultrastructure and Bionanotechnology (LUBN), National Institute of Hygiene and Epidemiology (NIHE), No. 1 Yecxanh Street, Hai Ba Trung District, Hanoi (Viet Nam); Quy, Nguyen Van [International Training Institute for Materials Science (ITIMS), Hanoi University of Science and Technology (HUST), 01 Dai Co Viet Street, Hai Ba Trung District, Hanoi (Viet Nam); Duong, Thanh-Tung [Department of Materials Engineering, Chungnam National University, Daeduk Science Town, 305-764 Daejeon (Korea, Republic of); Phan, Vu Ngoc [Department of Nanoscience and Nanotechnology, Advanced Institute for Science and Technology (AIST), Hanoi University of Science and Technology (HUST), No. 1 Dai Co Viet Street, Hai Ba Trung District, Hanoi (Viet Nam); Le, Anh-Tuan, E-mail: tuan.leanh1@hust.edu.vn [Department of Nanoscience and Nanotechnology, Advanced Institute for Science and Technology (AIST), Hanoi University of Science and Technology (HUST), No. 1 Dai Co Viet Street, Hai Ba Trung District, Hanoi (Viet Nam)

    2014-12-05

    Highlights: • A photochemical method for effective decoration of the Ag-NPs on GO nanosheets is presented. • The average size of the Ag-NPs on the GO nanosheets obtained ∼6–7 nm with uniform size distribution. • Surface interaction of Ag-NPs with GO nanosheets leads to surface plasmon-enhanced luminescence. - Abstract: Nanohybrid materials based on silver nanoparticles (Ag-NPs) and graphene oxide (GO) are attracting considerable research interest because of their potential many applications including surface-enhanced Raman scattering, catalysis, sensors, biomedicine and antimicrobials. In this study, we established a simple and effective method of preparing a finely dispersed Ag-GO aqueous solution using modified Hummer and photochemical technique. The Ag-NPs formation on GO nanosheets was analyzed by X-ray diffraction, transmission electron microscopy, Raman spectroscopy, and Fourier-transform infrared spectroscopy. The average size of Ag-NPs on the GO nanosheets was approximately 6–7 nm with nearly uniform size distribution. The Ag-GO nanohybrid also exhibits an adsorption band at 435 nm because of the presence of Ag-NPs on the GO nanosheets. Photoluminescence emission of the Ag-GO nanohybrid was found at 400 and 530 nm, which can be attributed to the interaction between the luminescence of exploited GO nanosheets and localized surface plasmon resonance from metallic Ag-NPs. The observed excellent optical properties of the as-prepared Ag-GO nanohybrid showed a significant potential for optoelectronics applications.

  14. Nitrogen Incorporation in CH4-N2 Photochemical Aerosol Produced by Far Ultraviolet Irradiation

    Science.gov (United States)

    Jimenez, Jose L.; Yung, Yuk L.; Toon, Owen B.; Tolbert, Margaret A.

    2012-01-01

    Abstract Nitrile incorporation into Titan aerosol accompanying hydrocarbon chemistry is thought to be driven by extreme UV wavelengths (λphotochemistry contains a surprising amount of nitrogen, up to 16% by mass, a result of photolysis in the far UV. The proportion of nitrogenated organics to hydrocarbon species is shown to be correlated with that of N2 in the irradiated gas. The aerosol mass greatly decreases when N2 is removed, which indicates that N2 plays a major role in aerosol production. Because direct dissociation of N2 is highly improbable given the immeasurably low cross section at the wavelengths studied, the chemical activation of N2 must occur via another pathway. Any chemical activation of N2 at wavelengths >120 nm is presently unaccounted for in atmospheric photochemical models. We suggest that reaction with CH radicals produced from CH4 photolysis may provide a mechanism for incorporating N into the molecular structure of the aerosol. Further work is needed to understand the chemistry involved, as these processes may have significant implications for how we view prebiotic chemistry on early Earth and similar planets. Key Words: Titan—Photochemical aerosol—CH4-N2 photolysis—Far UV—Nitrogen activation. Astrobiology 12, 315–326. PMID:22519972

  15. Lagrangian photochemical modeling studies of the 1987 Antarctic spring vortex. II - Seasonal trends in ozone

    Science.gov (United States)

    Austin, J.; Jones, R. L.; Mckenna, D. S.; Buckland, A. T.; Anderson, J. G.; Fahey, D. W.; Farmer, C. B.; Heidt, L. E.; Proffitt, M. H.; Vedder, J. F.

    1989-01-01

    A photochemical model consisting of 40 species and 107 reactions is integrated along 80-day air parcel trajectories calculated in the lower stratosphere for the springtime Antarctic. For the trajectory starting at 58 deg S, which may be regarded as outside the circumpolar vortex, only a small change in O3 occurs in the model. In contrast, for the air parcel starting in the vortex at 74 deg S, the O3 concentration is reduced by 93 percent during the 80 days from the beginning of August to late October. The model results for several species are compared with measurements from the Airborne Antarctic Ozone Experiment and, in general, good agreement is obtained. In the model, the dentrification of the air parcels in polar stratospheric clouds increases the amount of chlorine present in active form. Heterogeneous reactions maintain high active chlorine which destroys O3 via the formation of the ClO dimer. Results of calculations with reduced concentrations of inorganic chlorine show considerably reduced O3 destruction rates and compare favorably with the behavior of total O3 since the late 1970s. The remaining major uncertainties in the photochemical aspects of the Antarctic ozone hole are highlighted.

  16. One-step surface selective modification of UV-curable hard coatings with photochemical metal organics

    Science.gov (United States)

    Lee, Yoon Kwang; Park, Chang-Sun; Park, Hyung-Ho

    2016-12-01

    An organic-inorganic hybrid bi-layer film with a selective distribution of inorganic components was synthesized from a one-pot process of UV irradiation. A photochemical metal oxide precursor (Sr 2-ethylhexanoate) varying from 0 to 4 wt% was dispersed in UV-curable coating materials. Under UV exposure, the bi-layer started reacting simultaneously but at different rates due to differences in the two UV-condensable components' reactivity. The effects of the dispersed inorganic component on the surface morphology and mechanical properties were investigated by atomic force microscopy and nanoindentation, respectively. The reaction process and rates were studied from linkage change using Fourier transform infrared spectroscopy at various UV exposure times (0-30 min). The elemental distribution and the interface on the coating layer were characterized by X-ray photoelectron spectroscopy from Ar etching, revealing continuous and gradual composition changes in depth. The results showed that a flattened and surface-selectively hardened SrO containing the coating film could be obtained by this simple process. Consequently, a small ratio of photochemical metal oxide reinforced the organic hard coating film's mechanical properties through the formation of an effective SrO top layer.

  17. Photochemical functionalization of gallium nitride thin films with molecular and biomolecular layers.

    Science.gov (United States)

    Kim, Heesuk; Colavita, Paula E; Metz, Kevin M; Nichols, Beth M; Sun, Bin; Uhlrich, John; Wang, Xiaoyu; Kuech, Thomas F; Hamers, Robert J

    2006-09-12

    We demonstrate that photochemical functionalization can be used to functionalize and photopattern the surface of gallium nitride crystalline thin films with well-defined molecular and biomolecular layers. GaN(0001) surfaces exposed to a hydrogen plasma will react with organic molecules bearing an alkene (C=C) group when illuminated with 254 nm light. Using a bifunctional molecule with an alkene group at one end and a protected amine group at the other, this process can be used to link the alkene group to the surface, leaving the protected amine exposed. Using a simple contact mask, we demonstrate the ability to directly pattern the spatial distribution of these protected amine groups on the surface with a lateral resolution of <12 mum. After deprotection of the amines, single-stranded DNA oligonucleotides were linked to the surface using a bifunctional cross-linker. Measurements using fluorescently labeled complementary and noncomplementary sequences show that the DNA-modified GaN surfaces exhibit excellent selectivity, while repeated cycles of hybridization and denaturation in urea show good stability. These results demonstrate that photochemical functionalization can be used as an attractive starting point for interfacing molecular and biomolecular systems with GaN and other compound semiconductors.

  18. Photochemical cycling of iron in the surface ocean mediated by microbial iron(III)-binding ligands

    Science.gov (United States)

    Barbeau, K.; Rue, E. L.; Bruland, K. W.; Butler, A.

    2001-09-01

    Iron is a limiting nutrient for primary production in large areas of the oceans. Dissolved iron(III) in the upper oceans occurs almost entirely in the form of complexes with strong organic ligands presumed to be of biological origin. Although the importance of organic ligands to aquatic iron cycling is becoming clear, the mechanism by which they are involved in this process remains uncertain. Here we report observations of photochemical reactions involving Fe(III) bound to siderophores-high-affinity iron(III) ligands produced by bacteria to facilitate iron acquisition. We show that photolysis of Fe(III)-siderophore complexes leads to the formation of lower-affinity Fe(III) ligands and the reduction of Fe(III), increasing the availability of siderophore-bound iron for uptake by planktonic assemblages. These photochemical reactions are mediated by the α-hydroxy acid moiety, a group which has generally been found to be present in the marine siderophores that have been characterized. We suggest that Fe(III)-binding ligands can enhance the photolytic production of reactive iron species in the euphotic zone and so influence iron availability in aquatic systems.

  19. Nitrogen Incorporation in CH4-N2 Photochemical Aerosol Produced by Far UV Irradiation

    Science.gov (United States)

    Trainer, Melissa G.; Jimenez, Jose L.; Yung, Yuk L.; Toon, Owen B.; Tolbert, Margaret A.

    2012-01-01

    Nitrile incorporation into Titan aerosol accompanying hydrocarbon chemistry is thought to be driven by extreme UV wavelengths (lambda nitrogenated species. We have examined the chemical properties of photochemical aerosol produced at far UV wavelengths using a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS), which allows for elemental analysis of particle-phase products. Our results show that aerosol formed from CH4/N2 photochemistry contains a surprising amount of nitrogen, up to 16% by mass, a result of photolysis in the far UV. The proportion of nitrogenated organics to hydrocarbon species is shown to be correlated with that of N2 in the irradiated gas. The aerosol mass greatly decreases when N2 is removed, indicating that N2 plays a major role in aerosol production. Because direct dissociation of N2 is highly improbable given the immeasurably low cross-section at the wavelengths studied, the chemical activation of N2 must occur via another pathway. Any chemical activation of N2 at wavelengths > 120 nm is presently unaccounted for in atmospheric photochemical models. We suggest that reaction with CH radicals produced from CH4 photolysis may provide a mechanism for incorporating N into the molecular structure of the aerosol. Further work is needed to understand the chemistry involved, as these processes may have significant implications for prebiotic chemistry on the early Earth and similar planets.

  20. Photochemically-assisted synthesis of non-toxic and biocompatible gold nanoparticles.

    Science.gov (United States)

    Teixeira, Priscila R; Santos, Mayara S C; Silva, Ana Luísa G; Báo, Sônia N; Azevedo, Ricardo B; Sales, Maria José A; Paterno, Leonardo G

    2016-12-01

    This contribution describes the photochemically-assisted synthesis of aqueous colloidal suspensions of non-toxic and biocompatible spherical gold nanoparticles stabilized by branched polyethylenimine, or else Au-np-PEI. The method consists on 30min of photoexcitation (254nm, 16W) at room temperature of an aqueous diluted solution of chloroauric acid (HAuCl4) containing PEI. While the UV irradiation forms the [Au(3+)Cl4-]* excited species that succesively transforms into zero valent Au, PEI controls the nucleation step of nanoparticles formation. Varying the PEI to Au molar ratio permits one to tune the size of nanoparticles between 100nm to 8nm. The obtained colloidal suspensions display an intense plasmonic absorption band at 520-530nm and positive zeta potentials greater than +20mV. The cells viability for in vitro tests performed with human connective tissues and human breast adenocarcinoma (MCF-7) cell lines is over 80% and 90%, respectively, when they are incubated with Au-np-PEI formulations (25μgmL-1). The present photochemically-assisted synthesis is advantageous because it is fast and does not require for either hazardous or cytotoxic reductant agents and additional purification procedures. Copyright © 2016 Elsevier B.V. All rights reserved.

  1. Stability-Indicating Photochemical Method for the Assay of Riboflavin: Lumichrome Method

    Directory of Open Access Journals (Sweden)

    Iqbal Ahmad

    2015-01-01

    Full Text Available A stability-indicating photochemical method for the assay of riboflavin (RF in photodegraded samples and aged vitamin preparations has been developed. It is based on photochemical conversion of RF to lumichrome (LC in alkaline solution under controlled conditions of light intensity, temperature, pH, time of exposure, and distance. Under these conditions about two-thirds of RF is converted to LC and on the basis of the RF : LC ratio the concentration of RF can be determined in degraded solutions. The method involves the extraction of photolyzed solutions of RF (pH 2.0 with chloroform and determination of LC along with lumiflavin (LF by a two-component spectrometric method at 356 and 445 nm. The method has been validated and the results of the assay of RF in photodegraded solutions compare well with those of the standard USP fluorimetric method. The recovery of the method is 99–101% and the precision is within 2%. The method is stability-indicating and can be applied to the assay of RF in photodegraded solutions and aged vitamin preparations. The method is specific compared to that of the USP fluorimetric method in which the degraded LC may interfere with the fluorescence emission of RF.

  2. Photochemical fate and eco-genotoxicity assessment of the drug etodolac

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-06-15

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

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

    Science.gov (United States)

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

    2015-08-01

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

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

    Directory of Open Access Journals (Sweden)

    Thomas Zeuch

    2013-11-01

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

  5. Upconversion Nanoparticles/Hyaluronate-Rose Bengal Conjugate Complex for Noninvasive Photochemical Tissue Bonding.

    Science.gov (United States)

    Han, Seulgi; Hwang, Byung Woo; Jeon, Eun Young; Jung, Dooyup; Lee, Geon Hui; Keum, Do Hee; Kim, Ki Su; Yun, Seok Hyun; Cha, Hyung Joon; Hahn, Sei Kwang

    2017-10-24

    The recent progress in photonic nanomaterials has contributed greatly to the development of photomedicines. However, the finite depth of light penetration is still a serious limitation, constraining their clinical applications. Here, we developed a poly(allylamine) (PAAm)-modified upconversion nanoparticle/hyaluronate-rose bengal (UCNP/PAAm/HA-RB) conjugate complex for photochemical bonding of deep tissue with near-infrared (NIR) light illumination. Compared to the conventional invasive treatment via suturing and stapling, the UCNP/PAAm/HA-RB conjugate complex could be noninvasively delivered into the deep tissue and accelerate the tissue bonding upon NIR light illumination. HA in the outer layer of the complex facilitated the penetration of RB into the collagen layer of the dermis. The NIR light triggered UCNP of NaYF4: Yb/Er (Y:Yb:Er = 78:20:2) in the complex to illuminate visible green light under the skin tissue. The activated RB in the HA-RB conjugate by the green light induced radical formation for the cross-linking of incised collagen matrix. An in vitro light propagation test and collagen fibrillogenesis analysis, an in vivo animal tissue bonding test, and an ex vivo tensile strength test of dissected skin tissues confirmed the successful photochemical tissue bonding effect of the UCNP/PAAm/HA-RB conjugate complex.

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

    Directory of Open Access Journals (Sweden)

    B. Derstroff

    2017-08-01

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

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

    Science.gov (United States)

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

    2017-08-01

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

  8. Evaluated kinetic and photochemical data for atmospheric chemistry: Volume IV – gas phase reactions of organic halogen species

    Directory of Open Access Journals (Sweden)

    R. Atkinson

    2008-08-01

    Full Text Available This article, the fourth in the series, presents kinetic and photochemical data sheets evaluated by the IUPAC Subcommittee on Gas Kinetic Data Evaluation for Atmospheric Chemistry. It covers the gas phase and photochemical reactions of organic halogen species, which were last published in 1997, and were updated on the IUPAC website in 2006/07. The article consists of a summary sheet, containing the recommended kinetic parameters for the evaluated reactions, and four appendices containing the data sheets, which provide information upon which the recommendations are made.

  9. Evaluated kinetic and photochemical data for atmospheric chemistry: Volume I - gas phase reactions of Ox, HOx, NOx and SOx species

    Directory of Open Access Journals (Sweden)

    R. Atkinson

    2004-01-01

    Full Text Available This article, the first in the series, presents kinetic and photochemical data evaluated by the IUPAC Subcommittee on GasKinetic Data Evaluation for Atmospheric Chemistry. It covers the gas phase and photochemical reactions of Ox, HOx, NOx and SOx species, which were last published in 1997, and were updated on the IUPAC website in late 2001. The article consists of a summary sheet, containing the recommended kinetic parameters for the evaluated reactions, and five appendices containing the data sheets, which provide information upon which the recommendations are made.

  10. Evaluated kinetic and photochemical data for atmospheric chemistry: Volume II – gas phase reactions of organic species

    Directory of Open Access Journals (Sweden)

    R. Atkinson

    2006-01-01

    Full Text Available This article, the second in the series, presents kinetic and photochemical data evaluated by the IUPAC Subcommittee on Gas Kinetic Data Evaluation for Atmospheric Chemistry. It covers the gas phase and photochemical reactions of Organic species, which were last published in 1999, and were updated on the IUPAC website in late 2002, and subsequently during the preparation of this article. The article consists of a summary table of the recommended rate coefficients, containing the recommended kinetic parameters for the evaluated reactions, and eight appendices containing the data sheets, which provide information upon which the recommendations are made.

  11. Photochemically assisted fast abiotic oxidation of manganese and formation of δ-MnO 2 nanosheets in nitrate solution

    Energy Technology Data Exchange (ETDEWEB)

    Jung, Haesung; Chadha, Tandeep S.; Kim, Doyoon; Biswas, Pratim; Jun, Young-Shin (WU)

    2017-01-01

    This study introduces a new and previously unconsidered fast abiotic formation of Mn(IV) oxides. We report photochemically assisted fast abiotic oxidation of Mn2+ (aq) to Mn(IV) (s) by superoxide radicals generated from nitrate photolysis. This photochemical pathway generates randomly stacked layered birnessite (δ-MnO2) nanosheets.

  12. Photochemical transformation of nitrate in the presence of para-halogenated phenols in frozen solutions

    Science.gov (United States)

    Abida, O.; Osthoff, H. D.; Sutherland, T. C.

    2010-12-01

    Photochemical reactions leading to the chemical transformation of trace compounds in the atmosphere do not only occur in the atmospheric gas and liquid phases, but also in the tropospheric ice phase. The photochemical reactions of trace compounds embedded in ice have important implications for the composition of the atmospheric boundary layer in ice and snow covered regions and for interpretation of concentration profiles in snow and ice in the context of the composition of the past atmosphere. One of the prominent reactions is the photolysis of nitrate. This reaction is well established in natural waters, and is of interest since formation of highly mutagenic/carcinogenic nitro-compounds is possible. In contrast, the photochemical behaviour of nitrate in ice and snow is more complex. The photolysis of nitrate embedded in ice has been shown to generate OH radical, NO2(g) and NO(g) as primary photoproducts, but little is known how this photochemistry is affected by the presence of organic impurities embedded in the ice surface. In this work, we studied the effect of the presence of para-halogenated phenols on the photo-transformation of frozen nitrate solutions by Diffuse Reflective Infrared Fourier Transform Spectroscopy (DRIFTS). Moreover, the evolution of volatile nitrogen oxides to the gas phase was monitored by a commercial chemiluminescence NO/NOy monitor, chemical ionization mass spectrometry (CIMS), and thermal-dissociation cavity ring-down spectroscopy (TD-CRDS). In addition, some of the organic intermediate products were characterized by GC/MS and HPLC/PDA. We show that DRIFTS can provide a qualitative picture of the chemical transformations that take place at the ice surface and kinetic data on the phototransformation of nitrate. The photochemistry of frozen solutions of nitrate in the presence of various para-halogenated phenols was found to be dependent on the ice temperature, pH, the light intensity, and the concentration and nature of para

  13. Photochemically Driven Reduction of Hg(II) in the Presence of Particulate Organic Matter

    Science.gov (United States)

    Kocar, B. D.; Gelfond, C. E.

    2016-12-01

    Mercury(Hg) is a global pollutant with high toxicity that accumulates in biota and biomagnifies, posing a risk to organisms throughout the food chain. Hg is known to strongly associate with natural organic matter (NOM), affecting its speciation, solubility, mobility and toxicity. This project investigates Hg2+ photo-reduction in the presence of particulate organic matter (POM), a critical yet enigmatic process known to drive Hg re-emission from aqueous systems to the atmosphere. Two coupled processes transpiring during irradiation of Hg-POM are hypothesized to impart dominant controls on the fate of Hg: 1) photochemical transformations of POM resulting in altered chemical reactivity with Hg, and 2) photo-reduction of Hg2+ to Hg0 in the presence of POM. The former will affect the capacity of POM to bind Hg, thereby imparting controls on the photochemically driven transformation of POM-Hg. Owing to a high density of reactive functional groups, POM sorbs appreciable quantities of Hg, resulting in a large pool susceptible to transformation when exposed to sunlight. This capacity may be altered by irradiation, which results in changes to POM-associated functional groups known to bind Hg (e.g. sulfhydryl, carboxyl groups). Accordingly, we performed (batch) sorption isotherms of Hg to dark and irradiated POM, using ground Phragmites australis ("common reed") as a model source of POM. Analysis was performed using ICP-MS. We expected that coordination of Hg to POM would be lower in irradiated samples, resulting from the decrease in Hg associated (reduced) sulfur bearing functional groups as measured using XANES and EXAFS. However, an increase in oxygenated functional groups associated with POM lead to a large increase in the extent of Hg sorption to irradiated POM. Further analysis of the dark and irradiated POM was performed using FT-IR microscopy and STXM to determine changes in distribution and alteration of functional groups responsible for Hg sorption. Our results

  14. Aqueous photochemical degradation of hydroxylated PAHs: Kinetics, pathways, and multivariate effects of main water constituents

    Energy Technology Data Exchange (ETDEWEB)

    Ge, Linke; Na, Guangshui [Key Laboratory for Ecological Environment in Coastal Areas (SOA), National Marine Environmental Monitoring Center, Dalian 116023 (China); Chen, Chang-Er [Lancaster Environment Centre, Lancaster University, Lancaster LA1 4YQ (United Kingdom); Li, Jun [Key Laboratory for Ecological Environment in Coastal Areas (SOA), National Marine Environmental Monitoring Center, Dalian 116023 (China); College of Marine Science, Shanghai Ocean University, Shanghai 201306 (China); Ju, Maowei; Wang, Ying; Li, Kai [Key Laboratory for Ecological Environment in Coastal Areas (SOA), National Marine Environmental Monitoring Center, Dalian 116023 (China); Zhang, Peng, E-mail: pzhang@nmemc.org.cn [Key Laboratory for Ecological Environment in Coastal Areas (SOA), National Marine Environmental Monitoring Center, Dalian 116023 (China); Yao, Ziwei [Key Laboratory for Ecological Environment in Coastal Areas (SOA), National Marine Environmental Monitoring Center, Dalian 116023 (China)

    2016-03-15

    Hydroxylated polycyclic aromatic hydrocarbons (OH-PAHs) are contaminants of emerging concern in the aquatic environment, so it is of great significance to understand their environmental transformation and toxicity. This study investigated the aqueous photochemical behavior of four OH-PAHs, 9-Hydroxyfluorene (9-OHFL), 2-Hydroxyfluorene, 9-Hydroxyphenanthrene and 1-Hydroxypyrene, under simulated sunlight irradiation (λ > 290 nm). It was observed that their photodegradation followed the pseudo-first-order kinetics. Based on the determined quantum yields, their calculated solar apparent photodegradation half-lives in surface waters at 45° N latitude ranged from 0.4 min for 9-Hydroxyphenanthrene to 7.5 × 10{sup 3} min for 9-OHFL, indicating that the OH-PAHs would intrinsically photodegrade fast in sunlit surface waters. Furthermore, 9-OHFL as an example was found to undergo direct photolysis, and self-sensitized photooxidation via ·OH rather than {sup 1}O{sub 2} in pure water. The potential photoreactions involved photoinduced hydroxylation, dehydrogenation and isomerization based on product identification by GC–MS/MS. 9-OHFL photodegraded slower in natural waters than in pure water, which was attributed to the integrative effects of the most photoreactive species, such as Fe(III), NO{sub 3}{sup −}, Cl{sup −} and humic acid. The photomodified toxicity was further examined using Vibrio fischeri, and it was found that the toxicity of photolyzed 9-OHFL did not decrease significantly (p > 0.05) either in pure water or in seawater, implying the comparable or higher toxicity of some intermediates. These results are important for assessing the fate and risks of OH-PAHs in surface waters. - Graphical abstract: Aqueous photochemical behavior of 4 hydroxylated PAHs is first reported on revealing the kinetics, mechanisms, toxicity, and multivariate effects of water constituents. - Highlights: • It is first reported on aqueous photochemical behavior of 4 hydroxylated

  15. Photoacclimation and non-photochemical quenching under in situ irradiance in natural phytoplankton assemblages from the Amundsen Sea, Antarctica

    NARCIS (Netherlands)

    Alderkamp, Anne-Carlijn; Mills, Matthew M.; van Dijken, Gert L.; Arrigo, Kevin R.

    2013-01-01

    Photoacclimation strategies and sensitivity to photoinhibition were determined in natural phytoplankton assemblages during a phytoplankton bloom in the Amundsen Sea (Southern Ocean) in relation to community composition, pigment content, light, and iron (Fe). Non-photochemical quenching (qN) was

  16. Chemical kinetic and photochemical data for use in stratospheric modeling evaluation number 4: NASA panel for data evaluation

    Science.gov (United States)

    1981-01-01

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

  17. Development of advanced technologies for photochemical tritium recovery. Bi-quarterly program report, 1 April-30 September 1980

    Energy Technology Data Exchange (ETDEWEB)

    Herman, I.P.; Marling, J.B.

    1980-11-06

    The laboratory facility for photochemical tritium separation research has been completed. Methods for synthesizing the mono-tritiated halogenated methanes have been developed. Notably, CTF/sub 3/ has been synthesized and spectrally analyzed. The CTF/sub 3/ vibrational frequencies are found to be in quite good agreement with earlier calculations.

  18. Susceptibility of Diabetic Rats to Pulmonary and Systemic Effects of Inhaled Photochemically-Aged Atmosphere and Ozone (O3)

    Science.gov (United States)

    Susceptibility of Diabetic Rats to Pulmonary and Systemic Effects of Inhaled Photochemically-Aged Atmosphere and Ozone (O3)MC Schladweiler1, SJ Snow2, QT Krantz1, C King1, JD Krug2, N Modak2, A Henriquez3, V Bass4, DJ Miller3, JE Richards1, EH Boykin1, R Jaskot1, MI Gilmour1 and ...

  19. Photochemical induced growth and aggregation of metal nanoparticles in diode-array spectrophotometer via excited dimethyl-sulfoxide.

    Science.gov (United States)

    Zidki, Tomer; Cohen, Haim; Meyerstein, Dan

    2010-10-21

    Ag(0) and Au(0) nanoparticles suspended in dilute aqueous solutions containing (CH(3))(2)SO are photochemically unstable. The light source of a diode-array spectrophotometer induces, within less than a minute, particle growth and aggregation. The results indicate that this process is triggered by UV light absorption by the (CH(3))(2)SO.

  20. The effect of photochemical internalization of bleomycin in the treatment of urothelial carcinoma of the bladder: an in vitro study

    NARCIS (Netherlands)

    Arentsen, H.C.; Falke, J.; Høgset, A.; Oosterwijk, E.; Witjes, J.A.

    2014-01-01

    OBJECTIVES: In this in vitro study, we determined whether meso-tetraphenyl chlorin disulphonate (TPCS2a)-based photochemical delivery of bleomycin was able to potentiate the cytotoxicity of bleomycin on bladder cancer cells. MATERIALS AND METHODS: The human RT4, RT112, 253J, T24, and rat AY-27

  1. Synthesis and photochemical applications of processable polymers enclosing photoluminescent carbon quantum dots.

    Science.gov (United States)

    Mosconi, Dario; Mazzier, Daniela; Silvestrini, Simone; Privitera, Alberto; Marega, Carla; Franco, Lorenzo; Moretto, Alessandro

    2015-04-28

    Herein, we propose convenient routes to produce hybrid-polymers that covalently enclosed, or confined, N-doped carbon quantum dots (CQDs). We focus our attention on polyamide, polyurea-urethane, polyester, and polymethylmetacrylate polymers, some of the most common resources used to create everyday materials. These hybrid materials can be easily prepared and processed to obtain macroscopic objects of different shapes, i.e., fibers, transparent sheets, and bulky forms, where the characteristic luminescence properties of the native N-doped CQDs are preserved. More importantly we explore the potential use of these hybrid composites to achieve photochemical reactions as those of photoreduction of silver ions to silver nanoparticles (under UV-light), the selective photo-oxidation of benzylalcohol to the benzaldehyde (under vis-light), and the photocatalytic generation of H2 (under UV-light).

  2. Drop-photochemical deposition of aluminum oxide thin films from aqueous solutions

    Science.gov (United States)

    Sato, Shunta; Ichimura, Masaya

    2017-04-01

    Aluminum oxide thin films were deposited onto fluorine-doped tin oxide-coated glass by drop photochemical deposition for the first time. The deposition solution was deionized water containing aluminum sulfate and sodium thiosulfate. Small amount of the solution was dropped on the substrate and irradiated with UV light. The solution was replaced with new one after 5 min irradiation, and the process was repeated 10 times. A film was not deposited without thiosulfate ions in the solution. The deposited films were transparent, and their band gap was larger than 4 eV. The O/Al composition ratio was about 1.2, smaller than the stoichiometric ratio 1.5.

  3. Processing Binary and Fuzzy Logic by Chaotic Time Series Generated by a Hydrodynamic Photochemical Oscillator.

    Science.gov (United States)

    Gentili, Pier Luigi; Giubila, Maria Sole; Heron, B Mark

    2017-07-05

    This work demonstrates the computational power of a hydrodynamic photochemical oscillator based on a photochromic naphthopyran generating aperiodic time series. The chaotic character of the time series is tested by calculating its largest Lyapunov exponent and the correlation dimension of its attractor after building its phase space through the Takens' theorem. Then, the chaotic dynamic is shown to be suitable to implement all the fundamental Boolean two-inputs-one-output logic gates. Finally, the strategy to implement fuzzy logic systems (FLSs) based on the time series is described. Such FLSs promise to be useful in the field of computational linguistics, which is concerned with the development of artificial intelligent systems able to transform collections of numerical data into natural language texts. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. The Photochemical Branching Ratio in 1,6-Dinitropyrene Depends on the Excitation Energy.

    Science.gov (United States)

    Brister, Matthew M; Piñero-Santiago, Luis E; Morel, María; Arce, Rafael; Crespo-Hernández, Carlos E

    2016-12-15

    Nitropolycyclic aromatic hydrocarbons constitute one of the most disconcerting classes of pollutants. Photochemical degradation is thought to be a primary mode of their natural removal from the environment, but the microscopic mechanism leading to product formation as a function of excitation wavelength is poorly understood. In this Letter, it is revealed that excitation of 1,6-dinitropyrene with 425, 415, or 340 nm radiation leads to an increasing amount of radical production through photodissociation at the expense of triplet-state population-the two primary reaction pathways in this class of pollutants. Radical formation requires overcoming an energy barrier in the excited singlet manifold. This activation energy explains the large fraction of the initial singlet-state population that intersystem crosses to a doorway triplet state, instead of leading overwhelmingly to photodissociation. The unforeseen excitation wavelength dependence of this branching process is expected to regulate the photochemistry of 1,6-dinitropyrene and possibly of other nitroaromatic pollutants in the environment.

  5. Properties of gas sensors based on photochemically deposited nano- crystalline SnO{sub 2} films

    Energy Technology Data Exchange (ETDEWEB)

    Ichimura, Masaya; Baoleer, Aodeng; Sueyoshi, Tetsuya [Department of Engineering Physics, Electronics and Mechanics, Nagoya Institute of Technology, Gokiso, Showa, Nagoya 466-8555 (Japan)

    2010-04-15

    We fabricated highly sensitive room temperature hydrogen sensors based on SnO{sub 2} films. The films were deposited by the photochemical deposition. A solution containing SnSO{sub 4} with its pH adjusted to about 1.4 by HNO{sub 3} were dropped onto the glass substrate and irradiated with the UV light. After 5min irradiation, the substrate was washed with water and dried before dropping the new solution. The films were fabricated by repeating this process. The sample annealed at 200 C showed current increase by a factor >10{sup 4} within 1 min for 5000 ppm hydrogen at room temperature. The removal of hydrogen from the ambient caused only a small decrease in the current, but the current decreased by more than three order of magnitude almost instantly upon subsequent exposure to air. (copyright 2010 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  6. Photochemical deposition of FeS{sub x}O{sub y}

    Energy Technology Data Exchange (ETDEWEB)

    Dizaji, Hamid Rezagholipour [Department of Engineering Physics, Electronics and Mechanics, Nagoya Institute of Technology, Gokiso, Showa, Nagoya 466-8555 (Japan); Ichimura, Masaya [Department of Engineering Physics, Electronics and Mechanics, Nagoya Institute of Technology, Gokiso, Showa, Nagoya 466-8555 (Japan)], E-mail: ichimura.masaya@nitech.ac.jp

    2009-02-25

    FeS{sub x}O{sub y} thin films were deposited on indium-tin-coated glass substrates using the photochemical deposition technique from an aqueous solution containing FeSO{sub 4} and Na{sub 2}S{sub 2}O{sub 3}. The experiments were performed at room temperature with and without Fe powder attached on the substrate. A very thin film with S-rich composition was obtained without Fe powder. With Fe powder adhered on the substrate, Fe- and O-rich black films with a thickness larger than 1 {mu}m were obtained. From the photoelectrochemical measurement, the deposited FeS{sub x}O{sub y} film showed n-type conduction and photoconductivity.

  7. Photochemical and Photophysical Properties of Phthalocyanines Modified with Optically Active Alcohols

    Directory of Open Access Journals (Sweden)

    Aline A. Ramos

    2015-07-01

    Full Text Available Three phthalocyanine derivatives were synthesized and characterized: one modified with a racemic mixture of 1-(4-bromophenylethanol and two other macrocycles modified with each one of the enantioenriched isomers (R-1-(4-bromophenylethanol and (S-1-(4-bromophenylethanol. The compounds were characterized by 1H-NMR spectroscopy, mass spectrometry, UV-Vis absorption, and excitation and emission spectra. Additionally, partition coefficient values and the quantum yield of the generation of oxygen reactive species were determined. Interestingly, the phthalocyanine containing a (R-1-(4-bromophenylethoxy moiety showed higher quantum yield of reactive oxygen species generation than other compounds under the same conditions. In addition, the obtained fluorescence microscopy and cell viability results have shown that these phthalocyanines have different interactions with mammary MCF-7 cells. Therefore, our results indicate that the photochemical and biological properties of phthalocyanines with chiral ligands should be evaluated separately for each enantiomeric species.

  8. CALGRID Photochemical Modeling of Air Quality Impacts of Alternative Transportation Fuel Use in Los Angeles

    Energy Technology Data Exchange (ETDEWEB)

    Moore, G. E.; Londergan, R. J.; Fernau, M. E.

    1998-11-19

    The National Renewable Energy Laboratory has been conducting a comprehensive program to quantify and assess the air quality impacts of the emissions of ozone precursors, air toxins, and greenhouse gases from alternative fuel vehicles. This program includes both an emissions estimation component and a photochemical modeling component to study three fuels: reformulated gasoline, compressed natural gas, and 85% methanol (M85). This report describes the use of the CALGRID model in the Los Angeles modeling domain using the State-Wide Air Pollution Research Center (SAPRC90) chemical mechanism and an early version of the SAPRC93 mechanism. A variety of conclusions can be drawn from the results of this study, including results from chemical mechanism testing; development of meteorological inputs; model evaluation and comparison; and the analyses of the impacts of the emissions scenarios. The report summarizes the study's major findings in these areas.

  9. An Improved Fast Photochemical Oxidation of Proteins (FPOP) Platform for Protein Therapeutics

    Science.gov (United States)

    Zhang, Ying; Rempel, Don L.; Zhang, Hao; Gross, Michael L.

    2015-03-01

    Unlike small-molecule drugs, the size and dynamics of protein therapeutics challenge existing methods for assessing their high order structures (HOS). To extend fast photochemical oxidation of proteins (FPOP) to protein therapeutics, we modified its platform by introducing a mixing step prior to laser irradiation to minimize unwanted H2O2-induced oxidation. This improvement plus standardizing each step yield better reproducibility as determined by a fitting process whereby we used a non-FPOP spectrum as a template to report the unmodified level. We also tested different buffer systems for this modified FPOP platform with cytochrome c. The outcome is a standard oxidation profile that can be compared between different laboratories and regulatory agencies that wish to adopt FPOP for quality control purposes.

  10. From small aromatic molecules to functional nanostructured carbon by pulsed laser-induced photochemical stitching

    Directory of Open Access Journals (Sweden)

    R. R. Gokhale

    2012-06-01

    Full Text Available A novel route employing UV laser pulses (KrF Excimer, 248 nm to cleave small aromatic molecules and stitch the generated free radicals into functional nanostructured forms of carbon is introduced. The process differs distinctly from any strategies wherein the aromatic rings are broken in the primary process. It is demonstrated that this pulsed laser-induced photochemical stitching (PLPS process when applied to routine laboratory solvents (or toxic chemical wastes when discarded Chlorobenzene and o-Dichlorobenzene yields Carbon Nanospheres (CNSs comprising of graphene-like sheets assembled in onion-like configurations. This room temperature process implemented under normal laboratory conditions is versatile and clearly applicable to the whole family of haloaromatic compounds without and with additions of precursors or other nanomaterials. We further bring out its applicability for synthesis of metal-oxide based carbon nanocomposites.

  11. Multiple Enone-Directed Reactivity Modes Lead to the Selective Photochemical Fluorination of Polycyclic Terpenoid Derivatives.

    Science.gov (United States)

    Pitts, Cody Ross; Bume, Desta Doro; Harry, Stefan Andrew; Siegler, Maxime A; Lectka, Thomas

    2017-02-15

    In the realm of aliphatic fluorination, the problem of reactivity has been very successfully addressed in recent years. In contrast, the associated problem of selectivity, that is, directing fluorination to specific sites in complex molecules, remains a great, fundamental challenge. In this report, we show that the enone functional group, upon photoexcitation, provides a solution. Based solely on orientation of the oxygen atom, site-selective photochemical fluorination is achieved on steroids and bioactive polycycles with up to 65 different sp(3) C-H bonds. We have also found that γ-, β-, homoallylic, and allylic fluorination are all possible and predictable through the theoretical modes reported herein. Lastly, we present a preliminary mechanistic hypothesis characterized by intramolecular hydrogen atom transfer, radical fluorination, and ultimate restoration of the enone. In all, these results provide a leap forward in the design of selective fluorination of complex substrates that should be relevant to drug discovery, where fluorine plays a prominent role.

  12. Fabrication of gallium nitride nanowires by metal-assisted photochemical etching

    Science.gov (United States)

    Zhang, Miao-Rong; Jiang, Qing-Mei; Zhang, Shao-Hui; Wang, Zu-Gang; Hou, Fei; Pan, Ge-Bo

    2017-11-01

    Gallium nitride (GaN) nanowires (NWs) were fabricated by metal-assisted photochemical etching (MaPEtch). Gold nanoparticles (AuNPs) as metal catalyst were electrodeposited on the GaN substrate. SEM and HRTEM images show the surface of GaN NWs is smooth and clean without any impurity. SAED and FFT patterns demonstrate GaN NWs have single crystal structure, and the crystallographic orientation of GaN NWs is (0002) face. On the basis of the assumption of localized galvanic cells, combined with the energy levels and electrochemical potentials of reactants in this etching system, the generation, transfer and consumption of electron-hole pairs reveal the whole MaPEtch reaction process. Such easily fabricated GaN NWs have great potential for the assembly of GaN-based single-nanowire nanodevices.

  13. Gas chromatography-mass spectrometric identification of iodine species arising from photo-chemical vapor generation

    Energy Technology Data Exchange (ETDEWEB)

    Grinberg, Patricia; Mester, Zoltan [Institute for National Measurements Standards, National Research Council Canada, Ottawa, Ontario, K1A 0R6 (Canada); D' Ulivo, Alessandro [Institute for Chemical and Physical Processes, National Research Council, Via G. Moruzzi 1, Pisa, 56124 (Italy); Sturgeon, Ralph E. [Institute for National Measurements Standards, National Research Council Canada, Ottawa, Ontario, K1A 0R6 (Canada)], E-mail: ralph.sturgeon@nrc.ca

    2009-07-15

    Ultraviolet irradiation of aqueous solutions of iodide/iodate ion containing low molecular weight organic acids generates volatile iodine species that are amenable to detection by atomic spectrometry. In the presence of formic, acetic or propionic acids, photo-chemical generation results in the formation of HI, methyl- and ethyl-iodide respectively, the latter two products being directly identified by gas chromatography-mass spectrometry. Deuterium and {sup 13}C-labeled reagents were employed to elucidate the provenance of the alkyl group. Use of {sup 13}CH{sub 3}-COOH produced {sup 13}CH{sub 3}-I; deuterated acetic acid (D{sub 3}C-COOD) resulted in the formation of CD{sub 3}-I. These observations indicate direct transfer of the alkyl group from the carboxylic acid to iodide, consistent with the suggestion that the mechanism of synthesis involves radical induced reactions.

  14. Gas chromatography-mass spectrometric identification of iodine species arising from photo-chemical vapor generation

    Science.gov (United States)

    Grinberg, Patricia; Mester, Zoltan; D'Ulivo, Alessandro; Sturgeon, Ralph E.

    2009-07-01

    Ultraviolet irradiation of aqueous solutions of iodide/iodate ion containing low molecular weight organic acids generates volatile iodine species that are amenable to detection by atomic spectrometry. In the presence of formic, acetic or propionic acids, photo-chemical generation results in the formation of HI, methyl- and ethyl-iodide respectively, the latter two products being directly identified by gas chromatography-mass spectrometry. Deuterium and 13C-labeled reagents were employed to elucidate the provenance of the alkyl group. Use of 13CH 3-COOH produced 13CH 3-I; deuterated acetic acid (D 3C-COOD) resulted in the formation of CD 3-I. These observations indicate direct transfer of the alkyl group from the carboxylic acid to iodide, consistent with the suggestion that the mechanism of synthesis involves radical induced reactions.

  15. Synthesis and Photochemical Properties of 2,3;5,6-bis(cyclohexano)-BODIPY.

    Science.gov (United States)

    Kritskaya, Anna Yu; Bumagina, Natalia A; Antina, Elena V; Ksenofontov, Alexander A; Berezin, Mikhail B; Semeikin, Alexander S

    2017-12-27

    The boron-dipyrromethene (BODIPY) dye containing an annelated cyclohexyl rings at the 2,3 and 5,6-positions of pyrroles has been synthesized and characterized. Photochemical properties of the obtained compound have been investigated in different individual solvents. 2,3;5,6-Bis(cyclohexano)-BODIPY exhibits intense chromophore properties with maximum of S o → S 1 band in the 543-549 nm (A from 66000 to 96000 L/mol·cm). The complex is a fluorophore with a quantum yield up to ~ 100%. The influence of solvent polarity on the spectral properties was evaluated. To better understand the spectroscopic results, quantum chemical calculations were carried out. Photostability of dye was studied.Graphical Abstract.

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

    Directory of Open Access Journals (Sweden)

    Jaroslav Mosnáček

    2014-11-01

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

  17. Protein Footprinting by Carbenes on a Fast Photochemical Oxidation of Proteins (FPOP) Platform

    Science.gov (United States)

    Zhang, Bojie; Rempel, Don L.; Gross, Michael L.

    2016-03-01

    Protein footprinting combined with mass spectrometry provides a method to study protein structures and interactions. To improve further current protein footprinting methods, we adapted the fast photochemical oxidation of proteins (FPOP) platform to utilize carbenes as the footprinting reagent. A Nd-YAG laser provides 355 nm laser for carbene generation in situ from photoleucine as the carbene precursor in a flow system with calmodulin as the test protein. Reversed-phase liquid chromatography coupled with mass spectrometry is appropriate to analyze the modifications produced in this footprinting. By comparing the modification extent of apo and holo calmodulin on the peptide level, we can resolve different structural domains of the protein. Carbene footprinting in a flow system is promising.

  18. Tuning the Photoluminescence of Graphene Quantum Dots by Photochemical Doping with Nitrogen.

    Science.gov (United States)

    Xu, Xiaofen; Gao, Fuhua; Bai, Xiaohua; Liu, Fuchi; Kong, Wenjie; Li, Ming

    2017-11-20

    Nitrogen-doped graphene quantum dots (NGQDs) were synthesized by irradiating graphene quantum dots (GQDs) in an NH₃ atmosphere. The photoluminescence (PL) properties of the GQDs and the NGQDs samples were investigated. Compared with GQDs, a clear PL blue-shift of NGQDs could be achieved by regulating the irradiating time. The NGQDs obtained by irradiation of GQDs for 70 min had a high N content of 15.34 at % and a PL blue-shift of about 47 nm. This may be due to the fact that photochemical doping of GQDs with nitrogen can significantly enhance the contents of pyridine-like nitrogen, and also effectively decrease the contents of oxygen functional groups of NGQDs, thus leading to the observed obvious PL blue-shift.

  19. Tuning the Photoluminescence of Graphene Quantum Dots by Photochemical Doping with Nitrogen

    Directory of Open Access Journals (Sweden)

    Xiaofen Xu

    2017-11-01

    Full Text Available Nitrogen-doped graphene quantum dots (NGQDs were synthesized by irradiating graphene quantum dots (GQDs in an NH3 atmosphere. The photoluminescence (PL properties of the GQDs and the NGQDs samples were investigated. Compared with GQDs, a clear PL blue-shift of NGQDs could be achieved by regulating the irradiating time. The NGQDs obtained by irradiation of GQDs for 70 min had a high N content of 15.34 at % and a PL blue-shift of about 47 nm. This may be due to the fact that photochemical doping of GQDs with nitrogen can significantly enhance the contents of pyridine-like nitrogen, and also effectively decrease the contents of oxygen functional groups of NGQDs, thus leading to the observed obvious PL blue-shift.

  20. Light-induced changes in bottled white wine and underlying photochemical mechanisms.

    Science.gov (United States)

    Grant-Preece, Paris; Barril, Celia; Schmidtke, Leigh M; Scollary, Geoffrey R; Clark, Andrew C

    2017-03-04

    Bottled white wine may be exposed to UV-visible light for considerable periods of time before it is consumed. Light exposure may induce an off-flavor known as "sunlight" flavor, bleach the color of the wine, and/or increase browning and deplete sulfur dioxide. The changes that occur in bottled white wine exposed to light depend on the wine composition, the irradiation conditions, and the light exposure time. The light-induced changes in the aroma, volatile composition, color, and concentrations of oxygen and sulfur dioxide in bottled white wine are reviewed. In addition, the photochemical reactions thought to have a role in these changes are described. These include the riboflavin-sensitized oxidation of methionine, resulting in the formation of methanethiol and dimethyl disulfide, and the photodegradation of iron(III) tartrate, which gives rise to glyoxylic acid, an aldehyde known to react with flavan-3-ols to form yellow xanthylium cation pigments.

  1. Disulfur dioxide and its NUV absorption in the photochemical model of Venus atmosphere

    Science.gov (United States)

    Krasnopolsky, V.

    2017-09-01

    The Venus photochemical model (Krasnopolsky 2012) is updated by the data on S2O2 formation and photolysis (Frandsen et al. 2016) and improved densities of H2O, OCS, and H2 at 47 km (Krasnopolsky 2013). The basic model and four versions with small deviations in eddy diffusion and SO2 at 47 km are presented and agree with the observed variations of CO, H2O, SO2, SO, and OCS. Three methods are used to evaluate S2O2 abundance sufficient for the NUV absorption, and the required S2O2 exceeds the model prediction by a factor of 200. The SO profile by Na et al. (1994) with 12 ppb at 64-95 km significantly exceeds the model below 74 km. If SO ≈ 12 ppb at 64 km, then S2O2 contributes to but does not completely explain the NUV absorption.

  2. An ecological new approach for treating Cr(VI)-containing industrial wastewater: Photochemical reduction.

    Science.gov (United States)

    Liu, Jie; Huang, Kun; Xie, Keng; Yang, Ying; Liu, Huizhou

    2016-04-15

    An ecological new approach for photochemical reduction of Cr(VI) in aqueous solution by adding into water-soluble copolymer, polyethylene glycol (PEG), was investigated. Various influences including light intensity, initial solution pH value, PEG molecular weight and initial concentration ratio of PEG to Cr(VI) on photochemical reduction of Cr(VI) were discussed, and a possible reaction mechanism was proposed. Experimental results revealed that Cr(VI) could be reduced to Cr(III) by PEG under sunlight irradiation. The photo-reduction rate of Cr(VI) increased with the decrease of solution pH and PEG molecular weight, but increased with the light intensity. The reduction percentage of Cr(VI) increased with the initial concentration ratio of PEG to Cr(VI). When the initial solution pH value was below 3.0, almost all of Cr(VI) was completely reduced to Cr(III) within 20 min of 50 × 10(3) lux solar irradiation in the presence of PEG. After photo-reduction, PEG and Cr(III) in aqueous solutions could be recovered by adding into a high-concentrated Na2SO4 aqueous solution to induce the formation of a stable PEG-based aqueous biphasic system. By doing so, Na2SO4 in aqueous solution could also be removed. The present work highlights a promising new route for treating the industrial wastewater containing toxic Cr(VI) ions by adding into environmental-friendly PEG for photo-reduction of Cr(VI) to Cr(III), and then salting-out recovery of PEG and removal of Cr(III) in wastewater by adding into another high-salt wastewater, so that the high-salt wastewater could also be treated. Copyright © 2016 Elsevier Ltd. All rights reserved.

  3. Photochemical processing of aldrin and dieldrin in frozen aqueous solutions under arctic field conditions

    Energy Technology Data Exchange (ETDEWEB)

    Rowland, Glenn A.; Bausch, Alexandra R. [Department of Chemistry, Villanova University, Villanova, PA 19085 (United States); Grannas, Amanda M., E-mail: amanda.grannas@villanova.edu [Department of Chemistry, Villanova University, Villanova, PA 19085 (United States)

    2011-05-15

    Organochlorine (OC) contaminants are transported to the Polar Regions, where they have the potential to bioaccumulate, presenting a threat to the health of wildlife and indigenous communities. They deposit onto snowpack during winter, and accumulate until spring, when they experience prolonged solar irradiation until snowmelt occurs. Photochemical degradation rates for aldrin and dieldrin, in frozen aqueous solution made from MilliQ water, 500 {mu}M hydrogen peroxide solution or locally-collected melted snow were measured in a field campaign near Barrow, AK, during spring-summer 2008. Significant photoprocessing of both pesticides occurs; the reactions depend on temperature, depth within the snowpack and whether the predominant phase is ice or liquid water. The effect of species present in natural snowpack is comparable to 500 {mu}M hydrogen peroxide, pointing to the potential significance of snowpack-mediated reactions. Aldrin samples frozen at near 0 deg. C were more reactive than comparable liquid samples, implying that the microenvironments experienced on frozen ice surfaces are an important consideration. - Highlights: > Photodegradation rates for aldrin and dieldrin in frozen aqueous solutions made from MilliQ water, H{sub 2}O{sub 2} or melted snow are reported. > Photoprocessing depends on temperature, depth beneath the snowpack surface and dominant phase. > Species present in natural snowpack have a photosensitizing effect comparable to 500 {mu}M H{sub 2}O{sub 2}. > Aldrin samples frozen at near 0 deg. C were more reactive than comparable liquid samples. > Collectively we find that frozen aqueous surfaces play a unique role in aldrin and dieldrin photochemistry. - A field study finds that frozen aqueous solutions of aldrin and dieldrin undergo photochemical degradation under arctic snowpack conditions. The reactions are enhanced in frozen systems and by natural snowpack constituents.

  4. Sources and Potential Photochemical Roles of Formaldehyde in an Urban Atmosphere in South China

    Science.gov (United States)

    Wang, Chuan; Huang, Xiao-Feng; Han, Yu; Zhu, Bo; He, Ling-Yan

    2017-11-01

    Formaldehyde (HCHO) is an important intermediate in tropospheric photochemistry. However, study of its evolution characteristics under heavy pollution conditions in China is limited, especially for high temporal resolutions, making it difficult to analyze its sources and environmental impacts. In this study, ambient levels of HCHO were monitored using a proton-transfer reaction mass spectrometer at an urban site in the Pearl River Delta of China. Continuous monitoring campaigns were conducted in the spring, summer, fall, and winter in 2016. The highest averaged HCHO concentrations were observed in autumn (5.1 ± 3.1 ppbv) and summer (5.0 ± 4.4 ppbv), followed by winter (4.2 ± 2.2 ppbv) and spring (3.4 ± 1.6 ppbv). The daily maximum of HCHO occurs in the early afternoon and shows good correlations with O3 and the secondary organic aerosol tracer during the day, revealing close relationships between ambient HCHO and secondary formations in Shenzhen, especially in summer and autumn. The daytime HCHO is estimated to be the major contributor to O3 formation and OH radical production, indicating that HCHO plays a key role in the urban atmospheric photochemical reactions. Anthropogenic secondary formation was calculated to be the dominant source of HCHO using a photochemical age-based parameterization method, with an average proportion of 39%. The contributions of biogenic sources in summer (41%) and autumn (39%) are much higher than those in spring (26%) and winter (28%), while the contributions of anthropogenic primary sources in spring (20%) and winter (18%) are twice those in summer (9%) and autumn (9%).

  5. The Photochemical Oxidation of Siderite That Drove Hydrogen Based Microbial Redox Reactions in The Archean Biosphere

    Science.gov (United States)

    Kim, J. D.; Yee, N.; Falkowski, P. G.

    2012-12-01

    Hydrogen is the most abundant element in the universe and molecular hydrogen (H2) is a rich source of electron in a mildly reducing environment for microbial redox reactions, such as anoxygenic photosynthesis and methanogenesis. Subaerial volcanoes, ocean crust serpentinization and mid-ocean ridge volcanoes have been believed to be the major source of the hydrogen flux to the atmosphere. Although ferrous ion (Fe2+) photooxidation has been proposed as an alternative mechanism by which hydrogen gas was produced, ferruginous water in contact with a CO2-bearing atmosphere is supersaturated with respect to FeCO3 (siderite), thus the precipitation of siderite would have been thermodynamically favored in the Archean environment. Siderite is the critical mineral component of the oldest fossilized microbial mat. It has also been inferred as a component of chemical sedimentary protolith in the >3750 Ma Nuvvuagittuq supracrustal belt, Canada and the presence of siderite in the protolith suggests the occurrence of siderite extends to Hadean time. Analyses of photooxidation of siderite suggest a significant flux of hydrogen in the early atmosphere. Our estimate of the hydrogen production rate under Archean solar flux is approximately 50 times greater than the estimated hydrogen production rate by the volcanic activity based on a previous report (Tian et al. Science 2005). Our analyses on siderite photooxidation also suggest a mechanism by which banded iron formation (BIF) was formed. The photooxidation transforms siderite to magnetite/maghemite (spinnel iron oxide), while oxygenic oxidation of siderite leads to goethite, and subsequently to hematite (Fe3+2O3) upon dehydration. We will discuss the photochemical reaction, which was once one of the most ubiquitous photochemical reactions before the rise of oxygen in the atmosphere. Photooxidation of siderite over time by UV light From left to right: UV oxidized siderite, pristine siderite, oxidized siderite by oxygen

  6. Persistence and photochemical decay of springtime total ozone anomalies in the Canadian Middle Atmosphere Model

    Directory of Open Access Journals (Sweden)

    S. Tegtmeier

    2007-01-01

    Full Text Available The persistence and decay of springtime total ozone anomalies over the entire extratropics (midlatitudes plus polar regions is analysed using results from the Canadian Middle Atmosphere Model (CMAM, a comprehensive chemistry-climate model. As in the observations, interannual anomalies established through winter and spring persist with very high correlation coefficients (above 0.8 through summer until early autumn, while decaying in amplitude as a result of photochemical relaxation in the quiescent summertime stratosphere. The persistence and decay of the ozone anomalies in CMAM agrees extremely well with observations, even in the southern hemisphere when the model is run without heterogeneous chemistry (in which case there is no ozone hole and the seasonal cycle of ozone is quite different from observations. However in a version of CMAM with strong vertical diffusion, the northern hemisphere anomalies decay far too rapidly compared to observations. This shows that ozone anomaly persistence and decay does not depend on how the springtime anomalies are created or on their magnitude, but reflects the transport and photochemical decay in the model. The seasonality of the long-term trends over the entire extratropics is found to be explained by the persistence of the interannual anomalies, as in the observations, demonstrating that summertime ozone trends reflect winter/spring trends rather than any change in summertime ozone chemistry. However this mechanism fails in the northern hemisphere midlatitudes because of the relatively large impact, compared to observations, of the CMAM polar anomalies. As in the southern hemisphere, the influence of polar ozone loss in CMAM increases the midlatitude summertime loss, leading to a relatively weak seasonal dependence of ozone loss in the Northern Hemisphere compared to the observations.

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

    Science.gov (United States)

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

    2013-12-01

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

  8. Photochemical CVD of Ru on functionalized self-assembled monolayers from organometallic precursors

    Science.gov (United States)

    Johnson, Kelsea R.; Arevalo Rodriguez, Paul; Brewer, Christopher R.; Brannaka, Joseph A.; Shi, Zhiwei; Yang, Jing; Salazar, Bryan; McElwee-White, Lisa; Walker, Amy V.

    2017-02-01

    Chemical vapor deposition (CVD) is an attractive technique for the metallization of organic thin films because it is selective and the thickness of the deposited film can easily be controlled. However, thermal CVD processes often require high temperatures which are generally incompatible with organic films. In this paper, we perform proof-of-concept studies of photochemical CVD to metallize organic thin films. In this method, a precursor undergoes photolytic decomposition to generate thermally labile intermediates prior to adsorption on the sample. Three readily available Ru precursors, CpRu(CO)2Me, (η3-allyl)Ru(CO)3Br, and (COT)Ru(CO)3, were employed to investigate the role of precursor quantum yield, ligand chemistry, and the Ru oxidation state on the deposition. To investigate the role of the substrate chemistry on deposition, carboxylic acid-, hydroxyl-, and methyl-terminated self-assembled monolayers were used. The data indicate that moderate quantum yields for ligand loss (φ ≥ 0.4) are required for ruthenium deposition, and the deposition is wavelength dependent. Second, anionic polyhapto ligands such as cyclopentadienyl and allyl are more difficult to remove than carbonyls, halides, and alkyls. Third, in contrast to the atomic layer deposition, acid-base reactions between the precursor and the substrate are more effective for deposition than nucleophilic reactions. Finally, the data suggest that selective deposition can be achieved on organic thin films by judicious choice of precursor and functional groups present on the substrate. These studies thus provide guidelines for the rational design of new precursors specifically for selective photochemical CVD on organic substrates.

  9. Chemical composition and photochemical reactivity of exhaust from aircraft turbine engines

    Directory of Open Access Journals (Sweden)

    T. F. Lyon

    Full Text Available Assessment of the environmental impact of aircraft emissions is required by planners and policy makers. Seveal areas of concern are: 1. exposure of airport workers and urban residents to toxic chemicals emitted when the engines operate at low power (idle and taxi on the ground; 2. contributions to urban photochemical air pollution of aircraft volatile organic and nitrogen oxides emissions from operations around airports; and 3. emissions of nitrogen oxides and particles during high-altitude operation. The environmental impact of chemicals emitted from jet aircraft turbine engines has not been firmly established due to lack of data regarding emission rates and identities of the compounds emitted. This paper describes an experimental study of two different aircraft turbine engines designed to determine detailed organic emissions, as well as emissions of inorganic gases. Emissions were measured at several engine power settings. Measurements were made of detailed organic composition from C1 through C17, CO, CO2, NO, NOx, and polycyclic aromatic hydrocarbons. Measurements were made using a multi-port sampling pro be positioned directly behind the engine in the exhaust exit plane. The emission measurements have been used to determine the organic distribution by carbon number and the distribution by compound class at each engine power level. The sum of the organic species was compared with an independent measurement of total organic carbon to assess the carbon mass balance. A portion of the exhaust was captured and irradiated in outdoor smog chambers to assess the photochemical reactivity of the emissions with respect to ozone formation. The reactivity of emissions from the two engines was apportioned by chemical compound class.

  10. Chemical composition and photochemical reactivity of exhaust from aircraft turbine engines

    Directory of Open Access Journals (Sweden)

    C. W. Spicer

    1994-08-01

    Full Text Available Assessment of the environmental impact of aircraft emissions is required by planners and policy makers. Seveal areas of concern are: 1. exposure of airport workers and urban residents to toxic chemicals emitted when the engines operate at low power (idle and taxi on the ground; 2. contributions to urban photochemical air pollution of aircraft volatile organic and nitrogen oxides emissions from operations around airports; and 3. emissions of nitrogen oxides and particles during high-altitude operation. The environmental impact of chemicals emitted from jet aircraft turbine engines has not been firmly established due to lack of data regarding emission rates and identities of the compounds emitted. This paper describes an experimental study of two different aircraft turbine engines designed to determine detailed organic emissions, as well as emissions of inorganic gases. Emissions were measured at several engine power settings. Measurements were made of detailed organic composition from C1 through C17, CO, CO2, NO, NOx, and polycyclic aromatic hydrocarbons. Measurements were made using a multi-port sampling pro be positioned directly behind the engine in the exhaust exit plane. The emission measurements have been used to determine the organic distribution by carbon number and the distribution by compound class at each engine power level. The sum of the organic species was compared with an independent measurement of total organic carbon to assess the carbon mass balance. A portion of the exhaust was captured and irradiated in outdoor smog chambers to assess the photochemical reactivity of the emissions with respect to ozone formation. The reactivity of emissions from the two engines was apportioned by chemical compound class.

  11. Understanding the Atmosphere of 51 Eri b: Do Photochemical Hazes Cloud the Planets Spectrum?

    Science.gov (United States)

    Marley, Mark Scott; Zahnle, Kevin; Moses, J.; Morley, C.

    2015-01-01

    The first young giant planet to be discovered by the Gemini Planet Imager was the (is) approximately 2MJ planet 51 Eri b. This approximately 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. However for an object as cool as 700 K, the origin of the cloud coverage is somewhat puzzling, as the global silicate and iron clouds would be expected to have sunk well below the photosphere by this effective temperature. While strong vertical mixing in these low gravity atmospheres remains a plausible 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. 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.

  12. The susceptibility of the retina to photochemical damage from visible light.

    Science.gov (United States)

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

    2012-01-01

    The photoreceptor/RPE complex must maintain a delicate balance between maximizing the absorption of photons for vision and retinal image quality while simultaneously minimizing the risk of photodamage when exposed to bright light. We review the recent discovery of two new effects of light exposure on the photoreceptor/RPE complex in the context of current thinking about the causes of retinal phototoxicity. These effects are autofluorescence photobleaching in which exposure to bright light reduces lipofuscin autofluorescence and, at higher light levels, RPE disruption in which the pattern of autofluorescence is permanently altered following light exposure. Both effects occur following exposure to visible light at irradiances that were previously thought to be safe. Photopigment, retinoids involved in the visual cycle, and bisretinoids in lipofuscin have been implicated as possible photosensitizers for photochemical damage. The mechanism of RPE disruption may follow either of these paths. On the other hand, autofluorescence photobleaching is likely an indicator of photooxidation of lipofuscin. The permanent changes inherent in RPE disruption might require modification of the light safety standards. AF photobleaching recovers after several hours although the mechanisms by which this occurs are not yet clear. Understanding the mechanisms of phototoxicity is all the more important given the potential for increased susceptibility in the presence of ocular diseases that affect either the visual cycle and/or lipofuscin accumulation. In addition, knowledge of photochemical mechanisms can improve our understanding of some disease processes that may be influenced by light exposure, such as some forms of Leber's congenital amaurosis, and aid in the development of new therapies. Such treatment prior to intentional light exposures, as in ophthalmic examinations or surgeries, could provide an effective preventative strategy. Copyright © 2011 Elsevier Ltd. All rights reserved.

  13. Photochemical degradation of atenolol, carbamazepine, meprobamate, phenytoin and primidone in wastewater effluents

    Energy Technology Data Exchange (ETDEWEB)

    Dong, Mei Mei [Civil, Environmental and Architectural Engineering, 428 UCB, University of Colorado, Boulder, CO 80309 (United States); Southern Nevada Water Authority (SNWA), P.O. Box 99954, Las Vegas, NV 89193-9954 (United States); Trenholm, Rebecca [Southern Nevada Water Authority (SNWA), P.O. Box 99954, Las Vegas, NV 89193-9954 (United States); Rosario-Ortiz, Fernando L., E-mail: Fernando.rosario@colorado.edu [Civil, Environmental and Architectural Engineering, 428 UCB, University of Colorado, Boulder, CO 80309 (United States)

    2015-01-23

    Highlights: • The photochemical degradation of 5 compounds was evaluated in wastewater effluents. • Attenuation by sensitized photolysis was the most important degradation pathway. • Hydroxyl radical accounted for most of the degradation for aliphatic compounds. • Other transient oxidants could also significantly impact the degradation of the compounds. - Abstract: The photochemical degradation of five pharmaceuticals was examined in two secondary wastewater effluents. The compounds, which included atenolol, carbamazepine, meprobamate, phenytoin and primidone, were evaluated for both direct and sensitized photolysis. In the two wastewaters, direct photolysis did not lead to significant compound degradation; however, sensitized photolysis was an important removal pathway for the five pharmaceuticals. Upon solar irradiation, hydroxyl radical (HO·) was quantified using the hydroxylation of benzene and singlet oxygen ({sup 1}O{sub 2}) formation was monitored following the degradation of furfuryl alcohol. Degradation via sensitized photolysis was observed following five-day exposures for atenolol (69–91%), carbamazepine (67–98%), meprobamate (16–52%), phenytoin (44–85%), and primidone (34–88%). Varying removal is likely a result of the differences in reactivity with transient oxidants. Averaged steady state HO· concentrations ranged from 1.2 to 4.0 × 10{sup −16} M, whereas the concentrations of {sup 1}O{sub 2} were 6.0–7.6 × 10{sup −14} M. Partial removal due to presence of HO· indicates it was not the major sink for most compounds examined. Other transient oxidants, such as {sup 1}O{sub 2} and triplet state effluent organic matter, are likely to play important roles in fates of these compounds.

  14. Lombardia region photochemical characterization by means of modelling simulation; Caratterizzazione fotochimica dell'area lombarda

    Energy Technology Data Exchange (ETDEWEB)

    Gabusi, V.; Finzi, G. [Brescia Univ., Brescia (Italy). Dipt. di Elettronica per l' Automazione

    2001-08-01

    The following study is part of a project aimed to develop a comprehensive modelling system designed to analyse and select possible air quality strategies in metropolitan areas by means of emission abatement measure impact simulation. In this work, a system prototype is proposed, adopting selected software codices, which have been implemented and tested in a Northern Italy domain including the whole of Regione Lombardia, often affected by severe photochemical pollution episodes. The assessment of the relation between ozone, NO{sub x} and VOC is especially important as a starting point for environmental policy. So the modelling system has been applied for the evaluation and comparison of some different emission control strategies, in order to point out the photochemical regime of the domain. [Italian] Uno studio nel quadro di un progetto di ricerca finalizzato allo sviluppo di modelli per l'analisi e la scelta di strategie di risanamento della qualita' dell'aria in ambito metropolitano, attraverso la simulazione dell'impatto del contenimento delle emissioni. Il sistema modellistico e' stato implementato e testato su und dominio dell'Italia settentrionale, comprendente l'intera regione Lombardia, dove si verificano spesso episodi critici di inquinamento fotochimico. La valutazione della relazione fra l'ozono, gli NO{sub x} e i VOC, e' il punto di partenza nelle strategie di risanamento. Pertanto il sistema modellistico e' stato impiegato per la valutazione e il confronto di diverse strategie di controllo delle emissioni al fine di caratterizzare dal punto di vista fotochimico il dominio di indagine.

  15. Photochemical decomposition of perfluorooctanoic acid mediated by iron in strongly acidic conditions.

    Science.gov (United States)

    Ohno, Masaki; Ito, Masataka; Ohkura, Ryouichi; Mino A, Esteban R; Kose, Tomohiro; Okuda, Tetsuji; Nakai, Satoshi; Kawata, Kuniaki; Nishijima, Wataru

    2014-03-15

    The performance of a ferric ion mediated photochemical process for perfluorooctanoic acid (PFOA) decomposition in strongly acidic conditions of pH 2.0 was evaluated in comparison with those in weakly acidic conditions, pH 3.7 or pH 5.0, based on iron species composition and ferric ion regeneration. Complete decomposition of PFOA under UV irradiation was confirmed at pH 2.0, whereas perfluoroheptanoic acid (PFHpA) and other intermediates were accumulated in weakly acidic conditions. Iron states at each pH were evaluated using a chemical equilibrium model, Visual MINTEQ. The main iron species at pH 2.0 is Fe(3+) ion. Although Fe(3+) ion is consumed and is transformed to Fe(2+) ion by photochemical decomposition of PFOA and its intermediates, the produced Fe(2+) ion will change to Fe(3+) ion to restore chemical equilibrium. Continuous decomposition will occur at pH 2.0. However, half of the iron cannot be dissolved at pH 3.7. The main species of dissolved iron is Fe(OH)(2+). At pH 3.7 or higher pH, Fe(3+) ion will only be produced from the oxidation of Fe(2+) ion by hydroxyl radical produced by Fe(OH)(2+) under UV irradiation. These different mechanisms of Fe(3+) regeneration that prevail in strongly and weakly acidic conditions will engender different performances of the ferric ion. Copyright © 2014 Elsevier B.V. All rights reserved.

  16. Toxic Effects of Ethyl Cinnamate on the Photosynthesis and Physiological Characteristics of Chlorella vulgaris Based on Chlorophyll Fluorescence and Flow Cytometry Analysis

    Science.gov (United States)

    Jiao, Yang; Ouyang, Hui-Ling; Jiang, Yu-Jiao; Kong, Xiang-Zhen; He, Wei; Liu, Wen-Xiu; Yang, Bin; Xu, Fu-Liu

    2015-01-01

    The toxic effects of ethyl cinnamate on the photosynthetic and physiological characteristics of Chlorella vulgaris were studied based on chlorophyll fluorescence and flow cytometry analysis. Parameters, including biomass, F v/F m (maximal photochemical efficiency of PSII), ФPSII (actual photochemical efficiency of PSII in the light), FDA, and PI staining fluorescence, were measured. The results showed the following: (1) The inhibition on biomass increased as the exposure concentration increased. 1 mg/L ethyl cinnamate was sufficient to reduce the total biomass of C. vulgaris. The 48-h and 72-h EC50 values were 2.07 mg/L (1.94–2.20) and 1.89 mg/L (1.82–1.97). (2) After 24 h of exposure to 2–4 mg/L ethyl cinnamate, the photosynthesis of C. vulgaris almost ceased, manifesting in ФPSII being close to zero. After 72 h of exposure to 4 mg/L ethyl cinnamate, the F v/F m of C. vulgaris dropped to zero. (3) Ethyl cinnamate also affected the cellular physiology of C. vulgaris, but these effects resulted in the inhibition of cell yield rather than cell death. Exposure to ethyl cinnamate resulted in decreased esterase activities in C. vulgaris, increased average cell size, and altered intensities of chlorophyll a fluorescence. Overall, esterase activity was the most sensitive variable. PMID:26101784

  17. Toxic Effects of Ethyl Cinnamate on the Photosynthesis and Physiological Characteristics of Chlorella vulgaris Based on Chlorophyll Fluorescence and Flow Cytometry Analysis

    Directory of Open Access Journals (Sweden)

    Yang Jiao

    2015-01-01

    Full Text Available The toxic effects of ethyl cinnamate on the photosynthetic and physiological characteristics of Chlorella vulgaris were studied based on chlorophyll fluorescence and flow cytometry analysis. Parameters, including biomass, Fv/Fm (maximal photochemical efficiency of PSII, ФPSII (actual photochemical efficiency of PSII in the light, FDA, and PI staining fluorescence, were measured. The results showed the following: (1 The inhibition on biomass increased as the exposure concentration increased. 1 mg/L ethyl cinnamate was sufficient to reduce the total biomass of C. vulgaris. The 48-h and 72-h EC50 values were 2.07 mg/L (1.94–2.20 and 1.89 mg/L (1.82–1.97. (2 After 24 h of exposure to 2–4 mg/L ethyl cinnamate, the photosynthesis of C. vulgaris almost ceased, manifesting in ФPSII being close to zero. After 72 h of exposure to 4 mg/L ethyl cinnamate, the Fv/Fm of C. vulgaris dropped to zero. (3 Ethyl cinnamate also affected the cellular physiology of C. vulgaris, but these effects resulted in the inhibition of cell yield rather than cell death. Exposure to ethyl cinnamate resulted in decreased esterase activities in C. vulgaris, increased average cell size, and altered intensities of chlorophyll a fluorescence. Overall, esterase activity was the most sensitive variable.

  18. An optimal photochemical energy conversion and environmental effects in the reactive molecular dynamics; Optimale Photochemische Energiekonversion und Umgebungseffekte in Reaktiver Molekueldynamik

    Energy Technology Data Exchange (ETDEWEB)

    Fingerhut, Benjamin Philipp

    2011-02-08

    One of the main challenges in photochemical energy conversion is the design of charge separating units which are able to generate a long lived charge separated state, and to couple efficiently to an energy storage state. In part I of this work the energy conversion efficiency of a photochemical unit inspired by bacterial photosynthesis is investigated. The developed model is based on non-adiabatic multi step electron transfer to generate a trans-membrane potential gradient. Upon optimization with multi objective genetic algorithms, the biological strategies for high quantum efficiency in photosynthetic reaction centers are derived, which have to suppress loss channels such as charge recombination. The concepts of bacterial photosynthesis are extended to the design of artificial photochemical devices. The unified model consists of a charge separation unit and an energy storing system whereby the coupling between both units is assured by thermal repopulation according to the principle of detailed balance. The complete photosynthetic unit is characterized by the respective current-voltage relation and an upper limit for the overall energy efficiency is derived under AM1.5 global conditions. Such a realistic chemical solar energy conversion system can reach efficiencies, which are comparable to the limits of an ideal single-junction solar cell. In Part II of this work the reactive dynamics of two surrounding controlled photoreactions is investigated on a microscopic scale. In general the effect of the surrounding can be classified into intramolecular contributions, like steric or electronic effects, and intermolecular contributions like the solvent or the embedding in an enzyme. Both limiting cases are examined on the basis of two generic photoreactions. The Dewar DNA lesion follows quantitatively from the 6-4 lesion by UV-A/B irradiation and constitutes the stable end product of continuous solar irradiation. Here the detailed mechanism of the formally 4{pi

  19. Temperature-dependent responses of the photosynthetic and chlorophyll fluorescence attributes of apple (Malus domestica) leaves during a sustained high temperature event.

    Science.gov (United States)

    Greer, Dennis H

    2015-12-01

    The objective of this study was to follow changes in the temperature-dependent responses of photosynthesis and photosystem II performance in leaves of field-grown trees of Malus domestica (Borkh.) cv. 'Red Gala' before and after exposure to a long-term heat event occurring late in the growing season. Light-saturated photosynthesis was optimal at 25 °C before the heat event. The high temperatures caused a reduction in rates at low temperatures (15-20 °C) but increased rates at high temperatures (30-40 °C) and a shift in optimum to 30 °C. Rates at all temperatures increased after the heat event and the optimum shifted to 33 °C, indicative of some acclimation to the high temperatures occurring. Photosystem II attributes were all highly temperature-dependent. The operating quantum efficiency of PSII during the heat event declined, but mostly at high temperatures, partly because of decreased photochemical quenching but also from increased non-photochemical quenching. However, a further reduction in PSII operating efficiency occurred after the heat event subsided. Non-photochemical quenching had subsided, whereas photochemical quenching had increased in the post-heat event period and consistent with a greater fraction of open PSII reaction centres. What remained uncertain was why these effects on PSII performance appeared to have no effect on the process of light-saturated photosynthesis. However, the results provide an enhanced understanding of the impacts of sustained high temperatures on the photosynthetic process and its underlying reactions, notably photochemistry. Copyright © 2015 Elsevier Masson SAS. All rights reserved.

  20. Photochemical Deposition of Silver Nanoparticles on Clays and Exploring Their Antibacterial Activity.

    Science.gov (United States)

    Lombardo, Patrícia C; Poli, Alessandra L; Castro, Lucas F; Perussi, Janice R; Schmitt, Carla C

    2016-08-24

    Photochemical method was used to synthesize silver nanoparticles (AgNPs) in the presence of citrate or clay (SWy-1, SYn-1, and Laponite B) as stabilizers and Lucirin TPO as photoinitiator. During the photochemical synthesis, an appearance of the plasmon absorption band was seen around 400 nm, indicating the formation of AgNPs. X-ray diffraction results suggested that AgNPs prepared in SWy-1 were adsorbed into interlamellar space, and moreover, showed some clay exfoliation. In the case of SYn-1, AgNPs was not intercalated. For the AgNP/Lap B sample, the formation of an exfoliated structure occurred. Transmission electron microscopy revealed the spherical shape of AgNPs for all samples. The particle sizes obtained for AgNP/SWy-1, AgNP/SYn-1, and AgNP/Lap B were 2.6, 5.1, and 3.8 nm, respectively. AgNPs adsorbed on SYn-1 reveal nonuniform size and aggregation of some particles. However, AgNP/SWy-1 and AgNP/Lap B samples are more uniform and have diameters smaller than those prepared with SYn-1. This behavior is due to the ability to exfoliate these clays. The antibacterial activities of pure clays, AgNP/citrate, and AgNP/clays were investigated against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus). AgNPs in the presence of clays (AgNPs/SYn-1 and AgNPs/SWy-1) showed a lower survival index percentage compared to those obtained for pure clays and AgNPs. The AgNP/SWy-1 sample showed good antibacterial activity against both tested species and the lowest survival index of 3.9 and 4.3 against E. coli and S. aureus, respectively. AgNPs are located in the interlayer region of the SWy-1, which has acid sites. These acidic sites may contribute to the release of Ag(+) ions from the surface of AgNPs. On the other hand, Laponite B and AgNP/Lap B samples did not demonstrate any bactericidal activity.

  1. Unexpected morphological changes within hippocampal structures in a photochemical ring model of cerebral ischaemia.

    Science.gov (United States)

    Rafałowska, Janina; Gadamski, Roman; Dziewulska, Dorota; Zielonka, Piotr; Ogonowska, Wanda; Lazarewicz, Jerzy W

    2009-01-01

    A photochemical ring model of ischaemia was introduced in the middle of the nineteen eighties. Irradiation by a laser or arc lamp followed by intravenous injection of rose bengal resulted in thrombosis of pial and superficial cortical vessels. This ring model imitated focal ischaemic damage in humans. In our experiment twenty-seven Wistar rats of both sexes weighing 250-300 grams were examined. A photochemical ring model based on irradiation of the area of parietal bone 4 mm posteriorly to the bregma and 4 mm laterally from the sagittal suture was applied. A ring-shaped light beam with a wavelength of 510-540 nm with 5 mm diameter was generated by a high pressure discharge lamp at a power of 400 W. Two groups of rats treated and untreated with MK-801 and two rings of the thickness of 0.35 mm and 0.5 mm were used in the experiment. Morphological examination was performed in animals sacrificed 1 and 4 days after the irradiation. On formalin-fixed and paraffin-embedded slices HE staining method and immunoreaction with antibodies to ubiquitin were applied. Our material confirmed well known information about the dynamics of infarct breakdown, ischaemic-induced angiogenesis, glial reaction and other typical changes described previously in handbooks and numerous papers. In the experiment, morphological changes were more intensive after the irradiation by 0.5 mm than 0.35 mm irradiating rings and 4 days than one day after the irradiation. A surprising finding observed in some of the examined animals was more intensive neuronal damage after treatment with MK-801. Another unpredicted discovery was intensive morphological alterations found in CA4 and CA3 hippocampal sectors. Moreover, these alterations were not limited to the damaged hemisphere, but were also observed contralaterally. In some of the rats, ischaemic and necrotic cells were additionally found within both parasagittal areas. We connect this atypical localization of the ischaemic changes with dispersion of light

  2. Gas and particle phase chemical characterization of photochemical smog in Beijing and Hong Kong

    Science.gov (United States)

    Hallquist, Mattias; Le Breton, Michael; Guo, Song; Zhen Yu, Jian; Hallquist, Åsa. M.; Pathak, Ravi K.; Liu, Qianyun; Wang, Yuchen; Li, Jinjian; Chan, Chak K.; Wang, Yujue; Zheng, Jing; Yang, Yudong; Lu, Keding; Wu, Zhijun; Hu, Min

    2017-04-01

    Secondary chemistry transforming primary pollutants is of high relevance for Chinese photochemical smog. In particular, formation of ozone (O3) and particulate matter (PM), including Secondary Organic Aerosols (SOA), are of major concern regarding impacts on health, climate and ecosystems. The atmospheric oxidation processes leading to SOA formation are complex and involves thousands of different compounds, both of biogenic and anthropogenic origin. Furthermore, for a thorough understanding both the gas and the particle phase need to be considered. As part of an intercollaborative project to assess the photochemical smog in China, two major field campaigns were arranged in 2016; in Changping, Bejing during springtime and at HKUST, Hong Kong during the autumn. Alongside with other advanced instrumentations, a Time of Flight Chemical Ionisation Mass Spectrometer (ToF CIMS) utilising the Filiter Inlet for Gases and AEROsols (FIGAERO) was used to chemically characterize the gas and the particle phase. This specific instrument applies soft ionization limiting the fragmentation and one can usually identify molecular composition of hundreds of different parent molecules. In both Beijing and Hong Kong the iodide ionization scheme was utilised, making it possible to specifically detect oxygenated compounds such as carboxylic acids, organic nitrates and sulphates as well as some inorganic compounds e.g. N2O5, ClNO2, and HONO. For numerous compounds significant levels were detected in both the gas and particle phase enabling evaluation of partitioning and gas-to-particle transformation and its relationship to atmospheric conditions and estimated vapour pressures. Furthermore, the detection of molecular markers such as levoglucosan, C6H5NO3, C10H16NSO7, C5H8SO7, C5H8O4 can support source apportionment and atmospheric process description. In order to further investigate atmospheric ageing/processing a portable laminar flow reactor (Go:PAM) was for selected periods utilized to

  3. Photochemical decomposition of perfluorooctanoic acid mediated by iron in strongly acidic conditions

    Energy Technology Data Exchange (ETDEWEB)

    Ohno, Masaki, E-mail: mohno@hiroshima-u.ac.jp [Environmental Research and Management Center, Hiroshima University, 1-5-3 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8513 (Japan); Ito, Masataka; Ohkura, Ryouichi [Faculty of Applied Life Sciences, Niigata University of Pharmacy and Applied Life Sciences, 265-1, Higashijima, Akiha-ku, Niigata 956-8603 (Japan); Mino A, Esteban R. [Environmental Research and Management Center, Hiroshima University, 1-5-3 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8513 (Japan); Kose, Tomohiro [Faculty of Applied Life Sciences, Niigata University of Pharmacy and Applied Life Sciences, 265-1, Higashijima, Akiha-ku, Niigata 956-8603 (Japan); Okuda, Tetsuji [Environmental Research and Management Center, Hiroshima University, 1-5-3 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8513 (Japan); Nakai, Satoshi [Department of Chemical Engineering, Graduate School of Engineering, Hiroshima University, 1-4-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8527 (Japan); Kawata, Kuniaki [Faculty of Applied Life Sciences, Niigata University of Pharmacy and Applied Life Sciences, 265-1, Higashijima, Akiha-ku, Niigata 956-8603 (Japan); Nishijima, Wataru [Environmental Research and Management Center, Hiroshima University, 1-5-3 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8513 (Japan)

    2014-03-01

    Highlights: • Perfluorooctanoic acid (PFOA) was decomposed based on ferric ion performance. • Complete decomposition of PFOA was confirmed in strongly acidic conditions. • Fe{sup 2+} changed to Fe{sup 3+} to restore chemical equilibrium in this condition. • Fe{sup 3+} was only produced from Fe{sup 2+} by hydroxyl radical in weakly acidic conditions. • The Fe{sup 3+} regeneration mechanisms resulted in the performance of Fe{sup 3+} for PFOA. - Abstract: The performance of a ferric ion mediated photochemical process for perfluorooctanoic acid (PFOA) decomposition in strongly acidic conditions of pH 2.0 was evaluated in comparison with those in weakly acidic conditions, pH 3.7 or pH 5.0, based on iron species composition and ferric ion regeneration. Complete decomposition of PFOA under UV irradiation was confirmed at pH 2.0, whereas perfluoroheptanoic acid (PFHpA) and other intermediates were accumulated in weakly acidic conditions. Iron states at each pH were evaluated using a chemical equilibrium model, Visual MINTEQ. The main iron species at pH 2.0 is Fe{sup 3+} ion. Although Fe{sup 3+} ion is consumed and is transformed to Fe{sup 2+} ion by photochemical decomposition of PFOA and its intermediates, the produced Fe{sup 2+} ion will change to Fe{sup 3+} ion to restore chemical equilibrium. Continuous decomposition will occur at pH 2.0. However, half of the iron cannot be dissolved at pH 3.7. The main species of dissolved iron is Fe(OH){sup 2+}. At pH 3.7 or higher pH, Fe{sup 3+} ion will only be produced from the oxidation of Fe{sup 2+} ion by hydroxyl radical produced by Fe(OH){sup 2+} under UV irradiation. These different mechanisms of Fe{sup 3+} regeneration that prevail in strongly and weakly acidic conditions will engender different performances of the ferric ion.

  4. Non-photochemical quenching and xanthophyll cycle activities in six green algal species suggest mechanistic differences in the process of excess energy dissipation.

    Science.gov (United States)

    Quaas, Theresa; Berteotti, Silvia; Ballottari, Matteo; Flieger, Kerstin; Bassi, Roberto; Wilhelm, Christian; Goss, Reimund

    2015-01-01

    In the present study the non-photochemical quenching (NPQ) of four biofilm-forming and two planktonic green algae was investigated by fluorescence measurements, determinations of the light-driven proton gradient and determination of the violaxanthin cycle activity by pigment analysis. It was observed that, despite the common need for efficient photoprotection, the structural basis of NPQ was heterogeneous in the different species. Three species, namely Chlorella saccharophila, Chlorella vulgaris and Bracteacoccus minor, exhibited a zeaxanthin-dependent NPQ, while in the three other species, Tetracystis aeria, Pedinomonas minor and Chlamydomonas reinhardtii violaxanthin de-epoxidation was absent or unrelated to the establishment of NPQ. Acclimation of the algae to high light conditions induced an increase of the NPQ activity, suggesting that a significant part of the overall NPQ was rather inducible than constitutively present in the green algae. Comparing the differences in the NPQ mechanisms with the phylogenetic position of the six algal species led to the conclusion that the NPQ heterogeneity observed in the present study was not related to the phylogeny of the algae but to the environmental selection pressure. Finally, the difference in the NPQ mechanisms in the different species is discussed within the frame of the current NPQ models. Copyright © 2014 Elsevier GmbH. All rights reserved.

  5. Fe{sup 3+}-doped zeolites. Optimised conditions for the oxidative degradation of 2,4-xylidine in laboratory and solar photochemical reactors

    Energy Technology Data Exchange (ETDEWEB)

    Shahin, N.; Thanh, H. le; Bonfill, A.; Woerner, M.; Lang, J.; Bossmann, S.H.; Oliveros, E.; Braun, A.M. [Lehrstuhl fuer Umweltmesstechnik am Engler-Bunte Inst. der Univ. Karlsruhe (Germany)

    2003-07-01

    Among advanced oxidation processes (AOP), the photochemically enhanced Fenton reaction (photo-Fenton) may be considered as one of the most efficient for the degradation of contaminants in industrial wastewater. This process involves a series of complex reactions, which cannot be described completely by conventional models. Therefore, the experimental design methodology has been employed for modelling the experimental data obtained in a laboratory batch reactor as well as in a novel type of solar reactor. As heterogeneous Fenton catalyst, a Fe{sup 3+}-exchanged zeolite Y photocatalyst was employed. As a model pollutant, 2,4-dimethyl aniline (2,4-xylidine) was chosen, because its oxidative degradation chemistry is well known. The experimental design model has been used for describing the behaviour of the reaction system in sensitivity studies aimed at optimising the amounts of Fenton reagents (heterogeneous Fenton catalyst and hydrogen peroxide) employed in the process. The results show that this heterogeneous photo-Fenton process is very sensitive to the concentration of catalyst as well as of added hydrogen peroxide. (orig.)

  6. (CF3)2CFCH=CHF (HFO-1438ezy): OH Radical Rate Coefficient, Infrared Spectrum Measurements and Estimated Global Warming Potentials and Photochemical Ozone Creation Potential

    Science.gov (United States)

    Papadimitriou, V.; Burkholder, J. B.

    2015-12-01

    Short-lived hydrofluoroolefins (HFOs) are proposed replacement compounds for ozone depleting substances (ODSs) and longer-lived greenhouse gases that are used in various industrial and technological applications. HFOs are not ODSs and the presence of the highly reactive unsaturated bond toward the common atmospheric oxidants (OH, Cl, NO3 and O3) is expected to lead to shorter tropospheric lifetimes relative to those of saturated hydrofluorocarbons. The shorter lifetime reduces their direct contribution to Climate Change. In this study, rate coefficients for the gas-phase reaction of the OH radical with (CF3)2CFCH=CHF (HFO-1438ezy), between 214 and 380 K and 50-450 Torr (He, N2), were measured using pulsed laser photolysis-laser induced fluorescence (PLP/LIF) and relative rate methods. No pressure dependence was observed within this measurement range. The reaction displays a non-Arrhenius temperature dependence over this temperature range with a slightly positive temperature dependence above 280 K and near temperature independence at lower temperatures. The infrared spectrum of HFO-1438ezy was measured as part of this work. On the basis of the present measurements, the atmospheric lifetime of HFO-1438ezy as well as its radiative efficiency, global warming potential and photochemical ozone creation potential were estimated.

  7. Photochemically Induced ATRP of (Meth)Acrylates in the Presence of Air: The Effect of Light Intensity, Ligand, and Oxygen Concentration.

    Science.gov (United States)

    Borská, Katarína; Moravčíková, Daniela; Mosnáček, Jaroslav

    2017-07-01

    Well-defined poly(methyl methacrylate) (PMMA) and poly(methyl acrylate) (PMA) are prepared via photochemically induced atom transfer radical polymerization (photoATRP) using ppm amounts of CuBr2 /tris(2-pyridylmethyl)amine and CuBr2 /tris[2-(dimethylamino)ethyl]amine catalyst complexes, respectively, without degassing of polymerization mixture and with no need to introduce an external reducing agent to the system. The effect of ligand to CuBr2 ratio on kinetic and induction period during the polymerization of MMA and MA is investigated. The induction period is influenced also by the amount of oxygen in the polymerization system. Both the kinetics of MA polymerization and the induction period are affected by light intensity. Finally, the high livingness and initiation efficiency of the photoATRP system in the presence of air are proved by chain extension polymerizations. The presented system is valuable from an industrial point of view, since after optimization, well-defined and high-molar-mass poly(meth)acrylates can be prepared without the necessity of degassing the system, while the polymerization can be proceeded quickly and without an induction period. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Photochemical quenching of aqueous methylene blue by N, Nb co-doped TiO2 nanomaterials under visible light: a confirmatory UV/LC-MS study

    Science.gov (United States)

    Gupta, Kamini; Pandey, Ashutosh; Singh, R. P.

    2017-12-01

    Nanodimensional un-doped, Nb doped, N doped and N,Nb co-doped TiO2 particles have been prepared by the sol-gel procedure. Phase identification of the anatase particles was done by X-ray powder diffraction and Deby–Scherrer calculations revealed their particle sizes to range from 20 to 30 nm. The band gap energies of the samples were measured by UV–Vis-diffuse reflectance (UV-DRS) spectra. While un-doped TiO2 showed wide optical absorption in the UV region. The co-doped TiO2 particles exhibited narrow band gaps of ~2.7 eV, which showed absorption in the visible region. A decline in charge carrier recombination rates in the prepared samples was confirmed through photoluminescence (PL). The morphological appearances of the particles have been examined by scanning electron microscopy. X-ray photoelectron spectroscopy (XPS) of the samples confirmed the incorporations of N and Nb into the TiO2 matrices. The photocatalytic efficiencies of the prepared particles have been determined by the degradation of the non-biodegradable dye methylene blue (MB) under electromagnetic radiation. The co-doped sample showed superior photocatalytic activity under the visible light (λ  >  400) over the other samples. Photochemical quenching of aqueous MB was further analysed by UV/LC-MS which confirmed the attenuation of methylene blue.

  9. Indications of photochemical histories of Pacific air masses from measurements of atmospheric trace species at Point Arena, California

    Science.gov (United States)

    Parrish, D. D.; Hahn, C. J.; Williams, E. J.; Norton, R. B.; Fehsenfeld, F. C.; Singh, H. B.; Shetter, J. D.; Gandrud, B. W.; Ridley, B. A.

    1992-01-01

    Measurements were made of a suite of photochemically active trace species (including light hydrocarbons, ozone, peroxyacetyl nitrate, HNO3, NO3(-), NO(x), and NO(y)) in marine air collected during a 10-day period in April and May 1985 at Point Arena (California), a coastal inflow site. It was found that the mixing ratios of the alkanes, ozone, peroxyacetyl nitrate, and HNO3 correlated with variations in the origins of calculated air parcel trajectories and with variations in the ratios of the light alkanes. The highest levels of alkanes and the photochemical products were found in parcels that had been rapidly transported across the North Pacific Ocean from near the 600-mbar level above the east Asian coast. It is suggested that production over the continents, transport to the marine areas, and parallel removal processes account for much of the observed correlation.

  10. European scale modeling of sulfur, oxidized nitrogen and photochemical oxidants. Model development and evaluation for the 1994 growing season

    Energy Technology Data Exchange (ETDEWEB)

    Langner, J.; Bergstroem, R. [Swedish Meteorological and Hydrological Inst., Norrkoeping (Sweden); Pleijel, K. [Swedish Environmental Research Inst., Goeteborg (Sweden)

    1998-09-01

    A chemical mechanism, including the relevant reactions leading to the production of ozone and other photochemical oxidants, has been implemented in the MATCH regional tracer transport/chemistry/deposition model. The aim has been to develop a model platform that can be used as a basis for a range of regional scale studies involving atmospheric chemistry, including assessment of the importance of different sources of pollutants to the levels of photochemical oxidants and air pollutant forecasting. Meteorological input data to the model were taken from archived output from the operational version of HIRLAM at SMHI. Evaluation of model calculations over Europe for a six month period in 1994 for a range of chemical components show good results considering known sources of error and uncertainties in input data and model formulation. With limited further work the system is sufficiently good to be applied for scenario studies and for regional scale air pollutant forecasts 42 refs, 24 figs, 17 tabs

  11. Quantum Mechanics/Molecular Mechanics Free Energy Maps and Nonadiabatic Simulations for a Photochemical Reaction in DNA: Cyclobutane Thymine Dimer.

    Science.gov (United States)

    Mendieta-Moreno, Jesús I; Trabada, Daniel G; Mendieta, Jesús; Lewis, James P; Gómez-Puertas, Paulino; Ortega, José

    2016-11-03

    The absorption of ultraviolet radiation by DNA may result in harmful genetic lesions that affect DNA replication and transcription, ultimately causing mutations, cancer, and/or cell death. We analyze the most abundant photochemical reaction in DNA, the cyclobutane thymine dimer, using hybrid quantum mechanics/molecular mechanics (QM/MM) techniques and QM/MM nonadiabatic molecular dynamics. We find that, due to its double helix structure, DNA presents a free energy barrier between nonreactive and reactive conformations leading to the photolesion. Moreover, our nonadiabatic simulations show that most of the photoexcited reactive conformations return to standard B-DNA conformations after an ultrafast nonradiative decay to the ground state. This work highlights the importance of dynamical effects (free energy, excited-state dynamics) for the study of photochemical reactions in biological systems.

  12. Application of the Doehlert design to optimize the signal obtained in photochemically induced fluorescence for the determination of eight phenylureas.

    Science.gov (United States)

    Gil-García, M D; Martínez-Galera, M; Parrilla-Vázquez, P; Mughari, A R; Ortiz-Rodríguez, I M

    2008-03-01

    This work describes the optimization of a photochemically induced method for the detection of eight phenylureas has been developed by response surface methodology (RSM). These pesticides do not show native fluorescence but they were photolyzed into strongly fluorescent photoproducts under UV irradiation. The effect of the main variables affecting the yield of the photoderivatization reaction, and hence the fluorescence intensity, such as solvent, UV irradiation time and pH were optimized for each pesticide. A Doehlert design was applied in order to obtain maximum intensity fluorescence using response surface methodology. In general, a maximum was found for all pesticides using MeOH as organic solvent, except for diuron, whereas the effect of pH and irradiation time was different, according to each pesticide. Finally, the addition of beta-cyclodextrin upon the photochemically induced fluorescence intensity was investigate. The fluorescence intensity was only improved for monolinuron at a concentration of 4 x 10(-3) M of beta-cyclodextrin.

  13. Emissions from the petroleum related activity at Haltenbanken. Contribution to photochemical activity and acidification; Utslipp fra petroleumsrelatert aktivitet paa Haltenbanken. Bidrag til fotokjemisk oksidantdannelse og forsuring

    Energy Technology Data Exchange (ETDEWEB)

    Knudsen, S.; Johnsrud, M.; Solberg, S.; Walker, S.E.; Skjelkvaale, B.L.

    1996-01-01

    This work includes studies of effects from emissions of nitrogen oxides and hydrocarbons from Haltenbanken (Draugen, Heidrun, Njord, Norne) and Aasgard. It includes estimates of photochemical activity, air quality and deposition. 6 refs., 8 figs., 10 tabs.

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

    Science.gov (United States)

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

    2015-04-08

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

  15. OZONE PRODUCTION EFFICIENCY AND NOX DEPLETION IN AN URBAN PLUME: INTERPRETATION OF FIELD OBSERVATIONS AND IMPLICATIONS FOR EVALUATING O3-NOX-VOC SENSITIVITY

    Science.gov (United States)

    Ozone production efficiency (OPE) can be defined as the number of ozone (O3) molecules photochemically produced by a molecule of NOx (NO + NO2) before it is lost from the NOx - O3 cycle. Here, we consider observational and modeling techniques to evaluate various operational defi...

  16. Surfactant removal and silica condensation during the photochemical calcination of thin film silica mesophases.

    Science.gov (United States)

    Dattelbaum, Andrew M; Amweg, Meri L; Ruiz, Julia D; Ecke, Laurel E; Shreve, Andrew P; Parikh, Atul N

    2005-08-04

    The evolution of photochemical surfactant removal and silica condensation from organically templated thin film silica nanocomposites with mesoscopic ordering has been probed using a combined application of Fourier transform infrared (FT-IR) spectroscopy and single wavelength ellipsometry. Thin films of silica nanocomposites were prepared by a previously reported evaporation-induced self-assembly process. Specifically, oxidized silicon and gold substrates were withdrawn at 25 mm/min from a subcritical micelle concentration solution containing an ethylene oxide surfactant as a structure-directing agent and tetraethyl orthosilicate as a silica precursor. Real-time grazing incidence difference FT-IR spectra of the nanocomposite films on gold taken during exposure to short-wavelength ultraviolet light (184-257 nm) show that surfactant removal and silica condensation occur gradually and concomitantly. Surfactant removal and silica reconstructions were found to be nearly complete after 90 min of exposure. Further, a transient feature was observed in the FT-IR spectra around 1713 cm(-1) during the UV exposure process and was assigned to a carbonyl (C=O) stretching mode absorption, reflecting the transient formation of a partially oxidized surfactant intermediate. From these data we propose a stepwise model for surfactant removal from the nanocomposite films. Ellipsometrically determined index of refraction values collected as a function of UV exposure are also shown to support such a stepwise mechanism of surfactant removal from the ordered nanocomposite silica thin film mesophases studied here.

  17. Selective thermo/photochemical treatment of materials--a new trend in laser microtechnology

    Science.gov (United States)

    Metev, Simeon; Stephen, Andreas; Schwarz, Jorg; Wochnowski, Carsten

    2003-02-01

    Laser-induced technological chemical processes can significantly contribute to the development of new methods for micro treatment of materials and hence to the broadening of the application spectrum of laser microtechnology. In this paper three typical laser-activated chemical technological methods in liquids, gases and solids and their possible applications are presented and discussed: 1) Laser-induced liquid-phase jet-chemical etching of metals. In this method, laser radiation which is guided from a co-axially expanding liquid jet-stream initiates locally on a metal surface a thermochemical etching reaction, which leads to a selective material removal at high resolution (thermochemical CVD processes taking place in a photon-initiated stationary plasma maintained in the electromagnetic optical field of a high-power cw-CO2 laser radiation. This method allows synthesis of thin-film coatings in the open-air atmosphere without using vacuum or reaction chamber; 3) Laser-induced photochemical modification of the optical properties of polymers. This method is based on the local controllable change of the polymer structure leading to modification of the refractive index in the treated area. By numerous independently adjustable laser radiation parameters, for instance wavelength and irradiation dose, the modification process can be controllably driven in order to generate desired functional properties.

  18. Photochemically synthesized heparin-based silver nanoparticles: an antimicrobial activity study

    Science.gov (United States)

    Rodriguez-Torres, Maria del Pilar; Acosta-Torres, Laura Susana; Díaz-Torres, Luis Armando

    2017-08-01

    The antimicrobial activity of silver nanoparticles has been extensively studied in the last years. Such nanoparticles constitute a potential and promising approach for the development of new antimicrobial systems especially due to the fact that several microorganisms are developing resistance to some already existing antimicrobial agents, therefore making antibacterial and antimicrobial studies on alternative materials necessary to overcome this issue. Silver nanoparticle concentration and size are determining factors on the antimicrobial activity of these nano systems. Heparin is a polysaccharide that belongs to the glycosaminoglycans (GAGs) family, molecules formed by a base disaccharide whose components are joined by a glycosidic linkage that is a repeating unit along their structure. It is highly sulfated making it a negatively charged material that is also widely used as an anticoagulant in Medicine because its biocompatibility besides it is also produced within the human body, specifically in the mast cells. Heparin alone possesses antimicrobial activity although it has not been studied very much in detail, it only has been demonstrated that it inhibits E. coli, P. aeruginosa, S. aureus and S. epidermidis, so taking this into account, this study is dedicated to assess UV photochemically-synthesized (λ=254 nm) heparin-based silver nanoparticles antimicrobial activity using the agar disk diffusion method complemented by the broth microdilution method to estimate de minimum inhibitory concentration (MIC), that is the lowest concentration at which an antimicrobial will inhibit visible growth of a microorganism. The strains used were the ones aforementioned to assess the antimicrobial activity degree these heparinbased nanoparticles exhibit.

  19. Enhanced gene transfection by photochemical internalization of protomine sulfate/DNA complexes

    Science.gov (United States)

    Hirschberg, Henry; Mathews, Marlon B.; Shih, En-Chung; Madsen, Steen J.; Kwon, Young Jik

    2012-02-01

    Introduction: One of many limitations for cancer gene therapy is the inability of the therapeutic gene to transfect a sufficient number of tumor cells. Photochemical internalization (PCI) is a photodynamic therapy-based approach for improving the delivery of macromolecules and genes into the cell cytosol. The utility of PCI for the delivery of the GFP indicator gene on the same plasmid as a tumor suppressor gene (PTEN) was investigated in monolayers of U251 human glioma cells. Materials and Methods: U251 monolayers were incubated in AlPcS2a for 18 h. The monolayers were incubated with non-viral vectors for either 4 or 18 hrs. In all cases, light treatment was performed with a diode laser at a wavelength of 670 nm. The non-viral transfection agents, branched PEI or protomine sulfate (PS), were used with the plasmid construct (GFP-PTEN). Results: PS was much less toxic to the gliomas cells compared to BPEI but was highly inefficient at gene transfection. PCI resulted in a 5-10 fold increase in GFP protein expression compared to controls. Conclusions: Collectively, the results suggest that AlPcS2a-mediated PCI can be used to enhance transfection of tumor suppressor genes in glioma cells.

  20. Changes in droplet surface tension affect the observed hygroscopicity of photochemically aged biomass burning aerosol.

    Science.gov (United States)

    Giordano, Michael R; Short, Daniel Z; Hosseini, Seyedehsan; Lichtenberg, William; Asa-Awuku, Akua A

    2013-10-01

    This study examines the hygroscopic and surface tension properties as a function of photochemical aging of the aerosol emissions from biomass burning. Experiments were conducted in a chamber setting at the UC-Riverside Center for Environmental Research and Technology (CE-CERT) Atmospheric Processes Lab using two biomass fuel sources, manzanita and chamise. Cloud condensation nuclei (CCN) measurements and off-line filter sample analysis were conducted. The water-soluble organic carbon content and surface tension of the extracted filter samples were measured. Surface tension information was then examined with Köhler theory analysis to calculate the hygroscopicity parameter, κ. Laboratory measurement of biomass burning smoke from two chaparral fuels is shown to depress the surface tension of water by 30% or more at organic matter concentrations relevant at droplet activation. Accounting for surface tension depression can lower the calculated κ by a factor of 2. This work provides evidence for surface tension depression in an important aerosol system and may provide closure for differing sub- and supersaturated κ measurements.

  1. Enhanced Efficacy of Bleomycin in Bladder Cancer Cells by Photochemical Internalization

    Directory of Open Access Journals (Sweden)

    Yan Baglo

    2014-01-01

    Full Text Available Bleomycin is a cytotoxic chemotherapeutic agent widely used in cancer treatment. However, its efficacy in different cancers is low, possibly due to limited cellular internalization. In this study, a novel approach known as photochemical internalization (PCI was explored to enhance bleomycin delivery in bladder cancer cells (human T24 and rat AY-27, as bladder cancer is a potential indication for use of PCI with bleomycin. The PCI technique was mediated by the amphiphilic photosensitizer disulfonated tetraphenyl chlorin (TPCS2a and blue light (435 nm. Two additional strategies were explored to further enhance the cytotoxicity of bleomycin; a novel peptide drug ATX-101 which is known to impair DNA damage responses, and the protease inhibitor E-64 which may reduce bleomycin degradation by inhibition of bleomycin hydrolase. Our results demonstrate that the PCI technique enhances the bleomycin effect under appropriate conditions, and importantly we show that PCI-bleomycin treatment leads to increased levels of DNA damage supporting that the observed effect is due to increased bleomycin uptake. Impairing the DNA damage responses by ATX-101 further enhances the efficacy of the PCI-bleomycin treatment, while inhibiting the bleomycin hydrolase does not.

  2. Photochirogenesis: Photochemical models on the absolute asymmetric formation of amino acids in interstellar space

    Science.gov (United States)

    Meinert, Cornelia; de Marcellus, Pierre; Le Sergeant D'Hendecourt, Louis; Nahon, Laurent; Jones, Nykola C.; Hoffmann, Søren V.; Bredehöft, Jan Hendrik; Meierhenrich, Uwe J.

    2011-10-01

    Proteins of all living organisms including plants, animals, and humans are made up of amino acid monomers that show identical stereochemical L-configuration. Hypotheses for the origin of this symmetry breaking in biomolecules include the absolute asymmetric photochemistry model by which interstellar ultraviolet (UV) circularly polarized light (CPL) induces an enantiomeric excess in chiral organic molecules in the interstellar/circumstellar media. This scenario is supported by a) the detection of amino acids in the organic residues of UV-photo-processed interstellar ice analogues, b) the occurrence of L-enantiomer-enriched amino acids in carbonaceous meteorites, and c) the observation of CPL of the same helicity over large distance scales in the massive star-forming region of Orion. These topics are of high importance in topical biophysical research and will be discussed in this review. Further evidence that amino acids and other molecules of prebiotic interest are asymmetrically formed in space comes from studies on the enantioselective photolysis of amino acids by UV-CPL. Also, experiments have been performed on the absolute asymmetric photochemical synthesis of enantiomer-enriched amino acids from mixtures of astrophysically relevant achiral precursor molecules using UV-circularly polarized photons. Both approaches are based on circular dichroic transitions of amino acids that will be highlighted here as well. These results have strong implications on our current understanding of how life's precursor molecules were possibly built and how life selected the left-handed form of proteinogenic amino acids.

  3. Photochemical processing of aldrin and dieldrin in frozen aqueous solutions under arctic field conditions.

    Science.gov (United States)

    Rowland, Glenn A; Bausch, Alexandra R; Grannas, Amanda M

    2011-05-01

    Organochlorine (OC) contaminants are transported to the Polar Regions, where they have the potential to bioaccumulate, presenting a threat to the health of wildlife and indigenous communities. They deposit onto snowpack during winter, and accumulate until spring, when they experience prolonged solar irradiation until snowmelt occurs. Photochemical degradation rates for aldrin and dieldrin, in frozen aqueous solution made from MilliQ water, 500 μM hydrogen peroxide solution or locally-collected melted snow were measured in a field campaign near Barrow, AK, during spring-summer 2008. Significant photoprocessing of both pesticides occurs; the reactions depend on temperature, depth within the snowpack and whether the predominant phase is ice or liquid water. The effect of species present in natural snowpack is comparable to 500 μM hydrogen peroxide, pointing to the potential significance of snowpack-mediated reactions. Aldrin samples frozen at near 0 °C were more reactive than comparable liquid samples, implying that the microenvironments experienced on frozen ice surfaces are an important consideration. Copyright © 2011 Elsevier Ltd. All rights reserved.

  4. Supramolecular structures for photochemical energy conversion. Technical progress report, 1993--1996

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1996-06-01

    This research project is concerned with the design, synthesis and study by photochemical and spectroscopic methods of complex molecular devices that mimic some important aspects of photosynthetic electron and energy transfer. Properly engineered molecules of this type can functionally mimic photosynthetic light harvesting (singlet-singlet energy transfer between chromophores), photoprotection from light-initiated singlet oxygen damage (triplet-triplet energy transfer from chlorophylls to carotenoid polyenes), and, most importantly, photoinduced multistep electron transfer to generate charge-separated states that preserve some of the photon energy as chemical potential. During the last three years, progress has been made on several fronts, all of which are related to the overall goal. A biomimetic system based on carotenoid-porphyrin-quinone triads has been constructed that demonstrates photoinduced transmembrane charge separation which in turn drives transmembrane proton transfer. Another investigation has focused on the use of proton transfer reactions to stabilize the initial products of photoinduced electron transfer and thereby increase the yield of long-lived charge separation. A third study has investigated the influence of rigid molecular geometries and short donor-acceptor separations on photoinduced electron transfer reactions. Finally, generation and quenching of singlet molecular oxygen by chlorophyll aggregates has been studied. All four studies are described and results are discussed.

  5. Mercury speciation by differential photochemical vapor generation at UV-B vs. UV-C wavelength

    Science.gov (United States)

    Chen, Guoying; Lai, Bunhong; Mei, Ni; Liu, Jixin; Mao, Xuefei

    2017-11-01

    Photochemical vapor generation (PVG) is an effective sample introduction scheme for volatile mercury (Hg). Speciation of Hg++ and MeHg+ was fulfilled for the first time by differential PVG under UV-B vs. UV-C wavelength and applied to fish oil supplements. After liquid-liquid extraction, the aqueous extract was mixed with 0.4% anthranilic acid (AA)-20% formic acid (FA) in a quartz coil, and exposed sequentially to 311 nm or 254 nm UV light. The resulting Hg0 vapor was detected by atomic fluorescence spectrometry (AFS). At each wavelength, the AFS intensity was a linear function of Hg++ and MeHg+ concentrations, which were solvable from a set of two equations. This method achieved ultrahigh sensitivity with 0.50 and 0.63 ng mL- 1 limits of detection for Hg++ and MeHg+, respectively, and 73% recovery for MeHg+ at 10 ng mL- 1. Validation was performed by ICP-MS on total Hg. Obviation of chemical or chromatographic separation rendered this method rapid, green, and cost-effective.

  6. Reductive defluorination of perfluorooctanoic acid by hydrated electrons in a sulfite-mediated UV photochemical system.

    Science.gov (United States)

    Song, Zhou; Tang, Heqing; Wang, Nan; Zhu, Lihua

    2013-11-15

    A method for reductive degradation of perfluorooctanoic acid (PFOA) was established by using a sulfite/UV process. This process led to a PFOA removal of 100% at about 1h and a defluorination ratio of 88.5% at reaction time of 24h under N2 atmosphere, whereas the use of either UV irradiation or SO3(2-) alone induced little defluorination of PFOA under the same conditions. It was confirmed that the reductive defluorination of PFOA was achieved by hydrated electrons being generated from the photo-conversion of SO3(2-) as a mediator. Theoretical reaction kinetic analysis demonstrated that the generation of hydrated electrons was promoted by increasing either SO3(2-) concentration or solution pH, leading to the acceleration of the PFOA defluorination. Accompanying the reduction of PFOA, a small amount of short-chain perfluorocarboxylic acids, less fluorinated carboxylic acids and perfluorinated alkyl sulfonates were generated, all of which were able to be further degraded with further releasing of fluoride ions. Based on the generation, accumulation and distribution of intermediates, hydrated electrons induced defluorination pathway of PFOA was proposed in a sulfite-mediated UV photochemical system. Copyright © 2013 Elsevier B.V. All rights reserved.

  7. Effect of photochemical smog on the peripheral lymphocytes of nonsmoking college students

    Energy Technology Data Exchange (ETDEWEB)

    Magie, A.R.; Abbey, D.E.; Centerwall, W.R.

    1982-10-01

    The primary objective of this study was to determine whether the incidence of chromosome aberrations in peripheral lymphocytes of young adults emigrating from and immigrating to an area with perpetually high levels of photochemical air pollutants versus an area of low levels differed significantly from students indigenous to the respective areas. Three hundred and ninety-eight male and female first-year students at the La Sierra campus of Loma Linda University (high smog) and Pacific Union College (low smog) were preenrolled after completing a lifestyle questionnaire or responding to a similar telephone-administered questionnaire. They were assigned to groups according to their previous lifetime exposure to air pollution and the college in which they were matriculating. Blood samples and updated health histories were obtained from the students during September and November 1976. One hundred cells from each student were analyzed for chromosome and chromatid abberations. No statistically significant differences in the aberrates rates for the types of chromosome abnormalities studied were observed between the four exposure groups of students at each of the sampling periods or among the same students over the duration of the study. An exception of statistical significance was the elevated rate of stable changes in the initial blood sampling period for males in the low-to-high exposure group who had arrived on campus within 3 days of the blood sampling.

  8. Photoluminescence and AFM characterisation of photochemically etched highly resistive n-type silicon

    Energy Technology Data Exchange (ETDEWEB)

    Hadjersi, T.; Gabouze, N. [Unite de Developpement de la Technologie du Silicium (UDTS), 2, Bd. Frantz Fanon, B.P. 399 Alger-Gare, Alger (Algeria); Kooij, E.S. [Solid State Physics, MESA+ Research Institute, University of Twente, P.O. Box 217, 7500 AE Eschede (Netherlands); Yamamoto, N. [Communications Research Laboratory, Basic and Advanced Research, Division, 4-2-1, Nukui- kitamachi, Koganei,Tokyo, 184-8795 (Japan); Sakamaki, K.; Takai, H. [Tokyo Denki University, Department of Electrical Engineering, 2-2 Kanda-Nishiki-cyo, Chiyoda-ku, Tokyo, 101-8457 (Japan)

    2005-06-01

    A light-emitting layer has been made on highly resistive n-type silicon (6.4 k and ohm;cm) using photochemical etching in a mixture of HF with H{sub 2}O{sub 2}. The morphology of the porous films grown after exposure to a He-Ne laser (633 nm) at normal incidence was analysed by Atomic Force Microscopy (AFM). The results show that the film obtained are porous and the morphology of the porous layer obtained are shown to be similar to that obtained by the electrochemical method on highly doped silicon. Furthermore, excitation of the porous silicon layer formed on highly resistive silicon samples under He-Cd laser (325 nm) irradiation shows that the PL intensity increases with increasing etching time. The maximum PL spectrum peaked at 636 nm with a FWHM of about 0.3 eV. Finally, the quantum confinement effect has been invoked to explain the bright, visible, room temperature PL of porous silicon (PS). (copyright 2005 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  9. Photochemical and antimicrobial properties of silver nanoparticle-encapsulated chitosan functionalized with photoactive groups.

    Science.gov (United States)

    Mathew, Thomas V; Kuriakose, Sunny

    2013-10-01

    Chitosan was functionalized with 4-((E)-2-(3-hydroxynaphthalen-2-yl)diazen-1-yl)benzoic acid by the coupling of the hydroxyl functional groups of chitosan with carboxylic acid group of the dye by DCC coupling method. The silver nanoparticles were prepared by sol-gel method of nanoparticle synthesis. Silver nanoparticle-encapsulated functionalized chitosan was prepared by the phase transfer method. The products were characterized by FTIR, UV-Vis, fluorescence and NMR spectroscopic methods and by SEM and TEM analysis. The photochemical properties of silver nanoparticle-encapsulated chitosan functionalized with 4-((E)-2-(3-hydroxynaphthalen-2-yl)diazen-1-yl)benzoic acid was studied in detail. The light-fastening properties of the chromophoric system was enhanced when attached to chitosan, and it can be further improved by the encapsulation of silver nanoparticles. The antibacterial analysis of silver nanoparticle-encapsulated functionalized chitosan was carried out against Staphylococcus aureus and Escherichia coli and against fungal species such as Aspergillus flavus and Aspergillus terreus. This study showed that silver nanoparticles-encapsulated functionalized chitosan can be used for antibacterial and antifungal applications. © 2013.

  10. Detailed photochemical simulation of Nitryl Chloride chemistry: impacts of temperature and emission profiles

    Science.gov (United States)

    Rasoul, Tara; Kramer, Louisa; Pope, Francis; Sommariva, Roberto; Bloss, William

    2017-04-01

    A detailed photochemical box model utilizing the near-explicit Master Chemical Mechanism was extended to simulate heterogenous ClNO2 formation including condensed-phase reactions. The model has been validated against ClNO2 observations in an urban and rural environment and is employed to: (1) Evaluate the impact of nitryl chloride (ClNO2) chemistry on the formation of HOx, and abundance of NOx, O3, and VOCs in a range of typical urban background environments; (2) Assess the influence of temperature variations upon the production and impact of ClNO2 chemistry as this is of particular importance in future climate with potentially different global temperatures; and (3) Assess the impacts of potential changes in emission patterns to evaluate the interaction of this chemistry with changing source terms i.e. human behaviour. The simulations demonstrate that the formation of ClNO2 enhances the production of OH, HO2, CH3O2, HNO3, HCHO and O3, and decreases the NO, NO2, and H2O2 levels under typical mid-latitude continental boundary layer conditions. Moreover, the model shows that the production of ClNO2 and its impact on air quality is highly sensitive to atmospheric temperature in all seasons.

  11. Effluent organic nitrogen (EON): bioavailability and photochemical and salinity-mediated release.

    Science.gov (United States)

    Bronk, Deborah A; Roberts, Quinn N; Sanderson, Marta P; Canuel, Elizabeth A; Hatcher, Patrick G; Mesfioui, Rajaa; Filippino, Katherine C; Mulholland, Margaret R; Love, Nancy G

    2010-08-01

    The goal of this study was to investigate three potential ways that the soluble organic nitrogen (N) fraction of wastewater treatment plant (WWTP) effluents, termed effluent organic N (EON), could contribute to coastal eutrophication--direct biological removal, photochemical release of labile compounds, and salinity-mediated release of ammonium (NH4+). Effluents from two WWTPs were used in the experiments. For the bioassays, EON was added to water from four salinities (approximately 0 to 30) collected from the James River (VA) in August 2008, and then concentrations of N and phosphorus compounds were measured periodically over 48 h. Bioassay results, based on changes in DON concentrations, indicate that some fraction of the EON was removed and that the degree of EON removal varied between effluents and with salinity. Further, we caution that bioassay results should be interpreted within a broad context of detailed information on chemical characterization. EON from both WWTPs was also photoreactive, with labile NH4+ and dissolved primary amines released during exposure to sunlight. We also present the first data that demonstrate that when EON is exposed to higher salinities, increasing amounts of NH4+ are released, further facilitating EON use as effluent transits from freshwater through estuaries to the coast.

  12. Photochemical determination of O densities in the Martian thermosphere: Effect of a revised rate coefficient

    Science.gov (United States)

    Fox, Jane L.; Johnson, Austin S.; Ard, Shaun G.; Shuman, Nicholas S.; Viggiano, Albert A.

    2017-08-01

    We investigate the production and loss rates of O2+ in the photochemical equilibrium region of the Martian ionosphere near the subsolar point. We adopt neutral and ion densities measured by the Mars Atmosphere and Volatiles EvolutioN (MAVEN) Neutral Gas and Ion Mass Spectrometer (NGIMS), electron densities and temperatures measured by the Langmuir Probe and Waves, and ion temperatures measured by the Supra-Thermal and Thermal Ion Composition instruments on the MAVEN spacecraft. Contrary to the conventional wisdom, we find that loss of O2+ by dissociative recombination is balanced mainly by production due to the reaction of O+ with CO2, with a smaller contribution due to the reaction of CO2+ with O. We find that the O densities derived from this calculation are larger than those measured by the NGIMS instrument by a factor that averages about 4 over the range of 130-155 km. This general conclusion is supported by a newly measured rate coefficient for the reaction of O with CO2+, which is smaller by a factor of about 6 than the only value in the literature, which was measured 47 years ago.

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

    Science.gov (United States)

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

    2014-12-01

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

  14. Nonsymmetrical 3,4-dithienylmaleimides by cross-coupling reactions with indium organometallics: synthesis and photochemical studies.

    Science.gov (United States)

    Mosquera, Angeles; Férnandez, M Isabel; Canle Lopez, Moisés; Pérez Sestelo, José; Sarandeses, Luis A

    2014-10-27

    The synthesis and photochemical study of novel nonsymmetrical 1,2-dithienylethenes (DTEs) with a maleimide bridge have been carried out. The synthetic approach to the DTEs was based on successive selective palladium-catalyzed cross-coupling reactions of 5-susbtituted-2-methyl-3-thiophenyl indium reagents with 3,4-dichloromaleimides. The required organoindium reagents were prepared from 2-methyl-3,5-dibromothiophene by a selective (C-5) coupling reaction with triorganoindium compounds (R3 In) and subsequent metal-halogen exchange. The coupling reactions usually gave good yields and have a high atom economy with substoichiometric amounts of R3 In. The results of photochemical studies show that these novel dithienylmaleimides undergo a photocyclization reaction upon irradiation in the UV region and a photocycloreversion after excitation in the visible region, thus they can be used as photochemical switches. ON-OFF operations can be repeated in successive cycles without appreciable loss of effectiveness in the process. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Juggling Efficiency

    DEFF Research Database (Denmark)

    Andersen, Rikke Sand; Vedsted, Peter

    2015-01-01

    on institutional logics, we illustrate how a logic of efficiency organise and give shape to healthcare seeking practices as they manifest in local clinical settings. Overall, patient concerns are reconfigured to fit the local clinical setting and healthcare professionals and patients are required to juggle...... efficiency in order to deal with uncertainties and meet more complex or unpredictable needs. Lastly, building on the empirical case of cancer diagnostics, we discuss the implications of the pervasiveness of the logic of efficiency in the clinical setting and argue that provision of medical care in today......'s primary care settings requires careful balancing of increasing demands of efficiency, greater complexity of biomedical knowledge and consideration for individual patient needs....

  16. Comparative Effects of Salt Stress and Extreme pH Stress Combined on Glycinebetaine Accumulation, Photosynthetic Abilities and Growth Characters of Two Rice Genotypes

    Directory of Open Access Journals (Sweden)

    Suriyan CHA-UM

    2009-12-01

    Full Text Available Glycinebetaine (Glybet accumulation, photosynthetic efficiency and growth performance in indica rice cultivated under salt stress and extreme pH stress were investigated. Betaine aldehyde dehydrogenase (BADH activity and Glybet accumulation in the seedlings of salt-tolerant and salt-sensitive rice varieties grown under saline and acidic conditions peaked after treatment for 72 h and 96 h, respectively, and were higher than those grown under neutral pH and alkaline salt stress. A positive correlation was found between BADH activity and Glybet content in both salt-tolerant (r2 = 0.71 and salt-sensitive (r2 = 0.86 genotypes. The chlorophyll a, chlorophyll b, total chlorophyll and total carotenoids contents in the stressed seedlings significantly decreased under both acidic and alkaline stresses, especially in the salt-sensitive genotype. Similarly, the maximum quantum yield of PSII (Fv/Fm, photon yield of PSIIPSII, non-photochemical quenching (NPQ and net photosynthetic rate (Pn in the stressed seedlings were inhibited, leading to overall growth reduction. The positive correlations between chlorophyll a content and Fv/Fm, total chlorophyll content and ΦPSII, ΦPSII and Pn as well as Pn and leaf area in both salt-tolerant and salt-sensitive genotypes were found. Saline acidic and saline alkaline soils may play a key role affecting vegetative growth prior to the reproductive stage in rice plants.

  17. Interstellar/Precometary Organic Material and the Photochemical Evolution of Complex Organics

    Science.gov (United States)

    Allamandola, Lou J.; Bernstein, Max; Sandford, Scott; Witteborn, Fred (Technical Monitor)

    1996-01-01

    During the past two decades ground-, air-, and space-based infrared spectroscopic observations, combined with realistic laboratory simulations, have revolutionized our understanding of interstellar ice and dust, the raw materials from which planets, comets and stars form. Most interstellar material is concentrated in Large molecular clouds where simple molecules are formed by dust grain and gas phase reactions. Gaseous species striking the cold (10 K) dust will stick, forming an icy grain mantle. This accretion, coupled with energetic particle bombardment and UV photolysis, will produce a complex chemical mixture containing volatile, non-volatile, and isotopically fractionated species. Ices in molecular clouds contain the very simple molecules H2O, CH3OH, CO, CO2, H2, and perhaps some NH3 and H2CO, as well as more complex species including nitriles and ketones or esters. The evidence for these compounds as well as carbon rich materials such as polycyclic aromatic hydrocarbons (PAHs), microdiamonds, and amorphous carbon will be reviewed and the possible connections with comets and meteorites will be presented in the first part of the talk. The second part of the presentation will focus on interstellar/precometary ice photochemical evolution. The chemical composition and photochemical evolution of realistic interstellar/pre-cometary ice analogs containing methanol will be discussed. ultraviolet photolysis of these ices produces H2, H2CO, CO2, CO, CH4, HCO, and more complex molecules. Infrared spectroscopy, H-1 and C-13 nuclear magnetic resonance (NMR) spectroscopy, and gas chromatography-mass spectrometry demonstrate that when ices representative of interstellar grains and comets are exposed to UV radiation at low temperature a series of moderately complex organic molecules are formed in the ice including: CH3CH2OH (ethanol), HC(=O)NH2 (formamide), CH3C(=O)NH2 (acetamide), and R-C(integral)N (nitriles). Several of these are already known to be in the interstellar

  18. Batch efficiency

    CERN Document Server

    Schwickerath, U; Uria, C; CERN. Geneva. IT Department

    2010-01-01

    A frequent source of concern for resource providers is the efficient use of computing resources in their centers. This has a direct impact on requests for new resources. There are two different but strongly correlated aspects to be considered: while users are mostly interested in a good turn-around time for their jobs, resource providers are mostly interested in a high and efficient usage of their available resources. Both things, the box usage and the efficiency of individual user jobs, need to be closely monitored so that the sources of the inefficiencies can be identified. At CERN, the Lemon monitoring system is used for both purposes. Examples of such sources are poorly written user code, inefficient access to mass storage systems, and dedication of resources to specific user groups. As a first step for improvements CERN has launched a project to develop a scheduler add-on that allows careful overloading of worker nodes that run idle jobs.

  19. Long-Wavelength Limit of Photochemical Energy Conversion in Photosystem I

    Science.gov (United States)

    2014-01-01

    In Photosystem I (PS I) long-wavelength chlorophylls (LWC) of the core antenna are known to extend the spectral region up to 750 nm for absorbance of light that drives photochemistry. Here we present clear evidence that even far-red light with wavelengths beyond 800 nm, clearly outside the LWC absorption bands, can still induce photochemical charge separation in PS I throughout the full temperature range from 295 to 5 K. At room temperature, the photoaccumulation of P700+• was followed by the absorbance increase at 826 nm. At low temperatures (T absorbance difference spectrum in the QY region. P700 oxidation was observed upon selective excitation at 754, 785, and 808 nm, using monomeric and trimeric PS I core complexes of Thermosynechococcus elongatus and Arthrospira platensis, which differ in the amount of LWC. The results show that the LWC cannot be responsible for the long-wavelength excitation-induced charge separation at low temperatures, where thermal uphill energy transfer is frozen out. Direct energy conversion of the excitation energy from the LWC to the primary radical pair, e.g., via a superexchange mechanism, is excluded, because no dependence on the content of LWC was observed. Therefore, it is concluded that electron transfer through PS I is induced by direct excitation of a proposed charge transfer (CT) state in the reaction center. A direct signature of this CT state is seen in absorbance spectra of concentrated PS I samples, which reveal a weak and featureless absorbance band extending beyond 800 nm, in addition to the well-known bands of LWC (C708, C719 and C740) in the range between 700 and 750 nm. The present findings suggest that nature can exploit CT states for extending the long wavelength limit in PSI even beyond that of LWC. Similar mechanisms may work in other photosynthetic systems and in chemical systems capable of photoinduced electron transfer processes in general. PMID:24517238

  20. Drosophila TRPA1 isoforms detect UV light via photochemical production of H2O2

    Science.gov (United States)

    Guntur, Ananya R.; Gu, Pengyu; Takle, Kendra; Chen, Jingyi; Xiang, Yang; Yang, Chung-Hui

    2015-01-01

    The transient receptor potential A1 (TRPA1) channel is an evolutionarily conserved detector of temperature and irritant chemicals. Here, we show that two specific isoforms of TRPA1 in Drosophila are H2O2 sensitive and that they can detect strong UV light via sensing light-induced production of H2O2. We found that ectopic expression of these H2O2-sensitive Drosophila TRPA1 (dTRPA1) isoforms conferred UV sensitivity to light-insensitive HEK293 cells and Drosophila neurons, whereas expressing the H2O2-insensitive isoform did not. Curiously, when expressed in one specific group of motor neurons in adult flies, the H2O2-sensitive dTRPA1 isoforms were as competent as the blue light-gated channelrhodopsin-2 in triggering motor output in response to light. We found that the corpus cardiacum (CC) cells, a group of neuroendocrine cells that produce the adipokinetic hormone (AKH) in the larval ring gland endogenously express these H2O2-sensitive dTRPA1 isoforms and that they are UV sensitive. Sensitivity of CC cells required dTRPA1 and H2O2 production but not conventional phototransduction molecules. Our results suggest that specific isoforms of dTRPA1 can sense UV light via photochemical production of H2O2. We speculate that UV sensitivity conferred by these isoforms in CC cells may allow young larvae to activate stress response—a function of CC cells—when they encounter strong UV, an aversive stimulus for young larvae. PMID:26443856